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1.
A simple and green approach for the synthesis of well‐stabilized gold nanoparticles (AuNPs) using gum Acacia (GA) is presented here. The gum acacia acts as the reductant and stabilizer. The synthesized gold nanoparticles were characterized by using ultraviolet visible (UV‐Vis), fourier transform infrared spectroscopy (FTIR), x‐ray diffraction (XRD), dynamic light scattering (DLS) and transmission electron microscopy (TEM) techniques. The UV‐Vis study revealed a distinct surface plasmon resonance at 520 – 550 nm, due to the formation of AuNPs. FTIR analysis showed the evidence that –OH groups present in the gum matrix were responsible in reducing the tetra chloroauric acid into AuNPs. XRD studies confirmed the formation of well crystalline nanoparticles with fcc structure and the particle size ranges from 4 – 29 nm, as indicated by TEM analysis. The synthesized gold nanoparticles exhibited homogeneous catalytic activity. The two model reactions studied were the reduction of p‐nitro phenol and the reduction of hexacyanoferrate (III) by borohydride ions. Both the reactions were monitored by UV‐Vis spectroscopy. The kinetic investigations were carried out for the AuNPs‐catalyzed reactions at different temperatures and different amount of catalyst.  相似文献   

2.
The catalytic ability of gold nanoparticles (AuNPs) toward the formation of H2 in the electrocatalyzed Hydrogen Evolution Reaction (HER) is thoroughly studied, using screen-printed carbon electrodes (SPCEs) as electrotransducers. The AuNPs on the surface of the SPCE, provide free electroactive sites to the protons present in the acidic medium that are catalytically reduced to hydrogen by applying an adequate potential, with a resulting increment in the reaction rate of the HER measured here by the generated catalytic current. This catalytic current is related with the concentration of AuNPs in the sample and allows their quantification. Finally, this electrocatalytic method is applied for the first time, in the detection of AuNPs as labels in a magnetoimmunosandwich assay using SPCEs as electrotransducers, allowing the determination of human IgG at levels of 1 ng/mL.  相似文献   

3.
自Haruta与Hutchings于上世纪八十年代末发现金纳米催化剂优异的反应活性以来,科研人员对金催化的应用领域进行了广泛而深入地研究.对金催化科学和应用领域的研究一直在进行.大量的研究表明,金催化剂在各种选择性氧化反应中具有优异的催化性能(高活性和高选择性).然而,在催化加氢反应中,尽管金催化剂相比于铂族金属显示出优越的选择性,但是由于金催化剂选择性加氢反应的活性较差,使其在选择性催化加氢反应中的应用受到了极大的限制.研究表明,金催化剂较弱的活化氢气能力是其催化加氢反应活性低的主要原因.研究发现,氢气活化的活性中心可能是界面、负价金、低配位的金原子等.金催化剂具有明显的载体效应,金属-载体之间的相互作用能够显著地改变金催化剂的催化性能.Tauster等研究发现,铂族金属与还原性载体之间存在强相互作用,能够引发载体包覆金属表面,并且使得电子从载体向金属迁移,导致金属带负电.受金属-载体强相互作用(SMSI)效应的启发,本文探究了Au/TiO2催化剂中SMSI对金催化剂加氢性能的影响.在H2或O2气氛下高温焙烧Au/TiO2,获得一系列金催化剂(Au/TiO2-TA,T为焙烧温度(oC):300、400、500和600;A为气氛:H2或O2).对比在3-硝基苯乙烯(3-NS)选择性加氢反应中的活性发现,Au/TiO2-500H的TOF值是Au/TiO2-500O的3.3倍;动力学测试表明,Au/TiO2-500H和Au/TiO2-500O的反应表观活化能分别为79.5和105.1 kJ/mol.这表明两类催化剂催化活性中心的结构存在差异.X射线光电子能谱测试结果表明,Au/TiO2-H样品中Au带部分负电,而Au/TiO2-O中Au显示为金属态.HAADF-STEM和EELS显示,Au/TiO2-H中Au NPs的表面有TiOx物种,增加了Au-TiO2的界面.EPR结果表明,Au/TiO2-H中存在表面Ti3+物种,而Au/TiO2-O样品中则没有.为确认加氢反应的活性中心到底是界面还是负价金物种,本文探究了不同温度下氢气处理的Au/TiO2的结构与性能的关系,发现Au/TiO2-300H/400H/500H催化剂都显示出较好的催化3-NS加氢活性,而Au/TiO2-600H虽然具有更多的负价金物种,但是3-NS选择性加氢反应的活性反而降低,因此,负价金不是活性中心.这是因为不同温度处理的Au/TiO2-H样品中,SMSI的强弱不同,在300、400、500 oC下,SMSI能够增加Au-TiO2的界面长度,从而增强了3-NS加氢反应的活性;而温度达到600 oC,SMSI效应太强,Au NPs被包覆更密实,导致Au/TiO2-600H的3-NS选择性加氢反应的活性下降.密度泛函理论计算表明,Au/TiO2-H样品具有更低的H2解离活化能以及氢转移活化能.氢氘交换反应也进一步验证了SMSI有利于H2的活化.  相似文献   

4.
Gold nanoparticles of different morphologies have been synthesized on a silica‐based organic‐inorganic hybrid material for catalytic applications. The gold nanoparticles formations proceed through in situ chemical reduction of the AuCl4? anions previously adsorbed on 3‐(1‐imidazolyl)propyl‐silsesquioxane, which plays the role of substrate and stabilizer. Two distinct reducing agents, sodium citrate and sodium borohydride, were employed to generate gold nanoparticles of different sizes. UV‐vis diffuse reflectance as well as transmission electron microscopy were employed to evaluate the particle’s morphology. Modified carbon paste electrodes were prepared from these materials and their electrochemical behavior investigated using potassium ferrocyanide and 4‐nitrophenol as redox model compounds. Both AuNPs‐modified electrodes decreased the overpotential of 4‐nitrophenol reduction by around 90 mV compared to the unmodified electrode as evidenced by cyclic voltammetry experiment. However, the smaller diameter particles (borohydride‐reduced) produced more significant catalytic effect as a consequence of their large surface area. Regarding the sensing parameters, the sensitivity is higher for the borohydride‐reduced AuNPs while the values of limit of detection are of the same order of magnitude. Thus, the detection limit and sensitivity are 70.0±0.6 nM and 187 µA/mM for the citrate‐reduced AuNPs; and 75.0±2.2 nM and 238 µA/mM for the borohydride‐reduced AuNPs.  相似文献   

5.
Nickel nanoparticles supported on silica were prepared by hydrazine reduction in aqueous medium. The obtained solids were characterized by X-ray diffraction (XRD), Transmission Electronic Microscopy (TEM), Electron Diffraction (ED), hydrogen chemisorption, and Temperature Programmed Desorption of hydrogen (H2-TPD). The catalytic properties were evaluated for benzene hydrogenation in the temperature range 75–230 °C. XRD patterns reveal presence of the metallic nickel particles with fcc structure. Metal dispersion and hydrogen storage increase with decreasing metal particle size. The H2-TPD profiles exhibit two domains, one due to desorption of hydrogen from Ni metal and another due to spillover from metal to the support. The catalytic activity strongly depends on the metal loading. It increases with decreasing metal loading. This is attributed to metal surface area, which also increases with decreasing metal loading. Kinetic studies of benzene hydrogenation on the Ni catalysts showed that the benzene partial order is around −2. This significant negative value is ascribed to a strong adsorption of benzene on the catalyst surface.  相似文献   

6.
Metal–support cooperative catalysts have been developed for sustainable and environmentally benign molecular transformations. The active metal centers and supports in these catalysts could cooperatively activate substrates, resulting in high catalytic performance for liquid‐phase reactions under mild conditions. These catalysts involved hydrotalcite‐supported gold and silver nanoparticles with high catalytic activity for organic reactions such as aerobic oxidation, oxidative carbonylation, and chemoselective reduction of epoxides to alkenes and nitrostyrenes to aminostyrenes using alcohols and CO/H2O as reducing reagents. This high catalytic performance was due to cooperative catalysis between the metal nanoparticles and basic sites of the hydrotalcite support. To increase the metal–support cooperative effect, core–shell nanostructured catalysts consisting of gold or silver nanoparticles in the core and ceria supports in the shell were designed. These core–shell nanocomposite catalysts were effective for the chemoselective hydrogenation of nitrostyrenes to aminostyrenes, unsaturated aldehydes to allyl alcohols, and alkynes to alkenes using H2 as a clean reductant. In addition, these solid catalysts could be recovered easily from the reaction mixture by simple filtration, and were reusable with high catalytic activity.  相似文献   

7.
A facile method of confining gold nanoparticles (AuNPs) in silica nanochannels aligned perpendicularly to an underlying electrode surface is reported. The nanochannel surface carrying a layer of (3‐aminopropyl)triethoxy silane (APTS) displays a strong electrostatic interaction with AuCl4?, eventually resulting in the confinement of AuNPs inside the nanochannels after chemical reduction. As‐prepared AuNPs in APTS‐modified mesoporous silica film (APTS‐MSF) are highly dispersed with a narrow size distribution. Furthermore, these AuNPs are free of protecting ligands and exhibit a good electrochemical catalytic activity toward the oxidation of ascorbic acid.  相似文献   

8.
A series of organo‐soluble spherical gold nanoparticles (AuNPs) were prepared through the reduction of HAuCl4 by NaBH4 in the presence of amphiphilic hyperbranched polymers that had a hydrophilic hyperbranched polyethylenimine core and a hydrophobic shell formed by many palmitamide (C16) chains. For comparison, the corresponding linear polymeric analog derived from linear polyethylenimine was also used to prepare the organo‐soluble AuNPs. The obtained AuNPs were characterized by transmission electron microscopy. It was found that higher feed ratio of polymer to HAuCl4 and utilization of polymers with higher C16 density usually resulted in smaller AuNPs with relatively lower polydispersity. Except of the polymer having the pronounced low molecular weight, the molecular weight and the morphology of the amphiphilic polymers had almost no obvious effect on the size of the formed AuNPs. These organo‐soluble AuNPs could be used as efficient catalysts for the biphasic catalytic reduction of 4‐nitrophenol by NaBH4. Their apparent rate coefficients had correlation with the molecular weight of the used amphiphilic polymers, but were less relevant to the morphology of these polymers. These organo‐soluble AuNPs could be conveniently recovered and reused many times. The morphology of the capping polymers had obvious effect on the lifetime of the AuNPs catalysts in the catalytic reduction of 4‐nitrophenol. Except of the pronounced low molecular weight hyperbranched polymer, the other hyperbranched ones with relatively high molecular weight rendered the AuNPs to have bigger turnover number values than their linear analog. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011  相似文献   

9.
Resorcinarene‐functionalized gold nanoparticles (AuNPs) were prepared conveniently in aqueous solution in the presence of amphiphilic tetramethoxyresorcinarene tetraaminoamide. The obtained AuNPs were characterized and analyzed by UV‐vis, FT‐IR, XRD and TEM, respectively. The results showed that the size of AuNPs and the standard deviations were all decreasing with the increase of resorcinarene concentration. In addition, the catalytic activity of the obtained AuNPs in the reduction of aromatic nitro compounds was also investigated. In aqueous solution the reaction follows a first order kinetics and the size of AuNPs has influence on the rate of reduction.  相似文献   

10.
Copper(II) oxide nanoparticles supported on magnesia have been prepared from Cu(II) supported on magnesia by hydrogen reduction at 400 °C followed by storage under ambient conditions. X-ray photoelectron spectroscopy of the material clearly shows that immediately after the reduction copper(0)-metal nanoparticles are present on the magnesia support, but they undergo fast oxidation to copper oxide upon contact with the ambient for a short time. TEM images show that the catalytically active CuO/MgO material is formed of well-dispersed copper oxide nanoparticles supported on fibrous MgO. CuO/MgO exhibits a remarkable catalytic activity for the monoborylation of aromatic, aliphatic, terminal, and internal alkynes, the products being formed with high regio- (borylation at the less substituted carbon) and stereoselectivity (trans-configured). CuO/MgO exhibits complete chemoselectivity towards the monoborylation of alkynes in the presence of alkenes. Other metal nanoparticles such as gold or palladium are inactive towards borylation, but undergo undesirable oligomerization or partial hydrogenation of the C≡C triple bond. In contrast, platinum, either supported on magnesia or on nanoparticulate ceria, efficiently promotes the stereoselective diborylation of alkynes to yield a cis-configured diboronate alkene. By using platinum as the catalyst we have developed a tandem diborylation/hydrogenation reaction that gives vic-diboronated alkanes from alkynes in one pot.  相似文献   

11.
通过不对称修饰法制备了一种碗状双亲型的ZSM-5分子筛, 其拥有一个非极性的外表面和一个可修饰的极性内表面; 进一步利用经典的氨基接枝-原位还原过程, 选择性地在其内表面生长金纳米粒子. 通过X射线粉末衍射、 扫描电子显微镜、 透射电子显微镜、 红外光谱和X射线光电子能谱对材料进行了表征, 并考察了其催化硝基苯加氢制苯胺反应的性能. 在非常温和(室温、 水作溶剂及无需氮气保护)以及更低反应物浓度(0.03 mol/L, 低于室温下硝基苯在水中的溶解度)条件下, 该催化剂展现出与其它使用有机溶剂的催化剂相当的催化活性和选择性, 而且其催化性能明显高于其它以水为溶剂的催化剂, 这表明载体的双亲型结构是提升催化性能的主要原因. 该催化剂循环使用6次后, 其催化活性和选择性仍保持在相同等级.  相似文献   

12.
An enzyme-free, ultrasensitive electrochemical detection of kanamycin residue was achieved based on mimetic peroxidase activity of gold nanoparticles (AuNPs) and target-induced replacement of the aptamer. AuNPs which were synthesized using tyrosine as a reducing and capping agent, exhibited mimetic peroxidase activity. In the presence of kanamycin-specific aptamer, however, the single-stranded DNA (ssDNA) adsorbed on the surface of AuNPs via the interaction between the bases of ssDNA and AuNPs, and therefore blocked the catalytic site of AuNPs, and inhibited their peroxidase activity. While in the presence of target kanamycin, it bound with the adsorbed aptamer on AuNPs with high affinity, exposed the surface of AuNPs and recovered the peroxidase activity. Then AuNPs catalyzed the reaction between H2O2 and reduced thionine to produce oxidized thionine. The latter exhibited a distinct reduction peak on gold electrode in differential pulse voltammetry (DPV), and could be utilized to quantify the concentration of kanamycin. Under the optimized conditions, the proposed electrochemical assay showed an extremely high sensitivity towards kanamycin, with a linear relationship between the peak current and the concentration of kanamycin in the range of 0.1–60 nM, and a detection limit of 0.06 nM. Moreover, the established approach was successfully applied in the detection of kanamycin in honey samples. Therefore, the proposed electrochemical assay has great potential in the fields of food quality control and environmental monitoring.  相似文献   

13.
Ultrafine monodisperse gold nanoparticles (AuNPs) were synthesized by an elegant sputtering of gold onto 1- n-butyl-3-methylimidazolium hexafluorophosphate (BMI-PF(6)) ionic liquid. It was found that the BMI-PF(6) supramolecular aggregates were loosely coordinated to the gold nanoparticles and were replaceable with thiol molecules. The self-assembly of BMI-PF(6)-stabilized AuNPs onto a (3-mercaptopropyl)trimethoxysilane (MPS)-functionalized silicon surface in 2D arrays, followed by dodecanethiol (DDT) treatment, have been demonstrated using X-ray photoelectron spectroscopy, field emission scanning electron microscopy, and contact angle measurements. DDT treatment of tethered AuNPs revealed two types of interactions between AuNPs and the MPS-functionalized surface: (a) AuNPs anchor through Au-S chemisorption linkage resulting in strong immobilization and (b) some of the AuNPs are supported by physisorption, driven by BMI-PF(6). The attachment of these particles remains unchanged with sonication. The replacement of BMI-PF(6) aggregates from physisorbed AuNPs with DDT molecules advances the dilution of their interaction with the MPS-functionalized surface, and they subsequently detach from the silicon surface. The present finding is promising for the immobilization of ionic liquid-stabilized nanoparticles, which is very desirable for electronic and catalytic device fabrication. Additionally, these environmentally friendly AuNPs are expected to replace conventional citrate-stabilized AuNPs.  相似文献   

14.
The present research confirms the capacity of aqueous extract of Boswellia serrata grown under in vitro condition for the green synthesis of gold nanoparticles (AuNPs). Also, we showed the cytotoxicity, antioxidant, and anti-acute myeloid leukemia properties of AuNPs compared to mitoxantrone in a leukemic mouse model. The synthesized AuNPs were characterized using several techniques including XRD, TEM, FE-SEM, UV–Vis, and FT-IR. From the XRD pattern, four distinct diffraction peaks at 38.2°, 44.2°, 64.7° and 77.4° are indexed as (111), (200), (220) and (311) planes of FCC metallic gold. TEM and FE-SEM images revealed an average diameters of 15–30 nm for the nanoparticles. FT-IR findings offered antioxidant compounds in the nanoparticles were the sources of reducing power, reducing gold ions to AuNPs. UV–Vis revealed an absorption band at 536 nm that is related to the surface plasmon resonance of AuNPs. In vivo design, induction of acute myeloid leukemia was done by DMBA in 75 mice. Then, the mice were randomly divided into six subgroups, including untreated, control, HAuCl4, B. serrata, AuNPs, and mitoxantrone. AuNPs (In the dose of 1 mg/kg body weight) similar to mitoxantrone, significantly (p ≤ 0.05) increased the platelet, lymphocyte, and RBC parameters and the anti-inflammatory cytokines (IL4, IL5, IL10, IL13, and IFNα) and reduced the weights and volumes of liver and spleen and their sub-compartment, the total WBC, blast, monocyte, neutrophil, eosinophil, and basophil counts, and the pro-inflammatory cytokines (IL1, IL6, IL12, IL18, IFNY, and TNFα) as compared to the untreated mice. By quantitative Real-Time PCR, S1PR1 and S1PR5 mRNA expression in lymphocytes were significantly (p ≤ 0.05) increased by treating the leukemic mice with the AuNPs and mitoxantrone. In vitro design, AuNPs similar to mitoxantrone had low cell viability dose-dependently against Human HL-60/vcr, 32D-FLT3-ITD, and Murine C1498 cell lines without any cytotoxicity on HUVEC cell line. Besides, the DPPH assay showed similar antioxidant potentials for AuNPs and mitoxantrone. In conclusion, the results of this research indicated the excellent capacity of synthesized gold nanoparticles using B. serrata leaf aqueous extract in the treatment of acute myeloid leukemia in leukemic mice.  相似文献   

15.
We report an ecofriendly synthetic approach for the fabrication of biogenic gold nanoparticles (AuNPs) using electron-rich sea cucumber extract as a bio-reductant and stabilizing agent in reducing gold cations into AuNPs at the optimal conditions. The produced AuNPs are spherical in shape with an average particle size of 11 ± 1.5 nm in transmission electron microscopy (TEM) and exhibited a crystal structure of face-centered cubic in X-ray diffraction (XRD) analyses. Our results indicated that bioinspired AuNPs demonstrate superior catalytic activity in the safe and facile one-pot synthesis of polyhydroquinoline derivatives under solvent-free reaction conditions. This green route encompasses multiple benefits including highly recyclable bioinspired catalyst (5 cycles), short reaction times, convenient workout, high to excellent product yields (82%–97%), and nonhazardous conditions.  相似文献   

16.
A rhodium terpyridine complex catalyzed transfer hydrogenation of nitroarenes to anilines with i-PrOH as hydrogen source and water as solvent has been developed. The catalytic system can work at a substrate/catalyst (S/C) ratio of 2000, with a turnover frequency (TOF) up to 3360 h−1, which represents one of the most active catalytic transfer hydrogenation systems for nitroarene reduction. The catalytic system is operationally simple and the protocol could be scaled up to 20 gram scale. The water-soluble catalyst bearing a carboxyl group could be recycled 15 times without significant loss of activity.  相似文献   

17.
This paper introduces strategies for enhancement of a surface plasmon resonance (SPR) signal by adopting colloidal gold nanoparticles (AuNPs) and a SiO2 layer on a gold surface. AuNPs on SiO2 on a gold surface were compared with an unmodified gold surface and a SiO2 layer on a gold surface with no AuNPs attached. The modified surfaces showed significant changes in SPR signal when biomolecules were attached to the surface as compared with an unmodified gold surface. The detection limit of AuNPs immobilized on a SPR chip was 0.1 ng mL−1 for the prostate-specific antigen (PSA), a cancer marker, as measured with a spectrophotometer. Considering that the conventional ELISA method can detect ∼10 ng mL−1 of PSA, the strategy described here is much more sensitive (∼100 fold). The enhanced shift of the absorption curve resulted from the coupling of the surface and particle plasmons by the SiO2 layer and the AuNPs on the gold surface.  相似文献   

18.
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。  相似文献   

19.
According to chemotherapeutic properties of medicinal plants, pharmacologists have always tried to synthesize and formulate the new chemotherapeutic supplements or drugs of metallic nanoparticles using plants. In this study, Camellia sinensis leaf aqueous extract-based gold nanoparticles (AuNPs) are reported for the first time to exert a dietary therapeutic potential compared to Daunorubicin in an animal model of acute myeloid leukemia. The synthesized AuNPs were characterized using different techniques including UV-Vis., FT-IR spectroscopy, TEM, EDS, FE-SEM, and XRD. DPPH free radical scavenging test was done to evaluate the antioxidant potentials of HAuCl4, C. sinensis, AuNPs, and daunorubicin. For the analyzing of cytotoxicity effects of HAuCl4, C. sinensis, AuNPs, and daunorubicin, MTT assay was used on HUVEC, Human HL-60/vcr, 32D-FLT3-ITD, and Murine C1498 cell lines. In vivo design, induction of acute myeloid leukemia was done by 7,12-Dimethylbenz[a]anthracene (DMBA) in 75 mice. Then, the animals were randomly divided into six subgroups, including control, untreated, HAuCl4, C. sinensis, AuNPs, and daunorubicin. FTIR findings suggested antioxidant compounds in the nanoparticles were the sources of reducing power, reducing gold ions to AuNPs. SEM and TEM images exhibited a uniform spherical morphology and diameters of ~20-30 nm for the nanoparticles. DPPH test revealed similar antioxidant potentials for daunorubicin and AuNPs. These nanoparticles similar to daunorubicin had low cell viability dose-dependently against Human HL-60/vcr, 32D-FLT3-ITD, and Murine C1498 cell lines without any cytotoxicity on HUVEC cell line. AuNPs similar to daunorubicin, significantly (p≤0.05) increased the anti-inflammatory cytokines and the lymphocyte, platelet, and RBC parameters and decreased the weight and volume of liver and spleen, the pro-inflammatory cytokines, and the total WBC, blast, neutrophil, monocyte, eosinophil, and basophil counts, as compared to the untreated mice. According to the above results, it appears that AuNPs can be used as a chemotherapeutic drug for the treatment of acute myeloid leukemia in the clinical trial.  相似文献   

20.
利用柠檬酸钠还原法制备了13nm胶体金,透射电子显微镜表征其具有良好的单分散性,通过它与牛血清蛋白(BSA)作用的紫外-可见光谱表明其对蛋白具有良好的生物亲和性。以羊抗人免疫球蛋白G(IgG)修饰的金纳米粒子作探针,基于金纳米粒子免疫聚集导致其消光系数和分散度的变化建立了人IgG的比率光度分析方法。结果表明所制备的纳米金标记探针在人IgG浓度100ng/mL~100μg/mL范围内有良好的线性响应,加标法测定结果表明该法具有良好的回收率和精密度。以细胞色素C(CytoC)和辣根过氧化物酶(HRP)两种蛋白质作对照实验,发现所制备的金纳米探针对IgG具有高度的特异性。  相似文献   

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