Template-Directed Synthesis of Nanoplasmonic Arrays by Intracrystalline Metalization of Cross-Linked Lysozyme Crystals

摘要

Many protein crystals are distinguished by 3-D structures that contain well-ordered interpenetrating nanoporous and mes-oporous solvent channels often 0.5-10 nm in diameter. These channels provide a chemically heterogeneous and chiral environment that comprises 30-65 % of the total crystal volume with associated pore volumes and surface areas in the range of 0.9-3.6 mLg~(-1) and 800-3000 m~2g~(-1), respectively. The use of protein crystals for materials applications has been traditionally restricted by their mechanical and chemical fragility; however the onset of simple cross-linking technology has significantly extended the scope for protein aggregates and crystals in catalysis and drug delivery. separation science, and sensors. In general, cross-linking is achieved by soaking the protein crystals in a 1-5% aqueous glutaraldehyde solution containing a heterogeneous mixture of monomers and aldol-based oligomers of various lengths. Reaction of these species with lysine residues results in a network of Schiff-base coupled intermolecular linkages to produce cross-linked protein crystals with high structural fidelity.As a result, the glutaraldchydc-fixed crystals are physically robust, stable in organic solvents, and insoluble in water. Moreover, immersion of the cross-linked crystals in aqueous solutions of organic dyes, drugs, and antibiotics results in uptake of the guest molecules specifically within the solvent channels of the protein lattice.