树形大分子与金纳米颗粒复合体系构型与结合强度的分子动力学研究

通过在PAMAM型树形大分子上搭载不同尺寸的金纳米颗粒构建树形大分子-金纳米颗粒复合体系,采用经典分子动力学方法考察了金纳米颗粒尺寸、搭载数量及树形大分子聚乙二醇化修饰对复合体系构型、结合强度及在水中扩散系数的影响。结果表明,PAMAM型树形大分子经过聚乙二醇化修饰可负载更多的金纳米颗粒,使得有效包埋金纳米颗粒的同时自身尺寸未产生明显膨胀。研究结果为探索新型多功能造影剂在生物医药领域的应用具有重要意义。     

反应条件对纳米TiO_2结构和形貌的影响

以TiCl_4为原料,采用低温陈化的方法制备了金红石型和混合晶型纳米TiO_2粉体。研究了反应温度、反应物浓度、体系酸度等反应条件对产物结构、形貌以及粒径的影响。结果表明,当反应温度低于60℃时,产物为金红石型聚集体;当反应温度为100℃时,产物为混合晶型纳米球。随着反应物浓度的增大,球形颗粒的粒径逐渐增大。     

聚酰胺胺树状大分子作为种子的乳液聚合动力学及乳胶粒径

以聚酰胺胺(PAMAM)树状大分子作为种子,过硫酸铵(APS)为引发剂,十二烷基苯磺酸钠(DBS)为乳化剂,进行了苯丙乳液聚合动力学研究。考察了3.0GPAMAM树状大分子浓度、引发剂浓度、乳化剂浓度和反应温度对聚合动力学的影响,并研究了PAMAM树状大分子代数对乳胶粒子粒径的影响。实验结果表明,聚合反应速率随3.0GPAMAM树状大分子浓度的升高先增加后降低,随反应温度、引发剂浓度和乳化剂浓度升高而加快;在3.0GPAMAM树状大分子浓度小于2.392×10~(-4)mol/L时,聚合反应动力学关系式为Rp∝[3.0GPAMAM]~(0.87)[DBS]~(0.507)[APS]~(0.256),表观活化能为66.91k J/mol;随着PAMAM树状大分子代数的增加,乳胶粒子的粒径逐渐减小,并呈现单分散性。     

树状大分子的自组装表面修饰与荧光客体分子的相转移

研究了树枝状大分子PAMAM（G=4）外围氨基与脂肪酸的自组装行为;同时研究了为PAMAM（G=4）树状大分子所包裹的荧光客体分子PHL和RB通过上述树状大分子的表面修饰实现由水相向油相的转移以及在非极性正己烷相中的紫外及荧光性能,发现当十二酸浓度为10％时,41％的PHL分子和几乎100％的RB分子可由水相转移到正己烷相,且这些被包裹在自组装体系中的染料分子的荧光未被猝灭。     

纳米金刚石颗粒随CH4浓度生长的研究

利用等离子体增强热丝化学气相沉积,用CH4和H2为反应气体,在不同CH4浓度的情况下制备了纳米金刚石颗粒,并用高分辨扫描电子显微镜和显微Raman光谱仪对它们进行了表征.结果表明,纳米金刚石颗粒随CH4浓度的增大而增大.结合与CH4-H2等离子体有关的结果,对纳米金刚石颗粒随CH4浓度的生长进行了分析和讨论.     

纳米金颗粒在掺硼金刚石薄膜电极表面的自组装及其电化学性能分析

对阳极氧化后的掺硼金刚石(BDD)薄膜进行表面氨基化处理,使柠檬酸根包裹的纳米金颗粒(粒径约18nm)自组装到BDD薄膜的表面。通过改变纳米金溶液的pH值,在BDD薄膜表面制备出二维形貌分布均匀且相对覆盖度高(约30%)的纳米金颗粒。在[Fe(CN)6]3-/4-体系中,通过循环伏安分析和交流阻抗分析实验发现,纳米金颗粒修饰后的BDD电极表面异相电子转移速率常数(Kapp)由2.8×10-4提高到8.9×10-4。纳米金颗粒修饰的BDD电极对多巴胺的氧化电位由0.54V减小到0.3V,且氧化峰峰值得到提高,证实了纳米金颗粒对多巴胺的催化作用。     

石墨/树状大分子复合材料的分子动力学模拟

在COMPASS(Condensed-phase optimized molecular potentials for atomistic simulation studies)力场下, 对以氨(Amine)、 丁二胺(Butanediamine)为核的1代~3代(1G~3G)石墨/树状大分子纳米复合材料进行了分子动力学模拟(Molecular dynamics simulation)。介绍了复合体系的构建过程及分子动力学模拟细节, 从微观构形、 能量变化研究了正则系综(恒定的NVT)中6种插层复合物的稳定性及其机理, 最后利用径向分布函数(Radial distribution function)对能量变化结果进行了分析。结果表明, 当树状大分子体积较小时, 石墨层容易弯曲, 体系能量较高, 导致复合体系不稳定; 随着树状大分子代数的增加, 石墨层形变减小, 体系能量降低, 3代时树状大分子体系最稳定。      

胶态金纳米型时间-温度指示器性能研究

目的 探究基于金纳米颗粒的时间温度指示器（Time-temperature indicator, TTI）的变色机理及不同制备参数对其动力学参数的影响,为其在食品上的实际应用提供参考依据。方法 以明胶与氯金酸的还原反应为基础制备胶态金纳米型时间-温度指示器。通过紫外-可见分光光度计对TTI的吸光度进行测定,并将其与时间进行非线性拟合。采用单因素实验探讨制备参数对反应速率、变色寿命和活化能的影响。结果 TTI体系中生成的金纳米颗粒使得TTI呈现紫红色,金纳米颗粒数量的增加导致TTI的颜色变深。明胶用量减少而明胶-氯金酸质量比不变,以及明胶用量不变而明胶-氯金酸质量比增大的情况下,TTI体系的反应速率变慢,变色寿命延长。明胶-氯金酸质量比决定了TTI体系的活化能。TTI的活化能的范围为77.89～84.58 kJ/mol。结论 TTI具有监测因脂肪氧化而变质食品的潜能,通过调节TTI的制备参数可改变其变色寿命以匹配不同货架期的食品。     

一种在硅材料表面组装金纳米颗粒的新方法

以氯金酸、L-半胱氨酸为反应试剂,利用内电流和金硫自组装效应,在硅材料表面组装了较为均一的金纳米颗粒,并利用荧光分析与硅纳米线场效应晶体管对该方法进行了相关验证.结果表明:经氢氟酸处理后的硅材料,在氯金酸和L_半胱氨酸混合溶液中反应3 min可在硅表面得到较为均匀、稳定的金纳米颗粒层,其中,氯金酸浓度为0.5mmol/L,氯金酸和L-半耽氨酸浓度比为3∶1.荧光分析表明该方法组装的金颗粒表面已氨基功能化,使得金纳米颗粒修饰的硅材料在应用于生物检测时可直接醛基化修饰蛋白,简化了实验操作,同时,该方法可以在硅纳米线场效应晶体管中特异性组装金纳米颗粒,有力地支持了相关器件在疾病检测方面的应用.     

一种在硅材料表面组装金纳米颗粒的新方法

以氯金酸、L-半胱氨酸为反应试剂,利用内电流和金硫自组装效应,在硅材料表面组装了较为均一的金纳米颗粒,并利用荧光分析与硅纳米线场效应晶体管对该方法进行了相关验证。结果表明:经氢氟酸处理后的硅材料,在氯金酸和L-半胱氨酸混合溶液中反应3min可在硅表面得到较为均匀、稳定的金纳米颗粒层,其中,氯金酸浓度为0.5mmol/L,氯金酸和L-半胱氨酸浓度比为3∶1。荧光分析表明该方法组装的金颗粒表面已氨基功能化,使得金纳米颗粒修饰的硅材料在应用于生物检测时可直接醛基化修饰蛋白,简化了实验操作。同时,该方法可以在硅纳米线场效应晶体管中特异性组装金纳米颗粒,有力地支持了相关器件在疾病检测方面的应用。     

Dendrimer-entrapped gold nanoparticles as a platform for cancer-cell targeting and imaging

We present a general approach for the targeting and imaging of cancer cells using dendrimer-entrapped gold nanoparticles (Au DENPs). Au DENPs were found to be able to covalently link with targeting and imaging ligands for subsequent cancer-cell targeting and imaging. The Au DENPs linked with defined numbers of folic acid (FA) and fluorescein isothiocyanate (FI) molecules are water soluble, stable, and biocompatible. In vitro studies show that the FA- and FI-modified Au DENPs can specifically bind to KB cells (a human epithelial carcinoma cell line) that overexpress high-affinity folate receptors and they are internalized dominantly into lysosomes of target cells within 2 h. These findings demonstrate that Au DENPs may serve as a general platform for cancer imaging and therapeutics.     

以酯端基PAMAM树形分子为模板在N，M-二甲基甲酰胺溶剂中制备金纳米粒子

用UV-vis、FT-IR光谱研究了HAuCl4和酯端基聚酰胺胺(PAMAM)树形分子在N，N-二甲基甲酰胺(DMF)溶剂中的相互作用，提出HAuCl4与树形分子之间的络合机理：[AuCl4]^-离子与质子化叔胺基团形成离子对，Au^3 离子与PAMAM树形分子上的酯基和酰胺基团形成配位作用。在DMF溶剂中酯端基PAMAM树形分子与HAuCl4配位后用柠檬酸钠还原形成金纳米粒子，UV-vis光谱和TEM图像分析表明了随树形分子代数的增加，金纳米粒子的直径减小，并提出了树形分子-金纳米复合物的结构模型：(1)较低代数的树形分子环绕在金粒子的外围；(2)在较高代数的树形分子空腔内部封装金纳米粒子。     

水溶液中低代TEG—PAMAM树形分子存在下金纳米颗粒的制备

在水溶液中低代TEG—PAMAM树形分子存在时，用NaBH4还原HAuCI4制备出金纳米颗粒。用紫外可见吸收光谱（UV—Vis），红外光谱（FT-IR）和透射电子显微镜（TEM）对所制备的金纳米颗及其制备过程进行了表征，实验结果表明，以低代树形分子为模板，当HAuCI4与TEG—PAMAM物质量的比分别为2：1，1：1和1：2时，所制的金纳米颗粒的粒径分别为3．5±0．4nm，2．6±1．6nm和2．88±1．33nm，并且可在室温下储存数月。     

Synthesis of dendrimer-stabilized gold-polypyrrole core-shell nanoparticles

Core-shell composite nanoparticles consisting of a gold core and polypyrrole shell were prepared and stabilized with the poly(amidoamine) dendrimer. An in situ redox polymerization technique was used in which pyrrole reduced Au3+ to Au and then oxidized to polypyrrole. The presence of gold nanoparticles as a core was characterized by its surface plasmon absorption peak at 534 nm. Fourier transform infrared spectroscopy confirmed the presence of polypyrrole on the nanoparticle surfaces. The average diameter of the core-shell nanoparticle is 8.7 +/- 1.8 nm with a shell thickness of approximately 1.5-2.0 nm as estimated from the transmission electron microscopy image. Dissolution of the Au core using KCN enabled the formation of hollow polymer nanospheres.     

Effect of green GO/Au nanocomposite on in‐vitro amplification of human DNA

Recently nanomaterials have attracted interest for increasing efficiency of polymerase chain reaction (PCR) systems. Here, the authors report on the usefulness of green graphene oxide/gold (GO/Au) nanocomposites for enhancement of PCR reactions. In this study, green GO/Au nanocomposite was prepared with Matricaria chamomilla extract as reducing/capping agent for site‐directed nucleation of Au^o atoms on surface of GO sheets. The as‐prepared green GO/Au nanocomposites were then characterised with UV–VIS spectrophotometer and scanning electron microscopy. Later, the effect of these nanocomposites was studied on end‐point and real‐time PCR employed for amplification of human glyceraldehyde‐3‐phosphate dehydrogenase gene. The results indicated that GO/Au nanocomposite can improve both end‐point and real‐time PCR methods at the optimum concentrations, possibly through interaction between GO/Au nanocomposite and the materials in PCR reaction, and through providing increased thermal convection by the GO surface as well as the Au nanostructures. In conclusion, it can be suggested that green GO/Au nanocomposite is a biocompatible and eco‐friendly candidate as enhancer of in‐vitro molecular amplification strategies.Inspec keywords: graphene, molecular biophysics, nucleation, enzymes, gold, nanofabrication, nanocomposites, scanning electron microscopy, nanoparticles, DNA, nanomedicine, ultraviolet spectra, visible spectra, graphene compoundsOther keywords: green GO/Au nanocomposite, polymerase chain reaction systems, green graphene oxide/gold, PCR reaction, as‐prepared green GO/Au nanocomposites, real‐time PCR methods, Au nanostructures, in‐vitro amplification, human DNA, Matricaria chamomilla extract, site‐directed nucleation, Au, CO, CO‐Au     

纳米金的制备及在化妆品中的应用初探

采用柠檬酸钠还原氯金酸制备纳米金,利用X射线荧光能谱和透射电子显微镜对产品进行了表征,通过纳米金溶胶及溶胶中含有的柠檬酸钠和保护剂PVP对Hela细胞、CHO细胞的MTT试验,研究了纳米金溶胶及纳米金颗粒对细胞的毒性,结果表明,纳米金溶胶和纳米金颗粒对这两种细胞均没有产生毒性。将纳米金加入到化妆品基础配方中制备得到了稳定的乳状液,为纳米金用于高级化妆品可行性提供部分实验依据。     

Materials specificity and directed assembly of a gold-binding peptide

Adsorption studies of a genetically engineered gold-binding peptide, GBP1, were carried out using a quartz-crystal microbalance (QCM) to quantify its molecular affinity to noble metals. The peptide showed higher adsorption onto and lower desorption from a gold surface compared to a platinum substrate. The material specificity, that is, the preferential adsorption, of GBP1 was also demonstrated using gold and platinum micropatterned on a silicon wafer containing native oxide. The biotinylated three-repeat units of GBP1 were preferentially adsorbed onto gold regions delineated using streptavidin-conjugated quantum dots (SAQDs). These experiments not only demonstrate that an inorganic-binding peptide could preferentially adsorb onto a metal (Au) rather than an oxide (SiO2) but also onto one noble metal (Au) over another (Pt). This result shows the utility of an engineered peptide as a molecular erector in the directed immobilization of a nanoscale hybrid entity (SAQDs) over selected regions (Au) on a fairly complex substrate (Au and Pt micropatterned regions on silica). The selective and controlled adsorption of inorganic-binding peptides may have significant implications in nano- and nanobiotechnology, where they could be genetically tailored for specific use in the development of self-assembled molecular systems.     

PDDA／Au NPs复合分子沉积膜的制备、表征和摩擦学行为

采用小分子柠檬酸钠对金纳米粒子进行包覆改性,紫外光谱分析经改性的金纳米粒子表面共振吸收峰为526iun,激光纳米粒度仪分析表明其平均粒径为8．4nm．改性后的金纳米粒子通过分子沉积技术,与聚二烯丙基二甲基胺盐酸盐（PDDA）组装,制得单层和多层PDDA／Au NPs复合纳米粒子分子沉积（MD）膜（简称PDDA／Au NPs复合MD膜）．采用原子力显微镜（AFM）研究了PDDA／Au NPs复合MD膜的表面形貌以及摩擦、磨损行为．研究结果表明：该复合膜能降低基底的摩擦力,其中以3层膜降低摩擦力的效果最显著．在氮化硅探针扫描行程达到30次后,膜表面才开始出现磨损痕迹．随着扫描次数的增多,膜表面在探针剪切力的作用下逐渐由致密变得疏松,形成颗粒堆积,使表面粗糙度增大,摩擦力、磨损深度也随之增加．通过实验还发现这种复合膜存在两种非正常磨损现象,即磨损负增长和膜的脱落现象.     

Improved adhesion of Au thin films to SiOx/Si substrates by dendrimer mediation

Quantitative evidence of significantly improved interfacial adhesion between Au films and SiO_x/Si substrates induced by an organic dendrimer monolayer was presented. For dendrimer-mediated Au films, nanoscratch tests revealed a critical load that was two times higher than that for films without dendrimer mediation. Atomic force microscopy (AFM) examination of nanoindents revealed much constrained lateral flow of metals in the dendrimer-mediated Au films during nanoindentation, indicating enhanced adhesion due to the presence of the dendrimer layer.     

Electrochemical genosensor based on colloidal gold nanoparticles for the detection of Factor V Leiden mutation using disposable pencil graphite electrodes

Electrochemical genosensors for the detection of the Factor V Leiden mutation from polymerase chain reaction (PCR) amplicons using the oxidation signal of colloidal gold (Au) is described. A pencil graphite electrode (PGE) modified with target DNA, when hybridized with complementary probes conjugated to Au nanoparticles, responded with the appearance of a Au oxide wave at approximately +1.20 V. Specific probes were immobilized onto the Au nanoparticles in two different modes: (a) Inosine-substituted probes were covalently attached from their amino groups at the 5' end using N-(3-dimethylamino)propyl)-N'-ethylcarbodiimide hydrochloride (EDC) and N-hydroxysulfosuccinimide (NHS) as a coupling agent onto a carboxylate-terminated l-cysteine self-assembled monolayer (SAM) preformed on the Au nanoparticles, and (b) probes with a hexanethiol group at their 5' phosphate end formed a SAM on Au nanoparticles. The genosensor relies on the hybridization of the probes with their complementary targets, which are covalently immobilized at the PGE surface. Au-tagged 23-mer capture probes were challenged with the synthetic 23-mer target, 131-base single-stranded DNA or denatured 256-base polymerase chain reaction (PCR) amplicon. The appearance of the Au oxidation signal shortened the assay time and simplified the detection of the Factor V Leiden mutation from PCR amplified real samples. The discrimination between the homozygous and heterozygous mutations was also established by comparing the peak currents of the Au signals. Numerous factors affecting the hybridization and nonspecific binding events were optimized. The detection limit for the PCR amplicons was found to be as low as 0.78 fmol; thus, it is suitable for point-of-care applications.