One-pot synthesis of Ag-Au bimetallic nanoparticles with Au shell and their high catalytic activity for aerobic glucose oxidation

PVP-protected Ag(core)/Au(shell) bimetallic nanoparticles of enough small size, i.e., 1.4nm in diameter were synthesized in one-vessel using simultaneous reduction of the corresponding ions with rapid injection of NaBH(4), and characterized by HR-TEM. The Ag(core)/Au(shell) bimetallic nanoparticles show a high and durable catalytic activity for the aerobic glucose oxidation, and the catalyst can be stably kept for more than 2months under ambient conditions. The highest activity (16,890mol-glucoseh(-1)mol-metal(-1)) was observed for the bimetallic nanoparticles with Ag/Au atomic ratio of 2/8, the TOF value of which is several times higher than that of Au nanoparticles with nearly the same particle size. The higher catalytic activity of the prepared bimetallic nanoparticles than the usual Au nanoparticles can be ascribed to: (1) the small average diameter, usually less than 2.0nm, and (2) the electronic charge transfer effect from adjacent Ag atoms and protecting PVP to Au active sites. In contrast, the Ag-Au alloy nanoparticles, synthesized by dropwise addition of NaBH(4) into the starting solution and having the large mean particle size, showed a low catalytic activity.     

Pt nanoparticles modified Au nanowire array for amperometric and potentiometric detection of glucose

A new glucose biosensor, based on the modification of highly ordered Au nanowire arrays (ANs) with Pt nanoparticles (PtNPs) and subsequent surface adsorption of glucose oxidase (GOx), is described. Morphologies of ANs and ANs/PtNPs were observed by scanning electron microscope. The electrochemical properties of ANs, ANs/GOx, ANs/PtNPs, and ANs/PtNPs/GOx electrodes were compared by cyclic voltammetry. Results obtained from comparison of the cyclic voltammograms show that PtNPs modification enhances electrochemical catalytic activity of ANs to H₂O₂. Hence, ANs/PtNPs/GOx biosensor exhibits much better sensing to glucose than ANs/GOx. Optimum deposition time of ANs/PtNPs/GOx biosensor for both amperometric and potentiometric detection of glucose was achieved to be 150 s at deposition current of 1?×?10^?6 A. A sensitivity of 0.365 μA/mM with a linear range from 0.1 to 7 mM was achieved for amperometric detection; while for potentiometric detection the sensitivity is 33.4 mV/decade with a linear range from 0.1 to 7 mM.     

氮化硼负载的高分散Au-CuOx纳米颗粒用于低温CO氧化

负载型金催化剂显示出高的低温CO氧化活性,其催化性能与载体的性质密切相关.近年来,六方氮化硼作为一种新型催化材料引起了极大关注.已有研究表明,二维结构的氮化硼纳米片有利于传质扩散,并且暴露出大量的表面和边缘,作为新型非金属催化剂在烷烃氧化脱氢中表现出优异的活性.同时,CO氧化反应是强放热过程,氮化硼具有优良的导热性能,...     

Aptamer-wrapped gold nanoparticles for the colorimetric detection of omethoate

Organophosphorous pesticide(OP) contamination has serious adverse effects on human health and the environment. Due to the toxicity of OPs and the threat presented by their accidental or intentional release in populated areas, the determination and monitoring of these OPs in food products and environment is of great importance. OPs are present in very small quantities and therefore, methods for their detection need to be highly sensitive and selective. Here, we aimed to develop a simple and selective aptamer-based colorimetric assay for the detection of omethoate, which is one of the commonly used OPs. The principle of the assay is that single-stranded DNA(ss DNA)-wrapped gold nanoparticles(Au NPs) are resistant to salt-induced aggregation. By employing an "artificial antibody" organophosphorous pesticide-binding aptamer(OBA) as the recognition element, aptamer-wrapped Au NPs(Au-apta) show high selectivity towards omethoate, resulting in the disconnection of aptamers from Au NPs and the aggregation of Au NPs. As there is a significant color change from the interparticle plasmon coupling during the aggregation of Au NPs, the established assay showed good linearity between 0.1 and 10 μmol/L, with a low detection limit of 0.1 μmol/L. Other OPs such as profenofos, phorate, and isocarbophos would not interfere with the detection of omethoate despite having similar structures. Thus, the colorimetric method shows potential for use in the detection of omethoate in real soil samples.     

Direct-growth of polyaniline nanowires for enzyme-immobilization and glucose detection

Amperometric enzyme biosensor based on the glucose oxidase (GOx) incorporated polyaniline nanowires (PANI-NWs) on carbon cloth (CC) electrode was demonstrated. The simple, direct-growth of PANI-NWs on CC, via electrochemical polymerization, provides free-standing, template-independent, hence almost (interfacial) defects-free nanostructures. The defect-free interfaces, along with the excellently sensitive organic nanostructured-surface, as evident from its significantly large effective surface area (24 times the geometric area) for redox-sensing, allows efficient entrapment/immobilization and sensing of biomolecules, via rapid electron-transfer at NWs-CC. The GOx-immobilized PANI-NWs/CC, even in initial unoptimized stage, exhibited an excellent sensitivity, ～2.5 mA mM^?1 cm^?2, to glucose, over detection range 0–8 mM, adequate for clinical monitoring of human glucose levels. The report clearly reveals a cost-effective simple system possessing enormous potentiality for biosensors, bioenergy and bioelectronics applications.     

Enhanced catalytic DNAzyme for label-free colorimetric detection of DNA

A DNAzyme-based label-free method for the colorimetric detection of DNA is introduced, with a supramolecular hemin-G-quartet complex as the sensing element and a 36-mer single-strand DNA as the analyte that is detected at 10 nM.     

Direct deposition of gold nanoparticles onto polymer beads and glucose oxidation with H2O2

Gold nanoparticles (Au NPs) were deposited directly from aqueous solution of diethylenediaminegold(III) complex onto polymer beads commercially available, such as poly(methyl methacrylate) (PMMA), polystyrene (PS), and polyaniline (PANI) without surface modification. The dropwise addition of NaBH4 to reduce Au(III) was found to be very effective to obtain small Au0 NPs with a narrow size distribution except for PANI. The catalytic performance of Au NPs deposited on polymer beads for H2O2 decomposition and glucose oxidation with H2O2 were more significantly affected by the kinds of polymer supports than by the size of Au NPs. The equimolar oxidation of glucose with H2O2 could be operated by controlling the decomposition rate of H2O2 over Au/PMMA.     

Enzymatic deposition of Au nanoparticles on the designed electrode surface and its application in glucose detection

This paper reported the enzymatic deposition of Au nanoparticles (AuNPs) on the designed 3-mercapto-propionic acid/glucose oxidase/chitosan (MPA/GOD/Chit) modified glassy carbon electrode and its application in glucose detection. Chit served as GOD immobilization matrix and interacted with MPA through electrostatic attraction. AuNPs, without nano-seeds presented on the electrode surface, was produced through the glucose oxidase catalyzed oxidation of glucose. The mechanism of production of AuNPs was confirmed to be that enzymatic reaction products H(2)O(2) in the solution reduce gold complex to AuNPs. The characterizations of the electrode modified after each assembly step was investigated by cyclic voltammetry and electrochemical impedance spectroscopy. Scanning electron microscopy showed the average particle size of the AuNPs is 40nm with a narrow particle size distribution. The content of AuNPs on the electrode surfaces was measured by differential pulse stripping voltammetry. The electrochemical signals on voltammogram showed a linear increase with the glucose concentration in the range of 0.010-0.12mM with a detection limit of 4μM. This provided a method to the determination of glucose.     

Synthesis and properties of bismuth oxide nanoshell coated polyaniline nanoparticles for promising photovoltaic properties

A novel heterostructure made of polyaniline (PANI) nanoparticles coated by nanolayer of bismuth oxide Bi₂O₃ was synthesized. The structure was characterized by scanning electron microscopy, X‐ray diffraction, and transmission electron microscopy. These characterizations showed that the bismuth oxide nanoshell was pure and crystalline, and has thickness in the range of 10 nm. The experiment on photoluminescence (PL) of Bi₂O₃ nanoshell coated polyaniline nanoparticle, at room temperature, shows an emission band peaked at around 385 nm. When compared with the PL spectrum of Bi₂O₃ nanoparticles, about 100 times PL enhancement was found in the PL spectrum of Bi₂O₃ nanoshell coated polyaniline nanoparticle. The current density versus voltage (J–V) measurements in dark and illumination showed that this heterojunction has 4 orders of magnitude rectification in the dark and 3 orders of magnitude rectification under illumination. The obtained power conversion efficiency of polyaniline nanoparticles coated by nanoshell of bismuth oxide (η = 7.453%) was much enhanced compared with polyaniline alone (η = 8.33 × 10^?4%) this indicates that the prepared heterostructure represents a promising photovoltaic solar cell. Copyright © 2009 John Wiley & Sons, Ltd.     

Aptamer-functionalized Au nanoparticles for the amplified optical detection of thrombin

The catalytic enlargement of aptamer-functionalized Au nanoparticles amplifies the optical detection of aptamer-thrombin complexes in solution and on surfaces.     

On the catalytic oxidation of ascorbic acid at self-doping polyaniline films

Ascorbic acid molecules in either acid or conjugate base forms have been oxidized on self-doping carboxylated polyaniline thin films. The kinetic model proposed by Bartlett et al. has been successfully applied to the catalytic reactions. Active sites in the polymer have been identified as the rings having quinoid character. The existence of significant electrostatic repulsions between ionogenic groups at the self-doping polymer and negatively charged ascorbate molecules has been established thanks to the analysis of the pH dependence of the Michaelis constant. It has been found that in contrast to inorganic conductors the regeneration of active sites in polyaniline-based materials is slower at higher potentials. Such a behavior can be satisfactorily correlated with the potential dependence of the polymer electronic conductivity.     

Triarylcarbinol functionalized gold nanoparticles for the colorimetric detection of nerve agent simulants

Gold nanoparticles functionalized with a triarylcarbinol derivative have been used as colorimetric molecular probes for the naked-eye detection of the nerve agent simulants DCNP and DFP. The detection process is based on the compensation of charges at the surface of the nanoparticles which triggers their aggregation in solution with the resulting change in their plasmon band.     

Self-assembly of core-satellite gold nanoparticles for colorimetric detection of copper ions

Molecule-coated nanoparticles are hybrid materials which can be engineered with novel properties. The molecular coating of metal nanoparticles can provide chemical functionality, enabling assembly of the nanoparticles that are important for applications, such as biosensing devices. Herein, we report a new self-assembly of core-satellite gold nanoparticles linked by a simple amino acid l-Cysteine for biosensing of Cu²⁺. The plasmonic properties of core-satellite nano-assemblies were investigated, a new red shifted absorbance peak from about 600 to 800 nm was found, with specific wavelength depending on ratios with assembly of large and small gold nanoparticles. The spectral features obtained using surface-enhanced Raman spectroscopy (SERS) provided strong evidence for the assembly of the Cu²⁺ ions to the L-Cysteine molecules leading to the successful formation of the core-satellite Cu(l-Cysteine) complex on the gold surfaces. In addition, a linear relationship between the concentration of mediating Cu²⁺ and absorbance of self-assembled gold nanoparticles (GNPs) at 680 nm was obtained. These results strongly address the potential strategy for applying the functionalized GNPs as novel biosensing tools in trace detections of certain metal ions.     

Highly sensitive sensor for detection of NADH based on catalytic growth of Au nanoparticles on glassy carbon electrode

In this work, an electrochemical dihydronicotinamide adenine dinucleotide (NADH) sensor based on the catalytic growth of Au nanoparticles (Au NPs) on glassy carbon electrode was developed. Catalyzed by Au NPs immobilized on pretreated glassy carbon electrode, the reduction of AuCl₄ ^? in the presence of hydroquinone and cetyltrimethyl ammonium chloride led to the formation of enlarged Au NPs on the electrode surface. Spectrophotometry and high-resolution scanning electronic microscope (SEM) analysis of the sensor morphologies before and after biocatalytic reaction revealed a diameter growth of the nanoparticles. The catalytic growth of Au NPs on electrode surface remarkably facilitated the electron transfer and improved the performance of the sensor. Under optimal conditions, NADH could be detected in the range from 1.25?×?10^?6 to 3.08?×?10^?4 M, and the detection limit was 2.5?×?10^?7 M. The advantages of the proposed sensor, such as high precision and sensitivity, fast response, low cost, and good storage stability, made it suitable for on-line detection of NADH in complex biological systems and contaminant degradation processes.

A non-aggregation colorimetric assay for thrombin based on catalytic properties of silver nanoparticles

In this paper, we developed a simple and rapid colorimetric assay for protein detection based on the reduction of dye molecules catalyzed by silver nanoparticles (AgNPs). Aptamer-modified magnetic particles and aptamer-functionalized AgNPs were employed as capture and detection probes, respectively. Introduction of thrombin as target protein could form a sandwich-type complex involving catalytically active AgNPs, whose catalytic activity was monitored on the catalytic reduction of rhodamine B (RhB) by sodium borohydride (NaBH₄). The amount of immobilized AgNPs on the complex increased along with the increase of the thrombin concentration, thus the detection of thrombin was achieved via recording the decrease in absorbance corresponding to RhB. This method has adopted several advantages from the key factors involved, i.e., the sandwich binding of affinity aptamers contributed to the increased specificity; magnetic particles could result in rapid capture and separation processes; the conjugation of AgNPs would lead to a clear visual detection. It allows for the detection limit of thrombin down to picomolar level by the naked eye, with remarkable selectivity over other proteins. Moreover, it is possible to apply this method to the other targets with two binding sites as well.     

One-pot synthesis of copper nanoparticles on glass: applications for non-enzymatic glucose detection and catalytic reduction of 4-nitrophenol

Journal of Solid State Electrochemistry - Thin film of metallic Cu nanoparticles was synthesized by a one-pot chemical reduction method at ambient temperature. Cu(II) acetate monohydrate and...     

Solid-state storage of Ag nanoparticles in anion exchange resin beads and their recovery

This paper reports the idea and describes a method of reversible storage and recovery of silver nanoparticles (NPs) in anion exchange resin beads based on the principle of ion exchange. We also report that similar exchange of NPs was not possible with cation exchange resins. The Ag NPs were stored by simple exchange of anions of the resins, which were activated with OH- and NO3- ions. FTIR spectroscopic measurements support that the Ag NPs were exchanged with NO3- ions in the resins. The so-stored NPs could be regenerated by addition of NaBH4 solution to the resins. These NPs were recovered and subsequently utilized for catalytic reduction of an organic dye (eosin). Powder X-ray diffraction (XRD) pattern indicated storage of the NPs in the form of various oxides of silver in the resin, with the peak value of intensity corresponding to XRD of the NPs not changing with time. Scanning electron microscopic measurements show that the NPs in the beads were stable for over a month without the formation of any apparent agglomeration.     

Spherical polyelectrolyte brushes as bio-platforms to integrate platinum nanozyme and glucose oxidase for colorimetric detection of glucose

The integration of nanozyme and natural enzyme for cascade reactions has attracted great attention due to their huge potential applications in detection, biomedicine, and catalysis. Here the novel cascade bio-platforms were fabricated by using spherical poly[(2-methacryloyloxyethyl)trimethyl ammonium chloride] (PMOTA) brushes (SPB) as nanoreactors to prepare platinum nanoparticles in situ and as nanocarriers to immobilize glucose oxidase (GOX). The generated Pt nanoparticles possess high stability and peroxidase-like properties, which can catalyze the oxidation of 3,3′,5,5′-tetramethylbenzidine (TMB) in the presence of H₂O₂ to generate blue colored oxidized TMB (oxTMB). And the absorbed GOX can specifically catalyze the oxidation of glucose into gluconic acid and H₂O₂, while the produced H₂O₂ is subsequently catalyzed by the Pt nanozymes. Thus, the co-immobilized Pt nanozymes and GOX within SPB (SPB@Pt@GOX) acted as effective biosensors for colorimetric detection of glucose showing high selectivity and great feasibility. This work demonstrates a facile and general strategy to use SPB as bio-platforms to integrate nanozymes and natural enzymes for cascade reactions.     

Synthetic multivalent DNAzymes for enhanced hydrogen peroxide catalysis and sensitive colorimetric glucose detection

A peroxidase-mimic DNAzyme is a G-quadruplex (G₄) DNA–hemin complex, in which the G₄-DNA resembles an apoenzyme, and hemin is the cofactor for hydrogen peroxide (H₂O₂) catalysis. Twenty-one-mer CatG4 is a well-proven G₄-DNA as well as a hemin-binding aptamer for constituting a DNAzyme. This work studied if a multivalent DNAzyme with accelerated catalysis could be constructed using a multimeric CatG4 with hemin. We compared CatG4 monomer, dimer, trimer, and tetramer, which were prepared by custom oligo synthesis, for G₄ structure formation. According to circular dichroism (CD) analysis, we found that a CatG4 multimer exhibited more active G₄ conformation than the sum effect of equal-number CatG4 monomers. However, the DNAzyme kinetics was not improved monotonically along with the subunit number of a multimeric CatG4. It was the trivalent DNAzyme, trimeric CatG4:hemin, resulting in the rapidest H₂O₂ catalysis instead of a tetravalent one. We discovered that the trivalent DNAzyme’s highest catalytic rate was correlated to its most stable hemin-binding G₄ structure, evidenced by CD melting temperature analysis. Finally, a trivalent DNAzyme-based colorimetric glucose assay with a detection limit as low as 10 μM was demonstrated, and this assay did not need adenosine 5′-tri-phosphate disodium salt hydrate (ATP) as a DNAzyme boosting agent.