溶胶-凝胶法制备生物活性有机-无机杂化材料的研究进展

已经应用于临床的骨修复材料主要是生物活性陶瓷和金属如钛及其合金制成的生物材料,它们能与生物骨结合但与人体松质骨相比弹性模量高且柔韧性较低。需要研究一种具有与天然生物骨相类似力学性能的生物活性材料。目前已通过溶胶-凝胶法分别用PDMS、明胶、MPS及PTMO与无机系统合成了生物活性的有机-无机杂化材料,材料通过在有机基体中引入Ca2+和特殊的功能化基团如Si—OH等获得生物活性。其今后主要发展方向在于有机成分的引入以达到最佳的柔韧性和力学强度以及作用机理的研究以提高生物活性。

Synthesis and characterization of hybrid organic-inorganic materials based on EA-MAn-APTES and silica

Poly (EA-MAn-APTES)/silica hybrid materials were successfully prepared fromEthyl acrylate (EA), maleic anhydride (MAn) and tetraethoxysilane (TEOS) in the presence of acoupling agent 3-aminopropyltriethoxysilane (APTES),by free-radical solution polymerization and insitu sol-gel process. The mass fraction of TEOS varied from 0 to 25%. The hybrid materials werecharacterized by the methods of FT-IR spectra, solvent extraction, scanning electron microscope (SEM), transmission electron microscope (TEM), differential scanning calorimetry (DSC) andthermogravimetric analysis (TGA) measuring apparatus to get their structures, gel contents,morphologies, particle sizes and thermal performances. The results show that the covalent bonds arebetween organic and inorganic phases, gel contents in the hybrid materials are much higher, theSiO_2 phase is well dispersed in the polymer matrix, silicon dioxide exist at nanoscale in thecomposites and have excellent thermal stability.

Crystallographic Characterization of the Novel Inorganic-organic Hybrid Coordinated Polymer: [(C_(22)H_(50)N_2)(Ag_2I_4)]_n

A novel coordinated polymer [(C22H50N2)(Ag2I4)]n([C22H50N2]2+ = N,N?-1,2- ethylence-bis(N,N?-dimethyl octane ammonium) (EDO)) was synthesized by the reaction of AgI and EDO at room temperature with pH = 6.8, and structurally characterized by means of X-ray single- crystal diffraction. It crystallizes in triclinic, space group P1 with a = 9.6080(1), b = 12.7643(2), c = 7.2157(8) ? a = 100.835(8), ?= 91.030(3), ? = 91.297(9)o, (C21.50H48.50Ag2I4N2), Mr = 1058.46, V = 868.71(19) 3, Z = 1, Dc = 2.023g/cm3, F(000) = 497.5, ?MoKa) = 4.692 mm-1, the final R = 0.0623 and wR = 0.1949 for 2641 observed reflections with I > 2s(I). The title compound consists of cations ([C22H50N2]2+) and anion chain (Ag2I42-)∞ which are combined by static attracting forces in the crystal to form the so-called organic-inorganic hybrid material.

Aromatic bromination with hydrogen production on organic‐inorganic hybrid perovskite‐based photocatalysts under visible light irradiation

Aromatic bromides are important chemicals in nature and chemical industries.However,their tra‐ditional synthesis routes suffer from low atomic economy and pollutant formation.Herein,we show that organic-inorganic hybrid perovskite methylammonium lead bromide(MAPbBr_(3))nanocrystals stabilized in aqueous HBr solution can achieve simultaneous aromatic bromination and hydrogen evolution using HBr as the bromine source under visible light irradiation.By hybridizing MAPbBr_(3) with Pt/Ta_(2)O_(5) and poly(3,4‐ethylenedioxythiophene)polystyrene sulfonate as electron‐and hole‐transporting motifs,aromatic bromides were achieved from aromatic compounds with high yield(up to 99%)and selectivity(up to 99%)with the addition of N,N‐dimethylformamide or its analogs.The mechanistic studies revealed that the bromination proceeds via an electrophilic attack pathway and that HOBr may be the key intermediate in the bromination reaction.

Polarized Electronic Spectra of Organic/Inorganic Hybrid Materials of Chiral Schiff Base Ni（ll） or Cu（ll） Complexes and Disperse Red 1 or Azobenzene in PMMA Films

We have prepared new chiral Schiff base complexes, and copper（Ⅱ） （2） to investigate steric effect of ligands for 1 and bis（N-R-l-phenylethyl-5- methoxysalicydenaminato） nickel（Ⅱ） （1） 2 and known bis（N-R-l-phenylethyl-3,5-dichlorosalicydenaminato） nickel（Ⅱ） （3） and copper（Ⅱ） （4）. By using two kinds of photochromic dyes, disperse red 1 （DRI） and azobenzene （AZ）, we investigated the efficiency of increasing optical anisotropy of organic/inorganic hybrid materials of 1 through 4＋AZ or DRI＋PMMA in polymethylmethacrylate （PMMA） cast films by Weigert effect （and compared with cis-trans isomerization by alternate UV and visible light for 3 and 4 to previous study）. Gradual increase of optical anisotropy was observed for all the hybrid materials regardless of flexibility of Schiff base complexes, and the degree of dichroism and weak intermolecular interactions were discussed based on polarized absorption electronic spectra.

Immobilized nickel(Ⅱ) on organic-inorganic hybrid materials: The effective and reusable catalysts for Biginelli reaction

The immobilized nickel(II) on the organic-inorganic hybrid material was prepared and used as an effective catalyst for the Biginelli reaction.In the presence of the immobilized nickel catalyst,aromatic aldehydes reacted with ethyl acetoacetate and urea (or thiourea) smoothly to generate the corresponding Biginelli products in good to excellent yields without using any additive.The work-up procedure is very simple and practical.Furthermore,the silica-supported nickel(II) could be recovered and recycled for six consecutive trials without significant loss of its catalytic activity.

Unconventional chemical graphitization and functionalization of graphene oxide toward nanocomposites by degradation of ZnSe[DETA]0.5 hybrid nanobelts

The high surface energy of nanomaterials endows them a metastable nature,which greatly limits their application.However,in some cases,the degradation process derived from the poor stability of nanomaterials offers an unconventional approach to design and obtain functional nanomaterials.Herein,based on the poor stability of ZnSe-[DETA]0.5 hybrid nanobelts,we developed a new strategy to chemically graphitize and functionalize graphene oxide(GO).When ZnSe[DETA]0.5 hybrid nanobelts encountered a strong acid,they were attacked by H^+cations and could release highly reactive Se^2−anions into the reaction solution.Like other common reductants(such as N2H4·H2O),these Se^2−anions exhibited an excellent ability to restore the structure of GO.The structural restoration of GO was greatly affected by the reaction time,the volume of HCl,and the mass ratio between GO and ZnSe[DETA]0.5 nanobelts.By carefully controlling the reaction process and the post-processing process,we finally obtained several Se-based reduced GO(RGO)nanocomposites(such as ZnSe/Se-RGO,ZnSe-RGO,and Se-RGO)and various selenide/metal-RGO nanocomposites(such as Ag2Se-RGO,Cu2Se-RGO,and Pt-RGO).Although the original structure and composition of ZnSe[DETA]0.5 nanobelts are destroyed,the procedure presents an unconventional way to chemically graphitize and functionalize GO and thus provides a new material synthesis platform for nanocomposites.

A stable lead halide perovskite nanocrystals protected by PMMA

To enhance the stability in humidity is very crucial to hybrid organic-inorganic lead halide perovskites in a broad range of applications. This report describes a coating stratergy of perovskite nanocrystals via poly- methylmethacrylate-introdnced ligand-assisted reprecipita- tion, using the interactions between the Pb cations on the surface of perovskite nanocrystals and the functional ester carbonyl groups in polymethylmethacrylate framework. The hydrophobic framework shields the open metal sites of hybrid organic-inorganic lead halide perovskites from being attacked by water, effectively retarding the diffusion of water into the perovskite nanocrystals. The as-prepared films demonstrate high resistance to heat and moisture. Additionally, the in- troduction of polymethylmethacrylate into ligand-assisted reprecipitation can effectively control the bulk precipitation and promote the stability of the perovskite solution.