以C60为媒介的网状金纳米粒子聚集体的构筑

通过全甲基化环糊精和卟啉之间的"Click"反应,合成了一种不对称环糊精修饰的卟啉衍生物,并对其结构进行了表征.该化合物与氯金酸作用可以形成平均粒径为5 nm的水溶性金纳米粒子,该金纳米粒子进一步与C60作用形成网状纳米聚集体,并通过紫外光谱和透射电子显微镜验证了聚集体的结构.     

纳米(NH4)3PMo6W6O40的室温固相合成及形成机理

以H3PMo6W6O40•23H2O和(NH4)2C2O4•H2O为原料，采用室温固相反应合成出(NH4)3PMo6W6O40•6H2O产物，用元素分析、IR、UV-Vis、XRD、TEM、TG-DTA、BET等手段确定其组成、结构和性能.结果表明，产物为纳米粒子，平均粒径为10 nm.纳米粒子保持着杂多阴离子的Keggin特征结构，比表面积为167.6 m2•g－1，且在465 ℃以下具有良好的热稳定性.反应中反应热能、结晶水和生成物H2C2O4•2H2O对形成小粒径的(NH4)3PMo6W6O40纳米粒子起关键作用.     

多酸/Pt-Ni合金纳米粒子复合膜电极的制备及其对H_2O_2电催化性能研究

选用Dawson型多酸K_6[P_2W_(18)O_(62)]·14H_2O (P_2W_(18))和Pt-Ni合金纳米粒子作为电化学活性组分,制备了P_2W_(18)/Pt-Ni合金纳米粒子复合膜电极,采用循环伏安法研究了复合膜电极的电化学行为。实验结果表明,P_2W_(18)/Pt-Ni合金纳米粒子复合膜电极具有良好的重复性和稳定性,并展现出较P_2W_(18)电极更好的对H_2O_2的电催化活性。     

α-Fe2O3负载Ag复合纳米材料的制备、表征和气敏性能

采用简单的FeCl3溶液水热方法, 结合焙烧处理合成了α-Fe2O3 纳米粉体; 以所制备的α-Fe2O3为载体负载Ag纳米粒子, 得到Ag/α-Fe2O3 复合纳米材料. 使用X射线衍射、 透射电子显微镜、 氮气吸附-脱附和X射线光电子能谱等对样品进行表征, 并考察了Ag/α-Fe2O3复合材料在260℃下对甲醇、 乙醇、 乙醚、 丙酮、 正丁醇和正己醇等挥发性有机物的气敏行为. 结果表明, Ag/α-Fe2O3传感器对这几种挥发性有机物展示了较高的灵敏度和快速、 可逆的响应-恢复特性; 与纯α-Fe2O3相比, Ag/α-Fe2O3复合材料的气敏性能显著提高, 这可能与该复合材料表面独特的多孔结构和活性Ag纳米粒子对敏感反应的催化作用有关.     

碳化钨-二氧化钛纳米复合材料的制备及其电催化活性

 以纳米 TiO2 为载体, 偏钨酸铵为钨源, 采用机械化学法与原位还原碳化相结合的方法制备了碳化钨-TiO2 纳米复合材料, 并用 X 射线衍射和扫描电子显微镜等手段对样品的晶相和形貌进行了表征. 结果表明, 样品颗粒为不规则粒状, 并有不同程度的团聚, 样品的晶相组成与还原碳化时间有关, 主要有金红石相 TiO2, 非化学计量比氧化钛 (Ti6O11), W2C, W1C 和未定名碳化钨. 其中, TiO2 粒径 18.8~95.6 nm, W2C 粒径 17.4~24.2 nm, W1C 粒径 14.7~15.8 nm. 在三电极体系中, 采用循环伏安法测定了样品对对硝基苯酚的电催化活性. 结果表明, 样品的电催化活性与晶相组成有关, 且 W1C 与 TiO2 构成复合材料后, 两者之间存在明显的协同效应. 这说明 TiO2 是 W1C 的良好载体.     

金纳米粒子的微波法合成及在蛋白质检测中的应用

通过对微波反应器中氯金酸和柠檬酸钠混合物进行直接加热,快速、一步合成了金纳米粒子.通过调节反应初始混合物中氯金酸与柠檬酸钠的比例,可获得不同粒径窄分散的金纳米粒子.进一步将所合成的金纳米粒子功能化,考察了其在蛋白质检测中的应用.     

高活性Ag修饰TiO_2空心八面体光催化剂的简易模板诱导合成（英文）

贵金属修饰的Ti O2空心纳米光催化材料由于具有大的比表面积、低的质量密度、良好的表面渗透性、强的光吸收能力以及界面电荷的快速转移,因而表现出优异的光催化性能.为了制备结构可控且精良的贵金属修饰Ti O2空心纳米光催化材料,人们先后采用湿化学法、高温固相法、声化学法及光化学沉积法等.由于在制备过程中涉及多种异相材料的合成和结构控制,因此上述合成方法通常需要复杂且多步过程(有些过程甚至很容易导致结构破坏),从而限制了其在光催化领域的实际应用.本文开发了一种简单的模板诱导法,成功制备了Ag纳米粒子修饰的Ti O2空心八面体光催化剂.合成过程包括模板指导沉积和原位模板溶解.以Ag2O八面体为模板,TiF 4水溶液为前驱体,首先通过Ti F4水解形成Ti O2纳米粒子沉积在Ag2O模板表面,而Ti F4水解产生的酸性HF水溶液可原位溶解碱性的Ag2O模板,从而一步制得Ti O2空心八面体.同时,利用Ag2O以及Ag+离子的光敏特性,在光照条件下使Ag2O和Ag+离子生成Ag纳米颗粒,直接沉积在Ti O2空心八面体的内外表面,得到Ag/Ti O2光催化剂.由此可见,该合成方法具有明显的步骤少的优点.扫描电镜、透射电镜、能量散射和紫外-可见光谱等表征结果表明成功制得内外Ag纳米粒子修饰的Ti O2空心八面体光催化剂,其中TiO 2空心八面体的壁厚约为25 nm,边长约为1μm,而修饰在其表面的Ag纳米粒子尺寸仅为5–10 nm.此外,通过控制Ti F4前驱体浓度,还可制备核壳结构的Ag2O@Ti O2八面体以及不同壁厚Ag修饰的Ti O2空心八面体,表明该方法在Ag/Ti O2形貌合成上的多样性和可控性.为了获得良好的光催化活性,对制备的Ag纳米粒子修饰的Ti O2空心八面体光催化剂进行了不同温度的热处理.X射线衍射结果表明,即使在600 oC高温下,制备的Ag/Ti O2空心八面体光催化剂依然能够保持原有的特殊形貌和锐钛矿Ti O2晶型.该温度明显高于Ti O2从锐钛矿向金红石转变的温度.这说明合成的Ag/Ti O2能在保持高活性锐钛矿相的同时获得更好的结晶性.这可能是由于分散在Ti O2原始晶粒周围的Ag纳米粒子能阻止其进一步长大,从而抑制了其晶型转变.不同样品光催化降解甲基橙的结果表明,经600 oC高温热处理的样品表现出最高的光催化活性,相应的反应速率常数为0.11 min 1.这应得益于该光催化剂具有以下三个特点:(1)TiO 2空心八面体的薄壁结构能够缩短光照条件下光生电子和空穴从内部扩散到表面的距离;(2)由于贵金属Ag纳米粒子沉积在Ti O2薄壁的内外两个表面以及Ti O2和Ag形成肖脱基势垒,因此在它们接触的界面上能够发生更快的界面电荷转移;(3)高温处理导致Ti O2良好的晶化以及高活性锐钛矿Ti O2晶型的保持.     

荧光纳米粒子Ru(bpy)_3/SiO_2的制备及其应用于蛋白质微阵列芯片检测HIV p24抗原

以三联吡啶钌(Ru(bpy)3)为内核材料,通过反相微乳液法合成了表面带氨基的核壳结构荧光纳米粒子Ru(bpy)3/SiO2,利用透射电子显微镜、荧光光谱、紫外-可见光谱等手段进行表征,并进行了光稳定性、荧光分子泄露与纳米粒子表面氨基测定等实验,结果表明: 所合成的纳米粒子表面带氨基活性基团,每毫克纳米粒子约含385 nmol氨基,纳米粒子呈规则球形,大小均一,单分散性好,平均粒径为(70±6) nm,具有很好的光稳定性.用100 W氙灯在最大发射波长照射90 min后,其荧光强度仅衰减8%;在水溶液中不易发生染料泄露,连续超声1 h后,染料泄露少于0.05%.以合成的纳米粒子作荧光探针标记链霉亲和素后应用于蛋白质微阵列芯片检测HIV p24抗原.结果显示,荧光强度与p24浓度呈良好的正相关性,检出限为3.1 μg/L.本纳米粒子作为新型荧光探针,可应用于高灵敏检测的蛋白质微阵列芯片及荧光免疫分析等系统.     

一例Wells-Dawson型铌钨混配多酸的合成及光催化性能（英文）

在双氧水存在条件下,合成了一例Wells-Dawson型铌钨混配多酸K3.5Na4[H4.5(NbO2)6P2W12O5 6]·12.5H2O(1),X射线单晶结构分析表明,化合物1的多阴离子是一个六过氧铌基团取代的P2W12衍生物.六个铌原子分别与五个来自多酸框架上的氧原子和一个端位的过氧单元配位.另外,对化合物1的光催化产氢性能进行了初步研究.     

Au-Pd/石墨烯和Au-Pd/碳纳米管催化电化学氧化甲酸（英文）

利用化学还原法合成了石墨烯和碳纳米管负载的Au-Pd纳米粒子.石墨烯负载的Au-Pd纳米粒子(AuPd/G)的粒径远小于碳纳米管负载的Au-Pd纳米粒子(Au-Pd/CNTs)的粒径,且Au-Pd纳米粒子在复合材料上分布均匀.与碳纳米管负载的Au-Pd纳米粒子催化剂相比,石墨烯负载的Au-Pd催化剂对甲酸的催化显示出更好的电催化活性,结果表明作为Au-Pd纳米粒子的基底,石墨烯可以明显提高Au-Pd纳米粒子的电催化活性.在0.1mol/L H_2SO_4中,该纳米修饰电极对甲酸有良好的电催化作用,甲酸在电极上的氧化动力学过程为扩散控制过程.     

包封多酸化合物的固体脂质纳米粒的合成及生物活性研究

The solid lipid nanoparticles encapsulated polyoxometalate K₆[γ-(CpTi)₂SiW₁₀O₃₈] (abbreviated as (CpTi)₂SiW₁₀ Cp=η⁵-C₅H₅) have been prepared and structurally characterized by elemental ananlysis, IR, UV spectroscopy and TEM. The result showed that the polyoxometalate retained the parent structure after being encapsulated and the encapsulation increased the antitumoral activity of the polyoxometalate.     

CoW11Ti/淀粉纳米复合物的合成与表征

近年来, 多酸化合物的生物活性及药物性质研究十分活跃[1], 有些多酸化合物已作为抗HIV病毒及抗肿瘤药物应用于临床或进入临床研究[2,3]. 但由于它们的毒副作用大, 在水中稳定存在的pH值范围小, 在体内易分解, 故研究尚无突破性进展[1].     

纳米脂质体复合物-包封多酸化合物的合成,表征和生物活性研究

The polyoxometalate K6H[CoW11O39（CpTi）] （abbreviated as CoW11CpTi, Cp=η^5-C5H5） loaded nanosize-liposome complex has been prepared and structurally characterized by elemental analysis, IR and UV spectra. The particle size of the complex was distributed in the range of 100-250 nm with the average diameter of 132.6 nm. The result showed that the polyoxometalate retained the parent structure after being encapsulated by liposome and liposomal encapsulation increased the antitumoral activity of the polyoxometalate.     

Dawson结构杂多酸盐催化合成碳酸丙烯酯

碳酸丙烯酯(PC)是一种性能优良的高沸点、高极性的有机溶剂,在有机合成、化妆品、电池电解质和脱碳溶剂等领域中具有重要应用.     

Preparation,characterization and in vitro antitumoral activity of a nanosize liposome complex encapsulated polyoxotungstate K6H2[CoW11TiO40]

The nanosize liposome complex-encapsulated polyoxotungstate K₆H₂[CoW₁₁TiO₄₀] has been prepared and structurally characterized by i.r., u.v.–vis and e.s.r. spectra. The particle size of the liposome complex-encapsulated K₆H₂[CoW₁₁TiO₄₀], is distributed in two uncontinuous limits in which 98.9% of particles distributed in the limit of 62.8–76.7 nm, average diameter, is 69.4 nm. The result shows that the polyoxotungstate retains the parent structure after being encapsulated by liposome, and that liposomal encapsulation increase the antitumoral activity of the polyoxometalate.     

含硅多金属氧酸盐的抑菌作用

利用纸片扩散法研究了3种钒取代的硅钨酸盐α-1,2,3-K<,6>H[SiW<,9>V<,3>O<,40>],α-1,2-K<,6>[SiW<,10>V<,2>O<,40>]和α-K<,5>[SiW<,11>VO<,40>](以下分别简写为α-SiW<,9>V<,3>,α-SiW<,10>V<,2>,α-SiW<,11...     

Preparation and characterization of polyoxometalate/protein ultrathin films grown on electrode surfaces using layer-by-layer assembly

We report a new electrostatic layer-by-layer assembly method for the controlled deposition of electrocatalytically active enzymes onto electrode surfaces using polyoxometalate as the counteranion. Cytochrome c (cyt c), a redox active protein, and P(2)W(18)O(62)(6-), a Dawson-type polyoxometalate, were deposited onto glassy carbon electrodes by two procedures: static dipping and electrochemical cycling. Cyclic voltammetry and UV-vis spectroscopy reveal that approximately 1.5 x 10(-10) mol/cm(2) of P(2)W(18)O(62)(6-) and 2.2 x 10(-11) mol/cm(2) of cytochrome c are deposited per cycle, which correspond to approximately one monolayer of each molecule. The thicknesses of the resulting films measured by atomic force microscopy also indicate that the films are formed in a layer-by-layer fashion. Experimental factors that affect electron-transfer rate in these films, such as scan rate and film thickness, were systematically analyzed. The use of {P(2)W(18)O(62)(6-)/cyt c}n films to catalyze hydrogen peroxide reduction was demonstrated.     

Preparation, structure, and imaging of luminescent SiO2 nanoparticles by covalently grafting surfactant-encapsulated europium-substituted polyoxometalates

A novel route to the preparation of luminescent silica nanoparticles and coloration for living cells was demonstrated in this article. A europium-substituted polyoxometalate was encapsulated by a hydroxyl-group-terminated double-chain quaternary ammonium cation through an ion replacement process, yielding an organic-inorganic complex with core-shell structure bearing hydroxyl groups located at the periphery. The introduction of -OH groups not only increased the solubility of the complex in polar solvents but also caused it to embed into the inner matrix of silica nanoparticles covalently and be well-dispersed through an in situ sol-gel reaction with tetraethyl orthosilicate. Elemental analysis and spectral characterization confirmed the formation of prepared complexes with the anticipated chemical composition. Scanning and transmission electron microscopy images illustrated the size change of luminescent nanoparticles with smooth surfaces and well-dispersed polyoxometalate complexes inside of the silica matrix. X-ray photonic spectra and ζ-potential measurements revealed the chemical association between the silica matrix and the complex. Luminescent spectral characterization indicated the well-retained photophysical property of Eu-substituted polyoxometalate in silica nanoparticles. The surface amino-modified silica nanoparticles were applied to cell coloration, and the dyed Hela cells were observed through laser confocal fluorescence microscopy.     

Ionic liquid-enhanced photooxidation of water using the polyoxometalate anion [P2W18O62](6-) as the sensitizer

Simple polyoxometalate anions are known to be photoreduced in molecular solvents in the presence of 2-propanol or benzyl alcohol. The use of ionic liquids (ILs) as the solvent is now reported to also allow the photooxidation of water to be achieved. In particular, the photochemistry of the classic Dawson polyoxometalate salt K(6)[P(2)W(18)O(62)] has been studied in detail when water is present in the aprotic IL, 1-butyl-3-methylimidazolium tetrafluoroborate ([Bmim][BF(4)]) and the protic IL, diethanolamine hydrogen sulfate (DEAS). In these and other ILs, irradiation with white light (wavelength 275-750 nm) or UV light (wavelength 275-320 nm) leads to overall reduction of the [P(2)W(18)O(62)](6-) anion to [P(2)W(18)O(62)](7-) and concomitant oxidation of water to dioxygen and protons. The modified structure of bulk water present in ILs appears to facilitate its oxidation. Analogous results were obtained in aqueous solutions containing the protic IL as an electrolyte. The photoproducts (reduced polyoxometalate anion, dioxygen, and protons) were identified by, respectively, voltammetry, a Clark electrode, and monitoring of pH. The formal reversible potentials E(0)(F) for [P(2)W(18)O(62)](6-/7-/8-/9-/10-) couples are much more positive than in molecular solvents. The [P(2)W(18)O(62)](8-) and more reduced anions, if formed as intermediates, would efficiently reduce photoproducts H(+) or dioxygen to produce [P(2)W(18)O(62)](7-), rather than reform to [P(2)W(18)O(62)](6-). Thus, under photoirradiation conditions [P(2)W(18)O(62)](7-) acts as a kinetic sink so that in principle indirect splitting of water to produce dioxygen and dihydrogen can be achieved. The equivalent form of photooxidation does not occur in liquid water or in molecular solvents such as MeCN and MeCN/CH(2)Cl(2) containing added water, but does occur for solid K(6)[P(2)W(18)O(62)] in contact with water vapor.     

分光光度法同时测定无机多组分体系的研究III: 微量钨, 钼, 钛的测定

本文从配合物吸收光谱行为及矩阵运算角度分别探讨了CPA矩阵法AKC矩阵法中波长选择对分析结果误差的影响. 在前人有关钨, 钼, 钛单个元素光度测定研究的基础上, 确定了适宜于钨, 钼, 钛一苯基荧光酮-溴代十六烷基三甲铵三元配合物同时光度测定的最佳条件, 拟定了不经分离直接光度测定钨, 钼, 钛的方法.