pH敏感的金纳米颗粒的制备及表征

利用立方硅氧烷(odaaps)作为保护剂合成了金纳米颗粒,利用紫外-可见(UV-vis)吸收光谱、透射电镜(TEM)对纳米颗粒进行了表征。通过改变纳米溶胶的pH值,从而改变立方硅氧烷上羧基的存在形式,控制纳米颗粒表面的电荷,实现金纳米颗粒的可逆聚集与分散;当将其pH值降低至2.5时,颗粒能够完全沉淀,加碱调节其pH与原始值(pH=9)一致时,聚集的颗粒会自动重新分散形成溶胶,其具有与起始一致的高分散性。     

pH诱导两性离子配体修饰的金溶胶的浓缩与保存

研究了两性离子配体修饰的金纳米颗粒在酸性和碱性溶液中的稳定性和可逆聚集性. 测量了金溶胶在不同条件下的UV-Vis 吸收光谱, 通过光谱的变化揭示其稳定性和可逆聚集性. 结果表明: 经配体修饰的金纳米颗粒在酸性和碱性溶液中的稳定性有了很大的提高; 强酸性条件可诱导金溶胶失稳聚沉, 回调pH值又可使其重新分散. 利用这种pH依赖的可逆聚集特性, 可以将稀溶胶浓缩成浓溶胶或固体保存, 一旦需要又可加水恢复到分散的状态.     

大孔树脂对红霉素的吸附动力学研究

利用大孔吸附树脂Amberlite XAD16及HZ816对红霉素的吸附动力学实验,研究了温度、初始浓度、溶液pH值及搅拌速度等因素对吸附过程的影响.结果表明,Amberlite XAD16及HZ816对红霉素的吸附速率符合一级吸附动力学方程及颗粒内扩散方程,过程受液膜扩散阻力及颗粒内扩散阻力共同影响.同时,表观吸附速率常数与颗粒内扩散速率常数均随着温度的升高而增大,随着初始浓度的增大而增大,随着溶液pH值增大而增大,随着搅拌速度加快而增大.     

水性聚氨酯甲阶酚醛水分散液微观形态及杂化膜的性能

以自乳化型聚氨酯和甲阶酚醛制备了聚氨酯 酚醛复合水分散液 .pH值与酚醛溶解度的关系表明甲阶酚醛的溶解是酚羟基电离的结果 .聚氨酯 甲阶酚醛水分散液粒子的形态有核壳结构、不完善的核壳结构及纯聚氨酯颗粒三种 ,后者粒径最小 .随着酚醛用量的增大 ,粒子平均粒径增大 .酚醛含量增加使体系热稳定性、机械稳定性、冻融稳定性及临界聚沉值下降 ,pH值稳定范围变窄 .分散液稳定性和电性能考察证明 ,本复合分散液的稳定性主要由分散液的电性能所决定 ,属真溶胶 ,但在一定程度上也具有大分子溶液的特性 .复合液涂膜的性能较纯聚氨酯有所改善 ,尤其在添加了硅溶胶之后     

酸和碱催化制备二氧化硅溶胶及其稳定性

以正硅酸乙酯(TEOS)为原料,氨水和盐酸为催化剂,制备了SiO2溶胶;研究了pH值对溶胶的稳定性以及SiO2粒子生长方式的影响.结果表明,在酸性条件下,随着pH值的增加,凝胶时间呈现先变长后变短的趋势;而在碱性条件下,凝胶时间随pH的增大快速增加.透射电镜(TEM)和动态光散射(DLS)分析结果表明,溶胶中的SiO2粒子处于纳米量级,且两种催化条件下粒子的粒径分布存在明显差异.     

聚丙烯酸在纳米TiO2表面吸附行为的研究

讨论了聚丙烯酸在纳米TiO₂水悬浮体系中的吸附行为.红外光谱分析和吸附实验结果表明,纳米TiO₂通过氢键吸附PAA.PAA吸附量随着浓度的升高而增大直至饱和吸附量,且分子量越大,饱和吸附量越大.pH值增大,则饱和吸附量减小.在相同条件下,表面吸附层的厚度随PAA分子量、浓度和pH值增大而增大.这是由PAA在颗粒表面构型的变化所致.吸附PAA后的纳米TiO₂的表面电荷密度和ζ电位发生变化,pHiep值向低值方向移动.表面吸附自由能的计算结果说明,PAA在纳米TiO₂表面的吸附是自发过程.     

草鱼鳞胶原蛋白纳米银溶胶的制备及其对水中Cr(Ⅲ)的检测

以草鱼鳞胶原蛋白为稳定剂,AgNO_3为银源,茶多酚(TP)为还原剂,采用化学还原法快速合成了草鱼鳞胶原蛋白纳米银(Col-nAg)溶胶。考察了AgNO_3浓度、pH值及TP浓度对Col-nAg溶胶制备的影响。得到Col-nAg溶胶的最优制备条件为0.02 mol/L AgNO_3,pH 7.0和2 mol/L TP,所得纳米银平均粒径为4.45 nm,且可在4℃下保存60 d无明显变化。将Col-nAg溶胶用于Cr~(3+)检测,纳米银颗粒与Cr~(3+)之间发生非交联团聚,溶胶颜色由黄色变为褐色,纳米银粒径变大,检测范围为0～10μg/mL,检出限为0.5μg/mL。最优检测条件为pH 7.0,25℃下反应5 min。该反应对Cr~(3+)具有高选择性。     

乙二胺对溶胶-凝胶法合成La0.65Sr0.35MnO3的影响

利用溶胶-凝胶工艺制备了钙钛矿结构的亚锰酸盐化合物(La0.65Sr0.35MnO3),通过XRD和SEM研究了乙二胺和氨水对溶胶-凝胶工艺的影响.结果发现,当体系pH值调梧到8.0附近时,添加乙二胺有利于溶胶-凝胶的形成,而添加氨水的样品中有部分沉淀产生,不能很好地凝胶化.热处理后,添加乙二胺的样品形成的产物颗粒细小均匀,而添加氨水的样品出现了比较严重的团聚现象.分析表明:乙二胺在溶胶.凝胶形成过程中起着桥接、交联和螫合的作用,桥接和交联有利于凝胶化过程的发生和稳定,螯合作用有利于金属离子均匀分散在凝胶的三维网络结构中,从而减少后期热处理过程中的团聚.     

有机溶剂中溶胶-凝胶法制备纳米钙钛矿型氧化物

以柠檬酸作配位剂,无水乙醇为溶剂,采用有机溶剂的溶胶-凝胶法合成了纳米钙钛矿型氧化物LaMnO3及La1-xSrxMnO3.用TG/DTA对金属羧酸盐凝胶的热分解历程进行了分析,用XRD分析了所得产物的相组成,以TEM观察了不同制备条件下的纳米粉体的颗粒尺寸及其形貌特征.结果表明,与水溶液相比,在有机溶剂中能够获得尺寸更小的纳米钙钛矿粉体.研究了溶液pH值和柠檬酸用量对La1-xSrxMnO3前驱体溶胶凝胶稳定性的影响.通过实验确定最佳的工艺条件为pH=8,柠檬酸添加量与金属离子总量的比值为21.     

pH荧光纳米传感器的研制及表征

利用溶胶-凝胶技术制得了单分散性很好的二氧化硅纳米微球,通过共价偶联方式引入对pH变化敏感的荧光素异硫氰酸酯（FITC）,这种FITC功能化二氧化硅纳米微球（FITC功能化硅微球）可作为pH荧光纳米传感器。当pH值从4.0变至7.5时,荧光强度增大约30倍。该传感器灵敏度高,响应速度快,容易制备,光稳定性好,可望用于单细胞的pH分析。     

金纳米粒子在氨基表面上的组装-pH值的影响

用原子力显微镜（AFM）和表面增强喇曼光谱（SERS）研究了pH值对金纳米粒子在Au／巯基苯胺自组装膜表面上组装效果的影响．AFM结果表明，金纳米粒子在表面上的覆盖度随pH值表现出规律性的变化，巯基苯胺自组装膜的SERS强度随pH值的变化也有类似的趋势．在磁性环境下，氨基未质子化，金粒子难以组装上，而在酸性条件下，氨基质子化带正电，金粒子与基底容易结合．我们认为金纳米粒子和氨基之间的作用属于静电力，pH值同时影响膜表面氨基的质子化程度和金纳米粒子表面的带电量．     

Asymmetric dimers can be formed by dewetting half-shells of gold deposited on the surfaces of spherical oxide colloids

Asymmetric dimers consisting of gold microcrystals and spherical silica colloids have been fabricated by depositing thin films of gold onto the spherical colloids to form half-shells, followed by annealing at elevated temperatures. The capability and feasibility of this procedure have been demonstrated with silica and titania beads of 0.2-2 mum in diameter and gamma-Fe2O3/polystyrene@SiO2 core-shell particles 0.5 mum in size. The dimensions of gold microcrystals could be conveniently varied in the range of 100-650 nm by controlling the thickness of gold films and/or the diameter of the spherical colloids. This method provides another route to asymmetric dimers made of colloidal particles that could be different in size, chemical composition, surface functionality, density or sign of surface charge, bulk property, or a combination of these properties.     

Synthesis and characterization of colloidal gold particles as labels for antibodies as used in lateral flow devices

Based on well established citrate reduction protocols for the synthesis of colloidal gold particles, this work focuses on the characterization of these colloids for further use as color labels in lateral flow devices. A reproducible production method has been developed for the synthesis of well characterized colloidal gold particles to be employed in Lateral Flow Devices (LFDs). It has been demonstrated that when undertaking chemical reduction of gold salts with sodium citrate, the amount of reducing agent employed could be used to directly control the size of the resultant particles. A protocol was thereby developed for the synthesis of colloidal gold particles of pre-defined diameters in the range of 15 to 60 nm and of consistent size distribution. The absorption maxima (λ(max)) of the reaction solutions were analyzed by UV/VIS measurements to determine approximate particle sizes, which were confirmed with transmission electron microscopy (TEM) measurements. Colloidal gold particles of about 40 nm in diameter were synthesized and used for labeling monoclonal anti-mycotoxin antibodies (e.g. zearalenone). To deduce the extent of antibody coupling to these particles, smaller colloids with 15 nm diameter were labeled with anti-species specific antibodies. Both solutions were mixed and then scanned by TEM to obtain information about the success of coupling.     

The nanoscale description of acid penetration to the gold colloids encapsulated in silica sol–gel matrix

Various sizes of gold nano colloidal particles ranging from 5 nm to 100 nm of size were encapsulated in a silica based sol–gel, and these surfaces were exposed to a pH 1 acid solution. This enabled us to observe the process of solvent intrusion and interaction with gold colloids by the absorption spectrum as a function of time. The rate was analyzed by a single exponential analytical function, and the maximum rate was found for gold colloid of 15 nm size. The least acid interaction and colour change was observed for the size of 60 nm. It was speculated that the surface of these gold colloids were homogeneously covered by the sodium tetra-borate buffer which insulated silica gel layer, thus avoiding direct contact of the acid with the surface of the gold colloid. This study confirmed that the nano scale dopant size affects the rate of solvent penetration into a sol–gel cavity.     

巯基聚乙二醇5000修饰的金溶胶的稳定性: 从DLVO稳定到空间稳定

研究了α-甲氧基-ω-巯基聚乙二醇(mPEG-SH, 5000 MW)修饰的金溶胶的稳定性, 初步探讨了其稳定机制. 将线性mPEG-SH通过巯基化学吸附于金溶胶表面, 可形成高分子层包被的金溶胶. 研究结果表明, PEG修饰的金溶胶可以在pH＝1～13.5或盐浓度高达1.20 mol/L的较苛性条件下保持稳定. 这是由于金溶胶表面吸附的高分子保护层为溶胶提供了新的空间稳定, 取代了溶胶原来的DLVO稳定(实质是电荷稳定). 因而, PEG保护的金溶胶在很大程度上克服了DLVO稳定的溶胶对环境敏感、易聚沉的缺点, 能在复杂的条件(如生理条件)下应用. 鉴于PEG的水溶性、无毒性和生物亲和性, 这种具有较高稳定能力的金纳米粒子/PEG复合体结合了金纳米粒子和PEG的优异性能, 可作为生物纳米探针用于复杂条件下的生物分析.     

Ordered arrays of gold nanostructures from interfacially assembled Au@PNIPAM hybrid nanoparticles

In this Article, we report on the assembly of hybrid Au@PNIPAM core-shell particles at the air/water interface, their transfer onto solid substrates, and the controlled combustion of the organic material to produce arrays of gold nanoparticles. A detailed investigation on the assembly behavior of such soft hybrid colloids at the air/water interface was performed by correlating the surface pressure-area isotherms with SEM and AFM images from samples transferred at different surface pressures. The hybrid particles display a complex behavior at the interface, and we could distinguish three distinct phases with varying interparticle spacings at different compression. The transfer process presented enables the decoration of topologically structured substrates with gold nanoparticle arrays, and the order of the initial monolayers is retained in the arrays of inorganic gold nanoparticles. The change in monolayer morphology upon compression can therefore be used to tailor the interparticle distance between approximately 650 and 300 nm without exchanging the colloids. More sophisticated gold nanostructures can be patterned into symmetric arrays using a similar protocol, which we demonstrate for nanostars and nanorods.     

16-n-16型双子表面活性剂稳定纳米金的制备及其催化性能

双子表面活性剂由于其特殊的两亲结构可以作为纳米金颗粒(AuNPs)的表面稳定剂,但双子表面活性剂结构中的连接基团对AuNPs的粒径大小及稳定性有显著影响。本文制备了16-n-16(n=2,3,4和6)型双子表面活性剂稳定的金纳米溶胶,考察了体系pH对AuNPs稳定性的影响,并测试了其对4-硝基苯酚加氢还原体系的催化效果。结果表明,16-4-16和16-3-16对AuNPs的稳定性效果较好,所制备的AuNPs中,16-3-16-AuNPs在不同pH的环境中稳定性最好,而16-4-16-AuNPs在4-硝基苯酚加氢还原反应中的催化活性最佳。     

Synthesis and characterization of non-spherical gold colloids in block-copolymer micelles

Gold colloids of well-defined shape, size and polydispersity are synthesized by heterogeneous reduction of gold salts in amphiphilic block-copolymer micelles. The resulting hybride systems consisting of the noble metal colloid and the stabilizing shell of block-copolymers are characterized by electron microscopy and small-angle x-ray scattering. Opposite to classical noble metal colloids, the block-copolymer stabilized systems exhibit an extra-ordinary high colloidal stability which makes analysis and sample handling very simple.It turned out that non-spherical metal colloids are formed in the early stages of the reduction process where the amount of gold exceeds the reduction agent. At later stages, the colloids break up to globular subunits again. The reaction period of colloidal anisometry is reflected in a violet color of the reaction solution, which is caused by a typical structured, double-resonance plasmon band.Small-and wide-angle x-ray scattering reveal a quantitative measure for the size, shape, anisometry and local order in each step of the reduction process. It is suggested that the primary aubergine-shaped particles consist of globular primary particles which are glued together via non reacted gold salt. This observation gives rise to some interesting possibilities of the supramolecular handling of colloids.     

STUDIES OF ADHESION OF METAL PARTICLES TO SILICA PARTICLES BASED ON ZETA POTENTIAL MEASUREMENTS

The zeta-potentials of silica, copper, platinum and gold particles have been measured as a function of pH. The isoelectric points were found to be at pH 3.0, 5.8, 3.0 and 3.5, respectively. In the pH range 3.0 to 5.8 copper and silica particles are oppositely charged and accordingly the coating of silica with copper particles could be demonstrated. In the case of gold and platinum the sign of the charge is such that direct adhesion to silica particles cannot be expected and this was also demonstrated in the case of platinum.