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Rational Design of Multilayer Collagen Nanosheets with Compositional and Structural Control
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文摘
Two collagen-mimetic peptides, CPp>+p> and CPp>鈥?/b>p>, are reported in which the sequences comprise a multiblock architecture having positively charged N-terminal (Pro-Arg-Gly)3 and negatively charged C-terminal (Glu-Hyp-Gly)3 triad extensions, respectively. CPp>+p> rapidly self-associates into positively charged nanosheets based on a monolayer structure. In contrast, CPp>鈥?/b>p> self-assembles to form negatively charged monolayer nanosheets at a much slower rate, which can be accelerated in the presence of calcium(II) ion. A 2:1 mixture of unassociated CPp>鈥?/b>p> peptide with preformed CPp>+p> nanosheets generates structurally defined triple-layer nanosheets in which two CPp>鈥?/b>p> monolayers have formed on the identical surfaces of the CPp>+p> nanosheet template. Experimental data from electrostatic force microscopy (EFM) image analysis, zeta potential measurements, and charged nanoparticle binding assays support a negative surface charge state for the triple-layer nanosheets, which is the reverse of the positive surface charge state observed for the CPp>+p> monolayer nanosheets. The electrostatic complementarity between the CPp>+p> and CPp>鈥?/b>p> triple helical cohesive ends at the layer interfaces promotes a (CPp>鈥?/b>p>/CPp>+p>/CPp>鈥?/b>p>) compositional gradient along the z-direction of the nanosheet. This structurally informed approach represents an attractive strategy for the fabrication of two-dimensional nanostructures with compositional control.

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