制备有机-无机杂化纳米材料的研究进展

有机-无机杂化纳米材料由于小尺寸和兼具有机、无机材料的各种优良性质,在许多领域都有巨大的应用潜质。本文介绍了模板法、嵌段聚合物自组装、含特殊官能团的乙烯基单体直接聚合法等制备纳米有机-无机杂化材料的方法,并对各自的特点进行了说明。     

有机-无机杂化骨修复材料

寻找理想的骨修复材料一直是骨科领域的研究热点之一。骨修复材料已由最初单纯取代天然骨组织的惰性材料向具有诱导骨组织再生功能的生物活性材料发展,其中有机-无机杂化材料由于有机和无机组分在分子/纳米水平的复合使其能够最大程度地实现二者的优势互补和协同优化,近年来受到广泛关注。本文着重介绍了有机-无机杂化骨修复材料近些年来的研究进展,并对其发展趋势进行了展望。     

有机-无机杂化分离膜研究进展

有机-无机杂化膜材料结合了有机膜材料和无机膜材料的优良性能,已成为分离膜材料研究的一个热点。本文以有机、无机组分间相互作用类型对其进行分类,着重介绍组分间以化学键相结合的有机-无机杂化膜的优良特性,总结了影响此类杂化膜结构和性能的主要因素,概括了它在膜分离中的应用,提出了目前研究工作中存在的不足,并做出了简要的述评。     

有机-无机杂化高分子絮凝剂PAC-PDMDAAC的合成与表征

以过硫酸铵为引发剂,以乙二胺四乙酸四钠(Na4EDTA)为助剂合成了新型有机-无机杂化高分子絮凝剂聚合氯化铝-聚二甲基二烯丙基氯化铵(PAC-PDMDAAC).实验考查了DMDAAC单体质量分数、引发剂用量、反应温度以及反应时间对杂化絮凝剂合成的影响.结果表明杂化高分子絮凝剂的最佳合成条件为单体质量分数30%,引发剂质量分数0.7%,反应温度60℃,反应时间5 h.傅里叶红外光谱(FTIR)、热重分析(TGA)以及扫描电镜(SEM)测试结果表明,杂化聚合物PDMDAAC链端有—SO42-离子存在,其与带正电荷的羟基铝粒子以离子键形式键合.扫描电镜结果显示杂化絮凝剂具有更大的比表面积,易于发挥吸附架桥作用.采用Al-Ferron逐时络合比色法研究絮凝剂中Al形态,结果表明杂化絮凝剂中Alc部分,即不与Ferron发生络合反应的高聚物明显增多.由PAC、复配型PAC-PDMDAAC和杂化型PAC-PDMDAAC絮凝剂分别处理腐植酸-高岭土模拟水样和长江水,结果表明杂化型絮凝剂在浊度和UV254的去除率上优于其它二者.     

溶胶-凝胶法合成有机/无机杂化材料进展——1.组分间以化学键作用的有机/无机杂化材料

介绍了溶胶－凝胶法（Sol-gel process)制备组分间以化学键作用的有机／无机杂化材料的基本情况,根据合成方法进行分类,并指出其发展趋势。     

有机-无机杂化膜的研究进展

有机-无机杂化膜结合了传统有机膜与无机膜的优良性能,已成为膜领域的研究热点之一。本文综述了有机-无机杂化膜的研究现状,归纳了有机-无机杂化膜的分类、制备技术、应用及其优越性,并针对现存的问题及今后的研究发展提出了一些建议。     

有机-无机杂化氧化硅基介孔材料

有机基团可以通过嫁接或共聚的方法引入到氧化硅基介孔材料的孔表面或材料的骨架中,形成表面结合型和桥键型两大类有机-无机杂化氧化硅基介孔材料.本文综述了有机-无机杂化氧化硅基介孔材料的最新研究进展,介绍了其合成方法、应用及潜在的应用领域,详细总结了目前已报道的有机-无机杂化氧化硅基介孔材料的种类,展望了桥键型有机-无机杂化氧化硅基介孔材料的发展及应用前景.     

一种钴-取代型有机-无机杂化三维超分子多酸:合成、结构与表征

在水热条件下,成功合成了一例过渡金属钴修饰的有机-无机杂化Dawson型三维超分子多金属磷钨酸簇合物[Co(dap)_3]_2[H_2P_2W_(18)O_(62)]·11H_2O (1)(dap=1,2-丙二胺),采用X射线单晶衍射、元素分析、红外光谱及热重分析对化合物进行了结构分析和基本表征.化合物1属于正交晶系,Pnma空间群,单胞参数为a=2.688 92(7) nm,b=2.176 67(6) nm,c=1.480 93(5) nm,α=β=γ=90°.从超分子化学的角度来看,化合物1中的饱和Dawson型簇阴离子和金属-有机复合物之间通过广泛的氢键作用,进而形成有趣的4,8-连接的三维超分子网络结构.     

溶胶-凝胶法合成有机/无机杂化材料进展--2.组分间以次价力作用的有机/无机杂化材料

介绍了溶胶-凝胶法(Sol-gelprocess)制备组分间以次价力作用的有机/无机杂化材料的基本情况,根据合成方法进行分类,并指出其发展趋势。     

光固化环氧丙烯酸酯有机-无机杂化体系

二氧化硅杂化体系;溶胶-凝胶法;光固化环氧丙烯酸酯有机-无机杂化体系     

Synthesis of monodispersed organic-inorganic hybrid spheres

This paper describes the attempt to prepare a new group of monodispersed silica-polymer hybrid particles, which consists of silica and amide polymer: poly(vinylpyrrolidone) (PVP) and poly(2-ethyloxazoline) (POXZ). Preparation method is based on the growth of hybrid seeds by the addition of TEOS-polymer solution.Monodispersed PVP-silica hybrid particles of 1.24 µm in diameter were prepared by growing the hybrid seeds of 0.54 µm by the addition of TEOS-PVP solution with ammonia catalyst. In the case of POXZ-silica particles, addition of TEOS-POXZ solution to the solution containing 0.54 µm seeds resulted in monodispersed POXZ-silica hybrid particles and four times repetition of the addition for particle growth gave the hybrid particles of the diameter of 1.6 µm.Improvement of mechanical properties of hybrid particles was observed when the particles were heated at 100 200°C.     

Synthesis of molecular imprinted organic-inorganic hybrid polymer binding caffeine

Random copolymers of poly{(methacrylamide)-co-(vinyl trimethoxysilane)} and poly{(methacrylic acid)-co-(vinyl trimethoxysilane)} were synthesized via a free radical polymerization reaction. Acid catalyzed sol-gel process of tetraethylorthosilicate (TEOS) with aforementioned polymers in the presence of methyl xanthine class of alkaloid like caffeine resulted in the formation of highly transparent monoliths. Solvent extraction of the template leaves behind the recognition sites intact with high selectivity towards the print molecule. The ionic and non-specific adsorptions, which are considered to be the main disadvantages of the molecularly imprinted polymers (MIP), are prevented to a considerable extent by the end capping of surface silanol groups. The template binding efficiencies of MIP were determined by HPLC analysis.     

基于巯基-烯点击反应制备有机-无机杂化硼酸亲和整体柱用于糖蛋白的选择性富集

发展了以巯基-烯点击反应制备有机-无机杂化硼酸亲和整体柱的新方法。首先以四甲氧基硅烷(TMOS)和巯丙基三甲氧基硅烷(MPTMS)作为反应单体,采用溶胶-凝胶反应制备表面含巯基的硅胶整体柱。然后利用巯基-烯(thiol-ene)的点击反应在整体柱上修饰硼酸配基3-丙烯酰胺基苯硼酸(AAPBA),制成AAPBA-硅胶杂化亲和整体柱。对影响硼酸亲和整体柱性能的条件如TMOS与MPTMS的比例、聚乙二醇和甲醇的用量等进行了优化。并采用扫描电镜、红外光谱等分析仪器对整体柱形貌和机械稳定性能进行了表征。研究了AAPBA-硅胶杂化亲和整体柱的分离性能,结果表明,其在中性条件下对含有顺式二醇的生物小分子核苷具有良好的特异亲和能力,并已成功地应用于卵清蛋白、辣根过氧化物酶等糖蛋白的分离。基于巯基-烯反应的制备方法新颖、可靠,可用于制备多种不同类型的硼酸亲和整体柱,具有较大的应用前景。     

Silica-based mesoporous organic-inorganic hybrid materials

Mesoporous organic-inorganic hybrid materials, a new class of materials characterized by large specific surface areas and pore sizes between 2 and 15 nm, have been obtained through the coupling of inorganic and organic components by template synthesis. The incorporation of functionalities can be achieved in three ways: by subsequent attachment of organic components onto a pure silica matrix (grafting), by simultaneous reaction of condensable inorganic silica species and silylated organic compounds (co-condensation, one-pot synthesis), and by the use of bissilylated organic precursors that lead to periodic mesoporous organosilicas (PMOs). This Review gives an overview of the preparation, properties, and potential applications of these materials in the areas of catalysis, sorption, chromatography, and the construction of systems for controlled release of active compounds, as well as molecular switches, with the main focus being on PMOs.     

Two new Keggin-type polyoxometalate-based organic-inorganic hybrid compounds with metal ions and chelate ligands

Two new hybrid compounds with chemical formulas [Co(L₁)₂(H₂O)₂]₂[SiW₁₂O₄₀]·6H₂O (1) and [Cu₂(C₉H₂₂ N)₂(L₂)₂][SiW₁₂O₄₀]·2H₂O (2) (L₁ = 3,3′-diamino-5,5′-bis(1H-1,2,4-triazole), L₂ = 1,2-bis(3-(2-pyridyl)pyrazole-1-ylmethyl)benzene, C₉H₂₂ N = tripropylamine) were prepared in a hydrothermal reaction system containing Keggin-type polyoxometalates (POMs), transition metal (TM) salts (cobalt salts and copper salts), and chelate L₁/L₂ ligands. X-ray structural analysis reveals that 1 and 2 possess 3-D supramolecular host frameworks with large cavities and the polyoxoanions SiW₁₂ reside in these cavities as the guest templates. The photocatalytic activities of 1 and 2 were investigated. Both compounds show efficient catalytic activity for degradation of RhB with 1 > 2. The loading amount of the POM units and the structural features of these POM-based organic-inorganic hybrid compounds may be necessary factors that affect the activity of catalysts in the photocatalytic degradation.     

纳米颗粒透明分散体及其高性能有机无机复合材料

纳米颗粒分散是无机纳米材料在有机体系中应用的关键.本文提出了采用纳米颗粒液相分散体制备高度分散纳米透明有机无机复合材料的新方法,发明了超重力反应-萃取相转移方法制备纳米颗粒液相透明分散体技术,介绍了其制备原理和实施效果,以及其在纳米复合节能膜、纳米润滑油脂和高固含量光学材料等有机无机纳米复合材料中的最新研究进展.     

甲基官能化介孔固相微萃取涂层的合成与表征

采用一步法在碱性条件下以十六烷基三甲基溴化铵(CTAB)为模板剂,用正硅酸乙酯(TEOS)和甲基三甲氧基硅烷(MTMS)直接缩合制备了甲基改性的无机/有机介孔复合材料(Me-MCM-41),并用红外光谱(FTIR)、小角X射线衍射(SAXRD)、热重分析(TGA)、透射电镜(TEM)和氮气吸附-脱附等方法对样品进行了表征。结果表明,甲基成功键合至介孔材料孔道表面形成了无机/有机介孔复合体,该复合体不仅保持了MCM-41高度有序的的二维六方孔道结构,而且还具有较强的疏水性、较高的热稳定性,以及较大的比表面积、孔容和孔径。该材料作为固相微萃取的涂层与高效液相色谱联用对邻苯二甲酸二丁酯(DBP)具有较高的萃取效率。     

Design and synthesis of novel polyglycerol hybrid nanomaterials for potential applications in drug delivery systems

The synthesis of a new drug delivery system based on hybrid nanomaterials containing a β-CD core and hyperbranched PG is described. Conjugating PG branches onto β-CD not only increases its water solubility but also affects its host/guest properties deeply. It can form molecular inclusion complexes with small hydrophobic guest molecules such as ferrocene or FITC with reasonable release. In addition, the achievable payloads are significantly higher as for carriers such as hyperbranched PGs. Short-term in vitro cytotoxicity and hemocompatibility tests on L929 cell lines show that the hybrid nanomaterial is highly biocompatible. Due to their outstanding properties, β-CD-g-PG hybrid nanomaterials are introduced as promising materials for nanomedicine, e.g., for drug delivery issues.     

Synthesis and characterization of a one-dimensional polymeric copper(Ⅱ)-tetrathioporphyrazine

The title polymer PCuS4Pz was synthesized by reaction of 2,3-dicyano-5,6-dihydro-1,4-dithiin,pyromellitic dianhydride and urea with cuprous salt in optimized gentle method.The structure and properties of the PCuS4Pz were characterized by elemental analysis,X-ray powder diffraction,IR,UV-Vis,fluorescence and EPR spectra and variable-temperature magnetic susceptibility.The polymer is black sublimable crystallite and the degree of polymerization has been found to be n>4.The PCuS4Pz in H2SO4 exhibits intensive absorption bands at 236,342,656 and 767 nm and intensive fluorescence band at 410 nm or 464 nm under the excitation of the ultraviolet light of a determined wavelength at room temperature.It has been found that the polymer exhibits a weaker antiferromag-netic interaction (J=-2.cm-1,εff=1.68 B.M.) with an apparent spin S<1/2 in the ground state and its conductivity 298K is 1.01×10-5 S-cm-1 at 13.73 MPa.