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The 7th Japan-Taiwan joint meetingon neutron and X-ray scattering

Proceedings

March 11th ~ 12th, 2016

Edited by the organizing committee of The 7th Japan-Taiwan Joint meetingon neutron and X-ray scattering

Research Reactor Institute, Kyoto University

Preface
It is my honour to hold The 7th Japan-Taiwan joint meeting on neutron and X-ray scatteringin Kumatori. The Japan-Taiwan joint meeting on neutron and X-ray scattering has been heldbilaterally in Japan and Taiwan. In these meetings, we discuss the synchrotron X-ray and neutron
scattering studies on bio-materials, soft-materials and nano-materials, and in addition we also
discussed collaboration between Taiwan and Japan based on the synchrotron X-ray facility in
Hsinchu, Taiwan and the neutron scattering facilities as well as the synchrotron facilities in Japan.
The progress of this meeting is briefly followed. The 1st meeting was held at Tokai, Japan in
December, 2006, the 2nd meeting was held at Wulai, Taiwan in December, 2007, the 3rd meeting
was held at Kyoto, Japan in December, 2008, the 4th meeting was held at Yilan, Taiwan in March,
2010, the 5th meeting held at Tokai, Japan in February, 2013, the 6th meeting was held at Taipei,
Taiwan in March, 2014, and the 7th this meeting is held at Kumatori, Japan in March, 2016.
This meeting will provide the recent outstanding results in the fields of fundamental
polymer and biological sciences and their applications as well. In the fields of the X-ray and/or
neutron scattering, the methodological progress expands the research fields and gives us newscientific insights. This meeting invites the researchers developing new methodologies, such as
dynamics measurement utilizing nuclear Bragg resonance, subunit-kinetics measurement with
deuteration-assisted small-angle neutron scattering and so on. I am anticipating that the participants
find new methods to apply their research issues. In addition, neutron can be used not only for aprobe to investigate a material structure but also for the medical purpose. A special lecture of therecent achievement and future perspective of Boron Neutron Capture Therapy will be provided by
Prof. Ono, who is a pioneer of this therapy.
I am expecting that the collaboration between Taiwan and Japan will be enhanced throughthe scientific discussion and also personal understanding in this meeting.
Sincerely,
Masaaki Sugiyama
Chairman, The 7th Japan-Taiwan joint meeting on neutron and X-ray scatteringiPROGRAM
March 11th
9:00-9:25 Reception
9:25-9:35 Opening Remarks

Yuji Kawabata(Director of Research Reactor Institute, Kyoto University)
SESSION 1 Chair: Go Matsuba

9:35-9:55
The change with dispersion of silica in SBR under one-axis elongationby using time resolved USAXS method
Shotaro Nishitsuji (Yamagata University)
9:55-10:20
Phase and crystallization behaviors of copolymer blends withhydrogen-bonding interaction
Chieh-Tsung Lo (National Cheng Kung University)
10:20-10:45
Layer-by-Layer Single Crystals from Self-assembly of
Triple-Crystalline Block Copolymers
Yeo-Wan Chiang (National Sun Yat-Sen University)
SESSION 2 Chair: Chieh-Tsung Lo
11:00-11:25
Formation Mechanism of the Mesoporous Silica SBA-15 Thin Sheetwith Perpendicular Nanochannels
Chung-Yuan Mou (National Taiwan University)
11:25-11:50
Effect of Coherence on Small-Angle Scattering
Yuya Shinohara (University of Tokyo)
11:50-12:15
Dynamics of Glass-Formers Studied byGamma-ray quasi-elastic scattering method
Makina Saito (Kyoto University)
SPECIAL LECTURE Chair: Masaaki Sugiyama
13:30-14:15
Boron Neutron Capture Therapy (BNCT) includingiievery element of the achievements in radiation oncology
since the discovery of X-ray
Koji Ono (Kyoto University)
SESSION 3 Chair: Hideki Seto
14:15-14:40
X-ray reflectivity studies on the mixed thiol capped Au
nanoparticle/lipid monolayers
Tsang-Lang Lin (National Tsing Hua University)
14:40-15:05
Solvated structure and phase behavior of thermo-responsive
polymer in ionic liquid
Mitsuhiro Shibayama (University of Tokyo)
15:05-15:30
Biological Hydrogels Formed by Swollen Multilamellar Liposomes
Shih-Huang Tung (National Taiwan University)
SESSION 4 Chair: Rong-Ming Ho
15:45-16:10
Structural characterization ofpoly(3,4-ethylenedioxy-2,5-thiophene):poly(styrene sulfonate)
dispersions and corresponding spin-cast thin films via small-angle
X-ray scattering
An-Chung Su (National Tsing Hua University)
16:10-16:35
Structural Transitions of BAX after the Apoptotic Activation
Orion Shih (National Synchrotron Radiation Research Center)
16:35-17:00
Surface Characterization of Poly(flruoroalkyl acrylates) by
Surface X-ray Diffraction/Scattering and Neutron Reflectivity
Atsushi Takahara (Kyushu University)
17:00-17:20
Group Photoiii

March 12th
SESSION 5 Chair: Wei-Tsung Chuang
9:00-9:25
SAXS and SANS study on the structural change ofhuman stratum corneum induced by the treatment of
surfactant solution
Takuji Kume (Kao Corporation)
9:25-9:50
Small-angle neutron and X-ray scattering studies on metallocene
EPDM
Kazuki Mita (Mitsui Chemicals, Inc.)
9:50-10:15
Electrochemical Reaction of Carbon Film with Electrolyte Solution as
Studied by Time-slicing Neutron Reflectometry
Masashi Harada (Toyota Central R&D Labs., Inc.)SESSION 6 Chair: Tsang-Lang Lin
10:30-10:55
Fabrication of Perpendicular Nanoporous TiO2 Thin Films throughTemplated Synthesis of Dendron-Jacketed Block Copolymers
Wei-Tsung Chuang (National Synchrotron Radiation Research Center)
10:55-11:20
An Effect of Aggregation States in Nafion Thin Filmson Transport Properties
Daisuke Kawaguchi (Kyushu University)
11:20-11:45
Competition between Entropy and Enthalpy in the Binding of Melittinwith ULV Vesicles of Different Phosphate Lipid Chain Lengths
Chun-Jen Su (National Synchrotron Radiation Research Center)
SESSION 7 Chair: Mikihito Takenaka
13:00-13:25
SAXS combined with crystallography for structural studies onmacromolecular complexes and functional flexibility of protein
Shu-Ying Sherry Wang (National Cheng Kung University)iv

13:25-13:50
Liquid phase networks of conjugated polymers and carbon allotropes
Jrjeng Ruan (National Cheng Kung University)
13:50-14:15
Probing UV-Irradiated and pyrolyzed block copolymer micelles on asolid by grazing incident X-ray
Ya-Sen Sun (National Central University)
SESSION 8 Chair: U-ser Jeng
14:30-14:55
Dynamic quaternary structure of alpha-crystallin
Rintaro Inoue (Kyoto University)
14:55-15:20
The correlation between the mechanics of a lipid membrane and its
cellular functions
Yi-Fan Chen (National Central University)
15:20-15:45
Structural insights into molecular assembly in the proteasomal
systems
Tadashi Sato (Nagoya City University)
SESSION 9 Chair: Mistuhiro Shibayama
16:00-16:25
Current status and results on J-PARC/MLF
Hideki Seto (KEK)
16:25-16:50
Nanostructured Networks in Chiral Block Copolymers
Rong-Ming Ho (National Tsing Hua University)
16:50-17:15
Hierarchical Structure of Polymer/Nanoparticle Hybrid
Hsin-Lung Chen (National Tsing Hua University)
17:15
Closing Remarksv

The change with dispersion of silica in SBR under one-axis
elongation by using time resolved USAXS method
Shotaro Nishitsuji1, Sho Suzuki1 and Mikihito Takenaka2
1

Department of Polymer Science and Engineering, Graduate School of Science and Engineering, Yamagata
University
2
Department of Polymer Chemistry, Graduate School of Engineering, Kyoto University
E-mail: nishitsuji@yz.yamagata-u.ac.jp

Recently, from the viewpoint of the environmental problems and the depletion of fossil fuel resources,
the high performance of tire is required. To achieve more high performance, it is important to investigate therelationship between the dispersion of filler in the rubber/filler system and the improvement of themechanical properties. In the previous studies, the hierarchical structures in the rubber/filler system havebeen investigated by using a combined ultra small scattering and small angle scattering method of neutrons
and X-rays[1,2]. In this study, the change with the dispersion of silica in Styrene-Butadiene Rubber (SBR)
with one-axis elongation by using time resolved ultra small X-ray scattering (USAXS) was investigated.
SBR/Silica systems where the silica contents are 10, 15, 20, 25 vol% is prepared. Added weight fractionof the coupling agent to all the samples is 8 wt% of silica weight. Time resolved USAXS experiment was
conducted at BL19B2, SPring-8, JAPAN.
The scattering pattern at 25 % of silica content
before elongation and after elongation at 200 % asshown in Figure 1. Before elongation, thescattering pattern is isotropic. However, after
elongation, the scattering pattern is anisotropic
and is enhanced along elongation axis. This
indicates the inhomogeneity of the dispersion of
Fig.1 Scattering pattern at 25 % of silica
silica is enhanced along the elongation direction
content (a)before elongation and (b)after
by one-axis elongation. From the analysis byelongation at 200 %.
Unified Guinier/Power-law approach, several
characteristic parameters are estimated quantitatively, such as the size of aggregation and agglomerate,mass-fractal dimension. We will discuss the detail analysis by this approach and the change with thedispersion of silica in SBR quantitatively.
Acknowledgement : The samples in this study were provided from THE YOKOHAMA RUBBER CO.,LTD.

References[1] T. Koga, M. Takenaka, K. Aizawa, M. Nakamura, T. Hashimoto, Langmuir, 21, 11409 (2005).
[2] T. Koga, T. Hashimoto, M. Takenaka, K. Aizawa, N. Amino, M. Nakamura, D. Yamaguchi, S. Koizumi,
Macromolecules, 41, 453 (2008).

1

Name: Shotaro Nishitsuji （西辻 祥太郎）
Title and Affiliation: Assistant Professor, Department of Polymer Science and Engineering,
Graduate School of Science and Engineering, Yamagata University,
E-Mail: nishitsuji@yz.yamagata-u.ac.jp
Research Interests:- Polymer Physics- Small Angle X-ray Scattering- Polymer Blend

2Phase and crystallization behaviors of copolymer blends withhydrogen-bonding interaction
Chieh-Tsung Lo* and Yu-Wen Chen
Department of Chemical Engineering, National Cheng Kung University
E-mail: tsunglo@mail.ncku.edu.tw
We investigated the effect of the hydrogen-bonding interaction on the phase and crystallization behaviors ofbinary copolymer blends. In the blends composed of polystyrene-block-poly(ethylene oxide) (PS-b-PEO)
and polystyrene-block-poly(acrylic acid) (PS-b-PAA) block copolymers, the hydrogen bonding between
PEO and PAA improved the miscibility between the two molecules, which facilitated the localization ofPS-b-PAA at the interface of the PS-b-PEO microdomains. However, the formation of hydrogen bonding
decreased the crystallizable chain length of PEO, resulting in the occurrence of PEO crystallization withinmore confined region. As a result, the crystallization temperature of PEO decreased. By contrast, in theblends containing PS-b-PEO and polystyrene-graft-poly(acrylic acid) (PS-g-PAA) graft copolymer,
PS-g-PAA was sequestered into the PEO domains, which caused swelling and increased the interfacial
curvature that in turn, induced morphological transitions. Additionally, the hydrogen-bonded PEO and PAA
in the PS-b-PEO/PS-g-PAA blends occurred in the middle or the free end of the PEO chains. The packing of
PEO chains during crystallization was restricted by not only the chemically-linked PS-b-PEO interface but
also the hydrogen-bonded PAA. This caused a substantial increase in the surface fold energy of PEO. As aresult, a high degree of supercooling was needed to overcome the increased surface fold energy of PEO andcrystallization occurred at a low temperature.
PS-b-PEO

PS-b-PAA

PS-b-PEO/PS-b-PAA

PS-b-PEO

PS-g-PAA

PS-b-PEO/PS-g-PAA(a)(b)
Figure 1. Schematic illustration of the phase behavior of blends with presence of hydrogen-bonding
interaction. (a) PS-b-PEO/PS-b-PAA and (b) PS-b-PEO/PS-g-PAA.

3

Name: Chieh-Tsung Lo （羅介聰）Title and Affiliation: Professor, National Cheng Kung University
E-Mail: tsunglo@mail.ncku.edu.tw
Research Interests:- Polymer physics- Polymer nanocomposites- Polymer surfaces and interfaces

4Layer-by-Layer Single Crystals from Self-assembly of
Triple-Crystalline Block Copolymers
Yeo-Wan Chiang*, You-Yuan Hu, Jhen-Ning Li, Shih-Hung Huang
Department of Materials and Optoelectronic Science, Center for Nanoscience and Nanotechnology, National
Sun Yat-Sen University, Kaohsiung 80424, Taiwan
E-mail: ywchiang@mail.nsysu.edu.tw

Manipulation of crystalline textures of biocompatible block copolymers is critical for the applications in the
medical field. Here, we present the control of multiple-crystalline morphologies with flat-on chainorientation in biocompatible poly(ethylene oxide)-block-poly(ε-caprolactone)-block-poly(L-lactide)(PEO-PCL-PLLA) triblock copolymer thin films using melt and solvent-induced crystallization.[1] Only
single-crystalline morphologies of the first-crystallized blocks can be obtained in the melt-crystallized thinfilms due to confinement effect. With solvent annealing by PCL-selective toluene, single-crystalline PLLA
to double-crystalline PLLA/PCL and to triple-crystalline PLLA/PCL/PEO layered crystals in sequence areobserved for the first time. With the control of solvent selectivity, different sequential crystallization
involving first-crystallized PCL transferring to double-crystalline PCL/PLLA is obtained using
PEO-selective n-hexanol for annealing. Surprisingly, the crystalline growth of the tri-layered single crystal
exhibits specific layer-by-layer epitaxial relationship. As a result, the multiple-crystalline textures of the
PEO-PCL-PLLA thin films can be carried out by controlling solvent and polymer interaction.

References[1] Y.-W. Chiang,* S.-H. Huang, S.-W. Kuo, Macromolecules, 48, (2015) 8526.

5

Name: Yeo-Wan Chiang （蔣酉旺）Title: Assistant Professor, Department of Materials and Optoelectronic Science, National Sun
Yat-Sen University, Taiwan
E-mail: ywchiang@mail.nsysu.edu.tw
Research Interests:- Self-assembly of Block Copolymers and Supramolecules- Phase Behavior of Crystallizable Block Copolymers- Block Copolymer Photonic Crystals

6Formation Mechanism of the Mesoporous Silica SBA-15 Thin
Sheet with Perpendicular Nanochannels
Yi-Qi Yeh1, U-Ser Jeng1 and Chung-Yuan Mou2
1

2

National Synchrotron Radiation Research Center, Hsinchu 30076, Taiwan
Department of Chemistry, National Taiwan University, Taipei 10617, Taiwan
E-mail: cymou@ntu.edu.tw

Mesoporous silica SBA-15 thin sheets with perpendicular nanochannels, SBA(⊥), was synthesized byusing the ternary surfactant system of SDS (sodium dodecylsulfate) – CTAB (hexyltrimethylammonium
bromide) – P123 (PEO20-PPO70-PEO20).1-4 The SBA( ⊥ ) structural features, 2D hexagonally arrayed
nanochannels, was considered deriving from the nonionic triblock copolymer P123. The SDS-CTAB system
was proposed to function as a bilayer membrane to confine the co-organizing P123 and silicates. With
neutron scattering, P123 displays strong scattering length density (SLD) contrast than deuterated SDS(d-SDS), deuterated CTAB (d-CTAB), and silicates in D2O solvent. In X-ray scattering, silicates exhibits
strong SLD than the surfactants. In this report, we investigated the role of P123 micellization and theco-assembly process of silicate-surfactant system to realize the SBA(⊥) formation mechanism using both
SANS and SAXS.
The charge condensation effect (varing(d-SDA)/P123, Rc: 0~128.75, in SDS-CTAB-P123 surfactant
template) suggested a transformation of P123 micelles from sphere to prolate. An increase in aspect ratio of
prolate micelles with increasing ionic surfactant (d-SDS)/(d-CTAB) concentration until Rc 25.75. With
excess ionic surfactant, the aspect ratio of the prolate would be reduced. The charge optimization effect(varying (d-SDS)/(d-CTAB)), Ro: 1.2 - 2.0, in SDS-CTAB-P123 surfactant template) showed all the micelles
behaved as prolate micelle and the best recipe of Ro=1.5 exhibits the highest aspect ratio ~2.9.
The structural evolution during the co-assembly process of surfactant and silicates revealed threetransitions as following: (1) The surfactant-silicate prolates would align and form lamellae phase between
ionic surfactant bilayers in vesicle. (2) The surfactant-silicate prolates between two vesicles would
polymerize due to hydrogen-binding of silicates. The fluctuation between the bilayer would supposedly
reduce the lamellae ordering. (3) The enlogated surfactant-silicate prolates would transform into well-aligned
cylinders and form 2D hexagonal mesostructured. The TEM results also support the proposed surfactant
template and co-assembly processes.
References[1] B.C. Chen, H.P. Lin, M.C. Chao, C.Y. Mou and C.Y. Tang, Adv Mater. 2014, 16,1657[2] Y-Q. Yeh, H.P. Lin, Langmuir 2006, 22, 6[3] Y-Q. Yeh, C-Y. Tang, and C-Y. Mou, J. Colloid Interface Sci. 2011, 362, 354[4] Y-Q. Yeh, C-Y. Tang, and C-Y. Mou, APL Mater. 2014, 2, 113303

7

Name: Chung-Yuan Mou （牟中原）Title and Affiliation: Chair Professor, Department of Chemistry, National Taiwan University
E-Mail: cymou@ntu.edu.tw
Research Interests:- Catalytic oxidation by gold nanoparticles- Nanoporous nanomaterials as a drug/enzyme delivery carrier in Biomedicine- Studies of supercooled confined water8Effect of Coherence on Small-Angle Scattering
Yuya Shinohara and Yoshiyuki Amemiya
Department of Advanced Materials Science, Graduate School of Frontier Sciences,
The University of Tokyo
E-mail: yuya@k.u-tokyo.ac.jp
Coherence is a fundamental concept for discussing scattering phenomena. Despite its importance, it is mostly
ignored in the textbook of scattering of X-rays and neutron. Recent progress in X-ray brilliance makes it
possible to conduct experiments utilizing coherence of X-rays: coherent diffraction imaging for the
real-space visualization of materials’ structure and X-ray photon correlation spectroscopy for monitoring the
dynamics of nano-scale. In these techniques, the concept of coherence is explicitly utilized.
We have recently realized that the coherence may affect the scattering intensity profiles even when
the incident X-ray is not fully coherent [1]. According to standard textbooks of small-angle scattering,
scattering intensity profiles correspond to the fluctuation part of scattering length density, while a forward
scattering at q = 0 is not explicitly considered, where q is the magnitude of scattering vector. Recent
advances in X-ray brilliance and X-ray optics make it possible to conduct scattering measurement at
ultra-small angles with a small beam size. We have found that the measurement at such a low q leads to asignificant contribution from the forward scattering on the measured scattering intensity profiles. The degreeof contribution depends on the coherent length of incident X-rays, regardless of whether the beam is fully
coherent or not. In this presentation, we will discuss the effect of coherence on small-angle scattering andperspectives on ultra-small-angle scattering.

References[1] Y. Shinohara and Y. Amemiya, J. Appl. Cryst., 48, (2015) 1660-1664.

9Name: Yuya Shinohara （篠原 佑也）
Title and Affiliation: Assistant Professor, Department of Advanced Materials Science, Graduate
School of Frontier Sciences, The University of Tokyo
E-Mail: yuya@k.u-tokyo.ac.jp
Research Interests:- Development of X-ray scattering technique

10

Dynamics of Glass-Formers
quasi-elastic scattering method

StudiedbyGamma-ray

Makina Saito1, Makoto Seto1, Ryo Masuda1, Yasuhiro Kobayashi1, Shinji Kitao1,
Masayuki Kurokuzu1 and Yoshitaka Yoda2
1
2

Research Reactor Institute of Kyoto University
Japan Synchrotron Radiation Research InstituteE-mail: msaito@rri.kyoto-u.ac.jp

When liquids are cooled toward the glass transition temperature avoiding crystallization, the microscopic
relaxation time or viscosity, in some cases, changes more than 10 orders of magnitude in a narrowtemperature range without an apparent structural change. Understanding the mechanism is one of the mostimportant aim of the glass transition study. A relaxation process known as the α process, which is the
structural relaxation process associated with the molecular diffusion, is directly related to the dynamical
behaviour. With cooling the liquid, the other relaxation process emerges as its relaxation time branches fromthe relaxation time of the α process. The process is called the slow β (Johari–Goldstein) process and its
origin is still controversial. The branching process seems to be a key to understand the glass transition andthe molecular dynamics in deeply supercooled liquids.
To examine the decoupling phenomenon from the microscopic point of view, a typical glass formers
o-terphenyl [1] and polybutadiene have been studied [2] by the quasi-elastic scattering measurement known
as a time-domain interferometry (TDI) method using gamma rays from 57Fe nucleus excited by synchrotron
radiation [3]. This method is a time-domain analogue of the conventional Rayleigh scattering Mössbauerradiation method [4]. Generally by a quasi-elastic scattering method, the relaxation time of microscopic
structures with a certain microscopic length scale l~2π/q can be selectively studied, where q is themomentum transfer of the gamma ray to the liquid sample decided by selecting the scattering angle of thedetector. Owing to the atomic wavelength of the 57Fe gamma-ray ~ 0.087 nm (corresponding energy ~ 14.4
keV) and its relatively narrow energy width ~ 4.7 neV, the atomic and molecular dynamics can be studied in
the time range of ns ~ µs. We introduce a new result obtained by the TDI method on the glass formers.

References[1] M. Saito, S. Kitao, Y. Kobayashi, M. Kurokuzu, Y. Yoda and M. Seto, Phys. Rev. Lett., 109, (2012)
115705.
[2] T. Kanaya, R. Inoue, M. Saito, M. Seto, and Y. Yoda, J. Chem. Phys., 140, (2014) 144906.
[3] A. Q. R. Baron, H. Franz, A. Meyer, R. Rüffer, A. I. Chumakov, E. Burkel and W. Petry, Phys. Rev. Lett.,
79, (1997) 2823.
[4] D. C. Champeney and F. W. D. Woodhams, J. Phys. B., 1, 1620 (1968) and references therein.

11

Name: Makina Saito （齋藤 真器名）
Title and Affiliation: Assistant Professor, Research Reactor Institute, Kyoto university
E-Mail: msaito@rri.kyoto-u.ac.jp
Research Interests:- Topic 1 Quasi-elastic scattering- Topic 2 Glass transition phenomenon- Topic 3 Soft matter

12

Boron Neutron Capture Therapy (BNCT) including every	 element of the	 achievements in radiation oncology since thediscovery of X-ray
Koji Ono
Research Reactor Institute, Kyoto University
E-mail:onokoji@rri.kyoto-u.ac.jp
When the history of radiotherapy is traced , the achievements are summarized as below.
1. Focusing of the radiation dose on the tumor definitely increase the cure rate of tumor without increasing
the incidence and grade of adverse effects. The success by brachytherapy, treatment by small radioactive
source, is the solid evidence. This paradigm was also proved by IORT(intraoperative radiotherapy),
stereotactic RT, conformal RT, IMRT(intensity modulated RT), charged heavy particle therapy et al.
2. Physiologically moving organs like as the tongue were also treated successfully by brachytherapy. To
recreate this success in an external RT, the machine of which the X-ray beam can track the moving tumor
in the target organ on respiration, was developed in Japan.
3. High LET radiation is very effective for the tumors which are refractory to X-rays. Carbon ion therapy
was prove to successfully treat the soft tissue tumor or bone sarcomas which are radioresistant to X-rays.
as the tumour cell selective cancer therapy
BNCT includes every element of these achievements. The idea of BNCT was proposed in 1932 based on thefeature of 10B(n,α)7Li reaction. The cross section of this reaction is 2000 times larger than that of 14N(n,p)14C
reaction. Moreover the particles have extremely short ranges which are shorter than the diameter of generalcells, hence, these particles destroy the tumour cells selectively if 10B accumulates in tumour cells selectively.
The particles are also high LET radiation and then have large RBE (relative biological effectiveness). The
first clinical study started in 1951 in US after the 2nd World War because the nuclear reactor was necessary
as a neutron source. Unfortunately this trial failed to indicate the benefit of BNCT. The clinical research was
succeeded by Japanese researchers since 1968. They used better 10B-compound, BSH, and achieved fairly
nice result. It was 1987 when the clinical BNCT changed dramatically. BPA appeared as the clinicallyapplicable 2nd 10B-compound this year. BPA actively accumulates in cancer cells, with that, BNCT has
become cancer selective treatment in true meaning. Development of 18F-BPA PET(positron emission
tomography), proposal of CBE(compound biological effectiveness) factor, success of BNCT for therecurrent H & N cancer, the world's first cyclotron based neutron source for clinical BNCT and start of theclinical test in 2012 were major progresses of BNCT since the appearance of BPA. Many of theseachievements were developed by KURRI researchers and their colleagues.
BNCT seems to be acompleted form of radiotherapy.

13

Name: Koji Ono （小野 公二）
Title and Affiliation: Professor, Research Reactor Institute, Kyoto University
E-Mail: onokoji@rri.kyoto-u.ac.jp
Research Interests:- BNCT- Radiation Oncology- Radiation Biology

14

X-ray Reflectivity Studies on the Mixed Thiol Capped Au
Nanoparticle/Lipid Monolayers
Tsang-Lang Lin1, Han-Shiou Su1, Yi-Tang Chen1, Chin-Hua Hung1,
Yuan Hu1, Ming-Tao Lee2, U-Ser Jeng2
1

Department of Engineering and System Science, National Tsing Hua University, Hsinchu, Taiwan
30013, R.O.C.
2

National Synchrotron Radiation Research Center (NSRRC), Hsinchu, Taiwan, R.O.C.
E-mail: tllin@mx.nthu.edu.tw

The Langmuir-Blodgett films of thiol capped gold nanoparticles mixed with zwitterionic lipid,
dipalmitoylphosphatidylcholine (DPPC), were investigated by X-ray reflectivity, grazing-incident scattering,and transmission electron microscopy (TEM). The synthesized gold nanoparticles have an average diameteraround 2 nm, and the gold nanoparticles were capped with 1-propanethiol, 1-octanethiol and 1-dodecanethiol,
respectively. The monolayers were transferred onto silicon wafers for X-ray analysis and onto copper gridfor TEM analysis.
As revealed by X-ray reflectivity, for the mixed 1-octanethiol capped Au
nanoparticle/DPPC monolayer system, at low compression pressure, the 1-octanethiol capped Au
nanoparticles form a monolayer on top of disordered lipid monolayer. When the surface pressure isincreased, the disordered lipid monolayer becomes ordered and the 1-octanethiol capped Au nanoparticle
monolayer stays on top of it. It is favorable for the hydrophobic thiol capped Au nanoparticles to sit on thehydrophobic lipid tails instead of staying at the water surface. It seems that thiol capped Au nanoparticles
have strong affinity to form large closely packed domains on smooth hydrophobic surface. Since the thiol
capped Au nanoparticles would prefer to stay on top of the lipid monolayer to avoid contacting with water, it
would be difficult to disperse the thiol capped Au nanoparticles into the lipid monolayer. We also
investigated the morphology of these three thiol capped Au nanoparticle monolayers. At compression
pressure of 20 mN/m, the 1-propanethiol capped Au nanoparticles tend to form multiply folded layers as
revealed by TEM, while the 1-dodecanethiol capped Au nanoparticles form monolayers in grains withthread-like thiol-capped Au nanoparticle clusters forming the grain boundaries. It seems that the
1-dodecanethiol capped Au nanoparticle monolayer has better stability again compression as compared withthe 1-propanethiol capped Au nanoparticle monolayer.

15

Name: Tsang-Lang Lin （林滄浪）Title: Professor, National Tsing Hua University
E-Mail: tllin@mx.nthu.edu.tw
Research Interests:- Colloids and interfaces- Nanomaterials and biomaterials- Neutron and X-ray scattering

16

Solvated Structure and Phase Behavior of Thermo-responsive
Polymer in Ionic Liquid
Mitsuhiro Shibayama1, Kazu Hirosawa1, Kenta Fujii2, Takeshi Ueki, 3 Yuzo
Kitazawa,4 Ken Littrell5 and Masayoshi Watanabe4
1Institute for Solid State Physics, The University of Tokyo,
Graduate School of Science and Engineering, Yamaguchi University,
3
Polymer Materials Unit, National Institute for Materials Science,4
Department of Chemistry and Biotechnology, Yokohama National University,
5
Oak Ridge National Laboratory2

E-mail: sibayama@issp.u-tokyo.ac.jp
Ionic liquids (ILs) consist of only ion species, and thus, they have unique solvent property such as high ion
conductivity, electrochemical stability, nonvolatility and nonflammability. In polymer science, thecombination of polymer materials with ILs permits the fabrication of functional soft materials possessing theunique properties of ILs. Recently, stimuli-responsive polymers in ILs have been developed and received agreat deals of attention.1 For example, poly(benzyl methacrylate) (PBnMA) and its derivatives show lower
critical solution temperature (LCST) – type phase separation in hydrophobic IL ([C2mIm+][TFSA-]), andtheir phase-separating temperature (Tc) can be drastically changed by slight chemical modification on theside chain.2 We performed small-angle neutron scattering (SANS) study on one of the PBnMA derivatives,
PPhEtMA (poly(2-phenylethyl methacrylate)) in ionic liquid.
SANS experiments were carried out for PPhEtMA indeuterated ionic liquid, d8-[C2mIm+][TFSA-] at High-Flux
Isotope Reactor in Oak Ridge National Laboratory, USA.
d8-[C2mIm+][TFSA-] was prepared by the procedure wellestablished in our research group. Fig. 1 shows the SANS
profiles obtained for PPhEtMA in d8-[C2mIm+][TFSA-] atvarious temperatures, 288 K – 310 K. As can be seen fromthe figure, steep upturn was observed when temperature
exceeded Tc (~ 309 K in d8-[C2mIm+][TFSA-]), indicating
the appearance of large aggregates in this region. We
evaluated the second virial coefficient, A2 by Zimm plot.
The obtained A2 decreased and changed its sign from
Figure. 1 SANS profiles observed for
positive to negative with increasing temperature. The result
PPhEtMA/
d8-[C2mIm+][TFSA-]
indicated that compatibility of PPhEtMA into
solution at various temperature. The
solid lines shows the fitting results by
d8-[C2mIm+][TFSA-] decrease gradually with increasing
the Debye or Debye + Squared Lorentz
temperature.
functions.

References[1] T. Ueki, Polym. J., 1 (2014). [2] K. Kodama et al., Langmuir, 25, 3820 (2009).

17

Name: Mitsuhiro Shibayama （柴山 充弘）
Title and Affiliation: Professor, The University of Tokyo
E-Mail: sibayama@issp.u-tokyo.ac.jp
Research Interests:- Structure characterization of hydrogels and ionic gels
- Structure of polymer micelles- Molecular dynamics of thermosets

18Biological Hydrogels Formed by Swollen Multilamellar
Liposomes
Chih-Yang Cheng,1 Ting-Yu Wang,2 and Shih-Huang Tung1
1

Institute of Polymer Science and Engineering and 2Instrumentation Center, National Taiwan University,
Taipei, 10617 Taiwan
E-mail: shtung@ntu.edu.tw

The self-assembly of lecithin-bile salt mixtures in solutions has long been an important research
topic, not only because they are both biosurfactants closely relevant to physiological functions but also forthe potential biomedical applications. In this paper, we report an unusual biological hydrogel formed bymixing bile salts and lecithin at low bile salt/lecithin molar ratios (B0) in water. The gel can be prepared at a
total lipid concentration as low as ~ 15 wt% and the solid-like property of the solutions was confirmed bydynamic rheological measurements. We used cryo-TEM and SAXS/SANS techniques to probe theself-assembled structure and clearly evidence that the gel is made up of jammed swollen multilamellar
vesicles (liposomes), instead of typical fibrous networks found in conventional gels. A mechanism based on
the strong repulsion between bilayers due to the incorporation of negatively charged bile salts is proposed to
explain the swelling of the liposomes. In addition to gel, a series of phases, including viscoelastic, gel-like,and low-viscosity fluids, can be created by increasing B0. Such a variety of phase behaviors are caused by thetransformation of bilayers into cylindrical and spheroidal micelles upon the change of the effective moleculargeometry with B0.

References[1] C.-Y. Cheng, T.-Y. Wang, and S.-H. Tung, Langmuir, 31, (2015) 13312-13320.
[2] C.-Y. Cheng, H. Oh, T.-Y. Wang, S. R. Raghavan, and S.-H. Tung, Langmuir, 30, (2014) 10221-10230.

19

Name: Shih-Huang Tung （童世煌）Title and Affiliation: Associate Professor, National Taiwan University
E-Mail: shtung@ntu.edu.tw
Research Interests:- Self-assembly and phase behaviors of block copolymers- Self-Assembly of amphiphilic biomolecules- Rheology of complex fluids

20Structural characterization of poly(3,4-ethylenedioxy-2,5-thio
phene):poly(styrene sulfonate) dispersions and corresponding
spin-cast thin films via small-angle X-ray scattering
Jia-Jhen Kang,1 Hung-Ting Chen,1 Wei-Ru Wu,2 U-Ser Jeng,1,2 and An-Chung Su1
1

2

Department of Chemical Engineering, National Tsing Hua University, Hsinchu 30013, Taiwan
National Synchrotron Radiation Research Center, Hsinchu Science Park, Hsinchu 30076, Taiwan
E-mail: acsu@mx.nthu.edu.tw

Structural features of aqueous poly(3,4-ethylenedioxy-2,5-thiophene):poly(styrene sulfonate)(PEDOT:PSS) dispersions with the PPS-to-PEDOT mass ratio r = 2.5 or 6.0 in the concentration range of
0.2–1.2 wt% were characterized by means of small-angle X-ray scattering (SAXS). Results indicate thatthese dispersions generally comprise prolate nano-ellipsoids (with aspect ratio ν ≈ 5) of aggregated PEDOT
segments encircled by swollen coronae of anchored PSS chains. A major fraction (ϕP ≈ 0.9) of these micelles
are uniformly distributed in the aqueous matrix according to disordered packing of hard spheres. A minor
fraction (ϕF < 0.1) of these micelles loosely inter-connect into domains of fractal dimension DF ≈ 1.9. There
are also a minor fraction (ϕO < 0.1) of micelles with oblate core of ν ≈ 0.6, which corresponding to lateral
agglomerates of the “normal” prolate cores. With increasing polymer concentration, ϕF decreases whereas ϕO
increases, especially for the lower PSS content case of r = 2.5. This trend of agglomeration into oblate
PEDOT cores with increasing polymer concentration extends into spin-cast films, where grazing-incidence
small-angle X-ray scattering (GISAXS) profiles generally indicate interconnected prolate ellipsoids into
fractal domains of DF ≈ 2.5 but more significant presence (ϕO ≈ 0.2‒0.3) of oblate PEDOT-rich domains,
especially for the case of r = 2.5.

21

Name: An-Chung Su （蘇安仲）Title and Affiliation: Professor of Chemical Engineering, National Tsing Hua University
E-Mail: acsu@mx.nthu.edu.tw
Research Interests:- Structure-property relationship in polymeric systems- Semiconducting polymers- Nanomaterials

22Structural Transitions of BAX after the Apoptotic Activation
Orion Shih1, Yi-Qi Yeh1, Tai-Ching Sung2, Yun-Wei Chiang2 and U-Ser Jeng112

National Synchrotron Radiation Research Center, Hsinchu 30076, Taiwan
Department of Chemistry, National Tsing-Hua University, Hsinchu 30013, Taiwan
E-mail: shih.orion@nsrrc.org.tw

In stressed cells, apoptosis ensues when BAX proteins oligomerize and permeabilize the mitochondrial
outer membrane [1]. The mechanism utilized by BAX still remains elusive because BAX changes its
functional structures along the apoptotic signaling pathway from cytosolic monomer, oligomer, tomembrane-associated complex. This polymorphism of BAX poses a great challenge in tracing its structuraltransitions in functioning. Here we use a combination of electron spin resonance (ESR) and small angle
X-ray scattering (SAXS) to study the conformational changes of BAX before and after the apoptotic
activation. Particularly, an on-line HPLC is used to separate the BAX monomers, dimers, and oligomers in
the eluted sample solution along the flow path for in-situ SAXS data collection at the 23A SWAXS
endstation of National Synchrotron Radiation Research Center, Hsinchu, Taiwan [2].
The HPLC elution profile and previous ESR studies [3] indicate that there exist two forms of BAX
monomer, UM and UM’. Upon the engagement of BimBH3, UM and UM’ are transformed into aligand-bound monomer (BM) and a oligomer (O), respectively. We construct the solution structures of BAX
along the oligomerization pathway and show that BAX oligomers are assembled in solution via linear
polymerization-like α6 association. Our results specifically establish oligomerization interfaces andintermediates, which are important structural basis for manipulating BAX activity pharmacologically.

References[1] Antonsson, B., Montessuit, S., Sanchez, B., and Martinou, J. C. J. Biol. Chem. 276, (2001) 11615-11623.
[2] Jeng, U., Su, C., Su, C., Liao, K., Chuang, W., Lai, Y., Chang, J., Chen, Y., Huang, Y., Lee, M., Yu, K.,
Lin, J., Liu, D., Chang, C., Liu, C., Chang, C., and Liang, K. S. J. Appl. Cryst. 43, (2010) 110–121.
[3] Tsai, C., Liu, S., Hung, C., Jhong, S., Sung, T. and Chiang, Y. Structure 23, (2015) 139-148.

23

Name: Orion Shih （施怡之）Title and Affiliation: Postdoc, NSRRC
E-Mail: shih.orion@nsrrc.org.tw
Research Interests:- SAXS from biological macromolecules- NEXAFS of liquid microjets

24Surface Characterization of Poly(flruoroalkyl acrylates) by
Surface X-ray Diffraction/Scattering and Neutron Reflectivity
Atsushi Takahara1,2
1

2Institute for Materials Chemistry and Engineering, Kyushu University,
International Institute for Carbon-Neutral Energy Research (WPI-I2CNER)
Kyushu University
takahara@cstf.kyushu-u.ac.jp

Polymers with fluoroalkyl (Rf) groups are attractive to a broad range of applications in the paint andcoatings sector. Surface properties of the fluoropolymers with perfluoroalkyl (Rf) side groups depend on
the surface molecular aggregation structure and surface molecular motion. Surface molecular aggregation
structure and surface molecular motion of the poly(fluoroalkyl acrylate) (PFA-Cy, where y is thefluoromethylne number of the Rf groups) and poly(fluoroalkyl methacrylate) (PFMA-Cy) were investigatedby grazing incidence wide-angle X-ray diffraction (GI-WAXD) measurement, temperature dependence ofthe dynamic contact angle measurement, X-ray photoelectron spectroscopy (XPS) measurement inpseudo-hydrated state, and lateral force microscopy (LFM) measurement [1-3]. It was revealed thatcrystallization of FA side chain at the air interface contribute to the stable surface hydrophobicity of
PFA-Cy and PFMA-Cy.
We utilized scattering length density contrast of fluoroalkyl group for neutron reflectivity(NR). The
plasticization effects of compressed CO2 gas on the semicrystalline poly(FA-C8) brush thin films (40 nm inthickness) grafted-from Si substrates were studied by NR[4]. In situ NR measurements were performed
under the isothermal condition of T = 309 K (<< Tm). The results showed the significant increase in theswelling of the polymer brush with increasing CO2 pressure. This indicates that the large sorption of CO2
molecules induces the melting of the semicrystalline poly(FA-C8) brush at P > 4.1 MPa.
This work was partially supported by the Photon and Quantum Basic Research Coordinated Development Program of
MEXT, Japan

References[1][2]

K. Honda, M. Morita, H. Otsuka, A. Takahara, Macromolecules, 38, (2005) 5699.
K. Honda, H. Yakabe, T. Koga, S. Sasaki, O. Sakata, H. Otsuka, A. Takahara, Chem. Lett., 34,(2005) 1024.
[3]
K. Honda, M. Morita, O. Sakata, S. Sasaki, A. Takahara, Macromolecules, 43, (2010) 454.
[4]
H. Yamaguchi, P. Gin, H. Arita, M. Kobayashi, S. Bennett, S. K. Satija, M. Asada, T. Koga, A.
Takahara., RSC Adv., 3, (2013) 4778.

25

Name: Atsushi Takahara （高原 淳）
Title and Affiliation: Director and Professor, Institute for Materials Chemistry and Engineering,
Kyushu University
E-Mail: takahara@cstf.kyushu-u.ac.jp
Research Interests:- Polymer Surface and Interfaces- Nanocomposites- Quantum Beam Analysis

26

SAXS and SANS study on the structural change of humanstratum corneum induced by the treatment of surfactant
solutionsTakuji Kume1, Makoto Onoo1 and Ichiro Hatta2
1

2

Kao Corporation
Nagoya Industrial Science Research InstituteE-mail: kume.takuji@kao.co.jp

The outermost layer of the skin, stratum corneum (SC) consists of corneocytes and intercellularlipid matrix, as shown schematically in Figure 1. The structure of the SC plays an important role in thebarrier function [1, 2]. The surfactant used in skin cleansers sometimes induces swellings of SC. They areaccompanied by structural changes of keratin fibers in the corneocytes, and the changes of intercellular lipids
lamellar structure around the corneocytes. The aim of this research is to study the conformation change ofhuman SC, particularly the soft keratin conformation, induced by the treatment of surfactant solutions using
scattering analysis.
A problem emerged while conducting small-angle X-ray scattering (SAXS) measurements – thescattering of the surfactant micelles disturbed the observation of keratin fibers, particularly microfibril
structures. To resolve this problem, the influence of the scattering of surfactant micelles was eliminated byusing deuterated surfactant solutions in the small-angle neutron scattering (SANS) measurements, andobserving only keratin fibers in the heel SC powder (without the intercellular lipids lamellar structures) was
became possible [3]. Using this technique, we analyzed the swelling of the keratin fibers in SC powder
soaked with the surfactant solution of various conditions.
On the other hand, since the SANS
Corneocytes and	
  lipid	
  matrixes
measurement required long time, several hours perSC
one scan, it was difficult to pursue SC structuralchange in a short time (from several minutes to 1 20μmhour) after surfactant solution soak. Therefore, the SC
internal structure change was measured by SAXS fora short time using the structural orientation in the
Lipid matrix
stacked SC sheets. And the SAXS measurement
results after prolonged progress were compared with
Keratin fibers
One corneocyte
the SANS measurement results.
of	
  corneocyte
Figure 1. SchematicInside	
  diagramof stratum
corneum (SC) structure in the human skin

References[1] S. H. White et al., Biochemistry, 27, (1988) 3725.
[2] J. A. Bouwstra et al., Biochim. Biophys. Acta, 1212, (1994) 183.
[3] T. Kume et al., Hamon, 24, (2014) 15.

27

Name: Takuji Kume （久米 卓志）
Title and Affiliation: Dr., Analytical Science Research Labs. Kao Corporation
E-Mail: kume.takuji@kao.co.jp
Research Interests:- Colloid and surface chemistry- Soft matter- SAXS and SANS

28

Small-angle neutron and X-ray scattering studies on
metallocene EPDM
Kazuki Mita1, Kiminori Uchida1,
Keisuke Shishido1, Mitsunao Arino1, Yoshiharu Kikuchi1, Kotaro Ichino1
1

Mitsui Chemicals, Inc.

E-mail: Kazuki.Mita@mitsuichemicals.com

Linear ethylene-propylene-diene terpolymers (EPDM) and those having branch structures wereobtained by metallocene catalysts, and network structures of the EPDMs crosslinked by peroxide initiatedreactions were investigated by small-angle neutron scattering (SANS) and small-angle X-ray scattering(SAXS). The neutron experiment at the BL20 Materials and Life Science Experimental Facility of J-PARC
was performed under a user program (Proposal No. 2014AM0009). The synchrotron radiation experiments
were performed at the BL03XU SPring-8 with the approval of the Japan Synchrotron Radiation ResearchInstitute (JASRI) (Proposal No. 2013B7266, 2015A7216).

29

Name: Kazuki Mita （三田 一樹）
Title and Affiliation: Dr., Mitsui Chemicals, Inc.
E-Mail: Kazuki.Mita@mitsuichemicals.com
Research Interests:- Polymer physics- Crystal and network structures- Small-angle scattering

30

Electrochemical Reaction of Carbon Film with Electrolyte
Solution as Studied by Time-slicing Neutron Reflectometry
M. Harada1, H. Kawaura1, Y. Kondo1, H. Kondo1, Y. Suganuma1,
N. Takahashi1, J. Sugiyama1, Y. Seno1, N. L. Yamada2
1

Toyota Central R&D Labs., Inc., 2KEK
E-mail: harada@mosk.tytlabs.co.jp

Safety and durability of lithium ion batteries (LIBs) should be improved by understanding the natureof the solid-electrolyte interphase (SEI) that is formed at the boundary between the electrode and theelectrolyte in LIBs. Thus, we have measured neutron reflectivity (NR) for an interface between a carbon film
and a lithium-salt solution in a purpose-built half-cell under in-situ conditions.
The electrochemical reaction was conducted by linear sweep voltammetry from the open circuit voltage, 2.9
V, to 0.05 V against Li/Li+. When the potential fell below around 1.0 V at a rate of 0.2 mV/s, gradual change
was observed for the spectra of NR. By fitting the time-sliced NR spectra with calculated curves using aseries of scattering length density (SLD) profiles, time evolution of the profiles is demonstrated as shown in
Figure 1. Beside a decrease in SLD of carbon layer, growth of a thin layer was found at the interface between
the carbon and the solution, as the potential decreased down from 1.0 V. The SLD of the thin layer increased
by 130 %, and the layer thickened from 20 to 42 nm. While the decrease in the SLD of the C film is
attributed to the lithium insertion, the growth of thin layer could be assigned to the formation of the SEI.
Although the composition of the SEI cannot be analysed only by NR experiments, we can estimate that the
SEI should be the reaction products of the lithium electrolyte solution with less hydrogen and lithium atoms
having negative scattering length.

Growth of SEIC

SiSolution

TiOx

Figure 1 Evolution of the scattering length density profiles by decreasing the potential.
Growth of SEI is observed at the interface of the carbon and the solution.

31

Name: Masashi Harada （原田 雅史）
Title and Affiliation: Dr., Toyota Central R&D Labs., Inc
E-Mail: harada@mosk.tytlabs.co.jp
Research Interests:- Thin polymer film
- Colloidal dispersion- Semi-crystalline polymer

32

Fabrication of Perpendicular Nanoporous TiO2 Thin Films
through Templated Synthesis of Dendron-Jacketed Block
Copolymers
Wei-Tsung Chuang1, Yen-Ming,Hsu2, Ya-Sen Sun2, U-Ser Jeng1, Chun-Jen Su1
1

2

National Synchrotron Radiation Research Center, Taiwan
Department of Chemical and Materials Engineering, National Central University, Taoyuan, Taiwan
E-mail: weitsung@nsrrc.org.tw

Direct template synthesis of highly density nanoporous conversion into TiO2 (or metal oxides) is achallenge task for maintaining thermally robust and well-ordered framework. In this study we report aunique structural transformation process for perpendicular orientation of cylindrical microdomains in
Dendron-Jacketed Block Copolymers (DJBCP) 1-3 and design a DJBCP-template synthesis for TiO2 films
consisting of high-density nanoporous anatase with perpendicular porosity. In order to understand themechanism of the perpendicular orientation, we investigated time-resolved structural evolution of the doctor
blade-cast films annealed at 150 oC using by GISAXS, AFM and TEM measured ex situ. The thin films ofperpendicular cylinders can be fabricated into TiO2 nanopores via a designed DJBCP-templated synthesis.
This is a straightforward and cost-effective route to create large-area well-order 1D nanostructures forapplications in optics, electronic, sensing, drug delivery, separation and nanolithography, because verticallyaligned 1D nanostructures could potentially improve the charge-collection efficiency and effectively increase
diffusion of guest species form outside.

References[1] Wei-Tsung Chuang, Ting-Ya Lo, Yen-Chih Huang, Chun-Jen Su, U-Ser Jeng, Hwo-Shuenn Sheu, andRong-Ming Ho Macromolecules, 47, (2014), 6047-6054.
[2] Wei-Tsung Chuang, Yen-Chih Huang, Chun-Jen Su, U.-Ser Jeng and Hwo-Shuenn Sheu, Soft Matter, 8,(2012) 11163-11168.
[3] Wei-Tsung Chuang, H. S. Sheu, U. S. Jeng, J. J. Lee, H. H. Wu and P. D. Hong Chem. Mater., 21, (2009),
975-978.

33

Name: Wei-Tsung Chuang （莊偉綜）Title and Affiliation: Assistant Research Scientist, National Synchrotron Radiation ResearchCenterE-Mail: weitsung@nsrrc.org.tw
Research Interests:- Structure and phase transitions in soft materials- Polymer crystallization- Block copolymer self-assembly34

An Effect of Aggregation States in Nafion Thin Films on
Transport Properties
D. Kawaguchi1, Y. Ogata2, N. L. Yamada3 and K. Tanaka2
1

Education Center for Global Leaders in Molecular Systems for Devices, Kyushu University
2
Department of Applied Chemistry, Kyushu University
3
Neutron Science Laboratory, High Energy Accelerator Research Organization
E-mail: d-kawaguchi@cstf.kyushu-u.ac.jp

Nafion has been widely used as a proton exchange membrane in polymer electrolyte fuel cells (PEFC).
Excellent electrochemical and mechanical properties of Nafion are associated with the characteristic network
structure of the hydrated phase. Although downsizing PEFC is one of the interesting developments in thenear future, it appears to us that most studies for Nafion conducted so far are limited to bulk systems. In
this study, aggregation states, water sorption and proton conductivity in Nafion thin films prepared on quartz
substrates were examined.
A Nafion thin film was prepared on a quartz substrate by spin-coating from Nafion dispersion in thewater/alcohol mixture. The film was dried under vacuum at 313 K for 20 h and then immersed into D2O for
5 h to reach an equilibrium swollen state. A density profile of the film normal to the D2O interface was
examined by neutron reflectivity (NR) measurement using Soft(a)
Nafion in D2O
Interface Analyzer (SOFIA) at J-PARC.
10
Figure 1(a) shows a NR curve of the Nafion thin film in D2O.
10
The solid line denotes the best-fit calculated reflectivity to the10experimental one based on the model scattering density (b/V)
10
profile shown in Figure 1(b). The model containing interfacial
0.0
0.5
1.0
1.5
2.0
2.5
multi-layers with a total thickness of ca. 5 nm gave a better fitting
q / nm−1
for the experimental data. The interfacial layers having lower andInterfacial layers
higher (b/V) values than the internal region correspond to the(b)DOquartzNafionhydrophobic and D2O-contained hydrophilic ones, respectively.
8This result clearly indicates that multi-layer structure was formed at6
the substrate interface. This may be due to the strong interaction
4
between sulfonate groups in Nafion and quartz surface. The
2interfacial structure would affect the water sorption1) and proton
conductivity in Nafion thin films. We will show results in the
0
60
50 10
5
0
−5
presentation.
Distance from interface / nm
Reflectivity

0

−2

−4

−6

(b/V)×104 / nm-22Reference

Figure 1. (a) Neutron reflectivity
curve for a Nafion thin film on quartz[1] Y. Ogata, D. Kawaguchi, N. L. Yamada, K. Tanaka, ACS
substrate in D2O.
Experimental
Macro Lett, 2, (2013) 856.
data set is shown by symbol. The
best-fit calculated curve using amodel (b/V) profile shown in (b) isexpressed by a solid line.

35Name: Daisuke Kawaguchi （川口 大輔）
Title and Affiliation: Associate Professor, Kyushu University
E-Mail: d-kawaguchi@cstf.kyushu-u.ac.jp
Research Interests:- Polymer thin films and interfaces- Molecular motion of polymers

36Competition between entropy and enthalpy in the binding of
melittin with ULV vesicles of different phosphate lipid chain
lengths
Chun-Jen Su1, Wei-Ru Wu1, Wei-Tsung Chuang,1 Yen-Chih Huang,1 Po-Wei Yang1,
Po-Chang Lin, Chun-Yu Chen,1 Kung-Hwa Wei2, Chih-Ming Liu,2 An-Chung Su3
and U-Ser Jeng1,3,*
1National Synchrotron Radiation Research Center, Hsinchu Science Park, Hsinchu 30076, Taiwan
2
Department of Materials Science and Engineering, National Chiao Tung University, Hsinchu
30010, Taiwan
3
Department of Chemical Engineering, National Tsing Hua University, Hsinchu 30013, Taiwan
E-mail: su.cj@nsrrc.org.tw

Concomitant polymer crystallization and nanoscale phase separation during spin-coating ofpolythiophene/fullerene films for polymer solar cells (PSCs) are traced using simultaneous grazing
incidence small- and wide-angle X-ray scattering. The corresponding film thinning behavior
observed using time-resolved UV−Vis reflectance reveals features of shear-flow-enhanced sol−geltransition and transient layering from vertical phase separation during the spin-coating process. The
correlated results suggest that local phase separation, accelerated-nucleation-based polymer
crystallization and fullerene aggregation, is initiated primarily within a surface layer developed
during the sol−gel transition. Subsequently, the structural development is pinned, leaving only
constant solvent dissipation through the surface layer until final film coarsening. The hence
kinetically trapped network structure, featuring dispersed P3HT crystallites and PCBM
nano-aggregates, guides the subsequent development over the optimized bulk-heterojunction
structures of the spin-coated film. The shear-flow-enhanced surface layering process is a previously
missing piece of information in our integrated understanding of the PSC film-formation processduring spin-coating.

References[1] Wu, W.-R., Jeng, U., Su, C.-J., Wei, K.-H., Su, M.-S., Chiu, M.-Y., Chen, C.-Y., Su, W.-B., Su, C.-H. &Su, A.-C. ACS Nano 5, (2011) 6233−6243.

37

Name: Chun-Jen Su （蘇群仁）
Title and Affiliation: Assistant Researcher, National Synchrotron Radiation Research Center
E-Mail: su.cj@nsrrc.org.tw
Research Interests:- Biopolymer self-assembled structure- Polymer physics- Small-angle x-ray scattering

38

SAXS combined with crystallography for structural studies onmacromolecular complexes and functional flexibility ofprotein
Shu-Ying Wang1, U-Ser Jeng2, Michal Hammel3, and Xinquan Wang4
1

Dept. of Microbiology and Immunology, National Cheng Kung University, Tainan, Taiwan
2
National Synchrotron Radiation Research Center, Hsinchu, Taiwan
3
Lawrence Berkeley National Laboratory, Berkeley, CA, USA
4
Center for Structural Biology, Tsinghua University, Beijing, China
E-mail: sherry523@gmail.com

The understanding of interactions between biological molecules is essential to comprehend thecellular processes in living organisms. Crystallography is a powerful tool to provide the interactive schemesof macromolecular complexes at atomic level. However, it is sometimes challenging and time consuming tocrystallize large molecular machines. In this talk, I will present our work that combines crystallography andsmall-angle X-ray scattering (SAXS) to resolve the structures and functions of protein-DNA andprotein-protein complexes. First, I will introduce our study on the peroxide response regulator PerR, amember of ferric uptake regulator (Fur) family, from Streptococcus pyogenes. We determined the crystal
structure of PerR and resolved the first molecular architecture of PerR-DNA complex by SAXS analysis,
revealing a unique DNA-binding topology distinct from currently proposed DNA-binding models for Fur
family [1]. Second, I will introduce the work for studying the interactions between IL-1 cytokine members
and their receptors. The activation of IL-1 signaling cascade, initiated by cytokine binding toligand-recognition receptor and the following assembly of a co-receptor, triggers the subsequent intracellularsignaling pathways. We conducted crystallographic and SAXS studies to understand how the functional
flexibility of the IL-1 receptors contributes to specific interactions of cytokine-receptor complexes and how
the intrinsic flexibility within IL-1 receptors relevant to molecular recognition [2].

References[1] C.S. -H, Lin, S. -Y. Chao, J. C. Nix, et al., PLos ONE, 9(2), (2014) e89027.
[2] X. Liu, M. Hammel, Y. He, J. A. Tainer, U.-S. Jeng, L. Zhang, S. Wang and X. Wang, Proc. Natl. Acad.
Sci. 110, (2013) 14918.

39

Name: Shu-Ying Sherry Wang （王淑鶯）
Title and Affiliation: Associate Professor, National Cheng Kung University
E-Mail: sherry523@gmail.com
Research Interests:- Functional flexibility of macromolecules- IL-1 signaling complex- Zinc-finger DNA binding proteins40

Liquid phase networks of conjugated polymers and carbon
allotropes
Jrjeng Ruan, Jui-Hsien Lo and Yu-Chen Deng
1

Department of Materials Science and Engineering, National Cheng Kung University, Tainan 701, Taiwan
E-mail:jrjeng@mail.ncku.edu.tw

Semiconductive conjugated polymers, including polyfluorenes and polythiophenes, normally are not
miscible with insulating polymethylmethacrylate (PMMA) in molten state. Nevertheless, upon the
dissolution effect of selected solvents, the liquid phase of PMMA was discovered to coexist with separate
liquid phases of conjugated polymers. These polymer liquid phases are able to simultaneously distribute into
networks or granular domains upon the variation of mixing ratios. Moreover, as being influenced byfavourable π-π interactions with conjugated polymers, functional materials like carbon nanotubes andfullerene derivatives were found to preferably blend into one of polymer liquid phases in these two-phasesolutions, as shown in Figure 1. This is a new mechanism for establishing percolation network of functional
carbon allotropes within polymeric thin film, providing opportunities of enhancing performances in various
aspects, like heat and electronic conduction.
In addition to individual liquid phases of conjugated polymers, the network of phenyl-C61-butyric acidmethyl ester (PCBM) liquid phase was found to develop in solutions also upon the addition of conjugatedpolymers. The involved phase separation can be adjusted by concentration, mixing ratio and the length ofalkyl side chian attached on conjugated polymers as well. This prior phase separation is critical for later
crystallization of PCBM within precipitated thin film, and networks of PCBM single crystal was found able
to develop upon selected thermal treatment (Figure 2). Accordiing to these results, it is expected to establish
a fundamental mechanism to manipulate the development of complex liquid phases in solutions as a novel
way to reach desired structures of optoelectrical thin film.

Figure 1. Electronic micrograph of preferable
dispersion of carbon nanotubes within
networks regions of polyfluorene of
precipitated thin film

Figure 2. Electronic micrograph of networksof PCBM single crystals, which are covered
with overgrowth of board-like crystallites

41

Name: Jrjeng Ruan （阮至正）Title and Affiliation: Associate Professor, Department of Materials Science and Engineering,
National Cheng Kung University
E-Mail: jrjeng@mail.ncku.edu.tw
Research Interests:- Ordering assembly and crystallization behaviors of organic molecules- Polymer blends- Phase transition behaviors

42

Probing UV-Irradiated and pyrolyzed block copolymer
micelles on a solid by grazing incident X-ray
Jiun-You Liou, and Ya-Sen Sun*
Department of Chemical and Materials Engineering, National Central University, Taoyuan 32001, Taiwan*

E-mail: yssun@cc.ncu.edu.tw

We investigated the structural evolution of truncated micelles in ultrathin films ofpolystyrene-block-poly(2-vinylpyridine), PS-b-P2VP, of monolayer thickness on bare silicon substrates(SiOx/Si) with UV irradiation in air- (UVIA) and nitrogen-rich (UVIN) environments. The structural
evolution of micelles with UV irradiation was monitored with GISAXS measurements in situ while thesurface morphology was probed with an atomic force microscope ex situ and the chemical composition with
X-ray photoelectron spectra (XPS). This work provides clear evidence for an interpretation of relations
between the structural evolution and photochemical reactions in PS-b-P2VP truncated micelles with UVIA
and UVIN. Under UVIA treatment, photolysis and cross-linking reactions coexisted within the micelles;
photolysis occurred mainly at the top of the micelles whereas cross-linking occurred preferentially at thebottom. The shape and size of UVIA-treated truncated micelles were controlled predominantly by oxidative
photolysis reactions, which depended on the concentration gradient of free radicals and oxygen along themicelle height. Because of an interplay between photolysis and photo-crosslinking, the scattering lengthdensities (SLD) of PS and P2VP remained constant. In contrast, UVIN treatments enhanced the contrast in
SLD between the PS shell and P2VP core as cross-linking dominated over photolysis in the presence ofnitrogen. The enhancement of the SLD contrast was due to the varied degree of cross-linking under UVIN
for the PS and P2VP blocks.[1]Next, we developed a method to fabricate arrays of nanostructured carbon materials of high quality, via
direct pyrolysis of poly(styrene-b-2-vinylpyridine) (PS-b-P2VP) block copolymer (BCP) as thin films
without small organic molecules incorporated as carbon resources. Prior to pyrolysis, the nanodomains werecross-linked with UV radiation under nitrogen (UVIN). As upon pyrolysis thermal energies impart mobility
to nanodomains to overcome the constraints imposed by cross-linked chains, the free surface is inevitably
covered with the PS block that has a smaller surface energy; unless favorable interactions with the P2VP
block exist at the free surface, the outer layer of carbonaceous films is predominantly composed of thepyrolyzed PS block.[2-3]References[1] Jiun-You Liou and Ya-Sen Sun*, Soft Matter, 11, (2015) 7119.
[2] Yen-Hsing Lu, Jiun-You Liou, Chien-Fu Lin, and Ya-Sen Sun*, RSC Advances, 5, (2015) 105760.
[3]Ya-Sen Sun*, Wei-Hua Huang, Jiun-You Liou, Yen-Hsing Lu, Kuo-Chih Shih, Chien-Fu Lin, andShao-Liang Cheng, RSC Advances, 5, (2015) 105774.

43

Name: Ya-Sen Sun （孫亞賢）
Title: Associate professor, Department of Chemical and Materials Engineering, National Central
University, Taoyuan 32001, Taiwan
E-Mail: yssun@cc.ncu.edu.tw
Research Interests:- Polymer thin films- crystallization Behavior of
Homopolymers- Self-assembly of soft matters

Crystallizable

44

Block

Copolymers

andSemicrystalline

Dynamic Quaternary Structure of α -Crystallin
Rintaro Inoue1, Takumi Takata1, Norihiko Fujii2, Kentaro Ishii3, Susumu
Uchiyama3, 4, Nobuhiro Sato1, Yojiro Oba1, Kathleen Wood5, Koichi Kato3,
Noriko Fujii1 and Sugiyama Masaaki1
1Research Reactor Institute, Kyoto University.
2
Teikyo Univ., Radioisotope Res. Ctr.
3
Okazaki Institute for Integrative Bioscience, Okazaki.
4
Graduate School of Engineering, Osaka University.
5
Australian Nuclear Science and Technology Organization.
E-mail: rintaro@rri.kyoto-u.ac.jp
Most of proteins possess proper quaternary structures. Such quaternary structures are not necessary fixedto certain configurations, but rather are fluctuating due to internal dynamics. Interestingly, some of theproteins possess unique quaternary structures and the representative examples of such proteins are small
heat-shock proteins (sHSPs). A small monomer with molecular mass ranging from 9 to 43 kDa serves as abuilding component for assembling into larger oligomeric structures. Such oligomeric structures are strongly
influenced by even the subtle change of external environment.
The a-crystallin, which has the consensus amino acid sequence to sHSPs, is comprised of two subunits:
αA-crystallin and αB-crystallin. It normally existed as aggregated structure consisting of 20~40 subunits.
The determinations of oligomeric structure of α-crystallin were also tackled with various state-of-the art
experimental techniques due to the unavailability of its crystal structure, however no consensus on theoligomeric structure such as average number of subunits, degree of heterogeneity, spatial configuration ofeach subunit has been obtained. In addition, the experimental proofs for cooperative subunit kinetics between
α-crystallins have been reported by fluorescence resonance energy transfer (FRET), isoelectric focusing
method and mass spectrometry. Hence, α-crystallin are continuously engaged in cooperative subunit kinetics
between α-crystallins and they can exist as “Dynamic quaternary structure” mediated by such subunit
kinetics. We therefore can only access to their inherent feature through disclosing the mechanism ofcooperative subunits kinetics in a-crystallin.
One of the most fascinating properties in neutron scattering is its ability for discerning hydrogen (H) anddeuterium (D) through the difference in neutron scattering lengths between them. Deuteration assisted
small-angle neutron scattering (DA-SANS) must be a promising method for tracking subunit kinetics in
α-crystallins. In addition, mass spectrometry is an unique experimental method for taking the snapshot of
distribution of aggregation number.
In this presentation, we studied subunit kinetics of homo-aggregate of αB-crystallin through thecomplementary use of DA-SANS and mass spectrometry.

45

Name: Rintaro Inoue （井上 倫太郎）
Title and Affiliation: Associate Professor, Research Reactor Institute, Kyoto University
E-Mail: rintaro@rri.kyoto-u.ac.jp
Research Interests:- Dynamics and structure of biomolecule- Soft matter- Small angle scattering

46

The correlation between the mechanics of a lipid membrane
and its cellular functions
Yi-Fan Chen1
1

Department of Chemical and Materials Engineering, National Central University, Taoyuan, 32001,
Taiwan.
E-mail: yifanchen@ncu.edu.tw

The spontaneous curvature, C0, and the bending modulus, Kcp, are two collective properties of alipid membrane. These two properties manifest the mechanics of a biomembrane and are intertwined with its
biological functions. Contrary to the common perception, biomembranes assume nonlamellar structures inmany cellular events, with the tendency of forming a nonlamellar structure quantified by C0 and with theextent of the ease to deform biomembranes measured by Kcp. In this presentation, the physical principles
associating the mechanics with the functions of biomembranes and the biological relevance of the twocollective properties are revealed through exploring the correlations between C0 and [Ca2+] ([Ca2+] is an
important factor in many cellular events that involve the formation of nonlamellar biomembranes), andthrough those between C0/Kcp and the the membrane fusion (membrane fusion is a collection of cellular
events that see two disparate membranes, as well as the volumes enclosed by them, merged). From theC0-[Ca2+] correlations of different lipid speices, we recognize that the charge density of the lipid headgroupis dominant in dictating the structural preferences of anionic phospholipids, and that displaying differential
C0 sensitivities to [Ca2+] is crucial for anionic phospholipids to fulfil their differential biological roles.
Furthermore, the dependence on the two collective properties of the fusion capability indicates that aninter-membrane interaction that has seldom been characterized is in fact important to the fusion efficiency ofa lipid membrane, and that the negative C0-induced promotion of fusion is enabled via increasing theenergetic cost of maintaining the membranes in the planar conformation, with respect to transforming themto the nonlamellar structures of the fusion intermediates.

References[1] Y. -F. Chen*, K. -Y. Tsang, W. -F. Chang and Z. -A. Fan, Soft Matt., 11, (2015) 4041.

47

Name: Yi-Fan Chen （陳儀帆）
Title and Affiliation: Assistant professor, Department of Chemical and Materials Engineering,
National Central University
E-Mail: yifanchen@ncu.edu.tw
Research Interests:- Biological Physics- Soft Condensed Matter/Biological Liquid Crystals- Applications of High Pressure Physics- Application of Scattering and Crystallography Techniques

48Structural insights into molecular assembly in the proteasomal
systems
Tadashi Satoh1, Arunima Sikdar1,2,3, Kazuyoshi Murata4, Toshiya Kozai5,
Kentaro Ishii6, Masanori Noda7, Hiroki Kawamura1, Hirokazu Yagi1, Maho
Yagi-Utsumi1,3, Susumu Uchiyama6,7, Takayuki Uchihashi5, and Koichi Kato1,2,3,6
1

2

Faculty and Graduate School of Pharmaceutical Sciences, Nagoya City University
School of Physical Sciences, SOKENDAI (The Graduate School for Advanced Studies)
3
Institute for Molecular Science, National Institutes of Natural Sciences
4
National Institute for Physiological Science, National Institutes of Natural Sciences
5
Department of Physics, Kanazawa University
6
Okazaki Institute for Integrative Bioscience, National Institutes of Natural Sciences
7
Graduate School of Engineering, Osaka University
E-mail: tadashisatoh@phar.nagoya-cu.ac.jp

The proteasome is a huge proteolytic machine consisting of a number of subunits. For example, thecatalytic core particle is composed of seven different homologous α-subunits and seven different
homologous β-subunits. Accumulating evidence has revealed that the assembly of the eukaryotic proteasome
is not spontaneous self-organization but an ordered process assisted by assembly chaperones that transiently
associate with the assembly intermediates. Although several proteasome assembly intermediates have been
identified, a blueprint for molecular assembly of this huge machine remains to be clarified. We performed
biophysical studies of human proteasome subunits α6 and α7 and revealed that the isolated α7 subunit
exclusively exists as homo-tetradecamer in solution. We also proposed a “scrap and build” mechanism
whereby its double-ring structure is disassembled upon the addition of α6, resulting in a 1:7 hetero-octameric
α6-α7 complex [1].
In this study, we performed comprehensive biophysical studies including analytical ultracentrifugation,
mass spectrometry, X-ray crystallography, electron microscopy, and high-speed atomic force microscopy inthe eukaryotic and archaeal proteasomal systems. In the eukaryotic system, we expand our previous
investigations on human α6-α7 subunits to include the five remaining α1-α5 subunits to gain structural
insights into α-ring assembly mechanisms. In contrast to the eukaryotic proteasomes, archaeal proteasome
subunits are spontaneously assembled. Nevertheless, recent bioinformatic analysis identified archaeal
homologs of proteasome assembly chaperones. We demonstrated that these archaeal homologs adopt quitedistinct quaternary structures, i.e., homo-tetramer, homo-pentamer, and hetero-eicosamer, as compared withthe hetero-dimeric eukaryotic counterparts. We will present our latest results regarding dynamic processes ofproteasomes and interactions of the related proteins.

References[1] K. Ishii, M. Noda, H. Yagi, R. Thammaporn, S. Seetaha, T. Satoh, K. Kato, and S. Uchiyama, Sci Rep, 5,(2015) 18167.

49

Name: Tadashi Satoh （佐藤 匡史）
Title and Affiliation: Associate professor, Graduate School of Pharmaceutical Sciences, Nagoya
City University
E-Mail: tadashisatoh@phar.nagoya-cu.ac.jp
Research Interests:- Structural biology- Posttranslational modification- X-ray crystallography

50Current Status and Results on J-PARC/MLF
Toshiji Kanaya1 and Hideki Seto1
1

J-PARC Center, High Energy Accelerator Research Organization, 203-1 Shirakata, Tokai 319-1106, Japan
E-mail: hideki.seto@kek.jp

Last year, MLF has started operation from February 22 after the recovery from a small fire incident
in the second experimental hall. It stopped again due to a leakage of cooling water from the neutron target
vessel on April 30 during the 500 kW proton beam operation. After the improvement of the target vessel,
MLF restarted on October 27 at 500 kW for the user program. However, it stopped again due to the coolingwater leakage from the neutron target vessel. We are now investigating the cause of the problem to develop a
new type target vessel. The user program will restart at low power (~200 kW) in the middle of February
2016 by replacing the neutron target vessel to a reserved one.
In MLF, 21 neutron instruments have been funded. Within these instruments, 19 are in operation
for the user program and 2 instruments are under commissioning or construction. Now the experimental
hall is almost full with instruments, leaving only 2 ports are available for instruments in future.
World-class scientific outputs have been already created in various scientific fields, ranging frombasic science to industrial application. Since J-PARC is internationally open for users, we have got
experimental proposals from abroad more than 10% of the whole proposals. More than 20% of proposals
have come from industrial users and a half of them are proprietary use. This fact has revealed a newhorizon has come in the neutron scattering science in the 21st century.

51

Name: Hideki Seto （瀬戸 秀紀）
Title and Affiliation: Professor, Institute of Materials Structure Science, High Energy Accelerator
Research Organization
E-Mail: hideki.seto@kek.jp
Research Interests:- Softmatter Physics- Small Angle Scattering- Quasi-Elastic Neutron Scattering- Tribology

52

Nanostructured Networks in Chiral Block Copolymers
Rong-Ming Ho
Department of Chemical Engineering, National Tsing Hua University, Taiwan
E-mail: rmho@mx.nthu.edu.tw
The designs of nanostructured materials and corresponding morphologies have attracted intensive
attention because of their effectiveness in tuning electronic, optical, magnetic, and catalytic properties aswell as mechanical properties. Nanostructured networks are perhaps the most fascinating morphology due
to their high porosities and large specific surface areas as well as superior mechanical properties with
self-supporting character. Although many technologies have been explored to fabricate nanostructured
networks, self-assembly is one of the most important approaches to fabricate nanostructured materials with
precisely controlled structures and morphologies from constituted components. Here, we aim to exploit the
self-assembly of degradable block copolymers with chiral segments as a powerful tool to fabricate
well-defined nanostructured networks. Subsequently, the fabrication of well-ordered nanoporous polymers
with continuous nanochannels from the self-assembly of degradable block copolymers (BCPs), such as
gyroid-forming network morphologies, can be obtained by degeneration of constituted segment(s) and usedas templates for syntheses of various materials with different entities.

References[1] R.-M. Ho, et al., Macromolecules, 47, (2014) 7993. Front Cover Story[2] R.-M. Ho, et al., Chem. Soc. Rev., 44, (2015) 1974.

53

Name: Rong-Ming Ho （何榮銘）
Title and Affiliation: Distinguished Professor, Department of Chemical Engineering, National
Tsing Hua University, Taiwan
E-Mail: rmho@mx.nthu.edu.tw
Research Interests:- Self-assembly of Macromolecules and Supramolecules- Hybridization of organic and inorganic Materials- Nanopatterning Technologies from Bottom-up Methods- Block Copolymer Physics- Crystallization Behavior of Polymers

54

Hierarchical Structure of Polymer/Nanoparticle Hybrid
Yu-Chiao Lin1, Chun-Yu Chen2, Hsin-Lung Chen1* and Takeji Hashimoto1,3*,
1Deptartment of Chemical Engineering and Frontier Research Center on Fundamental and Applied Sciencesof Matters, National Tsing Hua University, Hsinchu 30013, Taiwan
2
National Synchrotron Radiation Research Center, Hsinchu 300, Taiwan
3
Quantum Beam Science Center, Japan Atomic Energy Agency, Tokai-Mura, Naka-gun, Ibaraki Pref.
319-1195, and Kyoto University, Kyoto 606-6501, Japan (Professor Emeritus).

E-mail: hlchen@che.nthu.edu.tw
Using small angle X-tray scattering (SAXS), we elucidated the spatial organization of palladium (Pd)nanoparticles (NPs) in the polymer matrix of poly(2-vinylpyridine) (P2VP) and the nature ofinter-nanoparticle interactions, where the NPs were synthesized in the presence of P2VP by the reduction of
palladium acetylacetonate (Pd(acac)2). The experimental SAXS profiles were analysed on the basis of ahierarchical structure model considering the following two types of interparticle potential: (i) hard-core
repulsion only (i.e., the hard-sphere interaction) and (ii) hard-core repulsion together with an attractive
potential well (i.e., the sticky hard-sphere interaction). The corresponding theoretical scattering functions,which were used for analysing the experimental SAXS profiles, were obtained within the context of the
Percus-Yevick closure and the Ornstein-Zernike equation in the fundamental liquid theory. The analyses
revealed that existence of the attractive potential well is indispensable to account for the experimental SAXS
profiles. Moreover, the morphology of the hybrids was found to be characterized by a hierarchical structurewith three levels, where about six primary NPs with the diameter of ca. 1.8 nm (level one) formed local
clusters (level two), and these clusters aggregated to build up a large-scale mass-fractal structure (level three)with the fractal dimension of ca. 2.3. The scattering function developed here is of general use forquantitatively characterizing the morphological structures of polymer/NP hybrids and in particular for
exploring the interaction potential of the NPs on the basis of the fundamental liquid theory.

55

Name: Hsin-Lung Chen （陳信龍）
Title and Affiliation: Professor, Department of Chemical Engineering, National Tsing Hua
University
E-Mail: hlchen@che.nthu.edu.tw
Research Interests:- Self-organization of DNA complexes for gene delivery and biomimetics- Phase behavior of block copolymers- Molecular aggregation of conjugated polymers- Hierarchical structure of polymer nanohybrids

56

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