Room-temperature synthesis of gold nanoparticles and nanoplates using Shewanella algae cell extract

Biosynthesis of spherical gold nanoparticles and gold nanoplates was achieved at room temperature and pH 2.8 when cell extract from the metal-reducing bacterium Shewanella algae was used as both a reducing and shape-controlling agent. Cell extract, prepared by sonicating a suspension of S. algae cells, was capable of reducing 1 mol/m³ aqueous AuCl₄ ⁻ ions into elemental gold within 10 min when H₂ gas was provided as an electron donor. The time interval lapsed since the beginning of the bioreductive reaction was found to be an important factor in controlling the morphology of biogenic gold nanoparticles. After 1 h, there was a large population of well-dispersed, spherical gold nanoparticles with a mean size of 9.6 nm. Gold nanoplates with an edge length of 100 nm appeared after 6 h, and 60% of the total nanoparticle population was due to gold nanoplates with an edge length of 100–200 nm after 24 h. The yield of gold nanoplates prepared with S. algae extract was four times higher than that prepared with resting cells of S. algae. The resulting biogenic gold nanoparticle suspensions showed a large variation in color, ranging from pale pink to purple due to changes in nanoparticle morphology.     

Rapid extra-/intracellular biosynthesis of gold nanoparticles by the fungus <Emphasis Type="Italic">Penicillium</Emphasis> sp.

In this work, the fungus Penicillium was used for rapid extra-/intracellular biosynthesis of gold nanoparticles. AuCl₄ ⁻ ions reacted with the cell filtrate of Penicillium sp. resulting in extracellular biosynthesis of gold nanoparticles within 1 min. Intracellular biosynthesis of gold nanoparticles was obtained by incubating AuCl₄ ⁻ solution with fungal biomass for 8 h. The gold nanoparticles were characterized by means of visual observation, UV–Vis absorption spectroscopy, X-ray diffraction (XRD), transmission electron microscopy (TEM), scanning electron microscopy (SEM), and energy-dispersive X-ray spectroscopy (EDX). The extracellular nanoparticles exhibited maximum absorbance at 545 nm in UV–Vis spectroscopy. The XRD spectrum showed Bragg reflections corresponding to the gold nanocrystals. TEM exhibited the formed spherical gold nanoparticles in the size range from 30 to 50 nm with an average size of 45 nm. SEM and TEM revealed that the intracellular gold nanoparticles were well dispersed on the cell wall and within the cell, and they are mostly spherical in shape with an average diameter of 50 nm. The presence of gold was confirmed by EDX analysis.     

Precipitation of gold nanoparticles on the quartz surface modified by titanium (IV) butoxide

Gold nanoparticles have been precipitated on the surface of quartz slides covered with titanium (IV) butoxide. UV irradiation of modified quartz slides immersed into water solutions of hydrogen tetrachloroaurate of different concentrations (2.5 × 10⁻⁴–1.0 × 10⁻² M) has been used for this purpose. Properties of produced samples have been investigated by UV–Vis spectroscopy, IR spectroscopy, SEM-EDX, TGA, and AFM. According to the obtained data, produced gold particles are distributed on modified quartz surface very uniformly and the average size of gold particles is about 30–50 nm.     

Laser-induced growth and reformation of gold and silver nanoparticles

The sizes, shapes, and growth rates of gold and silver nanoparticles stabilized with polyvinylpyrrolidone in water can be controlled by using picosecond laser pulses. The nucleation of small metal clusters formed with NaBH₄ addition to produce nanoparticles takes two months with aging but 30 min with laser irradiation. Laser pulses can also induce nanoparticles to have narrow size and shape distribution or to undergo aggregation into much larger particles. The latter process is more likely found when the metal is silver or the irradiation wavelength is short. Laser-induced growth and shape transformation processes are explained in terms of BH₄ ⁻ depletion, metal fusion, and electron ejection followed by disintegration.     

Facile fabrication and optical property of β-Bi<Subscript>2</Subscript>O<Subscript>3</Subscript> with novel porous nanoring and nanoplate superstructures

Novel β-Bi₂O₃ crystals with nanoring and nanoplate surperstructures, which are composed of porous nanoparticles with mean pore diameter of 8 nm, were produced via a facile soft chemistry route of solvent refluxing technique. Most of the rings have the average inner diameter of 200 nm and the mean rim thickness of 20 nm. Photoluminescence spectra of the nanorings at room temperature were investigated, which demonstrated that the rings presented excellent optical properties. The influence of aging time on the morphology and structure of β-Bi₂O₃ superstructures was also studied, indicating that the nanoring superstructures transformed into nanoplates after a long aging time. The formation mechanism of the β-Bi₂O₃ superstructures was also explored. This approach will be further extended to solvent-controlled fabrication of related oxides with novel complex superstructures.     

Synthesis of hydrophobic gold nanoclusters: growth mechanism study,luminescence property and catalytic application

One-pot synthesis of well dispersed, size-controlled gold nanoparticles with the average size of 10–15 nm and luminescent gold nanoclusters with average size of 1.7–2.0 nm were successfully achieved by thermal decomposition of gold organometallic precursor CH₃AuPPh₃ in the presence of thiol surfactants in o-xylene. Only difference between the preparations of two types of Au nanoparticles is the amount of thiol surfactant employed. The mechanistic study of formation of gold nanoparticles was carried out by analyzing the samples at different reaction time intervals and revealed that two-staged growth process was involved. The nanoclusters showed strong red emission with the maximum intensity at about 600 nm. The maximum room temperature photoluminescence quantum yield was measured as 1.2%. The catalytic ability of the Au nanoclusters to promote Suzuki–Miyaura coupling involving the C–C bond formation was also investigated.     

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.      

Ferritin as a photocatalyst and scaffold for gold nanoparticle synthesis

The ferrihydrite mineral core of ferritin is a semi-conductor capable of catalyzing oxidation/reduction reactions. This report shows that ferritin can photoreduce AuCl₄ ⁻ to form gold nanoparticles (AuNPs). An important goal was to identify innocent reaction conditions that prevented formation of AuNPs unless the sample was illuminated in the presence of ferritin. TRIS buffer satisfied this requirement and produced AuNPs with spherical morphology with diameters of 5.7 ± 1.6 nm and a surface plasmon resonance (SPR) peak at 530 nm. Size-exclusion chromatography of the AuNP–ferritin reaction mixture produced two fractions containing both ferritin and AuNPs. TEM analysis of the fraction close to where native ferritin normally elutes showed that AuNPs form inside ferritin. The other peak eluted at a volume indicating a particle size much larger than ferritin. TEM analysis revealed AuNPs adjacent to ferritin molecules suggesting that a dimeric ferritin–AuNP species forms. We propose that the ferritin protein shell acts as a nucleation site for AuNP formation leading to the AuNP-ferritin dimeric species. Ferrihydrite nanoparticles (~10 nm diameter) were unable to produce soluble AuNPs under identical conditions unless apo ferritin was present indicating that the ferritin protein shell was essential for stabilizing AuNPs in aqueous solution.     

Fabrication of magnetic gold nanorod particles for immunomagnetic separation and SERS application

The preparation and application of rod-shaped core–shell structured Fe₃O₄–Au nanoparticles for immunomagnetic separation and sensing were described for the first time with this study. To synthesize magnetic gold nanorod particles, the seed-mediated synthetic method was carried out and the resulting nanoparticles were characterized with transmission electron microscopy (TEM), ultraviolet visible spectroscopy (UV–Vis), energy-dispersive X-ray (EDX), and X-ray diffraction (XRD). Magnetic properties of the nanoparticles were also examined. Characterization of the magnetic gold nanorod particles has proven that the resulting nanoparticles were composed of Fe₃O₄ core and the gold shell. The rod-shaped gold-coated iron nanoparticles have an average diameter of 16 ± 2 nm and an average length of about 50 ± 5 nm (corresponding aspect ratio of 3). The saturation magnetization value for the magnetic gold nanorod particles was found to be 37 emu/g at 300 K. Rapid and room temperature reaction synthesis of magnetic gold nanorod particles and subsequent surface modification with E. coli antibodies provide immunomagnetic separation and SERS application. The analytical performance of the SERS-based homogenous sandwich immunoassay system with respect to linear range, detection limit, and response time is also presented.     

Organic-phase synthesis of self-assembled gold nanosheets

Amphiphilic gold nanoclusters with the diameter of 1.8 ± 0.2 nm were prepared by decomposition of organometallic gold precursor CH₃AuPPh₃ in the presence of mercaptoacids in o-xylene. Self-assembly of the 16-mercaptohexadecanoic acid protected gold clusters led to the formation of the nanosheets consisted of aligned gold clusters. The hydrogen bonding between the carboxylic groups attached on the adjacent gold clusters likely drives the self-assembly. This phenomenon was cross-verified by employing the preheated mercaptoacid-amine surfactant system where a part of the mercaptoacids and amines were converted into –NH₃ ⁺–⁻OOC– ion pair and interrupting a part of the hydrogen bonding sites to lead to the reduction in the size of the structures from nanosheets to nanobelts. Interestingly, we found the dependency of the luminescent properties on the extent of maintaining the self-assembly of the clusters intern dictated by the surfactants.     

A simple route to prepare stable hydroxyapatite nanoparticles suspension

A simple ultrasound assisted precipitation method with addition of glycosaminoglycans (GAGs) is proposed to prepare stable hydroxyapatite (HAP) nanoparticles suspension from the mixture of Ca(H₂PO₄)₂ solution and Ca(OH)₂ solution. The product was characterized by XRD, FT-IR, TEM, HRTEM and particle size, and zeta potential analyzer. TEM observation shows that the suspension is composed of 10–20 nm × 20–50 nm short rod-like and 10–30 nm similar spherical HAP nanoparticles. The number-averaged particle size of stable suspension is about 30 nm between 11.6 and 110.5 nm and the zeta potential is −60.9 mV. The increase of stability of HAP nanoparticles suspension mainly depends on the electrostatic effect and steric effect of GAGs. The HAP nanoparticles can be easily transported into the cancer cells and exhibit good potential as gene or drug carrier system.     

Silica coating of Co–Pt alloy nanoparticles prepared in the presence of poly(vinylpyrrolidone)

This article describes a method for silica coating of Co–Pt alloy nanoparticles prepared in the presence of poly(vinylpyrrolidone) (PVP) as a stabilizer. The Co–Pt nanoparticles were prepared in an aqueous solution at 25–80 °C from CoCl₂ (3.0 × 10⁻⁴ M), H₂PtCl₆ (3.0 × 10⁻⁴ M), PVP (0–10 g/L), and NaBH₄ (4.8 × 10⁻³–2.4 × 10⁻² M). The silica coating was performed for the Co–Pt nanoparticle colloid containing the PVP ([Co] = [Pt] = 3.0 × 10⁻⁵ M) at 25 °C in (1/4) (v/v) water/ethanol solution with tetraethoxyorthosilicate (TEOS) (7.2 × 10⁻⁵–7.2 × 10⁻³ M) and ammonia (0.1–1.0 M). Silica particles, which had an average size of 43 nm and contained multiple cores of Co–Pt nanoparticles with a size of ca. 8 nm, were produced at 1.4 × 10⁻³ M TEOS and 0.5 M ammonia after the preparation of Co–Pt nanoparticles at 80 °C, 5 g/L PVP, and 2.4 × 10⁻² M NaBH₄. Their core particles were fcc Co–Pt alloy crystallites. Their saturation magnetization was 2.0-emu/g sample, and their coercive field was 12 Oe.     

Shape evolution of gold nanoparticles

The tetraoctylammonium bromide-stabilized gold nanoparticles have been successfully fabricated. The shape evolution of these nanoparticles under different annealing temperatures has been investigated using high-resolution transmission electron microscopy. After an annealing at 100 °C for 30 min, the average diameters of the gold nanoparticles change a little. However, the shapes of gold nanoparticles change drastically, and facets appear in most nanoparticles. After an annealing at 200 °C for 30 min, not only the size but also the shape changes a lot. After an annealing at 300 °C for 30 min, two or more gold nanoparticles coalesce into bigger ones. In addition, because of the presence of Cu grid during the annealing, some gold particles become the nucleation sites of Cu₂O nanocubes, which possess a microstructure of gold-particle core/Cu₂O shell. These Au/Cu₂O heterostructure nanocubes can only be formed at a relatively high temperature (≥300 °C). The results can provide some insights on controlling the shapes of gold nanoparticles.     

Thermo- and pH-responsive hydrogel-coated gold nanoparticles prepared from rationally designed surface-confined initiators

Gold nanoparticles (~40 nm in diameter) were encapsulated by a hydrogel overlayer generated by the free radical polymerization of N-isopropylacrylamide-co-acrylic acid (NIPAM-co-AA), which was promoted by a specifically designed radical initiator covalently anchored to the surface of the gold core. The size and morphology of the shell/core nanoparticles were characterized by scanning electron microscopy and transmission electron microscopy. In addition, the optical properties of the nanoparticles were characterized by UV–Visible spectroscopy. Separately, the particle size was evaluated as a function of temperature and pH using dynamic light scattering. The shell/core hydrogel nanoparticles undergo reversible volume changes in water at a lower critical solution temperature (LCST) of ~34 °C as well as at pH values between 3 and 4. The unique composition and properties of these shell/core hydrogel nanoparticles make them attractive for use as nanoscale drug-delivery vehicles.     

Use of a silver ion selective electrode to assess mechanisms responsible for biological effects of silver nanoparticles

For a detailed analysis of the biological effects of silver nanoparticles, discrimination between effects related to the nano-scale size of the particles and effects of released silver ions is required. Silver ions are either present in the initial particle dispersion or released by the nanoparticles over time. The aim of this study is to monitor the free silver ion activity {Ag⁺} in the presence of silver nanoparticles using a silver ion selective electrode. Therefore, silver in the form of silver nanoparticles, 4.2 ± 1.4 nm and 2–30 nm in size, or silver nitrate was added to cell culture media in the absence or presence of A549 cells as a model for human type II alveolar epithelial cells. The free silver ion activity measured after the addition of silver nanoparticles was determined by the initial ionic silver content. The p {Ag⁺} values indicated that the cell culture media decrease the free silver ion activity due to binding of silver ions by constituents of the media. In the presence of A549 cells, the free silver ion activity was further reduced. The morphology of A549 cells, cultivated in DME medium containing 9.1% (v/v) FBS, was affected by adding AgNO₃ at concentrations of ≥30 μM after 24 h. In comparison, silver nanoparticles up to a concentration of 200 μM Ag did not affect cellular morphology. Our experiments indicate that the effect of silver nanoparticles is mainly mediated by silver ions. An effect of silver on cellular morphology was observed at p {Ag⁺} ≤ 9.2.     

Toxicity of amorphous silica nanoparticles in mouse keratinocytes

The present study was designed to examine the uptake, localization, and the cytotoxic effects of well-dispersed amorphous silica nanoparticles in mouse keratinocytes (HEL-30). Mouse keratinocytes were exposed for 24 h to various concentrations of amorphous silica nanoparticles in homogeneous suspensions of average size distribution (30, 48, 118, and 535 nm SiO₂) and then assessed for uptake and biochemical changes. Results of transmission electron microscopy revealed all sizes of silica were taken up into the cells and localized into the cytoplasm. The lactate dehydrogenase (LDH) assay shows LDH leakage was dose- and size-dependent with exposure to 30 and 48 nm nanoparticles. However, no LDH leakage was observed for either 118 or 535 nm nanoparticles. The mitochondrial viability assay (MTT) showed significant toxicity for 30 and 48 nm at high concentrations (100 μg/mL) compared to the 118 and 535 nm particles. Further studies were carried out to investigate if cellular reduced GSH and mitochondria membrane potential are involved in the mechanism of SiO₂ toxicity. The redox potential of cells (GSH) was reduced significantly at concentrations of 50, 100, and 200 μg/mL at 30 nm nanoparticle exposures. However, silica nanoparticles larger than 30 nm showed no changes in GSH levels. Reactive oxygen species (ROS) formation did not show any significant change between controls and the exposed cells. In summary, amorphous silica nanoparticles below 100 nm induced cytotoxicity suggest size of the particles is critical to produce biological effects.     

Domain state–dependent magnetic formation of Fe<Subscript>3</Subscript>O<Subscript>4</Subscript> nanoparticles analyzed via magnetic resonance

Magnetic properties, arising from surface exchange and interparticle interactions of the Fe₃O₄ (magnetite) nanoparticles, were investigated in the temperature range of 5–300 and 120–300 K using vibrating sample magnetometer technique and electron spin resonance spectroscopy, respectively. The research was based on to figure out the origin of intraparticle interactions and the change of interparticle interactions in wide size range Fe₃O₄ nanoparticles. The analyses were done for samples having almost same particle size distributions. The average particle sizes were changed in between 30 ± 2 and 34 ± 2 nm. The observed magnetization values were demonstrated the mixture of single-domain size particles, exhibiting both single-domain (SD) and superparamagnetic (SPM) states. The symmetry of resonance curves changed according to the ratio of SD and SPM-stated particles in mixture under located temperature. The changes of anisotropy up to domain state were understood by freezing magnetic moment in glycerol matrix from room temperature to 120 K under 5-kG field. The shift of H _R values to higher magnetic fields and the more symmetric resonance spectrum proved the effect of anisotropy and interparticle interactions fields on magnetic behave. In addition, the origin of intra-interaction was exposed from Fe³⁺ centers and exchange coupling in between Fe²⁺, Fe³⁺, and O⁻, and Fe³⁺ centers found from g factor (g).     

Methoxycarbonyl-terminated hyperbranched poly(amine-ester) as templates for synthesis of silver nanoparticles

Highly stable and spherical silver nanoparticles, stabilized by methoxycarbonyl-terminated hyperbranched poly(amine-ester) (HPAE-COOCH₃), were synthesized in water with reducing AgNO₃/HPAE-COOCH₃ using two methods, viz. NaBH₄ and ultraviolet irradiation. HPAE-COOCH₃ was found to play a key role in the formation of nanoparticles. UV–visible absorption, Transmission electron microscopic (TEM), and Fourier transform infrared spectroscopy (FT-IR) had been used to study the structure and characterization of the silver nanoparticles. The absorption peaks of the silver nanoparticles appear at ~420 nm in UV–visible absorption spectra; average particle size reduced by NaBH₄ is ~30 nm, which is ~10 and ~15 nm, respectively, when ultraviolet irradiation time is 12 and 24 h. FT-IR spectra confirm that there is strong interaction between silver nanoparticles and HPAE-COOCH₃. And silver nanoparticles/HPAE-COOCH₃ aqueous solution can keep stable for more than 3 months.     

Diffraction patterns and nonlinear optical properties of gold nanoparticles

Stable gold nanoparticles have been prepared by using soluble starch as both the reducing and stabilizing agents; this reaction was carried out at 40 °C for 5 h. The obtained gold nanoparticles were characterized by UV–Vis absorption spectroscopy, transmission electron microscopy (TEM) and z-scan technique. The size of these nanoparticles was found to be in the range of 12–22 nm as analyzed using transmission electron micrographs. The optical properties of gold nanoparticles have been measured showing the surface plasmon resonance. The second-order nonlinear optical (NLO) properties were investigated by using a continuous-wave (CW) He–Ne laser beam with a wavelength of 632.8 nm at three different incident intensities by means of single beam techniques. The nonlinear refractive indices of gold nanoparticles were obtained from close aperture z-scan in order of 10^?7 cm²/W. Then, they were compared with diffraction patterns observed in far-field. The nonlinear absorption of these nanoparticles was obtained from open aperture z-scan technique. The values of nonlinear absorption coefficient are obtained in order of 10^?1 cm/W.     

Silicon nanoparticles generated by femtosecond laser ablation in a liquid environment

Silicon nanoparticles were generated by femtosecond laser [387 nm, 180 fs, 1 kHz, pulse energy = 3.5 μJ (fluence = 0.8 J/cm²)] ablation of silicon in deionized water. Nanoparticles with diameters from ~5 up to ~200 nm were observed to be formed in the colloidal solution. Their size distribution follows log-normal function with statistical median diameter of ≈20 nm. Longer ablation time leads to a narrowing of the nanoparticle size distribution due to the interaction of the ablating laser beam with the produced nanoparticles. Raman spectroscopy measurements confirm that the nanoparticles exhibit phonon quantum confinement effects and indicate that under the present conditions of ablation they are partially amorphous.