Catalytic Gold Nanoparticles Research Articles

Synthesis of gold nanoparticles using soybean byproducts: applications in catalysis

AbstractThis study demonstrates the feasibility of extracting lecithin from oil industry byproducts in an eco‐friendly manner, with minimal use of water and without harmful chemicals. Liposomes can be generated directly from this extracted lecithin, enhancing the value of these byproducts and enabling the production of catalytic gold nanoparticles (AuNPs). Thin‐layer chromatography of the extracted lecithin revealed a phospholipid composition primarily consisting of phosphatidylethanolamine and phosphatidylcholine, and surface tension studies demonstrated similar behavior between the extracted and commercial lecithin. Liposome formation using sustainable lecithin (LPn) resulted in structures that were stable for at least 10 days, exhibiting a low polydispersity index (0.395) and uniform size (approximately 214 ± 7 nm). Gold nanoparticles were synthesized successfully in LPn loaded with [HAuCl4] by using different photoreduction methods: ultraviolet (UV) lamp, pulsed laser 355 nm, and sunlight irradiation. The AuNPs exhibited characteristic sizes (ranging from 5.03 to 6.78 nm) and optical properties typical of nanoparticles, including a distinct surface plasmon resonance. As a proof of concept, we also demonstrated that the synthesized AuNPs exhibited catalytic activity in UV‐induced cis‐trans isomerization reactions. Overall, the study highlights the potential of sustainable soy lecithin extraction for diverse applications, including nanoparticle synthesis and catalysis.

A Rapid and Easy Procedure of Enzyme Biosensor based on Nitrogen-Doped Graphene for Detection of Methyl Parathion in CHM

Methyl parathion (MP), an organophosphorus pesticide that is frequently used to control pests during the planting process of Chinese herbal medicine (CHM), has been used without sufficient control, leading to excessive residues on the surface of CHM, which has a serious impact on the quality and safety of CHM and their preparations. Consequently, it is crucial to carefully control MP during the cultivation, processing, and manufacture of CHM. Based on this, nitrogen-doped graphene (N-Gr) with a high conductivity and chitosan (CS) with good stability were used to modify the glassy carbon electrode (GCE). Subsequently, the prussian blue (PB) with catalytic activity and gold nanoparticles (AuNPs) with excellent biocompatibility were deposited by the electrodeposition method to form the AuNPs/PB/CS@N-Gr/GCE. Then, the acetylcholinesterase (AChE) was effectively immobilized on the electrode surface by covalent bonding between AuNPs and AChE through gold-sulfhydryl bonds. Finally, a rapid and easy procedure of enzyme biosensor (AChE/AuNPs/PB/CS@N-Gr/GCE) for sensitive detection of MP pesticide residues was fabricated. Herein, PB catalyzes the redox reaction of thiocholine, which is produced when acetylthiocholine iodide (ATCHI) undergoes efficient hydrolysis catalyzed by AChE. This process effectively promoted electron transfer, amplifying the sensor’s response signal. After the experimental conditions are optimized, the limit of detection (LOD) for MP is found to be 9.47 × 10−5 μg ml−1. Exhibits a good linear relationship within the concentration range of 1 × 10−3 μg ml−1 ∼ 1 × 101 μg ml−1. Significantly, the fabricated enzyme biosensor excels in swiftly and sensitively detecting trace amounts of MP in real examples. Furthermore, it exhibits robust stability and reproducibility. The excellent performance of this enzyme biosensor not only offers a rapid and easy way to identify and find minute amounts of trace MP pesticide residues in CHM, but also serves as a technical guide for the creation of new, portable, and on-site pesticide residue detection technology for law enforcement.

Zn/Al layered double hydroxide and carboxymethyl cellulose composite beads as support for the catalytic gold nanoparticles and their applications in the reduction of nitroarenes

Until now, many efficient catalysts have been reported that are used for the reduction of nitroarenes. However, a catalyst reusability is a challenge that is often faced in practical environment. In this report, we designed a hydrogel composite (CMC-LDH), which act as support and making it possible to address this challenge. In this research work, zinc/aluminum based layered double hydroxides (Zn/Al LDH) have been assembled with carboxymethyl cellulose (CMC) to prepare CMC/LDH hydrogel beads. The CMC/LDH hydrogel beads were prepared by the ionotropic gelation method. For CMC/LDH/Au preparation, the already prepared CMC/LDH beads were kept in gold ion (Au3+) solution, and their subsequent reduction with sodium borohydride (NaBH4). For the characterization of the prepared samples different instrumental techniques, such as Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), energy-dispersive X-ray spectroscopy, and scanning electron microscopy (SEM) were adopted. For the catalytic evaluation of CMC/LDH/Au, it was utilized as a catalyst in 4-NP and 4-NA reduction reactions. The continuity of the reaction was monitored by a UV–visible spectrophotometer. Rate constant (kapp) of 0.48474 min−1 and 0.7486 min−1 were obtained for 4-NP and 4-NA reduction, respectively. The hydrogel beads were recycled and reused for up to five successive cycles without significantly changing their catalytic efficiency.

Catalytic Gold Nanoparticle Assembly Programmed by DNAzyme Circuits.

Assembled gold nanoparticle (AuNP) superstructures can generate unique physicochemical characteristics and be used in various applications, thus becoming an attractive research field. Recently, several DNA-assisted gold nanoparticle assembly methods have been rigorously developed that typically require a non-catalytic equimolar molecular assembly to guarantee the designed assembly. Although efficient and accurate, exploring such non-catalytic nanoparticle assemblies in the complex cellular milieu under low trigger concentrations remains challenging. Therefore, developing a catalytic method that facilitates gold nanoparticle assemblies with relatively low DNA trigger concentrations is desirable. In this report, a catalytic method to program gold nanoparticle assemblies by DNAzyme circuits is presented, where only a small number of DNA triggers are able to induce the production of a large number of the desired nanoparticle assemblies. The feasibility of using logic DNAzyme circuits to control catalytic nanoparticle assemblies is experimentally verified. Additionally, catalytic AuNP assembly systems are established with cascading and feedback functions. The work provides an alternative research direction to enrich the tool library of nanoparticle assembly and their application in biosensing and nanomedicine.

Templating of catalytic gold and silver nanoparticles by waste plastic PET-derived hydrogel playing a dual role of a reductant and a matrix

The progressive accumulation of discarded plastic in the environment demands further development of waste management of plastic waste and conversion technologies of such waste to value-added materials. Recently, the conversion of plastic waste to functional materials via chemical recycling has attracted considerable attention. In this report, plastic waste (PET) was utilized for the preparation of a hydrogel-based catalyst via a cross-linking reaction of PET-derived oligo(terephthalamide)s followed by the electroless metallization. The polymeric matrix of PET-derived hydrogel plays multiple roles of (i) an adsorption media for noble metal ions such as Au3+ and Ag+, (ii) a reducing agent of Au3+ and Ag+ ions to Au0 and Ag0, and (iii) a matrix for the controlled growth of Au and Ag nanoparticles (AuNPs and AgNPs). The obtained hybrid hydrogels after metallization contained well-dispersed AuNPs and AgNPs of 6.1 ± 3.7 nm or 6.1 ± 1.4 nm size, respectively. The catalytic activities of the hybrid hydrogels with metal nanoparticles were studied in a model system of p-nitrophenol reduction in an aqueous solution. The hybrid materials of both Au@hydrogel and Ag@hydrogel were catalytically active for the reduction of p-nitrophenol, obeying the first-order kinetics. Importantly, the AuNPs or AgNPs in the hydrogel matrix preserved the original catalytic activity after multiple p-nitrophenol reduction reactions, showing a promising reusability of the catalysts. The proposed here approach aims to broaden the scope of conversion routes of plastic waste to value-added materials as well as to develop new types of polymeric matrices for templating and growth of metal nanoparticles for catalytic applications.

Identification of gas mixtures using gold-decorated metal oxide based sensor arrays and neural networks

With five sensors based on In2O3, SnO2, and TiO2 being designed, the sensor selectivity was enhanced by using composites of the metal oxides and decorating them with catalytic gold nanoparticles. An array of these sensors was used to sense three pollutant gases (CO, NO2, and NH3) with various concentrations. Further, a sensor array was used to sense two types of binary mixtures: (NO2 and CO) and (NH3 and NO2) with different concentrations. A principal component analysis was performed to evaluate the discriminative property of the sensor array. A deep neural network-based model was used to differentiate the distinct gases and their mixtures, with the input of response values. A discrimination efficiency of 100% was achieved in the cross-validated training and testing procedures with 100 iterations. For the discriminative analysis, a convolutional neural network-based model was used to circumvent processes such as feature extraction and response calculation. The CNN model could detect the presence of various gases and their mixtures with accuracies of 100% and 85% in 75 and 15 s, respectively.

Tannic Acid as a Versatile Template for Silica Monoliths Engineering with Catalytic Gold and Silver Nanoparticles.

Tannic acid in alkaline solutions in which sol-gel synthesis is usually performed with tetraethoxysilane is susceptible to various modifications, including formation of reactive radicals, oxidation under the action of atmospheric oxygen, self-association, and self-polymerization. Here, a precursor with ethylene glycol residues instead of ethanol was used, which made it possible to synthesize bionanocomposites of tannic acid and silica in one stage in neutral media under normal conditions without the addition of acid/alkali and organic solvents. Silica was fabricated in the form of optically transparent monoliths of various shapes with 2-4 nm pores, the radius of which well correlated with the size of a tannic acid macromolecule in a non-aggregated state. Polyphenol, which was remained in pores of silica matrix, served then as reducing agent to synthesize in situ gold and silver nanoparticles. As shown, these Au@SiO2 and Ag@SiO2 nanocomposites possessed localized surface plasmon resonance and high catalytic activity.

Superassembled Hierarchical Asymmetric Magnetic Mesoporous Nanorobots Driven by Smart Confined Catalytic Degradation.

Micro/nanoscale robotics has received great attention in many important fields. However, it is still a great challenge to construct nanorobots simultaneously possessing multifunctionality, well-controlled directionality, and fast and durable motion as well as fully compatible and biodegradable components. Here, a hierarchical, asymmetric, hollow, catalytic, magnetic, and mesoporous nanorobot has been fabricated through a multistep interfacial superassembly strategy. The multilayer composites consist of hollow silica nanoflasks sequentially coated with a highly magnetic responsive Fe3 O4 layer, a mesoporous silica layer with homogeneous vertical channels, and a layer of catalytic gold nanoparticles on both the inner and outer surfaces. Furthermore, para-nitrophenol was used as a model pollutant to trigger self-motility of the nanoflasks by confined catalytic degradation (CCD). We found that the bottleneck morphology and mesoporous surface both improved the catalytic nanoparticle loading capability and CCD effect, thus enabling efficient self-motility and a durable movement capacity of ∼100 h. In addition, the catalytic performance was improved by 180 % compared with that of solid spherical nanoparticles.

Varying protein architectures in 3-dimensions for scaffolding and modulating properties of catalytic gold nanoparticles.

Fabrication and development of nanoscale materials with tunable structural and functional properties require a dynamic arrangement of nanoparticles on architectural templates. The function of nanoparticles not only depends on the property of the nanoparticles but also on their spatial orientations. Proteins with self-assembling properties which can be genetically engineered to varying architectural designs for scaffolds can be used to develop different orientations of nanoparticles in three dimensions. Here, we report the use of naturally self-assembling bacterial micro-compartment shell protein (PduA) assemblies in 2D and its single-point mutant variant (PduA[K26A]) in 3D architectures for the reduction and fabrication of gold nanoparticles. Interestingly, the different spatial organization of gold nanoparticles resulted in a smaller size in the 3D architect scaffold. Here, we observed a two-fold increase in catalytic activity and six-fold higher affinity toward TMB (3,3',5,5'-tetramethylbenzidine) substrate as a measure of higher peroxidase activity (nanozymatic) in the case of PduA[K26A] 3D scaffold. This approach demonstrates that the hierarchical organization of scaffold enables the fine-tuning of nanoparticle properties, thus paving the way toward the design of new nanoscale materials.

Catalytic ferromagnetic gold nanoparticle immunoassay for the detection and differentiation of Mycobacterium tuberculosis and Mycobacterium bovis

A ferromagnetic gold nanoparticle based immune detection assay, exploiting the enhanced signal amplification of inorganic nanozymes, was developed and evaluated for its potential application in the detection of Mycobacterium tuberculosis complex (MTBC) organisms, and simultaneous identification of Mycobacterium bovis. Ferromagnetic gold nanoparticles (Au–Fe3O4 NPs) were prepared and their intrinsic peroxidase-like activity exploited to catalyse 3,3′,5’,5-tetramethylbenzidine (TMB) in the presence of hydrogen peroxide (H2O2). When the Au–Fe3O4 NPs were functionalised by direct coupling with MTBC-selective antibodies, a nanoparticle based immune detection assay (NPIDA) was developed which could detect Mycobacterium tuberculosis (MTB) and differentiate M. bovis. In the assay, the intrinsic magnetic capability of the functionalised Au–Fe3O4 NPs was used in sample preparation to capture target bacterial cells. These were incorporated into a novel immunoassay which used species selective monoclonal antibodies (mAb) to detect bound target. The formation of a blue TMB oxidation product, with a peak absorbance of 370 nm, indicated successful capture and identification of the target. The detection limit of the NPIDA for both MTB and M. bovis was determined to be comparable to conventional ELISA using the same antibodies. Although limited matrix effects were observed in either assay, the NPIDA offers a reduced time to confirmatory identification.This novel NPIDA was capable of simultaneous sample concentration, purification, immunological detection and speciation. To our knowledge, it represents the first immune-based diagnostic test capable of identifying MTBC organisms and simultaneously differentiating M. bovis.

Exploiting the Catalytic Ability of Polydopamine-Remodeling Gold Nanoparticles toward the Naked-Eye Detection of Cancer Cells at a Single-Cell Level

In this study, a catalytic polydopamine-remodeling gold nanoparticle sensitized with an antinucleolin AS1411 probe (pAu nanoprobe) is synthesized, where the surface of the gold nanoparticles (AuNPs) is modified with a spontaneous self-polymerization of a polydopamine coating that imparts the probe functionalization ability and antispecific protein binding while the intrinsic catalytic property of the AuNPs is preserved. The functionalized AS1411 probe exerts specific recognition with nucleolin protein that is found to be overexpressed on the surface of breast cancer cells (MDA-MB-231). Scanning electron microscopy (SEM) confirms that the specific binding of the pAu nanoprobe occurs at the cancer cell surface. Taking advantage of the catalytic ability of the pAu nanoprobe in reducing blue-colored methylene blue (MB) to colorless leuco-MB, a colorimetric biosensing platform is established based on the accessible catalytic active sites on the pAu nanoprobe toward MB. The specific binding inhibits the pAu nanoprobe from efficiently catalyzing the reduction of MB, resulting in a "turn-off" catalytic biosensing platform. The catalytic conversion of MB is inversely proportional to the concentration of the nucleolin protein and the cancer cells, yielding a detection limit of 15 pM of the nucleolin protein and two cancer cells. The presence of five orders of magnitude higher concentration of bovine serum albumin hardly affects the catalytic ability of the pAu nanoprobe, that is, 88% catalytic ability is still preserved, which validates the specificity of the proposed pAu nanoprobe. In particular, a distinct color contrast creates a significant signal-to-noise ratio so as to enable single-cell level detection of two cancer cells by naked-eye judgment. Moreover, the undiluted, real human serum samples spiked with the cancer cells were examined with an impressive recovery of 94 ± 0.3%, which holds great promise in cancer cell screening.

Catalytic Degradation of Methylene Blue Using Gold Nanoparticles Capped by Polyoxyethylene Cholesteryl Ether

Simple spontaneous and eco-friendly green synthesis method for ultra-stable and catalytic gold nanoparticles (AuNPs) were synthesized through Polyoxyethylene cholesteryl ether (ChEO10) and sodium tetrachloroaurate (III) dihydrate (Na [AuCl4]-2H2O) were prepared at 27 °C (AuNPs were formed in < 2 h). Here the creation of distinct AuNPs is supported by reductive ChEO10 surfactant solution via complexation and in-situ reduction of AuCl4− ions in which ChEO10 acts as self-reducing and stabilising agent. This method is considered as simple and green. The positive development of colloidal AuNPs was monitored by simple UV-Vis spectroscopy. The complete characterization of synthesizing AuNPs was done in the previous part. The resulting AuNPs reveal outstanding catalytic properties for degradation of Methyl Blue (MB) to Leucomethylene blue (LMB) in the presence of NaBH4. We further comment on challenges and future direction of this exciting and rapidly expanding area of research.

Decorating Au nanoparticles onto optimized P(tBA‐co‐DMAEMA) carriers for ameliorative catalytic capability

ABSTRACTGold nanoparticles are increasingly being explored as novel catalytic nanomaterials due to their great reductive capacity. However, the van der Waals forces between them would bring poor stabilities as well as attenuated catalytic properties in solution. Therefore, it is significant to find carriers that could prevent catalytic gold nanoparticles from agglomerating. Herein, hydrophilic dimethylaminoethyl methacrylate (DMAEMA) and hydrophobic tert‐butyl acrylate (tBA) were used as co‐monomers to synthesize copolymer P(tBA‐co‐DMAEMA) microspheres by one‐step emulsifier‐free emulsion polymerization. Afterward, the self‐assembly behaviors of the amphiphilic polymers P(tBA‐co‐DMAEMA) under different conditions like molar ratio of DMAEMA/tBA and ethanol/water were explored to reveal an optimal condition for obtaining copolymer with appropriate size and morphology. These microspheres were used as carriers for gold nanoparticles, since HAuCl4 could be simply reduced and stabilized on their surface. Furthermore, various conditions such as HAuCl4 content, adding method of HAuCl4, protonation time and reducing conditions were filtered for the decoration of gold nanoparticles on the shell of that assembled copolymer. This composite was applied as an excellent catalyst for hydrogenation of hazardous chemicals (4‐nitrophenol and nitrobenzene). And it shows improved catalytic performance for both 4‐nitrophenol in the aqueous system and nitrobenzene in the oil system. © 2020 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020, 137, 48920.

SM-1 Identification of Z-contrast image of twinned catalytic gold nanoparticles processed by Hough transformation using convolutional neural network

SM-1 Identification of Z-contrast image of twinned catalytic gold nanoparticles processed by Hough transformation using convolutional neural network

Single particle-based colorimetric assay of pyrophosphate ions and pyrophosphatase with dark-field microscope

We propose a sensitive colorimetric method for the detection of P2O74− and pyrophosphatase (PPase). Without Na4P2O7 and PPase, under the catalysis of gold nanoparticles (AuNPs), Cu(II) can be reduced to Cu by nicotinamide adenine dinucleotide (NADH), leading to the Cu-coating onto the surfaces of AuNPs, accompanied by the color change from green to red under the dark-field microscope observation. While in the presence of Na4P2O7, the formation of Au@Cu NPs is suppressed due to the strong complexation reaction between Cu(II) and Na4P2O7. Thus, the NPs exhibit uniform green color in the dark-field image. By quantitatively counting the integrated optical density (IOD) of red dots in the dark-field images, P2O74− concentration can be accurately determined. A linear logarithmic dependence on P2O74− concentrations from 0.1 nM to 10 mM with a limit of detection (LOD) of 0.0324 nM was obtained. The addition of PPase to the Na4P2O7-triggered dispersed AuNPs restores the formation of Au@Cu NPs owing to the hydrolysis of Na4P2O7 into sodium phosphate under the catalysis of PPase, resulting in reliable quantification of color change of NPs from red to green in the dark-field images. The LOD is as low as 0.0007 U/mL with a linear dynamic range of 0.005–10 U/mL.

Corrigendum to: Twinned/untwinned catalytic gold nanoparticles identified by applying a convolutional neural network to their Hough transformed Z-contrast images.

In this article, we demonstrate that a convolutional neural network (CNN) can be effectively used to determine the presence of twins in the atomic resolution scanning transmission electron microscopy (STEM) images of catalytic Au nanoparticles. In particular, the CNN screening of Hough transformed images resulted in significantly higher accuracy rates as compared to those obtained by applying this technique to the raw STEM images. The proposed method can be utilized for evaluating the statistical twining fraction of Au nanoparticles that strongly affects their catalytic activity.

Twinned/untwinned catalytic gold nanoparticles identified by applying a convolutional neural network to their Hough transformed Z-contrast images.

In this article, we demonstrate that a convolutional neural network (CNN) can be effectively used to determine the presence of twins in the atomic resolution scanning transmission electron microscopy (STEM) images of catalytic Au nanoparticles. In particular, the CNN screening of Hough transformed images resulted in significantly higher accuracy rates as compared to those obtained by applying this technique to the raw STEM images. The proposed method can be utilized for evaluating the statistical twining fraction of Au nanoparticles that strongly affects their catalytic activity.

Generation and Reactivity of Electron-Rich Carbenes on the Surface of Catalytic Gold Nanoparticles.

The reactive nature of carbenes can be modulated, and ultimately reversed, by receiving additional electron density from a metal. Here, it is shown that Au nanoparticles (NPs) generate an electron-rich carbene on surface after transferring electron density to the carbonyl group of an in situ activated diazoacetate, as assessed by Fourier transformed infrared (FT-IR) spectroscopy, magic angle spinning nuclear magnetic resonance (MAS NMR), and Raman spectroscopy. Density functional theory (DFT) calculations support the observed experimental values and unveil the participation of at least three different Au atoms during carbene stabilization. The surface stabilized carbene shows an extraordinary stability against nucleophiles and reacts with electrophiles to give new products. These findings showcase the ability of catalytic Au NPs to inject electron density in energetically high but symmetrically allowed valence orbitals of sluggish molecules.

Target switching catalytic hairpin assembly and gold nanoparticle colorimetric for EGFR mutant detection

The detection of circulating tumor DNAs (ctDNAs) with high sensitivity plays an important role in liquid biopsy diagnosis. For the detection of ctDNAs, we investigated the applicability of a two-ways CHA technique and found there were several problems such as sensitivity and selectivity. For this reason, we revised our technique to three-ways target switching catalytic hairpin assembly (TSCHA). Our target DNA is epidermal growth factor receptor (EGFR) mutation DNA. EGFR mutation DNA is very long DNA (84 mer) and it is hard to detect such a long DNA. However, with a TSCHA method, we can produce a short catalyst DNA (c-DNA) using long target DNA. After the catalytic reaction between DNAs, AuNPs aggregate and the detection solution become blue from red. We quantify the aggregation by observing UV–vis spectrum and can obtain LOD as low as 7.7 fM. Also the selectivity of the detection method is very high. Because of the high sensitivity, high selectivity, and simplicity, the TSCHA technique has great potential as a platform to detect mutant DNA in blood of cancer patients.

Platanus orientalis Leaf Mediated Rapid Synthesis of Catalytic Gold and Silver Nanoparticles

In an attempt to synthesize novel catalytic gold (AuNPs) and silver nanoparticles (AgNPs) we have used Platanus orientalis leaf extract for both reduction and capping. The synthesis was rapid which completed by 5 h as indicated by change in colour and development of prominent peak at 540 nm for AuNPs and 440 nm for AgNPs, as revealed by UV-visible spectroscopy. The phytogenic nanoparticles showed exotic shapes which included triangles, spheres, hexagons and pentagons as analyzed by high resolution transmission electron microscopy. The optimized processing parameters like salt concentration (1 mM concentration of HAuCl4 and 4 mM of AgNO3) and the reaction temperature (50°C) led to faster nanoparticles synthesis. Energy dispersive spectra and X-ray diffraction studies confirmed the elemental gold and silver in AuNPs and AgNPs. Detailed phytochemical characterization using biochemical techniques and gas chromatography mass spectrometry indicated the predominance of ascorbic acid, citric acid, reducing sugars and even starch which may together lead to simultaneous synthesis and capping. Further, AuNPs and AgNPs catalyzed the reduction of 4-nitrophenol (4-NP) to 4-aminophenol (4-AP) using NaBH4 with apparent rate constants of 1.908 × 10-4 min-1 and 3.071 × 10-4 min-1, respectively.