镧系元素钼系双11系列杂多蓝的离析和性质研究

本文首次报道了镧系元素钼系双11系列两电子杂多蓝K_yH_z[Ln(XMo_(11)O_(39)_2]·nH_2O(X=P,Ln=La、Ce、Pr、Nd、Sm、Gd;X=Si,Ln=Ce、Pr、Sm、Tb、Dy;X=Ge、Ln=Dy)的制备和离析方法.并通过元素分析、红外光谱、可见-紫外光谱、极谱、循环伏安、热分析、ESR、~(31)P NMR、XPS对产物进行了表征及性质研究.结果表明:杂多蓝阴离子结构较之还原前发生了轻微畸变,还原电子具有一定的离域性.在溶液中杂多蓝较还原前的杂多酸(盐)具有略强的氧化能力.溶液中杂多蓝的氧化能力Ln-P(2)>Ln-Si(2).热稳定性Ln-P(2)>Ln-Si(2).该系列杂多蓝还具有较好的抗碱解能力.     

杂多蓝研究的进展

杂多酸及其盐类以其特有的结构和物理化学性质,已经成为一类有广阔应用前景的酸型和氧化还原型催化剂,在催化领域越来越引人关注。杂多蓝是杂多酸及其盐的还原产物,由于杂多酸及其盐被还原后,大多数呈现深蓝色,所以习惯上称为“杂多蓝”(Heteropoly     

杂多蓝的研究 Ⅰ.具有Dawson结构的钼砷杂多蓝的制备及性质

本文详细地研究了具有 Dawson 结构的钼砷杂多酸(H_6As_2Mo_(18)O_(62))的两电子、四电子、六电子还原杂多蓝的制备条件,离析出了它们的钾盐、铵盐及四丁基胺盐.找到了合适的电解电位.通过电位滴定、极谱、电子光谱、红外光谱、X 射线粉末衍射和光电子能谱的研究,确证了所希望得到的产物.研究表明,杂多蓝的结构与还原前相比未发生明显变化.水溶液稳定性的研究指出,杂多蓝要比还原前的杂多阴离子稳定,存在的 pH 范围加宽.指认了可见-红外区出现的谱带.     

杂多蓝的研究 I. 具有Dawson结构的钼砷杂多蓝的制备及性质

本文详细地研究了具有Dawson结构的钼砷杂多酸(H6As2Mo18O62)的两电子、四电子、六电子还原杂多蓝的制备条件, 离析出了它们的钾盐、铵盐及四丁基胺盐。找到了合适的电解电位。通过电位滴定、极谱、电子光谱、红外光谱、X射线粉末衍射和光电子能谱的研究, 确证了所希望得到的产物。研究表明, 杂多蓝的结构与还原前相比未发生明显变化。水溶液稳定性的研究指出, 杂多蓝要比还原前的杂多阴离子稳定, 存在的PH范围加宽, 指认了可见-红外区出现的谱带。     

杂多蓝的研究 I. 具有Dawson结构的钼砷杂多蓝的制备及性质

本文详细地研究了具有Dawson结构的钼砷杂多酸(H6As2Mo18O62)的两电子、四电子、六电子还原杂多蓝的制备条件, 离析出了它们的钾盐、铵盐及四丁基胺盐。找到了合适的电解电位。通过电位滴定、极谱、电子光谱、红外光谱、X射线粉末衍射和光电子能谱的研究, 确证了所希望得到的产物。研究表明, 杂多蓝的结构与还原前相比未发生明显变化。水溶液稳定性的研究指出, 杂多蓝要比还原前的杂多阴离子稳定, 存在的PH范围加宽, 指认了可见-红外区出现的谱带。     

Keggin结构钼系杂多蓝的离析和性质研究

本文报道了八种1:12系列钼系杂多蓝KyHzXMo_(12)O_(40)·nHp(X=Si,P,As,Ge)的制备和离析方法,并通过元素分析、电位滴定、极谱、循环伏安、红外光谱、可见-紫外光谱、X射线粉末衍射、XPS和~(31)PNMR对产物进行了表征。测定了四电子钼硅杂多蓝的单晶结构,确定了还原钼原子的位置是第三位、七位、八位、十位。实验结果表明,杂多蓝仍基本保持了Keggin结构。首次系统研究了八种杂多蓝固体的ESR谱,发现二电子、四电子杂多蓝比一电子杂多蓝具有更小的电子离域程度;热性质研究表明,固体杂多蓝随还原程度增大,热稳定性增强;研究其氧化还原性质发现,在不同介质中,杂多蓝的氧化序发生变化,极谱半波电位与杂原子电负性线性相关。并发现P和As的杂多蓝具有极强的抗酸解能力。     

杂多化合物催化丙烷的选择性氧化

杂多化合物由杂多阴离子和阳离子组成,杂多阴离子具有一定的空间结构,多种不同结合强度的晶格氧能够在氧化-还原反应中起传递电子和氧的作用。杂多化合物具有很强的酸性,可用作双功能催化剂。本文以磷、钼、钒杂多酸中掺杂过渡金属离子Cs^2 、Cu^2 、Fe^3 为催化剂,对丙烷氧化反应进行了研究。     

Keggin型磷钼杂多蓝的制备新方法——射频氢等离子体固相还原法

将射频等离子体技术应用于杂多蓝的制备中, 成功地制备出四电子还原的磷钼杂多蓝, 并对所制备的杂多蓝进行了结构表征及性质研究, 探讨了磷钼杂多酸在射频氢等离子体中的还原行为.     

杂多蓝的结构及其光化学研究进展

本文介绍了关于杂多蓝(HPB)的结构及其光化学的最新研究进展,特别对新型结构HPB的合成、电子结构的计算化学、光致还原反应制备新型纳米金属材料、有机-无机光致变色复合薄膜、HPB对半导体材料的协同与敏化作用、以及特殊结构的HPB在光化学反应中的应用重点进行了阐述,并就合成新型结构杂多酸进而调变杂多蓝性质,及它们在光化学领域中的应用进行了展望。     

Keggin结构钼硅杂多蓝的合成及晶体结构研究

通过电化学还原的方法得到钼硅多酸的还原产物杂多蓝单晶H~8SiMo~12H~2O.测定了它的晶体结构.晶体空间群PI.a=1.3769(3)nm,b=1.4346(4)nm,c=1.4134(4)nm,a=120.47(2)°,β=110.70(2)°,γ=66.11(2)°;z=2,R=0.0608.确证杂多蓝阴离子呈现Keggin结构和与a-异构体特征,基本保持未还原杂多酸阴离子的结构.但是在结构畸变程度、键角和健长的变化以及结晶水的分布上 有明显不同.同时确定了杂多蓝阴离子结构中4个Mo^5+离子的位置.     

Pd/Al2O3表面上活性位性质及其与加氢反应动力学参数间的关系

近年发展起来的新的动态技术能够用于分离测定非均相催化反应的吸附平衡,吸附和表面反应速率系数,而中毒实验使人们能够测定催化剂表面上活性位的容量和强度性质。如果把两者结合起来(可称作动态中毒法)就有可能研究催化剂表面上活性位性质与其动力学参数间的关系。本文的目的,是要在作者早先工作的基础上,在三相浆态床反应器中,应用动态中毒法探索研究Pd/Al_2O_3催化剂表面上活性位性质及其与α-甲基苯乙烯     

CuI/2,2'-联吡啶/2,2,6,6-四甲基哌啶氧化物催化氧化醇生成腈的工艺

以高压反应釜为反应装置,采用CuI/Bipy(2,2'-联吡啶)/TEMPO(2,2,6,6-四甲基哌啶氧化物)催化体系,以氨水作氮源,分子氧作氧化剂,对醇催化氧化生成相应腈的方法进行了优化。 以苯甲醇的催化氧化反应为模型反应,考察了催化剂及其用量、溶剂、反应温度以及时间对催化性能的影响。 实验表明:在高压釜中,120 ℃、40×10⁵ Pa的氮氧混合气(φ(O₂)=8%)条件下,将催化剂摩尔分数降低至1%(脂肪醇催化剂摩尔分数为5%),反应时间缩短至8 h时,催化效果最佳。同时,该反应系统对于不同的芳香醇和脂肪醇的氧化均取得了90%以上的转化率和90%以上的产品收率。     

Reactivity differences between isolated and vicinal vinyl acetate functions in high pressure ethylene/vinyl acetate copolymers

Three ethylene/vinyl acetate copolymers (3.5, 12.0 and 18.8 mol% VA; average melt index 8.5 g/10 min) were transformed into ethylene/vinyl alcohol copolymers and ethylene/vinyl alcohol/vinyl acetate terpolymers by homogeneous saponification. The reaction rate increased with mol% VA. This feature originated in the reactivity differences beteen vicinal and isolated VA functions. Simultaneous steric and polarity effects caused the reaction rate differences. ¹H-NMR, i.r., dielectric measurements and additional saponification reactions confirmed the difference of reactivity.     

Synthesis of cyclic oligo(ethylene adipate)s and their melt polymerization to poly(ethylene adipate)

We present here the first synthesis of cyclic oligo(ethylene adipate)s(COEAs) via pseudo-high dilution condensation reaction of adipoyl chloride with ethylene glycol, and the synthesis of corresponding poly(ethylene adipate)(PEA) via the melt polymerization of COEAs. The structure of COEAs was characterized and proved by 1H-NMR and MALDI-TOF mass measurements. The effects of organic base, reaction temperature and the ratio of adipoyl chloride to ethylene glycol on the yield of COEAs were studied, and the optimum reaction condition was revealed. PEA, a diacid and diol based semi-crystalline green aliphatic polyester, was synthesized by the melt polymerization of COEAs using Ti(n-C4H9O)4 as catalyst and 1,10-decanediol as initiator at 200 °C, which follows the polycondensation-coupling ringopening polymerization method. Our strategy should be applicable to the synthesis of versatile aliphatic polyesters based on diacid and diol monomers, which have potential applications as biocompatible and biodegradable materials.     

Conformational properties of isotactic poly(2-hyroxyethyl methacrylate) in the mixed water-alcohol solvents

Conformational properties of isotactic poly(2-hydroxyethyl methacrylate) (PHEMA) have been studied in mixtures of water and several aliphatic alcohols by viscometry and fluorometry. The highest fluorescence intensity of auramine has been detected in aqueous isotactic PHEMA solution compared with several aliphatic alcohol systems. Upon aliphatic alcohol addition, there was the decrease of fluorescence intensity of auramine. As the number of aliphatic group of alcohol increases, the decrease of fluorescence intensity of auramine has been pronounced. And the sharp increases of the reduced viscosity of isotactic PHEMA in water-alcohol solvents were observed in the lower region of alcohol volume percentage with the increasing number of aliphatic group of alcohol. Nevertheless, the sharp increase of the reduced viscosity of isotactic PHEMA in ethyleneglycol-water solvent was obtained even at a low-volume percentage region of ethyleneglycol at which compact structures exist. Therefore, we consider that the increase of viscosity at this region is due to the hydrophilic side group of polymer-solvent interaction, forming hydrogen bonds. The experimental results suggest that compact structures of isotactic PHEMA in aqueous solution are caused by hydrophobic interactions by methyl group of polymer backbone, and the hydrophobic interaction by adding alcohols. Finally, our study brings the fact that the solvating sites of alcohols on the isotactic PHEMA molecule are strongly influenced by the number of hydroxyl and aliphatic group in alcohols.     

Deshydrogenation d'alcools en composes carbonyles par le systeme CuCl/O2/Ligande

The dehydrogenation of alcohols to the corresponding carbonyl compounds by CuCl/O₂/ligand (L) shows relative rates of dehydrogenation according to the type of alcohol used; primary or secondary benzyl alcohols > allylic alcohols or aliphatic alcohols > cyclic alcohols. The rate of this reaction was found to be dependent upon the nature of the ligands used; e.g. phenanthroline 1–10 > bipyridyl 2,2' > TMEDA, etc. When L = phenanthroline 1–10 the catalytic effect, of the system ROH/CuCl/L (3:1:1), was found to be similar to the system ROH/CuCl/L (1:2:2). The pure oxygen was replaced by air without any noticeable change in the rate of the reaction. The primary aliphatic alcohols lead to the aldehydes containing 1, 2, etc. carbon atoms fewer than the starting alcohols.     

Addition of water across Si-Ir bonds in iridium complexes with κ-P,P,Si (biPSi) pincer ligands

Electrophiles such as Me(+), Ag(+), or protons react with the five-coordinate Ir(III) complex [IrClH(biPSi)] (biPSi = κ-P,P,Si-Si(Me){(CH(2))(3)PPh(2)}(2)) by abstracting its chloride ligand. The resulting species can be stabilized by a variety of L ligands to give the cationic complexes [IrH(biPSi)L(2)](+). The derivative [IrH(biPSi)(NCMe)(2)](+) has been subjected to a kinetic study regarding the facile dissociations of its acetonitrile ligands. The presence of water changes the course of the reaction producing dihydride complexes that contain the silanol ligand κ-O,P,P-HOSi(Me){(CH(2))(3)PPh(2)}(2) (biPSiOH). The water activation product [IrH(2)(biPSiOH)(NCMe)](CF(3)SO(3)) undergoes insertion reactions with ethylene and phenylacetylene. The use of hydrolyzable fluorinated counterions such as PF(6)(-) or BF(4)(-) further modifies the reaction by provoking the incorporation of fluoride at the silicon atom of the former biPSi ligand. The dihydride resulting after such a process, [IrH(2)(biPSiF)(NCMe)(2)]BF(4) (biPSiF = κ-P(2)-FSi(Me){(CH(2))(3)PPh(2)}(2)), displays a trans-chelating diphosphine ligand. When dehydrogenating the Ir center, spontaneously or using ethylene as hydrogen acceptor, the diphosphine backbone undergoes a Si-C bond cleavage leading to a new Ir(III) species with κ-P,Si and κ-C,P chelate ligands.     

原子类型电拓扑指数在脂肪醇类化合物毒性预测研究中的应用

采用原子类型电拓扑指数(ETSIAT)为结构描述子, 对梨形四膜虫、番茄、红蜘蛛、发光细菌荧光素酶、呆鲦鱼以及鼠的脂肪醇毒性进行了定量构效关系(QSAR)研究. 在偏最小二乘法建立QSAR模型的基础上, 采用内部和外部两种验证方法对模型进行验证. 研究结果表明: ETSIAT可以很好地表征脂肪醇与多种生物毒性相关的结构信息, 所建模型具有良好的稳定性和外部预测能力. 偏最小二乘模型分析结果显示: 疏水性可能是影响脂肪醇毒性大小的主要因素, 其毒性随C链长度的增加而增强, 且相同C原子数的直链脂肪醇毒性明显高于支链脂肪醇; 由于空间位阻效应, 长链脂肪醇与短链脂肪醇可能存在不同的毒性作用机理.     

2-Chloroethylthiol esters of dic arboxylic acids

Mono- and bis(2-chloroethyl)thiol esters of aliphatic, aromatic, and heterocyclic dicarboxylic acids have been obtained by the reaction of the dicarboxylic acid chlorides with ethylene sulfide or 2-chloroethanethiol. The compounds were characterized by their electronic spectra.     

Facile nucleophilic fluorination of primary alkyl halides using tetrabutylammonium fluoride in a tert-alcohol medium

Nonpolar protic reaction media such as t-amyl alcohol allow the aliphatic, nucleophilic fluorination reaction of primary haloalkane systems to fluoroalkanes, using tetrabutylammonium fluoride (TBAF), to proceed chemo-selectively at a reasonable reaction rate under mild conditions to afford the fluoro-product in high yield. As an example, the nucleophilic fluorination of 2-(3-iodopropoxy)naphthalene (1a) as the primary haloalkane model compound, with TBAF in acetonitrile as a polar aprotic solvent, CsF in t-amyl alcohol as a nonpolar protic solvent, and TBAF in t-amyl alcohol for 1 h provided 2-(3-fluoropropoxy)naphthalene (2a) in 38, 5, and 76% yields, respectively.