Size-controlled assembly of gold nanoparticles induced by a tridentate thioether ligand

The ability to control the size and shape of nanoparticle assemblies is essential for the ultimate applications in sensors, catalysis, medical diagnostics, information storage, and quantum computation. This report demonstrates a novel mediator-template strategy toward this ability by exploring molecular driving forces exerted by a tridentate thioether as a mediator and tetraoctylammonium bromide as a templating agent. A combination of the ligand mediation, the surfactant templating, and their relative concentrations served as the driving forces. This combination leads to unprecedented spherical assemblies of gold nanoparticles in controllable sizes via manipulation of the relative concentrations of mediating and templating components.     

Mediator-template assembly of nanoparticles

The ability to construct size- and shape-controllable architectures using nanoparticles as building blocks is essential for the exploration of nanoparticle-structured properties. This paper reports findings of an investigation of a mediator-template strategy for the size-controllable assembly of nanoparticles. This strategy explores multidentate thioether ligands as molecular mediators and tetraalkylammonium-capped gold nanoparticles (5 nm) as templates toward the preparation of size-controllable and monodispersed spherical assemblies ( approximately 20-300-nm diameters). The combination of the mediation force of the multidentate thioether and the hydrophobic force of the tetraalkylammonium template establishes the interparticle linkage and stability. The morphological properties of the spherical assemblies have been characterized using TEM, AFM, and SAXS techniques. The finding of the soft-hard nature of the nanoparticle assemblies and their interactions with contacting substrates could form the basis of a new strategy for manipulating nanoscale linkages between nanoparticle assemblies, soldering nanoelectronics, and constructing nanosensor devices. The intriguing light scattering and optical absorption properties in response to assembly, disassembly, sizing, and interparticle spacing parameters have been characterized by dynamic light scattering and spectrophotometric measurements. The discovery of the controlled disassembly into individual nanoparticles and the size regulation by a third capping component could form the basis for applications in controlled drug delivery. The fundamental basis for the mediator-template strategy as a versatile assembly technique is further discussed in terms of experimental and theoretical correlations of the morphological and optical properties.     

High-definition self-assemblies driven by the hydrophobic effect: synthesis and properties of a supramolecular nanocapsule

High definition self-assemblies, those that possess order at the molecular level, are most commonly made from subunits possessing metals and metal coordination sites, or groups capable of partaking in hydrogen bonding. In other words, enthalpy is the driving force behind the free energy of assembly. The hydrophobic effect engenders the possibility of (nominally) relying not on enthalpy but entropy to drive assembly. Towards this idea, we describe how template molecules can trigger the dimerization of a cavitand in aqueous solution, and in doing so are encapsulated within the resulting capsule. Although not held together by (enthalpically) strong and directional non-covalent forces, these capsules possess considerable thermodynamic and kinetic stability. As a result, they display unusual and even unique properties. We discuss some of these, including the use of the capsule as a nanoscale reaction chamber and how they can bring about the separation of hydrocarbon gases.     

立方体纳米氧化亚铜反应动力学的理论及实验研究

为了探究纳米多相反应过程的动力学行为,本文通过液相还原法可控合成了粒度为55 nm的立方体氧化亚铜（Cu₂O）。基于纳米与块体Cu₂O的区别,采用原位微量热技术获取Cu₂O体系与HNO₃反应过程的热动力学精细信息,结合热动力学原理及动力学过渡态理论计算得到Cu₂O反应动力学参数,并建立立方体动力学模型讨论并佐证动力学实验结果。结果表明,纳米Cu₂O的反应速率常数大于块体,而表观活化能、指前因子、活化焓、活化熵和活化Gibbs自由能均小于块体;随着温度的升高,纳米Cu₂O的反应速率常数和活化Gibbs自由能均增大。动力学模型表明影响反应动力学参数的主要因素为：偏摩尔表面焓影响表观活化能,偏摩尔表面熵影响指前因子,偏摩尔表面Gibbs自由能影响反应速率常数。本文为纳米材料多相反应动力学参数的获取和分析应用提供了一种普适的理论模型和实验方法。     

立方体纳米Cu2O表面热力学函数的粒度及温度效应

液相还原法合成了4种粒度在40-120 nm的立方体纳米氧化亚铜（Cu₂O）。利用X射线衍射仪（XRD）、显微拉曼光谱仪和场发射扫描电子显微镜（FE-SEM）对纳米Cu₂O的物相组成及形貌结构进行了表征。采用原位微热量技术实时获取纳米/块体Cu₂O与HNO₃反应过程的热动力学信息,结合热化学循环及动力学过渡态理论计算得到纳米Cu₂O的表面热力学函数。在薛永强等建立的无内孔球形纳米颗粒的热力学模型基础上,发展了立方体纳米颗粒的热力学模型。最后由理论结合实验结果分析了粒度和温度对表面热力学函数的影响规律及原因。结果表明,摩尔表面Gibbs自由能、摩尔表面焓和摩尔表面熵均随粒度减小而增大,且与粒度的倒数呈线性关系,这与立方体热力学模型规律一致;随着温度的升高,摩尔表面焓和摩尔表面熵均增大,摩尔表面Gibbs自由能则减小。本文不仅丰富和发展了纳米热力学基本理论,还为纳米材料表面热力学研究及应用提供了方法和思路。     

A Thermochemical Study on Complex Nickel(Ⅱ) L-α-Histidine

IntroductionNickel is an essential trace biological element.L-α- Amino acids are the structural units of pro-teins.L- α- Histidine is one of the eight species ofamino acids which have to be absorbed from foodbecause they are not synthesized by organism.Thus,the investigation on the complexation ofnickel and L -α- histidine is of considerable practicaland fundamental importance.For the nickel com-plexes of amino acids,more extensive work hasbeen carried out[1— 3 ] . However,the thermochem…     

Purification of dodecanethiol derivatised gold nanoparticles

Monolayer protected gold nanoparticles synthesised by a two-phase method contain a significant amount of tetraoctylammonium bromide (TOABr), the quaternary ammonium salt used as the phase transfer reagent, as a persistently retained impurity. A simple purification protocol is described.     

A Thermochemical Study on Complex Nickel（Ⅲ）L—α—Histidine

The formation enthalpy ofcomplex nickel(Ⅱ）-histidine(His)in water was determined by means of microcalorimetry in the temperature range of 298.15-323.15K.The standard enthalpy of the formation of Ni(His)2^2 (aq) was calculated.On the basis of the experimental and the calculated results,three thermodynamic parameters(the activation enthaly,the activation entropy and the activation free energy),the rate constants,three kinetic parameters(the apparent activation energy,the pre-exponential constant and the reaction order)of the formation reaction of the title complex were obtained.     

Phase Chemistry and Thermochemstry on Coordination Behavior of Zinc Chloride with Leucine

The solubility property of the ZnCl2-Leu-H2O(Leu=L-a-leucine) system at 298.15K in the whole concentration range was investigatey by the semimicro-phase equilibrium method.The corresponding solubility diagram and refractive index diagram were constructed.The results indicated that there was one complex formed in this system.namely,Zn(Leu)Cl2.The complex is congruently soluble in water.Based on Phase equilibrium data,the complex was prepared.Its composition and properties were characterized by chemical analysis,elemental analysis,IR spectra,and TG-DTG.The thermochemical properties of coordination reaction of zinc chloride with L-a-leucine were investigated by a microcalorimeter.The enthalpies of solution of L-a-leucine in water and its zinc complex at infinite dilution and the enthalpy change of solid-liquid reaction wrer determined at 298.15K.The enthalpy change of soild phase reaction and the standard enthalpy of formation of zinc complex were claculated.On the basis of experimental and calculated results,three thermodynamic parameters(the activation enthalpy,the activation entropy and the activation free energy),the rate constant and three kinetic parameters(the activation energy,the preexponential constant and the reaction order) of the reaction,and the standard enthalpy of formation of Zn(Leu)^2 (aq) were obtained.The results showed that the title reaction took place easily at studied temperature.     

Synthesis of fluorescent carbon dots via microwave carbonization of citric acid in presence of tetraoctylammonium ion,and their application to cellular bioimaging

A jelly-like form of carbon dots (C-dots) was prepared by microwave-assisted synthesis from citric acid in the presence of tetraoctylammonium bromide. The effect of the concentration of tetraoctylammonium bromide was examined. The synthesized carbon dots were characterized by UV–vis, XRD, FTIR, fluorescence and HR-TEM. Fluorescence extends from 350 to 600 nm, and the corresponding excitation wavelengths range from 300 to 460 nm. Quantum yields are at around 0.11. A cytotoxicity study showed carbon dots to be cell permeable and biocompatible which renders them appropriate for imaging applications. The dots were used to image HeLa cell lines via the blue fluorescence of the dots.

C-dots were synthesized from citric acid by microwave heating in presence of varying concentrations of tetraoctylammonium bromide (TOAB) as a micellar template. The excellent optical properties of the nanoparticles make them well suitable for bio-imaging of HeLa cells.

     

发光反应型有机铵分子与CdSe纳米晶的组装

用巯基乙酸做稳定剂制备了水溶性CdSe纳米颗粒, 用十六烷基三甲基溴化铵(HTAB)、发光性(4-甲氧基均二苯乙烯基)二甲基乙基溴化铵 (MODAB)及末端含有双键的(4-甲基丙烯酰氧基均二苯乙烯基)二甲基乙基溴化铵(MSDAB)对该CdSe纳米颗粒进行了混合组装.通过改变三种有机分子的比例可以调控所得组装体的溶解性、聚合性及其发光性质.实验结果表明,当HTAB:MODAB:MSDAB=1:5.98～5.90:0.02～0.10(摩尔比)时,所得组装体具有较好的聚合性、溶解性和荧光性质.     

粒度对纳米体系化学反应热力学性质的影响

为了研究纳米粒子的粒度对化学反应热力学性质的影响规律, 以球形原子簇来模拟纳米金刚石颗粒, 用量子化学方法对粒度不同的金刚石纳米粒子与氧气反应的热力学性质进行了计算. 结果表明, 粒度对多相反应的标准摩尔反应焓△rH0m、标准摩尔反应熵△rS0m、标准摩尔反应吉布斯函数△rG0m和标准平衡常数K0均有明显的影响, 随着反应物粒径的减小, △rH0m、△rS0m和△rG0m均降低,而K0增大. 这些影响规律与实验结果基本一致.     

Thermochemistry on Coordination Behavior of Praseodymium Chloride Hydrate with Diethylammonium Diethyldithiocarbamate

The complex of praseodymium chloride lower hydrate with diethylammonium diethyldithiocarbamate (D-DDC) has been synthesized conveniently in absolute alcohol and dry N2 atmosphere. The title complex was identified as Et2NH2[Pr(S2CNEt2)4] by chemical and elemental analyses, the bonding characteristics of which were characterized by IR spectrum.The enthalpy of solution for praseodymium chloride hydrate and D-DDC in absolute alcohol at 298.15 K, and the enthalpy changes of liquid-phase reaction of formation for Et2NH2 [ Pr(S2CNEt2)4] at different temperatures were determined by miccocalorimetry. On the basis of experimental and calculated resuits, three thermodynamic parameters (the activation enthalpy, the activation entropy and the activation free energy),the rate constant and three kinetic parameters (the apparent activation energy, the pre-exponential constant and the reaction order) of liquid phase reaction of formation were obtained. The enthalpy change of the solid-phase title reaction at 298.15 K was calculated by a thermochemical cycle.     

硫酸锌与组氨酸固液反应的热动力学研究

用微热量计对硫酸锌与组氨酸在水中的固液反应进行了热动力学研究。通过实验和计算得出了该反应的热动力学参数（活化焓,活化熵及活化自由能）,速率常数和动力学参数（活化能,指前因子及反应级数）,并对温度改变对该反应的影响及配合物的合成条件进行了讨论。     

水合氯化镧与二乙氨基荒酸二乙铵配合行为的热化学

在干燥氮气气氛下，以无水乙醇为溶剂，制备了低水合氯化镧与二乙氨基荒酸 二乙铵（D-DDC）的配合物，确定其组成为Et_2NH_2[La(S_2CNEt_2)_4]。用微量热 法测定了298.15 K下水合氯化镧和D-DDC在无水乙醇中的溶解焓和不同温度下二乙 氨基荒酸镧液相生成反应的焓变。在实验和计算基础上，得到了液相生成反应的热 力学参数（活化焓、活化熵和活化自由能）、速率常数和动力学参数（表现活化能 、频率因子和反应基数），通过合理的热化学循环，求得了标题固相反应的焓变。     

Enthalpy and entropy of nanoparticle association from temperature-dependent cryo-TEM

Quantum dots form equilibrium structures in liquid dispersions, due to thermodynamic forces that are often hard to quantify. Analysis of these structures, visualized using cryogenic electron microscopy, yields their formation free energy. Here we show that the nanoparticle interaction free energy can be further separated into the enthalpic and entropic contributions, using the temperature dependence of the assembled structures. Monodisperse oleic acid-capped PbSe nanoparticles dispersed in decalin were used as a model system, and the temperature-dependent equilibrium structures were imaged by cryo-TEM, after quenching from different initial temperatures. The interaction enthalpy and entropy follow from van 't Hoff's exact equation for the temperature dependence of thermodynamic equilibria, now applied to associating nanoparticles. The enthalpic component gives the magnitude of the contact interaction, which is crucial information in understanding the energetics of the self-assembly of nanoparticles into ordered structures.     

Ruthenium(II) trisbipyridine functionalized gold nanorods. Morphological changes and excited-state interactions

Gold nanorods synthesized using cetyltrimethylammonium bromide and tetraoctylammonium bromide as stabilizers are functionalized with a thiol derivative of ruthenium(II) trisbipyridyl complex [(Ru(bpy)3(2+)-C5-SH] in dodecanethiol using a place-exchange reaction. The changes in the plasmon absorption bands and transmission electron micrographs indicate significant changes in the gold rod morphology during the place-exchange reaction. The (Ru(bpy)(3)2+-C5-SH in its excited state undergoes quick deactivation when bound to gold nanorods. More than 60% of the emission was quenched when [(Ru(bpy)3(2+)-C5-SH] was bound to gold nanorods. Emission decay analysis indicates that the energy transfer rate constant is greater than 10(10) s(-1).     

Pure surface plasmon resonance enhancement of the first hyperpolarizability of gold core-silver shell nanoparticles

We report the optical second harmonic (SH) response from gold core-silver shell nanoparticles supported at a liquid-liquid interface in the spectral region where the second harmonic generation (SHG) frequency is resonant with the surface plasmon (SP) resonance excitation of the nanoparticles. We compare these results with that obtained by classical linear optical absorption spectroscopy and show that the nonlinear optical response is dominated by the SP resonance enhancement with negligible contributions from the interband transitions. As a result, the SH spectrum exhibits two clear SP resonance bands attributed to the two SP resonances of the composite nanostructure formed by the gold core-silver shell nanoparticles. Absolute values of the hyperpolarizabilities are measured by hyper Rayleigh scattering (HRS) and compared that of pure gold nanoparticles. The hyperpolarizability measured at a harmonic energy of 3.0 eV, enhanced through excitation of the high energy SP resonance of the nanoparticle, increases with the silver content whereas the hyperpolarizability measured at a harmonic energy of 2.4 eV, enhanced through the excitation of the low energy SP resonance of the nanoparticle, decreases because of the shift of this resonance away from the harmonic frequency. The hyperpolarizability determined by HRS and the square root of the SHG intensities, scaling with the nanoparticle hyperpolarizability, have similar trends with respect to the silver content indicative of closely related adsorption properties yielding similar surface concentrations at the liquid-liquid interface.     

Use of nanoparticles for dye adsorption: Review

A very serious problem nowadays is the colored waters and especially the wastewaters from dyeing industries. Many techniques were already applied in order to treat those effluents, but one of the most simple, low-cost, effective, and successful is adsorption. A very promising class of materials used for this purpose is nanoparticles. This review summarizes some very important works of the last years regarding the use of nanoparticles as potential adsorbent materials for dye adsorption (mainly wastewaters). Widely-used models are described and analyzed for finding the best theoretical adsorption capacity (Langmuir, Freundlich, etc.), as well as some kinetic (pseudo-first, -second order, etc.), thermodynamic (free energy Gibbs, enthalpy, entropy), and desorption/regeneration studies are also discussed in details. Moreover, significant factors such as pH, agitation time, temperature, adsorbent dosage, and initial dye concentration are also reported extensively. Based on thermodynamic studies, meta-data analysis was carried out and commented.     

Synthesis of gold nanoparticles within a supramolecular gel-phase network

Gold nanoparticles with diameters of ca. 13 nm were synthesised by UV irradiation of a supramolecular organogel into which HAuCl4 and tetraoctylammonium bromide had been diffused-the gel network plays an essential role in nanoparticle stabilisation.