Surface‐Passivated SBA‐15‐Supported Gold Nanoparticles: Highly Improved Catalytic Activity and Selectivity toward Hydrophobic Substrates

Silanol groups on a silica surface affect the activity of immobilized catalysts because they can influence the hydrophilicity/hydrophobicity, matter transfer, or even transition state in a catalytic reaction. Previously, these silanol groups have usually been passivated by using surface‐passivation reagents, such as alkoxysilanes, bis‐silylamine reagents, chlorosilanes, etc., and surface passivation has typically been found in mesoporous‐silicas‐supported molecular catalysts and heteroatomic catalysts. However, this property has rarely been reported in mesoporous‐silicas‐supported metal‐nanoparticle catalysts. Herein, we prepared an almost‐superhydrophobic SBA‐15‐supported gold‐nanoparticle catalyst by using surface passivation, in which the catalytic activity increased more than 14 times for the reduction of nitrobenzene compared with non‐passivated SBA‐15. In addition, this catalyst can selectively catalyze hydrophobic molecules under our experimental conditions, owing to its high (almost superhydrophobic) hydrophobic properties.     

Efficient eco-friendly approach towards bimetallic nanoparticles synthesis and characterization using Exiguobacterium aestuarii by statistical optimization

ABSTRACT

Biogenic synthesis of bimetallic nanoparticles (gold – AuNp and selenium – SeNp) using inexpensive Tryptophan Enriched Banana Peel Media for the growth of marine isolate (Exiguobacterium aestuarii SBG4 MH185868). The response surface methodology is employed for optimizing production conditions. The surface plasmon resonance band showed λ_max at 540?nm (AuNp) and 284?nm (SeNp). FTIR and zeta potential analysis confirmed the stability, whereas XRD spectra revealed the nature of nanoparticles obtained at optimum conditions. SEM micrographs showed nanospheres of the following size: AuN, 30?±?5 nm and SeNp, 50?±?5 nm. Biocompatibility of Np evaluated by the hemolytic activity showed <20% hemolysis even at highest concentrations (100?µg/ml). AuNp showed the least cytotoxicity, whereas SeNp showed considerable cytotoxicity against the breast cancer cell lines MCF – 7 and MDA-MB-231. Hence, we utilized the environment-friendly growth media for the controlled synthesis of dual Np using single bacterial strain involving feasible steps in downstream processing.     

Facile Fabrication of Multi‐targeted and Stable Biochemical SERS Sensors

The direct transfer of single‐crystalline Au nanowires (NWs) onto Au substrates was achieved by a simple attachment and detachment process. In the presence of a lubricant, Au NWs grown vertically on a sapphire substrate were efficiently moved to an Au substrate through van der Waals interactions. We demonstrate that the transferred Au NWs on the Au substrate can act as sensitive, reproducible, and long‐term‐stable surface‐enhanced Raman scattering (SERS) sensors by detecting human α‐thrombin as well as Pb²⁺ and Hg²⁺ ions. These three biochemically and/or environmentally important analytes were successfully detected with high sensitivity and selectivity by Au NW‐SERS sensors bound by a thrombin‐binding aptamer. Furthermore, the as‐prepared sensors remained in working order after being stored under ambient conditions at room temperature for 80 days. Because Au NWs can be routinely transferred onto Au substrates and because the resultant Au NW‐SERS sensors are highly stable and provide with high sensitivity and reproducibility of detection, these sensors hold potential for practical use in biochemical sensing.     

Ultrasensitive electrochemical immunosensor for zeranol detection based on signal amplification strategy of nanoporous gold films and nano-montmorillonite as labels

Nano-montmorillonites belong to aluminosilicate clay minerals with innocuity, high specific surface area, ion exchange, and favorable adsorption property. Due to the excellent properties, montmorillonites can be used as labels for the electrochemical immunosensors. In this study, nano-montmorillonites were converted to sodium montmorillonites (Na-Mont) and further utilized for the immobilization of thionine (TH), horseradish peroxidase (HRP) and the secondary anti-zeranol antibody (Ab₂). The modified particles, Na-Mont-TH-HRP-Ab₂ were used as labels for immunosensors to detect zeranol. This protocol was used to prepare the immunosensor with the primary antibody (Ab₁) immobilized onto the nanoporous gold films (NPG) modified glassy carbon electrode (GCE) surface. Within zeranol concentration range (0.01–12 ng mL⁻¹), a linear calibration plot (Y = 0.4326 + 8.713 X, r = 0.9996) was obtained with a detection limit of 3 pg mL⁻¹ under optimal conditions. The proposed immunosensor showed good reproducibility, selectivity, and stability. This new type of immunosensors with montmorillonites and NPG as labels may provide potential applications for the detection of zeranol.     

Electrochemical immunosensor based on nanoporpus gold loading thionine for carcinoembryonic antigen

Nanoporous gold (NPG) has recently received considerable attention in analytical electrochemistry because of its good conductivity and large specific surface area. A facile layer-by-layer assembly technique fabricated NPG was used to construct an electrochemical immunosensor for carcinoembryonic antigen (CEA). NPG was fabricated on glassy carbon (GC) electrode by alternatively assembling gold nanoparticles (AuNPs) and silver nanoparticles (AgNPs) using 1,4-benzenedimethanethiol as a cross-linker, and then AgNPs were dissolved with HNO₃. The thionine was absorbed into the NPG and then gold nanostructure was electrodeposited on the surface through the electrochemical reduction of gold chloride tetrahydrate (HAuCl₄). The anti-CEA was directly adsorbed on gold nanostructure fixed on the GC electrode. The linear range of the immunosensor was from 10 pg mL⁻¹ to 100 ng mL⁻¹ with a detection limit of 3 pg mL⁻¹ (S/N = 3). The proposed immunosensor has high sensitivity, wide linear range, low detection limit, and good selectivity. The present method could be widely applied to construct other immunosensors.     

Intermolecular interactions of a size‐expanded guanine analogue with gold nanoclusters

The interactions between a size‐expanded Guanine analogue x‐Guanine (xG) and gold nanoclusters, Au_n (n = 2, 4, 6, and 8), were studied theoretically using density functional theory. Geometries of neutral complexes were optimized using the B3LYP functional with the 6‐31+G(d,p) basis set for xG and the LANL2DZ basis set for gold clusters. The binding modes, interaction strength, and the charge‐transfer properties of different Au_n‐xG complexes were investigated. Natural population analysis was performed for natural bond order charges. It was found that gold nanoclusters form stable complexes with xG and these binding results in a substantial amount of electronic charge being transferred from xG to the gold clusters. The vertical first ionization potential, electron affinity, Fermi Level, and the HOMO–LUMO gap of xG and its complexes with gold nanoclusters were also analyzed. © 2013 Wiley Periodicals, Inc.     

Efficient Two-Step Synthesis of 11,11′-Dithiobis[1-(2-bromo-2-methylpropionyloxy)undecane], a Conventional Initiator for Grafting Polymer Brushes from Gold Surfaces via ATRP

11,11′-Dithiobis[1-(2-bromo-2-methylpropionyloxy)undecane], a conventional initiator for grafting polymers from gold surfaces, was synthesized in two steps from 11-mercapto-1-undecanol in 88–92% overall yield. Oxidative dimerization of 11-mercapto-1-undecanol with a catalytic amount of sodium iodide and 30% hydrogen peroxide in ethyl acetate proceeded in 96% yield. Esterification with 2-bromoisobutyryl bromide in dichloromethane was clean and almost quantitative (92% yield) with pyridine used as base, whereas triethylamine gave a messy reaction (64% yield). Alternatively, esterification with 2-bromo-2-methyl-propanoic acid in dichloromethane occurred readily under Steglich's conditions with N,N′-dicyclohexylcarbodiimide (DCC) and a catalytic amount of dimethylaminopyridine (DMAP; 88% yield).     

Synthesis and Characterization of Self-Assembling Some Thiol Surfactants on Gold Nanoparticles

The purpose of this work is to study the self-assembling of some synthesized thiol surfactants namely (mercaptopropane-, mercaptohexane-, mercaptooctane-, and mercaptodecane sodium sulfonate) on the fabricated gold nanoparticles. The self-assembling of these surfactants on gold nanoparticles characterized using different techniques such as FTIR spectroscopy, UV spectroscopy, and transmission electron microscopy (TEM). Spectroscopic evidence suggests that the synthesized thiol surfactants have been attached to the gold nanoparticles. The effect of self-assembling of these surfactants on the size of the gold nanoparticles was studied using TEM images. The growth of the gold nanoparticles was investigated with respect to the increase of alkyl chain in the synthesized thiol surfactants. The results show that the stabilization of gold nanoparticles was affected by the increase in alkyl chain length of these surfactants. The effect of gold nanoparticles on the interfacial tension and the emulsion stability of these surfactants with crude oil was studied.     

Photocatalytic Activity of High Aspect Ratio TiO2 Nanorods

In this article, TiO₂ nanorods (aspect ratio >20) were prepared through a polyol process and doped with metal ions (Cu²⁺, Ni²⁺, Fe³⁺, and Cr³⁺). Compared with TiO₂ nanoparticles, the TiO₂ nanorods displayed relatively higher photocatalytic activity for the degradation of copper sulfophthalocyanine. Moreover, the photocatalytic activity was greatly enhanced when the metal ions were doped in the TiO₂ nanorods.