December 12, 2012, Den Haag Macroscopic Self-Assembly and Self-Healing through Molecular Recognition Osaka University Akira Harada
Molecular Recognition O O Host-Guest Chemistry O M + O O O O O Crown Ethers, Pedersen O CH 3 H H H 3 C H O Cyclophanes, Cram O CH 3 H H 3 C O O Supramolecular Chemistry O O N O N O O O M N + O N Cryptands, Lehn Development & use of molecules with structure-specific interactions
Biological Systems Macromolecular Recognition Enzyme -Substrate Antibody -Antigen DNA, RNA サイズ : 400 330 種類 : 40KB JPG Supramolecular Polymers Microtubules, Microfilaments, Cells
Macromolecular Recognition Main-chain Side-chain Supramolecular Polymers End-group
Cyclodextrins (CD) = H O CH 2 OH O H OH H H OH H 6 α β γ
JACS, 2004, 2007 Acc. Chem. 2009 Angew. Chem. 2011 Nature Highlight Mol.Necklace Nature,1992 Mol. Tube Nature, 1993, 1994 Mol. Abacus JACS, 2000,2003 JACS, 2006 JACS, JACS, 2007 2007 Sol-Gel Transition Mol. Shuttle Org. Lett, 2000 Electric Trap JACS, 2000 Angew. Chem. 2006, 2007, 2010 Nature Chem. 2011 Nature Commun..,2011, 2012, in press Cyclic Daisy Chain JACS, 2000 Chem. Soc. Rev., 2009 Angew. Chem. 2008 Unidirectional Threading JACS, 2006, Chem. Commun. 2009, Cover JACS, 2005, 2006 Chem. Rev., 2009 JACS, 2005, 2008
Polyrotaxane(Molecular Necklace) Chemistry (Textbook) 2011 Nature, 1992
Topological Gel Extension 張力 Disperse Pulley Effects 張力 Molecular Pulley トポロジカルゲル Highly Extensible, Swelling Biocompatible Venture (Ito et al.)
WORLD'S FIRST SELF-HEALING iphone CASE Nissan brings automotive innovation to the world of technology Jan 16, 2012 ID:87812 Nissan announces unique self-healing iphone case - the Nissan Scratch Shield iphone case Nissan's Scratch Shield paint is a world first in paint technology that allows fine scratches to quickly mend themselves Addition benefits such as scratch-resistant and easier-to-grip than normal glossy phone surfaces The outer paint' is made from polyrotaxane, when damage occurs to the coating in the form of a fine scratch, the chemical structure is able to react to change back to its original shape and fill the gap - 'healing' the blemish.
Polymeric Materials Scratch Polyrotaxanes Self-healing From HP of Ito Labo. (Tokyo)
Self-Healing Controlled by Redox Host (CD) Polymer + Guest (Ferrocene) Polymer Redox Responsive Self-Healing Supramolecular Hydrogels Oxidation + paa-βcd + No healing Reduction paa-fc Self-healable Nature Commun., 2011, 2, 511.
Host - Guest Gel (CH 2 CH) x -r-(ch 2 CH) y -r-(ch 2 CH - ) z - C=O NH 2 C=O NH C=O NH b-cd
Self-Healing of Host-Guest Gel Cut After 24 Hours 4
2010 年 Self-Healing & Self-Replicating systems will be realized
Can you see Molecular Recognition?
Polyacrylamide Gel (CH 2 CH) x -r-(ch 2 CH - ) y - C=O NH 2 C=O NH CH 2 NH C=O -(CHCH 2 ) z - 1) No Interactions with Protein (Elecrophoresis) 2) No Interactions with DNA, RNA (Sequencing) 3) No Interactions with Polysaccharides (GPC, SEC) 4) Little Interactions with small molecules
Host Gel Guest Gel (CH 2 CH) x -r-(ch 2 CH) y -r-(ch 2 CH - ) z - C=O NH 2 C=O NH a-cd b-cd g-cd C=O NH CH 2 NH C=O -(CHCH 2 ) z (CH 2 CH) x -r-(ch 2 CH) y -r-(ch 2 CH - ) z - C=O NH 2 C=O R R = Ad (Adamantane) C=O NH CH 2 NH n-bu: (CH 3 CH 2 CH 2 CH 2 O-) t-bu : CH 3 CH 3 -C- O- CH 3 C=O -(CHCH 2
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Adamantane Gel (Green) & b-cd Gel (Red)
Adamantane Gel (Green) & b-cd Gel (Red)
13 7
b-cd Gel (Red) & Adamantane Gel (Green) (
b-cd Gel (Red) & Adamantane Gel (Green)
Nature, 468, 479 2011, On-line publication
b-cd Gel (Red), n-bu Gel (Yellow), t-bu Gel (Green)
b-cd Gel (Red), n-bu Gel (Yellow), t-bu Gel (Green)
01 5 b-cd Gel (Red), a-cd Gel (Blue), n-bu Gel (Yellow), t-bu Gel (Green)
b-cd Gel (Red), a-cd Gel (Blue), n-bu Gel (Yellow), t-bu Gel (Green)
Macroscopic Self-Assembly through Molecular Recognition Nature Chem., 2011
Self-Assembly 1) Molecular Self-Assembly Well-defined Hydrogen-Bonds Ligand-Metal Bonds 2) Self-Assembly of Objects Capillary Forces Electrostatics Magnetics (Whitesides et al.)
Chemical Structures of Host and Guest gels Host Gel Guest Gel
Dissociation of Gel Assembly by UV Light UV vis + α-cd Gel(Blue) & Azo Gell (Yellow)
Switching of Gel Assembly by UV Light α-cd Gel (Blue), β-cd Gel (Red) Azo Gel (Yellow),
Sol-Gel Transition by Light + CD-CUR PAA-Azo UV (365 nm) visible light or D (60 C) Gel Sol Angew. Chem. 2010, Nature Asia Highlight
Photo-Resposive Materials formed by CD Polymer and Azobenzene Polymer Partially Corss-linked between Host polymers & Guest Polymers (Chemical Cross-linking) Reversible Cross-linking by Formation of Inclusion Complexes between Side-Chains 光により伸縮できるゲル完成光刺激によって伸縮するヒドロゲル
布 Acrylamide Gel Cloth Azo-αCD Gel λ= 365 or 430 nm Nature Commun., Accepted
Macrocopic Self-Assembly Mol. Tube Nature,1993, Nature 1994 Self-Healing Nature Commun., in press Nature Chem., 2011 Nature Highlight, 2010 Mol.Necklace Nature,1992 Mol. Abacus JACS, 2000,2003 Nature Commun., 2011 Artificial Polymerase Sol-Gel Transition Angew. Chem. 2006, 2007, 2010 Nature Asia, Highlight, 2010 Solvent Switching Artificial Muscle Nature Commun., accepted Acc. Chem. 2009 Angew. Chem. 2011, Nature, Highlight Angew. Chem. 2008, Hot Paper Photoswitchable Gel Assembly Nature Commun. 2012 Shape Memory Nature Commun., 2011
Harada Lab. (Osaka Univ.)