以SDS-PVP项链状软团簇为模板简易一锅法合成Cu2O中空亚微球

在SDS-PVP水溶液中采用N2H4•H2O还原CuSO4, 在pH (10±0.5), (40±1.0) ℃条件下反应55 min得到橙色Cu2O溶胶, 离心分离产物经XRD鉴定为Cu2O立方晶系晶体; SEM和TEM表明该法获得的晶体为形状规整、粒径分布窄的Cu2O中空亚微球, 并证实系由大量10 nm量级的原级Cu2O纳米晶粒组装而成. 根据实验事实推断, SDS-PVP项链状软团簇提供了“双重软模板”功能, 借助独特的“模板诱导两级组装”作用一锅法合成了Cu2O中空亚微球. Cu2O中空亚微球生长的可能途径为: 首先, 项链状软团簇中的SDS束缚胶束作为第一重软模板, 诱导一级组装10 nm量级的原级Cu2O纳米晶粒; 然后, 软团簇中立体桥联SDS束缚胶束的PVP链节作为第二重软模板, 诱导一定空间范围内的原级Cu2O纳米晶粒长大并进一步聚集/二级组装, 经一锅法合成得到次级Cu2O中空亚微球. 实验结果证明该一锅法温和、简便、快捷, Cu2O中空亚微球的粒径分布窄.     

纳米团簇的超分子自组装

在纳米材料的应用过程中, 纳米团簇或纳米粒子的组装将是非常关键的一步。纳米团簇的超分子化学组装方法可分为两类, 即胶态晶体法和模板法。胶态晶体法是利用胶体溶液的自组装特性将纳米团簇组装成超晶格, 可得到二维或三维有序的超晶格。模板法是利用纳米团簇与组装模板间的识别作用来带动团簇的组装, 可应用的模板有固体膜、单分子膜、有机分子、生物分子等。其中, 单分子膜模板是研究最多也是最为成熟的一种; 生物分子间严密的分子识别功能使其成为非常有发展前途的组装模板, 而且用生物分子模板有可能实现不同纳米团簇间的组装。     

在SDS-PVP团簇软模板中自组装多脚状金纳米粒子

利用十二烷基硫酸钠(SDS)与聚乙烯吡咯烷酮(PVP)组成的团簇为软模板, 在微波辅助下以柠檬酸钠为还原剂快速还原氯金酸生成金晶并自组装成多脚状金纳米粒子. TEM结果显示, 得到回转直径约为50 nm的多脚状纳米结构, 电子衍射(ED)证实其为多晶结构. XRD结果表明, 该多脚状金纳米结构主要沿(111)晶面生长, 构成该纳米结构的晶粒尺寸约为12.7 nm. SDS与PVP组成的团簇结构对金纳米粒子的形貌有显著影响, 固定PVP浓度时, 随着SDS浓度增大, 金纳米粒子的形貌由球形向多脚状转变, 同时还原产物水溶液的UV-Vis光谱在800 nm附近的吸收逐渐增强.     

L-天冬氨酸与阴离子表面活性剂SDS的相互作用

用电导法、表面张力法和荧光探针法测定了L-天冬氨酸(L-Asp)对十二烷基硫酸钠(SDS)胶束聚集性能的影响以及L-Asp在SDS胶束中的定位, 用循环伏安法研究了SDS/H₂O体系中L-Asp的电化学特性. 结果表明, L-Asp的加入能使SDS的临界胶束浓度cmc减小、胶束的聚集数增加. SDS表面胶束和SDS/n-C₄H₉OH/表面混合胶束均对L-Asp电化学氧化具有一定的催化作用.     

高分子模板作用下的正八面体微/纳米Cu2O晶体制备

探讨了羟乙基纤维素、壳聚糖、聚乙烯醇、聚丙烯酰胺、不同分子晕的聚乙二醇等高分子模板,存水合肼还原法制备微/纳米Cu2O晶体中的应用特性.通过X射线衍射、扫描电镜等埘Cu2O晶体进行了表征.本工作制得了粒径在300～500 nm的正八体微/纳米Cu2O晶体.结果显示,化学沉积法制备微/纳米Cu2O时,宜选用易形成单个均一胶团、不易形成空间网络结构、具有良好空间位阻效应且分子量适中的高分子化合物作为模板.本工作获得的水合肼还原法制备Cu2O的最佳条件为:反应温度55℃,nOH-:nCu2+=2∶1.     

荧光团杂化纳米SiO2微球作为生物标记探针的应用研究

近年来 ,无机发光量子点[1,2 ] 、荧光纳米乳液微球[3 ,4 ] 及发光团掺杂 Si O2 纳米粒子[5] 等纳米荧光探针的出现 ,为生物标记提供了新的发展领域 .将有机染料以共价方式包埋在 Si O2 中所得的复合材料具有独特的光学性质 ,然而其在生物标记方面的应用并未得到重视[6 ,7] .本实验通过控制荧光团修饰的硅烷前体在反相胶束体系中的水解缩合 ,合成了用于生物染色和诊断的高灵敏度、高稳定性的新型荧光团杂化纳米 Si O2 微球 ( NFHS微球 ) .在 NFHS微球中 ,荧光团以共价方式地均匀分散在 Si O2 网络结构中 ,避免了与外界体系中溶解氧的…     

十二烷基硫酸钠-水溶性非离子大分子间团簇化作用部位的1H和13C及2D NMR表征

运用 1H NMR, 13C NMR, 2D NOESY-NMR及2D ROESY-NMR等多种波谱技术联合表征典型阴离子表面活性剂十二烷基硫酸钠(SDS)与典型水溶性非离子大分子聚乙烯吡咯烷酮(PVP)或聚乙二醇(PEG)间的团簇化作用部位. NMR综合分析结果表明, SDS分子亲水头基邻近的C1~C2片段与PVP分子中内酰胺氮为中心的主链α-C、 五元环上羰基C1(记为P1)及C4(记为P4)片段给出较强的作用信号, 推断SDS分子亲水头基与PVP分子中内酰胺氮及其两者的相邻区域可能为形成团簇时SDS束缚胶束与PVP间超分子作用的主要部位. 而SDS束缚胶束与PEG形成团簇时, 除极性部位及其相邻区域的相互作用外, 部分PEG链节可能渗入到SDS束缚胶束的C3部位或更深的内部.     

漂浮法制备SiO2有序大孔材料

用漂浮组装方法以亚微米尺度单分散的聚苯乙烯(PS)微球作为模板, 在悬浮液气-液界面处组装PS模板微球与纳米级胶体颗粒, 形成二元胶体颗粒共混物, 再去除模板得到有序大孔材料.     

pH值调节方式对LAB辅助合成纳米Cu2O微球的影响与组装机理

以Cu(Ac)2为原料,两性表面活性剂月桂酰胺丙基甜菜碱(LAB)为模板,采用两种不同的调节pH值方式制备了Cu_2O纳米材料。表征结果表明两种调节pH值方式均可获得Cu_2O纳米微球,并都呈立方晶相,而且样品的红外吸收峰、固体紫外吸收峰都不同程度的发生了蓝移;第一种Cu_2O纳米微球由针状纳米粒子积聚而成,针状纳米粒子间空隙孔径主要分布在25~50 nm之间,比表面积为22 m~2·g~(-1),禁带宽度为2.15 eV;第二种Cu_2O纳米微球由小的纳米球状体堆积而成,球状体间孔道直径集中在25~50 nm和50~125 nm两个区域,比表面积为9 m~2·g~(-1),禁带宽度为2.46 eV。两种不同的调节pH值方式获得的Cu_2O纳米微球,其反应历程和自组装机理存在不同。     

磁性微球的制备及应用

磁性微球在生物医学和分离工程等多个领域都有广泛的应用,如固定化酶、靶向药物载体、核磁共振成像、细胞标记及分离、核酸和蛋白质分离纯化、环境治理等.近年来随着纳米新材料及制备工艺的不断创新,磁性微球的制备及应用都取得了大量进展.磁性微球的制备方法主要可以分为4类:(1)包裹法,在微球生成的同时将磁性纳米颗粒包裹在微球基质内,又可以细分为异质聚合法、乳化-溶剂挥发法、膜乳化和微流控技术、反相悬液-交联法、Stober法、聚合诱导胶体聚集法等;(2)模板组装法,在模板微球内部或表面组装磁性纳米颗粒,包括溶胀法、吸附法和静电自组装法等;(3)模板原位生成法,在模板微球的内部或表面原位生成磁性纳米颗粒,包括共沉淀、沉淀-氧化法、有机前驱体热分解法等;(4)溶剂(水)热法,以有机溶剂或水为介质,密闭体系中的反应物在一定的温度和溶液的自生压力下反应得到磁性微球.本文按照制备方法对近几年来磁性微球领域的研究进展进行了总结,包括反应原理、磁性微球的性质、表面功能化和应用介绍.     

简易合成纳米多层级镍中空亚微球及其催化苯酚加氢的研究

采用简易一锅法, 在十二烷基硫酸钠-聚乙烯吡咯烷酮水溶液中, 利用水合肼在65 ℃下还原Ni²⁺制备镍纳米材料, 并对其表面形貌和内部结构进行了表征. 结果表明, 该镍纳米材料是壳层中具有大量介孔的中空亚微球, 且表面呈现出松针状叠合的特殊形貌, 因此是纳米多层级结构, 较厚的壳层使其整体类似于封闭的鸟巢状. 以此镍中空亚微球催化苯酚选择性加氢反应, 150 ℃催化反应4 h苯酚的转化率接近100%, 主产物环己醇的选择性高达90%以上. 该镍中空亚微球循环使用20次催化活性基本没有下降, 而且循环使用20次之后的催化剂曝露于空气中表面未被氧化, 基本不会影响其催化活性, 表明该镍中空亚微球具有高的催化活性和优良的循环稳定性能, 有望作为良好的床层催化剂使用.     

Cu nanoparticles of low polydispersity synthesized by a double-template method and their stability

Cu nanoparticles of well-defined size and stability were synthesized with the aid of a double-template method. The templates consisted of sodium dodecyl sulfate (SDS) aggregates combined with and wrapped by poly(vinylpyrrolidone) (PVP) chains. Copper sulfate was reduced within the templates resulting in multicrystalline Cu nanoparticles. The size of the particles was uniform. They were capped by PVP–SDS complexes and the shape turned out to be non-spherical. PVP used in the experiments has an average molecular weight of 40,000. In this case, the particle dimensions were essentially determined by the chosen concentration of SDS in the reaction solution. No oxidation of the as-grown copper particles was detected even in the absence of inert gas protection during the synthesis process. When exposed to air at room temperature, Cu nanoparticles capped by PVP–SDS complexes showed much better resistance to oxidation than those without the capping agents. Furthermore, the steric and screening effect of the capping agents permitted the preparation of uniform colloidal dispersions stable over months. The material obtained by this double-template method was found to be very sensitive to the synthesis temperature. At synthesis temperatures above 40 °C, CuO instead of Cu was obtained.     

Conversion of Cu2O nanocrystals into hollow Cu2-xSe nanocages with the preservation of morphologies

With the use of PVP (polyvinylpyrrolidone) as capping reagent, cubic, octahedral and spherical Cu2O nanocrystals were obtained in aqueous media when different reducing agents were applied. After adding selenium sources at room temperature, these nanocrystals could be converted (based on the Kirkendall effect) into hollow Cu2-xSe nanocages that keep their corresponding orignial morphologies.     

Co-effect of soft template and microwave irradiation on morphological control of gold nanobranches

Short-range order sodium dodecyl sulfate (SDS)-bound micelles and long-range order poly(vinylpyrrolidone) (PVP)?CSDS supramolecular assemblies in PVP?CSDS aqueous solution illustrate the potential template application in directing hierarchical assembly of inorganic nanostructure. In this paper, ginger-like Au nanobranches with equivalent circle diameter around 50?nm were prepared in PVP?CSDS aqueous solution under microwave irradiation through a one-pot, facile, rapid, and morphology-controlled synthesis route. Based on the experimental results, the possible growth mechanism of the ginger-like gold nanobranches is inferred to be a template-mediated and microwave-assisted hierarchical assembly via the unique co-effect of PVP?CSDS soft template and microwave irradiation. At first, the precursors AuCl ₄ ^? surrounding the SDS-bound micelles were rapidly reduced to Au⁰ by sodium citrate assisted by microwave irradiation and simultaneously assembled into abundant Au nanocrystals with diameters around 10?nm according to the bound micelle templates. And then several tiny Au nanocrystals linked by PVP chains within a limited space were instantly mediated by the long-range order PVP?CSDS supramolecular assemblies to fabricate into polycrystal ginger-like Au nanobranches. X-ray diffraction (XRD) pattern indicates that the Au nanobranches are face-centered cubic phase, which is verified by high-resolution transmission electron microscopy (HRTEM) images and selected area electron diffraction (SAED) pattern.     

A facile synthesis of luminescent YVO4:Eu3+ hollow microspheres in virtue of template function of the SDS–PEG soft clusters

Hollow europium-doped yttrium orthovanadate (YVO₄:Eu³⁺) microspheres were fabricated via a sodium dodecyl sulfate (SDS)–polyethylene glycol (PEG)-assisted hydrothermal technique. The as-synthesized hollow YVO₄:Eu³⁺ microspheres were characterized by X-ray powder diffraction (XRD), scanning electron microscopy (SEM) and photoluminescence spectroscopy (PL). The obtained results showed that the morphology and size of the hollow microspheres have a strong dependence on the hydrothermal reaction time of the YVO₄:Eu³⁺ powders. It is believed that the SDS–PEG clusters perform a function of dual soft-template that results in a unique template-induced secondary assembly in the one-pot synthesis of hollow YVO₄:Eu³⁺ microspheres. The photoluminescence measurement revealed that the YVO₄:Eu³⁺ powders with a spherical hollow shape have better red luminescence compared to the YVO₄:Eu³⁺ solid microspheres. As a result, the controlled synthesis of hollow YVO₄:Eu³⁺ microspheres not only has a great theoretical significance in studying the three-dimensional control and selective synthesis of inorganic materials but also benefits the potential applications based on hollow YVO₄:Eu³⁺ microspheres owing to reducing the usage of expensive rare-earth elements.     

Superdispersible PVP-coated Fe3O4 nanocrystals prepared by a "one-pot" reaction

Poly( N-vinyl-2-pyrrolidone) (PVP)-coated Fe3O4 nanocrystals were prepared by a "one-pot" synthesis through the pyrolysis of ferric triacetylacetonate (Fe(acac)3) in N-vinyl-2-pyrrolidone (NVP). The polymerization of NVP was followed by measuring the shear viscosity of the reaction mixture. The PVP molecules formed in the reaction mixture was investigated by gel permeation chromatography. As the resultant Fe3O4 nanocrystals presented superdispersibility in 10 different types of organic solvents and aqueous solutions with different pH, including 0.01 M phosphate-buffered saline buffer, their hydrodynamic properties in both organic and aqueous systems were investigated by dynamic light-scattering. The results indicated that the PVP-coated Fe3O4 nanocrystals can completely be dispersed forming stable colloidal solutions in both organic solvents and water. Fourier transform infrared spectroscopy results suggested that PVP interacted with Fe3O4 via its carbonyl groups. Further surface analysis by X-ray photoelectron spectroscopy revealed that there were both coordinating and noncoordinating segments of PVP on the particle surface; the molar ratio between them was of 1:2.6.     

球状、立方状及空心立方状PbS纳米晶的控制合成及其形成机理

以醋酸铅为铅源,硫代乙酰胺为硫源,在表面活性剂十二烷基硫酸钠(SDS)和十六烷基三甲基溴化铵(CTAB)共同作用下,通过简单地调节水热反应的反应温度控制合成出球状、立方状和空心立方状PbS纳米晶。利用XRD、TEM对合成产物的结构和形貌进行了表征,发现合成的球状、立方状和空心立方状PbS纳米晶尺寸均一,直径为100 nm左右。对球状、立方状和空心立方状PbS纳米晶的形成机理进行了初探,结果表明反应温度较低时,水热反应初始阶段形成的PbS小颗粒呈球形,在表面活性剂SDS的烷基链模板和CTAB微胶束软模板共同作用下生成球状PbS纳米晶;反应温度较高时,水热反应初始阶段形成的PbS小颗粒由于自身的立方相岩盐晶体结构的影响有呈立方状趋势,在SDS和CTAB共同作用下产物堆积成空心立方体状或立方状。     

Crystallization and aggregation behaviors of calcium carbonate in the presence of poly(vinylpyrrolidone) and sodium dodecyl sulfate

An anionic surfactant interacts strongly with a polymer molecule to form a self-assembled structure, due to the attractive force of the hydrophobic association and electrostatic repulsion. In this crystallization medium, the surfactant-stabilized inorganic particles adsorbed on the polymer chains, as well as the bridging effect of polymer molecules, controlled the aggregation behavior of colloidal particles. In this presentation, the spontaneous precipitation of calcium carbonate (CaCO3) was conducted from the aqueous systems containing a water-soluble polymer (poly(vinylpyrrolidone), PVP) and an anionic surfactant (sodium dodecyl sulfate, SDS). When the SDS concentrations were lower than the onset of interaction between PVP and SDS, the precipitated CaCO3 crystals were typically hexahedron-shaped calcite; the increasing SDS concentration caused the morphologies of CaCO3 aggregates to change from the flower-shaped calcite to hollow spherical calcite, then to solid spherical vaterite. These results indicate that the self-organized configurations of the polymer/surfactant supramolecules dominate the morphologies of CaCO3 aggregates, implying that this simple and versatile method expands the morphological investigation of the mineralization process.     

Polyol合成法制备生物医药用超小粒径Fe3O4磁性纳米晶体

采用一罐polyol合成法还原Fe（Ⅲ）乙酰丙酮化合物制备了粒径可调、单分散、直径5nm以下的磁性Fe3O4纳米晶体．其晶粒表面为所用聚合物表面活性剂PVP所包覆．运用透射电镜／高分辨透射电镜、X射线衍射、振动样品磁强计和超导量子干涉仪对其结构和性能进行了表征．结果表明所制得的Fe3O4磁性纳米晶体在室温下显示出优良的超顺磁性,且结晶度高、分散性好、化学性质稳定同时表面易修饰．磁滞回线的模型分析说明该Fe3O4纳米晶粒是磁性单畴．该法制得的超顺磁Fe3O4纳米晶粒在生物和医学领域具有重要的应用价值．     

SDS-PVP水溶液中超细镍粉的制备

在十二烷基硫酸钠(SDS)-聚乙烯吡咯烷酮(PVP)混合水溶液中, 采用水合肼还原氯化镍制备超细镍粉. SEM结果表明, 该超细镍粉为球形, 表面呈现针状叠合的特殊形貌. XRD结果表明,该超细镍粉由平均粒径约为10 nm的面心立方结构(fcc)的原生纳米镍晶粒组成, 且主要沿(111)晶面生长. TEM清晰观察到原生纳米镍晶粒在PVP的空间桥联作用下自组装成超细镍粉的中间过程. SDS-PVP的组成对超细镍粉的粒径和表面形貌有显著影响, 在一定浓度范围内, 随着SDS或PVP浓度增大, 原生纳米镍晶粒和超细镍粉的平均粒径均呈减小趋势, 表明通过改变SDS-PVP组成可以调控超细镍粉的粒径和形貌.