水滑石类插层组装功能材料

水滑石类(LDHs)化合物是一类典型的阴离子型层状材料。LDHs的构筑单元和结构的可控性和多样性,为此类材料的应用研究提供了广阔前景。以LDHs的层状结构和可插层性为线索,介绍了LDHs的结构特征和制备化学,讨论了阴离子插层LDHs的组装原理和主-客体相互作用,对基于主体层板调控及主-客体相互作用的多种插层LDHs功能材料的制备和应用进行了综述,并对LDHs的结构创新和制备技术的研究方向进行了展望。     

Exploring the Effects of Glycosylation and Etherification of the Side Chains of the Anticancer Drug Mitoxantrone

Herein we report the synthesis and biological evaluation of symmetric and asymmetric analogues of the DNA intercalating drug mitoxantrone (MTX) in which the side chains of the parent drug were modified through glycosylation or methyl etherification. Several analogues with glycosylated side chains exhibited higher DNA affinity than the parent MTX. The most potent in vitro cytotoxicity was observed for MTX analogue 8 (1,4‐dimethoxy‐5,8‐bis[2‐(2‐methoxyethylamino)ethylamino]anthracene‐9,10‐dione) with methoxy ether containing side chains. Treatment of melanoma‐bearing mice with MTX or analogue 8 decreased the intraperitoneal tumor burden relative to untreated mice; the effect of 8 was less pronounced than that of MTX. In vitro metabolism assays of MTX with rabbit liver S9 fraction gave rise to several metabolites; almost no metabolites were detected for MTX analogue 8 . The results presented indicate that derivatization of the MTX side chain primary hydroxy groups may result in a significant improvement in DNA affinity and lower susceptibility to the formation of potentially toxic metabolites.     

聚合物／蒙脱土纳米复合材料研究进展

介绍和分析了目前聚合物／蒙脱土纳米复合材料研究的热点。包括有关带有极性基团的插层剂、反应性插层剂和带有POSS基团的插层剂的研究,以及有无相容剂存在下熔融插层制备纳米复合材料方面的研究。讨论了插层剂和相容剂的作用及其机理,并展望了本领域的发展方向。     

不饱和阳离子水性聚氨酯改性蒙脱土的制备与性能研究

合成出一种不饱和水基阳离子聚氨酯树脂（UCWPU）,以其作为插层剂并采用超声波助混技术对蒙脱土（MMT）进行有机改性,通过阳离子交换制备出含有不饱和官能团的活性有机蒙脱土（OMMT）。采用傅里叶变换红外光谱（FTIR）、广角X射线衍射（XRD）、透射电镜（TEM）、热失重分析（TGA）和显微电泳法等检测手段分别对改性后蒙脱土的结构、性能进行了分析表征。结果表明,改性后的蒙脱土层间距由原来的1．21nm增大到2．13nm,阳离子聚氨酯改性的蒙脱土粒子电性显正电。FT—IR和TGA测试结果表明UCWPU分子链稳定存在于蒙脱土层问。     

聚氨酯弹性体/有机蒙脱土纳米复合材料合成和性能

采用性能优异的有机插层剂对蒙脱土(MMT)进行改性,制备有机化蒙脱土(OMMT)。通过单体插层法合成了聚氨酯弹性体(EPU)/OMMT纳米复合材料;采用红外光谱(FTIR)、X衍射(WAXD)、透射电镜(TEM)等手段分析了材料结构,并比较了该纳米复合材料的物理机械性能。     

有机化试剂结构对粘弹性大分子插层蒙脱土的影响

以Gemini季铵盐、十六烷基二甲基甜菜碱和十二烷基三甲基溴化铵为有机化试剂对蒙脱土进行有机化处理和粘弹性大分子插层反应,通过XRD分析测试手段,研究了有机化试剂空间结构大小及可反应基团获得的有机化蒙脱土结构差异,以及粘弹性大分子对不同有机化结构蒙脱土的插层行为,结果表明Gemini季铵盐对蒙脱土进行有机化处理效果最好,粘弹性大分子插层Gemini季铵盐有机化蒙脱土的插层量大于含可反应基团的十六烷基二甲基甜菜碱有机化蒙脱土以及十二烷基三甲基溴化铵有机化蒙脱土的插层量。     

Synthesis and characterization of new reducing agent based on methylmethacrylate‐vinylpyridene copolymer–clay nanocomposites

Methylmethacrylate (MMA)‐vinylpyridine (VP) copolymer‐montmorillonite (MMT) nanocomposites were prepared, by direct interaction of sodium montmorillonite with various copolymers of MMA‐VP, using different ratios of VP. The interaction occurred through ion exchange between sodium cations in MMT and pyridinium ions in the copolymers. The resulting composites were reacted with lithium aluminum hydride forming the supported reagents. The structure of the resulting composites, as determined by elemental analysis, Infrared spectroscopy, and X‐ray diffraction, consisted of the insertions of MMA‐VP macromolecules between lamellar layers. Because of cooperative formation of electrostatic bonding the copolymers were strongly fixed to the inorganic surfaces. The absence of observable transition in the thermogram, using differential scanning calorimetry, confirmed the copolymer sandwiching between the inorganic layers. The thermal stability of nanocomposites was investigated by thermogravimetry analysis. The dispersion of the MMT particles in the polymer matrix was confirmed using scanning electron microscopy. The effectiveness of these materials has been examined in the reduction of potassium ferricyanide. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Vinylester resin‐clay hybrids using various intercalating agents

Vinylester resin‐clay hybrids were prepared by the mixing different types of organically‐modified montmorillonite (OMMT) with vinylester resin (VER) prepolymer, followed by thermal polymerization. VER prepolymer was synthesized from the reaction of diglycidylether of bisphenol‐A (DGEBA) with acrylic acid. Various types of organic ammonium salts have been used as intercalating agents for montmorillonite, including N,N‐dimethyl‐N‐(4‐vinylbenzyl)stearyl ammonium chloride (VSA), N‐allyl‐N,N‐dimethyl‐stearyl ammonium chloride (ASA) and N,N‐dimethyl‐stearyl ammonium chloride (SA). The dispersion of OMMT into VER matrix was studied by XRD, which indicates the dependence of the morphology mainly on the OMMT content. UV–vis spectra of the hybrids were used to give a quantitative value of the effect of OMMT content on the transparency of VER/OMMT hybrid films. Also, the Vickers test has been performed to study the effect of OMMT content on the surface hardness of the hybrid films. In addition, the thermal properties of the hybrids have been characterized by measuring the softening points and thermogravimetric analyses of the hybrids in comparison with the pure resin. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

三元乙丙橡胶/黏土纳米复合材料

利用熔融插层和双羟基甲基十二烷基氯化铵插层剂改性黏土的方法，制备了三元乙丙橡胶／黏土纳米复合材料。X射线衍射(XRD)和透射电镜(TEM)的测试结果表明，形成的纳米复合材料为剥离型。探索了制作该纳米复合材料的最佳工艺方法。研究了这种材料的力学性能及老化性能，分析了该有机黏土增强橡胶的机理。结果表明，在对黏土进行有机改性时，插层剂中的双羟基与黏土中的氧原子形成了氢键，而使黏土层间的相互作用减弱，层间距增大，使三元乙丙橡胶(EPDM)分子链插入黏土层间而导致黏土剥离是该纳米材料形成的主要原因。有机黏土用量为15份时，试样的拉伸强度高迭24．9MPa，扯断伸长率为666％；前者比纯EPDM提高了3～4倍，后者上升了140％。试样的撕裂强度也有明显的改善，而邵尔A型硬度却随有机黏土用量的增加没有明显的变化。同时，试样的耐热老化性能也有了明显的改善．     

Synthesis and Characterization of Trithiocarbonate-Organoclays Nanohybrids and Their Interaction with MCF-7 Cancer Cells

This work presents a new approach for the fabrication of organic/inorganic nanohybrids as anticancer drugs by an intercalation method using S,S-bis（α,α′-dimethyl-α″-acetic acid） （trithiocarbonate） as a modifier and two organoclays, such as reactive octadecylamine/MMT （montmorillonite） and non-reactive dimethyldidodecyl ammonium/MMT. The chemical and physical structures and the surface morphology of these covalently and non-covalently linked nanohybrids were investigated by FT-IR （Fourier translbrm infrared） spectroscopy, ^13C and ^29Si solid state NMR （nuclear magnetic resonance） spectroscopy, XRD （X-ray powder diffraction） and SEM （scanning electron microscopy） analyses, respectively. To evaluate the anticancer activities of the novel BATC/organoclay hybrids against MCF-7 breast cancer cells, a combination of different biochemical and biophysical testing techniques were used. Cell proliferation and cytotoxicity were detected in vitro using a real-time analysis. Cell death was confirmed by using apoptotic and necrotic analyses, the effects of which were detennined by the double staining and Annexin-V-FLUOS testing method. The results demonstrate that intercalated hybrid complexes containing a combination of various anticancer sites, such as free and complexed carboxyl, trithiocarbonate, amine and ammonium cations significantly induced cell death in breast cancer via their interactions with the DNA macromolecules of cancer cells by destroying the self-assemb｜ed structure of growing cells. Fabricated hybrid complexes may represent a new generation of effective and selective anticancer drug systems with a synthetic/natural origin for cancer chemotherapy.