树状大分子包裹金纳米颗粒的制备、尺寸控制和稳定性研究

作者以氨基封端的第五代聚酰胺胺(PAMAM)树状大分子为模板,借助静电相互作用将氯金酸盐吸引进入树状大分子内部,再由外加还原剂硼氢化钠将金盐原位还原,得到了树状大分子包裹的金纳米颗粒(Dendrimer-Entrapped Gold Nanoparticles,Au DENPs),并应用紫外、表面电势法、透射电镜和能量色散谱等手段对其结构进行表征。通过改变氯金酸与树状大分子的投料比,平均尺寸在1.9~2.8nm的Au DENPs被成功制备。制得的Au DENPs不仅在水、PBS缓冲液以及生理环境下稳定存在,还在较宽的pH(pH=5~8)与温度(4~50℃)范围内稳定,为其应用于生物医学领域提供了可能。     

Reversible Clustering of Gold Nanoparticles under Confinement

A limiting factor of solvent‐induced nanoparticle self‐assembly is the need for constant sample dilution in assembly/disassembly cycles. Changes in the nanoparticle concentration alter the kinetics of the subsequent assembly process, limiting optical signal recovery. Herein, we show that upon confining hydrophobic nanoparticles in permeable silica nanocapsules, the number of nanoparticles participating in cyclic aggregation remains constant despite bulk changes in solution, leading to highly reproducible plasmon band shifts at different solvent compositions.     

Small Size Effect and Concentration Response of Gold Nanoparticles in Electrochemiluminescence Reaction

Recent reports have used gold nanoparticles (AuNPs) as a co‐reactant for the electrochemiluminescence (ECL) reaction of ruthenium complex. However, understanding the size effect of AuNPs on ECL reaction is very meaningful to explore its unknowns and develop its applications at the molecular level. In this paper, we examined the behavior of various small‐size AuNPs in ECL reaction, focusing on changes in ECL caused by AuNPs size and reasons for this change. Although the luminescence spectra and excitation potential have hardly changed in ECL reaction, the difference of ECL intensities induced by different sizes AuNPs is very obviously. Our experimental results revealed disparate behaviors depending on AuNPs size: the small‐sized AuNPs can lead to stronger ECL, and ECL intensities increase as the addition of AuNPs concentration in the wider range. This small size effect is related to an intermediate process of charge‐discharge in electric double layer formed by adsorbing ruthenium complex with AuNPs, and the surface and quantum size effect of AuNPs may affect this intermediate process. More importantly, AuNPs can act as a marker, has the same small size effect and concentration response, and bring about a promising platform for biochemical analysis.     

Ethylene Polymerization by Metallocene Catalysts Supported over Siliceous Materials with Bimodal Pore Size Distribution

Summary: As known, the pore structure of the catalytic support plays a decisive role during the polymerization reactions determining intra-particle mass and heat transport phenomena. In this work, several ethylene polymerizations have been carried out by using as catalytic support different mesostructured materials with unimodal and bimodal pore size distributions in order to evaluate the influence of this pore size distribution on the catalytic behavior. Calcined mesoporous materials were impregnated with the catalytic system MAO/(nBuCp)₂ZrCl₂ and used for ethylene polymerization and ethylene/1-hexene copolymerizations, at 70 °C and 5 bar of ethylene pressure. Polyethylenes obtained were characterized by GPC, DSC and Crystaf. Results indicate that porous structure of the support has a significant influence on polymerization activity and polymer properties. Despite the catalyst bimodal pore size distribution, only ethylene/1-hexene copolymers presented a bimodal chemical composition distribution.     

Parametric Study of Gold Nanoparticles Synthesis under Micro-Continuous Flow Conditions

The synthesis of gold nanoparticles (GNPs) using chemical reduction in batch and microreactor methods has been reported. A parametric study of the effect of several parameters on the size of gold nanoparticles was performed in batch synthesis mode using the modified Martin method. The best-obtained conditions were used to synthesize gold nanoparticles using a glass chip microreactor, and the size of the resulting GNPs from both methods was compared. The presence of polyvinyl alcohol (SC) was used as a capping agent, and sodium borohydride (SB) was used as a reducing agent. Several parameters were studied, including HAuCl₄, SC, SB concentrations, the volumetric ratio of SB to gold precursor, pH, temperature, and mixing speed. Various techniques were used to characterize the resulting nanoparticles, including Atomic Absorbance spectroscopy (AAS), Ultraviolet-visible spectroscopy (UV-Vis), and dynamic light scratching (DLS). Optimum conditions were obtained for the synthesis of gold nanoparticles. Under similar reaction conditions, the microreactor consistently produced smaller nanoparticles in the range of 10.42–11.31 nm with a reaction time of less than 1 min.     

Plasmonic Properties and Size Programming: A Quantitative Study for Photosynthesized Gold Nanoparticles

A novel two‐component peak quantitative spectra deconvolution model is employed to elucidate the relationship between the plasmonic properties and the concentration‐dependent Au nanocrystals nucleation. The reactions with the initial concentration of starting reagent NaAuCl₄ from 0.75 mM to 0.1 mM are monitored. The peak area variation between component peak (b), large size nanoparticles (d ≥ 8.1 nm), and component peak (a), small size nanoparticles (d ≤ 8.0 nm), demonstrates that the initial concentration of NaAuCl₄ plays a decisive factor to determine the (b/a) ratio, i.e. the growth progresses of Au nanoparticles. If the initial concentration of NaAuCl₄ is higher than 0.2 mM, two independent growth progresses of Au nanoparticles are observed, and a continuous λ_max blue‐shift of surface plasmon absorption peak accompanied with the second growth progress is measured. On the other hand, in the reactions with the initial concentration of NaAuCl₄ lower than 0.2 mM, only one crystal growth progress of Au nanoparticles is shown, and the blue‐shift phenomenon of absorption peak induced by the second crystal growth progress no longer exists.     

Tailoring Ion Charge State Distribution in Tetramethyltin Clusters under Influence of Moderate Intensity Picosecond Laser Pulse: Role of Laser Wavelength and Rate of Energy Deposition

Systematic manipulation of ionic-outcome in laser-cluster interaction process has been realized for studies carried out on tetramethyltin (TMT) clusters under picosecond laser conditions, determined by choice of laser wavelength and intensity. As a function of laser intensity, TMT clusters exhibit gradual enhancement in overall ionization of its cluster constituents, up to a saturation level of ionization, which was distinct for different wavelengths (266, 355, and 532 nm). Simultaneously, systematic appearance of higher multiply charged atomic ions and shift in relative abundance of multiply charged atomic ions towards higher charge state was observed, using time-of-flight mass spectrometer. At saturation level, multiply charged atomic ions up to (C²⁺, Sn²⁺) at 266 nm, (C⁴⁺, Sn⁴⁺) at 355 nm, and (C⁴⁺, Sn⁶⁺) at 532 nm were detected. In addition, at 355 nm intra-cluster ion chemistry within the ionized cluster leads to generation of molecular hydrogen ion (H₂ ⁺) and triatomic molecular hydrogen ion (H₃ ⁺). Generation of multiply charged atomic ions is ascribed to efficient coupling of laser pulse with the cluster media, facilitated by inner-ionized electrons produced within the cluster, at the leading edge of laser pulse. Role of inner-ionized electrons is authenticated by measuring kinetic energy distribution of electrons liberated upon disintegration of excessively ionized cluster, under the influence of picosecond laser pulse.

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Study of Bimodal Drop Size Distributions of Emulsion

In order to increase the present understanding of bimodal emulsion drop size distributions, systematic series of experiments have been carried out to investigate the effects of formulation variables on bimodal drop size distributions, and probability distribution functions were proposed to analyze the distribution. The results show that, the span of the drop size and Sauter mean diameter become larger when the dispersed phase volume fraction becomes higher and rotor speed becomes lower; the Frechet function represents the experimental data satisfactorily. The prediction model of Sauter mean diameter established by combining the prediction theory of the maximum stable drop diameter and experimental analysis results can fit the experimental data well.     

金纳米粒子的细胞毒性

金纳米粒子(AuNPs)是构建用于诊断和治疗的纳米药物/探针的理想纳米材料之一,因此研究AuNPs与细胞的相互作用具有重要意义。 本文详细分析了金纳米簇(AuNCs)、球形金纳米粒子A(AuNPss)、金纳米球壳(AuNSs)和金纳米棒(AuNRs)等不同形貌的Au NPs对不同细胞模型的细胞毒性;讨论了AuNPs的理化性质(大小、形状、化学功能和表面电荷)对其细胞毒性的影响。 总结了AuNP细胞毒性研究遇到的挑战并提出相应解决方法。     

Size of Gold Nanoparticles Driving Selective Amide Synthesis through Aerobic Condensation of Aldehydes and Amines

Metal nanoparticles (NPs) have attracted much attention in many fields due to their intrinsic characteristics. It is generally accepted that smaller NPs (1.5–3 nm) are more active than larger NPs, and reverse cases are very rare. We report here the direct aerobic oxidative amide synthesis from aldehydes and amines catalyzed by polymer‐incarcerated gold (Au) NPs. A unique correlation between imine/amide selectivity and size of NPs was discovered; Au‐NPs of medium size (4.5–11 nm) were found to be optimal. High yields were obtained with a broad range of substrates, including primary amines. Au‐NPs of medium size could be recovered and reused several times without loss of activity, and they showed good activity and selectivity in amide formation from alcohols and amines.     

Size Modulation of Polymeric Nanoparticles under Controlled Dynamics of Microemulsion Droplets

Polyacrylamide nanoparticles of different size (<100 nm) were prepared in reverse micelles under various dynamic conditions of micellar systems. The nanoparticles were always larger than the aqueous core in which they were formed; however, the size of the nanoparticles could be controlled if the interdroplet interaction and coalescence rate in reverse micelles were regulated. Factors such as interfacial rigidity of the droplets, size of the aqueous core, temperature, and concentrations of acrylamide (monomer) andN,N′-methylenebisacrylamide (crosslinking agent) have a profound effect on the size of nanoparticles. By adjustment of these parameters in reverse micelles, nanoparticles ranging from about 10 to more than 100 nm have been prepared.     

Reversible Size Control of Liquid‐Metal Nanoparticles under Ultrasonication

This paper describes the reversible control of the size of liquid‐metal nanoparticles under ultrasonication. Gallium was utilized as a liquid metal, which has a melting point of 29.8 °C. Investigating the effects of ultrasonication (power, time, and temperature) on the formation of gallium nanoparticles revealed that the process is similar to the formation of oil in water (O/W) or water in oil (W/O) emulsions, as the temperature significantly affects the size of the gallium nanoparticles (GaNPs). Under ultrasonication, the balance between the break‐up and coalescence of the GaNPs can be adjusted by changing the temperature or adding acid through modulating the natural surface oxide layer (which can be removed with acid) and the stabilizing effect of the surfactant dodecanethiol. Coalescence was predominant at higher temperatures, whereas particle break‐up was found to be predominant at lower temperatures. Furthermore, the change in size was accompanied by a shift in the plasmonic absorption of the GaNPs in the UV region.     

Influence of Gold Nanoparticles of Varying Size in Improving the Lipase Activity within Cationic Reverse Micelles

Herein, we report the effect of gold nanoparticles (GNPs) in enhancing lipase activity in reverse micelles of cetyltrimethylammonium bromide (CTAB)/water/isooctane/n‐hexanol. The size and concentration of the nanoparticles were varied and their specific roles were assessed in detail. An overall enhancement of activity was observed in the GNP‐doped CTAB reverse micelles. The improvement in activity becomes more prominent with increasing concentration and size of the GNPs (0–52 μM and ca. 3–30 nm, respectively). The observed highest lipase activity (k₂=1070±12 cm³ g^?1 s^?1) in GNP‐doped CTAB reverse micelles ([GNP]: 52 μm, ca. 20 nm) is 2.5‐fold higher than in CTAB reverse micelles without GNPs. Improvement in the lipase activity is only specific to the GNP‐doped reverse micellar media, whereas GNP deactivates and structurally deforms the enzyme in aqueous media. The reason for this activation is probably due to the formation of larger‐sized reverse micelles in which the GNP acts as a polar core and the surfactants aggregate around the nanoparticle (‘GNP pool’) instead of only water. Lipase at the augmented interface of the GNP‐doped reverse micelle showed improved activity because of enhancement in both the substrate and enzyme concentrations and increased flexibility in the lipase conformation. The extent of the activation is greater in the case of the larger‐sized GNPs. A correlation has been established between the activity of lipase and its secondary structure by using circular dichroism and FTIR spectroscopic analysis. The generalized influence of GNP is verified in the reverse micelles of another surfactant, namely, cetyltripropylammonium bromide (CTPAB). TEM, dynamic light scattering (DLS), and UV/Vis spectroscopic analysis were utilized to characterize the GNPs and the organized aggregates. For the first time, CTAB‐based reverse micelles have been found to be an excellent host for lipase simply by doping with appropriately sized GNPs.     

甲烷氧化菌素催化纳米金合成

甲烷氧化菌素(methanobactin,mb)是具有过氧化氢还原酶活性的荧光肽.从甲基弯菌Methylosinus trichospo-rium IMV3011限铜培养介质中分离mb,采用紫外可见全波长扫描法观察mb催化对苯二酚还原氯金酸合成纳米金的作用和影响,当mb/氯金酸/对苯二酚反应液中mb的浓度分别是2.5×10-5mol/L、5.0×10-5mol/L和1.0×10-4mol/L时,形成的纳米金溶液的特征峰分别是561.5 nm(OD561=0.158)、548.0 nm(OD5 48=0.426)、536.5 nm(OD5 36=0.541),特征峰波长减小,对应的吸光值增大,表明mb能够催化对苯二酚还原氯金酸合成纳米金,并且可以通过调控mb的浓度控制纳米金的合成量及粒径大小.     

微波辅助4-十二烷氧基苄胺保护的憎水性纳米金原位还原合成

利用新型表面活性剂4-十二烷氧基苄胺(C₁₂OBA)构成的C₁₂OBA/正庚烷/正丁醇/HAuCl₄/NaOH(aq.) W/O型微乳液作为微反应器, 通过微波辐射加热的正丁醇原位还原法制备了C₁₂OBA包裹的憎水性金纳米粒子, 并通过紫外可见光谱(UV-vis)、透射电镜(TEM)、X射线衍射(XRD)、红外光谱(FT-IR)和接触角(CA)等分别进行了表征和分析. 结果显示, C₁₂OBA既可参与形成稳定的W/O型微乳液, 又可作为金粒子的良好保护剂. 微乳液内核中碱度的增加能增强位于膜相的正丁醇分子的还原能力. 在固定氯金酸用量时, C₁₂OBA/金的物质的量比增加有利于获得小尺寸、高单分散性的憎水性纳米金颗粒, 而体系的极性增加则导致金粒子的尺寸增大、单分散性下降. 通过本实验方法可方便快速地合成尺寸约为5 nm的具有高度单分散的憎水性金纳米粒子.     

Bisthiol-Assisted Multilayers' Self-Assembly of Gold Nanoparticles: Synthesis,Characterization, Size Control and Electrocatalytic Applications

The layer-by-layer (LBL) approach has been utilized to self-assemble multilayers films of citrate-stabilized gold nanoparticles (AuNPs) on polycrystalline gold (poly-Au) substrates. 1,4-benzenedimethanethiol (BDMT) was used as a cross linker to bind every two successive AuNPs layers. The transmission electron microscopy (TEM), and X-ray photoelectron spectroscopy (XPS) techniques were employed to confirm the existence of the alternative layers of AuNPs and BDMT in the self-assembled multilayers film. The AuNPs modified poly-Au electrode showed a significant electrocatalysis towards the reduction of oxygen (a positive potential shift of about 100 mV was observed in the reduction peak potential compared to that obtained at the bare poly-Au electrode). The AuNPs tend to aggregate during their assembling to different extent which markedly depends on the substrate geometry and roughness. An effort was dedicated to understand and control the aggregation phenomenon.     

Importance of Size and Distribution of Ni Nanoparticles for the Hydrodeoxygenation of Microalgae Oil

Improved synthetic approaches for preparing small‐sized Ni nanoparticles (d=3 nm) supported on HBEA zeolite have been explored and compared with the traditional impregnation method. The formation of surface nickel silicate/aluminate involved in the two precipitation processes are inferred to lead to the stronger interaction between the metal and the support. The lower Brønsted acid concentrations of these two Ni/HBEA catalysts compared with the parent zeolite caused by the partial exchange of Brønsted acid sites by Ni²⁺ cations do not influence the hydrodeoxygenation rates, but alter the product selectivity. Higher initial rates and higher stability have been achieved with these optimized catalysts for the hydrodeoxygenation of stearic acid and microalgae oil. Small metal particles facilitate high initial catalytic activity in the fresh sample and size uniformity ensures high catalyst stability.     

毛细管区带电泳测定纳米粒子粒径分布的探索

研究了采用毛细管区带电泳测定纳米粒子粒径分布的可能性。在合适的分散条件下,聚苯乙烯(PS)纳米粒子在进样及电泳迁移过程中不发生团聚。通过选择合适的电泳操作条件,PS纳米粒子可以按照粒径大小得到分离,且迁移时间及峰面积的重现性良好。     

Analysis of the Formation Process of Gold Nanoparticles by Surface-Assisted Laser Desorption/Ionization Mass Spectrometry

Chemical reactions of reducing agents in the gold nanoparticle (AuNP) formation process were characterized using surface-assisted laser desorption/ionization mass spectrometry (SALDI-MS). As the reaction of the AuNPs progresses, the produced AuNPs can serve as an efficient SALDI substrate. SALDI-MS revealed that the reducing agents and their oxidation products can be determined in the mass spectra. With respect to the transmission electron microscopic and UV-Vis spectroscopic examination of AuNPs, SALDI-MS results confirm not only the tendency toward AuNPs formation, but also reflect the information of the redox reaction process. Our results provide useful information for developing SALDI-MS methods to explore the chemical information regarding the surface behavior between adsorbates and nanomaterials.