Preparation of Monodispersed Copper Nanoparticles by an Environmentally Friendly Chemical Reduction

In this paper, highly dispersive nanosized copper particles with a mean particle size of less than 6 nm are prepared by an environmentally friendly chemical reduction method. Non-toxic L-ascorbic acid acts as both reducing agent and antioxidant in ethylene glycol in the absence of any other capping agent. Transmission electron microscopy （TEM） is used to characterize the size and morphology of Cu nanoparticles. The results of UV-Vis spectroscopy （UV-Vis）, energy dispersive spectroscopy （EDS） and high resolution TEM （HRTEM） illustrate that the resultant product is pure Cu nanocrystals. The size of Cu nanoparticles is remarkably impacted by the order of reagent addition, and the investigation reveals the reaction procedure of Cu^2＋ ions and L-ascorbic acid.     

Shape-controlled synthesis of highly monodisperse and small size gold nanoparticles

We describe here that fine control of nanoparticle shape and size can be achieved by systematic varia-tion of experimental parameters in the seeded growth procedure in aqueous solution. Cubic and spherical gold nanoparticles are obtained respectively. In particularly, the Au cubes are highly mono-disperse in 33±2 nm diameter. The experimental methods involve the preparation of Au seed particles and the subsequent addition of an appropriate quantity of Au seed solution to the aqueous growth solutions containing desired quantities of CTAB and ascorbic acid (AA). Here, AA is a weak reducing agent and CTAB is not only a stable agent for nanoparticles but also an inductive agent for leading increase in the face of nanoparticle. Ultraviolet visible spectroscopy (UV-vis), X-ray diffraction (XRD), transmission electron microscopy (TEM) are used to characterize the nanoparticles. The results show that the different size gold nanoparticles displayed high size homogenous distribution and formed mono-membrane at the air/solid interface.     

Immobilized silver nanoparticles on silica gel as an efficient catalyst in nitroarene reduction

<正>Nanoparticles have properties that can be fine-tuned by their size as well as shape.Hence,there is significant current interest in preparing nano-materials of small size dispersity and to arrange them in close-packed aggregates.This letter describes a way of synthesising silver nanoparticles and their protection to aggregate by silica gel.The combination of catalytic quantities of immobilized silver nanoparticles with reductive ability of NaBH_4 efficiently reduces aromatic nitroarenes to the corresponding amines in aqueous medium.Noteworthy is that highly chemoselective reactions were achieved in the presence of other functional groups such as halogen and carboxylic acid groups.The silver particles immobilized on silica gel are stable in the presence of oxygen for several months.     

三维有序大孔SiO2中的纳米银

A multi-step process was used for preparation of three-dimensionally ordered macroporous (3DOM) SiO2, in which fully accessible Ag nanoparticles are incorporated. The method involves the processes of assembly of polystyrene colloidal crystal, preparation of 3DOM SiO2, and incorporation of Ag nanoparticles within 3DOM SiO2 through in situ Tollens‘ reaction. XRD, SEM and EDXS determination show that the Ag particles deposited on the macroporous walls in nano dimension. The results indicate that lower concentration of silver ammoniate and for-maldehyde in the solution is favorable for forming a very narrow size distribution and uniform shape of nanoparticles. However, the higher the concentration of the solution and the more the loading times, the larger the possibility to form un-uniform particles. Ag nanoparticles can be sintered into larger and spheral particles by calcination at 600℃, but can resist sintering owing to their high dispersivity when loading amount is small. The study provided a simple approach to tailor Ag/3DOM SiO2 composite materials with desired morphology and size of Ag particles within the macropores.     

Norvancomycin-capped silver nanoparticles: Synthesis and antibacterial activities against E. coli

The synthesis of norvancomycin (NVan)-capped silver nanoparticles (Ag@NVan) and their notable in vitro antibacterial activities against E. coli, a Gram-negative bacterial strain (GNB), are reported here. Mercaptoacetic acid-stabilized spherical silver nanoparticles with a diameter of 16±4 nm are prepared by a simple chemical reaction. The formation process of the silver nanoparticles is investigated by UV-visible (UV-vis) spectroscopy and transmission electron microscopy (TEM). NVan is then grafted to the terminal carboxyl of the mercaptoacetic acid in the presence of N-(3-Dimethylaminopropyl)-N'-ethylcarbodiimide hydrochloride (EDAC). The TEM images of single bacteria treated with Ag@NVan show that plenty of Ag@NVan aggregate in the cell wall of E. coli. A possible antibacterial mechanism is proposed that silver nanoparticles may help destroy the stability of the outer membrane of E. coli, which makes NVan easier to bind to the nether part of the peptidoglycan structure. The antibacterial activities of silver nanoparticles on their own, together with the rigid polyvalent interaction between Ag@NVan and cell wall, enables Ag@NVan to be an effective inhibitor of GNB. This kind of bionanocomposites might be used as novel bactericidal materials and we also provide an effective synthesis method for preparing functional bioconjugated nanoparticles here.     

Synthesis and characterization of magnetic nanoparticles

Magnetic nanoparticles with average diameter in the range of 6.4-8.3 nni have been synthesized by a chemical co-precipitation of Fe(Ⅱ)and Fe(Ⅲ)salts in 1.5 M NH4OH solution.The size of the magnetic particles is dependent on both temperature and the ionic strength of the iron ion solutions.The magnetic particles formed at higher temperature or lower ionic strength were slightly larger than those formed at lower temperature or higher ionic strength respectively.In spite of the different reaction conditions,all the resultant nanoparticles are nearly spherical and have a similar crystalline structure.At 300 K,such prepared nanoparticles are superparam-agnetic.The saturation magnetizations for 7.8 and 6.4 nm particles are 71 and 63 emu/g respectively,which are only ~ 20-30% less than the saturation magnetization(90 emu/g)of bulk Fe3O4 Our results indicated that a control of the reaction conditions could be used to tailor the size of magnetic nanoparticles in free precipitation.     

Chemically binding Eu^3＋ onto CdS semiconductor nanoparticle surface

Europium ions were chemically bound to CdS nanoparticles surface by diethylenetri-aminepentaacetate (DTPA, 1) in a two-step synthetic route. First 1 was applied to chelate with cadmium on the surface of cadmium-rich CdS nanoparticles and act as a capping agent. Further, the purified 1-capped particles were used to bind with Eu~3 . The purified and redispersed particles were characterized by photoluminescence spectroscopy, TEM and SEM. It was observed that Eu~3 on the nanoparticle surface significantly increased the band gap emission and decreased the surface emission intensity of the CdS nanoparticles.     

Preparation, characterization and adhesive properties of di- and tri-hydroxy benzoyl chitosan nanoparticles

Modified chitosans with 3,4-di-hydroxy benzoyl groups (CS-DHBA) and 3,4,5-tri-hydroxy benzoyl groups (CS-THBA) were synthesized and their nanoparticles were prepared via ionic crosslinking by tripolyphosphate (TPP). The chemical structure and degree of substitution (DS) of di-and tri-hydroxy benzoyl chitosans are determined by FTIR and 1H-NMR spectroscopy. The morphology of particles, size distribution and zeta potential of nanoparticles were studied using transmission electron microscopy (TEM) and dynamic light scattering (DLS), respectively. The mean diameters of particles of CS-DHBA and CS-THBA nanoparticles were 144 nm and 112 nm, respectively. It was found that the particles size decreased slightly with decreasing the degree of substitution and increasing degree of deacetylation (DD), due to increasing of ionic crosslinking of ammonium ions and polyanions of tripolyphosphate. The TEM photographs of CS-DHBA show that these particles are spherical in shape, but the particles of CS-THBA show some aggregation. In addition, the solubility and the mechanical properties of the prepared modified chitosans and their nanoparticles were evaluated for bio-adhesive and biomedical application. The results of solubility tests indicated that, the CS-DHBA and CS-THBA have higher solubility at pH > 7 comparing to CS. Also the CS-DHBA, CS-THBA and their nanoparticles showed a significant adhesive capacity and enhanced tensile strength and tensile modulus.     

银纳米颗粒的合成及用于抗癌药氟他胺的电化学检测（英文）

Ag nanoparticles were synthesized on the surface of a glassy carbon electrode modified with p‐tert‐butylcalix[4]arene and p‐tert‐butylcalix[6]arene by the deposition of Ag+ at an open circuit potential followed by the electrochemical reduction of the Ag+.The presence of the calixarene layer on the electrode surface controlled the particle size and prevented agglomeration.Cyclic voltam‐metry showed that the Ag nanoparticles on the modified glassy carbon electrode had good catalytic ability for the reduction of flutamide.The effects of calixarene concentration,potential applied for the reduction of Ag+,number of calixarene layers,and p H value on the electrocatalytic activity of the Ag nanoparticles were investigated.The modified electrode had a linear range in differential pulse voltammetry of 10-1000 μmol/L with a detection limit of 9.33 μmol/L for flutamide at an S/N = 3.The method was applied to the detection of flutamide in practical samples.     

Synthesis of palladium-rhodium bimetallic nanoparticles for formic acid dehydrogenation

Herein,we report for the first time the synthesis of preformed bimetallic Pd-Rh nanoparticles with different Pd:Rh ratios(nominal molar ratio:80-20,60-40,40-60,20-80) and the corresponding Pd and Rh monometallic ones by sol immobilization using polyvinyl alcohol(PVA) as protecting agent and NaBH4 as reducing agent,using carbon nanofibers with high graphitization degree(HHT) as the desired support.The synthesized catalysts were characterized by means of Transmission Electron Microscopy(TEM) and inductively coupled plasma optical emission spectroscopy(ICP-OES).TEM shows that the average particle size of the Pd-Rh nanoparticles is the range of 3-4 nm,with the presence of few large agglomerated nanoparticles.For bimetallic catalysts,EDX-STEM analysis of individual nanoparticles demonstrated the presence of random-alloyed nanoparticles even in all cases Rh content is lower than the nominal one(calculated Pd:Rh molar ratio:90-10,69-31,49-51,40-60).The catalytic performance of the Pd-Rh catalysts was evaluated in the liquid phase dehydrogenation of formic acid to H2.It was found that Pd-Rh molar ratio strongly influences the catalytic performance.Pd-rich catalysts were more active than Rh-rich ones,with the highest activity observed for Pd90:Rh10(1792 h^-1),whereas Pd69:Rh31(921 h^-1) resulted the most stable during recycling tests.Finally,Pd90:Rh10 was chosen as a representative sample for the liquid-phase hydrogenation of muconic acid using formic acid as hydrogen donor,showing good yield to adipic acid.     

银纳米晶体的制备与表征

在聚乙烯吡咯烷酮存在的条件下,用水合肼还原硝酸银,通过控制反应条件成功制备出了粒径均一、有良好分散性的银纳米微粒,并以此为种子,利用种子诱导生长,在十六烷基三甲基溴化铵的棒状胶束环境中制备出了银纳米棒和纳米线.并用X射线衍射、透射电子显微镜、傅立叶红外光谱和紫外-可见光谱等手段对产品的形貌、结构进行了表征.     

Synthesis and characterization of magnetic Co nanoparticles: A comparison study of three different capping surfactants

This paper compares the performance of three long-chain acids—oleic and elaidic (both olefinic) and stearic (aliphatic)—as a capping agent in the synthesis of magnetic Co nanoparticles. The particles were formed through thermal decomposition of dicobalt octacarbonyl in toluene in the presence of the long-chain acid, and characterized by TEM, high-resolution TEM, and SQUID measurements. Infrared spectra revealed that some of the added olefinic acid was transformed from cis- to trans-configuration (for oleic acid) or from trans- to cis- (for elaidic acid) to facilitate the formation of a densely packed monolayer on the surface of Co nanoparticles. As compared to aliphatic acids, olefinic acids are advantageous for dense packing on small particles with high surface curvatures due to a bent shape of the cis-isomer. The presence of an olefinic acid is able to control particle growth, stabilize the colloidal suspension, and prevent the final product from oxidation by air. Our results indicate that oleic acid, elaidic acid, and a mixture of oleic/stearic acids or elaidic/stearic acids have roughly the same performance in serving as a capping agent for the synthesis of Co nanoparticles with a spherical shape and narrow size distribution.     

Green synthesis of silver nanoparticles for ammonia sensing

Silver nanoparticles synthesized by a reagent less method involving only UV radiation have been used in colorimetric assay for the detection of ammonia in solution. The silver nanoparticles were synthesized by the exposure of a silver nitrate solution to a low-power UV source in the presence of poly(methacrylic acid) (PMA), which acted both as reducing and capping agent. The synthesis of the silver nanoparticles was studied by monitoring the changes in position and amplitude of the localized plasmon resonance (LSPR) band using UV-vis spectroscopy. The morphology of the particles was studied using transmission electron microscopy which confirmed the formation of spherical particles with an average particle size around 8 nm. Interestingly, the silver nanoparticles solution was found to display a strong color shift from purple to yellow upon mixing with increasing concentration of ammonia ranging from 5 to 100 ppm. Hence, the nanoparticles prepared with this method could be used as colorimetric assay for sensing applications of ammonia in water.     

From discrete particles to spherical aggregates: a simple approach to the self-assembly of Au colloids

Here we demonstrate a simple, template-free approach to the formation of spherical gold aggregates through the reduction of HAuCl4 by NaBH4, in the presence of cysteine (Cys) as a capping agent. The resulting aggregates are quite stable in solution. The pH of the solution and the molar ratio of Au:Cys are two key empirical factors in the formation of such highly ordered aggregates. At slightly alkaline pH (7-10) and with Au:Cys ratios ranging from 1:0.5 to 1:2, spherical Au aggregates of 30-80 nm are formed. At lower Cys ratios (Au:Cys> or =1:0.5) very loosely linked aggregates are formed; however, at very high Cys ratios (Au:Cys< or =1:3), highly dispersed Au particles of 2-4 nm are obtained, which are virtually indistinguishable from the original colloidal form. Aggregate size is influenced markedly by component concentration; a 3-fold increase in standard levels resulted in Au spherical aggregates of a larger size, 200-500 nm. In addition, we used a combination of Cys and lysine (Lys) as a capping agent/cross-linker and found that the morphology of the Au colloid aggregates can be easily manipulated from a linear to a spherical form by adjusting the proportions of Cys and Lys in the capping agent/cross-linker mixture. The introduction of mercapto (SH)-containing organic acids reduced the cross-linking ability of Cys, especially in the case of long-chain acids. Complete disruption of the spherical aggregates highlights the importance of Cys per se. An explanation of this ordered self-assembly process is proposed, in the context of the known surface chemistry of Au colloids.     

Synthesis of positively charged silver nanoparticles via photoreduction of AgNO3 in branched polyethyleneimine/HEPES solutions

Branched polyethyleneimine (BPEI) and 4-(2-hydroxyethyl)-1-piperazineethanesulfonic acid (HEPES) were used collaboratively to reduce silver nitrate under UV irradiation for the synthesis of positively charged silver nanoparticles. The effects of molar ratio of the ingredients and the molecular weight of BPEI on the particle size and distribution were investigated. The mechanism for the reduction of Ag+ ions in the BPEI/HEPES mixtures entails oxidative cleavage of BPEI chains that results in the formation of positively charged BPEI fragments enriched with amide groups as well as in the production of formaldehyde, which serves as a reducing agent for Ag+ ions. The resultant silver nanoparticles are positively charged due to protonation of surface amino groups. Importantly, these positively charged Ag nanoparticles demonstrate superior SERS activity over negatively charged citrate reduced Ag nanoparticles for the detection of thiocyanate and perchlorate ions; therefore, they are promising candidates for sensing and detection of a variety of negatively charged analytes in aqueous solutions using surface-enhanced Raman spectroscopy (SERS).     

The green synthesis of fine particles of gold using an aqueous extract of <Emphasis Type="Italic">Monotheca buxifolia</Emphasis> (Flac.)

This study deals with the synthesis and physicochemical investigation of gold nanoparticles using an aqueous extract of Monotheca buxifolia (Flac.). On the treatment of aqueous solution of tetrachloroauric acid with the plant extract, gold nanoparticles were rapidly fabricated. The synthesized particles were characterized by UV–Vis spectrophotometry (UV), Fourier transform infrared spectroscopy (FTIR), energy dispersive X-ray (EDX) and Scanning electron microscopy (SEM). The formation of AuNPs was confirmed by noting the change in color through visual observations as well as via UV–Vis spectroscopy. UV?Vis spectrum of the aqueous medium containing gold nanoparticles showed an absorption peak at around 540 nm. FTIR was used to identify the chemical composition of gold nanoparticles and Au-capped plant extract. The presence of elemental gold was also confirmed through EDX analysis. SEM analysis of the gold nanoparticles showed that they have a uniform spherical shape with an average size in the range of 70–78 nm. This green system showed to be better capping and stabilizing agent for the fine particles. Further, the antioxidant activity of Monotheca buxifolia (Flac.) extract and Au-capped with the plant extract was also evaluated using FeCl₃/K₃[Fe(CN)]₆ in vitro assay.     

Effect of hydrophobicity inside PEO-PPO-PEO block copolymer micelles on the stabilization of gold nanoparticles: experiments

In this paper we present the effect of poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) block copolymer micelles and their hydrophobicity on the stabilization of gold nanoparticles. Gold nanoparticles were prepared by a method developed by Sakai et al. (Sakai, T.; Alexandridis, P. Langmuir 2004, 20, 8426). An absorption centered at 300-400 nm in time-dependent UV spectra provided evidence that the very first step of the synthesis was to form primary gold clusters. Then the gold clusters grew in size and were stabilized by block copolymer micelles. The stabilization capacities of the micelles were modulated by tuning the block copolymer concentration and composition and by adding salts. With good stabilization, gold particles were spherical and uniform in size with a diameter of 5-10 nm. Otherwise they were aggregates with irregular shapes such as triangular, hexagonal, and rodlike. The presence of a small amount of NaF significantly increased the stabilization capacity of the micelles and consequently modified the quality of the gold particles. Using FTIR and 1H NMR spectroscopy, micellization of the block copolymers and hydrophobicity of the micelles were proven very important for the stabilization. A higher hydrophobicity of the micelle cores was expected to favor the entrapment of primary gold clusters and the stabilization of gold nanoparticles.     

Green synthesis of silver nanoparticles using Thymus kotschyanus extract and evaluation of their antioxidant,antibacterial and cytotoxic effects

Present study used ecofriendly, cost efficient and easy method for synthesis of silver nanoparticles (Ag NPs) at the room temperature by Thymus Kotschyanus extract as reducing and capping agent. Various analytical technique including UV–Vis absorption spectroscopy determined presence of Ag NPs in the solution, the functional groups of Thymus Kotschyanus extract in the reduction and capping process of Ag NPs are approved by FT‐IR, crystallinity with the fcc plane approved from the X‐ray diffraction (XRD) pattern, energy dispersive spectroscopy (EDS) determined existence of elements in the sample, surface morphology, diverse shapes and size of present Ag NPs were showed by using scanning electron microscopy (SEM), atomic force microscopy (AFM) and high resolution transmission electron microscopy (HRTEM). Beginning and end destroy temperature of present silver nanoparticles were determined by thermal gravimetric spectroscopy (TGA). In addition, antibacterial, antioxidant and cytotoxicity properties of Ag NPs were studied. Agar disk and agar well diffusion are the methods to determined antibacterial properties of synthesized Ag NPs. Also MIC (Minimum Inhibitory Concentration) and MBC (Minimum Bactericidal Concentration) were recognized by macro broth dilution assay. DPPH free radical scavenging assay was used for antioxidant property and compare to butylated hydroxytoluene (BHT) as standard antioxidant that showed high antioxidant activity more than BHT. Synthesized Ag NPs have great cell viability in a dose depended manner and demonstrate that this method for synthesis silver nanoparticles provided nontoxic. The average diameter of synthesized Ag NPs was about 50–60 nm.     

Self-assembled metal colloid films: two approaches for preparing new SERS active substrates

In this paper, we propose two new approaches for preparing active substrates for surface-enhanced Raman scattering (SERS). In the first approach (method 1), one transfers AgI nanoparticles capped by negatively charged mercaptoacetic acid from a AgI colloid solution onto a quartz slide and then deoxidizes AgI to Ag nanoparticles on the substrate. The second approach (method 2) deoxidizes AgI to Ag nanoparticles in a colloid solution and then transfers the Ag nanoparticles capped by negatively charged mercaptoacetic acid onto a quartz slide. By transfer of the AgI/Ag nanoparticles from the colloid solutions to the solid substrates, the problem of instability of the colloid solutions can largely be overcome. The films thus prepared by both approaches retain the merits of metal colloid solutions while they discharge their shortcomings. Accordingly, the obtained Ag particle films are very suitable as SERS active substrates. SERS active substrates with different coverages can be formed in a layer-by-layer electrostatic assembly by exposing positively charged surfaces to the colloid solutions containing oppositely charged AgI/Ag nanoparticles. The SERS active substrates fabricated by the two novel methods have been characterized by means of atomic force microscopy (AFM) and ultraviolet-visible (UV-vis) spectroscopy. The results of AFM and UV-vis spectroscopy show that the Ag nanoparticles grow with the increase in the number of coverage and that most of them remain isolated even at high coverages. Consequently, the surface optical properties are dominated by the absorption due to the isolated Ag nanoparticles. The relationship between SERS intensity and surface morphology of the new active substrates has been investigated for Rhodamine 6G (R6G) adsorbed on them. It has been found that the SERS enhancement depends on the size and aggregation of the Ag particles on the substrates. Especially, we can obtain a stronger SERS signal from the substrate prepared by method 1, implying that for the metal nanoparticles capped with stabilizer molecules such as mercaptoacetic acid, the in situ deoxidization in the film is of great use in preparing SERS active substrates. Furthermore, we have found that the addition of Cl- into the AgI colloid solution changes the surface morphology of the SERS active substrates and favors stronger SERS enhancement.