生物矿化与仿生材料Biomim11_LangSAM课件.pptVIP

Biomimetic Synthesis with Langmuir-Films and SAMs Last lecture: Langmuir- and Langmuir-Blodgett-films crystallization under Langmuir-films (?molecular surface recognition“) Today: cooperative effects: combi-nation of monolayers (?molecu-lar surface recognition“) and additives in solution (“vectorial regulation”) Self assembled monolayers (SAMs): alternative to Langmuir films Literature: B. Heywood, S. Mann ?Template-directed nucleation and growth of inorganic materials“ Adv.Mater. 6 (1994) 9. G.Xu, N.Yao, I,Aksay, J.Groves “Biomimetic synthesis of macroscopic-scale calcium carbo-nate films: Evidence for a multistep assembly process” J.Am.Chem.Soc. 120 (1998) 11977. Langmuir-Films mit Porphyrins Amphiphil: tri-carboxyphenylporphyrin-iron(III) μ-oxo-dimer ?-A-Plot: significant interaction with Ca2+ solution film in liquid state film in a “condensed” state Interaction of Porphyrin- Amphiphil with Calcite Distance of -COOH groups in amphiphil corresponds with distance between Ca- ions in (00.1)-plane of calcite Interaction of Functionalized Surfaces with supersaturated Solutions Proper functionalization of the surface promote heterogeneous nucleation, homogeneous precipitation will occur simultaneously Mineralization of coherentCaCO3-films Molecular surface recognition: by Langmuir-film Vectorial regulation: poly-acrylic acid (PAA) as soluble inhibitor homogeneous nucleation is suppressed crystallization at interface is favored Microscopic Investigation of CaCO3-Films Scanning Electron Microscopy smooth surface at interface to Langmuir films regularity of film decreases to supersaturated solution Transmission Electron Microscopy highly crystalline regions within film next to Langmuir films Schematic Representation of Different Models of Film Formation Epitaxy: direct formation of film with orientation of template Stepwise process: by initial deposition of amorphous material, densification and crystallization SAMs Starting materials: trichlorosilanes with a