Step-addition Method for Enhancing the Yield of Gold Nanoparticles in Block Copolymer Solution

Triblock copolymer poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) (PEO-PPO-PEO) has been used to synthesize gold nanoparticles from hydrogen tetrachloroaureate (III) hydrate (HAuCl₄·3H₂O) salt in aqueous solution at room temperature. Measurements were performed using the triblock copolymer Pluronic P85 (EO₂₆PO₃₉EO₂₆) at a fixed concentration (1 wt%) mixed with varying HAuCl₄·3H₂O concentration in the range of 0.001 to 0.1 wt%. The surface plasmon resonance (SPR) band in UV-visible absorption spectra confirmed the formation of the gold nanoparticles. The maximum yield of the nanoparticles was found at 0.005 wt% of the salt solution. Small-angle neutron scattering (SANS) does not show any significant change in the scattering profile in these suspensions of the nanoparticles. A similar behavior was also observed in dynamic light scattering (DLS) experiments where autocorrelation function was found to be independent of the salt concentration. This can be understood since a high-block copolymer-to-gold ion ratio (r ～ 22) is required in the reduction reaction to produce gold particles. As a result, a very small fraction of the block copolymers were associated with the gold nanoparticles, and hence lead to a very low yield. Both SANS and DLS basically see the micelles of most of these block copolymers, which are not associated with nanoparticles. Based on this explanation, a step-addition method was used to enhance the yield of gold nanoparticles by manifold, where the gold salt is added in small steps to maintain higher value of r (>22), and therefore continuous formation of nanoparticles.     

Catalytic properties of gold nanoparticles immobilized on the surfaces of nanocarriers

Gold nanoparticles are immobilized in the hydrophilic coronas of spherical micelle carriers for high catalytic activity. The micelle is formed by self-assembly of block copolymer, polystyrene-b-poly (acrylic acid), in basic aqueous solution (pH 10) and has a polystyrene core and a poly (acrylic acid) corona. The gold nanoparticles are anchored into the poly (acrylic acid) corona by in situ reduction of the mixture of HAuCl₄ and micelle with NaBH₄. The sizes of the gold nanoparticles can be adjusted by changing the content of the HAuCl₄. In the process of catalyzing p-nitrophenol to p-aminophenol, the reaction shows one-order kinetics, furthermore, the reaction rate increases with the concentration of composites as well as reaction temperature. Comparing the composites with polystyrene as core and poly (4-vinylpyridine)/Au as corona, the catalytic activity of the present composites is higher, which is ascribed to their hydrophilic corona structure.     

In-situ formation of silver nanoparticles stabilized by amphiphilic star-shaped copolymer and their catalytic application

Silver nanoparticles (Ag NPs) were prepared via in situ reduction of silver nitrate (AgNO₃) using polymeric micelles as nanoreactors without any additional reductant. The micelles were constructed from the amphiphilic star-shaped copolymer composed of poly(?-caprolactone) (PCL) segment, 2-(dimethylamino)ethyl methacrylate (DMAEMA or DMA) units and oligo(ethylene glycol)monomethyl ether methacrylate (OEGMA or OEG) units. The Ag NPs stabilized by those star-shaped copolymers were characterized using UV-vis spectrum, DLS, TEM and FTIR. It confirmed that PDMAEMA exhibited the reducing property unless pH was above 7. The Ag NPs were sphere-like with a diameter of 10-20 nm, which was independent of the architecture of the copolymer and AgNO₃ concentration. Furthermore, the catalytic activity of these Ag NPs was investigated by monitoring the reduction of p-nitrophenol (4-NP) by NaBH₄. The result showed that the Ag NPs formed by coordination reduction can be effectively applied in catalytic reaction.     

Size control synthesis of starch capped-gold nanoparticles

Metallic gold nanoparticles have been synthesized by the reduction of chloroaurate anions [AuCl₄]⁻ solution with hydrazine in the aqueous starch and ethylene glycol solution at room temperature and at atmospheric pressure. The characterization of synthesized gold nanoparticles by UV–vis spectroscopy, high resolution transmission electron microscopy (HRTEM), electron diffraction analysis, X-ray diffraction (XRD), and X-rays photoelectron spectroscopy (XPS) indicate that average size of pure gold nanoparticles is 3.5 nm, they are spherical in shape and are pure metallic gold. The concentration effects of [AuCl₄]⁻ anions, starch, ethylene glycol, and hydrazine, on particle size, were investigated, and the stabilization mechanism of Au nanoparticles by starch polymer molecules was also studied by FT-IR and thermogravimetric analysis (TGA). FT-IR and TGA analysis shows that hydroxyl groups of starch are responsible of capping and stabilizing gold nanoparticles. The UV–vis spectrum of these samples shows that there is blue shift in surface plasmon resonance peak with decrease in particle size due to the quantum confinement effect, a supporting evidence of formation of gold nanoparticles and this shift remains stable even after 3 months.     

Facile strategy for stability control of gold nanoparticles synthesized by aqueous reduction method

A facile strategy for controlling sizes and stabilities of gold nanoparticles synthesized by aqueous reduction method was experimentally examined and reported. When pH of the solution of HAuCl₄ and Na₃C₆H₅O₇ was controlled by introducing either NaOH or HCl with different concentration, the zeta potential of suspension of gold nanoparticles changed accordingly. With the strategy using a control of pH in a range of 5–9, the zeta potential of synthesized gold nanoparticles was regulated in a range of −60 to −40 mV, resulting in a stable red suspension of gold nanoparticles. Under a condition with pH < 5.0, gold nanoparticles could agglomerate after being kept quiescently for a day due to an adsorption of H⁺ on their surface, which in turn enhanced the attractive van der Waals interaction. On the other hand, synthesis of gold nanoparticles with pH > 9.1 would provide a lower amount of gold nanoparticles due to the formation of NaAuO₂. Based on these results, a potential mechanism of gold nanoparticle synthesis was also discussed.     

Shape-controlled Synthesis of Gold Nanoparticles from Gold(III)-chelates of β-diketones

Chelating ligands with β-diketone skeleton have been employed for the first time as reductant to produce ligand stabilized gold nanoparticles of different shapes out of aqueous HAuCl₄ solutions. Evolution of stable gold nanoparticles happens to be first order with respect to gold particles having rate constants ∼ ∼10⁻² min⁻¹ and subsequent chlorine insertion in the β-diketone skeleton is reported as a general feature. Spherical or triangular or hexagonal particle evolution goes selectively under the influence of different β-diketones in terms of capping and reducing capabilities of the reductants.     

Ultrasound-assisted green synthesis of gold nanoparticles using citrus peel extract and their enhanced anti-inflammatory activity

Ultrasound and plant extract are two green approaches that have been used to synthesize gold nanoparticles (AuNPs); however, how the combination of ultrasound and citrus peel extract (CPE) affects the structure characteristics and the bioactivity of AuNPs remains unknown. Here we investigated the effects of ultrasound conditions on the particle size, stability, yield, phenolic encapsulation efficacy, and the anti-inflammatory activity of AuNPs. The results showed that temperature was positively correlated to the particle size and the anti-inflammatory activity of synthesized AuNPs. Increasing the power intensity significantly decreased the particle size, while increased the change of total phenolic content (ΔTPC) in the reaction mixture. The increase of ΔTPC caused the enhanced anti-inflammatory activity of AuNPs. The AuNPs synthesized with or without ultrasound treatment were characterized using UV–Vis, DLS, SEM, TEM, EDS, XRD, and FT-IR. The result verified the formation of negatively charged, spherical, stable, and monodispersed AuNPs. AuNPs synthesized with ultrasound (AuNPs-U) has smaller particle size (13.65 nm vs 16.80 nm), greater yield and anti-inflammatory activity (IC₅₀, 82.91 vs 157.71 μg/mL) than its non-ultrasound counterpart (AuNPs-NU). HPLC analysis showed that hesperidin was the key reductant for the synthesis of AuNPs. AuNPs-U also inhibited the mRNA and protein expression of iNOS and COX-2 in the LPS-induced Raw 264.7 cells. Our research elucidates the relationship between the reaction conditions and the structure characteristics and the anti-inflammatory activity of AuNPs synthesized using CPE with the help of ultrasound, thereafter, provides a feasible and economic way to synthesize AuNPs that can be used to ameliorate inflammation.     

Phyllanthin-assisted biosynthesis of silver and gold nanoparticles: a novel biological approach

Abstract  The anisotropic gold and spherical–quasi-spherical silver nanoparticles (NPs) were synthesized by reducing aqueous chloroauric acid (HAuCl₄) and silver nitrate (AgNO₃) solution with the extract of phyllanthin at room temperature. The rate of reduction of HAuCl₄ is greater than the AgNO₃ at constant amount of phyllanthin extract. The size and shape of the NPs can be controlled by varying the concentration of phyllanthin extract and thereby to tune their optical properties in the near-infrared region of the electromagnetic spectrum. The case of low concentration of extract with HAuCl₄ offers slow reduction rate along with the aid of electron-donating group containing extract leads to formation of hexagonal- or triangular-shaped gold NPs. Transmission electron microscopy (TEM) analysis revealed that the shape changes on the gold NPs from hexagonal to spherical particles with increasing initial concentration of phyllanthin extract. The Fourier transform infrared spectroscopy and thermogravimetric analyses reveal that the interaction between NPs and phyllanthin extract. The cyclic voltammograms of silver and gold NPs confirms the conversion of higher oxidation state to zero oxidation state. Graphical abstract  Anisotropic gold and silver nanoparticles were synthesized by a simple procedure using phyllanthin extract as reducing agent. The rate of bioreduction of AgNO₃ is lower than the HAuCl₄ at constant concentration of phyllanthin extract. The required size of the nanoparticles can be prepared by varying the concentration of phyllanthin with AgNO₃ and HAuCl₄.      

Increasing the stability of DNA-functionalized gold nanoparticles using mercaptoalkanes

In this work, the stability of DNA functionalized gold nanoparticles was examined in relation to their size, temperature, as well as the presence of mono- and bivalent ions. Furthermore, we report on the stabilizing effect of an additional post-functionalization with mercaptoalkanes, optionally bearing triethylene glycol (TEG) units. Although such so-called backfilling molecules are commonly used for planar gold surfaces, they have rarely been reported in combination with DNA-functionalized nanoparticles. Our results show that, conform the DLVO theory, smaller citrate-capped gold nanoparticles were more stable towards higher concentrations of salt. Citrate nanoparticles of 30 nm in size were only stable in sodium chloride concentrations up to ~0.05 M and up to 45 °C. The stability of these uncoated nanoparticles was even lower when bivalent salts were used (i.e. <2 × 10⁻⁴ M). Immobilization of DNA on these nanoparticles, on the other hand, improved the stability in salt solutions with at least one order of magnitude. The additional use of backfilling molecules stabilized the gold nanoparticles even further, without negatively affecting the DNA hybridization efficiency. DNA functionalization also had a positive impact on the thermal stability of the nanoparticles. Unfortunately, this beneficial effect was not observed after a subsequent backfilling step.

     

General approach for fabricating nanoparticle arrays via patterned block copolymer nanoreactors

A general approach to fabricate nanoparticle arrays of different kinds of materials is demonstrated in this paper. It was found that the center-to-center distance of the nanoparticles or the nanoclusters can be controlled using patterned block copolymer nanoreactors by adding polystyrene (PS) homopolymer to poly(styrene-b-4-vinylpyridine) (PS-b-P4VP) diblock copolymer thin film. The number of the nanoparticles formed in the P4VP nanodomains can also be adjusted by addition of polystyrene (PS) homopolymer to poly(styrene-b-4-vinylpyridine) (PS-b-P4VP) diblock copolymer. In fabrication of Au nanoparticle arrays, HAuCl₄ precursor was directly loaded into P4VP nanodomains of the diblock copolymer thin film by using a methanol solvent, which is a good solvent for P4VP but non-solvent for PS. The Au nanoparticle arrays were then obtained by reducing HAuCl₄ with sodium citrate dihydrate, and then in situ transferred to silicon substrate by a two-step calcination method. ZnO and Fe _x O _y nanoparticle arrays were also synthesized by this approach with thermal decomposition and double decomposition reactions, respectively. Additionally, the advantage of using two-step calcination method over the air plasma method was discussed.     

High yield preparation of silver nanowires by CuCl2-mediated polyol method and application in semitransparent conduction electrode

High yield preparation of silver nanowires (AgNWs) was prepared by polyol method. In this developed polyol process, uniform AgNWs have been successfully synthesized at higher yield by introducing CuCl₂·2H2O, when ethylene glycol is used as the solvent and reductant while poly vinyl pyrrolidone (PVP) is used as the capper agent. Then Ag thin films were made by screen printing using silver nanowires and nanoparticles as semitransparent conduction electrodes. The test results indicated that the electrical resistivity could be as low as 0.091 Ω/□, when the transparence rate can reach 45–46%, which shows great promise in the improvement of conductive antireflection coating.     

Pseudo-template synthesis of gold nanoparticles based on polyhydrosilanes

Highly stable colloidal gold nanoparticles are obtained in a pseudo-template system using a specific polyhydrosilane copolymeric structure. This process takes place in situ by microwaves activation of the polymer solution in a non-polar solvent followed by stirring with solid HAuCl₄ in natural light. The experimental procedure is very simple and the resulted colloidal gold solution is indefinitely stable. The specific surface plasmon resonance absorption band of the gold nanoparticles is strongly red shifted and is strictly related to their size. AFM correlated with DLS analysis showed flattened round shaped colloidal polymer-gold nanoparticles with large diameters. SEM-EDX combined analysis reveals that the polysilane-gold nanoparticles show a natural tendency to auto-assemble in close packed structures which form large areas over the polymer film surface.     

Patterning of gold nano-octahedra using electron irradiation combined with thermal treatment and post-cleaning process

A novel approach to pattern nanocrystalline gold (Au) octahedra is presented based on electron irradiation combined with thermal treatment and post-cleaning process using HAuCl₄-loaded poly(styrene-b-2-vinyl pyridine) (PS-b-P2VP) block copolymer (BCP) as a precursor material. The BCP tends to cross-link under electron irradiation, and thus a patterned film can be prepared by selectively irradiating an electron beam onto a precursor film using a shadow mask. A post-thermal treatment leads to the formation of crystalline Au nano-octahedra inside the patterned film with a help of the BCP acting as a capping agent. Subsequently, the BCP can be removed by O₂ plasma etching combined with oxidative degradation, with the Au nanoparticles remaining. As a result, a patterned film consisting of high-purity nanocrystalline Au octahedra is fabricated. The sizes of the Au octahedral nanoparticles can be readily controlled from 49 to 101 nm by changing the thickness of the precursor film. The patterned Au nano-octahedra films exhibit excellent surface-enhanced Raman scattering behavior with the maximum enhancement factor of ~10⁶.     

Green synthesis of gold and silver nanoparticles using gallic acid: catalytic activity and conversion yield toward the 4-nitrophenol reduction reaction

In the present report, gallic acid was used as both a reducing and stabilizing agent to synthesize gold and silver nanoparticles. The synthesized gold and silver nanoparticles exhibited characteristic surface plasmon resonance bands at 536 and 392 nm, respectively. Nanoparticles that were approximately spherical in shape were observed in high-resolution transmission electron microscopy and atomic force microscopy images. The hydrodynamic radius was determined to be 54.4 nm for gold nanoparticles and 33.7 nm for silver nanoparticles in aqueous medium. X-ray diffraction analyses confirmed that the synthesized nanoparticles possessed a face-centered cubic structure. FT-IR spectra demonstrated that the carboxylic acid functional groups of gallic acid contributed to the electrostatic binding onto the surface of the nanoparticles. Zeta potential values of ?41.98 mV for the gold nanoparticles and ?53.47 mV for the silver nanoparticles indicated that the synthesized nanoparticles possess excellent stability. On-the-shelf stability for 4 weeks also confirmed that the synthesized nanoparticles were quite stable without significant changes in their UV–visible spectra. The synthesized nanoparticles exhibited catalytic activity toward the reduction reaction of 4-nitrophenol to 4-aminophenol in the presence of sodium borohydride. The rate constant of the silver nanoparticles was higher than that of the gold nanoparticles in the catalytic reaction. Furthermore, the conversion yield (%) of 4-nitrophenol to 4-aminophenol was determined using reversed-phase high-performance liquid chromatography with UV detection at 254 nm. The silver nanoparticles exhibited an excellent conversion yield (96.7–99.9 %), suggesting that the synthesized silver nanoparticles are highly efficient catalysts for the 4-nitrophenol reduction reaction.     

Silica-coated manganite and Mn-based ferrite nanoparticles: a comparative study focused on cytotoxicity

Magnetic oxide nanoparticles provide a fascinating tool for biological research and medicine, serving as contrast agents, magnetic carriers, and core materials of theranostic systems. Although the applications rely mostly on iron oxides, more complex oxides such as perovskite manganites may provide a much better magnetic performance. To assess the risk of their potential use, in vitro toxicity of manganite nanoparticles was thoroughly analysed and compared with another prospective system of Mn–Zn ferrite nanoparticles. Magnetic nanoparticles of La_0.63Sr_0.37MnO₃ manganite were prepared by two distinct methods, namely the molten salt synthesis and the traditional sol–gel route, whereas nanoparticles of Mn_0.61Zn_0.42Fe_1.97O₄ ferrite, selected as a comparative material, were synthesized by a new procedure under hydrothermal conditions. Magnetic cores were coated with silica and, moreover, several samples of manganite nanoparticles with different thicknesses of silica shell were prepared. The size-fractionated and purified products were analysed using transmission electron microscopy, dynamic light scattering, measurement of the zeta-potential dependence on pH, IR spectroscopy, and SQUID magnetometry. The silica-coated products with accurately determined concentration by atomic absorption spectroscopy were subjected to a robust evaluation of their cytotoxicity by four different methods, including detailed analysis of the concentration dependence of toxicity, analysis of apoptosis, and experiments on three different cell lines. The results, comparing two manganese-containing systems, clearly indicated superior properties of the Mn–Zn ferrite, whose silica-coated nanoparticles show very limited toxic effects and thus constitute a promising material for bioapplications.     

A novel method of nanocrystal fabrication based on laser ablation in liquid environment

Metal nanoparticles can be prepared by a novel technique that consists of the laser ablation of a solid target immersed in a water solution of a metal salt. Silicon was chosen as the most adequate target to synthesize silver and gold nanoparticles from a water solution of either AgNO₃ or HAuCl₄. The influence of both the silver nitrate concentrations and the irradiation time of the Si target on the optical properties of the Au and Ag nanoparticles have been investigated. The crystalline nature of the metal nanoparticles has been determined by X-ray diffraction (XRD). Average size and particle size distribution have been measured by means of TEM. The absorbance spectra show the characteristic band of the surface resonant plasmon of silver and gold nanoparticles.     

Synthesis of AuNPs@RGO nanosheets for sustainable catalysis toward nitrophenols reduction

A facile, green and one-pot synthesis strategy for the convenient preparation of well-dispersed gold nanoparticles (AuNPs) decorated reduced graphene oxide (RGO) without using any other toxic chemicals and reductants is reported herein. The synthesized AuNPs@RGO hybrid nanomaterials were characterized by UV–visible absorption spectroscopy, FT-IR, XRD, Raman, SEM, TEM and EDX analysis. The AuNPs@RGO acts as an efficient catalyst for the reduction of organic nitroaromatics (2- & 4-nitro phenols) in the presence of NaBH₄. This newly synthesized hybrid AuNPs@RGO has superior catalytic activity over any other Au-nanomaterials ever reported. The rate of nitro aromatics reduction is found to be dependent on concentrations of substrate, reductant and catalyst. The mechanisms for the synthesis and catalytic reduction have been studied and discussed.     

Preparation and characterization of Co–Pt bimetallic magnetic nanoparticles

CoPt₃ nanoparticles are synthesized by a two-stage route using NaBH₄ as a reductant. The nanoparticles are characterized by thermogravimetry (TG) and differential thermal analysis (DTA), Fourier transform infrared (FT-IR), transmission electron microscopy (TEM) and X-ray diffraction (XRD). Structural and spectroscopic studies show that the nanoparticles adopt a face-centered-cubic (FCC) crystalline structure with an average particle size of 2.6 nm. SQUID studies reveal that as-synthesized nanoparticles are superparamagnetic at room temperature and ferromagnetic at 1.85 K with coercivity of 980 Oe. Annealing of the samples at 500 °C causes an increase of particle size and a decrease of coercivity.     

Preparation of Gold/triblock Copolymer Composite Nanoparticles

A kind of novel gold (Au)/hydroxylated poly (styrene-b-butadiene-b-styrene) triblock copolymer (HO-SBS) composite nanoparticles was synthesized by reduction of tetrachloroaurate ions in HO-SBS micelle. The Au–HO-SBS composite nanoparticles are composed by gold core about 35 nm in diameter and polymer shell about 7 nm in thickness. Formation of the Au/HO-SBS nanoparticles is indentified by infrared (IR) and UV-visible absorption spectroscopies. Transmission electron microscopy (TEM) result shows that the composite nanoparticles tend to aggregate into an ordered hexagonal array on carbon-coated grid.     

An isothermal titration calorimetry study of the interactions between an oxyphenylethylene/oxyethylene diblock copolymer and sodium dodecyl sulfate

Interactions between the diblock copolymer S₁₅E₆₃ and the surfactant sodium dodecyl sulfate (SDS) have been investigated by isothermal titration calorimetry (ITC) in the temperature range 10–40°C. At 20°C, the block copolymer is associated into micelles with a hydrodynamic radius of 11.6?nm, which is composed of a hydrophobic styrene oxide (S) core and a water-swollen oxypolyethylene (PEO) corona. The copolymer/surfactant system has been studied at a constant copolymer concentration of 0.25?wt% and over a wide range of surfactant concentration, from 7.5?×?10^?6 up to 0.3?M. The titration calorimetric data for SDS in the temperature range 10–20°C presents a first endothermic increase indicating the formation of mixed copolymer rich-surfactant micelles. From that point, important differences in the ITC plots for surfactant titrations in the presence and in the absence of the copolymer are present. A shallow second endothermic peak is assigned to the interaction between SDS molecules and copolymer molecules resulting from the beginning of micelle disruption. An exothermic peak indicates the end of this disruption where only SDS micelles attached to single copolymer monomers are present, as shown by DLS in a previous paper. At higher temperatures in the range 25–40°C, the first endothermic maximum is not totally shown because interactions between surfactant and block copolymer start at very low SDS concentrations. Moreover, the second endothermic peak is absent and the exothermic minimum is less pronounced as a consequence of the increased micellization of the block copolymer.