Synthesis of Core-Shell (Pd-Au) Bimetallic Nanoparticles in Microemulsions

Palladium-gold core-shell nanoparticles were synthesized in the aqueous domains of water in oil microemulsions by the sequential reduction of H₂PdCl₄ and HAuCl₄. The nanoparticles were characterized by ultraviolet-visible (UV-vis) spectroscopy and transmission electron microscopy (TEM). The UV-vis spectra confirm the presence of palladium nanoparticles after reducing H₂PdCl₄. These particles have been used as seeds for the core-shell particles. UV-vis spectra show that, after reducing HAuCl₄, the surface plasmon absorption of the nanoparticles is dominated by gold, revealing the encapsulation of the palladium seeds. These results agree with crystallographic analysis performed with high-resolution TEM pictures, as well as with selected area electron diffraction. The TEM pictures show the core-shell nanoparticles with an average diameter of 9.1 nm, as compared with 5 nm for the palladium seeds, in good agreement with the used Pd:Au molar ratio.     

Determination of Tryptophan using a p-Sulfonated Calix [4,6,8]arene Modified Gold Electrode

The ability of p-sulfonated calix[n]arenes (n = 4, 6, 8) to form complexes with tryptophan was studied. The electrochemical properties of these complexes immobilized on gold surfaces were examined by cyclic voltammetry. Parameters affecting the performance of the modified electrodes including the arene concentration, scan rate, applied potential, and pH were optimized. Under the optimal conditions, the method had a linear response to tryptophan between 1 × 10^?7 M and 1 × 10^?5 M with a detection limit of 3 × 10^?8 M. The interaction of the tryptophan–p-sulfonated calix[4]arene complex was more stable than the tryptophan–p-sulfonated calix[6]arene and p-sulfonated calix[8]arene complexes. Molecular modeling calculations indicated that electrostatic interactions and structural matching effects were predominant stabilizing factors. The modified electrodes demonstrated good reproducibility and high selectivity, illustrating their effectiveness for analytical measurements.     

Immobilization of gold nanoparticles on poly(methyl methacrylate) electrospun fibers exhibiting solid‐state surface plasmon effect

In this study, the surface plasmon effect of Au nanoparticles was successfully realized in the solid state by embedding the Au nanoparticles on the surface of the transparent polymer fibers for the first time. Electrospinning a poly(methyl methacrylate) (PMMA) and HAuCl₄ mixture followed by a wet chemical reduction, the gold nanoparticles were formed on the PMMA nanocomposite electrospun fibers in a well‐distributed manner to give photostable purple color. The Au nanoparticles were all sphere shaped with an average diameter of 12 nm. Specifically, simply adjusting HAuCl₄ salt concentration in the electrospinning solution, it is able to control the electrospun fiber diameter and gold nanoparticle content in the resulting PMMA/Au nanocomposite fibers. Therefore, the developed method described herein is simple and effective for the large volume production of PMMA/Au nanocomposite fibers. Copyright © 2011 John Wiley & Sons, Ltd.     

Determination of antioxidant activities in fruit juices based on rapid colorimetric measurement and characterisation of gold nanoparticles

A simple and green synthesis of gold nanoparticles (AuNPs) was achieved in tea solution and fruit juices with auric tetrachloride (HAuCl₄) without the addition of any other chemicals. Natural antioxidants present in tea leaves and fruit juices were able to reduce Au³⁺ ions to form AuNPs spheres with an average diameter of 22.9 ± 2.7 nm in the tea solution and 12.8 ± 2.4 nm in the orange juice. A colorimetric determination of antioxidant activities based on the formation of citrate-capped AuNPs has been developed. It was found that the colorimetric response of AuNPs was dependent on the concentration of antioxidants tested. As compared with the standard reference assay, i.e., the Folin–Ciocalteu method, the colorimetric method reported in this study showed a very good correlation (R² = 0.9996). The results indicate that the AuNPs-based colorimetric method provides a simple, effective and reliable measurement of the antioxidant capacity in the tested fruit juices.     

Preparation and Characterization of Heparin‐Stabilized Gold Nanoparticles

A simple method for preparing gold nanoparticles in aqueous solution has been developed by using glycosaminoglycan‐heparin as reducing and stabilizing agent and HAuCl₄ as precursor. The obtained gold nanoparticles were characterized by UV‐vis spectroscopy, resonance light scattering spectroscopy (RLS), transmission electron microscopy (TEM) and electrophoresis technology. The influence of reactant concentration for the preparation of gold nanoparticles was investigated. The results indicated that the gold nanoparticles carried negative charges in the aqueous solution and the size and shape of the gold nanoparticles could be controlled by changing the concentration of the heparin. Moreover, the gold nanoparticles obtained with relatively high concentration of heparin were very stable and had relative narrow size distribution.     

Synthesis, characterization and preliminary toxicity assays of NIR-active Au-silicate nanoparticles through a sol-gel processing

Monodisperse Au-silicate nanoparticles (10.7±1.6 nm in diameter) were prepared by reduction of aqueous solution containing 2 mM HAuCl₄ with sodium citrate (1 wt.%) in a hydrosol, in which small clusters of silicate formed by hydrolysis and polymerization of 3-aminopropyltrimethoxysilane (APTMS). APTMS covalently linked to reduced gold particles through its -NH₂ end-group. UV-vis spectra of the obtained Au-silicate nanoparticles showed a peak at ∼690 nm due to the interface effects between the Au and the silicate matrix. The Au-silicate nanoparticles exhibited near-IR (NIR) sensitivity. Cytotoxicity and limited hemocompatibility in vitro for the prepared Au-silicate nanoparticles were also investigated. It was shown that at lower concentration (<1 μg/ml), the Au-silicate nanoparticles were biocompatible without causing any cytotoxicity and hemolysis.     

Colorimetric detection of cadmium in water using L-cysteine Functionalized gold–silver nanoparticles

Abstract

A new simple colorimetric assay was developed for the selective and sensitive detection of cadmium (II) in water samples using L-cysteine functionalized gold–silver nanoparticles. The gold–silver nanoparticles were synthesized by reducing HAuCl₄ and AgNO₃ in aqueous medium and were further functionalized with L-cysteine. The formation of homogeneous gold–silver nanoparticles was characterized by transmission electron microscopy, energy-dispersive X-ray spectroscopy, particle size distribution, and ultraviolet–visible absorption methods. In the presence of cadmium (II), the aggregation of functionalized gold–silver nanoparticles caused by the interaction between cadmium (II) and L-cysteine resulted in a naked-eye visible color change of L-cysteine functionalized gold–silver nanoparticles from orange–yellow to green, which can be monitored by a simple ultraviolet–visible spectrophotometer. Under the optimal conditions, the absorbance ratio at 600–435?nm (A₆₀₀/A₄₃₅) was linear to the concentration of cadmium (II) from 0.4 to 38.6?μM, and the limit of detection of cadmium (II) was 44?nM. Interference measurements showed that the method exhibited good selectivity. The proposed method was successfully applied to the determination of cadmium (II) in environmental water samples. The results indicated that this simple, selective, and sensitive sensing system has good potential for practical applications.     

Protein Dimerization on a Phosphonated Calix[6]arene Disc

Complex formation between cationic cytochrome c and the water‐soluble, poly‐anionic p ‐phosphonatocalix[6]arene (pclx₆) was investigated. A crystal structure (at 1.8 Å resolution) revealed a remarkable dimeric disc of pclx₆ that acts like glue to mediate a symmetric (C ₂) protein dimer. The calixarene disc has a diameter of about 1.5 nm and masks about 360 Ų of protein surface. The key protein–calixarene contacts occur via two linchpin lysines, with additional contacts provided by a small hydrophobic patch. The protein–calixarene supramolecular assemblies were observed in solution by size‐exclusion chromatography with multi‐angle light scattering and NMR spectroscopy. Using isothermal titration calorimetry and NMR data, an apparent K _d in the low micromolar range was determined for the charge‐rich protein–calixarene complex. In contrast to p ‐sulfonatocalix[4]arene, the larger pclx₆ has a single, well‐defined binding site that mediates the assembly of cytochrome c in solution.     

Synthesis of gold nanoparticles in sol–gel glass porogens containing [bmim][BF4] ionic liquid

The [bmim][BF₄] ionic liquid effect on gold nanoparticles formation in silica sol–gel materials is studied in order to produce gel-derived glasses with optical properties. The characteristic red color from gold nanoparticles is observed for transparent glass monoliths obtained sintering, between 365 and 425 °C, a silica sol–gel precursor containing HAuCl₄·3H₂O and [bmim][BF₄], under normal atmospheric conditions. The effect of sintering the ionogel at different temperatures (T_sint) or times (t_sint) on the optical properties, shape, size, and distribution of gold nanoparticles is discussed. Presence of the gold particles is observed using transmission electron microscopy images followed by energy dispersive X-ray spectroscopy analysis. The thermal decomposition of [bmim][BF₄] in the ionogel is investigate using calorimetric and spectroscopic techniques, and by analysis of volatile compounds released by the sol–gel material during sintering. With these results a mechanism for the formation of the gold nanoparticles is proposed, where a first ionic liquid degradation step provides the reductive environment that enables the gold nanoparticles production at the range of temperatures between 350 and 425 °C. Upon sintering the synthesized materials the ionic liquid acts as a sacrificial additive and the ionic liquid thermal decomposition products enables the formation of gold nanoparticles in the sol–gel matrix.     

Photochemical synthesis of gold nanoparticles in aqueous dispersions of carboxylated polystyrene

Photochemical synthesis of gold nanoparticles in aqueous dispersions of carboxylated polystyrene with microsphere sizes of 100, 300, 500, and 1410 nm under the action of monochromatic light with an excitation wavelength of 254 nm was studied. Preliminary irradiation of the polymer dispersion induces formation of gold particles under dark conditions. Dependences of gold nanoparticles formation on the duration of preliminary polymer irradiation and concentration of introduced HAuCl₄ aqueous solution were determined. A mechanism of the polystyrene-assisted formation of gold nanoparticles was proposed. The size and structure of gold nanoparticles were determined.     

金纳米粒子自球形向棒状的转变和生长的光化学法研究

在含有HAuCl₄和十六烷基三甲基氯化铵(CTMAC)的DMF-H₂O-丙酮介质中, 以CTMAC形成的胶束为模板, 丙酮为光敏剂, 光化学还原法制备了不同长径比的棒状金纳米粒子. 通过改变DMF∶H₂O (V/V)的比例来改变溶液的极性, 增加胶束聚集数, 实现了自球形胶束向棒状的转变, 从而得到以金纳米棒占优势的金胶体溶液. 研究了HAuCl₄和CTMAC的浓度以及照射时间对金纳米棒生长的影响, 在最佳实验条件下, 获得了直径在20～22 nm, 长为0.5～3 μm的金纳米棒, 讨论了光化学反应和金纳米粒子在形成的棒状胶束中的自组装生长机理.     

Uranyl Microsensor: An Asymmetric Potentiometric Membrane Sensor Based on a New Calix[4]arene

The first asymmetric potentiometric UO₂(II) microsensor is introduced. 5,11,17,23-tetra-tertio butyl(25,27),-bis)2-)n-]2-hydroxy-5-dinitridphenilonitrilidine) amino etoxy(26,28)-di hydroxy calix[4]arene (HAECA) was synthesized. It was found that HAECA can be used as an excellent ionophore in construction of UO₂(II) microsensor. The best performance was obtained with a membrane composition containing 20% PVC, 73% dibutyl phthalate, 5% HAECA, and 2% sodium tetraphenyl borate. The proposed microsensor exhibits a Nernstian slope of 28.5 ± 0.3 mV per decade over a wide concentration range of 1.0 ×10^?10–1.0 × 10^?4 M and a detection limit of 6.0 × 10^?11 M. The potentiometric response of the sensor is independent to the pH of the solution in the range of 2.2–3.6.     

A Label-Free Deoxyribozymes Resonance Rayleigh Scattering Assay for Trace Lead(II) Based on Nanogold Catalysis of Chloroauric Acid-Vitamin C Particle Reaction

In pH 7.2 Tris-HCl buffer solution, the substrate strand DNA (SDNA) was hybridized to the enzyme strand DNA (EDNA) forming a double strand DNA (dsDNA). The SDNA in dsDNA could be cleaved by lead(II) to release a cleavaged single-stranded (ssDNA) that prevented the gold nanoparticles (AuNPs) from forming a stable AuNPs-ssDNA conjugate. The unconjugated AuNPs were aggregated to form AuNP aggregation (AuNPsA) that appeared as a resonance Rayleigh scattering (RS) peak at 532 nm. When the lead(II) concentration increased, the AuNPs-ssDNA increased, the AuNPsA decreased, the color changed from blue to red, and the RS intensity at 532 nm decreased. The decreased RS intensity ΔI _532 nm was linear to the lead(II) concentration in the range of 0.67–60 nmol/L, with a detection limit of 0.3 nmol/L. The AuNPs-ssDNA exhibited a strong catalytic effect on the reaction between chloroauric acid and vitamin C (VC) that can be detected by an RS method at 620 nm. When the lead(II) concentration increased, the intensity at 620 nm increased, and the increased intensity ΔI _620 nm was linear to the lead(II) concentration in the range of 1.33–120 pmol/L, with a detection limit of 0.5 pmol/L. The proposed method was applied to detect lead(II) in water samples, with satisfactory results.     

Biosynthesis of Gold Nanoparticles by Streptomyces sp. ERI-3 Supernatant and Process Optimization for Enhanced Production

In this study, we present a simple and eco-friendly method for extracellular biosynthesis of gold nanoparticles by Streptomyces sp. ERI-3 cell-free supernatant. The research was also aimed to evaluate the effects of different reaction parameters including incubation temperature, reaction time, HAuCl₄ concentration and pH on gold nanoparticles production. The UV?CVis spectroscopy was used to monitor the formation of gold nanoparticles. The synthesized gold nanoparticles were characterized with XRD, TEM, and SEM. The average particle size ranged from 10 to 30?nm with spherical shape at optimum conditions.     

Preparation and nonlinear optical properties of Au nanoparticles doped TiO2 thin films

Nano-sized noble metal nanoparticles doped dielectric composite films with large third-order nonlinear susceptibility due to the confinement and the enhancement of local field were considered to be applied for optical information processing devices, such as optical switch or all optical logical gates. In this paper, sol–gel titania thin films doped with gold nanoparticles (AuNPs, ~10 nm in average size) were prepared. AuNPs were firstly synthesized from HAuCl₄ in aqueous solution at ~60 °C, using trisodium citrate as the reducing agent, polyvinylpyrrolidone as the stable agent; then the particle size and optical absorption spectra of the AuNPs in aqueous solutions were characterized by transmitting electron microscopy and UV–Vis–NIR spectrometry. Sol–gel 2AuNPs–100TiO₂ (in %mol) thin films (5 layers, ~1 μm in thickness) were deposited on silica glass slides by multilayer dip-coating. After heat-treated at 300–1,000 °C in air, the AuNPs–TiO₂ thin films were investigated by X-ray diffraction, scanning electron microscopy and atomic force microscopy. The nonlinear optical properties of the AuNPs–TiO₂ thin films were measured with the Z-scan technique, using a femtosecond laser (200 fs) at the wavelength of 800 nm. The third-order nonlinear refractive index and nonlinear absorption coefficient of 2AuNPs–100TiO₂ films were at the order of 10^?12 cm²/W, and the order of 10^?6 cm/W, respectively, and the third-order optical nonlinear susceptibility χ⁽³⁾ was ~6.88 × 10^?10 esu.     

Synthesis of poly(o-phenylenediamine) hollow spheres and nanofibers using different oxidizing agents

Poly(o-phenylenediamine) (PoPD) hollow spheres (ca. 800 nm in outer diameter) were synthesized by a simple solution route using ammonium persulfate (APS) as the oxidizing agent, whereas PoPD nanofibers (0.5-2 μm in width and more than 100 μm in length) and gold nanoparticles (200-500 nm) were obtained when changing the oxidizing agent of APS to chlorauric acid (HAuCl₄). The chemical structures of PoPD hollow spheres and nanofibers were characterized by FTIR and XRD spectra. When using HAuCl₄ as the oxidizing agent, the products of PoPD nanofibers and gold nanoparticles could be separated by chemical methods. The monomer droplets were proposed to act as template to the formation of polymer hollow spheres while the oriented growth of polymer nanofibers might be catalyzed by gold nanoparticles.     

Formation of submicrometer-scale gold nanoparticle aggregates and their self-organization into “supracrystals”

Nearly spherical, submicrometer-scale gold nanoparticle aggregates about 250 nm in diameter are formed directly from an HAuCl₄-p-phenylenediamine aqueous solution at room temperature. The as-formed aggregates were characterized by various techniques, including scanning electron microscopy, transmission electron microscopy, and X-ray diffraction, and their formation mechanism is discussed. It is very interesting that “supracrystals” can be produced with the use of such gold aggregated nanoparticles. The text was submitted by the author in English.     

A facile approach to synthesize poly(4-vinylpyridine)/multi-walled carbon nanotubes nanocomposites: highly water-dispersible carbon nanotubes decorated with gold nanoparticles

A facile approach to attach high-density and uniform gold nanoparticles on individual multi-walled carbon nanotubes (MWNTs) is achieved. By simple grinding, water-soluble linear polymers poly(4-vinylpyridine) (PVP)-wrapped around nanotubes and thus rendered them reversibly soluble in water, ethanol, and DMF. Individual tubes are clearly observed after PVP-wrapped nanotubes were spin-coated onto a silicon wafer. Subsequently, Au nanoparticles were densely decorated on the individual MWNTs by in situ reduction of HAuCl₄ in the homogeneous aqueous solution of MWNTs–PVP to form stable water-dispersible Au/PVP/MWNTs hybrid. Morphology of Au nanoparticles was determined by scanning electron microscope and atomic force microscope. The diameter of the Au nanoparticles is controlled in the range of 3.5 to 13.5 nm. The presence of gold nanoparticles with decreased particle size was also detected by UV–Vis spectroscopy.     

Dendrimer-based biosensor for chemiluminescent detection of DNA hybridization

We report on a highly sensitive chemiluminescent (CL) biosensor for the sequenc-specific detection of DNA using a novel bio barcode DNA probe modified with gold nanoparticles that were covered with a dendrimer. The modified probe is composed of gold nanoparticles, a dendrimer, the CL reagent, and the DNA. The capture probe DNA was immobilized on magnetic beads covered with gold. It first hybridizes with the target DNA and then with one terminal end of the signal DNA on the barcoded DNA probe. CL was generated by adding H₂O₂ and Co(II) ions as the catalyst. The immobilization of dendrimer onto the gold nanoparticles can significantly enhance sensitivity and gives a detection limit of 6 fmol L^-1 of target DNA.

Gold nanoparticles,capped by carboxy-calix[4]resorcinarenes: effect of structure and concentration of macrocycles on the nanoparticles size and aggregation

Small (d_core?≈?2–5 nm) well-dispersed gold nanoparticles (AuNPs) stabilized by amphiphilic octacarboxy-calix[4]resorcinarenes with different substituents on the lower rim—methyl (С₁–CR), pentyl (С₅–CR) and undecyl (С₁₁–CR)—in an aqueous solution were obtained. The nanoparticles were studied by spectrophotometry, transmission electron microscopy, FTIR-spectroscopy, dynamic light scattering, small angle X-ray scattering and X-ray powder diffraction. The influence of HAuCl₄/macrocycle ratio during the synthesis on the nanoparticles size and aggregation only for weakly associated С₁–CR and С₅–CR was achieved. The self-association effect of С₁₁–CR on the nanoparticles stabilization is found. The existence of gold in the form of crystallites and their average sizes were defined. The average nanoparticle sizes were determined and the structure of macrocyclic shells on the surface of nanoparticles in an aqueous solution was proposed. The formation of cooperative calix[4]resorcinarene associates on the AuNPs surface due to the multiple supramolecular interactions leads to the creation of functional gold nanoparticles.