2009-8-161超分子化学导论之九超分子化学导论之九 Layer- by- Layer Assembly张张 希希 清华大学化学系清华大学化学系Layer- by- Layer (LbL) assemblyG. Decher, J. D. Hong, Makromol. Chem. Macromol. Symp. 1991, 46, 321. X. Zhang, J. C. Shen, Adv. Mater.1999, 11, 1139.0 010010020020030030040040050050060060070070019911991 19931993 19951995 19971997 19991999 20012001 20032003LbL techniqueNumber of publications per yearGlassMultilayer of colloidal particlesR. K. Iler, Journal of Colloid and Interface Science, 1966, 21, 569- 594.“A new technique has been developed by which alternate layers of positively and negatively charged colloidal particles can be deposited from sols onto a smooth surface such as glass”, by this way, “invisibly small particles, polyvalent ions, surfactants, and water-soluble polymers can be simply observed and studied.”, and even “proteins such as gelatin and bovine albumin(can) be adsorbed equally well”.9.1 基于氢键的自组装多层膜基于氢键的自组装多层膜Polymer blendsABABMultilayer buildup based on H-bondingIIINH2NH2NH2NH2NH2NH2HOOHOOHOOHOOHOOHOONH2NH2NH2NH2NH2NH2PVPNH2NH2NH2NH2NH2NH2 NNNHOOHOOHOOHOONHOONHOONPAAIII200240280320360400 wavelength (nm)0.0000.0500.1000.1500.2000.250absorbance0246810 number of bilayers0.0000.0200.0400.0600.080absorbance at 256 nm8642NmPoly(4-vinylpyridine)HOOnP Po ol ly y( (a ac cr ry yl li ic c a ac ci id d) )X. Zhang et.al. Macromol. Rapid Commun. 1997, 18, 509 (Jan. 24, submitted) M. F. Rubner, Macromolecules, 1997, 30, 2717 (Jan. 17 submitted)2009-8-162COOHOCOHOHNCONH2NH2NH2NH2NH2NH2NNNH OOH OOHOOHOONHOONHOONPoly(acrylic acid)Poly(4-vinylpyridine)H- bonding identified by FTIR1718 cm-11709 cm-10.001.002.003.004.00 2theta10100100010000100000countsper secondinarbitraryunitsMonitoring multilayer buildupWang LY et al Langmuir,1999, 15,1360.0.0000.1000.2000.300 concentration of PVP solution (g/L)1.41.82.22.6thickness of bilayer (nm)Bragg diffraction2dsin =n dKiessig fringed氢键给体密度对多层膜构筑的影响氢键给体密度对多层膜构筑的影响实验证明氢键是成膜的主要推动力，但其他分子间相互作用力的贡献不可忽视。实验证明氢键是成膜的主要推动力，但其他分子间相互作用力的贡献不可忽视。 X. Zhang, L. Wang et al Langmuir, 2000, 16, 10490; Langmuir, 2004, 20, 8892NNC2H5+ Br1-nn-HOOnNmPoly(acrylic acid)Poly(4-vinylpyridine)HOOnNmPoly(acrylic acid)Poly(4-vinylpyridine)pHpH敏感的氢键多层膜：构象重排导致的微孔薄膜敏感的氢键多层膜：构象重排导致的微孔薄膜付昱，张希 等 Macromolecules 2002, 35, 9451; Langmuir 2003, 19, 8497; Langmuir 2004, 20, 11828.美国美国Chem. Mater.副主编副主编Frank Caruso在在 Macromolecules 2005, 38, 3414一文中指一文中指 出出 : “Stockton and Rubner first reported hydrogen- bonded LbL assembly of polyaniline with a number of different alternating species: PVA, PAAm, PVPON, and PEO. Almost simultaneously, Zhang and co- workers demonstrated the use of hydrogen bonding to assemble multilayers comprising PVP and PAA”Layer-by-Layer deposition based on coordination bonding H. M. Xiong, X. Zhang, et al, Adv. Mater., 1998, 10, 529.H2S gasPVPPSS-Cu2SPSS-Cu2SPVPPSS(Cu 1/22+)2+)PSS Cu 1/2(Cu S nanoparticle2=NSOOO Cu2+2009-8-1639.2 共价键连接的多层膜共价键连接的多层膜Electrostatic force driven LbL assemblyStability is depending on pH, ionic strength etc.Ways to fabricate robust multilayer assembliesIonic self- assembly + in- situ chemical reaction(simplicity in operation)(under an external stimulus)Covalently attached multilayer assembliesBuilding blocks with charged pair groups which can undergo reaction.Ionic self- assemblyPost- photo induced reactionhUV- VIS absorption spectra of multilayer films of DAR/PSSN2+NHCH2SO3-CHCH2DARPSSSun J.Q. , Zhang X. et al., Chem. Commun. 1998, 1853200300400500600 Wavelength / nm0.000.100.200.300.400.50Absorbance02468 Number of bilayers0.000.100.20Absorbance at 380 nm- * transition of diazonium groupUV- VIS absorption spectra of eight bilayers of DAR/PSS under UV irradiationCHNHCH2OSO2CH22N+NHCH2SO3-CHCH2hn n200300400500600700 Wavelength/nm0.000.200.400.60Absorbance0 s 20 s 40 s 1 min 1.5 min 3 min 5 minUV irradiation with 30W mercury lamp at distance of 10 cm380nm290nm332nm孙俊奇孙俊奇 全国百篇优秀博士论文全国百篇优秀博士论文Building blocks for robust multilayer assemblyN HCH2N2+HSO4-nPolycations with diazonium groupSO3-CHCH2nPolyanions with sulfona groupPolyanions with carboxylic groupCHCH2COOHnDyes with sulfonate or carboxylate groupParticles with sulfonate or carboxylate groupSO3-SO3-SO3-SO3-NHN NHNSO3-SO3-SO3-SO3-SO3-SO3-SO3-SO3-COOHCOOHCOOHCOOHCOOHCOOHCOOHCOOHSun J.Q., Zhang X. et.al., Chem. Commun. 1999, 693; Langmuir, 2000, 16, 46202009-8-164N2+NHCH2ONHCH2CHCH2COCOO-CHCH2hn n12mSO3HSO3H SO3H SO3H SO3HSO3H SO3HSO3H SO3H SO3H SO3HSO3Hmask10min sonication in 0.25M SDS aqueous solution20s UV irradiation Layer- by- Layer self- assemblysubstratesubstratesubstratesubstrateDARPAASO3HShi F., Zhang X. et al. Adv. Mater. 2002, 14, 805N2+NHCH2ONHCH2CHCH2COCOO-CHCH2hn nSO3HSO3H SO3H SO3H SO3HSO3H SO3HSO3H SO3H SO3H SO3HSO3Hmask10min sonication in 0.25M SDS aqueous solution20s UV irradiation Layer- by- Layer self- assemblysubstratesubstratesubstratesubstrateDARPAASO3H聚电解质多层膜的图案化聚电解质多层膜的图案化Zhang X. et al. Adv. Mater. 2002, 14, 805- COOH/- SO3H- COOH/- OH- COOH/- NH2 (positive charge P