Self-Assembly In Supramolecular Chemistry -- Inspiration From Nature

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Self-Assembly In Supramolecular Chemistry -- Inspiration From Nature. Reporter: Zhengming Tang 唐铮铭 Supervisor : Prof. Jian Pei 2006.11.3. Outline. Introduction Lessons from nature Scientists’ efforts Conclusion and outlook Acknowledgement. Outline. Introduction - PowerPoint PPT Presentation

Text of Self-Assembly In Supramolecular Chemistry -- Inspiration From Nature

  • Self-Assembly In Supramolecular Chemistry -- Inspiration From NatureReporter: Zhengming Tang SupervisorProf. Jian Pei 2006.11.3

  • OutlineIntroductionLessons from natureScientists effortsConclusion and outlookAcknowledgement

  • OutlineIntroductionLessons from natureScientists effortsConclusion and outlookAcknowledgement

  • IntroductionSupramolecular chemistry, a term introduced by Jean-Marie Lehn, is chemistry beyond the molecule, that is the chemistry of molecular assemblies using noncovalent bonds.Jean-Marie Lehn, Science 2002, 295, 2400Freek J. M. Hoeben, E. W. Meijer, Chemical Reviews 2005, 105, 1491Nobel Prize in 1987: Pederson C , Cram D J, Lehn J M.

  • IntroductionFreek J. M. Hoeben, E. W. Meijer, Chemical Reviews 2005, 105, 1491

  • OutlineIntroductionLessons from natureScientists effortsConclusion and outlookAcknowledgement

  • Lessons from natureThe chemist finds illustration, inspiration, and stimulation in natural processes, as well as confidence and reassurance since they are proof that such highly complex systems can indeed be achieved on the basis of molecular components. Jean-Marie Lehn, 1995

    Nature has evolved functional assemblies over millions of years; hence, scientists often gather inspiration from the beautiful structures that are encountered. E. W. Meijer, 2005

  • Lessons from nature--AQP1selective water permeation

    Kazuyoshi Murata, Kaoru Mitsuoka, Teruhisa Hirai, Nature 2000, 407, 599-605.Hydrophobic effects

  • Lessons from nature--light-harvesting protein PE545

    Protein PE545 assembled with eight light-absorbing molecules plays a key role in this photosynthetic systemCentre for Quantum Information and Quantum Control, University of Toronto,Nature Materials 2006, 5, 683-696.

  • Lessons from nature--light-harvesting protein PE545

    Centre for Quantum Information and Quantum Control, University of Toronto,Nature Materials 2006, 5, 683-696.

  • Lessons from nature--DNA bound by base pairs

  • OutlineIntroductionLessons from natureScientists efforts Assembled by hydrogen bond Assembled by - interaction Assembled by metal-ligand Scientists bionic resultsConclusion and outlookAcknowledgement

  • OutlineIntroductionLessons from natureScientists efforts Assembled by hydrogen bond Assembled by - interaction Assembled by metal-ligand Scientists bionic resultsConclusion and outlookAcknowledgement

  • Scientists efforts Assembled by hydrogen bondThe discovery of the Hydrogen Bond could have won someone the Nobel Prize, but it didnt. George A. Jeffrey, Wolfram Saenger, 1991First noted in 1892 by Nernst

    Werner proposed his concept of Nebenvalenz (minor valence) in 1902

    The theory that the hydrogen atom was the center of this weak interaction were first made in 1920 by Huggins as well as Latimer and Rodebush.

    Bernal and Huggins proposed the actual term hydrogen bond in 1935

  • The essence of hydrogen bond Electrostatic or coulomb energy ( ECOU)

    2) Exchange repulsion (EEX)

    3) Polarization energy (EPOL)

    4) Charge-transfer energy or covalent bonding (ECHT)

    5) Dispersion forces (EDIS).Leonard J. Prins, Peter Timmerman, Angew. Chem. Int. Ed., 2001, 40, 2382-2426

  • The essence of hydrogen bondFelix H. Beijer, E. W. Meijer, J. Am. Chem. Soc. 1998, 120, 6761-6769

  • Assembled by hydrogen bondTakashi Kato, Norihiro Mizoshita, Angew. Chem. Int. Ed. , 2006, 45, 38 68.

  • Assembled by hydrogen bondTakashi Kato, Norihiro Mizoshita, Angew. Chem. Int. Ed. , 2006, 45, 38 68.

  • Assembled by hydrogen bondDesign strategyT. Yamaguchi, Takuzo Aida, J. Am. Chem. Soc. 2003, 125, 13934-13935

  • Assembled by hydrogen bondTEM micrographs of (a,b) 1acid with C60(c,d) 1acid alone.T. Yamaguchi, Takuzo Aida, J. Am. Chem. Soc. 2003, 125, 13934-13935

  • Assembled by hydrogen bondLeft: Titration of 1acid (1.2 M) with C70 ([C70]:[1acid] = 0:15:1)Right: Titration of 1ester (1.2 M) with C70 ([C70]:[1ester] = 0:16:1)

    T. Yamaguchi, Takuzo Aida, J. Am. Chem. Soc. 2003, 125, 13934-13935

  • Assembled by hydrogen bondSupramolecular peapodsT. Yamaguchi, Takuzo Aida, J. Am. Chem. Soc. 2003, 125, 13934-13935

  • OutlineIntroductionLessons from natureScientists efforts Assembled by hydrogen bond Assembled by - interaction Assembled by metal-ligand Scientists bionic resultsConclusion and outlookAcknowledgement

  • Assembled by - interactionM. O. Sinnokrot, C. David Sherrill, J. Am. Chem. Soc. 2004, 126, 7690-7697Some simple models:

  • Assembled by - interactionTEM photograph of an aggregate of G3-T17-G3. n=5--6Joke J. Apperloo, Rene A. J. Janssen, J. Am. Chem. Soc., 2001, 123, 6916-6924Rene A. J. Janssen, Jean M. J. Frechet, Macromolecules, 2000, 33, 7038-7043

  • Assembled by - interactionAbsorption and emission spectra of (a) molecularly dissolved (PL excited at 2.64 eV, solid lines) and aggregated (PL excited at 2.20 eV, dashed lines) G3-T11-G3 in dichloromethane and (b) molecularly dissolved (PL excited at 2.61 eV, solid lines) and aggregated (PL excitedat 2.11 eV, dashed lines) G3-T17-G3 in dichloromethane.Joke J. Apperloo, Rene A. J. Janssen, J. Am. Chem. Soc., 2001, 123, 6916-6924Rene A. J. Janssen, Jean M. J. Frechet, Macromolecules, 2000, 33, 7038-7043

  • Assembled by - interactionUV-vis (left) and fluorescence (right) spectra of 2 in THF and butanol.Blue shift: =50 nm for 1; = 71 nm for 2 Much lower fluorescence intensityA. P. H. J. Schenning, E. W. Meijer, J. Am. Chem. Soc. , 2002, 124, 1269-1275

  • Assembled by - interactionTemperature-dependent CD (a), UV/vis (b), and fluorescence (c) spectra of 1 in n-butanol (2.6*10-5 mol.L-1). The last: Temperature-dependent CD spectra of 1 in waterA. P. H. J. Schenning, E. W. Meijer, J. Am. Chem. Soc. , 2002, 124, 1269-1275

  • Assembled by - interaction AFM phase image showing the preferential orientation of large ribbons on graphite. STM topographic image showing the internal structure of a large ribbon on graphite. AFM phase image on silicon, showing left-handed helical aggregates.A. P. H. J. Schenning, E. W. Meijer, J. Am. Chem. Soc. , 2002, 124, 1269-1275The chirality of the monomers side chains imparts chirality to the aggregates

  • Assembled by - interactionPh. Leclere, E.W. Meijer, European Polymer Journal, 2004, 40, 885892

  • Assembled by - interactionPh. Leclere, E.W. Meijer, European Polymer Journal, 2004, 40, 885892

  • Assembled by - interactionPh. Leclere, E.W. Meijer, European Polymer Journal, 2004, 40, 885892AFM image of a thin deposit on mica of (a) 1a from THF; (b) 1b from THF; (c) 1c from THF; (d) 1d from toluene. The scale bar represents 500 nm.

  • Assembled by - interactionAFM images of conjugated chiral oligomers deposited on Si/SiOx: (a) 2a from toluene; (b) 2c from toluene; (c) and (d) 4c fromTHF. The scale bar represents 1.0 nm.Polarity of the silicon plays an important role in the expression of chiralityThermodynamic and kinetic control are also important

    Ph. Leclere, E.W. Meijer, European Polymer Journal, 2004, 40, 885892

  • Assembled by - interactionPh. Leclere, E.W. Meijer, European Polymer Journal, 2004, 40, 885892AFM images of: (a) 2a on graphite; (b) 2a on mica; (c) 3a on Si/SiOx; and (d) 3b on graphite. The scale bar represents 1.0 um.

  • Assembled by - interactionMolecular structure of the oligo(p-phenylenevinylene) derivatives OPV-x [for OPV-3, y =1; OPV-4, y=2; and OPV-5, y=3] and schematic representation of the self-assembly process.Pascal Jonkheijm, E. W. Meijer, Science, 2006, 313, 80

  • Assembled by - interactionSTM images of dimeric OPV4 monolayers on graphite(A) Image size is 12.1*12.1 nm2 (B) Molecular model representing the 2D ordering in A. STM image of mixed lamellae of OPV3 and OPV4 on a graphite surface from a concentrated 1,2,4-trichlorobenzene solution. A. Gesquiere, E. W. Meijer, Nano Lett., 2004, 4, 1175-1179

  • Assembled by - interactionTapping mode AFM images (5*5um2) of OPV4 on substrates drop cast from heptane solutions (6.7*10-6 M) on graphitePascal Jonkheijm, E. W. Meijer, J. Am. Chem. Soc., 2003, 125, 15949

  • Assembled by - interaction(D to F) Tapping-mode AFM images of self-assemblies of OPV-4 on graphite surfaces showing different degree of clustering depending on the concentration of the drop cast solutionPascal Jonkheijm, E. W. Meijer, J. Am. Chem. Soc., 2003, 125, 15949

  • Assembled by - interactionPascal Jonkheijm, E. W. Meijer, J. Am. Chem. Soc., 2003, 125, 15949TemperaturePolarity of solventSymmetry of moleculesThermodynamic conditions

  • Assembled by - interactionVariable temperature measurements (heating ramp, steps of 10 K) (a) UV/vis(b) fluorescence and (c) CD spectra for OPV-4 in dodecane solution (14 M). Pascal Jonkheijm, E. W. Meijer, Science, 2006, 313, 80

  • Assembled by - interactionPascal Jonkheijm, E. W. Meijer, Science, 2006, 313, 80

  • Assembled by - interactionThis opens the way to align these stacks so as to connect their ends to electrodes and study the electro-optical properties of these nanosized wires.Ph. Leclere, E.W. Meijer, European Polymer Journal, 2004, 40, 885892

  • OutlineIntroductionLessons from natureScientists efforts Assembled by hydrogen bond Assembled by - interaction Assembled by metal-ligand