夢の分子機械へ向けて 3人の紹介受賞理由 · toward molecular machines ......

夢の分子機械へ向けて

化学は創造の学問：

　東京大学大学院工学系研究科

藤田　誠

CSJフェスタ公開講座ノーベル賞解説講演　（H28.11.14 東京）

1

３人の紹介受賞理由

http://www.nobelprize.org/nobel_prizes/chemistry/laureates/2016/

2

ノーベル賞

どういう研究が選ばれるのですか？

2016ノーベル化学賞「分子機械」：どうして選ばれたのですか？

「分子機械」とは何ですか？

3

かつて、環がつながった分子への熱狂があった

分子の環がつながった空想上の化合物「カテナン」は、 19世紀初頭には化学者の間で考えられていた。

4

コップ一杯の水に環と紐を漂わせ、「手を触れることなく」環に紐を通しなさい

catenane rotaxane knot

当時の化学者への命題

5

Wasserman の挑戦（1960)

Frisch, H. L.; Wasserman, E. “Chemical Topology”, J. Am. Chem. Soc. 1961, 83, 3789-3795.

Wasserman, E. “The Preparation of Interlocking Rings: a Catenane”, J. Am. Chem. Soc. 1960, 82, 4433–4434

C34H63D5 C O

CHOH

(CH2)12

C34H63D5EtO (CH2)32 OEt

OO+

2. AcOH

C O

CHOH

(CH2)12

EtO (CH2)32 OEt

OO 1. Na xylene 140 ºC

2. AcOH

Zn (H2)DCl

1. Na xylene 140 ºC

C34H63D5

6

Schill のDirected Synthesis（1964)

Schill, G.; Lüttringhaus, A. “Preparation of Catena Compounds by Directed Synthesis.” Angew. Chem., Int. Ed. Engl. 1964, 3, 546–547.

C OO H N

(CH2)12

(CH2)12

(CH2)25

O

OH C OO H N

(CH2)12

(CH2)12

(CH2)25

HO

OC OO N

(CH2)12

(CH2)12

(CH2)25

O

C OAcO N

(CH2)12

(CH2)12

(CH2)25

AcOC

O N

(CH2)12

(CH2)12

(CH2)25

O

C OHO N

(CH2)12

(CH2)12

(CH2)25

HO

O

O

(CH2)12

(CH2)12 NH2

Cl

Cl(CH2)25

(CH2)25

HO

HO

O

O

(CH2)12

(CH2)12 NO2

Cl

Cl(CH2)25

O

O

(CH2)12

(CH2)12 H

Cl

Cl(CH2)25

(CH2)12MeO

MeO

(CH2)12

C O

7

Sauvage Template Synthesis (1983)

人工光合成（水の光分解）を目指した光誘起電子移動触媒の研究が発端（1970年代）

2 H2O 2 H2 + O2 hνcat.

J. Chem. Soc., Chem. Commun., 1983, 513

N

N

N

NN

NRu

2++

N

NNN

Cu

N

NCu

+OCH3

OCH3

NN

H3CO

H3CO

8


N

N

N

NN

NRu

2++

N

NNN

Cu

N

NCu

+OCH3

OCH3

NN

H3CO

H3CO

9

N

NCu

+O

O

NN

O

O

O

O

O

OO

O

O

O

N

NCu

+OH

OH

NN

HO

HO

N

N

O

O

NN

O

O

O

O

O

OO

O

O

O


- Cu+

C. O. Dietrich-Buchecker, J.-P. Sauvage, J.-P. Kintzinger, Tetrahedron Lett., 1983, 24, 5095

10



11



12

Sauvage Trefoil Knot (1988)

Angew. Chem. Int. Ed. Engl. 1989, 28, 189–192.

(X-ray)

13

Stoddart Organic Template Synthesis (1989)

Blue Box

Angew. Chem. Int. Ed. (1988)

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A [2] Catenane Made to Order

Stoddart Organic Template Synthesis (1989)

Angew. Chem. Int. Ed. 1989, 28, 1396

70%

15

NN

OO

OOO

O

4+

N

N N

N

Sauvage Ring Blue Box

M-30

16

Blue Box

Blue BoxBlue Box

“We propose to call this [5]catenane olympiadane.”

Olympiadane

Angew. Chem. Int. Ed. 1994, 33, 1286

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Borromean rings

ボロメオ家紋章マジョーレ湖（イタリア）に浮かぶボロメオ島

いつしか複雑なトポロジーを構築する「トポロジー化学」の最終標的となった

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Borromean rings

self-assembly

(X-ray)

(2004 by Stoddart)

Science, 2004, 304, 1308

19

コップ一杯の水に環と紐を漂わせ、「手を触れることなく」環に紐を通しなさい

catenane rotaxane knot

当時の化学者への命題19世紀から20世紀前半

Borromean ringsの合成をもって解決された。「トポロジー化学」の終焉

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Toward Molecular Machines

コップ一杯の水に部品を漂わせ、「手を触れることなく」機械を組み立て、作動させることはできるだろうか。

新たなる命題への挑戦

（Feynmanの命題）

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How small can you make machinery? This is the question that Nobel Laureate Richard Feynman, famed for his 1950s’ predictions of developments in nanotechnology, posed at the start of a visionary lecture in 1984. (中略） He was convinced it was possible to build machines with dimensions on the nanometre scale.

Richard Feynman’s Question:

How small can you make machinery?

Richard Feynman

22

Catenane in motion (Sauvage, 1994)

In 1994, Jean-Pierre Sauvage’s research group also succeeded in producing a catenane in which one ring rotated, in a controlled manner, one revolution around the other ring when energy was added. This was the first embryo of a non-biological molecular machine.

Cu(I): tetrahedral

Cu(II): trigonal pyramidalJ. Am. Chem. Soc. 1994, 304, 1308

1+

2+

胎芽、萌芽

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A Molecular Shuttle (Stoddart, 1994)

R. A. Bixxdll, E. Cordova, A. E. Kaifer, J. F. Stoddart, Nature 1994, 369, 133 - 137

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1970-1990 Sheffield1990-1997 Birmingham1997-2007 UCLA (55才で渡米）2008- Northwestern University

Born in Edinburgh in 1942

Professional Carriers

J. Fraser Stoddart

ホワイトハウスにて、大統領(Bill Clinton)に米国の将来の科学技術を提言する有識者会議のメンバーの一人

分子からのボトムアップナノテクノロジーの重要性を強調

G. M. C. P. Collier, E. W. Wong, Y. Luo, K. Beverly, J. Sampaio, F. M. Raymo, J. F. Stoddart, and J. R. Health. Science 289, 1172 (2000)

25

First Solvay Conference (1927)

Piccard Henriot Ehrenfest Herzen de Donder Schrödinger Verschaffelt Pauli Heisenberg Fowler Brillouin Debye Knudsen Bragg Kramers Dirac Compton de Broglie Born Bohr Langmuir Planck Curie Lorentz Einstein Langevin Guey Wilson Richardson

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80年の歳月を経て、第21回Solvay会議(2007)

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Chair: Jean-Pierre Sauvage

21st Solvay Conference on Chemistry “From Noncovalent Assemblies to Molecular Machines”

(November 28-December 1, 2007 @Metropole Hotel, Brussels)

SauvageStoddartFeringa Lehn

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SauvageStoddart Feringa

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“From Noncovalent Assemblies to Molecular Machines”

WILEY社よりSovay 会議議事録が出版される。

Edited by

Jean-Pierre Sauvage

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With a Foreword by Professor Jean-Pierre Sauvage and Professor Makoto Fujita

786 page

“The Nature of the Mechanical Bond”

written by C. J. Brunds & J. F. Stoddart

(2016)

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https://www.nobelprize.org/nobel_prizes/chemistry/laureates/2016/popular-chemistryprize2016.pdf

Molecular Elevator

(Stoddart,2004)

Science 2004, 303, 1845-1849

Molecular Muscle

(Sauvage,2000)

Angew. Chem. IE. 2000, 39, 3284.

32

Feringa - Harada: Unidirectional Motion

分子の１方向回転達成!

N. Koumura, R. W. J. Zijlstra , R. A. van Delden , N. Harada, B. L. Feringa, Nature 1999, 401, 152–155

Light-driven monodirectional molecular rotor

Nagatoshi Koumura1,2, Robert W. J. Zijlstra1, Richard A. van Delden1, Nobuyuki Harada2 & Ben L. Feringa1

1 Department of Organic and Molecular Inorganic Chemistry, Stratingh Institute, University of Groningen, Nijenborgh 4, 9747 AG Groningen, The Netherlands

2 Institute for Chemical Reaction Science, Tohoku University, 2-1-1 Katahira, Aoba, Sendai 980-8577, Japan

Attempts to fabricate mechanical devices on the molecular level1, 2 have yielded analogues of rotors3, gears4, switches5, shuttles6, 7, turnstiles8 and ratchets9. Molecular motors, however, have not yet been made, even though they are common in biological systems10. Rotary motion as such has been induced in interlocked systems11, 12, 13 and directly visualized for single molecules14, but the controlled conversion of energy into unidirectional rotary motion has remained difficult to achieve. Here we report repetitive, monodirectional rotation around a central carbon–carbon double bond in a chiral, helical alkene, with each 360° rotation involving four discrete isomerization steps activated by ultraviolet light or a change in the temperature of the system. We find that axial chirality and

33

Feringa - Harada: Unidirectional Motion

N. Koumura, R. W. J. Zijlstra , R. A. van Delden , N. Harada, B. L. Feringa, Nature 1999, 401, 152–155

Light-driven monodirectional molecular rotor

Nagatoshi Koumura1,2, Robert W. J. Zijlstra1, Richard A. van Delden1, Nobuyuki Harada2 & Ben L. Feringa1

1 Department of Organic and Molecular Inorganic Chemistry, Stratingh Institute, University of Groningen, Nijenborgh 4, 9747 AG Groningen, The Netherlands

2 Institute for Chemical Reaction Science, Tohoku University, 2-1-1 Katahira, Aoba, Sendai 980-8577, Japan

Attempts to fabricate mechanical devices on the molecular level1, 2 have yielded analogues of rotors3, gears4, switches5, shuttles6, 7, turnstiles8 and ratchets9. Molecular motors, however, have not yet been made, even though they are common in biological systems10. Rotary motion as such has been induced in interlocked systems11, 12, 13 and directly visualized for single molecules14, but the controlled conversion of energy into unidirectional rotary motion has remained difficult to achieve. Here we report repetitive, monodirectional rotation around a central carbon–carbon double bond in a chiral, helical alkene, with each 360° rotation involving four discrete isomerization steps activated by ultraviolet light or a change in the temperature of the system. We find that axial chirality and

分子の１方向回転達成!

34

From Switches to Motors

(M ,M )-c is

(M ,M )-tra ns

- sterically hindered alkene - two identical halfs - two chiral entities

資料提供：Ben Feringa

35

ミオシン・アクチンとは・・・２つのタンパク質フィラメントが滑りあう→→筋収縮

36

37

ATP合成酵素は生物分子回転モーター

38

www.nature.com/nature/journal/v440/n7081/ suppinfo/440163a.html).

Into Macroscopic Motion

Molecular machines: Nanomotor rotates microscale objects

Nature 2006, 440, 163

39

Four Wheel Driven Nanocar (2011)

Nature, 2011, 479, 208

40

Just like the molecules of life, Sauvage’s, Stoddart’s and Feringa’s artificial molecular systems perform a controlled

task. Chemistry has thus taken the first steps into a new world. Time has clearly shown the revolutionary effect of

miniaturising computer technology, whereas we have only seen the initial stages of what could result from the

miniaturisation of machines. In terms of development, the molecular motor is at about the same stage as the

electric motor was in the 1830s, when researchers proudly displayed various spinning cranks and wheels in their

laboratories without having any idea that they would lead to washing machines, fans and food processors.

So, 32 years after Feynman’s visionary lecture, we can still only guess at the thrilling developments ahead of us.

However, we do have a definite answer to his initial question – how small can you make machinery? At least 1,000

times thinner than a strand of hair.

Nobel委員会の受賞理由説明（結語）

Sauvage、Stoddart、Feringaの人工分子システムは、生体の分子と同じように、定められた仕事を実行した。化学は新しい世界への第一歩を踏み出した。近年、コンピュータ素子の微細化は革新的効果を示してきたが、一方で機械の微細化で何が起こるかは未だ最初のステージを見ているにすぎない。発展という観点からは、分子モーターは電気モータが1830年代に作られたころのステージに相当する。その頃、研究者は回転するクランクやタイヤを、まさかそれが洗濯機やファンや食品製造機につながるとは思いもよらずに、実験室で誇らしげに実演していた。ファインマンの展望講演から32年が経ち、我々は未だ未来に広がるスリリングな発展を想像しているにすぎない。しかし、彼の最初の問い「どれだけ小さい機械をつくれるか」という問いに対しては、明確な答えを得た。少なくとも、髪の毛の1/000の細さ以下である。

41

人は目標がないと前進できない。日々の目標からせいぜい1~2年先(せいぜい数年先)のスケール

化学者が描く夢の象徴

科学は夢や空想がないと前進できない。５０年～１００年先のスケール

分子化学者のひとつの夢「環がつながった分子」を実現したSauvage, Stoddartが次に描いた夢が分子機械。Feringaは、自然界にすでに存在する生物分子機械とのギャップを一気に縮め、夢の実現に大きな前進をしめした。

ノーベル賞はその夢を実現した人たちに与えられる。

結局、「分子機械」って？

42

NPd

N H2N

N

N

PdH2N

N

N

N

N

Pd

Pd

NH2

NH2

NH2

H2N NH2

•(NO3)8

Molecular Magic Rings

Nature, 1994, 367, 720

(x-ray)

43

研究をやっていて良かったと思うこと

Jean-Pierre Sauvage Makoto Fujita

人と心が通じあう分子は「世界共通言語」　言葉の壁を越えて、国を越えて、世代を越えて

44

MF in Strasbourg (April to September, 1997)

45

分子ノット（結び目）のX線結晶構造

NN

NN

O

OO O O

O

O

NN

NN

O

OO O

O

O

O

Cu+ Cu+

46

Published online 8 June 2007 | Nature

Stoddart 教授65才誕生日記念シンポジウム

May, 2007

次世代を託す若手研究者が集められた

47

at Fraser’s Birthday Symposium

48

一見、怖そうでとっつきにくそうな大物教授

実は優しいおじさん…

49

”Makoto, 　　　#!!△’’＆%＃◇$!▽=~&▶︎%$#%◎#!!△%＃◇$!▽=~&▶︎%$”

50

“Chemistry creates its object.”

“This creative quality, resembling that of art itself, distinguishes it essentially

from natural and historical science. The latter have an object given in

advance and independent of the will and the action of the scientist.”

Marcellin Berthelot (1827-1907)

51

化学は創造の学問

化学って何？- 突き詰めると物理？生物？-

52

化学の研究をやっていて良かったと思うこと

自分の作品、自分の世界を後世に残せるー化学は創造の学問ー

2016年ノーベル化学賞は「歴史的発見」ではなく「歴史的創造」に与えられた。化学の一番の醍醐味である。

53

at Second International Symposium on COE for Innovative Material Science based on Supramolecule

(@Kanazawa on Oct. 27, 2016)

Only Three Weeks after the Nobel Prize Announcement

54

Second International Symp. on COE for Innovative Material Science based on Supramolecule (Oct. 26-27, 2016, Kanazawa)“Basic science is the origin of everything!”

Jean-Pierre Sauvage October 27, 2016 in Kanazawa

55

Nobel week (December 5 -10, 2016, Stockholm)

56

Nobel Lectures (Thursday, December 8, 2016 at Stockholm University)

57

Nobel Prize Concert (Thursday, December 8, 2016 at Stockholm Concert Hall)

58

Nobel Prize Award Ceremony (Saturday, December 10, 2016 at Stockholm Concert Hall)

59

Nobel Prize Award Ceremony (Saturday, December 10, 2016 at Stockholm Concert Hall)

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夢の分子機械へ向けて 3人の紹介 受賞理由 · toward molecular machines ......

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夢の分子機械へ向けて 3人の紹介受賞理由 · toward molecular machines ......