纳米反应器研究进展

1、会计学1纳米反应器研究进展纳米反应器研究进展reactantsproductsInspired by NatureNanoReactorCompartmentalization /Accumulation / Confinement Stabilized specific transition states & products(Cascade Reaction in Time & Space)(Tuned Activity, Selectivity & Stability)Well-defined Reaction Environments Chemical Conv

2、ersions in NatureEnzyme - Cell nm mCoupling of Reactions in Time & SpaceReactorApplications:Target chemical synthesis, nanoparticle synthesis,catalysis, sensor, detectorMolecular NanoreactorSupramolecular & Macromolecular NanoreactorBiomacromolecular NanoreactorSpecific Binding Interaction (

3、directional, selective) Stabilized Transition State & Lowered Ea Renstein, D. G. Chem. Rev. 1987, 87, 1047. Kirby, A. J. Angew. Chem., Int. Ed. Engl. 1996, 35, 707.Selectively Recognize & Bind a Desired Substrate.Examples: crown ether, calixrene, cyclodextrin, etc. (Covalent-bonded or self-a

4、ssembled)Enzyme mimicEnzymeMimicP450Binding CavityBreslow, R.; Huang, Y.; Zhang, X.; Yang, J. Proc. Natl. Acad.Sci. U.S.A. 1997, 94, 11156.1234Breslow, R.; Huang, Y.; Zhang, X.; Yang, J. Proc. Natl. Acad.Sci. U.S.A. 1997, 94, 11156.Covalent Molecular Nanoreactor-Cyclodextrin Fixation EffectEnzyme mi

5、mic234Androstane-3,17-diolBreslow, R.; Zhang, X.; Huang, Y. J. Am. Chem. Soc. 1997, 119, 4535.No reactionMixture56Hof, F.; Craig, S. L.; Nuckolls, C.; Rebek, J., Jr. Angew. Chem.,Int. Ed. 2002, 41, 1488.Covalent Non-covalent (reversible)Y . Aoyama, Y. Tanaka, H. Toi, H. Ogoshi, J. Am. Chem. Soc. 198

6、8,110, 634.T . Heinz, D. M. Rudkevich, J. Rebek, Jr., Nature 1998, 394, 764.O . D. Fox, J. F. Y. Leung, J. M. Hunter, N. K. Dalley, R. G. Harrison, Inorg. Chem. 2000, 39, 783.directional and specificH-bondComplexationmore robustReaction AccelerationWith the Capsule 2: Rate acceleration: many years (

7、human life scale) to several days High selectivity: only 1,4-addition product was observed.Chen, J.; Rebek, J., Jr. Org. Lett. 2002, 4, 327.Not fitting-No reaction 1Yield: 88%.Yield: 90%.Yield: 92%.Confinement Effect“cavity-directed synthesis”bowl-shapetube-shapecage-shape Yoshizawa, M.; Kusukawa, T

8、.; Fujita, M.; Sakamoto, S.; Yamaguchi,K. J. Am. Chem. Soc. 2001, 123,10454.Yoshizawa, M.; Kusukawa, T.; Fujita, M.; Yamaguchi, K. J.Am. Chem. Soc. 2000, 122, 6311.Epoxidation of styrene1: lifetime 10 min & TON 100 mVOmpF: gate-keeperInorganic Porous Nanoreactor ZeoliteSol-gel derived porous sol

9、idMOF (Metal organic framework)Rigid structure, easy to process, vast availability in composition, porous structureMesoporous MaterialsFacile synthesisTuned surface/framework propertiesControllable pore size (100102 nm) and structureLarge pore volume and specific surface area Nanocatalysis (compartm

10、entalization)Drug deliveryAdsorption/separation/sensorNano-structured materials synthesis In-situ or post inclusionZeolite“Fish-in-net” for Enzyme Yang, X.; Li, Z.; Liu, B.; Klein-Hofmann, A.; Tian, G.; Feng, Y.; Ding,Y.; Su, D.; Xiao, F. Adv. Mater. 2006, 18, 410.Biomacromolecular Nanoreactor Tobac

11、co Mosaic Virus.2130 identical protein building blocks helical motif around the viral RNAa hollow tube of 300 x18 nm in size a central channel that has a diameter of 4 nm.By chemically controlling the surface charge of the virus, metallization was selectively performed on the outer cylindrical surfa

12、ce or in the inner cavity.Shenton, W.; Douglas, T.; Young, M.; Stubbs, G.; Mann, S. Adv.Mater. 1999, 11, 253.Dujardin, E.; Peet, C.; Stubbs, G.; Culver, J. N.; Mann, S. Nano Lett. 2003, 3, 413.Outside: lysine, arginine pKa 1112.5Inside: aspartic and glutamic acid pKa 13 and 68OutlookHierarchical-str

13、uctured NanoreactorsSingle-molecular nanoreactor with defined binding cavityMicelle and vesicle assemblies as potential cell membrane and enzyme mimicsNumerous new avenues provided by supramolecular chemistry Predefined binding sites (selective, reversible)Tunable cavity dimensionSmart environment-r

14、esponse (gate-keeping)Rigidity, processibility, compatibility.ChemistryMolecular BiologyConstruction of a Synthetic Cell ! Thank You for Your Attention !(14) . Walter, C. J.; Anderson, H. L.; Sanders, J. K. M. J. Chem. Soc.,Chem. Commun. 1993, 458.(15). Yoshizawa, M.; Kusukawa, T.; Fujita, M.; Yamag

15、uchi, K. J.Am. Chem. Soc. 2000, 122, 6311. (16). Kusukawa, T.; Yoshizawa, M.; Fujita,M. Angew. Chem., Int. Ed. 2001, 40, 1879.(17) Aoyagi, M.; Biradha, K.; Fujita, M. J. Am. Chem. Soc. 1999,121, 7457. (18) Fujita, M.; Yu, S.-Y.; Kusukawa, T.; Funaki, H.; Ogura, K.;Yamaguchi, K. Angew. Chem., Int. Ed

16、. 1998, 37, 2082. (19) Yu, S.-Y.;Kusukawa, T.; Biradha, K.; Fujita, M. J. Am. Chem. Soc. 2000, 122, 2665.(20) Fujita, M.; Oguro, D.; Miyazawa, M.; Yamaguchi, K.; Ogura, K.Nature 1995, 378, 469. (21) Kusukawa, T.; Fujita, M. Angew. Chem., Int.Ed. 1998, 37, 3142. (22) Ibukuro, F.; Kusukawa, T.; Fujita

17、, M. J. Am. Chem.Soc. 1998, 120, 8561. (22) Kusukawa, T.; Fujita, M. J. Am. Chem. Soc. 1999,121, 1397. (23) Kusukawa, T.; Yoshizawa, M.; Fujita, M. Angew. Chem.,Int. Ed. 2001, 40, 1879.Covalent Molecular Nanoreactor-Cyclodextrin 120-fold rate enhancement 99% selectivity, R= tButylBreslow, R.; Schmuc

18、k, C. J. Am. Chem. Soc. 1996, 118, 6601Breslow, R.; Anslyn, E. J. Am. Chem. Soc. 1989, 111, 8931.Ribonuclease mimicFixation EffectAngew. Chem. Int. Ed. 2006, ASAPEmulsionPeyratout, C. S.; Mohwald, H.; Dahne, L. Adv. Mater. 2003, 15, 1722.Polymer Capsule by LbLShip-in-bottlePSS: polystyrene sulfonate

19、PAH: poly(allylamine hydrochloride)PIC: diethylcyanine Lay-by-layerControlled stability and permeability by shell thickness, ion strength, pH, viscositypossess an innercompartment capable of accommodating guest molecules,the main difference being that they are notdynamic assembliesOMpfPorins are int

20、egral outer-membrane proteins of Gram-negative bacteria that function as molecular sieves (with exclusion limits of around 600 Da) and are responsible for the uptake of small molecular nutrients and the removal of waste products. Since porin exists only in (gram negative) bacteria, it is the ideal t

21、arget of antibacterial agents. Douglas, T.; Dickson, D. P. E.; Betteridge, S.; Charnock, J.;Garner, C. D.; Mann, S. Science 1995, 269, 54.Ueno, T.; Suzuki, M.; Goto, T.; Matsumoto, T.; Nagayama, K.;Watanabe, Y. Angew. Chem., Int. Ed. 2004, 43, 2527In another study, M13 viruses have been appliedas te

22、mplates for the synthesis of monodisperse,crystalline nanowires of different compositions. First,the genetically modified M13 virus scaffold was usedto assemble crystalline nanoparticles into a 1D array.This was followed by a mineralization process, andfinally the mineralized virus was annealed, all

23、owingthe polycrystalline assembly to form a single-crystalnanowire through the removal of the organic templateCpmv-Cowpea Mosaic Virus60 copies of an asymmetricunit which contains two protein subunits: a smallsubunit, the A domain, and a large subunit, the B+CdomainNature 1998, 394, 764.J. Chem. Soc

24、.,Chem. Commun. 1993, 458.Nature 1995, 378, 469.as catalysts in bimolecular reactions, as phase-transfer catalysts where the capsules act as shuttles that transport encapsulated guests from one solvent phase to another, as a confined reaction chambers which stabilize reactive intermediates or conver

25、t substrates with enhanced activity or selectivity98% yield without any other regio- and stereoisomersYoshizawa, M.; Takeyama, Y.; Kusukawa, T.; Fujita, M. Angew.Chem., Int. Ed. 2002, 41, 1347.Vriezema, D. M.; Hoogboom, J.; Velonia, K.; Takazawa, K.; Christianen, P. C. M.; Maan, J. C.; Rowan, A. E.;

26、 Nolte, R. J. M. Angew. Chem., Int. Ed. 2003, 42, 772.small 2005, 1, No. 5, 510 513Halloysite Nanotubes as BiomimeticNanoreactors*Chem. Eur. J. 2006, 12, 2441 2447Phototransformation of Stilbene in van der Waals NanocapsulesAmphiphilic Network as Nanoreactor forEnzymes in Organic SolventsNano Lett.,

27、 Vol. 5, No. 1, 2005, 45Molecularly Imprinted Nanoreactors for Regioselective Huisgen 1,3-DipolarCycloaddition ReactionJ. AM. CHEM. SOC. 2006, 128, 4178-4179To Combine Precursor Assembly and Layer-by-layer Deposition forIncorporation of Single-charged Species: Nanocontainers withCharge-selectivity a

28、nd NanoreactorsChem. Mater. 2005, 17, 6679-6685ReactorApplications:Target chemical synthesis, nanoparticle synthesis,catalysis, sensor, detectorMolecular NanoreactorSupramolecular & Macromolecular NanoreactorBiomacromolecular NanoreactorCombined advantages of homogeneous & heterogeneous cata

29、lysisDissolved in organic solvents, heterogeneous nature,recovered by ultrafiltration or precipitation in poor solventsReaction scope: Hydrogenation, oxidation, Heck, Suzuki, carbonylationNCH=CH2OPVP: poly(N-vinyl-2-pyrrolidone)The colloid metal catalyst kept in colloidal state for repeated use for 6 times last