Annual Report of User’s Meeting on”Condensed-matter Chemistry in Actinides and their
Applications” and”Production of Medical RIs by Reactor Irradiation”

CCA, KURNS, Kyoto University
Mar. 31, 2023

The originating Section of this publication in the KURNS, Kyoto University was: The CCA
lab. (The laboratory in the ﬁeld of Condensed-matter Chemistry on Actinides) 2,
Asashiro-Nishi, Kumatori-cho, Sennan-gun, Osaka 590-0494 JAPANAnnual Report of User’s Meeting on”Condensed-matter Chemistry in Actinides and their Applications” and”Production of Medical RIs by Reactor Irradiation”
Institute for Integrated Radiation and Nuclear Science (KURNS),
Kyoto University
Published by CCA, KURNS, Kyoto Univ. in Japan
Mar. 31, 2023

Preface
This workshop was co-organized by Prof. H. Yamagami (Kyoto Sangyo Univ.), who is atheoretical researcher of condensed matter physics of actinides, to provide a basis for current
and future research activities on actinide science. The actinide science stems from basic researchon condensed matter physics and chemistry, to research on nuclear fuel cycle and radioactive
waste as its application, and recently to basic research on 1F debris and nuclear medicine.
The community has held annual workshops at Tohoku University and Kyoto University since2008. Also, we co-chaired the executive committee of the Actinides International Conference”Actinides2017” which was held in Sendai, Japan, in 2017. This conference was held just prior
to the recent ”Actinides2023” conference in Denver (June 4-8, 2023), which was originallyplanned as ”Actinides2021” but postponed due to COVID-19.
Our institute (KURNS, Kyoto University) has decided to shut down our KUR reactor in 2026.
Based on discussions in Japan, a new research reactor will be built at Fukui, and the institutewill participate in its construction and operation of cooperative researches among universities.
On the other hand, the future of the Kumatori site, where the institute is currently located, iscurrently being discussed. Among the discussions, the core of the Kumatori site has gradually
been recognized as the hot laboratory, which is expected to play an important role in basic
research on actinides, radioactive wastes, and cancer treatments as nuclear research in a broad
sense.
Kyoto University and JAEA have been conducting overseas research to contribute to thedetailed design of the Fukui Reactor, including visits to the University of Missouri Reactor(MURR) in the United States, the High Flux Isotope Reactor (HFIR) and the RadiochemistryEngineering Development Center (REDC) at Oak Ridge National Laboratory (ORNL), andSHINE Technologies. As the saying goes, a picture is worth a thousand words, it was very
meaningful for us to hear in-depth research discussions with many researchers at various sites

2during this laboratory visit. When we discussed with them that we would like to share with theJapanese community at the research meeting, all the people we had discussions with agreed to
do so, despite the short time between the visit and the lecture. We would like to thank you again
for this valuable opportunity.
Since two years before, we have registered the report in the Kyoto University Academic
Repository KURENAI to make it available to a wider audience and to preserve it permanently.
We hope that the publication of this book in the repository will attract more people, especially
young people, to the ﬁeld of condensed matter chemistry of actinides and its applications.
June, 2023
Tomoo Yamamura
Professor, KURNS, Kyoto Univ.

Preface to the First Publication of the Report of the Topical Meeting on”Topical meeting on Condensed-matter Chemistry on Actinides”
This workshop was organized by Prof. Tomoo Yamamura and his colleageees at the Institutefor Integrated Radiation and Nuclear Science, Kyoto University, and the ﬁrst meeting was held
on February 7, 2020. This booklet is a report of the meeting.
Although the new coronavirus infection spread worldwide in these days, it was greatful tohold a meeting with 42 researchers from a wide range of ﬁelds in basic research of actinide
science, both domestic and overseas.
I would like to express my thoughts on the purpose of establishing this workshop. The
main focus of this group is ”basic research and its application in actinide science” in a broad
perspective, and we will deal with a wide range of research topics with an interest in experimentand theory, basics and applications. It is also a research group where researchers from various
research ﬁelds such as physics, chemistry, biology, engineering, and medicine come together.
The main participants are joint users of the Institute for Integrated Radiation and Nuclear Science,but many other researchers are also attracted by the activities of the group.
I hope that this workshop will provide an opportunity to learn about the latest research resultsfrom diﬀerent ﬁelds, to understand each ﬁeld from a new persrective, and to get feedback forour own research. Furthermore, it would be great if we could create new research themes andcollaborations that are cross-cutting and complementary among the ﬁelds. In order to achieve
the purpose, it is necessary for the meeting to be a place for open academic exchange anddiscussions, and I hope that you will continue to actively participate. In addition, due to theunique nature of the ﬁeld of actinide science, there is an urgent need to pass on sustainable
technologies and skills and to develop young human resources, and we welcome student-levelparticipation in this workshop.
We look forward to your continued cooperation in making this a successful and open forum
for active discussion.
4

March 23, 2020
Hiroshi Yamagami,
Kyoto Sangyo University

Contents

Chapter 1 Program

1

Chapter 2 Presentation Materials

5

2.1

T. Yamamura（KURNS, Kyoto Univ.）
Combined Research Institute, joint use of the relevant ﬁelds, facilities and futureplans . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

2.2

H. Yamagami（Kyoto Sangyo Univ.）
Goals of Specialized Research Groups . . . . . . . . . . . . . . . . . . . . . .

2.3

7

9

Y. Haga（ASRC, JAEA）
Single crystal growth and electronic structure of uranium compound superconductor UTe2 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

2.4

11

M. Nakase（Tokyo Inst. Tech.）
On a New Approach to Exploration of Novel Solvent Extraction Systems for
Minor Actinide Extraction for Next Generation Reprocessing . . . . . . . . . .

2.5

A. Ishii（Teikyo Univ. of Science）
New optical functions opened up by rare- earth hybrid materials . . . . . . . .

2.6

16

20

M. Nogami（Kindai Univ.）
Complexation behavior of actinyl ion- coordinating monoamide compounds with
FP ions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

2.7

27

K. Shirasaki（IMR, Tohoku Univ.）
Ac-228 solvent extraction by DGA . . . . . . . . . . . . . . . . . . . . . . . .

6

31

2.8

T. Kobayashi（SPring-8, JAEA）
Achievements in the facility utilization of the Combined Research Laboratory
and the current status with the SPring-8 JAEA Harima Lab. . . . . . . . . . . .

2.9

37

Y. Kasamatsu（Osaka Univ.）
Recent chemical researches on nobelium . . . . . . . . . . . . . . . . . . . . .

41

2.10 T. Yoshimura（IRS, Osaka Univ.）
Introduction to Institute for Radiation Sciences, Osaka University . . . . . . . .

46

2.11 Y. Sakurai（KURNS, Kyoto Univ.）
Report on Survey of Hot Labs and RI Studies in the U.S. (1) . . . . . . . . . .

48

2.12 H. Yoshinaga（KURNS, Kyoto Univ.）
Report on Survey of Hot Labs and RI Studies in the U.S. (2) . . . . . . . . . .

53

2.13 T. Yamamura（KURNS, Kyoto Univ.）
Discussions on facilities . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

54

2.14 M. Nakase（Tokyo Inst. Tech.）Opening of 2nd-day Discussions . . . . . . . . . . . . . . . . . . . . . . . . .

60

2.15 Greg Piefer（SHINE Technologies, Inc.）
Plan and prospect of SHINE Technology . . . . . . . . . . . . . . . . . . . . .

61

2.16 Laetitia H. Delmau（Oak Ridge National Laboratory）
Overview of the Cf-252 and Pm-147 Production Eﬀorts at ORNL . . . . . . . .

62

2.17 Rob Hall（MURR, Missouri University）
Recent activities, systems, and facilities of MURR for radiophermaceutical R&D 68
2.18 Toro Gonzalez（Oak Ridge National Laboratory）
Lanthanide-based and Poly(lactic-co-glycolic acid) Nanoparticles in Targeted
Alpha Therapy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

74

2.19 Julie G. Ezold（Oak Ridge National Laboratory）
Radiochemical Processing at Oak Ridge National Laboratory . . . . . . . . . .

79

2.20 K. Ishida（Kyoto Univ.）
Nuclear magnetic resonance in uranium compound superconductors . . . . . .

84

2.21 H. Shishido（Tohoku Univ.）
First-principles calculations for CALPHAD calculations of minor actinide fuels89

2.22 M. Abe（Hiroshima Univ.）
Development of relativistic electron correlation program for calculation of actinide compounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

94

2.23 H. Kimura（Kyoto Pharmaceutical Univ.）
Tumor-targeted radio-ceranostics drug discovery and clinical application . . . . 100
2.24 M. Suzuki（KURNS, Kyoto Univ.）
Quantum Beam Bio-Systems Analysis and Application Unit . . . . . . . . . . . 104
2.25 T. Suzuki（Nagaoka Univ. Tech.）
Dissolution of Thorium Oxide and Separation of Radium . . . . . . . . . . . . 109
Chapter 3 Y. Haga（ASRC, JAEA）
Concluding Remarks

112

Chapter 4 Summary of Discussion

116

Chapter 5 List of Participants

117

Chapter 6 Photos of the workshop

119Chapter 1

Program（Listed on the next page）

1

2

Hiroshi Yamagami
Yoshinori Haga

13:10~13:20 (10 min.)13:25~13:45 (20 min.)Hisao Yoshinaga
Tomoo Yamamura

16:45~17:00 (15 min.)

17:00~17:10 (10 min.)

Yoshinori Sakurai

16:30~16:45 (15 min.)

Yamamura

Takashi Yoshimura

16:05~16:25 (20 min.)

Yoshitaka
Kasamatsu

15:45~16:05 (20 min.)

NakaseTohru Kobayashi

15:20~15:40 (20 min.)

Kenji Shirasaki

15:00~15:20 (20 min.)Kasamatsu

Masanobu Nogami

14:30~14:50 (20 min.)Ayumi Ishii

14:10~14:30 (20 min.)

FukudaMasahiko Nakase

13:45~14:05 (20 min.)Yamagami

Tomoo Yamamura

Speaker

13:00~13:10 (10 min.)Mar. 2Chair

Time (JST)Date

Institute for Integrated
Radiation and Nuclear
Science, Kyoto University

KURNS, Kyoto Univ.

KURNS, Kyoto Univ.

1

Radioisotope ResearchCenter, Institute for
Radiation Sciences, Osaka
University

Graduate School of
Science, Osaka University

Actinide chemistry group,
Materials Sciences
research center, Japan
Atomic Energy Agency

IMR, Tohoku University

Kindai University

Teikyo University of
ScienceTokyo Institute ofTechnology

Advanced Science
Research Center, Japan
Atomic Energy Agency

Kyoto Sangyo University

Institute for Integrated
Radiation and Nuclear
Science, Kyoto University

Aﬃliation

Combined Research Institute, joint use of
the relevant fields, facilities and future plans
Goals of Specialized Research Groups
Single crystal growth and electronic
structure of uranium compoundsuperconductor UTe2

複合研、当該分野の共同利用、施設

専門研究会の目標
ウラン化合物超伝導体UTe2の単結晶

Ac-228 solvent extraction by DGA

Introduction to Institute for Radiation
Sciences, Osaka University

Report on Survey of Hot Labs and RIStudies in the U.S. (1)Report on Survey of Hot Labs and RIStudies in the U.S. (2)Discussions on facilities

大阪大学放射線科学基盤機構の紹介

米国ホットラボ視察報告(1)
米国ホットラボ視察報告(2)
施設に関する議論

重アクチノイド、ノーベリウムの化学 Recent chemical researches on nobelium
研究複合研の施設供用での成果とSPring-8 Achievements in the facility utilization of the
Combined Research Laboratory and the
JAEA播磨ラボとの現状について
current status with the SPring-8 JAEA
Harima Lab.

Ac-228を用いたDGAによる溶媒抽出

アクチニルイオン配位性モノアミド化 Complexation behavior of actinyl ioncoordinating monoamide compounds with
合物のFPイオンとの錯形成挙動
FP ions

希土類ハイブリッド材料が拓く新光機 New optical functions opened up by rareearth hybrid materials
能次世代再処理に向けたマイナーアクチ On a New Approach to Exploration of Novel
ノイド抽出のための新規溶媒抽出系探 Solvent Extraction Systems for Minor
Actinide Extraction for Next Generation
査の新しいアプローチについて
Reprocessing

育成と電子状態と将来計画

Title in English (Tentative)

Title in Japanese (Tentative)

Agenda of User’s meeting on “Condensed-matter Chemistry in Actinides and their Applications” and“Production of medical RIs by Reactor Irradiation”
Location: Main Conference Room, Office Building, KURNS, Kyoto University. (Hybrid)3

Mar. 3

Shirasaki

Sakurai

FukudaHaga

8:35~8:55 (20 min.)9:00~9:20 (20 min.)9:25~9:45 (20 min.)9:50~10:10 (20 min.)

Yoshinori Haga

Mari Toyama

12:20~12:30 (10 min.)

14:00~15:00 (60 min.)

Tatsuya Suzuki

Toyama12:00~12:20 (20 min.)Hiroyuki Kimura
Minoru Suzuki

Shirasaki

11:40~12:00 (20 min.)

11:20~11:40 (20 min.)Minori Abe

Hiroki Shishido

10:35~10:55 (20 min.)

10:55~11:15 (20 min.)

Kenji Ishida

Julie G. Ezold

Toro Gonzalez

Rob Hall

10:10~10:30 (20 min.)Yamagami

Greg Piefer

Nakase8:05~8:30 (25 min.)Laetitia H. Delmau

Masahiko Nakase

8:00~8:05 (5 min.)KURNS, Kyoto Univ.

Advanced Science
Research Center, Japan
Atomic Energy Agency

Nagaoka University ofTechnology

Institute for Integrated
Radiation and Nuclear
Science, Kyoto University

Kyoto Pharmaceutical
University

Hiroshima University

Tohoku University

Kyoto University

Oak Ridge National
Laboratory

Oak Ridge National
Laboratory

2

MURR, Missouri University

Oak Ridge National
Laboratory

SHINE Technologies, Inc.

Tokyo Institute ofTechnology

First-principles calculations for CALPHAD
calculations of minor actinide fuels

マイナーアクチノイド燃料のConcluding Remarks

Facility Tour (KUR, HL)

施設見学（KUR、HL）

Dissolution of Thorium Oxide andSeparation of Radium

Concluding Remarks

酸化トリウムの溶解とラジウム分離

量子ビーム生体システム解析・応用ユ Quantum Beam Bio-Systems Analysis andApplication Unit
ニットの成果腫瘍を標的としたラジオセラノスティ Tumor-targeted radio-ceranostics drug
discovery and clinical application
クス創薬と臨床応用

アクチノイド化合物計算に向けた相対 Development of relativistic electron
correlation program for calculation of論的電子相関プログラム開発
actinide compounds

CALPHAD計算に向けた第一原理計算

Nuclear magnetic resonance in uranium
compound superconductors

ウラン化合物超伝導体の核磁気共鳴

Radiochemical Processing at Oak Ridge
National Laboratory

Lanthanide-based and Poly(lactic-coglycolic acid) Nanoparticles in Targeted
Alpha Therapy

Recent activities, systems, and facilities of
MURR for radiophermaceutical R&D

Overview of the Cf-252 and Pm-147
Production Eﬀorts at ORNL

Plan and prospect of SHINE Technology

Opening of 2nd-day Discussions

4

Chapter 2

Presentation Materials

With the permission of the speakers, the materials of their presentations are included here.

5

6

2.1 T. Yamamura（KURNS, Kyoto Univ.）
Combined Research Institute, joint use of the relevant ﬁelds, facilities andfuture plans

事務作成資料、所員会議資料に基づき作成

KURNS and post-KUR
Present
2018H
30

FY
Kyoto
Univ.

2022年度「アクチノイドの物性化学と応用・原子炉照射医療用RI製造」専門研究会
Users meeting on “Condensed-matter Chemistry in Actinides and their Applications /Production of medical RIs by Reactor Irradiation”

KURNS
Beam
Facility

複合研、当該分野の共同利用、施設と将来計画

2019
R1

2020
R2

2021
R3

Third Medium-Term Objectives
and Plans

2023
R5

2025
R7

2026R
8

2027
R9

2028
R10

2029
R11

2030
R12

2031
R13

2032
R14

2033
R15

5th Medium-Term Objectives and Plans
KUR decommissioning

KUR Termination
Cyclotron maintenance and operation

Cyclotron operation

operation

Conceptual design

New RR

2024
R6

4th Medium-Term Objectives and Plans

KUR Operation
Adaptation to new
regulatory standards

LINAC

Combined Research Institute, joint use of this fields,
facilities and future plans

2022
R4

Detailed design and construction support

Implementation of activities

New research building + Renovation + Relocation

Building

Rental Laboratory in operations

2023.3.2 13:00-13:10
T. Yamamura, KURNS, Kyoto Univ.

KURNS

In addition to KUR
various Particle Beam and RIApplications

KUR Utilization Research

Name changed
Reorganization
KURNS
othersDiscussions on reorganization
Present（2022.2）

FY2026（plan）

Director

Director

Production of radioisotopes in our group

所員会議資料に基づき作成• Conventional production results (see table below)• Expected to produce ³+, ³- and ³-nuclides in the• Complementary activities in Japan• LINAC, Center for Electron Photonics, Tohoku Univ.

• Bremsstrahlung irradiation at LINAC• Production of medical nuclides (177Lu, 166Ho, etc.)• Short-lived RI supply platform (Osaka Univ.)

post-KUR period

X Division (Various Quantum Beam Utilization Research)
Materials, Life, Materials, Earth, Space, Environment New experimental andresearch reactors, medical applications Development of quantum beam sources
and accelerators

Division of Quantum Beam Material Science
組織再編

at Fukui reactor, support for separation andpurification
Th generator (under study)

RI application research, R&D for medical RI production, nuclear medicine research (including
animal and clinical experiments)
Basic and applied actinide research (including nuclear fuel and MA)Radiochemical analysis

Research Center for Safe Nuclear System

Nuclides produced and utilized at KUR and LINAC at KURNS
H
Li

Division Z (Reactor and Decommissioning Research)Particle Radiation Oncology Research Center

Nuclear Safety, Safety Management, Radiation, Radioactive Waste
SMR, Decommissioning, Nuclear Human Resource Development
Nuclear Social Science

Research Unit

BeNa

42 (12h) B
43 (22h) B

Frontier Center for Integrated Nuclear Science and Technology

Layer

Mg

K

Research Unit
Research Unit

CaSc

47 (4.5d) B

47 (3.4d) B

83 (86d) B

Cs

cooperation

Dotted lines indicate internal organizations
based on internal rules and regulations.

Y

Bottom

³

Ti

V

Cr

91 (59d) B

85 (65d) B

Ba

88 (106d) B

Ln

95 (64d) BFr(e.g. JRR-3, J-PARC, SPring-8, PF)

95 (35d) B

Ra

Ta

W

La

Ce

Pr

Ac

Th

Pa

A7JBU!I7/_X]GZ

HV


t

可視化技術=
分子イメージング技術
SPECT
単光子放射型
断層撮影

purity, specific activity, chemical purity
guidelines)

PET
陽電子放射
型断層撮影

s

u

r

核医学
治療

 T aefibgN(]L6
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Q@U!I

from research to commercial

community, separation and purification
technology development)[1] T. Yamamura, et al., Radiation Safety Management, 19 (2020) 35.
木村寛之先生の資料、鷲山幸信先生、日野正裕先生らとの議論を参考にしています。

5Ag

105 (35h) BMS

ReOs

188 (89h) T

193 (30h) MOF

13 (10m) B

15 (2.0m) B

18 (109m) P

24 (15h) B
22 (2.6y) B

Si

P

S

Cl

Ar

Se

Br

Kr

Te

I

Xe

Po

At

32 (14d) B
33 (25d) B
34 (32m) B

Zn

Ga

Ge

As

68 (67m) P

Cd
115 (53h) B

In

74 (18d) B

SnSb

115m (4.5h) B 119m (293d) M

101 (3.3y) B

103 (17d) B

105 (41d) B

109 (463d) B

111 (2.8d) P

Ir

Pt

Au

Hg

Tl

197 (18h) M

198 (2.7d) T
199 (3.1d) T

197 (18h) M

196 (6.2d) B

Sm

Eu

Gd

Tb

Pu

Am

Cm

Bk

Te

122 (2.7d)120 (16m)

Pb

Bi

125m (57.4d)M
129 (70m)M
127m (109d)M
129m (34d)M

126 (13d) B

Rn

121 (17d) M
121m (154d) M
125m (57d) M
129 (70m) M
127m (109d) M
129m (34d) M

Nd

Pm

U

Np

237 (6.8d) B

236 (23h) M

149 (53h) T

157 (15.2d) M
149 (93d) M

Dy

Ho
166 (27h) MT
164 (29m) M

169 (9.4d) M

170 (129d) M
168 (93d) M

Cf

Es

Fm

Md

161 (6.9d) MT

Er

Tm

Yb

Lu

No

Lr

177 (6.7d) T
172 (6.7d) M

m+

:';

7n

F

治療用RI
[I&]9
治療薬?>\WY`>k+

診断薬

chemistry based on the "speed of valence fluctuations"

UGe2
$

+

9M.1]%

診断薬" Various properties of 5f electron systems in physics and

R:FS
UPd2Al3, UNi2Al3, URu2Si2, UGe2, UCoGeβ-、αpoaefibg]07#,3*
T
chjdlP]C)
放出核種
qo-.1U:.1^]+

診断用RI

I&

5
O

m>7n

GV

:';[F]k<JTK ]D2

aefibg/#]P]C

4E"]= ]87

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peroxide

治療薬

セラノスティクス 放射性医薬品

Assembled insolution
Copyrighting" Expectations for complex laboratories" Intermediate scale stage of transition" Backup for Fukui Reactor (researchPdN

14 (5730y) B
11 (20m) B

Actinide Basics

Q.1

Nuclear medicine and medical RI supply" Regulatory science (transfer rate [1],64 (13h) PS
67 (62h) MS

Al

He
Ne

C

225 (10d) T

Q" Requirements for medical RI supply" Radionuclide purity, radiochemical

99m (6h) SCu
62 (9.7m) P
64 (13h) PSRh

89 (78d) B

Hf

145 (6h) M

3production

RuNi

61 (1.6h) M
56 (77d) M
57 (271d) M

BAn(e.g. JAEA, University of Fukui)" Much R&D is needed for mass

99 (66h) B

Co

52 (5.6d) B

Tc

180m (5.5h) M
181 (42d) M

228 (5.8y) T
224 (3.7d) T

Institutions related to new test and research reactors

the Spotlight in Recent Years

Mo

Fe

Field
Radiation
BasicAll
Mösbauer
³
PET
³+
SPECT
³
Therapy³-、³
Planned in Italic

186 (17h) T

Institutions with KUR alternative facilities" Theranostics Radiopharmaceuticals inMn

51 (28d) B

Nb

Sym
B
M
P
S
T

Emission³³+

Zr

134 (2.1y) B
136 (13d) B
137 (30y) B

KUR Alternative Facilities

Reaction

Upper (n,³) etc
Middle (³,n)

48 (16d) B

A place where a wide variety of budding researchers and young/female researchers can be active as PIs Establishment of an in-house or
education and human resource development (Double Degree Program in Nuclear Science and Engineering, etc.) Str
Rb
Srcharge of development of test reactors to be established in Fukui Prefecture

New Research Reactor Development
and Application Center(co-collaboration center, ~11 issues @ R4 in RI
production + PAA)

• Production of large amount of 228Ra and 224Ra from

Division Y (Various Radioactive Elements Utilization Research)

Division of Radiation Life Science

Complementary
activities at Kumatori
and Fukui sites

2

1

Division of Nuclear Engineering Science

The post KUR — Promoting New
Integrated Nuclear Science for Safe
Nuclear Energy and Nuclear Innovation

組織再編
Establish partnerships withの準備 KUR alternative facility
institutions and Fukui
Road map
Reactor-related
FY2020 FY2021
institutions.
Reorganization(3 divisions and 1 center)
As an internal organization
KURNS
Frontier Center establishedprotected image

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Li40K20[UO2(O2)(OH)]60・(H2O)214

177Lu-PSMA

U60 molecule produced instrong radiation fieldPhysical properties, etc.
unknown

各回 5.76 GBq
177Luによる腫瘍の治療効果[2]Chem. Rev., 2012, 113, 1097.

[2] Richard P. Baum, et al., J. Nucl. Med., 57 (2016) 1006.

7

Radiation-resistant phthalocyanine
complexes
Variation of crystal system and magnetismof uranium-phthalocyanine sandwich
complexes depending on their oxidation
state[1] C. Tabata, et al., J. Molecular
Structure, 1277 (2022) 134870.

Origin of linearity of [O=U=O]2+:
High-precision quantum chemical
calculations including relativistic eûects
and electron correlation[1] A. Sunaga, et a., J. Phys. Chem. A, 126(2022) 8606. https://doi.org/10.1021/
acs.jpca.2c05216

University hot laboratories in Japan(102)
使用済燃料室
昭61．R1-1．355

UO2 (s)Ｓ(066)

法(070)
Ｓ 22m測定室昭48．S1．25

池(134)
スーパーミラー評価保管室
平24．S1．29[a] C. Tabata, et al., CrystEngComm, 23 (2021) 8660.
[b] K. Shirasaki, et al., J. Nucl. Mater., 563 (2022) .
[c] C. Tabata, et al., CrystEngComm, 24 (2022) 3637.粒径、結晶系の制御

Kyoto Univ.-KURNS
Present / Future plan(107)
スーパーミラー製
昭61．S1．28

γ(X),n(128)
原子炉棟南ガスボンベ庫
平18．B1． 8(003)• Actinides 2017@Sendai (Co-Executive
Committee Chair)(032)
放射線野外監視所

4

2

p

(121)
イノベーション・リサーチ・ラボラトリ
（総合研究実験棟）
平16．R3．3,377(142)
臨界集合体実験棟守衛所
令1．S1．10(138)
グランド横プレハブ倉庫
平25. S1. 23(104) スーパーミラー前室昭60．B1．25

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号
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44

45

44

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44

廊下472
防火シャッター

0.80

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276

97

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Adjacent
tracerbuilding

64

イノベーション
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WC

42

64
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準備室

PS・EPS
9

コールド

26
WC

27

多目的
WC
9

32

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出入口

Temporary control area
Outside the control area (inside the perimeter
control area)

共同利用者
控室
39

37

%

ICP-MS/MS

全学生数

%

NMR

SEM-EDX

核医薬、デブリ

物質

低温構造
人

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TEM

用途

核医薬、デブリ、MA

Lu-177の比放

物質、生命

0.80

91
3.00

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玄関ホール

Labs for Nuclear Fuel-materials also
9managed on a lab-by-lab basis

研究例

20.53

：原子炉関係（今回改修対象外）【754㎡】+91㎡（096スーパーミラー中性子導管実験室）+25㎡（104スーパーミラー前室）+27㎡（119医療照射準備室）＝897㎡：設備室【478㎡】：実験室（ホット）【1,559㎡】

１階平面図（改修後）：イノベーション・コモンズ/実験室（コールド）【256㎡】：共用部【283㎡】
事

業

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平面図

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U.S. Research Reactor and Hot Laboratory Survey
for Detailed Design of a New Research Reactor(2023/2/20-26)
DT neutron forPrivate company

NRT
HND

99Mo, 177Lu production

SHINE@2/24

2/20
2/25-26

2/20

MURR@2/20
MURR (University)

ORNL@2/23

2/22
2/22

10 MW, 6.5d/w-52w/y, 85% of expenses are income

泉

佐

野

－

学部等名
表面の原子付着・配列状況
複合原子力科学研究所

打National Laboratory

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8

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10

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昭42．S1．13

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昭53．S1．18(020)

昭38．R1．48

Ｓ 事務部資料倉庫2
昭37．R1．53

(021)
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昭39．R1．33(022)
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スーパーミラー
中性子導管実験室
昭和58

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実験室
実験室

618

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非常用発電機室

分析内容

敷地面積
建築面積
核種の同定、

Ｔ ：耐力度調査済建物
Ｓ ：耐震診断済建物（039)中性子導管室 昭和48

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(092)
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昭45．B1．8

3.00

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医療照射
準備室
平11
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（104）
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昭和60
25
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26

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Biologicalexperiments, etc. bymoving
給気機械室

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14

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8.00

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44

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（核燃料）
204

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R=

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8.00

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16
112

276

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4.00

4.80

17.00

3.50

4.55

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4.00

1.10

ホット 核燃

使用済燃料
排気機械室

8.00

府

(028) 資料収蔵庫３
昭38．R1．161

大阪府泉南郡熊取町和田二丁目
複合原子力科学研究所 放射線野外監視所

3.52

(124)
汚濁負荷量測平15．S1．8(074)
廃棄物処理用薬品庫
昭49．B1．16（130）
廃棄物処理棟西ボンベ庫（1）平20.S1.4

地

3.20

8.00

24.00

3.00

4.00

4.00

5.50

4.00

4.00

5.50

4.00

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381,897㎡

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116.00

4.00

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25

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4.24

(024) Ｓ
事務棟

Ｓ
(110)
処理棟データ管理室
平1．S1．29

昭37.R.714• Operation with the Fukui Reactor as a complementary facility

複合原子力科学研究所

8.24

昭52．B1．5

Ｓ

大阪府泉南郡熊取町

8.00(017)廃棄物処理棟 Ｓ
昭39．S1．1,209(046)
Ｓ プロパンガスボンベ室

10.0M

10

(047)
研究員宿泊所
ガスボンベ室昭50．B1．3

M

取

泉佐野市

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8.00

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昭39.平18
R1.B1.706

for users in Japan• Characteristic measurement equipments: veryＳusefulＳ

案①両側通路案

8.00(088) Ｓ
施設系資料倉庫2
昭55.S1.13

5.0M

(025)
研究員宿泊所昭39．R2．544

Ｓ (026)
中央観測所

線• Safety Management and Open Lab• Temporarily controlled area: Highly sensitive equipment for frontier research• Enhancement of hot biological research capabilities

20.00

(108)
仮設ハウス教授室昭62．S1．24

5.0M

Ｓ

Ｓ

Ｓ

令1．S1．60(052)
環境放射能分析測定室昭57. R1. 79

Co-Creation Center (proposed) "Frontier Analysis Center(045)
プロパンガスボンベ室昭52．B1．5

Ｓ(144)
事務部資料倉庫

令1．S1．20
Ｓ (146)
複合研資料倉庫(103)
工作棟危険物置場
昭60．B1．4

東佐野

(120)
汚染物貯蔵庫平14．R1．300

Ｓ

(122)
学生棟
平16．S1．229(013)
熱特性実験室
RI倉庫
昭37．R1．495

(012)
工作棟
昭38.R2.411

(109)
屋外便所
昭63．B1．8

熊取

Laboratory-based management forcontamination and health and safety
Small compartment sizes
Hot Caveats
high dose RI production8

単色中性子実験室
昭45.50.61 S1.91

敷地面積 392㎡(065) Ｓ
研究棟附属会議室
昭45．S1．72
(083)
仮設ハウス
研究室棟(1)Ｓ昭53．S1．49(086)
仮設ハウス研究室棟(2)昭54．S1．73
21(098)
緊急用機器資材格納庫
昭57．S1．26

6.0M
10.0M
Researchlabs. ofＳ(011)
女子更衣室
昭44．W1．10(129)
universities
集中地震観測室

Ｓ

Ｓ

(127)
研究棟ガスボンベ庫
平18．B1．9
13

Ｓ

α

(040)
臨界集合体
実験棟
昭49．R2．2,585

Ｓ (064)

326,821㎡

Ｓ(094)
研究棟附属塵埃集積所
昭45．B1．5 Ｓ
4.0M(009)研究棟
昭39.49.61
R1．R3．
2,365(081)
研究炉管理室 Ｓ
昭52．S1．26

Ｓ

平18．S1．11(096)
スーパーミラー中性子導管実験室
昭58．R1．91

敷地面積

(038)
低温実験機械室
昭47．R1．126
3

2

(106)
冷中性子源操作室
昭61．S1．24(113)
冷中性子導管実験室
平4．S1．61

α, β

P(30)
24
(123)
緊急対策室棟
平14．S1．126

6

昭43．R1．82(105)
冷中性子源仮設実験室
昭60．S1．79

昭39.R1.41

Discussion of operational management (image)

Ｓ

Ｓ

Ｓ

(008)
危険物倉庫
昭39．R1．47

Ｓ
Ｓ
(007)
トレーサ棟
昭39．R2-1．
1,726

Copyrighting protected image

2

Ｓ パルス中性子実験室

昭53．R1．60

MA storage production process

Ｓ

Ｓ

(112)
粒子線腫瘍学研究センター実験室平3．S1．34

PlannedreactorＳ(099)
施設系資料倉庫1in Fukui
昭58．S1．13

室

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7

n

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熊取体
昭54．S

Ｓ

Ｓ

(005)
温室
昭39．S1．22(115)
原子炉棟高圧ボンベ室
平9．B1．15(117)
原子炉棟放射性排水タンク室
平10．B1．17

α,β,γ

電子線型加 器(ライナック)
制御室
昭46．B1．29

available for download, For FY2023: Mar 2-3)

(U,MA)O2 solid solution production from solution

55,679㎡

Ｓ (001)器(ライナック) (002)
施設管理室
電子線型加 器昭45．R1．110(ライナック)施設(140)
昭39．R1． 12m測定室
Ｓ 平14．S1．
平28．S1．13 (004)
昭38．R2－1．4,146419
原子炉棟・ホットラボラトリ

電子線型加

弘

Low temp. reaction (~100ºC)（Reimei 2010）[c](1996-2002)(035)
熊取職員宿舎8号棟
昭41．R4．624(036)
熊取職員宿舎9号棟
昭42．R4．704

Ｓ

主 池(1995-1996, 2018-)

4.0M

[a]

8.00

(126)
原子炉棟西ガスボンベ庫 借用
平18．B1．52(147)
ホットラボ機器収納庫
令1．S1．27

Ｓ

SCW (>374ºC, [b]>250 atm)(Gen-sys 2007) (U,Np)O2 (SS)U4+ (aq)坊

SPring-8

(034)
資料収蔵庫
昭40．R3．495

(033)
資料収蔵庫
昭40．R2．142

(006)
生物別棟
昭39．R1．96(139)
倉庫
平28．S1．25(119)
医療照射準備室
平11．S1．27(043)
粒子線腫瘍学研究センター
昭51．R2．900(116)
トレーサ棟ボンベ室
平9．B1．8

4.0M• Active fields in KURNS Hot Laboratory• RI utilization• Mössbauer spectroscopy• Neutron activation analysis (NAA)
My major fields• RI supply for medical use• Actinide condensed-matter phys./chem.
• Actinide/MA Applications• My activities:• Annual meeting on Actinides/RIs (2006-,(039)
中性子導管室
昭48．R1．80(048)
倉庫 昭52．B1．5

(133)
トイレ棟
平22．S1．9

4.0M

旧燃料プール浄化設備倉庫
昭47．S1．25

(132)
研究室棟
平22．S2．152(2002-2018)
JRR-3 Oarai(089) Ｓ
炭酸ガスボンベ小屋
昭51．62．B1．13

Ｓ(068)

researchers from universities and national
institutes

UO22+ (aq)Tohoku図 Univ.-IMR
Sendai

配Planned 置“Fukui Reactor”

0M• Arising from separate regulation laws in Japan• Kyoto Univ.: KURNS, Grad. Sch. Eng.
• Tohoku Univ.: IMR-Oarai, IMR-Sendai. IMRAM• Three Joint Usage/Research Centers accept

国立大学法人等施設実態調査（様式２）4.

materials

228/224Ra recovery technology from Th)

Electrolytic
Reduction

Joint Usage/Research Center with RI
and nuclear material in Japan(Period of TY as a faculty member)• Five university facilities for RI’s and nuclear• Reduction of waste volume and potential hazardousness of HLLW
• The development of MA separation and storage technology• Mesoscale physical property science research on debris• Recovery methods for useful elements and nuclides (e.g.,

3.5M

Actinide Applications

9.0M

I-2. 各分野の状況 f.

核医薬、デブ
ド

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S=
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所在地

学校番

大阪府泉南郡熊取町

028

くまとり

熊取

2.2 H. Yamagami（Kyoto Sangyo Univ.）
Goals of Specialized Research Groups

Users meeting on Condensed-matter Chemistry in Actinides
and their Applicationso|~_~¯í (Perspectives of this meetingÿ

First Meetingr31~þ

:2020~2o7oî/\|ÏÛÿ/_ûÿ

Second Meeting:2021~2o10ozoom_û

9:35~9:50

Third Meeting :2022~3o3o4ozoom_û

10:00~15:00

Fourth Meeting :2023~3o3o2ohybrid_û

10:00~15:00

9:35~9:50

îý/\ß/?ù|~b|~_~}ß{ãþ¯íÿo|~_1\ß/?ù|~b~q\{o~/ôxwv¯v²~w1
\ß/?ù|~b{zq»|~Ûsß/ù{·y»öüþ{ttvü<^¯|~_=ÿöüþ{sp¿¹zt/®~|~_w1÷ý¸·¿ø|~{Uq|~ºÜ²óhy»|~_²°2^¯|~_~o{ÿGoals of Specialized Research Groups Ā<²¿ñþ´ù~{gWx}~ßo=ÿóhÿ: (1) |~öüþxwv1ßtoww~²¿ñþ´ù~{gWÿùÿ~ÿ|~x}~ßo
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(5) ºü÷ózîm~|²óßw1åyîûxÛöûÞ~ü¯íÿKyoto Sangyo University, Hiroshi YamagamiÿìoÏÿ
1. {q\{o|~ ÿbõûo²°ÿ~~è|[u{þ~¼»sx2
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3. q\{o|~gW~±~o¿û{²~x±»ÿ\Þf²¯q»2_û~¹±¸õüû (Meeting Schedule)

March 3

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12 talks + 1 concluding remarks
2 opening remarks + 11 talks

First Meeting:2020~2o7oî/\|ÏÛÿ/_ûÿ

9:35~9:50

q\{o|~gW~±~o¿û{~ÿ\Þ

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Thank you for your attention!
We would appreciate an open and active discussion.

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9

10

2.3 Y. Haga（ASRC, JAEA）
Single crystal growth and electronic structure of uranium compound superconductor UTe2

1911
Hg

f-electron Heavy Fermion superconductors
compound

1961
Nb3Sn

Tc (K)

Ce / T (mJ/K2mol)Tm (K)

0.5~ 1000complexUPt3

0.45, 0.55

500

5 (fluctuating)

UBe13

0.9

1000

< 0.01

URu2Si2

1.4

60

17.5

1990 UPd2Al3

2

145

14.3

UNi2Al3

1

300

4

2.3

500

< 0.01

CeIrIn50.4

500< 0.01

PuCoGa5

18.5

70

<5

PuRhGa5

8.5

70

< 0.1

URhGe

0.15

150

10 (ferro)

芳賀芳範

CePt3Si

0.5

300

2.3

keywords: Heavy Fermion （重い伝導電子）

PrOs4Sb12

1.5

〜 500

< 0.1

1979 CeCu2Si2

Single crystal growth and electronic structure of uranium
compound superconductor UTe2

1986
cuprates

CeIn3 (p), CePd2Si2 (p), CeRh2Si2 (p)Y. Haga (JAEA)

CeCoIn52001

ウラン化合物超伝導体UTe2の単結晶育成と電子状態
2002

日本原子力研究開発機構（東海）先端基礎研究センター

2006 NpPd5Al2
2007 UCoGe
2019 UTe2

200

0.5

200

1.0
T (K)

1.5

2.0

µ0 H (T)Section

H (T)

HSCPM
HSCRE
HSCFP
Hm

20

Diagram

Copyright protected image

40
a axis0b axisϕ (°)

Updates20

10.

Weight10i .......

'~

'r

~-~

0

300

U1-xThxTe2

200x= 0.01x= 0.03x = 0.10

1400

40

.,

c)
o
'l

50
.........

20
~

'~

'r

--

15"'~"

Copyright protected image

600 ~--(~U)

1 U-Te phase diagram.

I

I )

',..

~

ff

1~
20

Tc (K)
1.74
no SC
2.00

1.79–2.06
1.72–1.87

2.0

70

80

,.......

90

30
40
50
AtomicPercenL

60Te]lurium

80

90

100

phase
>{5oo.cU-Te binary
L
i

~.

200
O

490"C

Te/U

UOTe

I

I
~ )

',..

700

Cairns et al., J. Phys: Condens. Matter 32 (2020) 415602.

70,.......

~ .........

__~260-1300"C

100,50oc ~--(~U)
9 "-.,*C"600~.........

0 ~l60~ .........

>{5oo.cL )k~1000 ,,~___(9tU

(D

'l

--

i

lO

1.5

Range of EDX
Te/U at. ratio

2.14
1.85

s

0 ~l

O
U

CVT Te/U
at. ratio

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protected
image
1.71
1.46–1.50

1740"C__~260-1300"C
(D

0

1.0

.,

15"'~" c~

c)
o

200

D. Aoki,…,YH arXiv:2206.01363

down to 50 mK.

0.5

s

c~
k~ 1000 ,,~___(9tU
)

1.0

c)

A
B
C

1740"C

f

0.5
³0/³N

γ + ATαα = 1.97(4)γ = 23(1) mJ/mol.K2,,,../........-~'-

1800
1600

0
0

S1

0.5 1.0 protected
1.5 2.0s6
Copyright
image
T (K)

Percent.
Rosa et al.,Tellurium
Commun. Mater. (2022) 3:33.
30
40
50
60

f

1400
Tellurium

Percent.
30

20~

i .......

Weight~-~1600
U-Te binary phase

.

S2

0

,,,../........-~'-

1800
UpdatesO

Copyright protected image

0.5

T (K)
Kinjo et al., Phys. Rev. B 2023

O

2000

1.0

-100
0.0

c axis2000

Diagram

b)

1.5

100

0

Ran et al., Nature Phys. 15, 1250 (2019)

HI: Phase

UTe2

2.0

100

40
θ (°)

2008
Fe comp.

2.5

a)GrowthCopyright protected image
LHSC

SCPM

20

high field phase

Unexplored
region

SCRE

SCPM
0

HHSC

HI: Phase

120

S1 = 75 mJ/mol.K
S2 = 81 mJ/mol.K

200

100

Rosuel et al., arXiv:2205.04524v3

UTe2 H || b

SCFP

FP

C/T - γN (mJ mol-1 K-2)

spin-triplet

0
0.0

(d)

40

SectionC/T (mJ mol-1 K-2)

Superconducting LF

60
FP

0

300

5

3 (ferro)

1.6 - 2.1

100

Copyright protected image

Ran et al., Science 365, 685 (2019)cNormalParamagnetic

20

10

< 0.1

150

Tc (K)

300

UTe2
H!b

spin-singlet ?

15

200

0.8

s1
s2
s3
s4
s5
s6
s7

Polarised Paramagnetic

Superconducting HF

25

Copyright protected image

4.9

Introduction: Sample dependence of UTe2

Unusual SC phase diagram30

2004
diamond

CeRhSi3 (p), CeIrSi3 (p), CeCoGe3 (p), UIr (p)Electronic specific heat 伝導電子の比熱：有効質量（通常 1 mJ/Kmol at 1K）

35

2001
MgB2

CeRhIn5 (p),50oc 9 "-.,*C"

1.333

U2Te3

1.5

U3Te5

1.667

FM

U7Te\ 12

1.714

FM

Copyright protected image

~

~.

490"C

....

\

....

U3Te4

149.57"C

UTe2

1.94 - 2.00

U2Te5

2.5

149.57"C~

ff(Te)--~

80

90

100

lO

Te

1~
20

Okamoto, H. Te-U (tellurium-uranium). J. PhaseUEquilibria 14, 129‒130 (1993).

30
40
50
AtomicPercenL

1 U-Te phase
diagram.
7b'EIh G.V. Ellert, V.G. Sevast'yanov, and V.tC Slovyanskikh,
Zk
84Noe: H. Noel, Mater.Res. Bull., 19,1171-1175 (1984).
Neorg. Khim., 20(1), 221-227 (1975) in Russian; TR: Russ. J. Inor89Noe: H. Noel and J.C. Levet, J. SolidState Chem., 79, 28-33 (1989) inganic Chem.,20(1), 120-124 (1975).
French.
7bTun S. Furseth, L. Brattas, and A. Kjekshus, Acta Chem. Scand., 29,
92Boe: D.R. Boehme, M.C. Nichols, R.L. Snyder, and D.P. Matheis, J.
623-631 (1975).
Alloys Compounds,179, 37-59 (1992).

7b'EIh G.V. Ellert, V.G. Sevast'yanov, and V.tC Slovyanskikh,
11 Zk
Neorg. Khim., 20(1), 221-227 (1975) in Russian; TR: Russ. J. Inorganic Chem.,20(1), 120-124 (1975).
7bTun S. Furseth, L. Brattas, and A. Kjekshus, Acta Chem. Scand., 29,
623-631 (1975).

~(Te)--~

60
70
80
90
100
Okamoto, H. Te-U (tellurium-uranium). J. PhaseTe]lurium
Te Equilibria 14, 129‒130 (1993).

84Noe: H. Noel, Mater.Res. Bull., 19,1171-1175 (1984).
89Noe: H. Noel and J.C. Levet, J. SolidState Chem., 79, 28-33 (1989) in
French.
92Boe: D.R. Boehme, M.C. Nichols, R.L. Snyder, and D.P. Matheis, J.
Alloys Compounds,179, 37-59 (1992).

Single-crystal XRD

Single-crystal XRD

Crystal structure (UTe2-type, Immm) confirmed for both NS and SC samples.
NS sample

Showing I / Imax < 0.1

SC sample

3

Lattice parameters4.1600(2)6.1219(4)13.9476(9)4.1618(5)6.1355(7)13.9698(13)

Uz
Te1 z
Te2 y
Eq. iso. atomic disp. Beq
U
Te1
Te2
Residuals (all data)
R1
wR2

0.13545(5)0.29755(5)0.24895(5)0.13520(4)0.29780(10)0.24910(3)

0.687
0.562
0.515

0.513
0.576
0.529

0.0222
0.05640.03090.0586

UTe2 (NS sample)
2

Fractional coordinates

U

Te1

4

Observed Intensity

a
b
c

Te2

10 9
8
7
6
5
4
3

2

3

10

2

3

3

10

4

5

6 7 8 9

2

4

3

10
Calculated Intensity

Y. Haga et al., J. Phys: Condens. Matter 34 (2022) 175601.

Single-crystal XRD

NS sample is strongly U deficient
0.023

Showing I / Imax < 0.1

3

3

0.022
R1

(1 2 3)

U1Te2

2

U0.962(2)Te2

2

0.021

Strongly deviating reflections
consist from strong FU and FTe
but cancel each other.

87
6(0 3 3)(2 1 3)

3

3

10

2

3

4

5

6 7 8 9

4

2

2

3

3

4

5

6 7 8 94

10Calculated Intensity

2

3

10

3

10

2

3

4

5

6 7 8 9

4

2

3

10
Calculated Intensity

Uranium site occupancy = 0.962(2) best fits.
- Consistent with EPMA (SC sample as internal std.)- Larger Te/U samples do not superconduct: agrees with
Cairns et al.
- No interstitial atoms- U/Te substitution unlikely
resulting formula (U0.91Te0.09)Te2 ³ U0.87Te2- No significant crystallographic change except for aslight volume reduction (0.3 %)- 7 % uranium deficiency observed in UTe(0 0 4)3(0 4 4)3(2 0 4)

10

1.5
1.4

3

2

10

(0 4 4)

3

1.6

U

2

10

0.019
1.7

1.3
0.3646(2 0 4)(1 0 1)(1 0 7)(0 2 8)(1 0 1)(1 0 7)(0 2 8)(0 0 4)

Resulting (weak) intensity issensitive to- Beq difference (corrected)- site occupancy

5
4

5
4

2

(0 1 3)(1 3 0)(3 1 0)5
4

3

10Calculated Intensity

Fractional Coordinates

8
7
6

8
7
6

(0 3 3)(2 1 3)3(1 1 0)4

10 9(3 1 0)4

10 90.36450.2026Te1
0.20250.20240.7491

Te2

0.7489BU, BTe2(1 1 0)(0 1 3)(1 3 0)4

10 90.7487
0.8

Te1

0.7

Te2

0.6
U

Secondary Extinction

UTe2 (NS sample)

Observed Intensity

Observed Intensity(1 2 3)

Goodness of Fit

0.020

3

0.5
0.004

0.003

0.002
0.94

Y. Haga et al., J. Phys: Condens. Matter 34 (2022) 175601.

Specific heat

0.96

0.98

Uranium site occupancy

Molten salt flux growth
PHYSICAL REVIEW MATERIALS 6, 073401 (2022)

0.8

SC sample prepared withcomposition 1.11:2
950/850 temperature gradientUTe2Single crystal growth of superconducting UTe2 by molten salt flux method
H. Sakai ,* P. Opletal , Y. Tokiwa , E. Yamamoto, Y. Tokunaga , S. Kambe, and Y. Haga

- Sharp single SC transition- Relatively high Tc = 1.8 K

2C/T (J/K mol)

0.6

0.4

0.2

SC
NS

0.04 5 6 7 8Advanced Science Research Center, Japan Atomic Energy Agency, Tokai, Ibaraki 319-1195, Japan

Highest Tc = 2.1 K fromrecent crystal- NS sample shows quite
different behavior up to hightemperature.

1

2

3

4 5 6 7810
Temperature (K)23

4 5 6 7

- Both SC and NS samples
have extra electronic/
magnetic contributions(Debye model : black line)

12

†

1.00

Observation of dHvA oscillations

1*

2

2

2

3

UTe2
70 mK

dHvA Signal (arb.units)First Observation of de Haas-van Alphen Effect and Fermi Surfaces in
Unconventional Superconductor UTe2
4

Dai Aoki , Hironori Sakai , Petr Opletal , Yoshifumi Tokiwa , Jun Ishizuka , Youichi Yanase ,Hisatomo Harima5 , Ai Nakamura1 , Dexin Li1 , Yoshiya Homma1 Yusei Shimizu1 , Georg Knebel6 ,Jacques Flouquet6 , and Yoshinori Haga2

H || 56.8 deg
11.8

1

-1
-2

0.1

90

UTe2

100

110

120

130

140

150

H (kOe)

1.5
1.0
0.5

0
0

1

2

0
0

3

T (K)

0.5
³0/³N

1.0

ln {A[1-exp(-³m*T/H)]/T} (arb.unit)

0.5
T (K)

3

´'

4

³2

5

6

7

2.0

0
0

2

´

dHvA Frequency (x 10 Oe)(b)

Tc (K)

-2

0.2

0.02

Ce/T (J K mol )-1

Ce/T (J K mol )

0.3

³1'

Cu

2.5
0.04

73 mK
77
83
90
100
110
120

UTe2
H || 29.3 deg

0

T (K)
0.4

³1

(a)

FFT Amplitude (arb.units)

Observation of dHvA oscillations(b)branch ³1
33 m0
Heff = 12.6 T
0.06

0.08

D. Aoki, et al., J. Phys. Soc. Jpn. 91, 083704 (2022).

Observation of dHvA oscillations

0.10
T (K)

0.12

More anomalies in pure samples
20(c) Theory

UTe2
U = 2.0 eV

UTe2

High entropy 15
SC

ThTe2
hole
electronholeelectron

7

dHvA Frequency (x 10 Oe)

10(b) Theory

Hc2 (T)(a) Experiment

³2
hole

5
³

#1
#2
30

60

90 0
a c

Field Angle (deg)1st order transitioncelectron

³1

0
0
c

Niu et al., PRL 124, 086601 (2020).

H || c-axis

10

hole

c

a

a

30

60

Field Angle (deg)a-axis

5

90 0
a c

30

arxiv.org:2210.11769
electron
60

0
0.0

90
a

0.5

1.0

1.5
T (K)

Field Angle (deg)

2.0

2.5

Hc2 || a significantly larger than standard samples (typically 6T = Lifshitz ?)Above 6T slope increases

D. Aoki, et al., J. Phys. Soc. Jpn. 91, 083704 (2022).

Summary
UTe2:- Sample-dependent physical properties arisingfrom uranium deficiency.

- High-quality crystal growth from molten salt
- clarifying intrinsic properties- no residual electronic density of state (T³0)- Quantum oscillations detected: Fermi surface- Multiple superconducting phases

13Question and answer session
Q: Are the defects related to the valence and oxidation number of uranium intrinsic to thesuperconducting properties of the present case? Is this phenomenon happen by chance in acompound with tellurium?
A: It happened by chance (with tellurium), but it is still deﬁnitely because it is uranium. There
are too many unusual superconductors in uranium. It is important to make it work by using
the ﬂexibility of uranium’s valence in combination with tellurium. But it is very diﬃcult tounderstand precisely.

Q: Was the molten salt suitable for growing high purity crystals by was the purity of themolten salt considerably high? Or are there no impurities in the molten salt for crystal growth?
A: We have not experimentally defermined the amount of trace impurities. However, X-ray
diﬀraction and compositional analysis have so far found no impurities other than uranotellurium.
One of the reasons for our success with molten salt is the reducing atmosphere.

Q: Did you start out by mixing that uranium and tellurium in a single substance and thenmolten it?
A: That is correct. The key is the initial composition ratio, starting with a uranium-richstoichiometric ratio.

Q: How do you know the uranium valence experimentally?
A: I would love to know. In this UTe2 , the formal valence of U is tetravalent because it iscompenentometric in the Fermi surface. The only way to determine the valence experimentallyis to look at the ion size, i.e., the structural parameters.

14

15

2.4 M. Nakase（Tokyo Inst. Tech.）
On a New Approach to Exploration of Novel Solvent Extraction Systems
for Minor Actinide Extraction for Next Generation Reprocessing

2

Background2023.3.02-03@Kumatori

ûTo realize a Zero-Carbon society by 2050, nuclear energy utilization is essentialûProblems related to nuclear waste should be solved, and reprocessing is one of the keys
ûHigher-burnup spent fuels and MOX spent fuels require MA partitioning for final disposal
ó Evaluation of the entire fuel cycle (scenario study) is needed<Users meeting on Condensed-matter Chemistry in Actinides andtheir Applications / Production of medical RIs by Reactor Irradiation

On a New Approach to Exploration ofNovel Solvent Extraction Systems for Minor Actinide Extraction
for Next Generation Reprocessing

MA partitioning!

Tokyo Institute of Technology, Institute of Innovative Research,
Fukushima Reconstruction and Revitalization Research Unit
Masahiko Nakase (Ph.D)

VISIT HERE´
https://nmb-code.jp/english

1

Tokyo Tech and JAEA developed an integrated nuclear fuelcycle simulator, <NMB4.0ÿ= which is available for free!

Machine Learning for solvent exploration

Background
Current status of MA partitioningûSeparation of trivalent RE and MA is difficult in highly acidic conditions (Am3+/ RE3+)
ûSafety of the next generation of reprocessing plants should be enhancedóThe current hydrocarbon diluent, such as n-dodecane, has a flash point and is flammable.
ûThe solubility of MA extractants into hydrocarbon diluent is not high, and the third phase can be formed.
Vertrel XF

HydrofluorocarbonÿHFCĀ

SF33

ûMaterial exploration requires strategic, systematic, and iterative
experiments (and calculation)ûPreparation of various kinds of diluents and extractants is expensiveûRI experiments generate radioactive waste

SF10

F

û Some of the Hydrofluorocarbon(HFC) andHydrofluoroolefin (HFO) have no flash point,
no toxicity, low ODP and inherently safeûApplicability to solvent extraction as diluent isalready proved.
*T.Yamamura, et al., J Nucl Sci Technol., 2010, C.Tabata et al., Solvent Extr Ion Exch, 2021
K.Shirasaki et al., ACS Adv, 2022

Cheminformatics

ü Conventional Method

Chemistry Informatics

H

Aq

Boiling point

55

33

110

XF + Extractant

Thermal stability

Excellent

good

Good

28.4

166

35.2

After extraction

Latent heat ofvaporization [kJ/kg]

110ûChemical properties can be tuned by the structural modification
ð Which diluent (structure) is suitable?
ð Are there any special diluents that can solve theproblem of MA extractants? (solubility, 3rd phase)ð How can we efficiently find the candidate?

Permittivity [#]55

33

Solubility to water
[ppm]

140

7-8×102

Ozone Depletion
Potential000Global Warming
Potential

1650

2.0

<10

> Introduction of Machine Learningû Efficient experiment becomes possible through many schemes; Quantitative Structure-Property
Relationships (QSPR) modeling, experimental design, active learning, transfer learning, etc...
ûMachine learning can help understand the correlation of factors and which factor is essentialûMachine learning is effective when the experiments are complex and expensive.

3

5

Approach and Goal

Machine Learning is compatible with nuclear chemistry!

*Report of FY2021, MEXT Innovative Nuclear
Research and Development Program Grant
Number JPMXD0221459189

4

100 mmol/L T2EH-DGA

SolubilityGoalĀ Develop the prediction scheme and find an excellent diluent for MA separation.
Experiments

Chemical calculation

Thermodynamic data(%E), chemical
properties (solubility, permittivity, density,
viscosity, reflectivity, water contents, etc.),complex structure, aggregation
Database
Machine LearningûCreate the regression modelsûReveal the complex relationships
between many factors and extractability

C=C-COOH, -OH

P0837

P0851

P1420

E0528

D4484

H0946

AdditivesĀAlcohol, Carboxyric acid

Solvent Effect,Anionic effectCOSMO Therm

HSPiP

DFT, MD CalcĀ Gaussian, LAMMPSûInverse modeling; candidate solventsûEngineering and applicability; Safety, process
design, radiation resistance, waste, regulation etc

Implementation

F

P0867

- Calculation of chemical properties; COSMO Therm, HSPiP software

Application

w

O0292

Design virtual molecules
O

First principle molecular
dynamics calculation

Complex structure and mechanism;
G, NBO charge, HOMO-LUMO
energy, third phase formation
Mechanistic studies

C3

C4

C5

C6

C7

C8~

ûF-solvent with small molecule size is better for solubilityûExtractant(DGA) with shorter chain length seems to be better for F-solvent

16

6

*Example Case

Prediction of solubility from the molecule structure
Nodes for Cheminformatics*Report of FY2021, MEXT Innovative Nuclear
Research and Development Program Grant
Number JPMXD0221459189

Extraction experiments

Nodes for analysis

Org

Extraction procedure and condition

ÿml
2ml

100mmol/L
T2EH-DGA

Aq

Shake
r.t. 30 min

Aq

Org

Quantative Analysis%E
MI schemes*Sample data

Convertto RDkit

Structuralfeatures

Solubility (experiment)

Prediction 1

For training

SMILE

vertrel XH

Prediction 2

For evaluation(AE3000)

Inversemodeling

Reflectivity

dodecane100

dodecane
XF

100

120

Permittivity

1-octanol(AMOLEA AS300)

Typical solvent

7

Solubility (estimation)

Reflectivityÿ Anton Paar Refractometer Abbemat3200
Specific weightÿ Anton Paar Density Meter DMA1001
PermittivityĀ self-made1Specific heatĀ self-made OthersĀ literature

Simple Regression
120

120

(Opteon SF33)

Obtained correlation- Similar regression attempts with DGA solubility were successful*Report of FY2021, MEXT Innovative Nuclear
Research and Development Program Grant
Number JPMXD0221459189%E

80

Nitrobenzene
1-Octanol

MCA

Viscosity

100

TolueneExperimental data

40

Toluene
Chloroform

20

Eu

Nd

40

40

Chloroform

1.4

1.45

1.5

1.55

1.6

0

10

Specific weight

dodecane 1-octanol

100
80

120

Eu

Chloroform

20
Zr

0

0.5

0.7

0.9

1.1

ÿg/cm3ÿ

1.3

Eu

Nd

1.5

Chloroform

1.7

50

100

Eu
150

Nd
200

Toluene
1.0

2.0

6

8

Vapor pressureÿE (experiment)

XF

SF33

XH

ÿE (predicted)

Nitrobenzene

80

Dodecane

100

60

90

Toluene80

Chloroform
Eu

Nd

70

Ce

0

100

200

ÿ#ÿ

Nitrobenzene

300

Regression model

1-octanol
0.1

0
250

1.5

4

Dodecane

Zr

Ce

DodecaneNitrobenzene

50[mPaûs]

20
Zr

0

60

120 1-Octanol

40

Toluene

0

Ce

2

100

20

Ce

Eu

Nd

0

400

0.3
500

600

ÿhPaÿ

Simple regression is not sufficiently anticipated in the %E

Five influential parameters were selected for regression
Intensionally masked

9

Multiple Regression by Python Code

Effect of solvents on extraction behavior of Actinide 3 Am

Environmental
setup

Am

DGA 100mM

û Vertrel XF showed higher D thann-dodecane, but the chemistry
seems to be similar (slopes)ûBig solvent effects were seenóRegression trial

Dataset prepared by extraction exp. and HSPiP calculation.

Data modification

Input (CSV)
normalization

10*HSPiP software

Generated factors from SMILES

Chloroform

0.5

40

dodecanenitrobenzene

40

TolueneZr01-octanol

60

40

Ce

Boiling point

80

60

Nd

30

Vertrel XF, XH

100

nitrobenzene

%E

20

Eu

To be reported

[nD]
120

70

20
Zr

0

Multiple Regression of %E
of Eu from SMILEs*Report of FY2021, MEXT Innovative Nuclear
Research and Development Program Grant
Number JPMXD0221459189

ÿE (experiment)
XF

90
80

Ce

8

HSP parameters

60

20
Zr

0

Ce
81.0
66.0
53.5
84.5
46.4
84.7
78.7
35.2
88.7
83.4
90.9

1-octanol

100

60

60

Zr
Eu
Nd
îý]
XF
96.5
96.5
88.5
XH
85.6
84.0
73.6
MCA
74.7
63.5
60.9
SF33
95.4
93.0
89.4
toluene
90.0
58.4
60.0
dodecane
99.4
98.3
92.1
1-octanol
98.7
91.5
83.5
chloroform
51.4
42.0
47.0
nitrobenzene
98.5
91.3
92.7
AS300
87.3
90.8
AE300098.8
95.8
Redÿ> 90%, Orangeÿ89ÿ80%, Greenÿ60ÿ79%, Blueÿ< 59%80

Nitrobenzene

SF33

ICPE-9000, Shimadzu

ó First step; simple regression trial

XH
80

vertrel MCA

ûAqÿMetal ion 10 mmol/L, HNO3 3 mol/LûOrgÿ100 mmol/L T2EHDGA
ûO/Aÿÿ2 ml / 2 mlĀûContact timeÿ30 min,Temp; 21<23#ûNo pre-equilibriation by acid

Used parameters;·D, ·P, ·H, ·HDon,·HAcc, MWt Density, Mvol, Area, Ovality, BPt, MPt, Tc, Pc,
Vc, Zc, AntA, AntB, AntC, Ant1T, logKow, logS, Henry, logOHR, RI, ·Hfus,·Hv@Bpt, Trouton, RER, Abr-a, Abr-b, EdmiW, Parachor, RD, ·Cp logh, Cond.,
SurfTen, MCI, ·Hcomb, ·Hform, ·Gform<Negative mean squared error>

Regression

3M HNO3, 20 mM

Ridge Regression:-169.69003051185084
Lasso Regression:-269.84053015936104 ó×
ElasticNet Regression: -211.93236531560
GBDT Regression:-158.2770978930236 ó7

To be reportedûPrediction of %E of Eu with different solvents becomes possible.
ó Application to Actinide extraction cases

12
12

Result17

Multiple Regression of %E of Am from SMILEs

13

Effect of solvents on extraction behavior of Actinide 3 Np, U
T2EH-DGA

Vertrel XF³Np4+

n-dodecane

Reduction

NpO2+

Np

U

DGA 10 mM

To be reported

UV-Vis-NIR

ICP-MSMS

DGA 100mMnDDÿU4+)

Vertrel XFÿU4+)

Vertrel XF
ÿUO22+)

nDDÿUO22+)

The slopes seem to be slightly different?

Preliminary regression test of %E of Am was done. Further extraction experiments andinverse modeling will be done

Python Scripts or Docker

14log[HNO3]

16

Conclusion and future perspective

Python to KNIME
Python ScriptûCheminformatics scheme is applied to the exploration of diluents for MA partitioningûRegression study was implemented by excel, HSPiP, Python, and KNIME.
- Simple regression was not successful as we expected, but multiple regression was successful.
û Upgrade the MI models and KNIME workflow
û Inverse modeling and confirm by MA extraction
û Understand the further mechanism of solvent effects and related phenomena.
û Apply advanced techniques of Machine Learning, such as transfer learning
Solvent Effect;
first principle MD calculation

Transfer Learning

Third phase and aggregate

Am

Am
Eu

Under Construction&>>>>>- You do not need to have a programming skill!
³Suitable for chemistry students?
- Latest knowledge of informatics can be used!

Pyscochemical properties

0.035

HSPiP

0.025

N(Bpy) & O(H2 O)

0.03

COSMO Therm
óMixture solvent

17

Actinide experiments
Laboratory for alpha-ray emitters, Tohoku Univ.
Oarai center, Tohoku Univ.
- Dr. K.Shirasaki and Dr. Li Dixin, Mrs C.Abe

Program Advisor
Dr. Kota Matsui+ Programmer

2

O(H O)

|FT|

0.02

Fund
ûMEXT Innovative Nuclear Research and Development
Program Grant Number JPMXD0221459189(foryounger scientists).
ûInternal fund of Mitsubishi Heavy Industries

18

Eu : MeTol-PTA = 1 : 4
Eu : Bpy = 1 : 4

0.015
C(Bpy) & C(PTA)

0.01
0.005
0

Acknowledgement

Transfer from Eu

Transfer learning +Bayesian estimation
Am3+ vs RE3+
Am3+ vs Cm3+
Ac3+ vs Am3+ vs La3+ vs Am3+
Ra2+ vs Alkali Earth2+
Python; ADAPT package ³ TrAdaBoostR2

Eu
N(PTA) & O(PTA)

Validation result

0

1

2

3

4
5
k [+]

6

7

8

Am

Am

Question and answer session
Q: In machine learning, there are methods that can be correctly represented for reasons
unknown.
A: By using ”KNIME,” we are trying to create a platform that allows a variety of methods.
We want to do everything: visualization tools, statistical processing, etc. We can do theinverstigation of mechanisms and the exploration of suitable solvents.

Q: Although it is a relatively simple system at the moment, there are methods to include theresults of ﬁrst-principles calculations of solids and molecules in machine learning, so that thephysical and chemical eﬀects of each parameter can be understood.
A: Yes. We would like to consider such a study. As a result of ﬁrst-principles calculations,
we can discuss the importance of energy, such as HOMO-LUMO, or conversely, the importanceof geometry.

Q: Is there a vertical correlation between lanthanides and actinides in the periodic table?
A: They are very similar. However, the wet separation technology is not highly separated, so
there is room for improvement.

192.5 A. Ishii（Teikyo Univ. of Science）
New optical functions opened up by rare- earth hybrid materials<Users meeting on Condensed-matter Chemistry in Actinides
and their Applications / Production of medical RIs by Reactor Irradiation=
March 2nd, 2023
Main Conference Room, Office Building, KURNS, Kyoto University

Optical properties of lanthanide ionsf-f transition (Ln3+)

30
5d,6s

Energy4f

Organic dye (ligandĀ:Energy donor

Vis
NIR

EnergyISHII Lab HP ³0

Eu Tb Ho Er Tm Yb

To Control NIR light &Preparation of Lanthanide-based Hybrid Materials !!
with organic dye

Lanthanide complex with organic dyes

hn

15
10

'Inner unoccupied 4f orbitals shieldedby occupied 5s and 5p orbitalsóVery sharp emission/absorption bands (UV to NIR)
'Electric dipole forbidden (Laporte forbidden) transitionóLong emission lifetime (ÿms),but a poor light absorption coefficient (ÿ1310)M21)cm21)

Optical properties of lanthanide ions

5d,6s

20

5

f-f transition (Ln3+)
5p

4f

Q

Teikyo Univ. of Science, JAPANE-mail: ayumi-i@ntu.ac.jp

5s

5p

4fn

Ayumi ISHII

4fn9

5s

25

Energy /cm-1

4fn9^_Þÿ´öúóùwý|óõYý
New Optical Functions opened up
by Rare-earth Hybrid Materials

UV

×103

NIR to Vis/UV

NIR light

Under UV lights

Up-conversion
emission (vis)

Copyright protected image

4f

EnergyTransferwith perovskite

Ln3+: Energy acceptor

One-photon
absorption(UVûVis)Coord. Chem. Rev. 2020

4fn
Q

UV to Vis
'Inner unoccupied 4f orbitals shieldedby occupied 5s and 5p orbitalsóVery sharp emission/absorption bands (UV to NIR)
'Electric dipole forbidden (Laporte forbidden) transitionóLong emission lifetime (ÿms),but a poor light absorption coefficient (ÿ1310)M21)cm21)

PbI62-

UV to NIR

Donor

EnergyNIR to Vis/UV

NIR light

Up-conversion
emission (vis)

Acceptor

Yb3+

Converting low-energy photons
into higher-energy photons

UC emission

Laser
excitation-2

Two-photon
emission
(NIR)

Yb3+

Up conversion

Solar spectrum

Visible light-1

Spectral Irradiance (W m nm )Yb3+
PbI62-

UV to NIR

Energytransfer

2.0

with perovskite
One-photon
absorption(UVûVis)Two-photon
emission(NIR)

Up-Conversion: UC

To Control NIR light &Preparation of Lanthanide-based Hybrid Materials !!
with organic dye

Yb3+

NIR light

1.5

1.0

0.5

0.0
300

400

500
600
700
Wavelength (nm)

800

900

Standard Tables for Reference Solar Spectral Irradiances: Direct Normaland Hemispherical on 37° Tilted Surface, ASTM G173-03 (2012)

20

1000

Lanthanide

Lanthanide

57

58

59

60

62

63

64

65

66

La

Ce

Pr

Nd Pm Sm

Eu

Gd

Tb

Dy

Tm3+

Yb3+

68

3F

Er3+

70

71

Tm
Yb Lu
Tm Yb

4F

2,3

4I
2F

10

4I

5/2

3H
5
3F
4
2F

3H
6

60

62

63

64

65

66

Pr

Nd Pm Sm

61

Eu

Gd

Tb

Dy

Tm3+

Yb3+

67

68

Er3+

1G
4
3F

69

Ho Er
Er

2,3

70

71

Tm
Yb Lu
Tm Yb

4F
7/2
2H
4S11/2
3/2
4F
9/2
4I

9/2

2F
4I
10
5/2 low*
11/2
ø Absorption
coefficient is extremely
3H
5
4I(1033106 mW/cm2).
³High incident light source
like
CW
laser
is
needed
13/2
3

13/2

4 ÿorganic dyesÿ· = 104-105 dm3mol21cm21Ā
*· = 1-10 dm3mol21cmF21

ø NIR excitation wavelength
is limited(mainly 980nm).
2F
3H
4I
0
7/2
6
15/2
ø Concentration of emitters (Er3+, Tm3+, etc) is less than 2%.
ø Low up-conversion
quantum(PLQY~1.5%)
Yb3+ (Energy donor):
NIRefficiency
absorption

15/2

Yb3+ (Energy donor): NIR absorption
Tm3+ (Energy acceptor): UV and blue luminescence
Er3+ (Energy acceptor): green & red luminescence

Tm3+ (Energy
acceptor):
UVfor
andefficient
blue luminescence
Ln materials
are not
suitablelight energy use,
especiallyat low acceptor):
excitationgreen
powers&Er3+ (Energy& red luminescence

Lanthanide

Ultra-efficient UC nanoparticles

57

58

59

60

62

63

64

65

66

La

Ce

Pr

Nd Pm Sm

Eu

Gd

Tb

Dy

Tm3+

Yb3+

61

67

68

Ho Er
Er

Er3+

1G
4

20
Energy / 103cm-1

59

Ce

3H
Ln-induced up-conversion
emission
4

11/2

4I

7/2

58

La

20

9/2

4I

57

7/2

2H
4S11/2
3/2
4F
9/2

3H
4

0

69

Ho Er
Er

1G
4

20
Energy / 103cm-1

67

Energy / 103cm-1

61

3F

2,3

69

70

71

Tm
Yb Lu
Tm Yb

Emission quantum yield:
ÿ10ÿ

4F
7/2
2H
4S11/2
3/2
4F
9/2

3

10

4I
9/2
Strategies forH4ultra-efficient
UC systems
2F
4

I11/2

5/2

3

5
4I
d Enhancement3Hof
NIR absorption
13/2
F4óSensitization by organic dyes
2F
3H
0 with highly absorption
coefficient 4I15/2
7/2
6
e Enhancement of UC emission intensity:
Yb3+ (Energy donor):
NIR absorptionof crystal
and core/shell structuresóOptimization
3+ (Energy acceptor): blue luminescenceTmfor 3+
suppressionof the energy deactivation

Excitation light(980nm, 100mW)

d Dye-sensitization
ÿe Inorganic shell

Er (Energy acceptor): green & red luminescence

Strategyd : Dye-sensitized up-conversion

Strategyd : Dye-sensitized up-conversion
Energy transfer from anorganic dye with a highabsorption coefficient
Organic dye:
Energy Donorhn

Complexation at the large
surface of nanoparticles
SEM image

4f orbital

Energytransfer

Ln3+:
Energy Acceptor

50 nm

Tm2O3
Coord. Chem. Rev. 2020
Electrochemistry 2021

Sci. Rep. 2017
Sci. Tech. Adv. Mater. 2019UC emission

UC emission

QY > 5 %Metal-to-metal
Energy transfer

Weak NIR light
Low power excitation
Wavelength-selectivity

Metal-to-metal
Energy transfer

Weak NIR lightYb3+ Ln3+

Low power excitation
Wavelength-selectivity

Ln=Er, Tm, Nd

Intramolecular
Energy transfer

Yb3+ Ln3+
Ln=Er, Tm, Nd

Intramolecular
Energy transfer

21

Cf. Up-converting NIR Detection in Lead Halide Perovskite with
Core-shell Nanoparticles

Cf. NIR sensitive perovskite solar cell with dye-sensitized UCNPs
CsPbBr3
ICG-Pb
NaNdF4
NaYbF4Au(+)
HTL>750nmGd2O2S:Er,Yb

CsPbI2Br + UCNPs
meso-TiO2

2.0
1.5

EQE=2.53ÿ
Jsc=2.47mA/cm2
Voc=1.06V
ff=0.45

1.0
0.5
0.0
0.0

0.2

Absorption ÿCsPbI2BrĀ

400

0.4 0.6 0.8
Voltage (V)

1.0

1.2

500

I-T curve @808nm , 10 mW/cm2, -0.5 V
0.008

NIR absorption(Indocyaninee dye)

0.007

600 700 800 900
Wavelength (nm)

0.005
0.004
0.003
0.002

1000

0.001

Electrochemistry, 89, 544-551 (2021)

Adv. Photon. Res. 2022., {Ø2020-093726,

To Control NIR light &Preparation of Lanthanide-based Hybrid Materials !!
with organic dye

EQE: 75%
R: 0.49 A/W

0.006

Absorption intensity

First observation of
power generation by
NIR light (sunlight)

2.5

J (mA/cm2)

UC emission
ÿEr3+ĀJ (A/cm2)

J-V curveÿIrradiation light ÿ750nm, 1sunĀ
Emission intensity

3.0

Gd2O2S:Er,Yb/Yb/
Nd-ICG-Pb/CsPbBr3

TCO(-)

200nm

0.000
0.0

5.0

10.0

15.0 20.0
Time (s)

25.0

30.0

Lead halide perovskites for applications in LEDs &Film-structure'Solution processability (low material costs)'Long carrier diffusion length (>1 ¿m)'Low trap density (less than 1016 cm23), Defects tolerance'Low exciton binding energy (~50 eV)'High optical absorption coefficient (~105 cm31)
Nano-structure'High PLQY (>50%, dispersed in solution)'High color purity (FWHM ~20 nm, size insensitive)'Tunable emission wavelength (400nm f » f 800nm)'Large number of surface defect (~1018 cm-3 for 10nm particle)

Halogen ion(Cl-, Br-, I-)

NIR to Vis/UV

Pb2+

NIR light

A-site cation(Cs+, CH3NH3+, HC(NH2)2+)

Up-conversion
emission (vis)with perovskite

Development of lead halide perovskite-based LEDs

One-photon
absorption(UVûVis)PbI62-

UV to NIR

Highest EQE (%)

Yb3+
Two-photon
emission
(NIR)

Yb3+

Organic or QDs LED

20

>20%

15
10
5

quasi-2D perovskite
Quantum dots
nanocrystal

0
2014

2015

2016
2017
Publication year

Suppression of non-radiative
recombination
by defect passivation layer

Lead-based perovskite LEDs
only emit below 800 nm ÿÿÿ
2018

2019

Cf. NIR Quantum-cutting in Ln3+3Yb3+ (Ln = Pr, Tb, Tm)

Converting one photon (absorption) into two photons (emission)óNIR emission efficiency higher than 100% (up to 200%).

High PLQYs over 100%!!

General luminescent materials
One-photon
absorption

Theoretical limit of luminescence efficiency ÿOne-photon
emission

Theoretical limit ofluminescence efficiency: 100%

Copyright protected image200ÿ
One-photon
absorption(UVûVis)Copyright protected image

Yb3+
Donor

Energy transfer(quantum cutting)

Q. Y. Zhang, et al., Appl. Phys. Lett. 2007, 91, 051903

Two-photon
emission(NIR)

Q.Y. Zhang, et al., Prog. Mater. Sci. 2010, 55, 353

Energy donor with UV light absorption is requiredûûû

Yb3+· Lanthanide ion : weak UV light absorption (f-f transition)
ï Lead chloride perovskite (CsPbCl3): strong UV light absorption

22

For highly efficient NIR luminescence of Yb ion &Halogen ion(Cl-, Br-, I-)

Pb2+

Sensitization from perovskite:

Quantum-cutting energy transfer
A-site cation

Perovskite (light absorber)
Energy transfer(Cs+, CH3NH3+, HC(NH2)2+)

Application forhighly efficient NIR LEDs!!

Perovskite (cations)

Lanthanide ions

Yb3+ (NIR emitter)
Cs+
Pb2+
Cl-

Lanthanide ion (Ln3+): CN (coordination number) g 6
Perovskite: CN = 6 for Pb2+ (B-site), CN = 12 for Cs+ (A-site)

Film-structure

Absorption coefficient:'Solution processability (low material costs)'Long carrier diffusion length (>1 ¿m)'Low trap density (less than 1016 cm23), Defects tolerance
900
950 1000 1050 1100'
Low(nm)exciton binding energy (~50 eV)
Wavelength'High optical absorption coefficient (~105 cm31)

105cm-1 (UV)850

Lanthanide ions are easily doped into the crystal lattice ofperovskites (ABX3)

Advanced Science, 7, 1903142 (2020)

Film formation of Yb3+ doped CsPbCl3 film

Photoluminescence properties of Yb3+ doped CsPbCl3 filmx5

Yb3+(9.1mol%):CsPbCl3

IPA(rinse)CsCl (0.07M)
in MeOH

Substrate

Heating
at 250oC

Heating
at 250oC

Heating
at 90oC

2F ³2F
5/2
7/2»det = 984 nm

Intensity (a.u.)

PbCl2(1M)+
YbCl3 (0-0.1M*)
in DMSO

Photoluminescence (solid line) and the excitation (dotted line) spectra

120 nm-thick

CsPbCl3»ex = 300 nm»ex = 300 nm»det = 415 nm

CsPbCl3
300

(220)

(211)

(200)

(210)

(111)

Intensity (a.u.)

(100)

(110)

XRD patterns

Yb3+(9.1mol%):CsPbCl3

10

15

20

25

30
35
2ñð(deg.)

40

45

50

400

500

600
700
800
Wavelength (nm)Photoluminescence properties of Yb3+ doped CsPbCl3 film
Concentration dependence of Yb3+ on photoluminescence intensity(excitation at 300 nm)

Yb3+(9.1mol%):CsPbCl3
2F ³2F
5/2
7/2

70

120000Concentration of Yb3+

Relative intensity

100000»ex = 300 nm

Efficient energy transfer
in the film

»det = 415 nm

80000
60000

9.1mol%7.4mol%4.8mol%2.9mol%1.0mol%

40000

500

600
700
800
Wavelength (nm)

900

1000

1100

0
900

NIR emission !

*No ff emission by direct excitation of Yb3+
even using a diode laser

23

50
40
30
20

20000

400

PLQY =62.3%

60

PLQY (%)

Intensity (a.u.)»det = 984 nm

300

1100

Cubic-phase perovskite crystal

Photoluminescence (solid line) and the excitation (dotted line) spectra»ex = 300 nm

1000*Further doping Yb3+ (>0.1M)
prevents a film formation of CsPbCl3.

Photoluminescence properties of Yb3+ doped CsPbCl3 film

CsPbCl3

900

10
950
1000 1050
Wavelength (nm)

1100

0

0 1 2 3 4 5 6 7 8 9 10
Yb3+ concentration (mol%)Highly efficient NIR LED based on the quantum cutting energy transfer

Cf. NIR PLQY over 100% in a layer structured perovskite film
J. Chem. Phys., 153, 194704 (2020)

NIR PLQY ÿ100ÿ
132% at 983nm(Yb)

PL spectra
13% at 1540nm (Er)The highest level of EQE for thin film type
NIR LEDs with emission over 900 nm !!
Advanced Science, 7, 1903142 (2020)

Conclusionÿ
Lanthanide-based hybrid materials and devices
with new NIR optoelectronic functions

with organic dye

NIR to Vis/UV

NIR light

Up-conversion
emission (vis)with perovskite
One-photon
absorption(UVûVis)Yb3+
PbI62-

UV to NIR

Two-photon
emission
(NIR)

Yb3+

24

Question and answer session
Q: Is the matching between the level of the material (dye) with large light absorption and thelevel of the rare earth important in the compounds emitting rare earth?
A: We focus on energy matching and interface coordination through bond formation.

Q: The upconversion is the process of bringing electrons up to a higher energy level of therare earths, and during the lifetime of that level, if energy is absorbed again, it can be pumped
further up?
A: That is correct. That is why we use levels with long lifetimes.

Q: It seems that the eﬃciency improves as the size is reduced from nano to micro, but is there
any eﬀect of other than particle size?
A: Crystal shape also has a signiﬁcant eﬀect. In rare-earth transition metals, it is common
for the transition probability to drop when the symmetry is high. Crystal lattices with distorted
symmetry shine more strongly.

25

26

2.6 M. Nogami（Kindai Univ.）
Complexation behavior of actinyl ion- coordinating monoamide compounds with FP ions

Users meeting on Condensed-matter Chemistry in Actinides and their Applications /Production of medical RIs by Reactor Irradiation, KURNS, Kyoto Univ., 2023.3.2

Background to develop compounds withselectivity for U(VI) in acidic HNO3 media

Complexation behavior of
actinyl ion-coordinating
monoamide compounds
With FP ionsMonoamide compounds in nuclear back-end
ü Decrease in generation of secondary
wastes would be possible because they
consist only of CHON atoms.

Monoamide structure:
R, R`, R= : hydrocarbon group

ü They have a carbonyl oxygen atom which
has a strong interaction with actinide (IV)and (VI) species.

Masanobu Nogami

Monoamide extractants selectively extract
U(VI) and Pu(IV) in acidic HNO3 media.

Kindai Univ.,
Osaka, Japan

Complex of monoamide
extractant and U(VI)

Similar adsorptivity is expected for resins.

Synthesis of silica-supported monoamide resins

Synthesis of silica-supported monoamide resins- 1 step reaction (polymerization) -- 2 step reaction -Putting silica beads into flask
Pore producing
solvents+

Evacuation into vacuum
CH2Cl

Addition of raw oil (monoamide monomer,
DVB, pore producing solvents) into flask

4 kinds of liquid(monomer, etc.)

CH2Cl

18hr

CH2

m/p-DVB

m/p-chloromethylstyrene(CMS)

Porous silica

N - CH3
C=O

120oC, 66hr

Stepwise polymerizationfrom R.T. up to 900C in total 18h
NaH, DMF

O H
CH3 - C - N - CH3

Wash of product with acetone(Removal of pore producing solvents)

CH3
MVBAA

O
CH3 - C - N - CH3

120oC

N-methylacetamide

Wash with water

Synthetic scheme of Silica-MVBAA

Resin product

Synthetic scheme

Adsorptivity of silica-supportedmonoamide resins : HNO3 system (2)Adsorptivity of silica-supportedmonoamide resins : HNO3 system (1)Kd

ü VBAP is non-adsorptive.

DMAA
VP
MVBAA
VBAP
VBPP
VMAA

120

N

N 3 CH3

Coordination of carbonyl oxygen atoms to U(VI)
was difficult, because cyclic structures containing
nitrogen atom generates steric hinderance.

80

Chain-type

C=Oü Kd values of MVBAA, VBPP, VMAA are low.

No adsorption of FP ions

CH3vinylpyrroridone

Sr(II)Cs(I)
Ce(III)Sm(III)
Dy(III)
V(IV)
Fe(III)
Zr(IV)
Mo(VI)
Ru(III)Rh(III)
Pd(II)
U(VI)

2

10

Kd
1

2 3 4
[HNO3]/M

5

DMAA VP

MVBAA

1

10

6
0

10

Complex of monoamide
extractant and U(VI)
VBAP VBPP VMAA

Adsorption of some FP ions(VP)

(DMAA)

dimethylacrylamide

40

00

0

3

6

9

12

[HNO3][1]M. Nogami, et al., J. Radioanal. Nucl. Chem., 273, 37 (2007).

[1]M. Nogami, et al., J. Radioanal. Nucl. Chem., 273, 37 (2007)[2]M. Nogami, et al., Prog. Nucl. Energy, 50, 462-465 (2008).

27

Cyclic-type

O=

Zr(IV) [2]Pd(II) [3]Re(VII) [3]Mo(VI) [2]
U(VI) [2]102

Kd

4 kinds of liquid + silica + initiators

101

100

0

2

4

[HNO3]

6[2]M. Nogami, et al., Prog. Nucl. Energy, 50, 462-465 (2008)[3]S. Nakamura, et al., ANUP2016, Sendai, Japan, P-07 (2016)

Adsorptivity of silica-supportedmonoamide resins to FP ions : HCl system

Adsorptivity of silica-supportedmonoamide resins : HNO3 system (3)DMAA[3]

VMAA[3]Zr(IV)
Mo(VI)
Ru(III)
Pd(II)
Nd(III)
Re(VII)

Kd

60

300

300

300

200

200

200

Kd

100
80

Attention was paid to common point
for VP and VMAA, i.e., distance
between main chains and donor
atoms (N, O).

100

100

0
0 1 2 3 4 5 6[HCl]/M

40

0
0 1 2 3 4 5 6[HCl]/M

20
0
0

1

2

3
4
[HNO3]/M

5

6

DMAA

VP

[3]S. Nakamura, et al., ANUP2016, Sendai, Japan, P-07 (2016)

VMAA

VBPP

MVBAA

0
0 1 2 3 4 5 6[HCl]/M

Adsorption of some FPions
Kd value for Re(VII) has
maximum at around 1M
HCl

DMAA

VP

VMAA

VBAP

VBAP
MVBAA
VBPP
VMAA [3]VP[3]DMAA [3]

800
Kd

VP

100

VMAA, VP

Investigation on adsorption mechanism
for Re(VII) in HCl system

Adsorptivity of silica-supportedmonoamide resins to Re(VII): HCl system
DMAA

DMAA
Zr(IV)
Mo(V)
Mo(VI)
Pd(II)
Nd(III)
Re(VII)

VMAA[3]S. Nakamura, et al., ANUP2016, Sendai, Japan, P-07 (2016)

1000

VP[3]

Kd

Adsorption of some FP ions

VMAA[3]

No adsorption of FP ions

Identical adsorptivity withthose of cyclic-type resins

Kd

Chain-type

Chemical species of Re(VII) changewith increasing concentration of HCl.

600
400

Kd values are increased with increasing distance offunctional monoamide groups from main chain.

200

Copyright protected image

õVP, VMAA, VBPP

00

1

2

3

4

[HCl]/M

5

Maximum values at around 1M

6õMVBAA, VBAP
Kd values are increased with increasing
concentration of HCl.

DMAA

VP

VMAA

MVBAA

Adsorptivities of various monoamide
resins to Re(VII) are found todifferent in the range of 0.1~1M HCl.

VBPP

VBAP

Change in chemical forms of Re(VII)depending on HCl concentration[4]Different adsorptivity in the range of 0.1~1M HCl[4]R. R. Srivastava, et al., Hydrometallurgy, 157, 33-38 (2015)[3]S. Nakamura, et al., ANUP2016, Sendai, Japan, P-07 (2016)28

It is suggested that adsorption
mechanism for ReO4- has significant
differences.

Question and answer session
Q: What is the adsorption mechanism?
A: In nitric acid solution, metal ions form complexes and become electrically neutral, similar
to liquid extraction. In hydrochloric acid solution, electrostatic interaction is more dominant.
Of course, in either aqueous solution system, there are both contributions.

Q: You say you don’t have a clear understanding of the role of oxygen and nitrogen in amides.
Is there already information, for example, on what kind of behavior would be produced byhanging only carbonyls in a polymer, or tertiary amines?
A: In the nitric acid solution system, the uranyl ion is a hard acid and has a high aﬃnity foroxygen atoms. There have been studies on the use of ketones (C=O) and other compounds that
do not contain nitrogen, such as ether bonds (C-O-C), to capture uranium supplements.

Q: Then what is the role of nitrogen?
A: Nitrogen protonates to secondary ammonium in acidic solutions, so we would like to
study its eﬀect. With the help of computational chemistry professors, we should have a better
understanding.

Q: It was mentioned that the coeﬃcient of extraction is large in a cyclic structure. Since thisnitrogen is covered when the ring structure changes, why is there a nitrogen eﬀect?
A: It must be a matter of electron density.

Q: Surely there must be an eﬀect of electron attraction aﬀecting the electron density of oxygen
rather than direct coordination.
A: I agree.

Q: If the extractant is loaded on the ﬁxed layer, the extraction rate of elements other than uranium would also increase. What considerations should be made when structuring the separation
process?
29

A: Am I correct in my understanding that, in general, various elements are more likely to besupplemented if they are made solid?

Q: Since there is no diluent, the dilution rate cannot be adjusted.
A: That is correct that there is no diluent. However, the results on the left side of this slide
show typical results where only uranium is really supplemented.

Q: But the KD is above 1 for other elements.
A: Yes, but it should be possible to separate them in a chromatographic column. Extraction
is diﬃcult.

30

2.7 K. Shirasaki（IMR, Tohoku Univ.）
Ac-228 solvent extraction by DGA

Users meeting on Condensed-matter Chemistry in Actinides and their Applications /Production of medical RIs by Reactor Irradiation, KURNS, Kyoto University, 2023/3/2-3/3

Contents
1. Background of 228Ac and Ac solvent extraction by DGA
2. Purpose of this study

228Ac solvent extraction by DGA

3. Experimental
4. Results
ü Preparation of 228Ac generator

Institute for Materials Research, Tohoku University
Kenji Shirasaki, Shingo Sugahara
Tokyo Institute of Technology
Masahiko Nakaseü Solvent extraction by TODGA or T2EHDGA

5. Conclusion

1

2

Targeted alpha therapy (TAT) using 225Ac

Circumstances surrounding Actinium
w The main reason for the absence ofcommercial applications based on actinium(except 225Ac)...

w Actinium chemistry has experienced a strong revival in the past two decades due to thedevelopment of a new type of cancer therapy, called 88Targeted Alpha Therapy (TAT)=w One of the isotopes of actinium, 225Ac, is seen as one of the most promising candidates fortargeted alpha therapy
ü its ideal short half-life of 10 days
ü decay chain that has no long-lived daughterü delivers 4 high-energy alpha particles, along with two beta particles

ü rareü radioactive

w 227Ac ( t

1/2 = 21.8 y): longest-lived isotope

ü present in the environment due the decay of 235U
ü extremely diluted in natural sources

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w Hence, actinium materials cannot readily bestockpiled and must be periodically produced
in nuclear reactors, cyclotrons, or particle
accelerators...

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Decay chain of uranium-233
comprising actinium-225 and its
daughters.

The sole purpose of studying Ac chemistry israre, challenging, and extremely costly.

Deblonde G. J.-P., et al. The coordination properties and ionic radiusof actinium: A 120-year-old enigma. Coordination Chemistry
Reviews. 2021;446:214130(The Chemistry of the Actinide and Transactinide Elements, 3rd ed., Springer)

3

Position of actinium (Z = 89, symbol 88Ac=) in the periodic
table of the elements. For comparison purposes, the adjacentelements belonging to the 6th and 7th rows arehighlighted and their preferred oxidation state in aqueous
solution is indicated.
The current availability of purified 227Ac for research in
US is below the milligram level.

4

Actinium isotope (228Ac) advantage

Chemical properties of Actinium

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half-live longer
than 1 hour

Kratochwil C, et al. 225Ac-PSMA-617 for PSMA-Targeted ³-Radiation
Therapy of Metastatic Castration-Resistant Prostate Cancer. The
Journal of Nuclear Medicine. 2016;57:1941-1944

Deblonde G. J.-P., et al. The coordination properties and ionic radiusof actinium: A 120-year-old enigma. Coordination Chemistry
Reviews. 2021;446:214130

Table Nuclear properties of actinium isotopes

w The position of actinium in the periodic
table also makes it an elusive element
since...

Decay chain (Th series)
232ü the first member of the actinide series
ü its natural oxidation state in solution is +III
ü its ion, Ac3+, has an empty valence shell(electronic configuration: [Rn] 5f 0)

a b3
228Ra
5.57 y³-Spectrum from a solution of 228Ac
eluted from the generator

228Th
b3 1.9116 yTh

1.4x1010 y

228

Ac

Aldrich K.E., et al., Preparation of an Actinium-228 Generator.
Inorganic Chemistry. 2020;59:3200-3206a6.15 h224

Copyright protected imageRa

3.66 da
220Rnw Unlike many other f-element ions (Eu3+,

55.6 saTb3+, Dy3+, UO22+, Pu4+, Cm3+...)
ü spectroscopically silent with no fluorescence
properties nor practical absorbance band in
the UV3visible 3 NIR domains

212
Po
b3 2.99x10-7 s

216Po
0.145 s

a b3

212Bi

w Bulk chemistry experiments cannot be
performed
w Ac3+ has no perfect surrogate

b

208

Tl

3.053 m31a35.94% 208
Pb
a 3

10.64 h564.06%

60.55 m212Pbstablew An actinium isotope (228Ac, t1/2 = 6.15 h) :ü nuclear properties are well-suited for ³-spectroscopyü easily resolved from the long-lived 228Th daughter productü rapidly regenerates after being harvested from the 228Ra (t1/2 =5.75 y) parent
6

228Ac Generator

Separation of Actinium

The change in 228Ra and 228Ac activities
vs. time when 228Ac is routinely <milked=
from the 228Ac generator

w DGA extraction chromatography
Mastren T., et al., Simultaneous
separation of actinium and radiumisotopes from a proton irradiatedthorium matrix. Scientific reports.
2017;7:8216

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0.1 M HNO3
Ln(III)

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Projected activity of
the 228Ac generator (basedon the parent 228Ra activity)

Radchenko V., et al., Application of ion
exchange chromatography to the separationof actinium from proton-irradiated thorium
metal for analytical purposes. J.
Chromatograph A. 2015;1380:55-63

10 M HNO3
Ac(III)

w Load and wash conditions:ü g90% of Ra2+ and g80% of Ba2+ elute, while Ac3+ and Ln3+
are quantitatively retained
ü Residual Ra2+ and Ba2+ were further removed with 4 M
HNO3w The 228Ac generator provides frequent and long-term access (of many years) to thespectroscopically <friendly= 228Ac radionuclide

w The addition of 10 M nitric acid:w The 228Ac product can be routinely <milked= from the generator on a daily basis, inchemically pure form, with high specific activity and in excellent yield (>95%)

ü More than 99% of the retained Ac is eluted

w Ln3+ could be eluted with 0.1 M nitric acidw Development of DGA resin, which
offers a possibility for rapid, robust,and effective separation of Ac fromRa, is key in these techniques

78

Diglycolamide (DGA) extractants

Purpose of this study

wIn past two decades, diglycolamides have received particular attention of
separation groups engaged in the area of actinide partitioning, as theseligands display high affinity for trivalent metal ions as compared tohexavalent metal ions

To demonstrate the usefulness of 228Ac...
wPreparation of 228Ac generator based on previous study and evaluationof 228Ra yieldw 228Ac solvent extraction by two DGA extractants (TODGA andT2EHDGA) for fundamental investigation of actinium coordination
chemistry

Table Physicochemical properties ofvarious diglycolamide extractants

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Sasaki, Y. et al., S. Solv. Extr. Ion Exch. 2001, 19, 91.

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Variation of the DAm with aqueous
phase acidity. Extractant: 0.1 M
TODGA in n-dodecane
Ansari, S. A. et al., Solvent Extr. Ion Exch. 2005, 23, 463.

Copyright protected image

Crystal structures of La
TEDGA complex
T. Kawasaki et al., <Crystal Structures of Ln(III) (Ln = La, Pr, Nd, Sm, Eu, and Gd)
Complexes with N,N,N, -Tetraethyldiglycolamide Associated with Homoleptic[Ln(NO3)6)]3-=, Bulletin of the Chemical Society of Japan, 23 (2013) 2181-2188

910228Ac generator preparation process
Four-step separation process developed for isolating 228Ra
as a generator for 228Ac from natural 232Th

Generator preparation process(step1)
ThO2 dissolution in conc. HCl

w Step 1 removes the vast majorityof 232Th from 228Ra by hydroxide
precipitation

150#

ü ThO2 dissolution in HCl
ü addition of catalytic amount of HF

w Step 2 removes the contaminants
originated from 232Th starting material
and bulk Na+ introduced from NaOH
Copyright protected image

w Stock sol. (Th4+ in 0.1 M HCl):

100¿L HF

pH adjustment of sample by NaOH and HCl titrationw Th hydroxide precipitation

Sol. A
Sol. Cw Step 3 separates 228Ra from its
daughters, including 228Ac and 212Pb,
and trace-level impurities

Sol. Bw Step 4 separates organic impurities byfilterSol. A

Sol. B

Sol. Cü NaOH (30 wt%) is added toadjust the pH >8
ü voluminous pasty-white solidü the pH of the basic slurry is
adjusted to 6 < pH < 8 with HCl
ü filtrate and adjust HCl to 1M

Step1: <5.1 ppm Th, 100% 228Ra remain

Aldrich K.E. et al., Preparation of an Actinium-228 Generator. Inorganic Chemistry. 2020;59:3200-3206
11

32

12

Generator preparation process(step2)

Generator preparation process(step3)
w DGA extraction chromatography

w Cation exchange chromatography
Conditioning
Load
Vial wash(1M HCl) (228Ra + Th etc.
(1 M HCl)in 1 M HCl)

3CV

Wash
(1 M and2 M HCl)

Elution(3 M and 6
M HNO3)

Conditioning
Load
Wash
Vial wash(6M HNO3) (228Ra + 228Ac(6 M HNO3) (6M HNO3)
in 6 M HNO3)

~3 CV
1CV
~3 CV
~0.33CV
~3 CV
3 CV
×3
Cation exchange resin (50WX8, 100-200 mesh)

228

Th chloride , Na+, etc.

discard

1 CV
×3

1CV
×3

1 CV
×3

2 mL Column
Volume (CV)BDGA resin

2.5 mL
ColumnVolume (CV)Ra/Ac fraction

w Load and wash conditions:

1CV

~4CV

Elution(0.1 M HCl)228

discard228

Ra fraction

Ac fraction

w Load and wash conditions:

Step2: 97% 228Ra remain

Step3: ~100% 228Ra remain

ü Ac3+ are retainedü Ra2+ and Ac3+ are retainedü Neutral complexes, anions, and the majority of the Na+ pass through the column

ü The majority of the Ra2+ pass through the column

w Ac3+ products is then eluted with HCl and is isolated

w Ra2+ and Ac3+ products are then eluted with HNO 3 and are isolated
13

14

Summary of 228Ac generator preparation
Table 228Ra separation percentage in each steps
Aldrich et al.*This work

Step1
83 %
100 %

Step2
98 %
97 %

Step3
100 %
97 %

Tests of 228Ac solvent extractions
w Chemicals, apparatus and procedure

wThe 228Ac generator:

Total
81 %
94 %

*Aldrich K.E., et al., Preparation of an Actinium-228 Generator.
Inorganic Chemistry. 2020;59:3200-3206

Copyright protected image

n-dodecane
C12H26

CH3O

ü isolating the 228Ra parent andoperating the generator do not require
the addition of carrierü chemically pure and high specificactivityü small volumes of dilute acid, which
will facilitate matrix manipulation of
the product for subsequent
experimentsü a long shelf life which can provide
access to large quantities of 228Ac formany years

H3C

N

H3C

H3C

CH3

H3C

CH3
O

N

O

N

O

CH3

CH3

TODGA
C36H72N2O3

N

O
H3C

CH3

CH3

H3C

O

F

T2EHDGAC36H72N2O3

F

F

F

F

F

F

H

H

F

F

F

HFC-43
CF3(CHF)2C2F5

CH3Extractants: DGA

Diluents: non-polar solvents

Shaker (1,000 rpm, 25 ± 0.1 #)ü Separation and purification of 228Ac from 228Ac generator and adding
to the aqueous phaseü it is mixed with the organic phase containing DGA and started shaking
ü Stop after, aliquot of the aqueous phase is sampled and measured ³ray spectrum using Ge semiconductor detector

ca. 0.34 kBq 228Ra separated

Ge semiconductor detector

15

16228Ac extraction behavior by TODGA
(a)

(b)

228Ac extraction behavior by T2EHDGA
(a)

(c)

0.01 M TODGA
3 M HNO3

wEstimated extraction
reaction:(b)0.01 M TODGA
3 M HNO3

30 minSlope=3
1M

2M

3M

25mM
5mM

4M

6M

10mM

50mM

75mM

100mM

Dependence of nitric acid concentration (a) and T2EHDGA concentration (b)Dependence of shaking time (a), nitric acid concentration (b) and TODGA concentration (c) using ndodecane as diluent.

w Estimated extraction reaction*:
Ac !" + 3TODGA + 3NO3# ³ Ac NO! ! TODGA !

* Ignore the activity of chemical species in solutions

w Same behavior observed in
Lns and Am3+ extractions**

ü different fromTODGA condition interms with acidmolecule extraction
ü Diluent effect isclearly indicated inacid concentration
dependence

w Estimated extraction reaction*:
Ac !" + 3T2EHDGA + 3NO3# + HNO! ³ Ac NO! ! T2EHDGA ! HNO! $**Sasaki Y. et al., An Additional Insight into the Correlation
between the Distribution Ratios and the Aqueous Acidity of the
TODGA System. SEIE. 2007;25:187-204* Ignore the activity of chemical species in solutions
17

33

18

Ans and Lns extraction by DGA

Summary of 228Ac solvent extraction by DGA
wExtraction mechanism seems to be strongly dependent to side chain of
DGA motely:

wSeries extraction
behavior:
Copyright protected image

0.1 M TODGA

Ansari S. A. et al., Chemistry of Diglycolamides: Promising
Extractants for Actinide Partitioning. Chemical Reviews.
2012;112:1751-1772

Distribution of lanthanides andactinides by 0.01 M T2EHDGA
dissolved in HFC-43.

ü Similar tendency can beobserved both T2EHDGA
and TODGA* Ignore the activity of chemical species in solutions
Estimated extraction reaction*:
Ac !" + 3DGA + 3NO3# + HNO! ³ Ac NO! ! DGA ! HNO! $ü m = 0 for TODGA, 2 or 4 for T2EHDGAü Main factor of difference
between Ans and Lns isstill unclear...extractant ordiluent effect?

ü In T2EHDGA condition, diluent effect is clearly indicated in acid concentration
dependence (m = 2 for HFC-43 and 4 for n-dodecane)

wLns and Ans series extraction behavior shows similar tendency between
T2EHDGA and TODGA conditions

Distribution of lanthanides andactinides by 0.1 M TODGA dissolved
in n-dodecane from 1 M HNO3.

19

Conclusion
Good demonstration the usefulness of 228Ac
w Quantitative purification of 228Ac was possible, reproducing results from theprevious studyü 228Ra yield is 94% in total process

w The difference of 228Ac solvent extraction by two DGA extractants (TODGA
and T2EHDGA) provides some insights
ü Extraction mechanism seems to be strongly dependent to side chain of DGA motelyü Lns and Ans series extraction behavior shows same tendency in two DGA extractants

Thank you for your attention
21

34

20

Question and answer session
Q: In the process of producing actinium-228, you say that thorium precipitated perfectly with
pH adjustment, what do you do when you extract it from thorium again?
A: Precipitate it in the form of hydroxide, dry the hydroxide and store it in solid form, anddissolve it again in nitric or hydrochloric acid. Radium-228 can be recovered relatively easily
this way.

Q: Isn’t the accumulation of solid alpha waste of metal nitrates and chlorides a problem?
A: That is correct and is an improvement of this method.

Q: Why was actinium deviated from the straight line in the last ﬁgure (comparing the extraction
capacity of the actinide and lanthanide series in terms of distribution ratio)? Is it due to the mass
eﬀect of actinium or the lack of f orbital electrons in the actinium ions?
A: In the case of TODGA, the actinium extraction experiment has not yet been completed,
and we believe that it will probably ride on the straight line. However, the reason why the
distribution ratios of the actinide and lanthanide series are reversed in TODGA and T2EHDGA
is currently unknown, and we would like to clarify whether this is due to the diluent (HFC anddodecane) or the structure of the extractant DGA.

35

36

2.8 T. Kobayashi（SPring-8, JAEA）
Achievements in the facility utilization of the Combined Research Laboratory and the current status with the SPring-8 JAEA Harima Lab.

q\{}~rÿ
ükì÷öú~göYW{·y»|~ü

Users meeting on Condensed-matter Chemistry in Actinides and their Applications/
Production of medical RIs by Reactor Irradiation / Mar. 2023

Achievements in the facility utilization of the
Combined Research Laboratory and the current
status with the SPring-8 JAEA Harima Lab.

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38

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ý¯{}Wû_0{}ºÜøÛ1q}ÍÛ}{·y»wzy1

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ç_vÏ ßÝ ßOûmÛ¬ÿ ÿ »ó¿ü÷ ÷ ïûßýç_è÷ßßú²û¿´ð»n³÷ý»¹gþ~gùWXAFSÍÿĀĀĀ ç_û}zðóùë°~{Ûûþß{gßï³{î¯x~gÝ|XÿYÿ[VY

HAXPESÍ ç_è÷Wß¹öü·÷óç_ ÿ2]ÿmÛç_ ÿ1]

ðû¿WV÷ûùüñóø
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ARPESÍ ç_{îù|~»ó¿ü/SPring-8w~ß[Ûù|~Āó¿¸óù´þùü·÷óý^ó}{¹~ü²ā¿ûÞà

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õ_ß[{gù|¿w]

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UFeGa5

AmO2+*

C

hn 2

U

Ga

µ

Fe

µ

hn 1

AmO22+

f9
AmO2+¼ù¹þW_~|~

f

B
A
O

µ

Es{¸»~Z¶ùóW\{~ÿ[ök

µ

Ra~W
µ

(

Ûyg~UN{Uqv
SPring-8

Ra~|Üë° ¾üõ³´R
RIßÿ

ÿþßùo÷|~
ôÛÞÿ

¸ýßÏm

÷öúV÷

ôÛ¬÷P
Si4+ , Al3 +O 2-

Am²s\ÿ~ÿx~]
q\ÿÿþ1þ½1Þ¿¼²}{¼»[x{Al 3+ , Mg 2 + , Fe 2+

\gx~~{×ë÷OH -Ïe²]·úúº~ë
nû_m~ÛygUN

Si 4+ , Al3+

~÷_ÜV÷~mWë×ÎïÚ~|~{¹|}Ý}\ïÚx
Accelerator
ON

Amßß[Ûÿl
ù|¿w]

[^_zyāÿü÷Ā´¹~{}w|÷V

Se1Cs~
þë{×B|}Ý}\ïÚ
ó÷Ïm{w]

A
O

OFF

ÿ5]

ÿ2]

ßÛû´āü¸óÀ ç_ ÿ2]» ßÞú ç_ ÿ2]ðû¿ðû¿ûß²¼}÷ÿ[ök»nÿ}ûýuÿ30-100 ÅĀNEDOÏmÿ \Z¸ýû¾üwý|~÷³ó¸÷ó÷³ó¸÷ó÷ ýy ö{|~ë²ÿ0mÛûv1o÷ûómÛ1ÿ÷ïvÿíøw{Ā ýp ³m
ÏÛ}îÿíøw{Ā _÷ Üû 0y^þûþÞ_rÜû1 1]

Pd
Pt
Rh

OO{~
ë×ÎïÚ

39

ÿ2]

XMCDÍ ç_

ÿ2]STXMÍ ç_ÿ2]÷ü¿q}W
ç_ :1]
mÛç_ ÿÿ]Question and answer session
Q: You showed data that oxidation progressed due to gamma irradiation and water immersion;
XPS should also show the bulk distribution. Is the depth proﬁle known?
A: This experiment is XAFS, not photoelectron spectroscopy. Depth proﬁle is considered
important.
A: No, it is not. Unlike ﬂuorescence, absorption data includes information from the surface
to the bulk.

Q: Isn’t it important to know how deep the oxide ﬁlm is formed on the surface?
A: That is exactly right. At this time, we only have information that reﬂects a large amountof the surface and a large amount of the bulk, and this is all we know. In the future, we would
like to examine the extent to which oxidation has progressed on the surface through experiments
such as angular resolution.

Q: Isn’t it time to start accepting debris?
A: We will be able to report that we have measured the actual debris as early as next ﬁscal
year. Currently, we are working on establishing various operational systems.

40

2.9 Y. Kasamatsu（Osaka Univ.）
Recent chemical researches on nobelium

Heavy element chemistry1

周期表の最下段

H

重ア¿チþイù1
þーùúウム~化学研究2

第７周期元素の化学

He

3

4

5

6

7

8

9

10

Li

Be

B

C

N

O

F

Ne

11

原子番号 Z > ĀÿÿÿHeavy elementsĀ

12

Na Mg
19

20

K

Ca

37

全て人工合成、人類にとっての新元素！

16

17

18

S

Cl

Ar

34

35

40

41

42

71

72

61

62

63

114

92

93

U

Np Pu Am Cm Bk Cf Es Fm Md No Lr

101

102

103

104

105

75

107

Ru

Energy, eV−4• 外û(d, f)軌道→拡張

80

111

112

81

113

83

84

115

116

117

118

0
−2

• 内û(s, p)軌道→ß縮

108

79

Rf Db Sg Bh Hs Mt Ds Rg Cn Nh Fl Mc Lv Ts Og

主z研究対象Relativistic effects

74

54

110

91

Fr Ra Ac Th Pa

73

86

109

100

70

85

106

99

69

82

87

98

68

Xe

Pb Bi Po At Rn

97

67

I

78

96

66

53

Pt Au Hg Tl

95

65

51

77

94

64

50

36

52

Sn Sb Te

Ir

90

60

49

76

89

59

48

W Re Os

88

58

47

Cs Ba La Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu Hf TaÿRecent chemical researches onnobeliumĀ
Graduate School of Science,
Osaka Univ.
Yoshitaka KASAMATSU

15

33

Zr Nb Mo Tc Ru Rh Pd Ag Cd In

46

30

P

39

45

29

32

Y

44

28

14

38

43

27

Si

Rb Sr
57

26

31

24

Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr

56

25

13

23

V

55

21

Al
22

Sc Ti

−6

nr

rel

5s

5s1/2

Os
rel

nr

6s1/2

−10

4d

Hs
rel

7s

6s

−8

6d5/2

4d5/2

7s1/2
5d5/2

4d3/2

−12

• ¹ôン軌道相互作用

nr

5d

−14

5d3/2

6d3/2

6d

−16

相対論効果が重元素の化学的性質{影響⇒特徴的z化学的性質ÿ実験Ā
第8族元素の軌道の非相対論効果(nr) と化学的gî|\ï元素間~
相対論効果⇕相対論計算⇐(rel) のエネルギー計算値|期g{¹逸脱す»ÿ能g
元素の理解 ⇐相対論の理解⇐
M. Sh‰del and D. Shaughnessy (eds.), The Chemistry of Superheavy Elements, (2014).

Actinides
90

91

92

93

94

95

Ac

Th

Pa

U

Np

Pu

Am Cm Bk

天然{存在

96

97

101

98

99

100

Cf

Es

Fm Md No Lr

原子炉w合成可能102➢Atomic number = 102, Heavy element

103➢In f-block elements, only No stably has +2 state in aq,
while all lanthanides and heavy actinides have +3

重イºン核融合

La Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu
4
3

H

SHEs化学ß験手法~
適用

An
Ln

logKex

He

Li Be
Na Mg

K Ca Sc Ti

2

Rb Sr

Solvent
extraction ofLn(III)xAn(III)by HDEHP
from HNO3

1
0
-1
-2
-3

o

３価アクチノイù重ア¿チþイù

89Nobelium²ûフ±研究会
2015.2.23

Actinide element chemistry

Y

V

B

C

N

O

F Ne

Al

Si

P

S

Cl Ar

Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr

Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te

Cs Ba Ln Hf Ta W Re Os Ir

I

Xe

No
n 5f14 7s2

Pt Au Hg Tl Pb Bi Po At Rn

Fr Ra An Rf Db Sg Bh Hs Mt Ds Rg Cn Nh Fl Mc Lv Ts Og

La
+3

Ce
+3

Pr
+3

Nd
+3

Pm
+3

Sm
+3

Eu
+3

Gd
+3

Tb
+3

Dy
+3

Ho
+3

Er
+3

Tm
+3

Yb
+3

Lu
+3

Ac
+3

Th
+4

Pa
+5

U
+6

Np
+5

Pu
+4

Am
+3

Cm
+3

Bk
+3

Cf
+3

Es
+3

Fm
+3

Md
+3

No
+2

Lr
+3

Stable oxidation state in aqueous solutions
Ac Th Pa U Np Pu Am Cm Bk Cf Es Fm Md No Lr

Nobelium

Recent researches on Noo
2族元素x比較

dブロック元素x比較
tri‐n-octylamine chloride/
塩酸系w~抽出挙×[1]塩酸系w~HDEHP»ùム{¹~溶出挙×[1]⁰SrCo-precipitation method

塩酸系w~陽イºン交換»ùム~溶出挙×[1]

•
•
•
•

⁵⁵No

⁴⁷Ca

Copyright protected image

No

Copyright protected image

Copyright protected image

Co-precipitation with samarium hydroxide
Co-precipitation with barium sulfate
Co-precipitation with calcium oxalate
Co-precipitation as malonate

Ba検出限界以Oカùムボúューム

カùムボúューム

➢ Similar to Ba (2ï元
素)Ionic radius (CN=6)[2] / ÅSolid-liquid extraction➢ Similar toCa➢ Similar to Ca
and Sr
Ca2+

Sr2+

Ba2+

1.00

1.18

1.35

• Extraction by crown ether resin• アüムùクùウンエüテû樹脂

塩酸系wzく2ï元素x錯rをす»系wNo~gîを調べい[1] R. J. Silva, et al., Inorg. Chem. 13, 2233 (1974).

7[2] R. D. Shannon, Acta Cryst. 32, 751 (1976).

412

Precipitation and Co-ppt- as sulfate

Precipitation and Co-ppt- as sulfate

47Ca: Produced by neutron irradiation at KURNS
85Sr, 133Ba: Produced by proton irradiation at RCNP

RI tracer in 0.01 M HCl 10 μL

Amount of carrier or metal

RI

Co-pptcarrier

ppt macroamount47Ca

Ba 20 µg

Ca 1 mg

85Sr

Ba 20 µg

Sr 1 mg

133Ba

Ba 20 µg

Ba 1 mg

226Ra

Ba 20 µg0.01 M HCl 20 µL

Carrier or metal 10 µL
200 μL water

Co-ppt (Ba 20 µg)

80Ca

Ammonium sulfate solution
ÿ0.001 M～2.0 M: 8 concentrationsĀ

Stirring (5 min)

60
40
20

Cup

0

γ-ray measurement with Ge
detector

Precipitate(ppt)

Suction0.001 M

0.005 Mppt or co-ppt yield %�㔴�㕝�㕝þ+�㔴�㕐ÿ�㕝
×100
=

0.1 M

0.5 M

1.0 M

8

Online experiment of 255No

ppt (macro) (Sr and Ba 1 mg)
TargetYield / %0.05 M

7

Co-ppt (Ba 20 µg)
Dissolution
in high[SO42-]1000.01 MNot precipitated in both co-ppt and ppt�㔴�㕝�㕝þ+�㔴�㕐ÿ�㕝+�㔴�㕓�㕖�㕙

Filtration(fil)

Precipitation and Co-ppt- as sulfate

Sr

ppt (macro) (Ca 1 mg)

100

Yield / %Experiment

ò熱管

Beam

加

He gas jet
KCl

RIKEN AVFcyclotron
248Cmÿ12C, 5n)255No (T器

natGd(12C, xn)162Yb (T

1/2 = 211 s)

1/2 = 18.9 min)

※162Ybのγ線測定{¸º生成物を確認

50
0.01M HCl 20μL

Carrier soln.

0orLigand soln.

Ba

Yield / %100

5 min 撹拌

共

½過棒

50
0
0.001 M

0.005 M

0.01 M

0.05 M

0.1 M

0.5 M

1.0 M

半自動吸引½過装置

He gas jet
KClCarrier soln.

Accelerator
0.01M HCl 20 µL

80

共沈試料
共 試料
共沈ß率/%

Carrier soln.

5 min 撹拌Ta皿
ÿ標準試料Ā

0.01
40 M HClw溶解後キャúア溶液
x(NH₄)₂ O₄溶液を入¼»

0.01 M HClw溶解した後、Ta皿{入¼»

0.5

1.0

試料

α-particle
α線測定
measurement

7740-8340 keV 255No

6
4

0
7000

2.0

7500
8000
Energy /keV

8500

吸引
自×連ÿα線測定装置

5

0
7000

7500
8000
Energy/keV

8500

環境中{存在す»214Po(7685 keV)のα線領域x被¹zい¸う{255No領域を
7740-8340 keVxし、イベンø数を»ウンøした

γ-ray
γ線測定
measurement✓ Alpha spectrum = expected for 255No✓ Cross section 389nb (ref. 420nb [9] )✓ Half-life 210s (ref. 212±24 s [10] )[自×吸引½過装置

214Po

10

2

(NH₄)₂SO₄濃度 /M

共

214Po

7740-8340 keV 255No

蒸発乾固後α線測定
γ線測定
0.1

STD

ppt
8

標準試料
Ca Sr
255Nox162Yb捕集(7.5 min)

吸引½過00.001 0.005 0.01 0.05
乾燥後α線測定ûγ線測定

100.1
0.1 oror 2.02.0M
M(NH₄)₂SO₄mL(NH₄)₂SO₄ 22 mL

60
255
Nox162Yb捕集(7.5 min)20配位子溶液を入¼、5
min撹拌

or

(NH₄)₂SO₄溶液

255No alpha spectrum[10](NH₄)₂SO₄ soln.

BaCl₂(20 µL/10 µL) : 0.01 M HCl : water= 1 : 1 : 20 220 µL

Ge[導体検出~Countsò熱管

自×連ÿα線測定装置

Results and discussion 255No

CountsTargetγ-raymeasurement

10

Online experiment of 255No
Beam

α-particle
measurement

試料

吸引

2.0 M

Qualitatively precipitation properties can be
9[1]木道則¹, 化学辞典1z,
東京化学\þ
(1989).
investigatedbased onthe coprecipitation
behavior

Yco-ppt = Yppt

½過棒

Ta皿
ÿSTDĀ

Almost all alpha counts in ROI originate
from the decay of 255No

Ge[導体検出~11[9] T.Sikkeland et al., Phys. Rev. 172, 1232 (1968). [10] M. Asai et al., Phys. Rev. C. 83, 014315 (2011).

42

12

Results and discussion 255No
90

共沈ß率/%
共沈ß率/%

Half-life
Yield (compared with Yb)
Evaporation yield
Beam current
Detection efficiency
Background of alpha counts
Tailing of α spectrum

100
100

100
80

共沈ß率/%

•
•
•
•
•
•
•

硫酸沈殿~gî[11]SO42-(2.44 Å)x2ï元素~イºン[ß差|小uいほy水和し{くくzº1沈殿をrす»

120
120

Coppt yields of 255No

各条件tx{数え255No~»ウンø数を}¼~¼255No捕集終了f~計数率(cps){直し共沈ß率を求め

Correction for

Results and discussion 255No

70
60
50

80
80

硫酸錯体~溶解度積[12]xイºン[ß[13]

60
60

40
40

40

CaSO4

20
20

30
20

00

10

0.001
0.001

0
0.1

2
2.0

0.005
0.005

0.01
0.01

Ca

(NH₄)₂SO₄濃度 /M

0.05
0.1
0.5
0.05
0.1
0.5
(NH₄)₂SO₄濃度/M/M(NH₄)₂SO₄濃度

SrCa

Ba

Sr

No

Ra

1.0
1.0

2.0
2.0

No

溶解度積
(logKsp)

M2+Ionic radius(CN=6)/Å

-4.63

1.00 (6配位)

SrSO4

-6.53

1.18 (6配位)BaSO4-10.001.35 (6配位)

RaSO4-14.381.48 (6配位)Ca ≤ No(1.1 Å 6配位) < Sr
(NH₄)₂SO₄濃度
Yield/%
error(+)
error(-)

Coprecipitation yield /%Count rate of co2ppt (�㕐�㕝ý)×100=
Count rate of STD (�㕐�㕝ý)

0.1 M
74.09
11.85
23.87

2.0 M
41.80
6.69
15.66

Previous works

Present result• Between Ca and Sr• Similar to Ca• No = Sr• No yield is higher
than Sr and Ca

No complex would
be more stable ?

[11] L. G. Sillén, A. E. Martell. (Eds.) Stability constants of metal-ion complexes. London: The Chemical Society (1964).
[12] R. D. Shannon., Acta Cryst. . 32, 751 (1976). [13] J. E. House, et al., Thermochimica Acta, 66, 365-368 (1983).

14

Results and discussion 255No

15

Recent researches on No

Calculation for sulfate of group 2 elements and No
硫酸錯体x金属イºンの電荷計算結果[8]Electron configulation

Charge of metal

MgSO4[Ne]3s0.04 5p0.01

1.94

CaSO4

[Ar]3d0.01 5s0.01

1.98
1.98

SrSO4

[Kr]4d0.01 6p0.01

BaSO4[Xe]5d0.01

1.98

RaSO4

[Rn]7s0.01 6d0.01

1.85

NoSO4

[Rn]7s0.04 5f13.98 6d0.10 7p0.02

1.86

ソõø：Gaussian 16 rev. C.01
n関数：B3LYP
ÿ底関数：6-31G* for Mg, Ca, S, O
SDD for Sr, Ba, Ra, No

Co-precipitation method••••

Co-precipitation with samarium hydroxide
Co-precipitation with barium sulfate
Co-precipitation with calcium oxalate
Co-precipitation as malonate

構造最適化u¼硫酸錯体

Solid-liquid extraction• Extraction by crown ether resin• アüムùクùウンエüテû樹脂

No~6d軌道|寄与し“No~共有結合性”(Covalent bonding for No)

Covalent bonding of No would contribute to stability ofsulfate complex of No => Higher Kd value than expected
7[8] 速水翔 阪学学院理学研究科修士論文 (2021).

Summary

Results of extraction exp. of No[M(H2O)n]2++DtBuCH18C6+2 NO32-⇒M(NO3)2DtBuCH18C6 + nH2O
(n=8 for Pb2+以外1n=7 for Pb2+)• 重ア¿チþイù元素1þーùúウム~化学研究をß験x理論~両面{¹進めvい»2
最近1硫酸バúウム共沈挙×やSrü¸ン抽出挙×~研究をþーùúウム{対しvß施す»sx|w}2(We have performed experimental and theoretical researches onnobelium. Here, I present the investigation of nobelium sulfate)~ß応{zq»各分子~エýû¾ーを1相対論的ß子化学計算{¸sv求め1
ß応エýû¾ーを調べ
Srüジン/3.5 M硝酸系~分配係数(Experimentally determined Kd values )

相対論的量子W学計算による計算値(Results of relativistic calculation)• 硫酸バúウム共沈ß験w1No|硫酸バúウム沈殿x共沈す»sx|分{s2イºン[ßを}くß映す»ß験{zいvNoCaxSr~中間~抽出率zyをctxいs結果|得¹¼vい|1本研究w2ï元素x異z»“No~共有結合g”を支cす»結果を得¹¼
(It was found that No forms coprecipitate with barium sulfate and theyields were higher than those of Ca and Sr. Higher stability of the No
complex may be due to covalent bonding between No and sulfate ion)
Consistent values with the experimentally determined ones were obtained byrelativistic calculation⇒Success in modeling

18

7

43

謝辞
s~場をz借ºしv1本研究を行う{あº[z»t支援を賜ºまし
方々{厚く御礼申し上rます
133Ba~ý造

理化学研究所Ï科ò速~センターò速~ºúüーター~皆様阪学x物理研究センター
ò速~ºúüーター~皆様
255No~ò速~ºンùイン共沈ß験阪学学院理学研究科
髙 咲希 様1渡邉 瑛介 様1中ÿ Ú平 様1速水 翔 様1益田 ü{郎 様1王 瑞麟 様1板倉 悠 様
理化学研究所Ï科ò速~センター
羽場 ß光 博士1重河 優 博士1YIN Xiaojie 博士1南部 明弘 様1
ò速~ºúüーター~皆様サü¸ºý業高等専門学校
横北 卓也 博士1944

Question and answer session
Q: Is it possible to have pure divalent in a nobelium complex?
A: Norberyllium is rather divalent stable.

Q: Is it also divalent in complexes?
A: Basically, it is stable in divalent form, and it is diﬃcult to oxidize it the other way around.
Some of the electrons from the nitrate ion seem to ﬂow into the d-orbital of nobelium, forminga covalent bond.

Q: How many atoms of nobelium are used in the experiment?
A: A few atoms or 10 atoms.

Q: Regarding electrochemical reactions, if divalent is the most stable form of Nobelium, howmany volts are used for divalent/trivalent?
A: About 1.3 V. It has already been reported and I am a co-author.

Q: It is very interesting that no-beryllium works like a binary genus. Does Lawrencium work
like three genera?
A: Yes. Actinium and lawrencium are very similar. Just one d, two s and one d. There aresome systems in which I see a tremendous diﬀerence between lawrencium and actinium, and I
am interested in what makes them diﬀerent, not the other way around.

Q: This is just a commentary, but this is the way you approach even ionic radii, for example,
with such a small sample. I was surprised. No, thank you very much indeed.
A: Really, thanks to the development of computation, we can ﬁnally have a discussion.

45

2.10

T. Yoshimura（IRS, Osaka Univ.）
Introduction to Institute for Radiation Sciences, Osaka University

1

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Sciences, Osaka University

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46

Question and answer session
Q: Is the program for undergraduates in Human Resource Development a College of Liberal
Arts program?
A: That’s right; it is primarily for ﬁrst-year students and covers the basics. In fact, after going
to Fukushima and receiving training, we hope that second-year students will be educated andbecome more knowledgeable.

Q: The lectures for graduate schools include the Graduate School of Science, but is the main
focus on doctors?
A: The main focus is on the Faculty of Science. Plus, it includes education and lectures forhealth science majors in the School of Medicine.

Q: I thought it was an opportunity for medical students to get an education since it is evenclinical with astatine.
A: The main focus is on the health sciences. At the moment, we have not yet reached thepoint where medical students are coming to take the course.

Q: In the area of safety management, I understood that there is a move to separate and manage
RI and nuclear fuel cleanly and clearly. Is this a decision that will work better?
A: First of all, the legal systems are diﬀerent, so it is easier to understand if they are separated.
However, those who actually use nuclear fuel are also those who always use RI and have indepth knowledge. Therefore, the actual situation is that although they are separated, they are
well managed within the company.

47

2.11

Y. Sakurai（KURNS, Kyoto Univ.）
Report on Survey of Hot Labs and RI Studies in the U.S. (1)PurposeReport on the Inspection and Investigationof the Hot Laboratory in the U.S.A. (1)" Investigation of the design, operation,utilization, etc. for major research reactors in
Europe and USA, and discussion with theconcerned persons, in order to reflect in the
future detailed design of the newly-installed
research reactor.

Yoshinori Sakurai
Division of Particle Radiation Medical Physics,
Particle Radiation Oncology Research Center,
Institute for Integrated Radiation and Nuclear Science, Kyoto University" In addition, inspection of RI production facility,
biological irradiation facility, hot lab, etc..

12

MemberTrip Period and Visit Destination

Institute for Integrated Radiation and Nuclear Science, Kyoto
University (KURNS)" Trip Period :February 20, 2023 (Mon) - February 26, 2023 (Sun)Tomoo YAMAMURA (Condensed-matter Chemistry in Actinides,
Division of Nuclear Engineering Science)
Yoshinori SAKURAI (Particle Radiation Medical Physics, Particle
Radiation Oncology Research Center)
Hisao YOSHINAGA (Management Team for Experimental Facilities,
Technical Office)" Visit Destination :(1) MURR (University of Missouri Research Reactor)ÿ
Columbia, Missouri 2/21 (Tue)(2) ORNL (Oak Ridge National Laboratory)ÿ
Oak Ridge, Tennessee 2/23 (Thu)(3) SHINE Technologiesÿ Janesville, Wisconsin 2/24 (Fri)Japan Atomic Energy Agency (JAEA)
Kazufumi TSUJIMOTO (Nuclear Science and Engineering Center,
Nuclear Science Research Institute)
Sho TOKUNAGA (Department of Research Reactor and Tandem
Accelerator, Nuclear Science Research Institute)3

Location of Visit Destination

4

Flight Route (2/20)

5

48

6

MURR (1)

MURR (2)" University of Missouri Research Reactor" Reactor power : 10 MWth
*Largest university-owned research reactor in USA" Fuel : Highly enriched uranium (93% enrichment)" Reflector : Beryllium and graphite" Operation : 1966*20-year license renewal in 2017
" Production of various RI including medical use*Consignment by companies, etc.
" Research facility for neutron capture therapy (NCT)* The XVII International Congress on Neutron Capture
Therapy (ICNCT-17) was held in October 2016

Entrance of MURR
7

MURR (3)8

MURR (4)

Schedule
10:00 am Kyoto University team arrives
10:15 am Welcome & Introductions
11:00 am Overview of MURR presentation
11:30 am Lunch
1:00 pm MURR Facility Tour
2:30 pm Discussion and Q&A
4:00 pm Adjourn

Copyrighting protected image

Guided by Mr. Chris Dohm (Manager of Special
Projects Group) and 7 other persons +³
9Outline of MURR (From HP and cover of notebook)

MURR (5)

MURR (6)" Hot laboratories
Manufacturing RI separation processing in hot cells
Quality system, infrastructure, staff and skills toprovide full GMP (Good Manufacturing Practice)products and services" Research facility for NCT
Si-Bi filters, thermal neutron flux : 8.47108 cm-2s-1
Shutter and irradiation system that moves up and down

10

Copyrighting protected image
Copyrighting protected image

Copyrighting protected image

Outline of hot laboratories (From HP)
1149

Outline of research facility for NCT

12

MURR (7)Flight Route (2/22)" Research ÿLife Sciences, Material Sciences, Social
Sciences, Research Isotopes & Radiochemicals" Education :Graduate & Undergraduate Programs in
Engineering, Chemistry, Physics, Biochemistry,
Arts and Science" Operation : 6.5 days / 1 week, 52 weeks / 1 year
" Annual budget ÿ 15% MU funding, 85% self-generated
13

ORNL (1)14

ORNL (2)" Oak Ridge National Laboratory" High Flux Isotope Reactor (HFIR)" Reactor power : 80 MWth" Fuel : Highly enriched uranium (93% enrichment)" Reflector : Beryllium" Operation : 1965" Production of various RI including medical use" Production of Pu-238, etc..
ORNL Visitors Center
15

ORNL (3)16

ORNL (4)

Schedule
10:00AM Pickup/Meet Visitors
10:15AM Welcome and Introductions
10:30AM Presentation: New Radioisotope Production
Research Reactor Project (Dr. Yamamura)
11:30AM HFIR Facility Tour
12:15PM Travel to Cafeteria
12:30PM LUNCH
1:30PM 4501 Facility Tour
2:15PM Travel to Melton Valley
2:30PM 7920 Facility Tour
3:15PM Discussions Closeout Meeting
4:00PM DEPART ORNL

Copyrighting protected image

Guided by Dr. Chris Bryan (Section Head of RI
Production Engineering & Analysis) +³
1750

Outline of HFIR (From HP and leaflet)

18

ORNL (5)ORNL (6)" Researchÿ

" Hot laboratories
For medical RI, separation processing of I-131,
Mo-99, Ac-227, Lu-177, etc.

Biological Materials andSystems
Chemistry, Geochemistry
and Environmental
Science
Computing, Modeling, andData Analytics
High Pressure Science
Materials and Engineering
Quantum Materials
Soft Matter and Polymers

Copyrighting protected image

One of hot laboratories
19

Flight Route (2/24)

20

SHINE Technologies (1)" Subcritical Hybrid Intense Neutron Emitter ³ SHINE" Subcritical system device combining DT reaction
and uranium solution" Production of medical Mo-99" Under construction of a large-scale production
facility. Target to start operation in 2024
" Also, production facility of medical Lu-177" Industrial use of nuclear fusion system" Wisconsin actively attracts venture companies³ Innovation Court1Innovation Drive
21

SHINE Technologies (2)22SHINE Technologies (3)Schedule
12:00am Meet & Greet SHINE HQ
Introductions
2:00pm Travel to and tour Chrysalis(Mo-99 Production Facility)
3:00pm Q&A, closing comments
4:00pm Guests depart

Guided by Dr. Greg Piefer (CEO & Founder) and
Mr. Todd Asmuth (President & Chief Strategy Officer) +³

Entrance of SHINE
23

51

24

SHINE Technologies (4)SHINE Technologies (5)" Eight units installed in the production
facility under construction" Adjacent to a small airport³ Products are transported by plane" Competitors are also nearby

Copyrighting protected image

Outline of one of the neutron generation systems (From HP)
25

Flight Route (2/25)

26

Whole Flight Route27

Summary" Visited three locations such as MURR, ORNL,
and SHINE" Felt the scale of activity related to RI production
and the degree of availability of the related
facilities, especially the hot laboratories, in USA.
" Impressive that 85% of MURR's annual budget
was self-generated related to RI production.
" Expect that the knowledge obtained from thisinspection visit will be reflected in the detailed
design of the new research reactor.
29

52

28

H. Yoshinaga（KURNS, Kyoto Univ.）

2.12

Report on Survey of Hot Labs and RI Studies in the U.S. (2)Payed Attention to
着目したところ• Management of Hot Laboratory(HL)• How they product RIs & Facilities for those Processes

米国ホットラボ視察・調査報告（２）• Work style of Staﬀs

Report on the hot laboratory in the USA(2)京都大学複合原子力科学研究所 技術室 吉永尚生
KURNS, Kyoto Univ. Hisao Yoshinaga
1

2

MURR

ORNL

次代へのSDGsな飛躍

伝統の継承• No Photo• Whole the Building is Radiation Control
Section• Even the Front desk
• Every staﬀ were specialized for single work.
Operator, Manufacturer, economist,
Researcher etc.

• Operator Trainie needs about 2 years• Developing Facility with all the MU.
• Only short Movie for HL of RI production
3

4

Summary

SHINE Tech. Inc.

Fukui炉のまえに• Plan of how activate KURNS is the most prior to post KUR• Simple Facility forespecially on RIs Production.

Irradiation• Eﬀective utilization and economic circulation

•

6

5

53

2.13

T. Yamamura（KURNS, Kyoto Univ.）
Discussions on facilities

Dr. Sakurai’s oﬃcial summary and Mr. Yoshinaga’s talk on the technical aspects and lifestyle
were comprehensive and interesting. Both MURR and HFIR, which we inspected this time, arealmost the same age as KUR and continue to be active. I felt that it is a pity that KUR is shutting
down with these MURR and HFIR behind it. The hot labs are also really interesting, like a
museum already. In one cell, they are separating molybdenum-99. Next to that is plutonium238, next to that is separation and production of californium, and next to that is extracting
einsteinium, which is being moved to the US and Japan for study. It is not the most up-to-date,but it is very organized and used. In Oak Ridge, for example, not only actinium-227, but whenit comes to 225, for example, it is produced at BNL and moved. So it is not necessarily thatthey only handle what they manufacture at their own facilities. In this sense, the method oftransportation was very important. We were actually shown a number of things. I was surprised
to see that the drums that we normally use to store waste were used for transportation between
BNL and ORNL. Another thing that stood out was the diﬀerence in the correspondents MURR
is very business oriented, and the business unit people explained to us how they do business.
Oak Ridge was really well-known and was handled by prominent researchers. SHINE, the lastone, was addressed by the CEO of the company’s founder. These people will be giving theirpresentations tomorrow, so I hope everyone will listen to them.

Any comments or suggestions?
Q: One thing that particularly surprised me was the very high rate of operation at the Universityof Missouri. Another thing is that it is 85% funded. It seems more like a commercial reactor
than a university research reactor. Does high availability of university research reactors lead tohigh research performance?
A: I have only heard about the BNCT related to myself, but it seems that they have a facility
and use it mainly for animal experiments for drug development. They also do about 200 animal
irradiations a year, and the activity is high not only for RI production but for other research as
54

well.

Q: Does the fact that you are allocating people to RI production mean that you have a separatestaﬀ for that purpose?
A: Yes, I think so, because RI production is basically a process in which the samples areirradiated as soon as they are placed, so we are making good use of that characteristic.

Q: Can it be operated continuously for that long? How do you maintain it?
A: The RI system does not need as much maintenance as in Japan because it is not tied downby the regulatory agency. 5 operation teams work in shifts and do maintenance as they noticethings, and if necessary, they stop the system from time to time to do maintenance. We don’t
have a period of time where we do inspections, and we don’t operate from one month to thenext. Also, the research reactor itself is very simple and they don’t think it is necessary to takethat much time.

Q: Is it possible to produce so much RI because you don’t stop?
A: We are able to keep the time and continue continuous production in this way. This is what
I saw as leading to a stable supply.

Q: It would be nice if this kind of thing could actually be done with new research reactors,
but I wonder if it is diﬃcult to do so in Japan.
A: I think so.

Q: At Oak Ridge, there were many hot cells in a row.
A: Probably not all of them are in operation. The cells that are being dismantled to recycle
fuel, and the ones that will become the main pellets at the end, are probably brought in fromother places and used in the ﬁnal assembly process. The other parts of the plant are still in
operation, but the picture shown in the previous section is not as good as it could be. Some of
the cells looked as if they had been disassembled long ago and left there for a long time. The
55

MURRs are designed for easy removal and replacement of fuel underwater, while the HFIRs
are one-piece units.

Q: Wasn’t the MURR originally designed for RI production?
A2: I don’t think so. There are holes of various sizes and various irradiation methods. Amongthem, there were pneumatic tubes similar to our pneumatic tubes, and there were also ones thatwere equivalent to long-term irradiation. In this situation, there was a period of decline as a
research reactor and research facility, and in order to earn compensation, we devised a way to use
the money earned from the manufacture and sale of RIs to cover the maintenance and researchbudget. The situation is similar to ours.

Q: It would have been good for KUR if we could have followed your example.
A2: I think each country has its own way of thinking, so it is not something that can be
imitated in general, but I would like to do my best.

Q: Regarding the SHINE story, if RI can be produced in a critical reactor, is the trend that it
does not have to be a nuclear reactor?
A3: I would like you to listen to the SHINE talk tomorrow. They are a company that does notrely on nuclear reactors, and specializes in continuing production by a single company.

Q: Regarding SHINE’s use of the DT reaction to produce neutrons, since the DT reactionuses tritium, I am interested in a system that does not leak tritium, such as a glove box. If it is
not such a system, then it needs to be adapted to Japanese regulations.
A: In fact, I could see the conﬁdence that they are making something that is viable as a system,in the form of ﬂying it in jet form and hitting the accelerated D. The founder of the company
originally studied fusion research in graduate school and earned a degree.

Q: Now you’re talking about a system that uses an accelerator to hit the material with deuterium,
probably tritium. Why is it necessary to combine it with a subcritical reactor? If you can place56

a system that does not use a subcritical reactor, the idea is that you can build a manufacturingbase in a place where you cannot place a research reactor.
A: I was originally interested in the SHINE system because I studied ADS. As for tritium,
we are making people inhale tritium gas, and then accelerating neutrons to separate the tritium.
The neutrons that come out are used to spark a ﬁssion reaction in the subcritical system tostart operation. But on the other hand, a company called NorthStar, also in Wisconsin, started
lutetium production here at the University of Missouri using the capture method. In parallel with
this, they are thinking of using an accelerator to produce the original lutetium. In the future,
we are thinking of going uranium-free, as you mentioned, and aiming to produce molybdenum
using only an accelerator and molybdenum without using uranium. I think the idea I mentioned
earlier is possible. However, at the moment, we are working on the production of molybdenumby uranium ﬁssion because it is more reliable.

Q: Is it correct that the reason you are using a subcritical reactor is simply to produce
molybdenum-99?
A: Yes, that is correct.

Q: So if you were not limited to molybdenum-99, you might be willing to move toward sucha system?
A: If, for example, the main focus were to produce actinium together, that could be possible.
Right now, we are doing it because it is convenient to recover molybdenum from ﬁssion.

Q: In your ﬁrst presentation, Mr. Sakurai, you mentioned that only highly enriched fuel isused, but I assume that the Fukui site will not be highly enriched. What kind of fuel will be
used will depend on what you want to achieve and the use of the hot laboratory. For example,
there are reports of reprocessing of fuels other than uranium oxide, such as silicide fuel andmolybdenum fuel, and in France and other countries, there are reports of reprocessing of small
amounts of diﬀerent fuels in research reactors, and such research is necessary. If possible, itwould be nice if the Fukui Reactor is capable of such research. If you have anything to share57

about this, please let us know.
A: First of all, the fuel used in the new research reactor in Fukui is 20% enriched Max fuel.
We cannot use highly enriched uranium like in the United States. There is some debate about
whether nuclear fuel can be used in a hot lab. If there is a strong request, I would be willing toconsider it.

Q: Thank you. If there is such an opportunity, I would like to experiment.
A: I would like you to raise the request.

Q: If you were to conduct an experiment using uranium, how much would you need?
A: I don’t usually use grams. If we could do about a gram, that would be great.

Q: We have also requested to use nuclear fuel in the hot laboratory in Fukui, and although it
may be less than a gram order, we have requested to be able to conduct small-scale experiments.

Q: After your visit to the U.S., how do you handle waste? I have heard that a large facility
would produce a tremendous amount of waste. When I did experiments at the Idaho National
Laboratory, they were not concerned about waste at all, so that is considered the biggest diﬀerence
between Japan and the U.S. This is an opportunity to show that when we create something new,
we also need to work together to establish laws for the disposal of the waste from the experiments.
Material informatics is useful because it is necessary to reduce waste. What was the US like inthis area?
A: Oak Ridge has plenty available, and the situation is completely diﬀerent from Japan, so if
you want to conduct such experiments, you will have to go to the US. When a system for waste
disposal at research institutes and other facilities is established, there is a possibility that waste
could be disposed of more smoothly, but the high cost will never change. That is a little diﬀerent
from a place where there are many facilities in the desert and we don’t have to worry so muchabout waste.

58

Q: Thank you very much. We need more young Japanese actinide researchers to conduct
experiments at overseas facilities and bring their ﬁndings to us, and we need to increase thenumber of collaborators. I may have a diﬀerent point of view, but experiments in the U.S. should
be conducted separately from the situation in Japan.
A: It would be good if we can establish a win-win relationship with the INL and otherinstitutions in the U.S.

59

2.14

M. Nakase（Tokyo Inst. Tech.）Opening of 2nd-day Discussions

Good morning, everybody. I am Masahiko Nakase from Tokyo Institute of Technology. Thankyou very much for joining this interesting meeting. Today we have some English speakers from
US.

60

2.15

Greg Piefer（SHINE Technologies, Inc.）
Plan and prospect of SHINE Technology

SHINE’s Scalable Path
to Fusion
MARCH 2023

| Company Confidential – Not for Redistribution | © SHINE Technologies, LLC

Question and answer session
Q: Do you have any special techniques or new ideas to ensure adequate separation of criticalproducts?
A: We actually made a test batch of Mo-99 and GE was able to test it in a dry generator andprove that it is equivalent to Mo-99 made in a nuclear reactor. Basically, what we are using iswhat has already been published.

Q: Scientists have shown the eﬀectiveness of Ac-225 for cancer treatment in 2016; do you
have plans to produce alpha-radiators?
A: However, we prefer to focus on what we re uniquely good at. We knew we could
concentrate ytterbium in-house, and that combined with our ability to produce neutrons andperform advanced separation gave us good technology to scale up production, and we had an
inherent advantage over other producers.

61

1

2.16

Laetitia H. Delmau（Oak Ridge National Laboratory）
Overview of the Cf-252 and Pm-147 Production Eﬀorts at ORNL

Isotope production and research has been a missionof ORNL from the beginning

Overview of the Cf-252 and Pm-147
Production Efforts at ORNL

1946

First shipment of a radioisotope
to a hospital for cancer research

1960sLætitia H. Delmau, Julie. G. Ezold, Richard T. Mayes>100,000 radioisotope shipments
annually with applications inresearch, medicine, and industry

ORNL focuses on isotopes

Kyoto Symposium, Kyoto, Japan, March 3, 2023

Today not available in the private

Calutron mass
separators

sector¥

ORNL is managed by UT-Battelle LLC for the US Department of Energy

Graphitereactor

RSTD February 2023 Seminar

2

Realizing Seaborg’s vision:
A “very high flux reactor” for heavy element production

Heavy element production program at ORNLHFIR and REDC enable heavy
element production at ORNL

• Irradiation of curium in Seaborg’s• HFIR and REDC began operation• Recovery of “substantial

suggested “very high flux reactor”

in 1965 and 1966at least until 2040

98

97

• High-end aspects of isotope production(heavy actinides, specialty medical isotopes),
neutron scattering, and materials irradiation

Cm

96• Unique capabilities for radioisotope separations

94(>400 isotope shipments annually to universities,
hospitals, industry, and other research institutions)

Pu

95

Am

Pu 238

Pu 239Cm 24293

Np

Np 237

Cm 243

Cm 244, (n,f)
Am 241

Am 242

Pu 240Pu 241Es-, (n,f)Cf 249Cf

Fm 254

Fm 255

Fm 256

Es 253

Es 254

Es 255Bk
Cm 245, -, EC-

Cf 250

Cf 251

Cf 252

Cf 253

Cf 254, (n,f),, SF-, (n,f)SF

Bk 249

Bk 250

Bk 251, (n,f)Cm 246, (n,f)--Cm 248

Cm 249Cm 250, (n,f)

, SF

-

SF

Am 244---

Pu 242

Pu 243

Pu 244

Pu 245

Pu 246---Am 245

Cm 247Am 243-, EC, (n,f)Z

Fm

99

Fm 257SF

weighable quantities(say milligrams) of berkelium,
californium, and einsteinium”• Operation is expected to continue

100

Am 246

Np 238N

Irradiated Cm target processing at REDC

Actinide/lanthanide separations via LiCl-based anion
exchange

Irradiatedtargets
Aluminum
dissolution

Caustic
solubleFP & Al• Separation of Cm, rare earth fission

products, and transcurium
elements

HFIR
irradiation

AHIB‡ cationexchange
Bk

Cf

Es

Fm

• Uses a strong base, Dowex 1 ´ 10

Targetfabrication

Nitric aciddissolution
HDEHP†
extraction

resin, in a tantalum column

Waste
organic

Oxide
preparation

LiCl anion
exchange

Lanthanide
FP

Am/Cm
product
Trans
Cm
Hydroxide
precipitation†‡

5

RSTD February 2023 Seminar

4

3• Complexes for each element form

Hydroxide
precipitation

Di(2-ethylhexyl) phosphoric acid
Alpha-hydroxyisobutyrate

at varying strengths, allowing
for different rates of movement

Oxalateprecipitation• Rare earth elements are eluted

nominally at 10M LiCl, Am/Cm at
9M LiCl, and transcurium elementswith 8M HCl

Am/Cm
product

RSTD February 2023 Seminar

6

62

RSTD February 2023 Seminar

Some major scientific impactsof the heavy element products

Transcurium element separations via cation exchangeelution using AHIB
• Conversion from chloride form

to nitrate by hydroxide
precipitation, filtration, and redissolution in HNO3

Discovery of new
heavier elements
and isotopes using
heavy element
radionuclides
as accelerator/
cyclotron targets• Elemental separationby ammonium alphahydroxyisobutyrate(AHIB)at varying values of pH

Basic researchon the physics
of heavy elements• Electron behavior in
orbitals• Nuclear properties

followed with neutron
and alpha probes

Copyrighting
protected
image

Typical alpha detector readings ofcolumn effluent during CX run elution• Key is small, uniform particle sizeof resin and high pressure
operation to achieve good flowrate

253Es (0.17 mg,
self-illuminated)
RSTD February 2023 Seminar

7

8

Basic researchon the chemistryof heavy actinides• Chemically stablecompounds• Crystal structureof salts• Nuclear reactions• Column is heated ~70°C• Element (band) separation

Discovery of
bimodal fission
in some nuclides
with Z ³ 100• Solution chemistry

The heavy element program
was endorsed twice by the
National Research Council• Spectroscopy

100+ publications resulted eachyear from research using heavy
element products
E.K. Hulet, “Bimodal Symmetric Fission
Observed in the Heaviest Elements,” Phys.
Rev. Lett. 56, 313–316 (1986)

RSTD February 2023 Seminar

Promethium: ORNL’s First Elemental Discovery

Promethium-147 is a High Demand Radioisotope• Isolated in 1945 (ORNL) from irradiated uranium by Joseph A.

• 147Pm is used as a beta gauge, in radio-luminescent paints,

Marinsky, Lawrence E. Glendenin, and Charles D. Coryell

and nuclear batteries– Announced in 1947 at the ACS meeting in New York City

– 2.62-year half-life– 927 Ci/g

• Name suggested by Charles Coryell from the Titan Prometheus– Decays via b- emission (62 keV avg) to 147Sm– Prometheus stole fire from Mt Olympus and brought it to humans in– g-emission @ 121.220 keV 0.00285 % intensity

Greek mythology– Reminiscent of how promethium is made in nuclear reactors– Considered a pure b- emitter• Formerly produced at the Mayak Production Association
Copyrighting
protected
image

Copyrighting
protected
image

Copyrighting
protected image

Joseph Marinsky

Lawrence GlendeninCharles Coryell• US has not produced 147Pm in over 50 years– Last production was at the fission product plants at INL, ORNL, and

PNNL by isolating from irradiated uranium

9*H. H. Van Tuyl, Promethium Isotopic Power Data Sheets. 1965, Pacific Northwest Laboratory, Richland, WA. BNWC-45– ORNL dispensed 147Pm from these fission plants

RSTD February 2023 Seminar

10

Historical Production of 147Pm

RSTD February 2023 Seminar

Separations Development in 1969

• Fission product plants in US separated

lanthanides from irradiated U fuels• Ion exchange, oxalate precipitation andrecrystallization– Multi-stage recrystallizations– Solvent extraction– Ion Exchange– Zinc-displacement IX

Copyrighting protected image

Copyrighting protected image

Copyrighting protected image

Lantz and Parker purifying fission products• G. W. Parker and P. M. Lantz purified 4.5

mg in 1948

• F. Weigel and co-workers later produced

Kg quantities– First to make elemental metal
11

RSTD February 2023 Seminar

12

63

Lowe, DP-1194, 1969

RSTD February 2023 Seminar

Promethium Project – “Cold” Test

Overall flowsheet Pu-238 production – Pm harvesting

63 IrradiatedTargets

Remove Al

Dissolve Pu
and Np

Separate Pu
from Np andFPs

Remove P,
Th, FPs

Remove Np;
Convert to
Oxide

Caustic
Dissolution

Acid
Dissolution

Solvent
Extraction

Pu Anion
Exchange

Pu Cation
Exchange

FPs

P, FPs, Th, Np

Np

Al

Optimization ofelution pattern to
avoid transferring
Ce and Eu to thecave.

Plutonium
Oxide
Product

Cold tests donewith scaled-downgeometry
proportional tocolumns that would
be acceptable in
cell.

Np to
TargetFabrication

233
Pa
RemovalNp Anion
Exchange

Hot Cell recovery of Pm from Pu campaign wastes.

P, FPs,Th, PuNp Cation
Exchange
147Pm

Cm, Pu,RSTD
Th,February
Pa 2023 Seminar

13

Continuous Improvement

Pm-147 Processing Flowsheet

Three Hot Cell runs so far• DGA

RSTD February 2023 Seminar

14

Raffinatewith fission
products

Run 1 (P4
Demonstration)

Run 2 (P4-2 Recovery)

Run 3 (P5)6 L of raffinate

60L of Raffinate

130L of Raffinate

290 mL Resin

290 mL Resin

250 mL Resin

Elution by HNO3 & HCl

Elution by HNO3 & HCl

Gradient HNO3 Elution

Eluted 147Pm in HCl

Eluted 147Pm in HNO3 with
98.9% rejection of 144Ce &Eluted 147Pm in HNO3

96% rejection of 155Eu

DGA
Resin

Trivalent
Recovery

Cave
Transfer

Non-trivalentfission products(Ru-106, Cs-137)

Concentration
Via DGA Resin

Actinides

Unwanted
Fission
Products(Ru-106)

TALSPEAK
Ln(Ce, Pm, Eu)with 99.7% rejection of
144Ce & >99.5%
rejection of 155Eu

Evaporation & Pm-147
Shipment

LN DGA Resin(adjacent Ln
rejection)
Ln

RSTD February 2023 Seminar

15

147Pm Production: Solvent Extraction

Trivalent Actinide Lanthanide Separation with
Phosphorus-Reagent Extraction from Aqueous
Komplexes (TALSPEAK)• Removal of 244Cm from 147Pm• Use of camphor-bis(triazenylpyridine), CA-BTP

RSTD February 2023 Seminar

16• Developed at ORNL in 1960’s

CA-BTP• Separates actinides from lanthanides– Works well

– Di-2-(ethylhexyl)phosphoric acid (HDEHP) in diluent– Experimental sample (no secure procurement)(dodecane)• Cyanex 301– Lactate buffer with diethylenetriamine-N,N,N’,N’’,N’’-– Bis-(2,4,4-trimethylpentyl)-dithiophosphinic acidpentaacetic acid (DTPA, actinide holdback reagent)

Cyanex 301– Strip Ln from HDEHP/dodecane with strong acid– Degrades in nitric acid -> use dilute HCl– Excellent An rejection projected• TALSPEAK
17

Lactic Acid
Lactic Acid

DTPA

HDEHP RSTD February 2023 Seminar

18

64

DTPA

HDEHP
RSTD February 2023 Seminar

Continuous Improvement: Curium Removal

TALSPEAK vs. Camphor-BTP• TALSPEAK works, but…

• TALSPEAK:– Waste issues compound separation challenges

Camphor-BTP

TALSPEAK– High product losses– Severe 147Pm losses during separation adding time and cost

– Back extraction of 147Pm– Law of diminishing returns• What options do we have?

• Camphor-BTP– Initial testing with an R&D sample of camphor-BTP showed promise• R&D sample from TN Tech

– 244Cm extracted• Residual from student research with L. Delmau, Kayron Rogers and Dale Ensor– 147Pm stays in aq phase– Marshallton Labs contracted to produce camphor-BTP for larger testing– Decreased 147Pm losses– Development of Cm/Pm separation using BTP-based ligands begin at– Less time for separation

REDC• Remember that gremlin…
RSTD February 2023 Seminar

19

RSTD February 2023 Seminar

20

Promethium Project

Mining 147Pm from Fission Products

Further purification of Pm from strong gamma emitters in Cave or Glove Box.

• Re-established the domestic 147Pm production at ORNL

Separation of Pm from Am/Cm. Solvent extraction.

– Revalorize 238Pu waste stream

Polishing to reject adjacent lanthanides• ORNL is currently the only known supplier of 147Pm• Optimization on-going– An/Ln separation with BTP ligands– Adjacent Ln separation– Integration into the 238Pu production schedule

13 Ci Each
> 98% purity
RSTD February 2023 Seminar

21

22

Acknowledgments• Emory Collins• Dennis Benker• Tony Dyer
• Thomas Dyke
• Matt Silveira• April Miller• REDC shift personnel• REDC Shift Supervision• Analytical Group

23

This work is supported by the US Department ofEnergy Isotope Program, managed by the Officeof Science for Isotope R&D and Production.

RSTD February 2023 Seminar

65

2 Ci
16 % Purity

9 Ci
94 % Purity
RSTD February 2023 Seminar

Question and answer session
Q: For Pm-147 separations, how is the chemical purity checked after production?
A: ICP-MS can be used, but this only yields a maximum of 147, which may contain samarium147 since it is a decay product. However, data can be measured and compared by liquid
ventilation.

Q: When you ask me to obtain a heavy element, please let me know.
A: Which element or isotope are you interested in?

Q: I’m interested in ... That’s about it.
A: Does that mean I need to make a request very soon? We will start the next California
campaign. We will start the next campaign in three weeks; you will need to contact NDEC.

Q: How do we get Neptunium-237?
A: Neptunium-237 was produced in large quantities at Savannah River in the 1960s and thenmoved from Savannah River National Laboratory to Idaho National Laboratory, where it isstored. Basically, neptunium was produced at Savannah River as long ago as 1915.

Q: So it was stored by uranium radiation?
A: We don’t know exactly how it was produced. I think it was probably produced by uranium
irradiation, but I don’t know the details of how it was produced 15 years ago.

66

67

2.17

Rob Hall（MURR, Missouri University）
Recent activities, systems, and facilities of MURR for radiophermaceutical R&D

Welcome to MURR®
Condensed-matter Chemistry inActinides and their Applications /Production of medical RIs by
Reactor Irradiation

March 3, 2023
2
Saving Lives, Creating Livelihoods … through Research & Education

Saving Lives, Creating Livelihoods … through Research & Education

University of Missouri Crown Jewel

Improving Quality of Life

MURR® is a Unique National Resource
Research&
Development

Education

Our Core
Missions:
Research &Education

 October 1966 = First Reactor Start-up
 Facility operates 24 hours a day;
6 ½ days per week; 52 weeks a year –like no other!

Products&
Services 250 Full & Part-time Scientists & Staff
 50 Students – Learning while helping!

ReactorOperations

 20 Year NRC License granted in Jan 2017
“Cancer, unlike politics and religion is not a topic of controversy. No one is for it.”-S. Mooney, 1989, A Snowflake in My Hand

Modular Design+ Replaceable Components= A Renewable Resource

3

4

Saving Lives, Creating Livelihoods … through Research & Education

Saving Lives, Creating Livelihoods … through Research & Education

Leading Research Reactor
The most powerful of the Nation’s 24 University Research Reactors

5

6

Saving Lives, Creating Livelihoods … through Research & Education

Saving Lives, Creating Livelihoods … through Research & Education

68

Research & Development

Research & Development

Life Sciences Radiopharmaceutical Research Trace Element Epidemiology
 Plants Radiotracer Imaging
 Radioisotope Tracers

Material Sciences Triple Axis Spectrometer Neutron Reflectometer Multi-detector Powder Diffractometer High Resolution Powder Diffractometer

7

8

Saving Lives, Creating Livelihoods … through Research & Education

Saving Lives, Creating Livelihoods … through Research & Education

Education

Reactor Operations
6 personmanagement staff
5 Operations Crews
3-5 persons
1 Lead Senior
1 Senior
1 Operator
1 Trainee
12 hour rotating
shiftsArchaeometry

Every 5th week is a
training week9

10

Saving Lives, Creating Livelihoods … through Research & Education

Saving Lives, Creating Livelihoods … through Research & Education

Working Together

Products and Services

Academia and Industry Collaborating to Improve Lives

Each and every week MURR supplies the active ingredients for:
• TheraSpheres® - liver cancer• Lutathera® - neuroendocrine tumors• I-131 – thyroid cancer• RadioGenix® - cardiac and bone scans• Pluvicto® - prostate cancer

Blending all four
MU mission elements:
1.
2.
3.
4.

Research
Education
Service
Economic Development

11

12

Saving Lives, Creating Livelihoods … through Research & Education

Saving Lives, Creating Livelihoods … through Research & Education

69

Targeted Radiotherapy & Diagnostics

Metal-Ligand
Conjugate

Receptor

Organic
Linker

Tumor
Cell

LigandIodine I-131 sodium iodide

Main Hot Cell Facility

16.5 MeV Pet Trace Cyclotron(technetium Tc 99m generator)

Irradiations Laboratory

13

14

Saving Lives, Creating Livelihoods … through Research & Education

Saving Lives, Creating Livelihoods … through Research & Education

I-131 Production Suite(Active Pharmaceutical Ingredient)

Mo-99 Hot Cells(Intermediate Final Product)
CA Lu-177 Production Suite(Active Pharmaceutical Ingredient)

NCA Lu-177 Production Suite(Active Pharmaceutical Ingredient)

15
Saving Lives, Creating Livelihoods … through Research & Education

Saving Lives, Creating Livelihoods … through Research & Education

MURR’s Future

15,600 SF

Saving Lives, Creating Livelihoods … through Research & Education

Saving Lives, Creating Livelihoods … through Research & Education

70

16

MURR Nextgen• One respondent said that the biggest risk to their supply chain is security of supply of medical
isotopes like I-131, as medical isotopes cannot be stockpiled. When supply issues occur cancer
patients don’t get the required therapy to stop disease or lengthen and improve quality of life. To
enhance security of supply of just in time medical isotopes an “In country – For country” approachis a good supply strategy.
• All respondents were of the strong opinion that the University of Missouri is the only partner
capable of delivering on a new reactor in the US. All respondents echoed that the MURR reactor isworld renowned for its uniqueness as the only reactor that runs 52 weeks a year where others are
only operating maybe half of the time.
• Executives have confidence in MURR’s reliability, scientific and safety expertise, their operational
strength coupled with their ability to meet the commercial needs of industry, as they have done for
decades, remains unmatched.
• “Building the new reactor at MURR is critical. The University has decades of experience runninga reactor and of working with business. MURR has demonstrated that they can run a reactor ina way that meets the commercial needs of industry and have done so for decades.”20
Saving Lives, Creating Livelihoods … through Research & Education

Saving Lives, Creating Livelihoods … through Research & Education

Questions?

21

22

Saving Lives, Creating Livelihoods … through Research & Education

Saving Lives, Creating Livelihoods … through Research & Education

71

Question and answer session
Q: Do you produce elements other than iodine, molybdenum, and ruthenium?
A: Yes, we produce a variety of isotopes. Of course, these are the major drug-type isotopes
we produce in large quantities. It depends on what the researcher wants to produce, whether it
can be made in a reactor, and the reason for wanting to study it. It certainly does. We would
encourage any university personnel interested in partnering with the University of Missouri
Research Reactor to contact us and see where our interests align and where we might be able tocollaborate.

Q: Do you produce other raw materials in your cyclotrons?
A: Our cyclotron is primarily used for pet imaging. We have access to it during oﬀ hours
so that we can produce other isotopes. However, my specialty is not in the world of cyclotron
production. So if you would like to send me an email, I would be happy to answer it.

Q: What do you think if you didn’t have a reactor on campus, but could use other reactors likethe HFTR and transfer isotopes produced from the HFTR? Would that work?
A: Actually, it is possible; the HFTR’s powerful reactors irradiate the isotopes, which are thenprocessed and distributed to researchers. So it is possible. In the future, we may be able to domuch more. But what we want is to have our own 21 reactors running every week to better serve
the medical ISO community. 15 min.

72

73

2.18

Toro Gonzalez（Oak Ridge National Laboratory）
Lanthanide-based and Poly(lactic-co-glycolic acid) Nanoparticles in Targeted Alpha Therapy

Motivation

227Ac

´

Targeted alpha therapy vs.
External beam therapy

Lanthanide-based and Poly(lactic-coglycolic acid) Nanoparticles in Targeted
Alpha Therapy

"
"
"
"

(18.7 d)227Th

(11.4 d)223Ra³

Specific targeting of tumor cells
Enhanced therapeutic efficacy
Reduce side effects
Efficient treatment of cancer

³
219Rn

³

Miguel Toro-Gonzalez, Sandra Davern

215Po

Oak Ridge National Laboratory

³
211Pb

March 3rd, 2023

´

Tumor

Users meeting on Condensed-matter Chemistry in Actinides
and their Applications / Production of medical RIs by Reactor
Irradiation

211Bi

´
ORNL is managed by UT-Battelle, LLC for the US Department of Energy

Motivation

207Tl

³

´
207Pb

Tumor cells

2

³

211Po

Tumor

OutlineNanoparticles as radionuclide delivery platforms intargeted alpha therapy• Production methods for 225Ac and 227Th/223Ra

Decay daughter

Radioimmunoconjugates• Lanthanide-based nanoparticles

Radionuclide
Bifunctional chelator
Targeting vector
e.g., monoclonal antibody• Poly(lactic-co-glycolic acid) nanoparticles• Targeted alpha therapy with nanoparticles³, ´-, ³• Summary
Challenges""""• Acknowledgements

Relocation of decay daughter(s) from tumor site
Potential radiotoxicity to healthy tissues
Decrease therapeutic efficacy
Require higher activity/dose to achieve a therapeutic effect3

4

Production methods for 225Ac and 227Th/223Ra
Current production methods for 225Ac

Production methods for
225Ac and 227Th/223Ra• Decay of 233U³229Th ³225Ra ³225Ac– ORNL world’s largest current producer (800-1000 mCi annually)• High energy proton (80-200 MeV) spallation of natural Th targets

ORNL perspective and experience–

232Th[p, x]225Ac reaction– DOE Isotope Program Tri-Lab Initiative BNL, LANL, and ORNL

Methods in development involving reactor irradiation• Production of 229Th or 225Ra via fast neutron irradiation of 230Th or 226Ra–

230Th[n,2n]229Th and 226Ra[n,2n] 225Ra reactions• Production of 229Th by multiple and single neutron capture of 226Ra and228Ra targets in a high flux nuclear reactor

–
6

74

226Ra[3n,2 ³-]229Th and 228Ra[n,³-]229Th

reactionsProduction methods for 225Ac and 227Th/223Ra

Production methods for 225Ac and 227Th/223Ra• Processing of 225Ac produced by high energy proton• ORNL is a qualified supplier of 227Ac to Bayer for
Column 3• 226Ra targets are prepared from legacy medical

devices• Targets are irradiated in the High Flux Isotope

Reactor• Dissolution and processing of irradiated targets in

Column 6

Column 5

Evaporation/
dissolving

Glovebox processing
Column 4

Evaporation/
dissolving

Column 2

Column 1

Xofigo® production

Dissolving

Targetdissolution

Hot cell processing

hot cells and gloveboxes• 227Ac is chemically separated and purified forshipment

7

Multiple ion exchange chromatography columns for 225Ac
purification within hot cells and gloveboxes

Evaporation/
dissolving
8

Lanthanide-based nanoparticles
GdPO4

Lanthanide-based
nanoparticles• Crystal structures with highresistance to radiation damage1– Rhabdophane– Monazite– Zircon• Potential to incorporate multivalent

Copyright protected image

cations2

La0.8Ce0.2PO4• Luminescence and magnetic

properties

Woodward et al. Bioconjugate Chemistry (2011)10

1J. Alloys Compd. 653, 279–289 (2015)
2 Radiochim. Acta 105, 961–984 (2017)

Rhabdophane

Monazite

Lanthanide-based nanoparticles

Lanthanide-based nanoparticles
Assessment of radioisotope encapsulation and retention

Dialysis – time study

-ray spectroscopy

Centrifugation

Dialysate aliquot
Supernatant

Dialysate – deionized water,
phosphate buffered saline (%) =!" × #×100
$% ()/  (%) =Influence of Ln3+ concentration

& 2 '()*×100
&Influence of Ln3+ composition" LaxEu1-xPO4 – radioisotope leakage was influenced by radioisotope oxidation state (156Eu3+ vs. 85Sr2+)5" LnPO4 – 156Eu3+ leakage influenced by Ln3+ ionic radii (higher of smaller Ln3+ = Yb3+ and Lu3+)5

11

12

75

Lanthanide-based nanoparticles

Lanthanide-based nanoparticles

14

Toro-González, M. et al. Nanoscale 12, 9744–9755 (2020)

M. Toro-González et al., Journal of Materials Chemistry B, 2018.

Lanthanide-based nanoparticles

Lanthanide vanadate nanoparticles

Precipitation method – Gd(225Ac)VO4 and Gd(227Th)VO4

Precipitation method – Gd(223Ra)VO4

225Ac RY = 67.9 ± 2.4 %227Th RY = 66.8 ± 7.2 %223Ra RY = 72.3 ± 3.0 %"""223Ra RY = 34.1 ± 2.9 %• Synthesis conditions influenced theLower 225Ac radiochemicalyield in the precipitation
method compared tocitrate method
Tetravalent actinide 227Th ispreferentially incorporated
within xenotime structure
Similar 227Th radiochemicalyield in both citrate andprecipitation methods

radiochemical yield and retentionof radioisotopes• Precipitation of 223Ra hydroxides,

leads to slow interaction with VO43–
species and continuous increase inleakage• Precipitation method can be

optimized to enhanceradiochemical yield and decrease
radioisotope leakage

Na3VO4 added dropwise
into GdCl3/223Ra solution

15

Core + 2 shells

Partial retention of 225Ac, 221Fr, and 213Bi in Gd0.8Eu0.2(225Ac)VO4@Gd0.8Eu0.2VO4 nanoparticles- 225Ac retention was influenced by the formation of 225Ac-citrate complexes- 221Fr retention is dependent on the number of shells- 213Bi retention is assumed to be affected by concentration of surface carboxyl groups" 10-fold decrease in radionuclide leakage after deposition of 2 shells" 96.8 ± 2.3 % and 94.4 ± 3.8 % 227Th radiochemical yield for core and core +2 shells
13

Decay daughters

Core

225Ac

Toro-González, M. et al. Radiochim. Acta (2020)

16

Toro-González, M. et al. Radiochim. Acta (2020)

Lanthanide-based nanoparticles

GdCl3 added dropwise
into Na3VO4/223Ra solution

Summary

Precipitation method – La(223Ra, 140Ba)VO4• Encapsulation and retention of 223Ra, 225Ac, 227Th, and decay daughters inlanthanide-based nanoparticles is influenced by:– Number of shells– Synthetic approach– Composition• Targeted alpha therapy with nanoparticles shows promising therapeutic

efficacy

LaCl3/223Ra/140Ba added
dropwise into Na3VO4 solution
Suspension pH 4.9
17

Na3VO4 added dropwise into
LaCl3/223Ra/140Ba solution
Suspension pH 4.9

Na3VO4 added dropwise into
LaCl3/223Ra/140Ba solution,
followed by KOH
Suspension pH 11
18

Toro-González, M. et al. Journal of Nanotheranostics (2021)

76

Acknowledgments• Organizers of the Users meeting on Condensed-matter Chemistry inActinides and their Applications / Production of medical RIs by Reactor
Irradiation• Research sponsored by the Laboratory Directed Research andDevelopment Program of Oak Ridge National Laboratory, managed by
UT-Battelle, LLC, for the US Department of Energy.

• A portion of this research was conducted at the Center for Nanophase

Materials Sciences, which is a DOE Office of Science User Facility.

• The GEM Fellow Internship Program at ORNL.
• DOE Isotope Program and REDC Laboratory Chemical Operations for

supplying 225Ac, 227Th, and 223Ra.

• ARM initiative team.
19

77

Question and answer session
Q: How the nanoparticle can interact with cancer cells?
A: I was showing here is when we work with nanoparticles, what interferes passive targetingor active targeting. In the passive targeting, blood circulation enables us to accumulate on thetumor. The regulator conjugates of targeting vector attached enables the nanoparticle to interact
with cancer cells.

Q: I have a quite small question. In your second or third slide you showed us the Ac-225 emits
ﬁve alpha particles. But as far as I know, Ac-225 emits four alpha particles.
A: Yes. So this last one that I include here, is Bismuth 209.

Q: I understand the beneﬁts of nanoparticles, but at the same time I am curious as to how
these nanoparticles are metabolized in the body. Is it easy to eliminate them?
A: Polylactic acid and glycol are metabolized by the body and broken down into lactic acidand glycolic acid. The question is, what happens to the nanoparticles? However, the challenge
is that if they do not reach speciﬁc tumor cancer cells, the radionuclides are lost and may betargeted elsewhere altogether.
This will be wouldn’t require a lot of study saying what’s going to happen with those nanoparticles in your body.

78

2.19

Julie G. Ezold（Oak Ridge National Laboratory）
Radiochemical Processing at Oak Ridge National Laboratory

Radiochemical Processing at Oak Ridge
National Laboratory

Outline• A Little Elemental History• Discovery

Julie Ezold

and Production

Cf-252 Program Manager
Oak Ridge National Laboratory• What’s Next

March 2023
Oak Ridge, Tennessee

ORNL is managed by UT-Battelle, LLC for the US Department of Energy

1869: Mendeleev’s organization of the known elements

1913: Moseley’s demonstration of the roleof atomic number• Demonstrated trends/similarities

by arranging elements in a two-dimensional
network according to their chemical properties• In 1913, Moseley showed that the number ofprotons in the nucleus is the determining factor in
the periodic law• Reordered elements despite their accepted masses(early indication that atomic mass was not thedetermining factor)• Moseley’s work revealed gaps at atomic numbers

43 and 61 (later filled by technetium andpromethium)• Allowed gaps in the table, predicting 10 new

elements (7 actually exist)

Copyright protected image• By 1939, there were 91 known elements with

Copyright protected image

uranium (Z=92) having the highest atomic number
and element 61 missing

In 1906, Mendeleev camewithin one vote of winning
the Nobel Prize

X-ray spectra of the elements, showing
the proportionality of frequency withatomic number[Moseley, Phil. Mag. (1913)]

Henry Gwyn
Jeffreys Moseley(1887–1915)

Mendeleev’s periodic table(1869)
3

4

The ‘Island of Stability’

Transuranics and the missing element 61
1930s

1940s−1950s

1960s

Fermi proposed creatingtransuranium elements
by irradiating uranium
with neutrons (he missed
the discovery of fission)

Seaborg and co-workers
synthesized elements
93–103; Seaborg proposeda new row in the periodic
table (the actinides) toaccommodate theseelements

To further transuranic
research, Seaborg
advocated constructionof a high-flux reactor
and radiochemical
processing complex at
Oak Ridge

Jakob Marinsky (pictured)and Larry Glendenin
discovered element 61(promethium) at
ORNL’s Graphite Reactor

The possibilityof an “Island of
Stability” of superheavy elements withgreatly increased
lifetimes was
originally postulated
by Seaborg

Seaborg’s discoveryof the transuranics led
him to modify theperiodic table

When neutrons andprotons completely
fill the energy levelsof a given nucleus,
the nuclear binding isstrongest, leading tolonger lifetimes

Heaviest stable
isotope (Pb-208) has
closed nuclear shells
for both protons (82)and neutrons (126)

Next “doubly magic”
nucleus occurs
around Z=114–126
and N=184, thepresumed center of
the “Island of
Stability”

Copyright protected image

ORNL scientists separated themissing element 61 from fission
products in 1945, completingthe lanthanide series

Image from Wikipedia

5

6

79

Oak Ridge National Laboratory

Realizing Seaborg’s vision: A ‘very high flux reactor’ forheavy element production program at ORNL
Letter to AEC Chairman Lewis Strauss,
October 24, 1957
• Future progress in “the field of new transuranium

elements” requires production of “substantial weighable
quantities (say milligrams) of berkelium, californium,
and einsteinium”• With support from Seaborg, ORNL designed andMeltonValleyconstructed the HFIR and the REDC to
produce these elements

BethelValley

96

Z

94

Pu

93

Np

Cm

95

Am

Pu 238

Pu 239Cm 242Am 241

Am 242

Pu 240Pu 241

Np 237

Cm 245

Cf 249Fm 256

Es 254

Es 255, -, EC-

Cf 250

Cf 251

Cf 252

Cf 253

Cf 254, (n,f),, SF-, (n,f)SF

Bk 250

Bk 251---

Cm 246

Cm 247

Cm 248

Cm 249Cm 250, (n,f)

, SF

-

SF

Am 245

Am 246Am 244---

Pu 242

Pu 243

Pu 244

Pu 245

Pu 246---

Fm 255

Es 253

Bk 249Am 243-, (n,f)Fm 254

Fm 257SF, (n,f), (n,f)-, EC, (n,f)

Es

Bk

97

, (n,f)

Fm

99

Cf

98

Cm 244

Cm 243100

Np 238N
7

8

ORNL’s actinide production and research complex
HFIR

High-power (85-MW) compact coreprovides intense thermal neutron
fluxes in a central flux trap

REDC

Heavily shielded hot cells for target
preparation and processing
irradiated materials from HFIRHigh Flux Isotope Reactor (HFIR) andRadiochemical Engineering Development
Center enable heavy element production
at Oak Ridge National Laboratory

Isotope production (gram quantitiesof 252Cf), neutron scattering, andmaterials irradiation• HFIR and REDC began operation in 1965 and 1966, respectively• HFIR operation is expected to continue at least until 2040
• High-end aspects of isotope production (heavy actinides,

specialty medical isotopes), neutron scattering, and materials
irradiation

Copyright protected image• Unique capabilities for radioisotope separations (>400 isotope

shipments annually to universities, hospitals, industry, and otherresearch institutions)

Alvin Weinberg,
June 1967
9

10

Radiochemical Engineering Development Center (REDC)
Unique capabilities for radiochemical processing and related R&D

HFIR: Unique capabilities• Heavily shielded hot cells forradiation control and alpha containment• Shielded caves for radiochemical• Highest thermal flux in Western world– 2.1 × 1015 n/cm2-s thermal– 1 × 1014 n/cm2-s epithermal (< 1 MeV)
– 4.7 × 1014 n/cm2-s fast (> 1 MeV)

processing and R&D• Glove box labs for final product purification

and R&D• Radiochemical labs for sample preparation• Brightest cold neutron source in world

and analysis• Delivers 6–7 cycles per year
• Missions:– Neutron scattering research– Isotope production– Material irradiation– Neutron activation analyses• Cold labs for chemical makeup, cold

testing, and target fabrication

HFIR operations are supportedby the Office of Basic Energy Sciencesin DOE’s Office of Science

REDC is fully utilized for research and production
for industrial, medical, and research partners

11

12

80

High Flux Isotope Reactor irradiation

Remote Cm target fabrication at REDC
• 35 pellets per target• Maximum 10 g actinides per target• Maximum allowable heat flux

• Nine irradiation cycles (250 days) over 18
months• 90 days for target cooling to allow decayof 131I

1.24 x 106 Btu-h-1-ft-2• Remote welding, hydrostatic compression,

shroud installation• ~240 mg of 252Cf and ~24 mg of 249Bk
contained in seven targets• Remote QA inspection| Radiography (pre- and post-compression)| He leak tested to <1.0 x 10-8 std-cc/s

13

14

Bk finishing operations – in hot cells

Irradiated Cm target processing at REDC

Convert Bk/Cf/impurities of low HNO3/AHIB into a solution of 8 M HNO3 byconcentration using a CX column

Irradiatedtargets
Aluminum
dissolution

Adjust Bk/Cf/impurities of 8 M HNO3 intoa solution of 8 M HNO3-0.3 M NaBrO3
Bk(III)  Bk(IV)

HFIRirradiation

0.5 M HDEHP-dodecane
Caustic
solubleFP & AlHDEHP†
extraction

Waste
organic
LiCl anion
exchange

AHIB‡ cationexchange
Bk

Cf

Es

8 M HNO3-1 M H2O2

Targetfabrication

Nitric aciddissolution

Fm

BERKEX: Solvent Extraction
HDEHP extract Bk(IV) into organic

Oxide
preparation
Lanthanide
FP

Am/Cm
product
Trans
Cm
Hydroxide
precipitation

Oxalateprecipitation

500 mL 8 M HNO3-H2O2(Bk, Ce, impurities)

8 M HNO3-0.3 M NaBrO3
Raffinate/Scrub/Cf
Waste HDEHPHydroxide
precipitation

Am/Cm
product

Among lanthnides, only Ce stays with Bk, due to formation of Ce(IV)
HDEHP: Di-(2-ethylhexyl)phosphoric acid
AHIB: Alpha-Hydroxyisobutyric acid
CX: cation exchange† Di(2-ethylhexyl) phosphoric acid
‡Alpha-hydroxyisobutyrate15

16

249Bk purification process in glove box
CX resin
separation of
cation impurities

VolumeReduction
Assembly

Super-heavy element discoveries enabledby ORNL-produced materials and isotopes~22 mg 249Bk utilized
as target material
Element

Dry down setup
for conversion

Yearproduced
TargetDry down of Bk
product from initial
CX separation

Glove
Box

Bk / Cf
separations withcooling jacket

Highly purified material:
Only 1.7 ng 252Cf

17

18

81

104

105

106

113

Rutherfordium

Dubnium

Seaborgium

Nihonium

1964

1970

1974

2004

242Pu, 249Cf

249Bk,

249,250Cf

249Cf

243Am
(decayfrom 115)

114

115

116

117

118

2000

2004

2005

2010

2006

244Pu

243Am

245,248Cm

249Bk

249Cf

Flerovium Moscovium Livermorium Tennessine Oganesson

Mining old californium sources to synthesize
the heaviest nuclei to dateAcknowledgments• 252Cf substantially decays

after several decades

ORNL’s
Rose Boll
and Shelley
Van Cleveprocess
recovered
mixed-Cftargetmaterial• A mixture of 249–251Cf remains, ~36% 251Cf(heaviest SHE target material)• Mixed-Cf material processed

and fabricated into targets at REDC

• Experiment underway to synthesize new• Research supported by the

US Department of Energy Isotope Program,managed by the Office of Science• This research used resources of the Oak Ridge

High Flux Isotope Reactor, which is a DOE Officeof Science User Facility

heaviest nuclei of Z=118 (A=295, 296)

• ORNL is managed by UT-Battelle, LLC

for the US Department of Energy
under contract DE-AC05-00OR22725

Cf isotopic distribution as produced in HFIRand after several decades
IsotopeHalf-life(years)Atomicpercent(as produced)

Recently recovered fromdecayed sources (mg)

249Cf

351y

3.41%

7.6 mg

250Cf

13.1y

8.7%

• Chuck Alexander (ret.), Dennis Benker, Emory

Collins, Lætitia Delmau, & Shelley VanCleve

2.5 mg

251Cf

898y

2.60%

5.7 mg

252Cf

2.65y

85.27%

0.0007 mg

19

20

Discussion

21

82Question and answer session
Q: So you are currently developing the production of Lu-177 by indirect method?
A: Lu-177 and the production method is not in my ﬁeld. Miguel, could you please explain
this point?
A: (Miguel) Not if I understand correctly.

Q: In the second or third slide, you also manufacture Ac-225 by proton irradiation. Does yourlaboratory also process the proton irradiation process for Th-232?
A: We do not do proton irradiation process processing. We work in the so-called TRI-LAB.
Targets are irradiated at either Brookhaven National Laboratory or Los Angeles Special Institute.
The targets are then separated and puriﬁed at Oak Ridge.

Q: So you are just producing Ac-225 from the decay of Th-229?
A: Yes, that is what we do with respect to one facility, and we do it at the other facility. We
process targets that have been exposed to accelerator radiation at another national lab.

83

K. Ishida（Kyoto Univ.）

2.20

Nuclear magnetic resonance in uranium compound superconductors

U-based Ferromagnetic Superconductors

3rd March 2023
1
Kumatori Workshop

U-based Ferromagnetic
Superconductors

D. Aoki et al., Nature
413, 613 (2001)

K. Kinjo, G. Nakamine, M. Manago, T. Hattori, S. Kitagawa, K. Ishida,
Y. TokunagaA, H. SakaiA, S. KambeA, N. K. SatoB, K. DeguchiB
T. YamamuraC, Y. ShimizuC, A. NakmuraC, D. LiC, Y. HommaC, F. HondaC, D. AokiC

S. S. Saxena
G. G. Lonzarich
U. of Cambridge

Kyoto Univ., A ASRC, Japan Atomic Agency, BNagoya Univ., CIMR, Tohoku Univ.

Kyoto Univ.

J. A. E. A.

2
S. Ran et al., Science
365 684-687 (2019)

N. T. Huy et al., PRL
99, 067006 (2007)

UTe2

UGe2

URhGe

UCoGe

TCurie (K)

52

9.5

~3

M0 (mB)

1.48

0.4

0.05

Easy Axis

a

c

c

a

PSC (GPa)~1.2

0 Ambient

0 Ambient

0 Ambient

TSC (K)

0.8

0.26

0.7

1.65

PM
ー

S. RanS. S. Saxena et al.
Nature 406, 587 (00)

G. Nakamine

K. Kinjo

Nagoya Univ.

N. K. Sato,K. Deguchi,

M. Manago, S. Kitagawa, T. Hattori

H. SakaiY. Tokunaga

S. Kambe

Tohoku Univ. (IMR)

T. Yamamura Y. Shimizu, A. Nakamura, Y. Homma, D. X. Li,

F. Honda,

UGe2

D. Aoki

Summary of 59Co-NQR on UCoGe (Zero field)

3

UMGe

Suppression of Superconductivity by Magnetic Field

Collaboration with N. K. Sato Group

T. Ohta et al. JPSJ 79, 023707 (‘10)

CoGe

4d 1 5s 2

Y : [Kr]U : [Rn] 5f n, 6d 1 7s 2Y

YCoGegn = 6.6 mJ /mol K

2

D. Aoki et al., J.
Phys. Soc. Jpn 85,
073713 (2016)

S. Kitagawa et al.,J. Phys. Soc. Jpn
87, 013701 (2018)þÿý2
þ�㕇 T = Tc
Second-Order Transition (SOT)First-Order Transition (FOT)

Hc2orb(0 K) = －0.73Tc
VortexH

superconducting(SC) current

No SC & FM down to 100 mK⇒ SC and FM originate from U-5f electrons

5Interesting Properties of FM SC
H-boosted Superconductivity

Hc2P(0 K) =NMR measurement

Zeeman energy > SC energy

sample : RRR ≃ 96
(D. Aoki, Tohokui Univ.)Āac measurement for TSC✓We measured T-dependence of Āac in fields
along the b-axis and a-axis.
✓ We use the rotation device with piezo device
which can be used in dilution refrigerator.
Hǁb

D. Aoki et al.
J. Phys. Soc. Jpn.
78, 113709 (2009)

Thermometer

Angle precision ∼ 0.05 °NMR probe with rotator

84

2�㔇�㔵

6

✓We measured 1/�㕇1 and 1/�㕇2 in high fieldalong the b-axis and a-axis.
✓We use cryogen-free 25 T magnet @IMR
Tohoku Univ.

The similar enhancement is also observed in UTe2

Δ(0)Experimental✓Higher quality sample by D. Aoki et al. (RRR ≃ 96)✓Sample direction is controlled by uniaxial rotation probe.

D. Aoki and J. Flouquet: J. Phy. Soc. Jpn. 83, 061011 (2014)

URhGe: Reentrant SC was reported in 8 T < m0H < 14 T.
UCoGe: SC becomes robust in 5 T < m0H < 13 T.

H(Spin-singlet pairing)

Kinetic energy > SC energy

Karube J. Phys. Soc. Jpn. 80, 064711 (2011)

Case II

4

Pauli-departing EffectOrbital-departing Effectc.f. reference: YCoGe (Pnma with similar lattice constant.)

UTe2

RotatorAngle precision ∼ 0.01 °
6

∆

7

Result : ÿ/�㕻ÿ �㕻, ÿ/�㕻Ā �㕻 in H || a and b

1/T1: Nuclear spin-lattice relaxation rate

1/�㕇1 ∝ fluctuations ꓕ H
1~ 3 (SK)−1�㕇1 �㕇 �㔻∥ādetects the magnetic fluctuations (G)perpendicular to the applied H direction

and T-indep. in T <10 K

88What we can know from 1/T1 & 1/T2?

⇒ c-axis fluctuations are dominant.

1~ 3 (SK)−1�㕇1 �㕇 �㔻∥ā

G⏊
Hx
G⏊
Magnetic fluctuations: TCurie

detects G parallel to H, along with the 1/T1 components

20

10

0

Gz

G||

1/T2: Nuclear spin-lattice relaxation rate

Hx

Gy

�㔇0 ÿ
(T)

※ NMR measurement : �㕇 ≥ 1.5 K(paramagnetic or ferromagnetic state)

T dep. of 1/�㕇1 and 1/�㕇2 wasalmost unchanged by H ǁ a.

Gc(w0) is dominant.

➢ 1/�㕇1 , 1/�㕇2 and Tcurie are suppressed by H ǁ b.
➢ Qualitatively, T dep. of 1/�㕇1 is the same as that of7 1/�㕇2 .

T dependence of 1/T1T in H // b

9 98This is in contrast to the case of URhGe.

SC properties, cAC measurements

10• Highly anisotropic Hc2• SC is enhanced by H // b

• SC is significantly
suppressed by H // cD. Aoki et al. JPSJ 78,
113709 (2009)�㔃 ÿ = �㕇Curie 1 2 �㔇0 ÿĀ Τ14∝ Āā (ÿ)
SCR: 3-D FM

1∝Ā�㕇1 �㕇

2

H // aB. Wu et al. Nat.
Comm. 8, 14480(2017)

q (H) is consistent with the mean-field theory

Relationship between FM fluctuations and Superconductivity

11

H // c
10

Theoretical Studies (Magnetic Glue) Tada & Fujimoto
J.Phys.Conf. Ser. 449 012029 (2013)

Case II

H // c (easy axis) suppresses FM fluctuations and superconductivity
Y. Tadaq dependence of 1/T1 in the bc plane

S. Fujimotoq dependence of Hc2
Hcb-axisT. Hattori

Phys. Rev. B 67,
06401 (2013)

Spin-triplet superconductivity

T. Hattori et al., Phys. Rev.
Lett. 108, 066403 (2012)

Aoki & Flouquet
JPSJ 83, 061011 (2014)

Superconductivity is observed in the Hrange where (dHc)2 is enhanced⇒Longitudinal mode is related with SC

85

Y. Tada et al. J. Phys. Conf. Ser. 449 012029 (2013)

Y. Tada, S. Takayoshi and S. Fujimoto
Phys. Rev. B 93, 174512 (2016)

Triplet pairing by spin-fluctuation exchange

1313

V. P. Mineev Physics-Uspekhi 60 (2) 121-148 (2017)

In H // b (a),Pairing interaction: <the attraction of one electron by the magnetic polarization
cloud of the other = ← electron – magnon interaction�㕇SC ~ �㔖exp 2

S(r) : operator of the electron spin density
cij(r) : medium susceptibility
I : exchange constant

V. P. Mineev

cij(r)

Pairs of electrons in a ferromagnetic metals occurs in an anisotropic medium due
to polarization of the electron liquid and the localized moments.

1�㕁0 (�㔤)Āā (ÿĀ(ÿ) ) cos2 ÿ + �㕁0 (�㔤)ĀĀ ÿ (ÿĀ(ÿ) ) sin2 ÿ Ā 2�㕇SC ÿĀ(ÿ) ~ �㔖exp 2

H b(a)tan ÿ =

ÿĀ(ÿ)
ℎ

�㗼1
Āā (ÿĀ(ÿ) ), where we use the relation ofĀā ÿ ∝ �㕇1 ÿ �㕇 −1

ε : cut-off energy for the pairing interaction
1+l : effective mass renormalization
N0(k): density of electronic states on the FS.
czz : z component of static susceptibility

V. P. Mineev, PRB 103, 144508 (2021)hExchange
field // c

In UCoGe, Āā ≫ ĀĀ and h ≫ ÿĀ(ÿ)
we simply assume

I

Following the BCS formalism and introducing the physical properties,

1414

Application (1) : TSC enhancement by H // b

czz is the main source of the critical temperature dependence in the magnetic field.
13

Application (2) : TSC sudden suppression by H // c

14

1515

16

Reentrant Superconductivity in URhGe

F. Levy and A. Huxley et al. Nat. Phys. 3, 460 (2007)

SC is significantly suppressed by H // cA. Huxley

In H // c,F. Levy andA. Huxley et al.
Science 309,
1343 (2005)

�㗼2
�㕇SC ÿā ~ �㔖exp 2
Āā ÿā

1/�㕇2 Ā ∝T. Hattori et al. PRL
108, 066403 (2012)

Āā ÿ

ā

ā

∝ �㕇1 ÿ �㕇�㗿ÿĀ 2

Relationship between critical fluctuations and SC−1

Y. Tokunaga

15

Summary

Y. Tokunaga et al. PRL 114 (2015) 216401

17

In FM superconductors UCoGe & URhGe,
1) Superconductivity occurs in the FM region ⇒ Microscopic coexistence of FM and SC
2) Ising-type FM fluctuations develop at low T ⇒ Longitudinal (c-axis) mode of the moments

3) The FM fluctuations controlled by H are coupled with superconductivity.
⇒ The Ising-type FM fluctuations induces the spin-triplet superconductivity• Magnetic-fluctuation mediated unconventional SC

V. P. Mineev, PRB 103, 144508 (2021)
P. Monthoux et al. Nature 450, 1177 (2007)

cf. BCS (Conventional) superconductor

electron-phonon
interaction�㕘B �㕇ā = 1.14ℏ�㔔�㔷 exp 21�㕁(�㔸F )�㕉

Y. J. Uemura, JPCM 16, S4515 (2004)

spin-triplet SC UTe2

86

Y. Tokunaga et al. PRB 93, 201112 (2016)

Question and answer session
Q: You explain superconductivity by linking it to this magnetic ﬂuctuation, but you think thateven in UCoGe, in magnetic ﬁeld B, it is similar to a certain type of magnetic instability possible
in URhGe.
A: This is a phase diagram of magnetic properties. You said that if the magnetic ﬁeld is parallelto the b axis, the ferromagnetism would taper like this, but it doesn’t exhibit that behavior. So thediﬀerent behavior of connectivity A and B is due to the diﬀerence in the magnetic dependence ofthe thermomagnetic properties. But I don’t know why the magnetic dependence is so diﬀerent
between the A and B axes.

Q: But anyway, there seems to be a similarity between UCoGe and URhGe.
A: It is more localized in URhGe, but as you know these are system compounds and magnetic
structures, but it could be as diﬀerent as that.27 min

Q: How do you think this calculation is valid for unknowns?
A: That is the most diﬃcult part of the calculation.

Q: The heat capacity deviates slightly from the adapted value.
A: I imagine that if we can use the results of this calculation as input for CALPHAD. Is thisconcept okay?

Q: Yes, it is okay.
A: Thank you.

87

88

H. Shishido（Tohoku Univ.）

2.21

First-principles calculations for CALPHAD calculations of minor actinide fuels

1. Introduction

1.1 Severe problems on fusion reactor development
Controlled fusion reaction will beachieved by the ITER project.

First-principles calculations for
CALPHAD calculations ofminor actinides fuels

Copyright protected image

Demo design is not fixed due toremaining engineering issues
Fig. ITER[1]1) the divertor system loaded by extremely high heat flux2) maintenance of components loaded by neutrons

Hiroki Shishido

Even after the Demo construction, , ,Department of Quantum Energy Engineering,

Scaling up

DEMO reactors

Graduate School of Engineering,

Commercial reactors

The power increase brings more severe
heat load to the divertor.

Tohoku University

As one of the options,
Transmutation of minor actinides (MA) and fission productgenerated from nuclear power plants.
2

1[1] https://www.iter.org/

1. Introduction

1. Introduction

1.2 Closed nuclear fuel cycle with a fusion reactor [2]

1.3 MA transmutation in a fusion reactor
Core plasma

Conventional cycle

New additional cycle

Power generation

U, Pu
U
Fuel
production

FusionreactorFast
reactor
LWR

Longlived FP

Copyright protected image

U, Pu

Reprocessing

ûMA
ûFP

Separation

Other FP

Copyright protected image

Transmutation cycle

Fig. Toroidal cross section
Divertor

Blanket material
production

MA

Table Summary of the burn-up characteristics [4]Loaded MA [ton]Storage (detoxified soon)

To contribute to <Geological repository=[2] H. Hashizume et al., presented at the 14th International
Symposium on Fusion Nuclear Technology, 2019 Budapest, Hungary.

Fig. Poloidal cross section

Fig. Helical fusion reactor FFHR-d1[3]Fuel
production

MA loading position

80*support factor =Fusion power [MW]1,000

Heat generation rate
in fuel[W/cm3]

Copyright protected
imageTransmuted
MA/year in a fusion reactor

119

58

In reactor core [W/cm3]

55.7

13.6

Support factor [-]

28.3

22.6

Generated MA/year from a 1GWe PWR[3] A. Sagara et al., Fusion Engineering and Design 89 (2014) 2114-2120.
[4] Y. Furudate, H. Shishido et al., Prog. Nucl. Energy 103 (2008) 28.

3

1. Introduction

4

1. Introduction

1.4 Pu transmuted from MA

1.4 Pu transmuted from MA (Cont9d)
Conventional cycle
Power generation

Fast
Pu? reactor
Pu? LWR

Fuel
production

Copyright protected image

U, Pu

Pu

New additional cycle
FusionreactorLonglived FP

ReprocessingMA

Separation

Transmutation cycle

Blanket material
production

MA

Fuel
production

FP

Other FP
237Np ³ 238Np ³ 238Pu(n, ´)³ decay
T1/2 = 2.4 d[7] A. Sasahara et al., Journal of Nuclear Science and Technology 41 (2004) 448-456.

Storage (detoxified soon)

Is it possible to re-utilize the transmuted Pu
in a fission reactor?
High level waste ³ Energy resource?
5

6

89

1. Introduction

1. Introduction

1.5 Transmuted Pu in a fast reactor§ Development of fuel containing only MA fortransmutation systems4(Np, Am, Cm)O2.

Inner core
Outer core

§ First, we have considered conducting a numericalanalysis using the CALPHAD method to evaluate
the phase diagram.

Reflector

Copyright protected image

Primary control
Secondary control

Transmuted
Pu ratio

Fig. Radial core layout[8]§ Since thermodynamic quantities are required as
inputs to CALPHAD, we have worked on thepredictive evaluation of these quantities by firstprinciples calculations.

Table Comparison of Pu isotope ratio
238Pu

239Pu

240Pu

241Pu

242Pu

MOX fuel

2.2

59.5

26.7

3.9

7.6

Pu transmutedfrom MA

82.2

4.8

2.6

0.6

10.0

Possibility to maintaina constant level of keffduring operation[8] OECD/NEA, NEA/NSC/R(2015)9, (2016).

78

2. Today9s presentation contents

3. Materials and methods

3.1 DFT simulation

The presentation provides:

Materials

1) Density functional theory (DFT) based electronic
structure calculations for UO2, AmO2, and NpAmO2

Calculation cell

UO2, AmO2, NpAmO2

ð Structure optimization
ð Density of states
2) Phonon calculations based on the DFT calculation

ð Free energy
ð Heat capacity at constant pressure

UO2, AmO2(Fm-3m)9

3. Materials and methods

3.2 Phonon calculation

WIEN2k[9]Density functional theory calculation based onall-electron calculation method

Phonopy[10]Thermal properties (free energy, heat capacity, and entropy)
related to phonon in solids are calculated using DFT
calculation results

Exchange3Correlation functional: PBE
Sampling k points: 1,000
RMTKmax = 8.5
SCF convergence condition: 1025 Ry
Not considered electron spin polarization[9] P. Blaha et al., J. Chem. Phys. 152, 074101 (2020).

10

3. Materials and methods

3.1 DFT simulation

"
"
"
"
"

NpAmO2 (a) P4/mmm, (b) R-3m

Quasi harmonic approximation[11]Copyright protected image

1112[10] A. Togo, J. Phys. Soc. Jpn. 92, 012001 (2023). [11] K. Toyoura, J. MMIJ 129, 270-277 (2013).

90

4. Electronic structure calculation

4. Electronic structure calculation

4.1 Structure optimization3UO2 and AmO2

4.2 Density of states3UO2

Energy3volume curve

Experiment
UO2 band gap= 2.0032.50 eV[15, 16]

AmO2

UO2

GGA+U[17] or TB-mBJ[18]were employed &band gap f 0.5 eV

Density of states (DOS) for UO2

The calculation conditions need to be reviewed for
accurate evaluation of the electronic state.
[12] F. Gronvold et al., Nature 162, 69-70 (1948).
[13] F. D. Murnaghan, Proc. Natl. Acad. Sci. USA. 30, 244-247 (1944).
[14] C. Hurtgen et al., Inorg. Nucl. Chem. Lett. 13, 179-188 (1977).

[15] T.T. Meek et al., Mater. Lett. 59, 1085-1088 (2005).
[16] S.W. Yu et al., Phys. Rev. B 83, 165102 (2011).
[17] A.I Liechtenstein et al., Phys. Rev. B 52, R5467-R5470 (1995).
[18] D. Koller et al., Phys. Rev. B 85, 155109 (2012).

13

4. Electronic structure calculation

14

5. Phonon calculations

4.3 Structure optimization3NpAmO2

5.1 Thermal properties3UO2

P4/mmm

R-3m
Energy3volume curve
The E3V curves were rattled because of the loose
convergence determination of the DFT calculations.

NpAmO2 mixture R_3m is more stable?

[19] JAEA, Thermodynamic database for nuclear fuels and reactor materials.

15

6. Summary1) Density functional theory (DFT) calculations
7 The results of structural optimization correspond to theexperimental results.
7 Applying GGA+U and TB-mBJ did not improve the band
gap underestimation.
7 Since there are some problems specific to the all-electron
method, it is necessary to review the calculation
conditions in the future.

2) Phonon calculations based on the DFT calculation
7 Although only UO2 was implemented, it was confirmedthat the heat capacity can be generally evaluated.
17

91

16

Question and answer session
Q: How do you think this calculation is valid for unknowns?
A: That is the most diﬃcult part of the calculation.

Q: The heat capacity deviates slightly from the adapted value.
A: I imagine that if we can use the results of this calculation as input for CALPHAD. Is thisconcept okay?

Q: Yes, it is okay.
A: Thank you.

92

93

M. Abe（Hiroshima Univ.）

2.22

Development of relativistic electron correlation program for calculation of actinide
compoundsア¿チþイù化合{をタü²ッøxす»背景

2022年度<ア¿チþイùの物g化学と応用・原子炉照射医療用RI製造に関する専門研究_=2023年3月2, 3日 京都大学原子力複合研究所・オンùイン

ÿ島第Nß発事故{¸»放射性ß棄{

ア¿チþイù化合{計算{Uけ
相ÿ論öÿ[相関÷ロÀùĀ開発
89

90

91

92

93

94

95

96

97

98

99

燃料r分
(UO2)

ß験|究{¸»燃料÷öú~性質ën~難しさ

燃料被覆管
(Zr)

100 101 102 103

Ac Th Pa U Np Pu Am Cm Bk Cf Es Fm Md No Lr

コン¿úーø

制御棒材料

燃料÷öú

ア¿チþイù化合{~混合{ア¿チþイù化合{~v論計算{zけ»問題ùd

[1] JAEA ”Characterization of fuel debris” https://www.jaea.go.jp/english/04/ntokai/fukushimaア¿チþイù

エýû¾ü®差 [a.u.]

30
25

15
10

２成分
近似ý

5
0
10

20

30

40

50

60

70

80

90

厳密z相ÿ論ý(4成Vý){¹~エýû¾ü®ÿ[2](Ï) CASPT2, MRCI, MRCC

CASPT2ý

v論e 4成Výx厳密2成Vý~比較

5

4成分Diracý

�㔻4Dirac Ψ4 = �㔸Ψ4

+ ⋯ ⋯ + C�㕁

O性z
Φ2

Φ3

→ 高精þ相対論ýが必要[2] J Seino et al, Chem. Phys. Lett. 461 ,2008, 327–331

二次z

Φ1

7 2成V近似ý (Ú精þ)多参照ÿ[相関v論x高精þ相対論ýを
同時{取º扱え»実}öz÷ロÀùð~開発を実施→ 多参照ÿ[相関v論が必要+C3

100 110原[号ア¿チþイùß[ÿｄ軌道やｆ軌道|擬縮× 非相ÿ論× 低精þ相ÿ論ý

低精þ
相対論ý

20

0

多参照ÿ[相関v論

+C2

4

非相対論ý

35

,

,

完y性z
C1
(CAS)

研究施設
の不¿

v論計算{よ»ア¿チþイù化合物~
化öû物vö性質~解明へ~待40…

v論d 多参照ÿ[相関v論n定の難しさア¿チþイù~ß[号 : Z = 89 ~ 103 (重元素)

軌道|(擬)縮→ 複u~ÿ[Ý置|重要単参照ÿ[相関v論

安全g確保
が困難

ア¿チþイù化合{~v論計算{zけ»問題ùe3

ÿ[相関v論{tいv
軌道|離散ö
→ ÿt~ÿ[Ý置|重要

高い
研究コスø

海水の注水

原子炉構造材料

広大ÿ 阿ø穣里û野u紘平ûßuÿþ
都û大ÿ波u雅彦ûo¿直輝û]u均û佐åo汰留û岩ÿ寿ÿÿ

2�㕁CASÕw×ºう»yv~ÿ[Ý置{ÿしv1|0ۧ = ෍ �㔶�㕖 |Φ�㕖 ۧ線}合をxº1Ý置係uCをYVö{~Û�㕖

CASPT2ý
0次波 関u |0ۧ {¹さ¹{1,2ÿ[励起しÝ置を
摂 ö{考慮す»ýý�㕈 † �㔻4 �㕈 ≈

�㔻2+
0

0
�㔻22

厳密2成分ý

�㔻2+ Ψ2 = �㔸 + Ψ2

4成分Diracý

厳密2成分ý(X2Cý)得¹¼»ë

ÿ[ëx陽ÿ[ë

ÿ[ë

計算³スø

Úい

低い

計算~正確性Úい4成Výx{|同等Φ�㕁

CASCIý

ユニタúüYû

6

厳密2成分ýÿ精þを落xさz{低コスøw計算可能[3] M Hayami et al, J. Chem. Com. 39, 27, 2333

94

量[化計算÷ロÀùĀ~比較
DIRAC
４成VDiracý

7

厳密Ā成Vý

7

CASCI(CASSCF)
CASPT2

DIRAC{ÿuくCASCI/CASPT2
計算ý~確û

o|究~þöxýý

7ア¿チþイù化合{~計算をÿ能xす»DIRAC{ÿuくCASCI/CASPT2÷ロÀùĀ(D-CASPT2)~確ûUTChem MOLCAS Gaussian

7

×
×

×

×

×

△

×

7

7

△

7

7

×

厳密Ā成Vý

＋多参照ÿ[相関ý8|究Õ容tUTChemxDIRACを比較, 接続÷ロÀùðを移植û変更(2ÿ[積V~冗÷性~除去，ÿ称性~ãzy)

ア¿チþイù
化合{x~適ß|ÿ能{z»u能~ã (IVOý~適}）[4] M Abe et al, J. Chem. Phys. 2006, 125, 234110

o|究~þöxýý

u能~ã

9ア¿チþイù化合{~計算をÿ能xす»DIRAC{ÿuくCASCI/CASPT2÷ロÀùĀ(D-CASPT2)~確û

IVO (Improved Virtual Orbital) ý

10

CASSCFý計算³スø|Úい → 参照関uÿIVO-CASCIýIVO(Improved Virtual Orbital)ý[5]ÿ底状態~HOMO{¹1ÿ[励起し状態{ÿしv¸ºg適z軌道を成す»こxwî想軌道~記ÿを}善î想軌道Õw
ユニタúü変換物vöz
意味が乏しい|究Õ容tUTChemxDIRACを比較, 接続÷ロÀùðを移植û変更(2ÿ[積V~冗÷性~除去，ÿ称性~ãzy)u能~ã (IVOý~適}）[4] M Abe et al, J. Chem. Phys. 2006, 125, 234110

計算~詳}[5] S Huzinaga, J. Chem. Phys. 1971, 54, 1948-1951

計算~詳}

11

• ÷ロÀùĀ DIRAC2212• ÷ロÀùĀ DIRAC22

ßÍしCASCI/CASPT2z¸びRASCI/RASPT2

ßÍしCASCI/CASPT2z¸びRASCI/RASPT2• ÿÿûøニアンÿ X2C (厳密2成V相ÿ論ý)• ÿÿûøニアンÿ X2C (厳密2成V相ÿ論ý)

4成VDirac (4成V相ÿ論ý)

4成VDirac (4成V相ÿ論ý)d÷ロÀùð _~確認
ûU-CASPT2xD-CASPT2~比較 (N2, NO, H2O)
ûCs1C1{ÿす»計算~ßÍ (ñタþüû，非対称CH4)û厳密2成Vý~適ß (UO22+)
ûIVOýを適ßし1V光Ûuを計算 (N2)d÷ロÀùð _~確認
ûU-CASPT2xD-CASPT2~比較 (N2, NO, H2O)
ûCs1C1{ÿす»計算~ßÍ (ñタþüû，非対称CH4)û厳密2成Vý~適ß (UO22+)
ûIVOýを適ßし1V光Ûuを計算 (N2)eア¿チþイù化合物~計算へ~応} (UO22+)
ûMO係u~ë÷x性z~設ÛûV光Ûu (平衡核Ý離，ë離エýû¾ü)ûポöンシャû曲線x励起エýû¾üeア¿チþイù化合物~計算へ~応} (UO22+)
ûMO係u~ë÷x性z~設ÛûV光Ûu (平衡核Ý離，ë離エýû¾ü)ûポöンシャû曲線x励起エýû¾ü

95

d÷ロÀùĀ

作~}証 (U-CASPT2x~比較Ād÷ロÀùĀ 作~}証 (Cs、C1{対y»計算~実装Ā1413

U-CASPT2ÿCsxC1ÿ称性~計算ßÍさ¼vいzい2
Ô成gþÿCAS1Ý置/HF＝CASCI1MP2＝CASPT2エýû¾ü

先Ì|究~U-CASPT2xo|究~D-CASPT2~}ÿを比較
N2 (C32h)

NO (C32)

STO-3G, 12スピþüû 6ÿ[STO-3G, 12スピþüû 6ÿ[U-CASPT2

D-CASPT2

U-CASPT2

D-CASPT2

HF-103.04546316-103.04546311-127.5470334-127.5470333

CASCI-103.05416899-103.05416893-127.6558412-127.6558411

CASPT2-103.26008134-103.26008128-127.8379457-127.8379456

H2O (C2)[単Oÿa.u.]

U-CASPT2

D-CASPT2-74.883904471-74.883904464

CASCI-74.884304152-74.884304146

CASPT2-75.040813153-75.040813152

d÷ロÀùĀ

U-CASPT2xD-CASPT2
ut®ÿ~範öw
完y{N致作~}証 (厳密2成Vý~適ß)

厳密
2成分ý

20.1

4成分
相対論ý

93.0

657.7

926.0

29.1
23.1

94.4
89.5

MP2

-111.55628122-37.58766131

CASPT2-111.55628125-37.58766134[単Oÿa.u.]作~}証 (IVOý) N2V[~V光Ûu

16ÿ底関uÿdyall.3zp

状態ÿÿ底状態(Ω=0g)
性zÿ12スピþüû, 6ÿ[HF

1131.8 1368.4
1134.4 2830.7-107.6MP2
CCSD-108.1

CCSD(T)-108.6

CASCI-109.1

CASPT2

IVO-CASCI

厳密2成Vý 積VYûø~計算³スø|大幅{低下

IVO-CASPT2

ア¿チþイùを°重ß[系~計算をÿ実öz時w計算可能{z»ûHF, MP2, CCSD, CCSD(T)中～÷距離w破綻

ûIVO-CASPT2がÛÛした
ポöンシャû曲線を描画-109.6
0.5

2.5

4.5

6.5

}合÷[Å]

作~}証 (IVOý) N2V[~V光Ûu

計算~詳}

17

Re [Å]

ωe [cm-1]

Be [cm-1]

αe [cm-1]

De[kcal/mol]

CCSD(T)

1.10062394.5

1.98780.0166

901.6

CASCI

1.09942406.81.99220.0144240.1

CASPT2

1.09912407.81.99350.0168

196.6

IVO-CASCI

1.09392506.22.01240.0157

213.4

IVO-CASPT2

1.09882386.3

1.99430.0184208.0

実験値[6]

1.09772358.6

1.99820.0173

228.4

Re : 平衡核間距離(Å)ωe : 調和振動数(cm-1)
Be : Þ転定数(cm-1)
αe : 非調和項(cm-1)
De : ë離エýû¾ー(kcal/mol)-37.460336926-107.1

合計[MPI8並列計算, 単Oÿû, U:dyall.c2vz, O:6-31G+*, 12スピþüû 4ÿ[]d÷ロÀùĀ

-37.460336926-111.13616466

N2分子のポテンシャル曲線エýû¾ー [a.u.]

HF-111.13616466

DIRAC{ßÍさ¼vい»ÿ称性C32h1C321C2、 Cs、C1 {ÿしv
D-CASPT2正常{作UO22+V[~エýû¾ü計算過程~計算f
CASCI/CASPT2
DIRAC
積分
そ~他 CASCI CASPT2
変換

HF

CASCI

d÷ロÀùĀ

15

非対称CH4 (C1)
STO-3G, 2スピþüû 2ÿ[HFxCASCI1MP2xCASPT2エýû¾üut®ÿ~範öw完y{N致6-31G, 10スピþüû 6ÿ[HFñタþüû (Cs)
cc-pVDZ, 10スピþüû 6ÿ[18• ÷ロÀùĀ DIRAC22
ßÍしCASCI/CASPT2z¸びRASCI/RASPT2• ÿÿûøニアンÿ X2C (厳密2成V相ÿ論ý)

4成VDirac (4成V相ÿ論ý)d÷ロÀùð _~確認
ûU-CASPT2xD-CASPT2~比較 (N2, NO, H2O)
ûCs1C1{ÿす»計算~ßÍ (ñタþüû，非対称CH4)û厳密2成Vý~適ß (UO22+)
ûIVOýを適ßし1V光Ûuを計算 (N2)ûCASPT2ý|すyv~ut{zいv1¸い計算}ÿを得vい»ûIVOýを適ßす»x1CASPT2ý{zいv1すyv~ut|ß験t{近Þく→ IVOý~適}効果あº[6] https://webbook.nist.gov/chemistry/form-ser/ NIST Chemistry WebBook96eア¿チþイù化合物~計算へ~応} (UO22+)
ûMO係u~ë÷x性z~設ÛûV光Ûu (平衡核Ý離，ë離エýû¾ü)ûポöンシャû曲線x励起エýû¾üeア¿チþイù化合{x~ß} (UO22+計算~性z)HOMOûLUMOÞ近~V[軌道~ë÷ (Ru-o=1.75Å)
エýû¾ü

ÿ底関uÿU:dyall.c2vz, O:6-31G+*

25

U ｆ 50% ｐ 12% O p 36%-0.377U ｆ 38% ｐ 20% O p 36%-0.404U ｆ 98%-0.414U ｆ 90%-0.414U ｄ 100%-0.422U ｆ 72%-0.426U ｄ 87%-0.427U ｆ 95%-0.429U ｓ 61% (LUMO)-1.023U ｐ 37% O ｓ 40% ｐ 21% (HOMO)-1.024O ｐ 90% U ｆ 8%

-1.039O ｐ 52% ｓ 36% U ｄ 12%-1.046

U ｐ 39% O ｓ 46% ｐ 11%-1.056O ｐ 72% U ｄ 26%-1.059O ｐ 72% U ｄ 26%-1.431U ｐ 53% O ｓ 44% ｐ 2%

相ÿエýû¾ü [eV]-0.354

大}z
性z|
必要

状態ÿÿ底状態(Ω=0g)

MP2

20

性zÿ28スピþüû, 12ÿ[RASPT215HF

CASCI/CASPT2w計算Oÿ

10

RASCI

Ý置{制限を加えRASCI/RASPT2ý
(共同|究 広大/野u)
を}いv計算

5

0
1

2

-5

3

4

5

U-OÝ離[Å]

HF

UxO~
軌道成分が
混合

MP2

eア¿チþイù化合{x~ß} (UO22+~V光Ûu)ÿ底関uÿU:dyall.c2vz, O:6-31G+*

25

相ÿエýû¾ü [eV]RAS2

+ ⋯ + CN

RAS1
O性z

20

性zÿ28スピþüû, 12ÿ[RASPT215HF

CASCI/CASPT2w計算Oÿ

10

RASCI

Ý置{制限を加えRASCI/RASPT2ý
(共同|究 広大/野u)
を}いv計算

5

1

2

-5

3

4

5

U-OÝ離[Å]

HF

MP2

解離エýû¾ü~v論値を新しくó案eア¿チþイù化合{x~ß} (UO22+~励起エýû¾ü)
6∆�㕻�㗎�㖆 [eV]ÿÿ底状態~Rew×s
ÿ底状態{¹~エýû¾üÿ

4g

5

RASPT2エýû¾ü[eV]

4
3

2

性z

0g

1

2g

1g

Ω Re [Å] ∆�㕻�㗎�㖆 [eV]

3g

0g

1.5

6%

SO-CASPT2[7]Re∆�㕻�㗎�㖆2g

3g

021% 21%24

Ω=0g(ÿ底状態)x1g, 2g, 3g, 4g(励起状態){ÿす»計算

oÝ離ÿRu-o=3ÅĀ

12%

RASPT2De [eV]

関u~ë÷ÿ主zÿ[Ý置{tいv

98% 単Ý置RASCIRe [Å]eア¿チþイù化合{x~ß}(多参照ÿ[相関v論~必要性) 23
波

状態ÿÿ底状態(Ω=0g)

MP20• RASCI~ßÍ
• CASzをRAS1,RAS2,RAS3~3t{Vけ»• RAS1ホüû~uを制限• RAS2制限zし• RAS3ÿ[uを制限• RASPT2• RASCI|w}¼CASPT2をうけwßÿ

平衡Ý離Þ近ÿRu-o=1.75ÅĀ

22

30

RAS3
+C3

RASPT2De [eV]

二次z

+C2

RASCI

Re [Å]

解離エýû¾ü~v論値を新しくó案

参考ÿ RASCI/RASPT2~ßÍ (広大û野u) 21|0ۧ = C12030

z軌道~成分[a.u.]

U5f,6d由g~軌道が擬縮退eア¿チþイù化合{x~ß} (UO22+~V光Ûu)

19

1.75

}合÷[Å]

2

1g
4g

先Ì|究(SO-CASPT2)xRASPT2~比較
励起配置~準OÿÛ性ö{一致励起エýû¾üÿ2g状態以外よく一致

6%3Åïß~oû÷Ý離w多配置性|}±v顕著

ÿ底関uや性z~×ºýx~依存性をÎß}討

多参照ÿ[相関v論~必要性を再確認[7] Pierloot, K.; van Besien, E. J. Chem. Phys. 2005, 123, 204309

97

}論

25

相ÿ論öCASPT2÷ロÀùĀ(D-CASPT2)~開発✓DIRAC{ßÍさ¼vい»ÿ称性wあ»C32h1C321C21 Cs1C1x~÷ロÀùĀ適ß{成功✓厳密2成Vý~計算{適ß✓IVOýを適ßし1CASPT2ý~計算}ÿを}善ア¿チþイù化合{~計算x~ß}✓UO22+~平衡核Ý離xë離エýû¾üを算û✓UO22+~ポöンシャû曲線を描し1励起エýû¾üを計算

本|究w開発した÷ロÀùðwア¿チþイù分[~
厳密2成分-CASPT2計算が可能xzった

98Question and answer session
Q: Taking the UO2 story as an example, is it better to incorporate all of the orbitals whensome are in the form of incorporation?
A: It probably depends on whether the electron conﬁguration you are looking for is in the
excited state or the ground state, and what the composition of the excited state is. The ﬁne tuning
you point out is necessary.

Q: Because of the cost, if you take out what you don’t want and put in orbitals in even diﬀerent
places, wouldn’t that improve convergence and lower the energy more and more?
A: Yes, it would.

Q: You were just working on UO2 . Do you have any such plans to do calculations on this kindof material in the future?
A: I think that we can immediately work on how the basic electronic state and electronic
structure will change when we change to an actinide system.

Q: Is it correct to think of changing the actinide atoms in the oxide system?
A: Yes, that is correct.

99

H. Kimura（Kyoto Pharmaceutical Univ.）

2.23

Tumor-targeted radio-ceranostics drug discovery and clinical applicationºí

Tumor-targeted radio-theranostics drug
discovery and clinical applicationÿv»ùþ¹ö³¿¹

Diagnostics

Therapeutics

Theranostics­v²ãø{øþö{º¿1ºíxÿv²û÷ö{ßýV[´ñü¸óÀâÛ=ÿWâÛ

\g\OS}Õ}vý

Úþ{t{uö{õÿø²ÿW

ÿyw{{­Õxwvu¼vt»­vÿ

SPECT

123I-»÷»ûÿºí­Ā

PET

Single Photon
Emission Computed
Tomography[Y[\ßí|î

131I-»÷»ûÿÿv­Ā

Positron Emission
Tomographyÿÿ[\ßí|î

111In-´öúôòþöñ¶½»¿óÿºí­Ā
90Y-´öúôòþöñ¶½»¿óÿÿv­Āÿv}\g\OS}ºí}\g\OS}

ÿv­

ºí­

õÿ{­v²øþö{ÔKyoto Pharmaceutical University
Hiroyuki Kimura

ºí­

ÿv­

ù¸º»ùþ¹ö³¿¹÷ýüö

Erythropoietin-producing hepatocellular (Eph) Receptor

Relationship between metastasis, invasion and Eph receptors in cancer cells

Normal cell

Tumor cell

intracellular

Ephrinextracellular

Ligand binding
domain (LBD)

û Identified by Hirai et al. in 1987 fromerythropoietin-producing liver cancer
cells 1)
ûA type of receptor-type tyrosine
kinase 2

intracellularû Decreased expression of Ephrin 4)
û Increased expression of some Ephreceptors 4)

extracellularûBoth receptors and ligands arepresent on the cell membrane 2)

Ligand-independent activation of Ephreceptors 4)

Fibronectin typeIII domain
û Expressed in nerve cells, liver, lungs,

etc. in normal tissues 3)

intracellularû Related to adhesion to neighboring
cells, cell proliferation and migration 3)

Increased proliferation, migration, andinvasive functions of cancer cells 4)

intracellular

Kinase domain
1) Hirai, H. et al, Science 1987, 238, 171731720
2) Nicholas, W. G. et al, Cell Tissue Res. 1997, 290, 2273241
3) Miao, H. et al, Int. J. Biochem. Cell Biol. 2009, 41, 7623770

4) Pasquale, E. B. Nat. Rev. Cancer 2010, 10, 1653180

Eph receptor A2 (EphA2) and cancer
Expressed in various solid
tumorsCurrent status of therapeutic drug development targeting EphA2

EphA2 expression levels have been linked tocancer grade and cancer patient survival
Stage III

NormalAntibody(DS-8895a, SHM16)8)

peptide (Ephrin, Ephrin-Fc, BT5528)8)
LBD
Vaccine8)

Copyright protected image

Tumor-Associated Antigen CAR-T cells8)

Stage IV

Stage I

Copyright protected image

Fibronectin typeIII domain

Comparison of EphA2 expression innormal human brain and astrocytoma 6)

EphA2 Low
Cancer cell line encyclopedia{³u¼vt»|³}Þ{zq»EphA2~~ÿßÿ5)

Kinase domain

Copyright protected image

EphA2 High5) Giordano, G. et al, Cells 2021, 10, 2893
6) Zelinski, D. P. et al, Cancer Res. 2001, 61, 230132306
7) Nikas, I. et al, Diagnostics 2022, 12, 366

Breast Cancer
PatientsEphA2 expression
level and survival 7)

Small molecules(Dasatinib, ALW-II-41-27, MEDI-547)8)
11) Xiao, T. et al, J. Hematol. Oncol. 2020, 13, 113

100

Confirmation of EphA2 expression in cancer cells

Development Strategy for Imaging Probes Targeting EphA2
peptides(BCY6164)9)LBD

Antibody(DS-8895a, 1C1)10,11)

MDA-MB-231
U87MG
HT1080ÿ glioma ĀÿsarcomaĀÿbreast cancerĀ
EphA2 (130 kDa)

ø Antibody and peptide
imaging probes do not
perform well enough³-actin (42 kDa)
EphA2/³-actin

Fibronectin type III
domain

Tumor

1.15

1.30

0.94

U87MG

HT1080

MDA-MB-231

0.89

1.02

0.82

EphA2 (130 kDa)³-actin (42 kDa)

Novel imaging probes
targeting EphA2 need to
be developed

Kinase domain

EphA2/³-actin

9) Mudd, G. E. et al, .J. Med. Chem. 2020. 63, 410734116
10) Cai, W. et al, J. Nucl. Med. Mol. Imaging 2007, 34, 202432036
11) Burvenich, I. J. G. et al, J. Nucl. Med. 2016, 57, 9743980

Research Outline

BnDTPA-EphA2-230-1
0.1 M MES buffer pH=5.5
InCl3
20-25 °C 11 h
natIn-BnDTPA-EphA2-230-1

EphA2-230-1
0.1 M NaHCO3 pH=9.5
20-25 °C 124 h

BnDTPA
H2N
S

O

HO

OH
N

N

N

HO

H2N
S

O
O

O
HO

OH

H2N

S

H2N

N
H

H2N
S

N
H

N
H

N
H

NH2

Radioactive nuclide for SPECT
Half-life : 2.805 day
111In

N
H

BnDTPA-EphA2-230-1

S
N
H

N
H

N
H

PD-10 column

BnDTPAEphA2-230-1

DTPA

H2N

S
N
H

BnDTPA-EphA2-230-1

NH2

N
H

EphA2-230-1

DTPA

N
H

EphA2-230-1

MALDI-TOF-MS(microflex®)

S

NH2

N
H

Cell-Binding Study
Biodistribution study

SPECT/CT imaging

000

1600001.5

113.4 DTPAs was introduced per EphA2-230-1.

In introduction rate :96.2%

Radiolabeling
EphA2-230-1
0.1 M NaHCO3 pH=9.5
BnDTPA
20-25 °C 124 h

U87MG (1×105 cell)+

BnDTPA-EphA2-230-1

Sample (1.6-100 ¿g/mL)

Autoradiography

MALDI-TOF-MS
BnDTPA-EphA2-230-1

2% Fatal Bovine Serum (FBS)
Phosphate-Buffered Saline
60 min, 4 °C

EphA2-230-1

MALDI-TOF-MS(microflex®)

Phycoerythrin-conjugatedgoat anti-mouse IgG
secondary antibody

154670.711
154670.711

147432.740

Mobile phase:
MES buffer
saturated with
EDTA

000

101

Autoradiography(amersham Typhoon)
TLC:
Aluminum
silica-TLC

Matrix :3,5-Dimethoxy4-hydrocinnamicacid

BnDTPA- and natIn-BnDTPAEphA2-230-1 retained sufficientbinding to EphA2.

BnDTPA-EphA2-230-1
0.1 M MES buffer pH=5.5
20-25 °C 11 h
[111In]In-BnDTPA-EphA2-230-1[111In]InCl3

Ultrafiltration

PD-10 columnûEphA2-230-1ûBnDTPA-EphA2-230-1ûnatIn-BnDTPA-EphA2-230-1

FACSCaliber

0.0

Theoretical value of In concentration ÿ
1.56 ng/mL

Binding Affinity for EphA2

2% FBS
Phosphate-Buffered Saline
30 min, 4 °C

In concentration(ng/mL)
0.0

EphA2-230-1
BnDTPA-EphA2230-1
natIn-BnDTPAEphA2-230-1

147432.740

Matrix:
3,5-Dimethoxy4-hydrocinnamic
acid

N
H

H2N

N
H

ICP-MS (Agilent 7700X/Mass Hunter)

154670.711
154670.711

Sample[111In]In-BnDTPA-

S
N
H

Ultrafiltration
ICP-MS analysis

MALDI-TOF-MS analysis

Indium-111

H2N

NH2

Monoclonal antibody(EphA2-230-1)

N
H

N
H

S-2-(4-Isothiocyanatobenzyl)diethylenetriamine
pentaacetic acid (BnDTPA)

SN
H}Þ1ëZ²ûò¸ýüø
³
òñß1ÿÿ³
îÙ
³
öýó½óÀ
³
Nk÷_ßß
÷EphA2÷_EphA2 (D4A2) XP®
Rabbit mAb
÷³²¿ñó÷_³-Actin (13E5) Rabbit mAb
4°C, overnight³
Îk÷_ßß
goat anti-rabbit-IgG H&L (HRP)(ab6721)RT, 1 h³
îßBnDTPA Conjugates with the Antibody

NCSO

Western blot
procedure

Cell

Paper
LBDÿ29,10)
Fibronectin type III ÿ111)

160000

1

Radio-TLC
111In-EDTA[111In]InBnDTPAEphA2-230-1[111In]In-BnDTPA-EphA2-230-1
Radiochemical yield ÿ85.1% (n=2)
Radiochemical purity ÿ98.5%

Cell-Binding Study (U87MG cell)

Cell-Binding Study (U87MG cell)

5 min shake

1, 2, 4, 24 h

10 minUptake

BCA assay andmeasure radioactivity

Internalization

FBS free medium +[111In]In-BnDTPA-EphA2-230-1(3.7 kBq)
1, 2, 4, 24 h

10 minRemovemedium

25

0.1 M
NaOH

Wash (0.2 M
CH3COOH,
0.5 M NaCl)

5 min
shake
BCA assay andmeasure radioactivity

FBS freemediumBlocking

FBS free medium +[111In]In-BnDTPA-EphA2-230-1(3.7 kBq)

Removemedium

0.1 M
NaOH

FBS free medium +EphA2-230-1 (12.5 ¿g/mL)+[111In]In-BnDTPA-EphA2-230-1(3.7 kBq)

Removemediumblocking

15
10

0
0

BCA assay andmeasure radioactivity
FBS free medium+
EphA2-230-1(12.5 ¿g/mL)internalization

5

5 min
shake

1, 2, 4 h

10 minuptake20
CUR%/mg protein

FBS freemedium

5

10

15

20

25

Time (h)

0.1 M
NaOH

[111In]In-BnDTPA-EphA2-230-1 was shown to be taken up into U87MG cells in a timedependent manner. On the other hand, [111In]In-BnDTPA-EphA2-230-1 was barely taken up
into the cells in the blocking group at 4 h. This cold-target inhibition assay demonstrates thatthe cellular uptake of [111In] In-BnDTPA-EphA2-230-1 is mediated by EphA2 but not bynonspecific endocytosis in U87MG cells.

Biodistribution of [111In]In-BnDTPA-EphA2-230-1

SPECT/CT ([111In]In-BnDTPA-EphA2-230-1)[111In]In-BnDTPA-EphA2-230-1ûCellÿU87MGûDose : 37 kBq / 100 µL

Time Course
Intravenous administration of[111In]In-BnDTPA-EphA2-230-1(7.2 MBq)

T/B

SPECT:³-CUBE CT: X-CUBE
ÿMolecubes companyĀ

Cell:U87MG (Human Glioblastoma)
Animal:BALB/c nu/nu mouse (male)
10 weeks 24.5 g
Acquisition parameters for SPECT

Time (hour) 0

CT (5 min)
3D image

Anesthetized (isoflurane: 2.5%)
SPECT (60 min)
72 h

73 h
Slice image

ïCollimator: GP mouse collimatorï Injected radioactivity :7.2 MBq/100 µL
ï Acquisition :72 hour after injection of[111In]In-BnDTPA-EphA2-230-1
ï Acquisition time : 60 min
ï Reconstruction: 3D-MLEM

Acquisition parameters for X-ray CT
ï Tube voltage: 50 kVHigh uptake of [111In]In-BnDTPA-EphA2-230-1 in the tumor was confirmed andcontinued to increase for 72 h.

ï Tube current: 100 ¿A
ï Reconstruction: ISRA

[177Lu]Ln-BnNOTA-mAb

SPECT imaging :[177Lu]Ln2O3

microtube± 0.3M AcONa

30 µL± NOTA-mAb

25 ¿L (50 µg)± 177LuCl330 ¿L (10 MBq)

<40#, 1hr>
Autoradiography(amersham Typhoon)

Radio-TLC
177Lu-EDTA[177Ln]LnBnNOTA-ÿAb

Radiochemical yield ÿ88%
Introduction rate of NOTA :ÿ~ÿ

NOTA:
ÿ~Ā

The implanted U87MG tumors in the right limbs
were clearly visualized

NOTA:
Ā~ā

102

Question and answer session
Q: Am I correct in understanding that as long as lutetium does not interfere?
A: Yes. But in fact this is labeled because of the number of introductions.

Q: Do you know what causes the slightly lower uptake of indium DTPA?
A: Maybe in this case, the number of indium DTPA is a little high, 13.

Q: When using lutetium, wasn’t it DTPA?
A: NOTA.

Q: If we change to NOTA, does the aﬃnity still decrease if the introduction rate of that is
high?
A: Even with a similar number of installations, NOTA is more compact and has a higher
aﬃnity.

Q: I would like to ask one question from the medical ﬁeld. Is it possible to make a labeledformulation of gallium-68 instead of indium?
A: Yes. It looks like the formulation is ready. What about zirconium?
A: Zirconium is labeled with deﬁlostamine, so it is ready.

Q: If there seems to be a demand for upgrading with a complexing agent (chelating agent), I
would like to try a little.
A: Various ligands are being developed overseas. I would be very interested in any joint
research with you.

103

M. Suzuki（KURNS, Kyoto Univ.）

2.24

Quantum Beam Bio-Systems Analysis and Application Unit

Quantum Beam Bio-Systems
Analysis and Application
Unit

e

中性子

f

捕獲

反応
ガンマ線放出ÿガùúニウðĀ

中性子

陽子放出

Minoru Suzuki1 Yusuke Wada 1,2, Takushi Takata1

ÿ窒素Ā

1 Particle Radiation Oncology Research Center

原子核

Institute for Integrated Radiation and Nuclear Science, Kyoto
University
2 Veterinary Medical Center, School of Veterinary Science, Osaka
Metropolitan University,

X

原子核 X＋１
ÿエネû¾ーが高くzるĀヘúウð原子核ÿ²ûフ±粒子Ā
放出
ÿホウ素Ā

d

ホウ素 中性子 捕獲 反応e

中性子

ホウ素中性子捕捉療法f

中性子ヘúウð原子核ÿ²ûフ±粒
子Ā

が³}胞

癌}胞選択
重粒子線
治療

9 マイ¿ロñーター

ホウ素

正常}胞

4 マイ¿ロñーター

úチウð原子核

10 マイ¿ロñーター

4

世界初~悪性胸膜中皮腫へ~BNCTa)b)

Suzuki M, et al.
Radiother Oncol. 2008;88:192-195.

104

W学療法不応~多発肝転移症例➢BNCT_ß~CT画像b)a) Before BNCT

1 month after BNCT

京都大学複合原子力科学研究所û研究炉ÿKURĀ~症例ÿ癌腫、症例数一覧Ā

➢肝逸脱酵素ÿAST, ALTĀ~遷移250

72回ÿ約13%)~BNCT
脳、頭頸部、皮膚腫瘍
以外~疾患

AST
ALT

200
150

100
50

c)

Upper Limitof Normal

0

4.5 month after BNCT

-40 -30 -20 -10 0 10 20 30 40 50 60
Days from BNCT

BNCT医療機関{バøンタッチ
加

原子炉
大発研究~
社会実Í

600例~é床症例

器+

関西BNCT共同利用
センタü

南東XBNCT研究
センタüToday’s topics
Basic research for theapplication of BNCTin the veterinary field

1. Introduction
・Concept of <One Health= in BNCT research・Clinical veterinary BNCT using a reactor andan accelerator.

Minoru Suzuki1 Yusuke Wada 1,2, Takushi Takata1

2. Basic researches for the application of BNCTin the veterinary field

1 Particle Radiation Oncology Research Center

Institute for Integrated Radiation and Nuclear Science, Kyoto University
2 Veterinary Medical Center, School of Veterinary Science, Osaka Metropolitan University,

105

Background
Veterinary Medical Center (VMC)
at Osaka Metropolitan University(OMU)

Background

Institute for Integrated Radiation and
Nuclear Science ,Kyoto University(KURUNS)

If a branch BNCT clinic (OMU) is settled at KURNS, BNCT forcompanion animals must be performed under the low (Veterinary
Practice Act).

15 minutes
by car

C-BENS
NeuCure�㰬

C-BENS
NeuCure�㰬Collaborative research agreement has been signed.

106What is One Health？

Collaborative, multisectional, andtransdisciplinary approach in BNCTOne Health Basics | One Health | CDC

One Health is a collaborative, multisectional, and transdisciplinary
approach — working at the local, regional, national, and global levels— with the goal of achieving optimal health outcomes recognizing
the interconnection between people, animals, plants, and their sharedenvironment.

Radiation
biology

Effect of BNCT on
normal tissues

One Health

Human
BNCT

癌愛玩 物
Veterinary
BNCT

BNCT for all the tumor
developed in companion animals.
such as multiple liver or lung tumors.

Due to the commonality of human and animal diseases,
collaboration between medicine and veterinary medicine will
improve the health of both.

BNCT for the shallow-seated tumors.

MedicalPhysics/
Accelerator
Engineering

Chemistry /Pharmacy

VET-BNCT-1

VET-BNCT-3

VET-BNCT-2

2020
2004
2009

・Oral malignant melanomaÿn = 33Ā
・Osteosarcoma in extremitiesÿn = 9Ā

SCC (Cats) (n = 3)
10B concentration ratio
Tumor/Blood
Case 1: 2.7Case 2: 4.3Case 3: 2.3, 2.6

Copyright protected image

・Oral malignant melanoma ÿn = 2Ā・Intranasal tumor ÿn = 3Ā
BPA : 350 mg/kg IV
Reactor
Dose：30–52 Gy-Eq / 2 Fr, q3–5 weeks

BPA 300 mg/kg IV or 157Gd intratumorally
Reactor
Thermal neutron fluence：2.97×1012/cm2

17 days

2 weeks

Neutron aloneÿn = 5Ā
BNCT (n = 14)
GdNCT (n = 14)

Copyright protected image%*Measurement at 3 hours after
Response: 3 SD
Reactorthe administration of
Thermal neutron fluence：1.8×1011/cm2 Toxicity: none
BPA (300 mg/kg IV)
Survival: 5 mo, 2.5 mo, 9.5 moÿgamma-ray：0.28±0.06 GyĀ
Rao M, et al. Appl Radiat Isot 2004;61:947–952.

VET-BNCT-4

100
80
60
40
20
0

Respons rate of malignant
melanoama

Copyright protected image

Copyright protected image
Neutron

BNCT
CR

PR

Response: 5 PR
Toxicity:
mild-moderate mucositis

GdNCT
SD

Mitin VN, et al. Appl Radiat Isot 2009;67:S299–S301.

Schwint AE, et al. Biology. 2020;9:327.

Today’s topics

2022

Copyright protected image

No.

転帰

1

SD

2

PR

3

SD

4

SD

5

SD

BSH 100 mg/kg IV

6

PR

Accelerator

7

PR

Thermal neutron fluence

8SD

1.21–2.60×1014/cm2
Tumor： 39.5–51.0 Gy-eq
Skin： 13.3–19.3 Gy-eq

9

PR？

10

Dye at a few hours
after BNCT

1. Introduction
・Concept of <One Health= in BNCT research・Clinical veterinary BNCT using a reactor andan accelerator.

2. Basic researches for the application of BNCTin the veterinary fieldKanygin V, et al. Biology. 2020;11:138.

107

Question and answer session
Q: What are the common boron chemicals used overseas?
A: BPA is mainly used. Another boron scrubber called BSH is also used.

Q: How many pets are required?
A: We don’t have an absolute number. The University’s Veterinary Clinical Center is promoting the same, rather precise, radioactive treatment as for people.

Q: How can phosphorus 32 be produced?
A: Probably because the whole body was irradiated this time, so there is phosphorus in thefeces in the abdomen, which is then radiolabeled.

Q: The whole body was irradiated this time, so such results were obtained. If the irradiation
were limited to the head and neck, would the amount of phosphorus-32 emitted be less?
A: That is correct.

108

2.25

T. Suzuki（Nagaoka Univ. Tech.）
Dissolution of Thorium Oxide and Separation of Radium

現検討しvい»内容

酸化øú¶ム~溶解xùジ¶ム分離

e照射

Ac-225:

Dissolution of Thorium Oxide andSeparation of Radium

4.0min. 62.7min.

14.9d

5.75y
d抽û

7.34×103yf分離Th-decay series
232Th → 228Ra → 228Ac → 228Th→ 224Ra → 220Rn → 216Po → 212Pb

鈴木達也1 尹鳳1麻卓然
長岡技Û科学大学

gジ·ネüータ希_Þ残渣等{含~¼»
Th系列~Ra-228を分離し1og子を照射し1
Ac-225を生rす»ジ·ネüータxす»2

福谷 哲1外山真理1田端千紘1山村朝雄
京都大学複合科学研究所
1

2

研究計画
Th化合物溶解ûRa-228抽出

化学転換{¸»溶解法

・úーティング法{¸»抽û・化学転換法{¸»溶解・ピýúùン樹脂等吸wvを用いた分離・沈殿法等{¸»分離Generation of
ThaXb+ThaObXc+etc
X: halogen ion
Add Halide

中性子照射用タüゲット作製

中性子照射û照射後分離試験

10.0d

228Ra(n,γ) 229Ra → 229Ac → 229Th → 225Ra → 225Ac

・og子断面積~小さい母体をcsた
化学的{安定且t照射後分離~容易z元素w構rさ¼»
ターゲッø~開発

Heating

HalideThO2

・Ra-228~照射挙動~確認
・照射したターゲッø{¹~Th-229~抽û分離
・Thを吸wさせ1Ac~を分離す»吸wv
ÿジ·ネüータĀ~開発

ThO2

Reaction of ThO2
with Halides
Halides: (CCl3)2 ,CBr4, AlCl3, etc.

ThaXb
Dissolve in 30mlof conc. HClor conc. HNO3

î和4~þ～6~þ~w{実施予定î和4~þ～6~þ~w{予算確保z¸び
準備|w}¼実施したい2

溶解試験

CCl4, C2Cl4

3

CeO2 を用いた予備実験

溶解試験(CCl3)2 , CBr4

4

ThO2 を用いた予備実験

化学変換{適当zハýゲン化物z¸び条件を探»2 CCl4比較~ため
実施2

塩酸w溶{した場合x
硝酸w溶{した場合
塩酸~方|溶解率|高い傾向|あ»2
温þ溶解f間x~
相間|認め¹¼»2

実験条件:
温þ 300 ℃
加ñf間 4h
塩酸w溶{した場合x
硝酸w溶{した場合
塩酸~方|溶解率|高い傾向|あ»2

CCl3CCl3 や CBr4 が
有効

5

6

109

ピýúùン樹脂を用いた核種吸w特g
CH2CH CH2CH CH2CH2 CH CH2

ピýúùン樹脂

103

U(VI) in HCl

O
Kd / mL/g

N

10

10

2

U(VI) in HNO 3

1

Th(IV) in HNO 3
0

2

4

6

[Acid] /M

20%架橋þ~ピýúùン樹脂を用いた
吸w挙動2
7

110

Question and answer session
Q: ThO2 is applied with hydroﬂuoric acid and nitric hydroﬂuoric acid, and radium ions are
separated by ion exchange. Do you want to develop a new method?
A: Actually, we would like to separate them in one shot by precipitation method.

Q: If we use an aluminum compound as a source of halogen, won’t aluminum do somethingbad?
A: Aluminum is not adsorbed, so separation is easy.

Q: Regarding thorium adsorption, why is there such a diﬀerence between hydrochloric acidand nitric acid?
A: It is the nature of actinides that nitric acid complexes well with tetravalent actinides, buthydrochloric acid does not.

Q: When adsorbing on pyrrolidone, what form does the actinide take?
A: This is the O of pyrrolidone.

Q: Is it the O in pyrrolidone and its interaction with nitric acid?
A: In the case of nitric acid, the nitric acid is complexed with thorium, and the whole thing
becomes neutralized.

Q: Neutron irradiation of thorium 228 in a very long chain starting with thorium 232 will givethorium 229 in the (n, γ) reaction. What is the yield of thorium-229?
A: I think this is quite low.

Q: I am looking for data on the cross section of radium-228, but I can’t ﬁnd it.
A: I believe Nuclide Karte has a cross section for radium-228. It is not entirely absent. There
was only one point.

111

Chapter 3

Y. Haga（ASRC, JAEA）
Concluding Remarks112• 基礎研究：アクチノイド、ランタノイド、超アクチノイド• RI製造と応用• 環境・安全・デブリ
KUR シャットダウン

Concluding remarkson

ホットラボ拡充福井研究炉

Users meeting on Condensed-matter Chemistryin Actinides and their Applications /Production of medical RIs by Reactor Irradiation

教育・人材育成

Yoshinori Haga (JAEA)• 基礎研究：アクチノイド、ランタノイド、超アクチノイド
異分野（？）との交流・新たな視点• RI製造と応用

大阪大学の取り組み

アメリカの状況（国立研究所、大学、民間）• 環境・安全・デブリ

計算科学の活用、実用化

研究コミュニティの形成へ—研究資金獲得
京都大学・文科省
科研費（学術変革領域等）

多分野をつなぐ共通概念を柱にハイブリッド会議の有効活用！

113

Q: I would like to ask a question on my part. I would like to talk about the previous slide interms of a common concept to connect communities and other ﬁelds as a pillar. I showed you theconcept at the time of the foundation S by Prof. Noriaki Sato at Tohoku University, centering on
the alpha radiator laboratory, in my ﬁrst talk yesterday, where chemistry and physics are in thatintermediate region between 4f localization and d itinerancy in terms of the speed of valence
ﬂuctuation of the 5f electron, both in physics and chemistry, It was a common understanding that
it was very interesting, and it all came from there. There was J-Physics in the ﬁeld of condensed
matter physics.
A: It is over, but its successor will start this year. It will probably be a little diﬀerent.

Q: J-Physics must have some kind of interdisciplinarity, but what is the central concept thatconnects the two? If there are two J-Physics programs, what is the central concept of each?
A: First of all, J-Physics is f-orbital. f-orbital is the orbital nuclear momentum (SP1/2), whichis called freedom, and the total angular momentum J is the J in J-Physics, and we are trying
to investigate how the degree of freedom is reﬂected in physical properties, both in discussions
and experiments. The keywords are the orbitals and charge distribution, and there was a trend to
expand the charge distribution by multipoles and organize it. In the upcoming J-Physics project,
the idea of extending this idea to include not only one atom but also other atoms in the charge
distribution by using extended multipoles was proposed and established theoretically. It is likescaling it up to make it with real materials this time, and is an area where material explorationis very much in the spotlight.

Thank you very much.

We have been allowed to proceed in the form of the fourth time so far. It is still necessary
to think about how we are thinking about something that connects all of you, like an adhesive.
First of all, we are all connected through the use of this facility at Kyoto University, so even if
there is talk of a shutdown in the future, we need to think in such a way that we can be connected
within that context, and since we are now considering new facilities such as a hot laboratory,114

we need to consider such things to some extent. We would be very happy if we could create aplace where everyone can interact with each other while considering such a possibility to someextent. I hope that you will actively participate in the conference.
Thank you very much for your very useful reports and discussions during the two long days.
Thank you very much. Thank you very much. I would like to ﬁnd some kind of group, somekind of concept that can be connected, including the things you just mentioned. Also, I hope wecan create a ripple eﬀect.

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Chapter 4

Summary of Discussion

Active discussions were held on the fundamentals and applications of actinide property
chemistry. The interests and issues raised by the speakers can be found in their respective
presentation materials. The community of basic actinide science (physics, chemistry, medical
science, materials science, etc.) is small. In contrast, this ﬁeld becomes more important as many
new subjects appear, presented in this workshop. Considering the current situation, it is quite
important to promote the collaborations between actinide researchers of diﬀerent ﬁelds over theworld.
The importance of the emerging young researcher who can act as an intermediary between
basic research and nuclear engineering was strongly pointed out. For the purpose, the organization of a new international collaboration system for wide actinide research by the young
researchers was mentioned of.
Concluding remark was also given from the theoretical side. Key points in this meeting are(1) 5f electrons in actinides and (2) basic character of 5f electrons. The latter include actinide
contraction, relativistic eﬀect, and occupation number and valence (common in physics andchemistry) electron conﬁguration.

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Chapter 5

List of Participants

The following people participated in the meeting. Thank you very much.
Participantsaﬃliations

Kenji Shirasaki
Dexin Li
Hiroki Shishido
KohshinWashiyama
Masahiko Nakase
Tatsuya Suzuki
Koki Yamamoto
Minoru Suzuki
Tomoo Yamamura
Masaaki Sugiyama
Tsuyoshi Misawa
Yoshinori Sakurai
Koichi Takamiya
Mari Toyama
Nobuhiro Sato
Natsuko Kondo
Toshimasa Yoshiie
Hisao Yoshinaga
Miki Tanihira
Tsubasa Watanabe
Yuji Kawabata
Yasuko Marui
Toshiharu
Takahashi
Yuji Nakamoto
Yoichi Shimizu
Takumi Saito
Kenji Ishida
Takashi Yoshimura

IMR, Tohoku University
Institute for Materials Research Actinide Materials Science, Tohoku University
Tohoku University
Advanced Clinical Research Center, Fukushima Global Medical Science Center, Fukushima Medical University
Tokyo Institute of Technology
Nagaoka University of Technology
Kyoto University
Institute for Integrated Radiation and Nuclear Science, Kyoto University
Institute for Integrated Radiation and Nuclear Science, Kyoto University
Institute for Integrated Radiation and Nuclear Science, Kyoto University
Institute for Integrated Radiation and Nuclear Science, Kyoto University
Institute for Integrated Radiation and Nuclear Science, Kyoto University
KURNS, Kyoto Univ.
Institute for Integrated Radiation and Nuclear Science, Kyoto University
Institute for Integrated Radiation and Nuclear Science, Kyoto University
Institute for Integrated Radiation and Nuclear Science, Kyoto University
Institute for Integrated Radiation and Nuclear Science, Kyoto University
Institute for Integrated Radiation and Nuclear Science, Kyoto University
Institute for Integrated Radiation and Nuclear Science, Kyoto University
Institute for Integrated Radiation and Nuclear Science, Kyoto University
Institute for Integrated Radiation and Nuclear Science, Kyoto University
Institute for Integrated Radiation and Nuclear Science, Kyoto University
Institute for Integrated Radiation and Nuclear Science, Kyoto University

Yoshitaka
Kasamatsu
Takamitsu Fukuda
Minori Abe
Takafumi Kitazawa
Masanobu Nogami
Hidetaka Nakai
Yoshinori Haga
Tohru Kobayashi
Kenji Yoshii
Sho Tokunaga

Kyoto University
Radiology and Nuclear MedicineService, Hospital, Kyoto University
Kyoto University
Kyoto University
Radioisotope Research Center, Institute for Radiation Sciences, Osaka University
Graduate School of Science, Osaka University
Graduate School of Science Department of Chemistry, Osaka University
Hiroshima University
Department of Chemistry, Faculty of Science, Toho University
Kindai University
Kindai University
Advanced Science Research Center, Japan Atomic Energy Agency
Actinide chemistry group, Materials Sciences research center, Japan Atomic
Energy Agency
Japan Atomic Energy Agency
Japan Atomic Energy Agency

117

Participantsaﬃliations

Kazufumi
Tsujimoto
Tsuyoshi Yaita
Yuma Sekiguchi
Takahito Watanabe
Mizuho Maeda
Takahiro Sasaki
Taisuke Tsukamoto
Takashi Shimada
Hiroyuki Kimura
Rob HallFukasawa Tetsuo
Toro Gonzalez
Laetitia H. Delmau
Julie G. Ezold
Greg Piefer
Hiroshi Yamagami
Ayumi Ishii

Japan Atomic Energy Agency
Japan Atomic Energy Agency
Central Research Institute of Electric Power Industry
Hitachi, Ltd.
Hitachi, Ltd.
Hitachi, Ltd.
Mitsubishi Heavy Industries, Ltd.
Kyoto Pharmaceutical University
MURR, Missouri University
NFD
Oak Ridge National Laboratory
Oak Ridge National Laboratory
Oak Ridge National Laboratory
SHINE Technologies, Inc.
Kyoto Sangyo University
Teikyo University of Science118

Chapter 6

Photos of the workshop

Photos of the lectures are shown in the order of the program.

Fig. 6.1: Tomoo Yamamura, KURNS, Fig.
6.2: Hiroshi Yamagami, Kyoto
Kyoto Univ.
Sangyo University

Fig. 6.3: Yoshinori Haga, Advanced SciFig. 6.4: Masahiko Nakase, Tokyo Instience Research Center, Japan Atomic Entute of Technology
ergy Agency

119

Fig. 6.5: Ayumi Ishii, Teikyo University Fig. 6.6: Masanobu Nogami, Kindai Uniof Science
versityFig. 6.8: Tohru Kobayashi, Actinide chemFig. 6.7: Kenji Shirasaki, IMR, Tohoku
istry group, Materials Sciences research
University
center, Japan Atomic Energy Agency

Fig. 6.10: Takashi Yoshimura, RadioisoFig. 6.9: Yoshitaka Kasamatsu, Graduate
tope Research Center, Institute for RadiaSchool of Science, Osaka University
tion Sciences, Osaka University120

Fig. 6.11: Yoshinori Sakurai, KURNS, Fig. 6.12: Hisao Yoshinaga, KURNS,
Kyoto Univ.
Kyoto Univ.

Fig. 6.13: Greg Piefer, SHINE Technolo- Fig. 6.14: Laetitia H. Delmau, Oak Ridgegies, Inc.
National Laboratory

Fig. 6.15: Rob Hall, MURR, Missouri Fig. 6.16: Toro Gonzalez, Oak Ridge
University
National Laboratory

121Fig. 6.17: Julie G. Ezold, Oak Ridge
Fig. 6.18: Kenji Ishida, Kyoto University
National Laboratory

Fig. 6.19: Hiroki Shishido, Tohoku Uni- Fig. 6.20: Minori Abe, Hiroshima Univerversity
sity

122

Fig. 6.21: Hiroyuki Kimura, Kyoto Pharmaceutical University

Fig. 6.22: Minoru Suzuki, KURNS, Kyoto
Univ.

Fig. 6.23: Tatsuya Suzuki, Nagaoka University of Technology

123