核/壳型CdTe@SiO2荧光纳米复合粒子的制备与表征

利用反相微乳法, 以巯基乙酸修饰的水溶性CdTe量子点为核, 包覆SiO₂, 制备得到核壳型CdTe@SiO₂荧光纳米复合粒子. 用紫外-可见(UV-vis)分光光度计, 荧光(PL)分光光度计, 红外(FT-IR)光谱仪, 透射电子显微镜(TEM)等分析测试手段, 对得到的荧光纳米复合粒子的性能进行表征, 结果表明: 得到的CdTe@SiO₂纳米复合粒子是核壳型结构, 由SiO₂壳层包覆多个量子点, 其大小均匀, 水溶性好, 有效地提高了量子点的稳定性, 大大增强了其抗光漂白性能, 为该材料的进一步生物应用打下了良好的基础.     

聚乙烯吡咯烷酮碱性水溶液中金纳米花的简易合成

以聚乙烯吡咯烷酮(PVP)兼作保护剂和还原剂在碱性水溶液中直接还原HAuCl₄制备出了60-80 nm的三维(3D)金纳米花. 产物的透射电子显微镜(TEM)和扫描电子显微镜(SEM)图像显示, 金纳米花表面布满10-15 nm左右的纳米触角, X射线衍射(XRD)表征揭示产物为金的面心立方晶体, 选区电子衍射(SAED)花样说明金纳米花为多晶结构. 金纳米花的生长经历了三个关键步骤, 即初级纳米晶聚集成多脚状纳米粒子, 随后在合适的PVP/HAuCl₄浓度比及NaOH浓度下, 多脚状纳米粒子进一步聚集形成疏松的花状粒子, 最终经过Ostwald熟化形成致密的花状产物. 一定HAuCl₄浓度下PVP/HAuCl₄浓度比和NaOH浓度对产物的形貌影响显著, 因此通过同时调控合适的PVP/HAuCl₄浓度比和NaOH浓度, 就能得到适应各种应用需求的尺度可控和纳米触角形貌可控的金纳米花.     

用ATRP方法制备聚苯乙烯/纳米二氧化硅杂化粒子

采用过量的甲苯-2,4-二异氰酸酯(TDI)对SiO₂纳米粒子表面进行修饰, 将原子转移自由基聚合(ATRP)引发剂引入到SiO₂粒子表面合成大分子引发剂, 采用ATRP技术将聚苯乙烯(PS)大分子链接枝到SiO₂表面制备出以纳米二氧化硅为核, 聚苯乙烯为壳的PS/SiO₂杂化粒子. 利用红外光谱(FTIR)、核磁共振谱( NMR)、凝胶色谱(GPC)等实验手段对杂化粒子及表面接枝聚苯乙烯进行了表征分析.     

碳化钨/碳化二钨核壳结构纳米复合材料的制备及电化学性能

以偏钨酸铵为钨源, 铁黄(FeOOH)为载体, 将表面包覆法与原位还原碳化技术相结合, 制备出了具有核壳结构的碳化钨(WC)/碳化二钨(W₂C)纳米复合材料; 应用X射线衍射(XRD)分析、透射电子显微镜(TEM)和X射线能量散射谱(EDS)等手段对不同阶段样品的晶相、形貌、微结构和化学组成等特征进行了表征. 结果表明, 负载体经煅烧后, 载体及包裹层的物相均发生了变化, 形貌也相应地发生了改变; 经盐酸处理及还原碳化后, 样品由WC和W₂C纳米颗粒构成, 并构成了以W₂C为壳, 以WC为核的典型核壳结构; 结合表征结果对核壳结构的形成机理进行了探讨. 采用三电极体系循环伏安法测试了样品在酸性、中性和碱性溶液中对甲醇的电催化氧化活性. 结果表明, 与颗粒状碳化钨和介孔空心球状碳化钨相比, 样品的电催化活性有了明显的提高. 这说明W₂C与WC构成核壳结构纳米复合材料后, 其电化学性能有了明显的提升, 核壳结构纳米复合材料是提高碳化钨催化材料活性的有效途径之一.     

应用于局域表面等离激元共振扫描显微探针的球形Au@Ag纳米粒子的合成及介电敏感性检测

局域表面等离激元共振(LSPR)显微探针的检测灵敏性主要取决于针尖上修饰的纳米粒子的LSPR性质.本文采用阴离子辅助法,在水溶液中通过调节Au核与Ag⁺的物质的量之比,实现Au核上不同厚度的Ag壳层包覆,可控地一步合成均一性好、银壳层较厚(≥10 nm)的核壳比不同的球形Au@Ag纳米粒子.通过扫描电镜(SEM)、透射电镜(TEM)及扫描透射电子显微镜X射线能谱(STM-EDS)线扫描分析对不同核壳比的Au@Ag纳米粒子进行形貌组成表征,证实了所合成核壳结构的可控性.将不同核壳比的Au@Ag纳米粒子置于不同折射率溶液中进行纳米粒子介电敏感性的研究,表明7.5 nm Au@28 nm Ag的纳米结构具有最高的品质因子.同时将不同核壳比的Au@Ag纳米粒子置于不同折射率的非导电性基底上进行单颗纳米粒子散射性质的研究,结果表明7.5 nm Au@28 nm Ag纳米粒子适合作为LSPR显微探针的高检测灵敏性纳米结构之一.     

基于PAA——PAN嵌段共聚物胶束制备磁性碳纳米粒子

本文采用原子转移自由基聚合方法合成了聚丙烯酸叔丁酯-聚丙烯腈嵌段共聚物(PtBA-b-PAN), 酸解得到聚丙烯酸-聚丙烯腈两亲嵌段共聚物(PAA-b-PAN). 随后, PAA-b-PAN嵌段共聚物在水溶液中自组装形成以PAA为壳, PAN为核的胶束. 用此胶束为模板, 加入FeCl₃溶液后得到了壳层负载Fe³⁺的聚合物纳米粒子, 经230 ℃空气中预氧化, 600 ℃氮气氛煅烧, 得到了核壳结构的, 具有磁性的碳纳米粒子. 用1H NMR, IR, GPC, TGA, TEM, XRD, AGM等技术对嵌段共聚物及纳米粒子进行了表征, 结果表明纳米粒子的壳层含γ-Fe₂O₃, Fe_2.5C混合物, 核含碳, 直径为35 ± 5 nm, 饱和磁化强度为2.16 emu/g. 在分离、吸波和传感器等方面具有潜在的应用前景.     

金核银壳纳米粒子薄膜的制备及SERS活性研究

采用柠檬酸化学还原法制备金溶胶, 通过自组装技术在石英片表面制备金纳米粒子薄膜, 在银增强剂混合溶液中反应获得金核银壳纳米粒子薄膜. 用紫外-可见吸收光谱仪和原子力显微镜(AFM)研究了不同条件下制备的金核银壳纳米粒子薄膜的光谱特性和表面形貌, 并以结晶紫为探针分子测量了金核银壳纳米粒子薄膜的表面增强拉曼光谱(SERS). 结果表明, 金纳米粒子薄膜的分布、银增强剂反应时间的长短对金核银壳纳米粒子薄膜的形成均有重要影响. 制备过程中, 可以通过控制反应条件获得一定粒径的、具有良好表面增强拉曼散射活性的金核银壳纳米粒子薄膜.     

种子生长法制备Au@Ag核壳纳米粒子

Au@Ag核壳纳米粒子由于具有优异的局部等离子共振性质 (LSPR),近年来引起人们极大的关注,目前,在成像、催化、信息存储、生化传感等领域已经得到了广泛的应用。在制备Au@Ag核壳纳米粒子的方法中,种子生长法的应用最为广泛,因为它可以实现对Ag壳尺寸及形貌的有效控制。本文综述了影响Au@Ag核壳纳米粒子核壳结构尺寸、形貌、Ag壳厚度以及覆盖均匀程度的一些主要因素,包括Au种子的形貌和浓度、AgNO₃浓度、封端剂、还原剂以及其他一些影响因素。研究发现,Au@Ag核壳纳米粒子在表面增强拉曼光谱 (SERS) 方面具有广泛的应用前景。     

Au@SiO2核壳纳米粒子的制备及其表面增强拉曼光谱

采用柠檬酸钠还原氯金酸法制备金溶胶, 以正硅酸乙酯(TEOS)为硅源, 氨水作催化剂, 制备以金为核, 二氧化硅为壳的核壳纳米粒子. 金纳米粒子的粒径可以通过柠檬酸钠和氯金酸的比例控制, 通过调节TEOS的量和反应的时间可以控制二氧化硅壳层的厚度. 以苯硫酚为探针分子研究了核壳结构纳米粒子的表面增强拉曼散射(SERS)效应与二氧化硅壳层厚度之间的关系. 研究结果表明, 金内核电磁场增强效应随着二氧化硅壳层厚度的增加逐渐减弱, 且其衰减速度比具有相同尺度的双金属核壳结构纳米粒子的慢. 此外, 探针分子主要以物理作用吸附在二氧化硅的表面, 可通过洗涤方法将探针分子除去, 从而可使该复合结构基底用于循环SERS分析.     

均匀共沉淀法制备钛酸钡-钡铁氧体核-壳结构粒子

用均匀共沉淀法制备了钛酸钡-钡铁氧体核-壳粒子, 研究了沉淀反应温度、尿素/金属离子摩尔比值(R)和BaTiO₃浓度对核-壳粒子形貌和结构的影响, 探讨了钛酸钡-钡铁氧体核-壳粒子在焙烧时的形成过程及其磁性能. 采用透射电子显微镜(TEM)、X射线衍射(XRD)分析仪对钛酸钡-钡铁氧体前驱物核-壳粒子及钛酸钡-钡铁氧体核-壳粒子的形貌和结构进行了表征, 采用振动样品磁强计(VSM)研究了钛酸钡-钡铁氧体核-壳粒子的磁性能. 结果表明: 当沉淀反应温度为100 °C, R为180, BaTiO₃浓度为2.5 g·L^-1时, 金属离子沉淀完全, 得到的钛酸钡-钡铁氧体前驱物核-壳粒子包覆层均匀、完整、光滑, 厚度约为10 nm. 过高的温度和R值都会导致大量独立颗粒杂质的生成; 随着BaTiO₃浓度的增大, 包覆层厚度有减小的趋势. 当焙烧温度为900 °C时, 壳层中开始形成BaFe₁₂O₁₉相, 其形成过程为晶态的α-Fe₂O₃和BaCO₃首先生成中间相BaFe₂O₄, 然后由BaFe₂O₄和α-Fe₂O₃反应得到最终的BaFe₁₂O₁₉. 当焙烧温度为1000 °C时, 壳层完全转化为BaFe₁₂O₁₉相. 随着焙烧温度从900 °C升高到1000 °C, 所得BaTiO₃-BaFe₁₂O₁₉核-壳粒子的饱和磁化强度从16.5 A·m²·kg^-1增加到39.5 A·m²·kg^-1, 矫顽力从340 kA·m^-1略微降低到316 kA·m^-1.     

Construction of simple gold nanoparticle aggregates with controlled plasmon–plasmon interactions

We have developed a colloidal assembly for the study of plasmon–plasmon interactions between gold nanoparticles. Colloidal aggregates of controlled size and interparticle spacing were synthesized on silica nanoparticle substrates. Following the immobilization of isolated gold nanoparticles onto silica nanoparticles, the surfaces of the adsorbed gold nanoparticles were functionalized with 4-aminobenzenethiol. This molecular linker attached additional gold nanoparticles to the ‘parent' gold nanoparticle, forming small nanoparticle aggregates. The optical absorption spectrum of these clusters differed from that of gold colloid in a manner consistent with plasmon–plasmon interactions between the gold nanoparticles.     

Tailored core-shell-shell nanostructures: sandwiching gold nanoparticles between silica cores and tunable silica shells

Size tunable and structure tailored core-shell-shell nanospheres containing silica cores, gold nanoparticle shells, and controlled thicknesses of smooth, corrugated, or porous silica shells over the gold nanoparticles have been synthesized. The synthesis involved the deposition of gold nanoparticles on silica cores, followed by sol-gel processing of tetraethoxysilane (TEOS) or sodium silicate to form dense or porous silica shells, respectively, over the gold nanoparticles. The structures and sizes of the resulting core-shell-shell nanospheres were found to heavily depend on the sizes of the core nanoparticles, the relative population of the gold nanoparticles on each core, and the concentration of TEOS. While a higher TEOS concentration resulted in thicker and more uniform silica shells around individual larger silica cores (approximately > or =250 nm in diameter), the same TEOS concentration resulted in aggregated and twin core-shell-shell nanostructures for smaller silica cores (approximately < or =110 nm in diameter). The thinner silica shells were synthesized by using a lower TEOS concentration. By using sodium silicate (Ung et al. J. Phys. Chem. B 1999, 103, 6770), the porous silica shells were synthesized. Controlled chemical etching of the core-shell-shell nanoparticles with an aqueous KCN solution resulted in corrugated silica shells around the gold nanoparticles or corrugated silica nanospheres with few or no gold nanoparticles. This has allowed synthesis of new types of core-shell-shell nanoparticles with tailored corrugated shells. The nanoporous silica shells provided accessible structures to the embedded metal nanoparticles as observed from the electrochemical response of the gold nanoparticles.     

Polystyrene‐Core–Silica‐Shell Hybrid Particles Containing Gold and Magnetic Nanoparticles

Polystyrene‐core–silica‐shell hybrid particles were synthesized by combining the self‐assembly of nanoparticles and the polymer with a silica coating strategy. The core–shell hybrid particles are composed of gold‐nanoparticle‐decorated polystyrene (PS‐AuNP) colloids as the core and silica particles as the shell. PS‐AuNP colloids were generated by the self‐assembly of the PS‐grafted AuNPs. The silica coating improved the thermal stability and dispersibility of the AuNPs. By removing the “free” PS of the core, hollow particles with a hydrophobic cage having a AuNP corona and an inert silica shell were obtained. Also, Fe₃O₄ nanoparticles were encapsulated in the core, which resulted in magnetic core–shell hybrid particles by the same strategy. These particles have potential applications in biomolecular separation and high‐temperature catalysis and as nanoreactors.     

不同受限状态下链硫醇的非线性光学响应

以和频(SFG)振动光谱技术探测了正十二硫醇(DDT)在不同受限状态下的分子振动信号,包括金属基底上的自组装单层(SAM)分子,放置在二氧化硅基底上的表面DDT化的金纳米粒子以及金纳米粒子的甲苯溶液.在三种状态下都探测到了来自于DDT分子的振动光谱,振动光谱的区别提供了在不同受限态下DDT分子的结构信息.在金属基底上DDT分子排列规整,放置在二氧化硅基底上的金纳米粒子表面的DDT分子具有一定的柔性,在空气-甲苯溶液界面金纳米粒子表面的DDT分子高度无序.此外,光谱实验显示,金纳米粒子表面的分子振动信号产生了局域场增强的效应,相对于金基底上的自组装单层分子而言,增强系数为102-103,取决于光谱的偏振组合.     

不同受限状态下链硫醇的非线性光学响应

以和频(SFG)振动光谱技术探测了正十二硫醇(DDT)在不同受限状态下的分子振动信号, 包括金属基底上的自组装单层(SAM)分子, 放置在二氧化硅基底上的表面DDT化的金纳米粒子以及金纳米粒子的甲苯溶液. 在三种状态下都探测到了来自于DDT分子的振动光谱, 振动光谱的区别提供了在不同受限态下DDT分子的结构信息. 在金属基底上DDT分子排列规整, 放置在二氧化硅基底上的金纳米粒子表面的DDT分子具有一定的柔性, 在空气-甲苯溶液界面金纳米粒子表面的DDT分子高度无序. 此外, 光谱实验显示, 金纳米粒子表面的分子振动信号产生了局域场增强的效应, 相对于金基底上的自组装单层分子而言, 增强系数为10²-10³, 取决于光谱的偏振组合.     

Investigation of the effect of dual-size coatings on the hydrophobicity of cotton surface

A series of silica nanoparticles with two different length scales were introduced onto the cotton substrates to study the correlation between the surface structure and observed hydrophobicity. SiO₂ nanoparticles of 7, 12, 20, and 40 nm in size were individually functionalized using 3-aminopropyl triethoxysilane or 3-glycidoxypropyltrimethoxysilane. Amino functionalized silica nanoparticles were durably attached to the cotton surface that was previously treated with epichlorohydrin. By depositing an additional layer of epoxy modified silica nanoparticles, a dual-size hierarchical coating was obtained. It was found that the order of deposition of particles to develop dual-size coatings determines the surface roughness, hydrophobicity and the amount of silica loaded on the cotton substrate. Deposition of the bigger nanoparticles on top of smaller ones resulted in rougher surfaces, higher hydrophobicity and higher amount of silica loading onto the cotton surface. A strong correlation between the size ratio of deposited nanoparticle combinations and the amount of silica loading was observed. It was found that there is also a direct relationship between the surface roughness and the hydrophobicity of the samples generated. Based upon these correlations, it is now possible to tune surface roughness and subsequent wettability by controlling the sizes of the dual-type nanoparticle layers.     

Charged silsesquioxane used as a vehicle for gold nanoparticles to perform the synthesis of catalyst xerogels

The water soluble charged silsesquioxane that contains the bridged 1,4-diazoniabicyclo[2.2.2]octane chloride group, was used as stabilizing agent and size controller in the synthesis of gold nanoparticles smaller than 15?nm in aqueous medium. The gold nanoparticle dispersion was converted in solid powder form by evaporation. This powder presented organized structure imposed by the presence of charged organic group, similar to organized structure already observed for pure silsesquioxane. The gold nanoparticles in solid powder form presented high storage stability for several months, at ambient conditions, and can be completely redispersed in water again. After redispersion, the optical properties of gold nanoparticles, observed by ultra-violet and visible spectroscopy, and their morphological characteristics, investigated by transmission electron microscopy, are preserved. The gold nanoparticle aqueous dispersion was used as a vehicle of nanoparticles in the synthesis of sol?Cgel silica based hybrid material. This xerogel was characterized by N₂ adsorption?Cdesorption isotherms, showing 260?m²g^?1, and it was applied in a satisfactory way as catalyst for p-nitrophenol reduction to p-aminephenol.     

Gold nanoparticle/charged silsesquioxane films immobilized onto Al/SiO2 surface applied on the electrooxidation of nitrite

In this work, gold nanoparticles lower than 10?nm were prepared in an aqueous medium using two charged silsesquioxanes, the propylpyridinium chloride and propyl-1-azonia-4-azabicyclo[2.2.2]octane chloride, as stabilizer agents which revealed to be water-soluble. This stabilization method is innovative allowing thin films containing gold nanoparticles to be obtained, and it was used for the first time in the preparation of carbon paste electrodes (CPEs). The charged silsesquioxanes were characterized by liquid ¹³C NMR. The gold nanoparticle/silsesquioxane systems were characterized by ultraviolet–visible spectroscopy (UV–Vis) and transmission electron microscopy. In sequence, they were immobilized on silica matrix coated with aluminum oxide. The resulting solid materials designated as Au-Py/AlSi and Au-Db/AlSi were characterized by infrared spectroscopy and N₂ adsorption/desorption isotherms. The results showed that the gold nanoparticle/silsesquioxane systems are strongly adhered to the surface-forming thin films. The Au-Py/AlSi and Au-Db/AlSi materials were used to prepare CPEs for the electrooxidation of nitrite (NO ₂ ^? ) using cyclic voltammetry and differential pulse voltammetry. The Au-Py/AlSi and Au-Db/AlSi CPEs showed high sensitivity and detection limits of 71.87 and 53.66?μA?mmol^–1?L and 1.3 and 3.0?μmol?L^–1, respectively.     

Asymmetrical flow field-flow fractionation with multi-angle light scattering detection for the analysis of structured nanoparticles

Synthesis and applications of new functional nanoparticles are topics of increasing interest in many fields of nanotechnology. Chemical modifications of inorganic nanoparticles are often necessary to improve their features as spectroscopic tracers or chemical sensors, and to increase water solubility and biocompatibility for applications in nano-biotechnology. Analysis and characterization of structured nanoparticles are then key steps for their synthesis optimization and final quality control. Many properties of structured nanoparticles are size-dependent. Particle size distribution analysis then provides fundamental analytical information. Asymmetrical flow field-flow fractionation (AF4) with multi-angle light scattering (MALS) detection is able to size-separate and to characterize nanosized analytes in dispersion. In this work we focus on the central role of AF4-MALS to analyze and characterize different types of structured nanoparticles that are finding increasing applications in nano-biotechnology and nanomedicine: polymer-coated gold nanoparticles, fluorescent silica nanoparticles, and quantum dots. AF4 not only size-fractionated these nanoparticles and measured their hydrodynamic radius (r_h) distribution but it also separated them from the unbound, relatively low-M_r components of the nanoparticle structures which were still present in the sample solution. On-line MALS detection on real-time gave the gyration radius (r_g) distribution of the fractionated nanoparticles. Additional information on nanoparticle morphology was then obtained from the r_h/r_g index. Stability of the nanoparticle dispersions was finally investigated. Aggregation of the fluorescent silica nanoparticles was found to depend on the concentration at which they were dispersed. Partial release of the polymeric coating from water-soluble QDs was found when shear stress was induced by increasing flowrates during fractionation.     

Synthesis of gold–poly(methyl methacrylate) core–shell nanoparticles by surface‐confined atom transfer radical polymerization at elevated temperature

Surface‐confined atom transfer radical polymerization was used to prepare gold nanoparticle–poly(methyl methacrylate) core–shell particles at elevated temperature. First, gold nanoparticles were prepared by the one‐pot borohydride reduction of tetrachloroaurate in the presence of 11‐mercapto‐1‐undecanol (MUD). MUD‐capped gold nanoparticles were then exchanged with 3‐mercaptopropyltrimethoxysilane (MPS) to prepare a self‐assembled monolayer (SAM) of MPS on the gold nanoparticle surfaces and subsequently hydrolyzed with hydrochloric acid. The extent of exchange of MUD with MPS was determined by NMR. The resulting crosslinked silica‐primer layer stabilized the SAM of MPS and was allowed to react with the initiator [(chloromethyl)phenylethyl] trimethoxysilane. Atom transfer radical polymerization was conducted on the Cl‐terminated gold nanoparticles with the CuCl/2,2′‐bipyridyl catalyst system at elevated temperature. The rates of polymerization with the initiator‐modified gold nanoparticles exhibited first‐order kinetics with respect to the monomer, and the number‐average molecular weight of the cleaved graft polymer increased linearly with the monomer conversion. The presence of the polymer on the gold nanoparticle surface was identified by Fourier transform infrared spectroscopy and transmission electron microscopy. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 3631–3642, 2005