Catalytic Reduction of p‐Nitrophenol and Hexacyanoferrate (III) by Borohydride Using Green Synthesized Gold Nanoparticles

A simple and green approach for the synthesis of well‐stabilized gold nanoparticles (AuNPs) using gum Acacia (GA) is presented here. The gum acacia acts as the reductant and stabilizer. The synthesized gold nanoparticles were characterized by using ultraviolet visible (UV‐Vis), fourier transform infrared spectroscopy (FTIR), x‐ray diffraction (XRD), dynamic light scattering (DLS) and transmission electron microscopy (TEM) techniques. The UV‐Vis study revealed a distinct surface plasmon resonance at 520 – 550 nm, due to the formation of AuNPs. FTIR analysis showed the evidence that –OH groups present in the gum matrix were responsible in reducing the tetra chloroauric acid into AuNPs. XRD studies confirmed the formation of well crystalline nanoparticles with fcc structure and the particle size ranges from 4 – 29 nm, as indicated by TEM analysis. The synthesized gold nanoparticles exhibited homogeneous catalytic activity. The two model reactions studied were the reduction of p‐nitro phenol and the reduction of hexacyanoferrate (III) by borohydride ions. Both the reactions were monitored by UV‐Vis spectroscopy. The kinetic investigations were carried out for the AuNPs‐catalyzed reactions at different temperatures and different amount of catalyst.     

Synthesis of gold and silver nanoparticles using purified URAK

This study aims at developing a new eco-friendly process for the synthesis of silver nanoparticles (AgNPs) and gold nanoparticles (AuNPs) using purified URAK. URAK is a fibrinolytic enzyme produced by Bacillus cereus NK1. The enzyme was purified and used for the synthesis of AuNPs and AgNPs. The enzyme produced AgNPs when incubated with 1 mM AgNO3 for 24 h and AuNPs when incubated with 1 mM HAuCl4 for 60 h. But when NaOH was added, the synthesis was rapid and occurred within 5 min for AgNPs and 12 h for AuNPs. The synthesized nanoparticles were characterized by a peak at 440 nm and 550 nm in the UV-visible spectrum. TEM analysis showed that AgNPs of the size 60 nm and AuNPs of size 20 nm were synthesized. XRD confirmed the crystalline nature of the nanoparticles and AFM showed the morphology of the nanoparticle to be spherical. FT-IR showed that protein was responsible for the synthesis of the nanoparticles. This process is highly simple, versatile and produces AgNPs and AuNPs in environmental friendly manner. Moreover, the synthesized nanoparticles were found to contain immobilized enzyme. Also, URAK was tested on RAW 264.7 macrophage cell line and was found to be non-cytotoxic until 100 μg/ml.     

Microwave-Assisted Green Synthesis of Gold Nanoparticles Using Olibanum Gum (Boswellia serrate) and its Catalytic Reduction of 4-Nitrophenol and Hexacyanoferrate (III) by Sodium Borohydride

In this work we report straightforward, an economically viable, one-step microwave-assisted green synthesis of well stabilized gold nanoparticles (AuNPs) by reducing chloroauric acid with natural water soluble olibanum gum (Boswellia serrate). The olibanum gum acts as a dual role of reducing and capping agent for synthesis of AuNPs. The formation of AuNPs was confirmed using UV–Vis spectroscopy, Fourier transform infrared spectroscopy, X-ray diffraction, transmission electron microscopy and electron diffraction. The results indicated that the synthesized NPs were well dispersed and spherical in shape had an average diameter of 3 ± 2 nm. The reaction parameters significantly affected the formation of NPs, as the concentration of gum and irradiation time increases the formation of NPs particles increases and size of particles are reduced. In addition, it has been shown that these olibanum gum capped AuNPs functioned as effective homogeneous catalyst for the reduction of two model reactions hexacyanoferrate(III) and 4-nitrophenol by sodium borohydride. The kinetic investigations were carried out at different amount of AuNPs and different temperatures.     

Structure and Stability of Gold Nanoparticles Synthesized Using <Emphasis Type="Italic">Schinus molle</Emphasis> L. Extract

In this work, we exhibited the results of the green synthesis of gold nanoparticles by aqueous extract of Schinus molle L. leaves. The chemical reaction was carried out by varying the plant extract/precursor salt ratio concentration in the aqueous solution. The structural characterization of the nanoparticles was performed using X-ray diffraction (XRD), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). XRD analysis showed that the as-synthesized AuNPs have a face-centered cubic structure. SEM and TEM observations indicated that most of the obtained particles have multiple twinning structures (MTP). The synthesized Au-MTP have particle sizes in the range of 10–60 nm, most of them with an average size of about 24 nm. However, triangular Au plate particles were also obtained, having an average size of 180 nm. Fourier transforms infrared spectroscopy and shows that the functional groups responsible for the chemical reduction of AuNPs are phenolic compounds present in the S. molle L. leaf.     

Polymer-induced synthesis of stable gold and silver nanoparticles and subsequent ligand exchange in water

A simple, inexpensive, single-step synthesis of gold and silver nanoparticles using poly(allylamine) (PAAm) as a reducing and stabilizing agent is reported. The synthetic process was carried out in aqueous solution, making the method versatile and environmentally friendly. The synthesized polymer-stabilized nanoparticles are stable in water without particle aggregation at room temperature for at least a month. We demonstrate successful ligand exchange on the polymer-stabilized gold nanoparticles (AuNPs) with a variety of omega-functionalized acid-, alcohol-, amine-, and biotin-terminated alkylthiols. The methodologies, including ligand exchange, also are applicable for the generation of finely dispersed silver nanoparticles. The synthesized gold and silver nanoparticles are characterized by UV-visible absorption spectroscopy and transmission electron microscopy (TEM). The different ligand-stabilized AuNPs are also analyzed by Fourier transform infrared (FTIR) spectroscopy.     

Polymer Cages as Universal Tools for the Precise Bottom‐Up Synthesis of Metal Nanoparticles

A template synthesis allows the preparation of monodisperse nanoparticles with high reproducibility and independent from self‐assembly requirements. Tailor‐made polymer cages were used for the preparation of nanoparticles, which were made of cross‐linked macromolecules with pendant thiol groups. Gold nanoparticles (AuNPs) were prepared in the polymer cages in situ, by using different amounts of cages versus gold. The polymer cages exhibited a certain capacity, below which the AuNPs could be grown with excellent control over the size and shape. Control experiments with a linear diblock copolymer showed a continuous increase in the AuNP size as the gold feed increased. This completely different behavior regarding the AuNP size evolution was attributed to the flexibility of the polymer chain depending on cross‐linking. Moreover, the polymer cages were suitable for the encapsulation of AgNPs, PdNPs, and PtNPs by the in situ method.     

Photopolymerization of diacetylene-capped gold nanoparticles

Gold nanoparticles (AuNPs) coated with the diacetylene henicosa-10,12-diyn-1-yl (DS9) disulfide were successfully prepared by direct synthesis in toluene solutions. The average size of the nanohybrid metal core was finely adjusted by manipulation of the preparative conditions in the diameter range from 1.6 to 7.5 nm, as determined by TEM characterization. The topochemical polymerization of DS9 chemisorbed onto the gold nanoclusters of different size was carried out in colloidal suspensions by exposure to UV radiation and the process was monitored by UV-Vis and Raman spectroscopies. The results showed that in these assemblies the monomer undergoes an intra-particle polymerization and that the dominant polydiacetylene phase present is ruled by the core size. The deposition of the photoirradiated colloids onto different substrates was found to leave the polydiacetylene conjugation unaltered.     

Spectroscopic and microscopic investigation of gold nanoparticle formation: ligand and temperature effects on rate and particle size

We report a spectroscopic and microscopic investigation of the synthesis of gold nanoparticles (AuNPs) with average sizes of less than 5 nm. The slow reduction and AuNP formation processes that occur by using 9-borabicyclo[3.3.1]nonane (9-BBN) as a reducing agent enabled a time-dependent investigation based on standard UV-vis spectroscopy and transmission electron microscopy (TEM) analyses. This is in contrast to other borohydride-based syntheses of thiolate monolayer protected AuNPs which form particles very rapidly. We investigated the formation of 1-octadecanethiol (ODT) protected AuNPs with average diameters of 1.5-4.3 nm. By studying the progression of nanoparticle formation over time, we find that the nucleation rate and the growth time, which are interlinked with the amount of ODT and the temperature, influence the size and the size dispersion of the AuNPs. High-resolution TEM (HRTEM) analyses also suggest that the nanoparticles are highly single crystalline throughout the synthesis and appear to be formed by a diffusion-controlled Ostwald-ripening growth mechanism.     

Cisplatin-tethered gold nanoparticles that exhibit enhanced reproducibility, drug loading, and stability: a step closer to pharmaceutical approval?

Gold nanoparticles (AuNPs) can be used as delivery vehicles for platinum anticancer drugs, improving their targeting and uptake into cells. Here, we examine the appropriateness of different-sized AuNPs as components of platinum-based drug-delivery systems, investigating their controlled synthesis, reproducibility, consistency of drug loading, and stability. The active component of cisplatin was tethered to 25, 55, and 90 nm AuNPs, with the nanoparticles being almost spherical in nature and demonstrating good batch-to-batch reproducibility (24.37 ± 0.62, 55.2 ± 1.75, and 89.1 ± 2.32 nm). The size distribution of 25 nm AuNPs has been significantly improved, compared with a previous method that produces polydispersed nanoparticles. Attachment of platinum to the AuNP surface through a poly(ethylene glycol) (PEG) linker exhibits an increase in the drug loading with increasing particle size: 25 nm (815 ± 106 drug molecules per AuNP), 55 nm (14216 ± 880), and 90 nm (54487 ± 15996). The stability of the naked, PEGylated, and platinum-conjugated nanoparticles has been examined over time under various conditions. When stored at 4 °C, there is minimal variation in the diameter for all three AuNP sizes; variation after 28 days for the 25 nm AuNPs was 2.4%; 55 nm, 3.3%; and 90 nm, 3.6%. The 25 nm AuNPs also demonstrate minimal changes in UV-visible absorbance over the same time period.     

Biosynthesis of Au nanoparticles using olive leaf extract: 1st Nano Updates

The biological synthesis of gold nanoparticles (AuNPs) of various shapes (triangle, hexagonal, and spherical) using hot water olive leaf extracts as reducing agent is reported. The size and the shape of Au nanoparticles are modulated by varying the ratio of metal salt and extract in the reaction medium. Only 20 min were required for the conversion into gold nanoparticles at room temperature, suggesting a reaction rate higher or comparable to those of nanoparticles synthesis by chemical methods. The variation of the pH of the reaction medium gives AuNPs nanoparticles of different shapes. The nanoparticles obtained are characterized by UV–Vis spectroscopy, photoluminescence, transmission electron microscopy (TEM), X-ray diffraction (XRD), FTIR spectroscopy and thermogravimetric analysis. The TEM images showed that a mixture of shapes (triangular, hexagonal and spherical) structures was formed at lower leaf broth concentration and high pH, while smaller spherical shapes were obtained at higher leaf broth concentration and low pH.     

Effect of Latent Heat in Boiling Water on the Synthesis of Gold Nanoparticles of Different Sizes by using the Turkevich Method

The Turkevich method, involving the reduction of HAuCl₄ with citrate in boiling water, allows the facile production of monodisperse, quasispherical gold nanoparticles (AuNPs). Although, it is well‐known that the size of the AuNPs obtained with the same recipe vary slightly (as little as approximately 4 nm), but noticeably, from one report to another, it has rarely been studied. The present work demonstrates that this size variation can be reconciled by the small, but noticeable, effect that the latent heat in boiling water has on the size of the AuNPs obtained by using the Turkevich method. The increase in latent heat during water boiling caused an approximately 3 nm reduction in the size of the as‐prepared AuNPs; this reduction in size is mainly a result of accelerated nucleation driven by the extra heat. It was further demonstrated that, the heating temperature can be utilized as an additional measure to adjust the growth rate of AuNPs during the reduction of HAuCl₄ with citrate in boiling water. Therefore, the latent heat of boiling solvents may provide one way to control nucleation and growth in the synthesis of monodisperse nanoparticles.     

Vibrational spectroscopic characterization of 4-acylamidobenzenethiol-stabilized gold nanoparticles

A simple preparation method of gold nanoparticles (AuNPs) with 4-acylamidobenzenethiol derivative (BD) was improved to obtain the larger size of AuNPs which exhibited localized surface plasmon resonance. The spectroscopic characterizations of two kinds of BD-stabilized AuNPs were carried out by means of ATR-FTIR and Raman spectroscopy in order to clarify the conformation and orientation of BDs adsorbed on AuNPs. The relation between the stability of AuNPs and the adsorbed states of BDs were also discussed. The average sizes of the resulting AuNPs were 18 nm for BD1 and 30 nm for BD2, respectively. It was found that the BD1-capped AuNPs formed large aggregates. The results of vibrational spectroscopy revealed that loosely packed self-assembled monolayer (SAM) of BD1 molecules was formed on the surface of the AuNPs; on the other hand, densely packed SAM was formed in the case of BD2. We concluded the difference behavior between the two types of molecules was caused by the functional groups. The sulfuryl groups of BD2 induced highly ordered SAM and suppressed aggregate formation of AuNPs.     

用辛烷基硫醇单层保护Au纳米粒子制备CO氧化催化剂Au/γ-Al2O3

采用两相法合成出含活性组分Au的辛烷基硫醇单层保护Au纳米粒子(C8AuNPs)的正己烷溶胶, 用“逐次浸润”法将C8AuNPs负载在γ-Al2O3上, 经真空干燥及活化处理制得Au/γ-Al2O3催化剂. 所制得的Au催化剂前体C8AuNPs/γ-Al2O3表面Au粒子平均粒径可控制在2-3 nm范围内, 且分布比较单一; 催化剂活性评价600 h后, 其表面Au的粒径仍主要分布在2-4 nm范围内; 真空干燥温度影响Au催化剂的粒子尺寸和催化活性, 随着真空干燥温度的提高, Au纳米粒子的粒径增大. 将所制备的催化剂用于低温CO氧化反应, 催化活性评价结果表明, 经25 ℃真空干燥制得的2.5%(质量分数, w)Au/γ-Al2O3具有较高的活性和长期稳定性, 其催化CO完全转化的最低温度为-19 ℃, 在15 ℃下CO完全转化时Au/γ-Al2O3的单程寿命至少900 h; 4.0%(w) Au/γ-Al2O3在15 ℃和进料中含水条件下对CO完全氧化的单程寿命不低于2000 h, 可见催化剂具有强的抗潮湿中毒特性. 综合上述实验结果, 讨论了影响Au/γ-Al2O3催化剂活性的可能因素.     

Continuous Electroformation of Gold Nanoparticles in Nanoliter Droplet Reactors

Gold nanoparticles (AuNPs) are employed in numerous applications, including optics, biosensing and catalysis. Here, we demonstrate the stabilizer-free electrochemical synthesis of AuNPs inside nanoliter-sized reactors. Droplets encapsulating a gold precursor are formed on a microfluidic device and exposed to an electrical current by guiding them through a pair of electrodes. We exploit the naturally occurring recirculation flows inside confined droplets (moving in rectangular microchannels) to prevent the aggregation of nanoparticles after nucleation. Therefore, AuNPs with sizes in the range of 30 to 100 nm were produced without the need of additional capping agents. The average particle size is defined by the precursor concentration and droplet velocity, while the charge dose given by the electric field strength has a minor effect. This method opens the way to fine-tune the electrochemical production of gold nanoparticles, and we believe it is a versatile method for the formation of other metal nanoparticles.     

Biosynthesis and characterization of gold nanoparticles produced by laccase from Paraconiothyrium variabile

During recent years investigation on the development of eco-friendly processes for production of gold nanoparticles (GNPs) have received much attention due to hazardous effects of chemical compounds used for nanoparticle preparation. In the present study, the purified laccase from Paraconiothyrium variabile was applied for synthesis of Au nanoparticles (AuNPs) and the properties of produced nanoparticles were characterized. The UV-vis spectrum of formed AuNPs showed a peak at 530 nm related to surface plasmon absorbance of GNPs represented the formation of gold nanoparticles after 20 min incubation of HAuCl(4) (0.6 mM) in the presence of 73 U laccase at 70°C. Transmission electron microscopy (TEM) image of AuNPs showed well dispersed nanoparticles in the range of 71-266 nm as determined by the laser light scattering method. The pattern of energy dispersive X-ray (EDX) of the prepared GNPs confirmed the structure of gold nanocrystals.     

Effect of gold nanoparticles synthesized using the aqueous extract of Satureja hortensis leaf on enhancing the shelf life and removing Escherichia coli O157:H7 and Listeria monocytogenes in minced camel's meat: The role of nanotechnology in the food industry

Because herbal nanoparticles have antimicrobial properties, researchers have tried to synthesize them to aid in increasing the shelf time of food and food products. In this regard, gold nanoparticles (AuNPs) synthesized by plants are particularly important. In this study, fresh and clean leaves of Satureja hortensis were selected for the synthesis of AuNPs. We also evaluated the efficacy of these nanoparticles to increase the shelf life of and remove Escherichia coli O157:H7 and Listeria monocytogenes from minced camel's meat. The nanoparticles were analyzed by UV–visible spectroscopy, field emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), Fourier-transform infrared (FT-IR) spectroscopy, energy dispersive X-ray spectroscopy, and X-ray diffraction tests. The FT-IR spectroscopy results demonstrated that the antioxidant compounds in the plant were the sources of reducing power, reducing gold ions to AuNPs. FE-SEM and TEM images revealed the size of the nanoparticles to be 22.26 nm. The 2,2-diphenyl-1-picrylhydrazyl test revealed similar antioxidant potentials for S. hortensis, AuNPs, and butylated hydroxytoluene. S. hortensis and AuNPs had high cell viability dose-dependently against the human umbilical vein endothelial cell line. At the beginning of the food industry part of this experiment, all samples of control, S. hortensis, and AuNPs were preserved at 4°C for 20 days. During these 20 days, the sensory, chemical, and microbiological parameters were assessed for all samples. AuNPs significantly inhibited the growth of E. coli and L. monocytogenes. In addition, AuNPs significantly increased the protein carbonyl content, thiobarbituric acid reactive substances, pH, peroxide value, total volatile base nitrogen, and sensory attributes (color, odor, and overall acceptability). The best results were seen in AuNPs (1%). These findings reveal that the inclusion of S. hortensis extract improves the solubility of AuNPs, which led to a notable enhancement in their preservative and antibacterial effects.     

Biofunctionalized silver and gold nanoparticles as potential curative agents

In this study, the bark of an important medicinal plant, Indigofera aspalathoides is utilized as a bioreductant for the synthesis of silver nanoparticles (AgNPs) and gold nanoparticles (AuNPs). The formation of nanoparticles was monitored, and the reaction parameters were optimized by UV–Vis spectroscopy. The attachment of biocomponents as stabilizer was proved employing Fourier‐transform infrared (FT‐IR) studies. Through transmission electron microscopy (TEM), the morphology was found to be predominantly spherical and a mixture of triangle and hexagon in the case of AgNPs and AuNPs, respectively. The crystallite size of AgNPs and AuNPs was affirmed through X‐ray diffraction (XRD) studies using Sherrer formula as 22.03 and 47.70 nm, respectively. DPPH method was adopted to analyse the free‐radical quenching ability, and the AgNPs, AuNPs and extract showed inhibition of 76%, 89% and 59% at a concentration of 200 μg ml^?1, and the corresponding IC₅₀ values were 86.49, 55.20 and 149.19 μg ml^?1. The binding of nanoparticles to calf‐thymus DNA (CT‐DNA) was through groove and the high binding constants (8.49 × 10⁶ M^?1 and 2.34 × 10⁷ M^?1 for AgNPs and AuNPs) point out the potential of these nanoparticles as curative drugs. The MTT assay showed that AgNPs were 100% toxic, and the low IC₅₀ value suggests that this can be used in the medicinal field as a safe drug.     

Catalytic reduction of 4-nitrophenol using biogenic gold and silver nanoparticles derived from Breynia rhamnoides

A simple, green method is described for the synthesis of Gold (Au) and Silver (Ag) nanoparticles (NPs) from the stem extract of Breynia rhamnoides. Unlike other biological methods for NP synthesis, the uniqueness of our method lies in its fast synthesis rates (~7 min for AuNPs) and the ability to tune the nanoparticle size (and subsequently their catalytic activity) via the extract concentration used in the experiment. The phenolic glycosides and reducing sugars present in the extract are largely responsible for the rapid reduction rates of Au(3+) ions to AuNPs. Efficient reduction of 4-nitrophenol (4-NP) to 4-aminophenol (4-AP) in the presence of AuNPs (or AgNPs) and NaBH(4) was observed and was found to depend upon the nanoparticle size or the stem extract concentration used for synthesis.     

Novel marine-based gold nanocatalyst in solvent-free synthesis of polyhydroquinoline derivatives: Green and sustainable protocol

We report an ecofriendly synthetic approach for the fabrication of biogenic gold nanoparticles (AuNPs) using electron-rich sea cucumber extract as a bio-reductant and stabilizing agent in reducing gold cations into AuNPs at the optimal conditions. The produced AuNPs are spherical in shape with an average particle size of 11 ± 1.5 nm in transmission electron microscopy (TEM) and exhibited a crystal structure of face-centered cubic in X-ray diffraction (XRD) analyses. Our results indicated that bioinspired AuNPs demonstrate superior catalytic activity in the safe and facile one-pot synthesis of polyhydroquinoline derivatives under solvent-free reaction conditions. This green route encompasses multiple benefits including highly recyclable bioinspired catalyst (5 cycles), short reaction times, convenient workout, high to excellent product yields (82%–97%), and nonhazardous conditions.     

Nanocomposites of nanocrystalline cellulose for enzyme immobilization

We describe the synthesis, characterization and use of a composite material made of a renewable source and metallic nanoparticles for biosensing applications. Nanocrystalline cellulose (NCC) is a product isolated from natural cellulose fibers, which is of approximately 100 nm long and 10 nm wide in size. We augmented the surface area and tailored the chemical affinity of NCC by optimally dressing it with gold nanoparticles (AuNPs). The deposition of AuNPs on NCC was controlled by using cationic polyethylenimine (PEI) at different pHs. AuNPs were thiol-functionalized using different linkers prior to enzyme immobilization. The enzyme (glucose oxidase or GOx) was conjugated on the composite by carbodiimide coupling, and subsequent activation of linker-carboxylic acid group. Our results showed that GOx was attached to the surface of the NCC nanocomposite. Moreover, the amount of GOx loaded onto the support depended on the length of the thiol-linker used. The lower value (20.3 mg/mg of support) was obtained with the longer thiol-linker (11 carbon chain) compared to 25.2 mg/mg of support for the smaller thiol-linker (3 carbon chain).