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.     

Polyoxometalate‐Engineered Building Blocks with Gold Cores for the Self‐Assembly of Responsive Water‐Soluble Nanostructures

The controlled assembly of gold nanoparticles (AuNPs) with the size of quantum dots into predictable structures is extremely challenging as it requires the quantitatively and topologically precise placement of anisotropic domains on their small, approximately spherical surfaces. We herein address this problem by using polyoxometalate leaving groups to transform 2 nm diameter gold cores into reactive building blocks with hydrophilic and hydrophobic surface domains whose relative sizes can be precisely tuned to give dimers, clusters, and larger micelle‐like organizations. Using cryo‐TEM imaging and ¹H DOSY NMR spectroscopy, we then provide an unprecedented “solution‐state” picture of how the micelle‐like structures respond to hydrophobic guests by encapsulating them within 250 nm diameter vesicles whose walls are comprised of amphiphilic AuNP membranes. These findings provide a versatile new option for transforming very small AuNPs into precisely tailored building blocks for the rational design of functional water‐soluble assemblies.     

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.     

One-pot aqueous phase growth of biocompatible 15-130 nm gold nanoparticles stabilized with bidentate PEG

We describe a new, single pot, aqueous phase method for synthesizing water soluble gold nanoparticles (AuNPs) over a size range of 15-130 nm. Poly(ethylene glycol)-appended thioctic acid ligands were used to control the growth rates and stabilize the AuNPs. Critical factors that enable the controlled growth of the AuNPs over this size range include the pH, the choice of reducing agent, the reaction temperature and the sequential addition of gold precursor and ligand with specific ligand-to-gold ratios. We describe the synthetic procedure in detail. Optical and structural characterization of the AuNPs was accomplished using UV-vis absorption spectroscopy, dynamic light scattering, and transmission and scanning electron microscopy.     

Gold Nanoparticle Assemblies on Surfaces: Reactivity Tuning through Capping‐Layer and Cross‐Linker Design

The immobilization of metal nanoparticles (NPs) with molecular control over their organization is challenging. Herein, we report the formation of molecularly cross‐linked AuNP assemblies using a layer‐by‐layer approach. We observed four types of assemblies: 1) small aggregates of individual AuNPs, 2) large aggregates of individual AuNPs, 3) networks of fused AuNPs, and 4) gold islands. Interestingly, these assemblies with the different cross‐linkers and capping layers represent different stages in the complete fusion of AuNPs to afford islands of continuous gold. We demonstrate that the stability toward fusion of the nanoparticles of the on‐surface structures can be controlled by the reactivity of the cross‐linkers and the hydrophilicity/hydrophobicity of the nanoparticles.     

Ligand Control over the Electronic Properties within the Metallic Core of Gold Nanoparticles

The behavior of electrons within the metallic core of gold nanoparticles (AuNPs) can be controlled by the nature of the surface chemistry of the AuNPs. Specifically, the conduction electron spin resonance (CESR) spectra of AuNPs of diameter 1.8–1.9 nm are sensitive to ligand exchange of hexanethiol for 4‐bromothiophenol on the surface of the nanoparticle. Chemisorption of the aromatic ligand leads to a shift in the metallic electron’s g‐factor toward the value expected for pure gold systems, suggesting an increase in metallic character for the electrons within the gold core. Analysis by UV/Vis absorption spectroscopy reveals a concomitant bathochromic shift of the surface plasmon resonance band of the AuNP, indicating that other electronic properties of AuNPs are also affected by the ligand exchange. In total, our results demonstrate that the chemical nature of the ligand controls the valence band structure of AuNPs.     

组装在贵金属基底上的金纳米粒子对CO的电化学催化氧化

研究了组装在Au, Pt电极表面的金纳米粒子对CO的电化学催化氧化行为, 首次在实验上观察到较大粒径金纳米粒子(粒径＞10 nm)对CO的电催化氧化活性. 考察了金粒子表面金氧化物对粒子电催化活性的影响, 发现表面金氧化物的形成是金纳米粒子对CO具有电催化氧化活性的前提. 对于相同粒径的金纳米粒子, 随着粒子表面金氧化物量的增加,催化活性增大.     

Characterization of Labeled Gold Nanoparticles for Surface-Enhanced Raman Scattering

Noble metal nanoparticles (NP) such as gold (AuNPs) and silver nanoparticles (AgNPs) can produce ultrasensitive surface-enhanced Raman scattering (SERS) signals owing to their plasmonic properties. AuNPs have been widely investigated for their biocompatibility and potential to be used in clinical diagnostics and therapeutics or combined for theranostics. In this work, labeled AuNPs in suspension were characterized in terms of size dependency of their localized surface plasmon resonance (LSPR), dynamic light scattering (DLS), and SERS activity. The study was conducted using a set of four Raman labels or reporters, i.e., small molecules with large scattering cross-section and a thiol moiety for chemisorption on the AuNP, namely 4-mercaptobenzoic acid (4-MBA), 2-naphthalenethiol (2-NT), 4-acetamidothiophenol (4-AATP), and biphenyl-4-thiol (BPT), to investigate their viability for SERS tagging of spherical AuNPs of different size in the range 5 nm to 100 nm. The results showed that, when using 785 nm laser excitation, the SERS signal increases with the increasing size of AuNP up to 60 or 80 nm. The signal is highest for BPT labelled 80 nm AuNPs followed by 4-AATP labeled 60 nm AuNPs, making BPT and 4-AATP the preferred candidates for Raman labelling of spherical gold within the range of 5 nm to 100 nm in diameter.     

Gold‐Nanoparticle‐Mediated Jigsaw‐Puzzle‐like Assembly of Supersized Plasmonic DNA Origami

DNA origami has rapidly emerged as a powerful and programmable method to construct functional nanostructures. However, the size limitation of approximately 100 nm in classic DNA origami hampers its plasmonic applications. Herein, we report a jigsaw‐puzzle‐like assembly strategy mediated by gold nanoparticles (AuNPs) to break the size limitation of DNA origami. We demonstrated that oligonucleotide‐functionalized AuNPs function as universal joint units for the one‐pot assembly of parent DNA origami of triangular shape to form sub‐microscale super‐origami nanostructures. AuNPs anchored at predefined positions of the super‐origami exhibited strong interparticle plasmonic coupling. This AuNP‐mediated strategy offers new opportunities to drive macroscopic self‐assembly and to fabricate well‐defined nanophotonic materials and devices.     

Comparative study of amphiphilic hyperbranched and linear polymer stabilized organo‐soluble gold nanoparticles as efficient recyclable catalysts in the biphasic reduction of 4‐nitrophenol

A series of organo‐soluble spherical gold nanoparticles (AuNPs) were prepared through the reduction of HAuCl₄ by NaBH₄ in the presence of amphiphilic hyperbranched polymers that had a hydrophilic hyperbranched polyethylenimine core and a hydrophobic shell formed by many palmitamide (C16) chains. For comparison, the corresponding linear polymeric analog derived from linear polyethylenimine was also used to prepare the organo‐soluble AuNPs. The obtained AuNPs were characterized by transmission electron microscopy. It was found that higher feed ratio of polymer to HAuCl₄ and utilization of polymers with higher C16 density usually resulted in smaller AuNPs with relatively lower polydispersity. Except of the polymer having the pronounced low molecular weight, the molecular weight and the morphology of the amphiphilic polymers had almost no obvious effect on the size of the formed AuNPs. These organo‐soluble AuNPs could be used as efficient catalysts for the biphasic catalytic reduction of 4‐nitrophenol by NaBH₄. Their apparent rate coefficients had correlation with the molecular weight of the used amphiphilic polymers, but were less relevant to the morphology of these polymers. These organo‐soluble AuNPs could be conveniently recovered and reused many times. The morphology of the capping polymers had obvious effect on the lifetime of the AuNPs catalysts in the catalytic reduction of 4‐nitrophenol. Except of the pronounced low molecular weight hyperbranched polymer, the other hyperbranched ones with relatively high molecular weight rendered the AuNPs to have bigger turnover number values than their linear analog. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Collisional electrochemistry of laser-ablated gold nanoparticles by electrocatalytic oxidation of glucose

We report the electrochemistry of gold nanoparticles (AuNPs), prepared by Laser Ablation Synthesis in Solution (LASiS), via the electrocatalytic oxidation of glucose upon single nanoparticle collisions at inert microelectrodes. Spherical AuNPs with diameters in the range 20–30 nm, as determined by transmission electron microscopy, were synthesized by LASiS of a gold plate immersed in water. Nanoparticle collisions were electrochemically detected through the AuNP-catalysed oxidation of glucose at carbon fiber microelectrodes in alkaline solution, enabling the electrocatalytic detection of single AuNPs. This approach provides a basis for detecting and understanding the electrocatalytic properties of pristine nanoparticles in aqueous solutions.     

Polyoxometalate-Engineered Building Blocks with Gold Cores for the Self-Assembly of Responsive Water-Soluble Nanostructures

The controlled assembly of gold nanoparticles (AuNPs) with the size of quantum dots into predictable structures is extremely challenging as it requires the quantitatively and topologically precise placement of anisotropic domains on their small, approximately spherical surfaces. We herein address this problem by using polyoxometalate leaving groups to transform 2 nm diameter gold cores into reactive building blocks with hydrophilic and hydrophobic surface domains whose relative sizes can be precisely tuned to give dimers, clusters, and larger micelle-like organizations. Using cryo-TEM imaging and ¹H DOSY NMR spectroscopy, we then provide an unprecedented “solution-state” picture of how the micelle-like structures respond to hydrophobic guests by encapsulating them within 250 nm diameter vesicles whose walls are comprised of amphiphilic AuNP membranes. These findings provide a versatile new option for transforming very small AuNPs into precisely tailored building blocks for the rational design of functional water-soluble assemblies.     

Linear Tetraphenylmethane‐Based Thioether Oligomers Stabilising an Entire Gold Nanoparticle by Enwrapping

The design and synthesis of a novel linear thioether‐based ligand subunit with a tetraphenylmethane core used in the stabilisation of gold nanoparticles (AuNPs) are presented. Mono‐, tri, penta‐ and heptamers of the ligand have been synthesised and used to stabilise AuNPs by enwrapping. With the exception of the monomer, all ligands provide reliable long‐term stability and redispersibility for the coated nanoparticles in common organic solvents. Despite variation of the oligomer length, all stable particles were of the same size within error tolerance (1.16±0.32 nm for the trimer, 1.15±0.30 nm for the pentamer, 1.17±0.34 nm for the heptamer), as investigated by transmission electron microscopy (TEM). These findings suggest that not only the number of sulfur atoms in the ligand, but also its bulkiness play a crucial role in stabilising the AuNPs. These findings are supported by thermogravimetric analysis (TGA), showing that AuNPs stabilised by the penta‐ or heptamer are passivated by a single ligand. Thermal stability measurements suggest a correlation between ligand coverage and thermal stability, further supporting these findings.     

Gold nanoparticles prepared by glycinate ionic liquid assisted multi-photon photoreduction

We have successfully prepared gold nanoparticles (AuNPs) with flower-like and spherical morphology through multi-photon photoreduction (MPR) of an aqueous solution of HAuCl(4) and (2-hydroxyethyl) trimethylammonium glycinate ([HETMA][Gly]) ionic liquid (IL) through the use of a femtosecond laser. The results of (1)H NMR and UV-Vis absorption indicated that AuNPs were produced from the photoreduction of the [Gly]-Au(iii) complex. Spherical AuNPs of about 2.5 nm were obtained on the solution when irradiated for 2 h, then aggregated into flower-like AuNPs of several tens of nanometers assisted by the IL with an increase in the irradiation time. Furthermore, precipitates of spherical AuNPs with the size of around 15 nm were formed after being irradiated for 6 h. The mechanisms of the MPR reaction and controlled growth of AuNPs have also been discussed.     

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.     

Mixed charged zwitterionic self-assembled monolayers as a facile way to stabilize large gold nanoparticles

Here we report a facile way of stabilizing large gold nanoparticles (AuNPs) by mixed charged zwitterionic self-assembled monolayers (SAMs). The citrate-capped AuNPs with diameters ranging from 16 nm to even ～100 nm are well stabilized via a simple place exchange reaction with a 1:1 molar ratio mixture of negatively charged sodium 10-mercaptodecanesulfonic acid (HS-C10-S) and positively charged (10-mercaptodecyl)-trimethyl-ammonium bromide (HS-C10-N4). The 16 nm AuNPs protected by mixed charged zwitterionic SAMs not only show much better stability than the single negatively or positively charged AuNPs, but also exhibit exciting stability as well as those modified by monohydroxy (1-mercaptoundec-11-yl) tetraethylene glycol (HS-C11-EG4). Importantly, 16 nm AuNPs protected by mixed SAMs exhibit good stability in cell culture medium with 10% FBS and strong protein resistance, especially with excellent resistance against plasma adsorption. Moreover, the mixed charged zwitterionic SAMs are also able to well-stabilize larger AuNPs with a diameter of 50 nm, and to help remarkably improve their stability in saline solution compared with HS-C11-EG4 protected ones. When it comes to AuNPs with a diameter of 100 nm, the mixed charged zwitterionic SAM protected nanoparticles retain a smaller hydrodynamic diameter and even better long-term stability than those modified by mercaptopolyethylene glycol (M(w) = 2000, HS-PEG2000). The above results demonstrated that the mixed charged zwitterionic SAMs are able to have a similar effect on stabilizing the large gold nanoparticles just like the single-component zwitterionic SAMs. Concerning its ease of preparation, versatility, and excellent properties, the strategy based on the mixed charged zwitterionic SAM protection might provide a promising method to surface tailoring of nanoparticles for biomedical application.     

Amphiphilic Janus gold nanoparticles via combining "solid-state grafting-to" and "grafting-from" methods

Despite the great efforts that have been made toward obtaining Janus architectures, synthesizing sub-10 nanometer Janus nanoparticles (NPs) modified with different types of polymers remains a challenging task. In this Communication, "solid-state grafting-to" and "grafting-from" methods were combined to obtain Janus gold NPs (AuNPs) modified with two types of polymer chains on the opposite sides of the NP. We used functionalized polymer single crystals as the solid substrates to immobilize AuNPs. We then used atom transfer radical polymerization to grow polymer chains on the "free" side of the AuNPs. Amphiphilic polyethylene oxide (PEO)-Au-poly(methyl methacrylate), PEO-Au-poly(tert-butyl acrylate) and hydrophilic PEO-Au-poly(acrylic acid) were synthesized. The Janus nature was demonstrated using a platinum-nanoparticle-decoration method. Using polymer single crystals as the reaction substrates is advantageous because they afford higher throughput compared with self-assembled monolayers. Dissolution of the single crystal also leads to NPs with defined polymer patches. We anticipate that our approach could serve as a generic method for synthesizing polymer-functionalized, sub-10 nm Janus NPs. This unique system holds promises for achieving controlled assembly and tunable optic and electronic properties of NPs.     

Colloidal stability evolution and completely reversible aggregation of gold nanoparticles functionalized with rationally designed free radical initiators

A series of molecular adsorbates having various chain lengths of terminal poly(ethylene glycol methyl ether) (PEG) moieties, thiol head groups, and intervening free radical initiator moieties was used to functionalize the surface of gold nanoparticles (AuNPs). The bulky PEG groups stabilized the functionalized AuNPs by providing steric hindrance against AuNP aggregation, such aggregation being a major problem in the modification and manipulation of metal nanoparticles. UV–vis spectroscopy was used to evaluate the stability of the adsorbate-functionalized AuNPs as a function of AuNP size (～15, 40, and 90 nm in diameter) and PEG chain length (Mn 350, 750, and 2,000). The longer PEG chains (Mn 750 and 2,000) afforded stability to AuNPs with smaller gold cores (～15 and 40 nm in diameter) for up to several days without any marked aggregation. In contrast, the adsorbate-functionalized AuNPs with the largest gold cores (～90 nm) were noticeably less stable than those with the smaller gold cores. Importantly, the adsorbate-functionalized AuNPs could be isolated in solvent-free “dried” form and readily dispersed in aqueous buffer solution (both acidic and basic) and various organic solvents (protic and aprotic). This isolation–redispersion (i.e., aggregation/deaggregation) process was completely reversible. The chemisorption of the PEG-terminated initiator on the surface of the AuNPs was verified by Fourier transform infrared (FT-IR) spectroscopy and X-ray photoelectron spectroscopy (XPS). As a whole, the strategy reported here affords colloidally stable, free radical initiator-functionalized AuNPs and offers a promising general method for encapsulating metal nanoparticles within polymer shells.

The Effect of Ligand Denticity in Size‐Selective Synthesis of Calix[n]arene‐Stabilized Gold Nanoparticles: A Multitechnique Approach

A series of gold nanoparticles (AuNPs) stabilized by monodentate, bidentate, and tridentate thiolate calix[n]arene ligands 1 – 3 was prepared by using the Brust–Schiffrin two‐phase direct synthesis and characterized with NMR spectroscopy, elemental analysis, transmission electron microscopy (TEM), and X‐ray photoelectron spectroscopy (XPS). The experimental data show that the particular multidentate structure of calix[n]arene derivatives 2 and 3 introduces a control element in the preparation of the gold nanoparticles that allows, in the particular experimental conditions here reported, to obtain very small (≈1 nm) AuNPs. These are the first experimental findings that identify a role of ligand “denticity” in the determination of the nuclearity of nanoparticles.     

Synthesis of cationic hyperbranched multiarm copolymer and its application in self-reducing and stabilizing gold nanoparticles

A novel hyperbranched multiarm copolymer of HBPO-star-PDEAEMA with a hydrophobic poly(3-ethyl-3-(hydroxymethyl) oxetane)(HBPO) core and many cationic poly(2-(N,N-diethylamino) ethyl methacrylate)(PDEAEMA) arms has been synthesized through an atom transfer radical polymerization(ATRP) method,and been applied to spontaneously reduce and stabilize gold nanoparticles(AuNPs) in water without other additional agents.The size of the nanoparticles could be effectively controlled at about 4 nm,and the nanoparticles ...