Synthesis and characterization of RuS2 nanostructures

Small naked ruthenium sulfide nanoparticles (NPs) with narrow size distribution (2.5 +/- 0.4 nm of diameter) were synthesized in DMSO colloidal dispersions, under mild reaction conditions and using commercial RuCl3 as precursor. To test the chemical reactivity with soft and hard bases, fresh presynthesized RuS2 colloids were mixed with triethylamine (N(Et)3) and ammonium tetrathiomolybdate ((NH4)2MoS4) dimethyl sulfoxide solutions. Naked N(Et)3 and [MoS4](2-)-capped RuS2 nanoparticle colloids were characterized using UV-visible electronic absorption and emission spectroscopies and high-resolution transmission electron microscopy (HR-TEM). It has also been shown that capped RuS2-[MoS4]2- nanoparticles yield MoO3 crystalline matrix by means of HR-TEM experiments. The emission spectra of RuS2 and N(Et)3-RuS2 dispersions show that both nanosized materials have strong fluorescence. The existence of the ruthenium precursor species in solution was established by cyclic voltammetry. Moreover, naked RuS2 NPs were mixed with a chemical mixture with composition similar to gasoline (dibenzothiophene (Bz2S, 400 ppm), hexane, and toluene (55:45% v/v)). The reaction mixture consisted of two phases; in the polar phase, we found evidences of a strong interaction of Bz2S and toluene with the naked RuS2 NPs. We have also obtained self-organized thin films of capped N(Et)3- and RuS2-[MoS4]2- nanoparticles. In both cases, the shape and thickness of the resulting thin films were controlled by a dynamic vacuum procedure. The thin films have been characterized by atomic force microscopy, scanning electron microscopy, HR-TEM, energy dispersion spectroscopy, X-ray diffraction, and absorbance and fluorescence spectroscopies.     

Preparation and Exploration on the Electrochemical Behavior of Nickel Oxide Nanoparticles Coated Bacterial Nanowires

The controlled synthesis of nickel oxide nanoparticle (NiO NPs) were synthesized by homogeneous precipitation method and have been characterized using UV–visible spectrophotometer, fourier transform-infrared spectroscopy, X-ray diffraction, atomic force microscope, scanning electron microscope and high resolution-transmission electron microscope. The synthesized NiO NPs was spherical in shape with an average size ranged between 3 and 5 nm. Subsequently, synthesis of NiO NPs coated on a bacterial nanowires (BNWs) film pre-cast on a glassy carbon electrode surface and the morphology and nature of the prepared composite was characterized using HR-TEM. The electro-chemical behavior of NiO NPs coated bacterial nanowires (NiO NPs-BNWs) was observed using cyclic voltammetry, linear sweep voltammetry and electrochemical impedance spectroscopy analysis. Highly comparable electrochemical conductivity of NiO NPs-BNWs was observed in this study. The BNWs sample exhibited a polarization resistance (Rp) to be 4457 Ω and the NiO NPs-BNWs sample exhibited polarization resistance (Rp) about 2270.4 Ω. The BNWs exhibited a CPE-T value to be 6.26 µF cm^?2 and the NiO NPs-BNWs sample exhibited CPE-T to be 9.32 µF cm^?2. The enhancement of peak currents is ascribed to the short heterogeneous electron transfer among the NiO NPs-BNWs. The defined nanolayer provides a novel platform for the next generation electrochemical applications.     

Iron nanoparticles: the core-shell structure and unique properties for Ni(II) sequestration

It is demonstrated that iron nanoparticles function as a sorbent and a reductant for the sequestration of Ni(II) in water. A relatively high capacity of nickel removal is observed (0.13 g Ni/g Fe, or 4.43 mequiv Ni(II)/g), which is over 100% higher than the best inorganic sorbents available. High-resolution X-ray photoelectron spectroscopy (HR-XPS) confirms that the zerovalent iron nanoparticles have a core-shell structure and exhibit characteristics of both hydrous iron oxides (i.e., as a sorbent) and metallic iron (i.e., as a reductant). Ni(II) quickly forms a surface complex and is then reduced to metallic nickel on the nanoparticle surface. The dual properties of iron nanoparticles may offer efficient and unique solutions for the separation and transformation of metal ions and other environmental contaminants.     

流变相法制备包覆型零价纳米铁及其表征

以FeSO4.7H2O∶KBH4=1∶2(摩尔比)为固相介质,0.06 g/ml羧甲基纤维素水溶液为液相介质,固液比1∶2,调制成流变相体系反应2 h制备出包覆型纳米零价铁;采用XRD、TEM等手段对合成的纳米零价铁进行表征。     

Effect of selected ligands on the U(VI) immobilization by zerovalent iron

Summary Theeffect ofCl^-, CO₃^2-, EDTA, NO₂^-, NO₃^-, PO₄^3-, SO₄^2-, and humic substances (HS)on the U(VI)co-precipitation from aqueous solutions by zerovalent iron (ZVI) was investigated in the neutral pH range.Batch experiments without shaking were conducted for 14 days mostly with five different ZVI materials (15 g/l), selected ligands (10mM) and an U(VI) solution (20 mg/l, 0.084mM). Apart from Cl^-, all tested ligands induced a decrease ofU(VI)coprecipitation. This decrease is attributed to the surface adsorption and complexation of the ligands at the reactive sites on the surface of ZVI and their corrosion products. The decrease ofU(VI)removal was not uniform with the five ZVI materials. Generally, groundwater with elevated EDTA concentration could not be remediated with the ZVI barrier technology. The response of the system on the pre-treating by two ZVI materials in 250mM HCl indicated that in situ generated corrosion products favor an irreversible U(VI) uptake. Thus for the long term performance of ZVI barrier, the iron dissolution should continue in such a way that fresh iron oxide be always available for U(VI) coprecipitation.     

A facile and green synthetic approach toward fabrication of starch-stabilized magnetite nanoparticles

A facile and green synthetic approach for fabrication of starch-stabilized magnetite nanoparticles was implemented at moderate temperature. This synthesis involved the use of iron salts, potato starch,sodium hydroxide and deionized water as iron precursors, stabilizer, reducing agent and solvent respectively. The nanoparticles(NPs) were characterized by UV-vis, PXRD, HR-TEM, FESEM, EDX, VSM and FT-IR spectroscopy. The ultrasonic assisted co-precipitation technique provides well formation of highly distributed starch/Fe_3O_4-NPs. Based on UV–vis analysis, the sample showed the characteristic of surface plasmon resonance in the presence of Fe_3O_4-NPs. The PXRD pattern depicted the characteristic of the cubic lattice structure of Fe_3O_4-NPs. HR-TEM analysis showed the good dispersion of NPs with a mean diameter and standard deviation of 10.68 4.207 nm. The d spacing measured from the lattice images were found to be around 0.30 nm and 0.52 nm attributed to the Fe3O4 and starch, respectively. FESEM analysis confirmed the formation of spherical starch/Fe_3O_4-NPs with the emission of elements of C, O and Fe by EDX analysis. The magnetic properties illustrated by VSM analysis indicated that the as synthesized sample has a saturation magnetization and coercivity of 5.30 emu/g and 22.898 G respectively.Additionally, the FTIR analysis confirmed the binding of starch with Fe_3O_4-NPs. This method was cost effective, facile and eco-friendly alternative for preparation of NPs.     

One‐step Hydrothermal Synthesis and Assembly of Copper and Silver Nanoparticles to Aggregates in Glyoxal Reduction System

A simple hydrothermal process has been developed for the synthesis and assembly of copper and silver nanoparticles to aggregates. The reduction of Cu²⁺ and Ag⁺ ions to the zerovalent metal was performed by glyoxal in the absence of any external agent. The produced glyoxylic acid (GA) in the redox process stabi‐ lized metallic copper and silver particles and rendered them oxidation resistant for several months and dispersible in polar organic solvents and water. Detailed nanostructures of synthesized products were characterized by transmission electron microscopy (TEM), scanning electron microscopy (SEM), and X‐ray diffraction (XRD). The results demonstrated that assembly of nanoparticles to aggregates and their regularity were dependent on the reaction conditions such as temperature and concentration of the starting material. The Ostwald ripening process was proposed to explain the formation of copper nanoparticles by TEM observation at several times during the reaction. The existence of the surface stabilizing agent was identified by Fourier Transform infrared spectroscopy (FT‐IR) and thermogravimetric analyses (TGA).     

Biomolecule-nanoparticle hybrids as functional units for nanobiotechnology

Biomolecule-metal or semiconductor nanoparticle (NP) hybrid systems combine the recognition and catalytic properties of biomolecules with the unique electronic and optical properties of NPs. This enables the application of the hybrid systems in developing new electronic and optical biosensors, to synthesize nanowires and nanocircuits, and to fabricate new devices. Metal NPs are employed as nano-connectors that activate redox enzymes, and they act as electrical or optical labels for biorecognition events. Similarly, semiconductor NPs act as optical probes for biorecognition processes. Double-stranded DNA or protein chains that are modified with metallic nanoclusters act as templates for the synthesis of metallic nanowires. The nanowires are used as building blocks to assemble nano-devices such as a transistor or a nanotransporter.     

Direct‐methanol Fuel Cell Based on Functionalized Graphene Oxide with Mono‐metallic and Bi‐metallic Nanoparticles: Electrochemical Performances of Nanomaterials for Methanol Oxidation

The catalysts based on 2‐aminoethanethiol functionalized graphene oxide (AETGO) with several mono‐metallic and bi‐metallic nanoparticles such as rod gold (rAuNPs), rod silver (rAgNPs), rod gold‐platinum (rAu‐Pt NPs) and rod silver‐platinum (rAg‐Pt NPs) were synthesized. The successful synthesis of nanomaterials was confirmed by various methods. The effective surface area (ESA) of the rAu‐Pt NPs/AETGO is 1.44, 1.64 and 2.40 times higher than those of rAg‐Pt NPs/AETGO, rAuNPs/AETGO and rAgNPs/AETGO, respectively, under the same amount of Pt. The rAu‐Pt NPs/AETGO exhibited a higher peak current for methanol oxidation than those of comparable rAg‐Pt NPs/AETGO under the same amount of Pt loading.     

Synthesis, characterization, and antifouling potential of functionalized copper nanoparticles

The synthesis, characterization, and antimicrobial properties of functionalized copper nanoparticle/polymer composites are reported. Copper nanoparticles (Cu NPs) are stabilized by surface attachment of the acrylic functionality that can be copolymerized with other acrylic monomers, thus, becoming an integral part of the polymer backbone. Biological experiments show that Cu NP/polymer composites exhibit antimicrobial activity similar to that of conventional copper-based biocides. Atomic absorption spectroscopy shows the smallest amount of copper ions leaching from chemically bound acrylated Cu NPs compared to the nonfunctionalized biocides. These composites have a strong potential for use in antibacterial or marine antifouling coatings.     

Facile synthesis of photoluminescent ZnS and ZnSe nanopowders

The solid state thermal, one pot, efficient chemical reaction between Zn and S or Se elements in a closed reactor at 650 degrees C/60 min under their autogenic pressure in an inert atmosphere yielded luminescent ZnS and ZnSe semiconducting nanopowders (NPs). Scanning and Transmission electron microscopy measurements confirmed the size and shape of the as formed ZnS and ZnSe NPs. The wide size distributions of ZnS and ZnSe NPs are confirmed by UV-vis and TEM measurements. The crystalline wurtzite phase of ZnS and face centered cubic phase of ZnSe NPs is revealed from XRD and HR-TEM measurements. The obtained Raman scattering bands also supports the formation of pure ZnS and ZnSe phases. At room temperature, a strong visible green emission centered at approximately 525 nm is measured for ZnS, while ZnSe NPs showed a broad red emission band extending from 550 to 760 nm. The putative reaction mechanism is based on the low melting and boiling points of reactants (Zn, S and Se) under their autogenic pressure in an inert atmosphere.     

Chloride ion effects on synthesis and directed assembly of copper nanoparticles in liquid and compressed alkane microemulsions

Microemulsions are effective media for solution-based synthesis of metallic nanoparticles where surfactants and other ionic species influence the directed assembly of the nanomaterials with specific sizes, geometries, and compositions. This study demonstrates the effects of chloride ion on the synthesis of copper nanoparticles within the sodium bis(2-ethylhexyl)sulfosuccinate (AOT) reverse micelle system utilizing both liquid isooctane and compressed propane as the bulk solvent. Copper nanoparticle synthesis can be achieved in the presence of HCl in the micelle core, taking advantage of the buffering action of the AOT surfactant. The concentration of chloride ions influence the particle growth rate and dispersion in liquid isooctane. The presence of chloride ions during particle synthesis in compressed propane has a significant effect on the geometry and structure of the copper nanomaterials produced. Chloride ion addition to the compressed propane/Cu(AOT)(2)-AOT/water reverse micelle system at 20 degrees C and 310 bar results in the formation of diamond-shaped copper nanoparticle assemblies. The copper nanoparticle assemblies exhibit unique structure and retain this structure through repeated solvent processing steps, allowing separation and recovery of the assembled diamond-shaped copper nanoparticle structures.     

Iron nanoparticles catalyzing the asymmetric transfer hydrogenation of ketones

Investigation into the mechanism of transfer hydrogenation using trans-[Fe(NCMe)CO(PPh(2)C(6)H(4)CH═NCHR-)(2)][BF(4)](2), where R = H (1) or R = Ph (2) (from R,R-dpen), has led to strong evidence that the active species in catalysis are iron(0) nanoparticles (Fe NPs) functionalized with achiral (with 1) and chiral (with 2) PNNP-type tetradentate ligands. Support for this proposition is given in terms of in operando techniques such as a kinetic investigation of the induction period during catalysis as well as poisoning experiments using substoichiometric amounts of various poisoning agents. Further support for the presence of Fe(0) NPs includes STEM microscopy imaging with EDX analysis, XPS analysis, and SQUID magnetometry analysis of catalytic solutions. Further evidence of Fe NPs acting as the active catalyst is given in terms of a polymer-supported substrate experiment whereby the NPs are too large to permeate the pores of a functionalized polymer. Final support is given in terms of a combined poisoning/STEM/EDX experiment whereby the poisoning agent is shown to be bound to the Fe NPs. This paper provides evidence of a rare example of asymmetric catalysis with nonprecious metal, zerovalent nanoparticles.     

Potato Peels Mediated Synthesis of Cu(II)-nanoparticles from Tyrosinase Reacted with bis-(N-aminoethylethanolamine) (Tyr-Cu(II)-AEEA NPs) and Their Cytotoxicity against Michigan Cancer Foundation-7 Breast Cancer Cell Line

The synthesis of nanoparticles is most important in the context of cancer therapy, particularly copper nanoparticles, which are widely used. In this work, copper(II)-tyrosinase was isolated from potato peel powder. Copper nanoparticles (Tyr-Cu(II)-AEEA NPs) were synthesized via the reaction of tyrosinase with N-aminoethylethanolamine to produce Cu(II)-NPs and these were characterized by means of FT-IR, UV-Spectroscopy, XRD, SEM, TEM and a particle size analyzer. These Tyr-Cu(II)-AEEA NPs were tested as anticancer agents against MCF-7 breast cancer cells. Fluorescence microscopy and DNA fragmentation were also performed, which revealed the inhibiting potentials of Cu(II)-AEEA NPs and consequent cell death; Tyr-Cu(II)-AEEA NPs show potential cytotoxicity activity and this nano material could be contemplated as an anticancer medicament in future investigations.     

Voltammetric Detection of Copper Ions on a Gold Electrode Modified with a N-methyl-2-naphthyl-cyclam film

A voltammetric sensor based on a methyl-naphthyl cyclam (1,4,8,11-tetraazacyclotetradecane) film deposited through dip coating on gold electrodes allowed the sensitive detection of copper (II). The obtained film was characterized in terms of the composition and morphology using Fourier transform infrared (FTIR) spectroscopy and atomic force microscopy. In the presence of divalent metallic ions (copper and nickel) and trivalent metallic ions (iron), at pH 7 and 7.7, the current density of the ionic oxidation peak maximum was determined using square wave voltammetry. The relative variation of this current density varies linearly with the base-ten logarithm of the ion concentration. From this calibration curve, a detection limit of 7?×?10^?12?M was obtained for copper (II) at pH 7. At this pH value, the sensitivity of detection of copper (II) was 2.5 times higher than for nickel (II) and 5.8 times higher than for iron (III). The methyl-naphthyl cyclam film-modified gold sensor was validated for the detection of copper in spiked urine samples.     

Determination of the oxide layer thickness in core-shell zerovalent iron nanoparticles

Zerovalent iron (nZVI) nanoparticles have long been used in the electronic and chemical industries due to their magnetic and catalytic properties. Increasingly, applications of nZVI have also been reported in environmental engineering because of their ability to degrade a wide variety of toxic pollutants in soil and water. It is generally assumed that nZVI has a core-shell morphology with zerovalent iron as the core and iron oxide/hydroxide in the shell. This study presents a detailed characterization of the nZVI shell thickness using three independent methods. High-resolution transmission electron microscopy analysis provides direct evidence of the core-shell structure and indicates that the shell thickness of fresh nZVI was predominantly in the range of 2-4 nm. The shell thickness was also determined from high-resolution X-ray photoelectron spectroscopy (HR-XPS) analysis through comparison of the relative integrated intensities of metallic and oxidized iron with a geometric correction applied to account for the curved overlayer. The XPS analysis yielded an average shell thickness in the range of 2.3-2.8 nm. Finally, complete oxidation reaction of the nZVI particles by Cu(II) was used as an indication of the zerovalent iron content of the particles, and these observations further correlate the chemical reactivity of the particles and their shell thicknesses. The three methods yielded remarkably similar results, providing a reliable determination of the shell thickness, which fills an essential gap in our knowledge about the nZVI structure. The methods presented in this work can also be applied to the study of the aging process of nZVI and may also prove useful for the measurement and characterization of other metallic nanoparticles.     

One-pot synthesis and characterization of three kinds of thiol-organosilica nanoparticles

Using a one-pot synthesis, thiol-organosilica nanoparticles (NPs) made from (3-mercaptopropyl)trimethoxysilane, (3-mercaptopropyl)triethoxysilane, and (3-mercaptopropyl)methyldimethoxysilane have been successfully prepared. We compared the synthesis processes of thiol-organosilica NPs made of these three kinds of organosilicates, as well as particles made from tetraethoxysilicate (TEOS), at concentrations varying between 6.25 and 200 mM. We examined three types of synthetic conditions: the St?ber method, in which particles are prepared in 65% ethanol, and two entirely aqueous solvent syntheses, containing either 2% or 27% ammonium hydroxide. The synthetic mixtures were examined using transmission electron microscopy (TEM) to evaluate the as-prepared NPs. The formation trends and rates for these organosilica NPs vary with differing organosilicate precursors, concentrations, and synthetic conditions. The St?ber method is not suitable for formation of thiol-organosilica NPs as compared with the case of TEOS, but the conditions without ethanol and with 27% ammonium hydroxide are suitable for the formation of thiol-organosilica NPs. The size distributions of the formed NPs were evaluated using TEM and dynamic light scattering. The mean diameters of NPs increase with increasing concentrations of silicate, but the size distributions of NPs prepared under various conditions also differ between silicate sources. Thiol-organosilica NPs internally functionalized with fluorescent dye were also prepared using a one-pot synthesis and were characterized using fluorescence microscopy. The thiol-organosilica NPs retain fluorescent dye maleimide very well. In addition, rhodamine B-doped thiol-organosilica NPs show higher fluorescence than thiol-organosilica NPs prepared with rhodamine red maleimide. The surface of thiol-organosilica NPs contains exposed thiol residues, allowing the covalent attachment of fluorescent dye maleimide and protein maleimide. This is the first report describing the synthesis of thiol-organosilica NPs made of three kinds of thiol-organosilicates, differences in nanoparticle formation due to the kinds and concentrations of thiol-organosilicate and due to synthetic conditions, and the advantages of thiol-organosilica NPs due to the existence of both interior and exterior thiol residues.     

A sensitive fluorimetric biosensor for detection of DNA hybridization based on Fe/Au core/shell nanoparticles

In this study, we reported a sensitive fluorescent biosensor for detection of DNA hybridization based on Fe/Au core/shell (Fe@Au) nanoparticles (NPs). First, Fe@Au NPs were synthesized using a reverse micelle method, with gold as the shell and iron as the core. The nanoparticle size was confirmed by transmission electron microscopy (TEM). Scanning electron microscopy (SEM) was performed in order to elucidate the morphology of the Fe@Au NPs. Then probe DNA with -SH at the 5'-phosphate end was covalently immobilized onto the surface of the Fe@Au NPs. The DNA hybridization event can be detected by a fluorescent method and methylene blue (MB) as the fluorescent probe. The decline of the fluorescence intensity of MB (ΔF) was linear with the concentration of the complementary DNA from 3.0 × 10(-13) to 1.0 × 10(-9) M with a detection limit of 1.0 × 10(-13) M (S/N = 3). In addition, this approach of DNA detection exhibited excellent selectivity, even for single-mismatched DNA detection.     

Mixed Co/Fe oxide nanoparticles in block copolymer micelles

Small iron oxide and Co-doped iron oxide nanoparticles (NPs) were synthesized in a commercial amphiphilic block copolymer, poly(ethylene oxide)-b-poly(methacrylic acid) (PEO 68-b-PMAA8), in aqueous solutions. The structure and composition of the micelles containing guest molecules (metal salts) or NPs (metal oxides) were studied using transmission electron microscopy, dynamic light scattering, X-ray photoelectron spectroscopy, and X-ray powder diffraction. The enlarged micelle cores after incorporation of metal salts are believed to be formed by both PMAA blocks containing metal species and penetrating PEO chains. The nanoparticle size distributions in PEO 68-b-PMAA8 were determined using small-angle X-ray scattering (SAXS) in bulk. Two independent methods for SAXS data interpretation for comprehensive analysis of volume distributions of metal oxide NPs showed presence of both small particles and larger entities containing metal species which are ascribed to organization of block copolymer micelles in bulk. The magnetometry measurements revealed that the NPs are superparamagnetic and their characteristics depend on the method of the NP synthesis. The important advantage of the PEO 68-b-PMAA8 stabilized magnetic nanoparticles described in this paper is their remarkable solubility and stability in water and buffers.