人工分子机器.ppt

1、Artificial Molecular Machines,There is Plenty of Room at the Bottom,J. Fraser Stoddart, Stoddart Research Group,Vincenzo Balzani, Photochemistry and Supramoecular,T. Ross Kelly, Kelly Lab of Boston College, USA,Nobuyuki Tamaoki, Molecular Smart System Group, National,T. Ross. Kelly,What would be the

2、 utility of such machines? Who knows? I cannot see exactly what would happen, but I can hardly doubt that when we have some control of the arrangement of things on a molecular scale we will get an enormously greater range of possible properties that substances can have, and of the different things w

3、e can do. Richard P. Feynman Nobel Laureate in Physics (1959),University of California at Los Angeles, USA,Chemistry Group, Universit di Bologna, Italy,Institute of Advanced Industrial Science and Technology, Japan,Molecular Machines,A molecular machine: an assembly of a definite number of molecular

4、 components is designed to perform mechanical movements(output) as a consequence of appropriate external stimulations(input).,The kind of energy input supplied to make them work The type of movement performed by their components The way in which their operation can be monitored and controlled The po

5、ssibility to repeat the operation at will and establish a cyclic process The timescale needed to complete a cycle of operation The function performed by the molecular machine,Chemical Energy,Electrical Energy,Light Energy,Biomotor Molecules：ATP Synthase,J. Am. Chem. Soc. 113, 5133 (1991),J. Fraser S

6、toddart,“ring”,University of California, Los Angeles, USA,MeCNAgPF6 RT 7 Days,2,3,4PF6-,5. 4 PF6,4.2PF6,“stopper”,“thread”,2PF6-,“ring”,“recognition site”,“stopper”,“thread”,“recognition site”,Molecular Shuttle,Template-Directed Synthetic Strategies,The threading followed by stoppering approach,The

7、clipping approach,The slippaging approach,1,2,3,Molecular Elevator,Vincenzo Balzani,Science 303, 1845 (2004),J. Fraser Stoddart,Universit di Bologna, Italy,1H3+,3H33+,2,12+,23H33+,Dibenzo24 crow-8 (DB24C8),(i)3,5-di-tert-butylbenzylbromide (ii)the counterion-exchange (NH4PF6/MeOH/H2O) at elevated te

8、mperature (75),In a CHCl3/MeCN solution (3.0 mL, 2:1), form a 1:1 adduct (superbundle).,6H39+,Height : 2.5nm Diameter : 3.5nm,Hm,Hh,He,Hd,Hi,1H NMR Spectra of 5H3PF69,He, Hd,Hi,Hh,Hm,Electrochemical Experiments,6H39+,56+,66+,5H39+,6H39+,Potential values of BIPY2+ units, in V versus SCE,BIPY2+ units:

9、0.40V and 0.80V,6H39+: 0.35V and 0.80V,The three BIPY2+unitsof 6H39+,(i) are equivalent,(ii) behave independently of one another,(iii) are not engaged in electron donor-acceptor interactions,5H39+,Titration Experiments,The distance ： 0.7nm The force ：200pN (piconewtons: 10-12N),The base-acid control

10、 mechanism might be accompanied by the switching “on” and “off” of a potentially attractive hosting capacity.,A potentially large cavity (1.5nm by 0.8nm), whose sides contain three amine functions and whose floor and roof are defined by aromatic rings, could play host to some large guest molecules.

11、.,A,Linear Artificial Molecular Muscles,NP,CBPQT4+,B,TTF,J. Am. Chem. Soc. 127, 9745 (2005),Chemical-Driven Molecular Rotor,Nature 401, 150 (1999),78 atoms 4 years,1,3,4,5,6,2,120,Animation of a ProposedMolecular Motor,Acc. Chem. Res. 34, 514 (2001),360,Light-Driven MonodirectionalMolecular Rotor,Na

12、ture 401, 152 (1999),E = 8.6 kcalmol-1 60 ,-55,(90:10),（5 : 95）,Irradiation of (P,P)-trans-1 at 280nm at 60 will result in the formation of all three other states of the four-step isomerization cycle.,E = 11.0 kcalmol-1 20 ,360,Mechanically InterlockedMolecular Rotor,Nature 424, 174 (2003),Unidirect

13、ional Rotation,Org. Lett. 6, 2595 (2004),J. Am. Chem. Soc. 125, 5612 (2003),Angew. Chem. Int. Ed. 44, 87 (2005),Novel Molecular Machine,Applications,Appl. Phys. A. 80, 1197 (2005),TTF,DNP,CBPQT4+,Conclusion and Expectation,Artificial Molecular Machines Based on Biomolecules (ATP synthase, DNA, Prote

14、in folding/unfolding ) Interfacing Artificial Molecular Machines with Surfaces and Solid Supports,Multiform artificial molecular machines have been synthesized and investigated. The all-important problem that now needs to be tackled and solved is how to develop robust fabrication methods to realize

15、devices in a routine manner. Further simulation and modeling is needed to bridge the gap from the design, synthesis and operation of molecules in solution to their performance in solid state devices.,Y. Liu, A. H. Flood, P. A. Bonvallet et al., J. Am. Chem. Soc. 127, 9745 (2005).,D. A. Leigh, J. K.

16、Y. Wong, F. O. Dehez et al., Nature 424, 174 (2003).,P. L. Anelli, N. Spencer, J. F. Stoddart et al., J. Am. Chem. Soc. 113, 5133 (1991).,J. D. Badjic, V. Balzani, A Credi et al., Science 303, 1845 (2004).,T. R. Kelly, H. D. Silva, R. A. Silva et al., Nature 401, 150 ( 1999).,T. R. Kelly, Acc. Chem. Res. 34, 514 ( 2001) .,N. Koumura, R. W. J. Zijlstra, R. A. Delden et al., Nature 401, 152 (1999).,References,1,2,3,4,5,6,7,Y. Luo, C. P. Collier, J. O. Jeppesen, ChemPhysChem 3, 519 (2002).,Y. Li, H. Li, Y. Li, Org. Lett. 2005, In Press.,T. R. Kelly, Angew. Chem. Int. Ed. 44, 4124