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Hollow γ-Al2O3 microspheres as highly “active” supports for Au nanoparticle catalysts in CO oxidation 空心γ-Al2O3微球作为CO氧化中金纳米颗粒催化剂的高“活性”载体
IF 2.2 4区 工程技术 Q2 Chemistry Pub Date : 2013-12-05 DOI: 10.1007/s13404-013-0128-3
Jie Wang, Zhen-Hao Hu, Yu-Xin Miao, Wen-Cui Li

Consisted of closely packed nanoflakes, γ-Al2O3 hollow microspheres with ca. 4–6?μm in diameter, and 500–700?nm in shell thickness have been hydrothermally synthesized through utilizing Al(NO3)3·9H2O as precursor, urea as precipitant agent and sulfate K2SO4, (NH4)2SO4, or KAl(SO4)2·12H2O as additive, followed by a calcination step. The samples were further characterized by thermogravimetric analysis, scanning electron microscope, x-ray powder diffraction, nitrogen adsorption, and in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) of adsorbed CO etc. The morphology of alumina products was strongly dependent on the presence of SO4 2?. Then via a deposition–precipitation method, 3?wt.% Au nanoparticles supported on γ-Al2O3 hollow microspheres exhibit excellent performance with a complete CO conversion at 0?°C (T 100%?=?0?°C) and 50?% conversion at ?25?°C (T 50%?=??25?°C). The good catalytic activity is associated with the special hollow microsphere structures assembled by nanoflakes of γ-Al2O3 support. The DRIFTS confirms the presence of Auδ+ and Au0 on the surface of γ-Al2O3 hollow microspheres. As a contrast, Au catalyst prepared using alumina support with undefined morphology shows low activity under the same catalytic test conditions (T 100%?=?190?°C, T 50%?=?80?°C).

由紧密排列的纳米片,γ-Al2O3空心微球组成,约为4-6 ?直径500-700 ?以Al(NO3)3·9H2O为前驱体,尿素为沉淀剂,硫酸K2SO4、(NH4)2SO4或KAl(SO4)2·12H2O为添加剂,经过煅烧步骤,水热合成了壳厚为nm的膜。采用热重分析、扫描电镜、x射线粉末衍射、氮气吸附、CO的原位漫反射红外傅立叶变换光谱(DRIFTS)等方法对样品进行了表征。氧化铝产品的形貌强烈依赖于so422的存在。然后通过沉积-沉淀法,得到3?γ-Al2O3空心微球负载的% Au纳米颗粒表现出优异的性能,在0?°C (T 100% = 0°C)和50°C%的转换?25?°c(50°c = 25°c)。良好的催化活性与γ-Al2O3纳米片组成的特殊空心微球结构有关。drift证实了γ-Al2O3空心微球表面存在Auδ+和Au0。相比之下,在相同的催化测试条件下,使用形态不明的氧化铝载体制备的Au催化剂表现出较低的活性(T 100%?=?190?)°c, 50°c = 80°c)。
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引用次数: 15
Facile one-pot synthesis of amoxicillin-coated gold nanoparticles and their antimicrobial activity 阿莫西林包覆金纳米颗粒的简易一锅合成及其抗菌活性研究
IF 2.2 4区 工程技术 Q2 Chemistry Pub Date : 2013-12-04 DOI: 10.1007/s13404-013-0129-2
Marco Demurtas, Carole C. Perry

Nanomaterials have been the object of intense study due to promising applications in a number of different disciplines. In particular, medicine and biology have seen the potential of these novel materials with their nanoscale properties for use in diverse areas such as imaging, sensing and drug vectorisation. Gold nanoparticles (GNPs) are considered a very useful platform to create a valid and efficient drug delivery/carrier system due to their facile and well-studied synthesis, easy surface functionalization and biocompatibility. In the present study, stable antibiotic conjugated GNPs were synthesised by a one-step reaction using a poorly water soluble antibiotic, amoxicillin. Amoxicillin, a member of the penicillin family, reduces the chloroauric acid to form nanoparticles and at the same time coats them to afford the functionalised nanomaterial. A range of techniques including UV–vis spectroscopy, dynamic light scattering (DLS), transmission electron microscopy (TEM) and thermogravimetric analysis (TGA) were used to ascertain the gold/drug molar ratio and the optimum temperature for synthesis of uniform monodisperse particles in the ca. 30–40?nm size range. Amoxicillin-conjugated gold showed an enhancement of antibacterial activity against Escherichia coli compared to the antibiotic alone.

纳米材料由于在许多不同学科中具有广阔的应用前景,一直是人们研究的热点。特别是,医学和生物学已经看到了这些具有纳米级特性的新材料在成像、传感和药物矢量化等不同领域的潜力。金纳米粒子(GNPs)被认为是创建有效和高效的药物传递/载体系统的非常有用的平台,因为它们易于合成和充分研究,易于表面功能化和生物相容性。在本研究中,稳定的抗生素偶联GNPs是通过一步反应合成的,使用一种水溶性差的抗生素,阿莫西林。阿莫西林是青霉素家族的一员,它将氯金酸还原成纳米颗粒,同时包裹在纳米颗粒上,以提供功能化的纳米材料。采用紫外可见光谱、动态光散射(DLS)、透射电子显微镜(TEM)和热重分析(TGA)等技术确定了金/药的摩尔比和在30 ~ 40℃范围内合成均匀单分散颗粒的最佳温度。Nm尺寸范围。阿莫西林偶联金对大肠杆菌的抗菌活性比单独使用阿莫西林增强。
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引用次数: 45
Shape-dependent electrocatalytic activity of free gold nanoparticles toward glucose oxidation 形状依赖的游离金纳米颗粒对葡萄糖氧化的电催化活性
IF 2.2 4区 工程技术 Q2 Chemistry Pub Date : 2013-11-26 DOI: 10.1007/s13404-013-0119-4
Seydou Hebié, K. Boniface Kokoh, Karine Servat, Teko W. Napporn

The synthesis of shape and size-controlled free gold nanoparticles (AuNPs) was achieved by wet chemical methods. The UV–vis spectroscopy measurements and transmission electron microscopy characterizations confirmed the fine distribution in size and shape of the AuNPs. The zeta potential measurements permitted the evaluation of the stability of the AuNPs suspension. For the first time, the shape dependence on the electrocatalytic activity of these NPs is thoroughly investigated. The underpotential deposition (UPD) of lead reveals that their crystallographic facets are affected by their shape and growth process. Moreover, the glucose oxidation reaction strongly depends on the shape of AuNPs. Indeed, the gold nanocuboids (GNCs) and the spherical gold nanoparticles (GNSs) are significantly more active than the gold nanorods (GNRs) followed by the polyhedrons (GNPs). The oxidation process occurs at low potential for GNCs whereas the current densities are slightly higher for GNSs electrodes. Most importantly, the control of the shape and structure of nanomaterials is of high technological interest because of the strong correlation between these parameters and their optical, electrical and electrocatalytic properties.

采用湿化学方法合成了形状和尺寸可控的游离金纳米颗粒(AuNPs)。紫外-可见光谱测量和透射电镜表征证实了aunp在大小和形状上的精细分布。zeta电位测量允许评估AuNPs悬浮液的稳定性。首次深入研究了NPs的形状对电催化活性的依赖性。铅的欠电位沉积(UPD)表明其晶体形貌受其形状和生长过程的影响。此外,葡萄糖氧化反应强烈依赖于aunp的形状。事实上,金纳米立方体(GNCs)和球形金纳米颗粒(GNSs)的活性明显高于金纳米棒(gnr),其次是多面体(GNPs)。GNCs电极的氧化过程发生在低电位下,而GNSs电极的电流密度略高。最重要的是,纳米材料的形状和结构的控制具有很高的技术价值,因为这些参数与其光学、电学和电催化性能之间存在很强的相关性。
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引用次数: 46
The colour of gold-silver-copper alloys 金银铜合金的颜色
IF 2.2 4区 工程技术 Q2 Chemistry Pub Date : 2013-11-20 DOI: 10.1007/BF03216549
Randall M. German, Matthew M. Guzowski, David C. Wright

The first colour diagram of the gold-silver-copper system was published over 30 years ago by Josef Leuser. This was based on visual, and therefore subjective, colour assessment. Renewed interest in the colour characteristics of gold alloys, as well as the development of improved instrumentation for their measurement, have stimulated recent research on the subject. This has now progressed to the point where objective, quantitative information on the relationship between alloy colour and composition is available.

30多年前,约瑟夫·洛伊泽(Josef Leuser)发表了金-银-铜体系的第一张彩色图。这是基于视觉的,因此是主观的色彩评估。对金合金颜色特征的重新关注,以及改进的测量仪器的发展,刺激了最近对这一主题的研究。现在已经发展到可以获得关于合金颜色和成分之间关系的客观、定量信息的地步。
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引用次数: 21
Gold in solar cells 太阳能电池中的黄金
IF 2.2 4区 工程技术 Q2 Chemistry Pub Date : 2013-11-20 DOI: 10.1007/BF03216545
Edward W. Williams

The cost of producing electricity from solar energy by means of solar cells is still high and limits the use of such devices to special situations. Gold has important roles not only in older types of cells but also in newer types which are being developed to achieve increased efficiencies.

利用太阳能电池从太阳能发电的成本仍然很高,限制了这种装置在特殊情况下的使用。金不仅在旧类型的细胞中发挥着重要作用,而且在正在开发以提高效率的新型细胞中也发挥着重要作用。
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引用次数: 7
The anodic behaviour of gold 金的阳极行为
IF 2.2 4区 工程技术 Q2 Chemistry Pub Date : 2013-11-20 DOI: 10.1007/BF03216548
Michael J. Nicol

The dissolution of gold in alkaline solutions containing cyanide ions is of great importance and its application in the MacArthur-Forrest process towards the end of the last century revolutionized the extraction of gold from its ores. Because of this, and its use in many industrial processes involving gold, it has been widely studied. What is known — and still unknown — about this reaction constitutes the main theme of this second instalment of a review of the anodic behaviour of gold.

金在含氰化物离子的碱性溶液中的溶解是非常重要的,它在上世纪末麦克阿瑟-福雷斯特法中的应用彻底改变了从矿石中提取金的方法。由于这一点,以及它在许多涉及黄金的工业过程中的应用,它得到了广泛的研究。关于这一反应的已知和未知,构成了本文第二期《金的阳极行为评论》的主题。
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引用次数: 86
Alloying colloidal silver nanoparticles with gold disproportionally controls antibacterial and toxic effects 将胶体银纳米颗粒与金合金不成比例地控制抗菌和毒性作用
IF 2.2 4区 工程技术 Q2 Chemistry Pub Date : 2013-11-17 DOI: 10.1007/s13404-013-0125-6
Sebastian Grade, Jörg Eberhard, Jurij Jakobi, Andreas Winkel, Meike Stiesch, Stephan Barcikowski

Elemental silver nanoparticles are an effective antibacterial substance and are found as additive in various medical applications. Gold nanoparticles are used due to their optical properties in microscopy and cancer therapy. These advantages might be combined within alloyed nanoparticles of both elements and thereby open new fields of interest in research and medical treatment. In this context, laser ablation of solid alloys in liquid gives access to colloidal silver–gold alloy nanoparticles with a homogeneous ultrastructure. Elemental and alloy silver–gold nanoparticles with increasing molar fractions of silver (50, 80, and 100?%) were produced and stabilized with citrate or albumin (BSA). Particles were embedded in agar at concentrations of 3–100?μg?cm?3 and tested on clinical relevant Staphylococcus aureus regarding their antibacterial properties. Cytotoxic effects were measured within the same particle concentration range using human gingival fibroblasts (HGFib). As expected, a reduced fraction of silver in the nanoalloys decreased the antibacterial effect on S. aureus according to the evaluated minimal inhibitory concentrations. However, this decrease turned out stronger than expected by its relative mass per particle, due to the electrochemical, disproportionally high effect of gold on the bioresponse to silver within silver–gold nanoalloy particles. BSA was able to stabilize all colloids and maintain antibacterial activity, whereas sodium citrate reduced antibacterial effects and cytotoxicity even at high nanoparticle concentrations. The alloying of silver with gold by laser ablation in liquid produced nanoparticles with both reduced antibacterial and cytotoxic properties in comparison to silver nanoparticles but still retains the application spectrum of both elements combined in one colloid. In particular, alloying with gold may render silver nanoparticles more biocompatible, and allows bioconjugation via established thiol chemistry.

元素银纳米颗粒是一种有效的抗菌物质,在各种医疗应用中被用作添加剂。金纳米颗粒由于其光学特性而被用于显微镜和癌症治疗。这些优点可以在两种元素的合金纳米颗粒中结合起来,从而在研究和医疗方面开辟新的兴趣领域。在这种情况下,激光烧蚀液体中的固体合金可以获得具有均匀超微结构的胶体银-金合金纳米颗粒。制备了增加银的摩尔分数(50%、80%和100%)的元素和合金银-金纳米颗粒,并用柠檬酸盐或白蛋白(BSA)稳定。将颗粒包埋在浓度为3-100 μg - cm的琼脂中。3、对临床相关金黄色葡萄球菌进行抗菌性能测试。使用人牙龈成纤维细胞(HGFib)在相同的颗粒浓度范围内测量细胞毒性效应。正如预期的那样,根据评估的最小抑制浓度,纳米合金中银含量的降低降低了对金黄色葡萄球菌的抗菌效果。然而,由于在银-金纳米合金颗粒中,金的电化学、不成比例的高影响对银的生物反应,这种减少结果比预期的要强烈。牛血清白蛋白能够稳定所有胶体并保持抗菌活性,而柠檬酸钠即使在高纳米颗粒浓度下也会降低抗菌效果和细胞毒性。在液体中通过激光烧蚀将银与金合金化,产生的纳米颗粒与银纳米颗粒相比,抗菌和细胞毒性降低,但仍然保留了两种元素结合在一个胶体中的应用光谱。特别是,与金合金化可以使银纳米粒子更具生物相容性,并允许通过已建立的硫醇化学进行生物偶联。
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引用次数: 61
In vivo uptake and cellular distribution of gold nanoshells in a preclinical model of xenografted human renal cancer 金纳米壳在异种移植人类肾癌临床前模型中的体内摄取和细胞分布
IF 2.2 4区 工程技术 Q2 Chemistry Pub Date : 2013-11-17 DOI: 10.1007/s13404-013-0115-8
Mariana Pannerec-Varna, Philippe Ratajczak, Guilhem Bousquet, Irmine Ferreira, Christophe Leboeuf, Raphaël Boisgard, Guillaume Gapihan, Jérôme Verine, Bruno Palpant, Emmanuel Bossy, Eric Doris, Joel Poupon, Emmanuel Fort, Anne Janin

Large-sized gold nanoparticles, promising imaging and therapeutic tools in human cancer, need long-term studies evaluating tissue bio-distribution in blood, organs and tumor. In a preclinical model of mouse xenografted with human renal cancer, we analysed the bio-distribution of a single dose (160?μg/kg) intravenously injected of poly-ethylene glycol (PEG)ylated gold nanoshells (~150?nm), in blood, normal and tumoral tissues. Using inductively coupled plasma mass spectrometry (ICP-MS), dark field and electron microscopy, we performed a sequential study of nanoshell uptake and distribution in the tumor. We also studied microscopically the organs most sensitive to efficient anticancer drugs to detect a possible long-term toxicity. Gold quantities significantly decreased in blood between early and late time points, whereas they significantly increased in liver and spleen. In addition, gold nanoshells did not induce any tissue damage, such as necrosis, inflammatory infiltrate or fibrosis in mouse liver, spleen, kidney or bone marrow after 6?months. In human renal cancer xenografts, ICP-MS showed an early decrease of gold, with 1-week stability before decrease at Day 15. Dark field microscopy showed gold particles within the vessel lumen 5 to 30?min after nanoshell injection, while 24?h later, gold particle distribution was mainly intracellular. Electron microscopy identified nanoshells within blood vessels at 5 and 30?min, within endothelial cells at 3 and 6?h and within cytoplasms of macrophages in the tumoral tissue after 24?h. In conclusion, no toxicity was observed in mice 6?months after administration of PEGylated gold nanoshells and the distribution kinetics progressed from intravascular flow at 30?min to intratumoral cells 24?h later.

大尺寸的金纳米颗粒是人类癌症中有前景的成像和治疗工具,需要长期研究来评估血液、器官和肿瘤中的组织生物分布。在人类肾癌异种移植小鼠临床前模型中,我们分析了单剂量(160 μg/kg)静脉注射聚乙二醇(PEG)基化金纳米壳(~150 μ nm)在血液、正常组织和肿瘤组织中的生物分布。利用电感耦合等离子体质谱(ICP-MS)、暗场和电子显微镜,我们对肿瘤中纳米壳的摄取和分布进行了顺序研究。我们还从显微镜下研究了对有效抗癌药物最敏感的器官,以检测可能的长期毒性。早、晚期血中金含量显著降低,肝、脾中金含量显著升高。此外,金纳米壳在6个月后未引起小鼠肝脏、脾脏、肾脏或骨髓的任何组织损伤,如坏死、炎症浸润或纤维化。在人类肾癌异种移植物中,ICP-MS显示早期金含量下降,在第15天下降之前保持1周的稳定性。暗场显微镜显示血管腔内有金颗粒5 ~ 30?注射纳米壳后Min,而24?H后,金颗粒主要分布在细胞内。电子显微镜在5和30?内皮细胞在3和6?H和24 H后肿瘤组织内巨噬细胞胞质内。结论:对小鼠6?在给予聚乙二醇化金纳米壳几个月后,分布动力学从30?最小到瘤内细胞24?h。
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引用次数: 16
Spinodal decomposition related to age-hardening and cuboidal structures in a dental low-carat gold alloy with relatively high Cu/Ag content ratio 一种高铜银比低克拉金合金的时效硬化和立方结构与Spinodal分解有关
IF 2.2 4区 工程技术 Q2 Chemistry Pub Date : 2013-11-10 DOI: 10.1007/s13404-013-0116-7
Ji-In Jeong, Hyung-Il Kim, Gwang-Young Lee, Yong Hoon Kwon, Hyo-Joung Seol

A dental Au–Ag–Cu–Pd alloy with a relatively low Au content and a high Cu/Ag content ratio was examined to determine the correlation between the microstructural changes by the spinodal decomposition and age-hardening behaviour using a hardness test, X-ray diffraction study, field emission scanning electron microscopy and energy-dispersive X-ray spectrometry. Separation of the parent α0 phase occurred by spinodal decomposition during aging at 350?°C after the solution treatment at 750?°C, and not by a nucleation and growth mechanism, resulting in the formation of the stable Ag-rich α1 and AuCu I phases through a metastable state. Hardening resulted from the coherency lattice strain which occurred along the a-axis between the metastable Ag-rich α1′ and AuCu I′ phases. In addition, lattice distortion occurred along the c-axis between the stable Ag-rich α1 and AuCu I phases due to the tetragonality of the AuCu I ordered phase. The transformation of the stable Ag-rich α1 and AuCu I phases from the metastable state introduced the formation of the fine and uniform cuboidal structures, which compensated for the increased gap in the lattice parameters through the phase transformation. Replacement of the fine cuboidal structures with the coarser lamellar structures occurred without a phase transformation, and resulted in softening by reducing the interfaces between the stable Ag-rich α1 and AuCu I phases.

采用硬度测试、x射线衍射研究、场发射扫描电镜和能量色散x射线能谱分析等方法,研究了一种相对低Au含量和高Cu/Ag含量比的牙科Au - Ag - Cu - pd合金的spinodal分解与时效硬化行为之间的关系。在350℃时效过程中,母相α0发生了分离。750℃固溶处理后°C,而不是通过一个成核和生长机制,导致通过亚稳态形成稳定的富银α1和AuCu I相。在亚稳富银α1′相和AuCu I′相之间沿a轴发生的相干点阵应变导致硬化。此外,由于AuCu I有序相的四方性,在稳定的富银α1相和AuCu I相之间沿c轴发生了晶格畸变。稳定的富银α1和AuCu I相从亚稳态转变为精细均匀的立方结构,通过相变弥补了晶格参数间隙的增加。在未发生相变的情况下,细小的立方结构被较粗的片层结构所取代,并通过减少稳定的富银α1与AuCu I相之间的界面而导致软化。
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引用次数: 2
One-pot organometallic synthesis of well-controlled gold nanoparticles by gas reduction of Au(I) precursor: a spectroscopic NMR study 用Au(I)前驱体气体还原法制备可控金纳米颗粒的一锅有机金属合成:核磁共振光谱研究
IF 2.2 4区 工程技术 Q2 Chemistry Pub Date : 2013-10-30 DOI: 10.1007/s13404-013-0117-6
Pierre-Jean Debouttière, Yannick Coppel, Philippe Behra, Bruno Chaudret, Katia Fajerwerg

A stable colloidal solution of gold nanoparticles (AuNPs) has been prepared in tetrahydrofuran by gas reduction of AuCl(tetrahydrothiophene) and alkylamines (1-octylamine,1-dodecylamine, and 1-hexadecylamine) as stabilizing agents. Carbon monoxide is a better reducing agent than hydrogen. The important parameters for control of the synthesis of AuNPs are the temperature, the molar ratio of ligand/metal, and the structure of the stabilizing agent. A high concentration of long alkyl chains (10?eq.) favours the control of the growth of AuNPs of defined size and shape with a diameter of 4.7?nm and a narrow size distribution. For the first time, liquid-state combined with solid-state NMR spectroscopies were used in order to determine the role of the long chain alkylamines in the synthesis of AuNPs in CO atmosphere. This combination enables the understanding of the complex chemistry of the surface of AuNPs involved in the stabilization of the AuNPs. Indeed, carbamide species were formed during the synthesis. They were strongly coordinated to the surface of AuNPs and exchange phenomena of the alkylamines present in solution occurred, too.

在四氢呋喃中,以四氢噻吩(AuCl)和烷基胺(1-辛基胺、1-十二烷基胺和1-十六烷基胺)为稳定剂,气体还原法制备了稳定的纳米金胶体溶液。一氧化碳是比氢更好的还原剂。控制AuNPs合成的重要参数是温度、配体/金属的摩尔比和稳定剂的结构。高浓度的长烷基链(10?eq.)有利于控制直径为4.7?Nm,尺寸分布窄。为了确定长链烷基胺在CO气氛下合成AuNPs过程中的作用,首次采用液相和固态相结合的核磁共振光谱技术。这种结合使人们能够理解AuNPs表面的复杂化学成分,这些化学成分参与了AuNPs的稳定。事实上,在合成过程中形成了尿素物种。它们与aunp表面有很强的配位作用,并发生了溶液中烷基胺的交换现象。
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引用次数: 7
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Gold Bulletin
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