別記様式5-1（第7条関係）（27首都大管国第1405号・29首都大管国第909号・一部改正）

帰国留学生短期研究報告書（外国人研究者用）
Research Report (Foreign Researcher)2019 年year

8 月month

5 日day

首都大学東京学長 殿Dear President, Tokyo Metropolitan University
外国人研究者氏名（カタカナまたは漢字）※パスポートと同一の氏名

Foreign Researcher（In alphabet）※Your name as written in your passport

Rajbangshi Subas
受入研究者氏名（カタカナまたは漢字）Research Advisor（In alphabet）

Professor Dr. Ken-ichi Sugiura
国籍

Nationality

Bangladeshi
所

属

機関

Affiliation

Jahangirnagar University, Savar, Dhaka,Bangladesh
職名Position

Associate Professor
研究期

間Period of Research
10 th May 2019 to 6 th August 2019

専攻分野Major FieldChemistry①研究課題 / Theme of Research （全角390文字/半角780文字以内）(Within two-bite 390 characters in Japanese/ one-bite 780 letters in English)

Chemiluminescence of Axially Chiral Pyrene-Luminol and Their Chiroptical Properties

②研究概要 / Outline of Research （全角390文字/半角780文字以内）(Within two-bite 390 characters in Japanese/ one-bite 780 letters in English)
Chemiluminescence displaying significant roles in the current research of chemistry, because of its extensively usedin analytical, biochemical and in forensics for the detection of bloodstains, that is invisible to the naked eye. The
chemiluminescence property of luminol was first reported by Albrecht in1928. When luminol is mixed with anoxidizing agent in aqueous solution, it exhibits a striking blue chemiluminescence, which is catalyzed by iron. For
this reason, the visual detection of bloodstains can be detected by spraying a luminol aqueous solution in a darkened
environment due to the catalytic effect of the iron-containing heme group. For this reason, we synthesized luminol
analogues of axial chiral pyrene with a hope of great interest Chemiluminescence world.

③研究成果/Results of Research（全角390文字/半角780文字以内）(Within two-bite 390 characters in Japanese/ one-bite 780 letters in English)

Axially chiral pyrene-luminol compound was synthesized through a series of reaction starting from 2-hydroxy-7-tert -butyl pyrene
and 3-methyl phthalic anhydride. The total synthesis procedure was the combination of three different synthetic pathways. In step
#1, At first Bromination was carried out on 3-methyl phthalic anhydride, which gave 4-bromo-3-methyl phthalic anhydride. This
4-bromo-3-methyl phthalic anhydride was then converted to 4-bromo-3-methyl N -hexyl phthalamide. In step #2, alkylation wasperformed on 2-hydroxy-7-tert -butyl pyrene, that resulted 2-butoxy-7-tert -butyl pyrene. Then bromination was carried out on
this compound with NBS, that gave only 1-bromo-2-butoxy-7-tert -pyrene. Treatment of this compound withbis(pinacolato)diboron in the presence of Pd2(bda)3 catalyst gave 1-boronic ester-2-butoxy-7-tert -pyrene. In step #3, Suzuki
coupling was performed between 4-bromo-3-methyl N -hexyl phthalamide and 1-boronic ester-2-butoxy-7-tert -pyrene withPd(dppf)Cl2.CH2Cl2 catalyst, that resulted pyrene phthalamide compound. In the final step, treatment of pyrene phthalamide with

④今後の研究計画 / Further Research Plan（全角390文字/半角780文字以内）(Within two-bite 390 characters in Japanese/ one-bite 780 letters in English)
Considering the result obtained from the axially chiral luminol compound, coordinated by 4-bromo-3-methyl N-hexyl
phthalamide and 1-boronic ester-2-butoxy-7-tert-pyrene, we are now interested to investigate the CPL properties of new axiallychiral compound. For these purposes, we will try to separate the (R) and (S) enantiomer of this compound. We will also measure
the CD spectra of this compound. We will also observe the chemiluminescence properties of this compound. We hope that thisnew complexes will introduce new properties, which will expand the new research on chemiluminescene chemistry.

⑤東京と海外諸都市との相互理解・友好親善関係の推進についての展望 / Vision for Contributionof Strength of Mutual Understanding/Friendship Between Tokyo and International Cities (全角390文字/半角780文字以内） (Within two-bite 390 characters in Japanese/ one-bite 780 letters in English)
The follow-up research fellowship offered by the Tokyo Metropolitan University will develope new the reserch field on the homecountry of the foreign researchers. The research knowledge, that I obtained during this period will help my institution to build up
a new research area in this field. My home University is Jahangirnagar University, Dhaka, Bangladesh. From this research ourUniversity student will learn know knowledge about the axial chirality and luminol chemistry. I think they will be interested inthis field and will do more research in this field, which will help us to develope our University as well as develope our country
because our University is a leading University in Bangladesh. Moreover, Japan is the best friend of Bangladesh, that has keep
touch in most of the development of Bangladesh. Through the fellowship offered by Tokyo Metropolitan Government and by
Japan Government, most of the Bangladeshi get the opportunity to get their higher study from Japan. In this way it has alreadymade a mutual understanding between the Tokyo and the Dhaka, Bangladesh.

別記様式5-2（第7条関係）（27首都大管国第1405号・29首都大管国第909号・一部改正）

帰国留学生短期研究報告書（受入研究者用）
Research Report (Research Advisor)
2019 年8 月 7日yearmonthday
首都大学東京学長 殿Dear President, Tokyo Metropolitan University
受入研究者氏名（カタカナまたは漢字）Research Advisor（In alphabet）

杉浦健一

Ken-ichi Sugiura

職名

Position

教授

Professor

受入研究科名Graduate School

理学研究科

Graduate School of Science

外国人研究者氏名（カタカナまたは漢字）

Foreign Researcher（In alphabet）

シャヘッド・ラナ

Shahed Rana

国

Nationality

籍

バングラデシュ人民共和国

Bangladesh

所

Affiliation

属

機

関

ジャハンギルナガル大学

Jahangirnagar University

研

間Period of Research

2019年5月10日～2019年8月6日

2019/5/10-2019/8/6

専

Major Field

究

攻期

分

合成化学

野

synthetic chemistry※以下の点に注意の上、受入研究者の立場で報告してください。
①研究指導概要：外国人研究者にどのような研究指導をしたか。
②研究指導成果：今回の研究で外国人研究者にどのような成果が見えたか。
③今後の計画：今後、指導者としてどのように交流をとりながら研究をすすめていくか。
①研究概要 / Outline of Research（全角390文字/半角780文字以内）
近年、不斉な化合物の分光挙動に興味が持たれている。一方、蛍に代表される生物の発光現象には、不斉な蛍光色素が関与していることが知られている。そこで、本研究では、受け入れ研究者が以前に合成したビピレノールを化学発光の手段によって光らせる実験の計画を指導した。

②研究成果 / Results of Research（全角390文字/半角780文字以内）
具体的には、代表的な化学発光物質であるルミノールに着目し、これにビピレノールを連結させることを計画した。両者を結合させるためには鈴木カップリング反応を用いた。具体的には、ビピレノールの方にボロン酸を、ルミノールの方にハロゲンを導入し反応を行った。得られた化合物は分光学的に同定した。定性的に発光挙動を評価したところ、目視で光を発することを確認することができた。

③今後の計画 / Further Research Plan（全角390文字/半角780文字以内）
帰国後、必要なデータを収取し、論文発表の準備を行っている。

首都大学東京帰国留学生短期研究支援制度

平成30年度

研究報告書＜外国人研究者プロフィール/Profile＞
外国人研究者

シャヘッド・ラナ

Foreign Researcher

Shahed Rana

国

バングラデシュ人民共和国

籍

Nationality

Bangladesh

所属機関

ジャハンギルナガル大学

Affiliation

Jahangirnagar University

外国人研究者の写真（写真貼り付け）

現在の職名
Position

Associate Professor

研究期間

2019年5月10日～2019年8月6日

Period of Stay

2019/5/10-2019/8/6

専攻分野

合成化学

Major Field

synthetic chemistry

受入研究者

杉浦健一

職名

教授

Research Advisor

Ken-ichi Sugiura

Position

Professor

受入研究科

理学研究科

Graduate School/Department

Graduate School of Science

写真タイトル 日/英＜外国人研究者からの報告/Foreign Researcher Report＞①研究課題/Theme of Research

Chemiluminescence of Axially Chiral Pyrene-Luminol and Their Chiroptical Properties②研究概要/Outline of Research

Chemiluminescence displaying significant roles in the current research of chemistry, because of its extensively used in analytical,
biochemical and in forensics for the detection of bloodstains, that is invisible to the naked eye. The chemiluminescence property of luminol
was first reported by Albrecht in1928. When luminol is mixed with an oxidizing agent in aqueous solution, it exhibits a striking blue
chemiluminescence, which is catalyzed by iron. For this reason, the visual detection of bloodstains can be detected by spraying a luminol
aqueous solution in a darkened environment due to the catalytic effect of the iron-containing heme group. For this reason, we synthesized
luminol analogues of axial chiral pyrene with a hope of great interest Chemiluminescence world.

③研究成果/Results of Research

Axially chiral pyrene-luminol compound was synthesized through a series of reaction starting from 2-hydroxy-7-tert-butyl pyrene and 3-methyl phthalic anhydride. The total
synthesis procedure was the combination of three different synthetic pathways. In step #1, At first Bromination was carried out on 3-methyl phthalic anhydride, which gave 4bromo-3-methyl phthalic anhydride. This 4-bromo-3-methyl phthalic anhydride was then converted to 4-bromo-3-methyl N-hexyl phthalamide. In step #2, alkylation wasperformed on 2-hydroxy-7-tert-butyl pyrene, that resulted 2-butoxy-7-tert-butyl pyrene. Then bromination was carried out on this compound with NBS, that gave only 1-bromo2-butoxy-7-tert-pyrene. Treatment of this compound with bis(pinacolato)diboron in the presence of Pd2(bda)3 catalyst gave 1-boronic ester-2-butoxy-7-tert-pyrene. In step #3,Suzuki coupling was performed between 4-bromo-3-methyl N-hexyl phthalamide and 1-boronic ester-2-butoxy-7-tert-pyrene with Pd(dppf)Cl2.CH2Cl2 catalyst, that resulted
pyrene phthalamide compound. In the final step, treatment of pyrene phthalamide with hydrazine afforded the target axially chiral pyrene-luminol compound.

④今後の計画/

Further Research Plan

Considering the result obtained from the axially chiral luminol compound, coordinated by 4-bromo-3-methyl N-hexyl phthalamide and 1boronic ester-2-butoxy-7-tert-pyrene, we are now interested to investigate the CPL properties of new axially chiral compound. For thesepurposes, we will try to separate the (R) and (S) enantiomer of this compound. We will also measure the CD spectra of this compound. We
will also observe the chemiluminescence properties of this compound. We hope that this new complexes will introduce new properties,
which will expand the new research on chemiluminescene chemistry.

⑤東京と海外諸都市との相互理解・友好親善関係の推進についての計画 /Further Plan of Contribution of Strength of Mutual Understanding/Friendship Between Tokyo and International cities
The follow-up research fellowship offered by the Tokyo Metropolitan University will develope new the reserch field on the home country of
the foreign researchers. The research knowledge, that I obtained during this period will help my institution to build up a new research areain this field. My home University is Jahangirnagar University, Dhaka, Bangladesh. From this research our University student will learn know
knowledge about the axial chirality and luminol chemistry. I think they will be interested in this field and will do more research in this field,
which will help us to develope our University as well as develope our country because our University is a leading University in Bangladesh.
Moreover, Japan is the best friend of Bangladesh, that has keep touch in most of the development of Bangladesh. Through the fellowshipoffered by Tokyo Metropolitan Government and by Japan Government, most of the Bangladeshi get the opportunity to get their higher

＜受入研究者からの報告/Research Advisor Report＞
①研究概要

/

Outline of Research

近年、不斉な化合物の分光挙動に興味が持たれている。一方、蛍に代表される生物の発光現象には、不斉な蛍光色素が関与していることが知られている。そこで、本研究では、受け入れ研究者が以前に合成したビピレノールを化学発光の手段によって光らせる実験の計画を指導した。

②研究成果/Results of Research

具体的には、代表的な化学発光物質であるルミノールに着目し、これにビピレノールを連結させることを計画した。両者を結合させるた
めには鈴木カップリング反応を用いた。具体的には、ビピレノールの方にボロン酸を、ルミノールの方にハロゲンを導入し反応を行った。得られた化合物は分光学的に同定した。定性的に発光挙動を評価したところ、目視で光を発することを確認することができた。

③今後の計画/

Further Research Plan

帰国後、必要なデータを収取し、論文発表の準備を行っている。

写真貼り付け

写真貼り付け写真タイトル 日/英写真タイトル 日/英