两个基于四氮唑衍生物的配位聚合物的合成

在水热条件下,5-(4-吡啶基)四氮唑(4-PTZ)分别与氯化锌和氯化镉反应,得到2个基于此配体的配位聚合物,它们的分子式分别为{[Zn(4-PTZ)₂Cl₂]·4H₂O}n(1)和{[Cd₃(4-PTZ)₂(H₂O)₂Cl₆]·3H₂O}n(2),且表现出不同的配位模式.这2个化合物均结晶在单斜晶系,化合物1的晶胞参数分别为:a=0.69175(8)nm;b=2.6688(3)nm;c=1.12266(12)nm;β=93.5350(10)°;V=2.0687(4)nm³;Z=4;R₁=0.0318(I>2σ(I));wR₂=0.0829;空间群为P2₁/n.化合物2的晶胞参数分别为:a=1.89713(13)nm;b=1.05579(7)nm;c=1.44649(10)nm;β=102.4890(10)°;V=2.8287(3)nm³;Z=4;R₁=0.0262(I>2σ(I));wR₂=0.1343;空间群为C₂/c.通过元素分析、红外光谱分析和热重分析对该化合物进行了表征,另外荧光测定结果显示化合物1和2的固态粉末在室温下均表现出较强的紫外荧光发射特性.     

靶向DNA的刚性配体的双核芳基钌配合物

以刚性配体1,3-bib（1,3-二（1H-咪唑-1-基）苯）与[Ru（η⁶-p-bip）Cl₂]₂（p-bip,联苯基团）为原料,合成了3种双核芳基钌配合物[Ru₂（η⁶-p-bip）₂（1,3-bib）₂XY]X₂（X=Y=Cl^-（1）,X=Y=Br^-（2）,X=I^-和Y=Cl^-（3）,并用核磁和质谱等对配合物进行了表征。配合物1的单晶衍射结果表明其具有一种刚性双核M₂L₂碗状结构,空腔中心有一个阴离子Cl^-。配合物3对A549细胞有较高的抗癌活性（IC₅₀=13.9 μmol·L^-1）,与顺铂细胞毒性（IC₅₀=15.2 μmol·L^-1）相当。紫外吸收光谱、圆二色谱、凝胶电泳法研究表明配合物1~3与DNA发生强烈的相互作用并且诱发DNA发生解旋。     

含苯并咪唑三足配体的金属配位化合物的合成及对碘的吸附性能

通过溶剂热法合成了2种新型金属配位化合物[Co₃(L1)₂Cl₆]_n(1)和{[Cu (L1)(SO₄)]·2CH₃OH}_n(2),其中L1=2,2′,2″-三(1-苯并咪唑基)乙基胺,是一种中性苯并咪唑三足有机配体。单晶X射线衍射分析表明化合物1是一维链状结构、化合物2是三维结构;红外光谱和粉末X射线衍射表征证实化合物1和2的纯度较高。热重分析表明化合物1和2是耐热性的材料。碘吸附实验表明,2个化合物对环己烷溶液中的碘和气态碘都有很高的捕获性能且具有良好的循环利用性。同时,它们的吸附动力学最符合准二级模型,吸附过程以化学吸附为主。吸附机理研究进一步表明化合物的结构中含有苯、氮杂环等活性基团,间接增加了与碘的吸附位点,提高了与碘的化学反应性和碘的去除率。     

表面相变及Pt负载的BiOBr纳米片的协同光催化效应

通过热处理手段考察了BiOBr纳米片的表面相变过程。通过XRD,Raman,SEM,TEM,UV-Vis-DRS等手段对不同热处理温度下样品的结构进行表征。结果表明,高温热处理下（≥400℃）,BiOBr相向Bi₂₄O₃₁Br₁₀相转变,可形成BiOBr/Bi₂₄O₃₁Br₁₀异质结。通过气相乙醛的降解,并与商用P₂₅TiO₂做比较来评估催化剂的光催化性能,测得活性顺序为：P₂₅TiO₂>BiOBr>BiOBr/Bi₂₄O₃₁Br₁₀。能带结构分析可知BiOBr与Bi₂₄O₃₁Br₁₀间形成I型异质结不利于电荷分离,因而活性降低。然而,当同样条件下于上述催化剂表面负载Pt后,测得光催化活性顺序为：（BiOBr/Bi₂₄O₃₁Br₁₀）-Pt> BiOBr-Pt >P25 TiO₂-Pt。（BiOBr/Bi₂₄O₃₁Br₁₀）-Pt的最高活性归因于BiOBr/Bi₂₄O₃₁Br₁₀异质结与Pt负载的协同分离光生载流子过程,即与BiOBr/Bi₂₄O₃₁Br₁₀界面的光生空穴转移,BiOBr/Pt及Bi₂₄O₃₁Br₁₀/Pt界面的光生电子转移、累积及开启双电子还原O₂的一系列过程有关。     

由邻苯二甲酸和Medpq配体构筑的锌的配合物的水热合成及晶体测定

A metal-organic coordination polymer [Zn(Pht)(Medpq)]_n (Pht=phthalic acid, Medpq=2-methyldipyrido[3,2-f:2′,3′-h]quinoxaline) (1) has been hydrothermally synthesized and structurally characterized by elemental analysis, IR spectrum, TG and X-ray single-crystal structure analysis. Title complex crystallizes in the monoclinic system, space group Cc, with a=1.027 4(4) nm, b=2.955 7(11) nm, c=0.685 2(3) nm, β=112.941°, V=1.916 3(13) nm³, C₂₃H₁₄N₄O₄Zn, M_r=475.75, D_c=1.649 g·cm^-3, μ(Mo Kα)=1.324 mm^-1, F(000)=968, Z=4, the final R=0.038 8 and wR=0.071 7 for 2 697 observed reflections (I>2σ(I)). In the crystal structure, the Zinc atom is six-coordinated with four carboxylate oxygen atoms from two different carboxylate groups and two nitrogen atoms from Medpq ligand, showing a slightly distorted octahedral geometry. Furthermore, it exhibits a one-dimensional structure with Pht-Zn-Medpq as building units. CCDC: 716600.     

水对苯硼酸参与的偶联反应的促进作用

水;离子液体;PEG;苯硼酸;Suzuki偶联反应;Suzuki-Type偶联反应     

薰衣草化学成分的研究

采用各种柱色谱方法对新疆产薰衣草花的95%乙醇提取物的化学成分进行分离纯化, 分离得到9个化合物, 根据理化性质和光谱数据分别鉴定为5'-β-D-glucopyranosyloxyjasmonic butyl ester (1), 5'-β-D-glucopyranosyloxyjasmonic acid (2), dichotomoside E (3), 丁二酸(4), 咖啡酸(5), 3-甲氧基-4-O-β-D-葡萄糖苷-阿魏酸(6), β-谷甾醇(7), 熊果酸(8), 胡萝卜苷(9). 其中化合物1为新化合物, 化合物2～9均为首次从薰衣草中分离得到.     

锰的两种配位聚合物的合成和晶体结构

用水热法合成2个新的三维配位聚合物：[Mn₂(Pyzca)₂Cl₂]_n (1)和[Mn₂(Pyzca)₂Br₂]_n (PyzcaH=2-Pyrazinecarboxylic acid) (2)，并对这2个聚合物进行了元素分析、红外光谱、X-射线单晶等表征。配合物1和2的晶体都属于三斜晶系，P1空间群。配合物1和2分别通过环和分子间氢键连接无限延伸形成三维网格状结构。     

氧化铁改性蛭石的制备、表征及吸附氟的特性

采用共沉淀法制备了3种不同含铁量的氧化铁改性蛭石(Verm-Fe_x,x=5,10,20),研究了纯蛭石(Verm)和Verm-Fe_x的表面性质及吸附氟的特性。与样品Verm比较,3种Verm-Fe_x中Verm的d₍₀₀₂₎层间距略有升高;Verm-Fe_x的孔体积、表面积、表面分形度均随含铁量的增加而升高,其中微孔体积和外表面积的增加幅度更明显。4种样品的等电点(IEP)也随含铁量的增加而明显升高;初始pH＝5.0时,它们的表面ζ电位分别为-16.4,-6.1,10.5和28.4 mV。4种样品对氟的等温吸附数据用单吸附位Langmuir模型拟合(R²=0.973~0.995)时,Verm的R²最高;双吸附位Langmuir模型可很好地描述3种Verm-Fe_x样品的等温吸附过程(R²=0.991~0.998);Freundlich模型对4种样品吸附数据的拟合度较差(R²=0.835~0.937),但R²随样品含铁量的增加而略微升高。初始pH=5.0时,Verm和Verm-Fe_x(x=5,10,20)对氟的最大吸附容量(q_max)分别为3.18,6.76,9.27和12.43 mg·g^-1。可见,Verm-Fe_x(尤其含铁量较高的产物)对表生环境中氟的吸附固定性能明显高于Verm。     

氧化铁改性蛭石的制备、表征及吸附氟的特性

采用共沉淀法制备了3种不同含铁量的氧化铁改性蛭石（Verm-Fe_x,x=5,10,20）,研究了纯蛭石（Verm）和Verm-Fe_x的表面性质及吸附氟的特性。与样品Verm比较,3种Verm-Fe_x中Verm的d_（002）层间距略有升高;Verm-Fe_x的孔体积、表面积、表面分形度均随含铁量的增加而升高,其中微孔体积和外表面积的增加幅度更明显。4种样品的等电点（IEP）也随含铁量的增加而明显升高;初始pH＝5.0时,它们的表面ζ电位分别为-16.4,-6.1,10.5和28.4 mV。4种样品对氟的等温吸附数据用单吸附位Langmuir模型拟合（R²=0.973~0.995）时,Verm的R²最高;双吸附位Langmuir模型可很好地描述3种Verm-Fe_x样品的等温吸附过程（R²=0.991~0.998）;Freundlich模型对4种样品吸附数据的拟合度较差（R²=0.835~0.937）,但R²随样品含铁量的增加而略微升高。初始pH=5.0时,Verm和Verm-Fe_x（x=5,10,20）对氟的最大吸附容量（q_max）分别为3.18,6.76,9.27和12.43 mg·g^-1。可见,Verm-Fe_x（尤其含铁量较高的产物）对表生环境中氟的吸附固定性能明显高于Verm。     

The influence of intercalation rate and degree of substitution on the electrorheological activity of a novel ternary intercalated nanocomposite

Kaolinite/dimethylsulfoxide (DMSO)/carboxymethyl starch (CMS) ternary nanocomposites were prepared according to the combination of intercalation and solution reaction. The results show that the intercalation rate (IR) of kaolinite in the ternary composite is adjusted by changing the mass rate, and the basal spacing of kaolinite was swelled from 0.715 to 1.120 nm. At the suitable component ratio of ternary nanocomposite, the optimum electrorheological (ER) effect can be attained. It is apparent that the notable ER effect of ternary ER fluid was attributed to the prominent dielectric property of the ternary nanocomposite electrorheological fluids (ERF), which is closely associated with the IR. With the increase of degree of substitution, the ER effect of ternary composite ERF is enhanced.     

PEG在微波诱导下对高岭石插层及剥片的研究

利用微波能量，快速制备了高岭石/DMSO插层复合物，并以其为前驱体，在熔融状态，微波诱导聚乙二醇(PEG)置换出高岭石层间的DMSO，微波继续协同PEG作用，可以实现其对高岭石的剥片。同时提出了微波作用机理和微波条件下插层物对高岭石的剥片机理。采用X-射线衍射、FTIR光谱、TG-DTA、TEM等技术对插层复合物进行了表征。     

高岭石插层效率评价

用基于X射线衍射分析(XRD)的插层率、基于热重分析(TGA)的热失重率和基于红外光谱分析(FTIR)的3 600 cm^-1谱带与3 700 cm^-1谱带强度比值对高岭石/二甲基亚砜(DMSO)插层复合物和高岭石/N-甲基甲酰胺(NMF)插层复合物的插层效率进行了综合评价。结果表明,当插层反应进行到1、6和25 d,高岭石/DMSO的插层率分别为5%、52%和89%;而高岭石/NMF的插层率则分别为93%、94%和95%。与此同时,高岭石/DMSO的热失重率分别为1.06%、8.06%和17.46%;而高岭石/NMF的失重率分别为6%、6.5%和14.2%。在红外光谱图中,高岭石/DMSO复合物的3 600与3 700 cm^-1带强度比分别为1.03,1.141和1.628,而高岭石/NMF复合物分别为1.403,1.433和1.612。3种评价方法显示很好的一致性,相对而言,在插层作用的初期,XRD方法比较灵敏,而在插层作用的后期,TGA和FTIR方法则显得更为灵敏和有效。     

高岭石纳米卷的制备与表征

本文以层状茂名高岭石为原材料,利用二甲亚砜、甲醇、十六烷基三甲基氯化铵(CTAC)插层处理成功制备了高岭石纳米卷。利用X射线衍射、红外光谱、扫描电镜、透射电镜、N2吸附-脱附、29Si CP/MAS NMR表征插层前后高岭石结构与形貌的变化。分析表明,高岭石片层的卷曲和剥离同时进行,随着CTAC甲醇溶液浓度的增加以及反应时间的延长,高岭石纳米卷的外径增加,而内径基本保持不变。高岭石纳米卷形成机理与CTAC分子的插层减弱了高岭石层与层之间作用以及表面活性剂的模板效应有关。     

Intercalation of Benzamide into Kaolinite

Well-crystallized kaolinite (K) was initially reacted at 60 degrees C with a water/dimethylsulfoxide (DMSO) mixture and the resulting intercalation derivative (K-DMSO) was characterized by powder X-ray diffractometry (PXRD), thermal analysis (simultaneous TG and DSC), and Fourier-transformed infrared spectroscopy (FTIR). Benzamide crystals were then melted with the K-DMSO derivative at 140 degrees C for 4 days, when a gradual displacement of DMSO by benzamide was observed within the interlayer spacing of the modified kaolinite. The resulting material, after extensive washing with acetone, was characterized and compared to the results obtained previously for the K-DMSO composite. Benzamide intercalation proceeded by gradual displacement of DMSO molecules until completion. The structural stabilization of the K-BZ derivative was explained through the establishment of hydrogen bonds between the carbonyl oxygen atoms of the intercalated benzamide and aluminol groups present at the surface of the kaolinite layer. The interlamellar spacing of K-BZ was shown to be possibly occupied by benzamide molecules that were located at a 68 degrees orientation in relation to the layer surface. Unlike most intercalation molecules such as DMSO, variations in the interplanar spacing of kaolinite were consistent with the nonkeying of any other part of the molecule between the aluminosilicate interlayers. Copyright 2000 Academic Press.     

Intercalation of cyclic imides in kaolinite

The intercalation of two cyclic imides, succinimide and glutarimide, in the interlayer spaces of kaolinite was obtained from a "soft guest-displacement method" by displacing previously intercalated guest molecules. The dimethyl sulfoxide (DMSO)-kaolinite preintercalate was particularly efficient for that purpose. The intercalation exchange was done from a concentrated aqueous solution of the cyclic imides, at ambient temperature, in a relatively short time. Complete displacement of DMSO by the cyclic imides was confirmed by the results of several independent characterizations, including XRD, TG/DTA, FTIR, and (13)C MAS NMR analyses including dipolar dephasing experiments. The imide intercalates are two dimensionally constrained in the kaolinite interlayer spaces, and are structurally organized in a flattened configuration with their cycle roughly parallel to the ab plane of the kaolinite layers. Elemental analysis gives the following compositions: Al(2)Si(2)O(5)(OH)(4)(C(4)H(5)NO(2))(0.65) and Al(2)Si(2)O(5)(OH)(4)(C(5)H(7)NO(2))(0.49), respectively for succinimide and glutarimide. The results of the TG/DTA analyses showed enhanced thermal stabilities of the imide intercalates compared with the starting materials. The intercalation process from the aqueous solution is reversible: in prolonged contact with water, the imide molecules are released, resulting in the rebuilding of the kaolinite structure. These results demonstrate the potential use of kaolinite as a slow-releasing agent for molecules structurally related to the cyclic imides of this study.     

高岭土／羧甲基淀粉复合颗粒的制备及其协同电流变效应

通过二次插层取代法，以二甲基亚砜为前驱体，羧甲基淀粉二次插层取代制备 了高岭土/羧甲基淀粉纳米复合材料。结合XRD，FTIR，SEM和EDS等测试手段对复合 材料的结构进行了表征。研究结果发现，羧甲基淀粉经过二次插层取代引起了高岭 土片层之间的剥离，形成剥离型纳米复合材料。该复合材料制备成电流变液出现了 较大的协同效应，具有很好的电流变行为，并发现电流变性能与复合物中羧甲基淀 粉的含量有密切关系。     

Characterization of kaolinite/emulsion-polymerization styrene butadiene rubber (ESBR) nanocomposite prepared by latex blending method: Dynamic mechanic properties and mechanism

The latex blending method was chosen to prepare Kaolinite/emulsion-polymerization styrene butadiene rubber (ESBR) nanocomposite to improve the interaction between filler particles and rubber matrix chains. The influences of kaolinite particles size, filler contents, and flocculants types on dynamic mechanical properties and the relative reinforcement mechanism of the prepared composite were systematic investigated and proposed. The transmission electron microscopy (TEM) and scanning electron microscopy (SEM) showed that the kaolinite particles were finely dispersed into the rubber matrix and arranged in parallel orientation. The prepared nanocomposites by latex blending exhibited improved crosslinking characteristic and dynamic mechanical parameters. The KAl (SO₄)₂ flocculant presented obvious modification in dynamic properties and crosslinking characteristic. Both the decrease in kaolinite particle size and the increase in kaolinite content can greatly improve the storage modulus and reinforcing effect of kaolinite/ESBR nanocomposites. The dynamic reinforcement mechanism of kaolinite can be explained by filler network including a certain thickness of rubber shell on the surface of kaolinite lamellar structure and the aggregations network between kaolinite particles The optimum way to balance the dynamic properties of rubber nanocomposites at different temperatures is to reduce the surface difference between kaolinite and rubber matrix and the degree of filler-filler networking on the basis of kaolinite with nanoscale (nanometer effect).     

Preparation of poly(ethylene terephthalate)/organoclay nanocomposites using a polyester ionomer as a compatibilizer

In this work, poly(ethylene terephthalate)/organically modified montmorillonite (PET/o‐MMT) nanocomposites were prepared via direct melt compounding in a twin‐screw extruder. The main objective was to study the effects of using a polyester ionomer (PETi) as a compatibilizer to promote the intercalation and/or exfoliation of the o‐MMT in the PET. The o‐MMT content was 0, 1, 3, or 5 wt % and the PETi/o‐MMT mass ratio was 0/1, 1/1, or 3/1. The PETi was efficient to promote the intercalation/exfoliation of the o‐MMT in the PET matrix, as revealed by wide angle X‐ray scattering and transmission electron microscopy. Rheological characterization showed that the PET/o‐MMT nanocomposites exhibited a higher complex viscosity at low frequencies than PET, which is characteristic of materials presenting yield strength. Moreover, the higher the content and/or the degree of intercalation/exfoliation of the o‐MMT, the more the nanocomposite behaved like a solid because of a percolated structure formed by the o‐MMT layers, and the more the storage and loss modulus, G′ and G″, became independent of the frequency at low frequencies. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 3084–3091, 2007     

Fluorene‐based polyester nanocomposites via in situ interlayer polymerization

Fluorene‐based polyester nanocomposites were prepared by in situ polymerization of equivalent weights of 9,9′‐dihexylfluorene‐2,7‐dicarboxylic acid and 4,4′‐dihydroxy‐1,4‐diphenoxybutane (DPB‐OH) in the presence of octadecyl‐montmorillonite (C₁₈‐MMT) as an organoclay. We investigated the intercalation of the organoclay among the polymer chains, with the aim of improving the thermal properties of the polyester. It was found that the addition of only a small amount of organoclay was enough to improve the polyester's thermal properties. The maximum enhancement of the thermal properties of the fluorene‐based polyester nanocomposites was observed with the dispersion of 5 wt% organoclay. Copyright © 2008 John Wiley & Sons, Ltd.