Exploring the interactions between gold nanoparticles and analytes through surface‐assisted laser desorption/ionization mass spectrometry

Surface‐assisted laser desorption/ionization mass spectrometry (SALDI‐MS) is applied to provide strong evidence for the chemical reactions of functionalized gold nanoparticles (Au NPs) with analytes – Hg²⁺ ions induced MPA?Au NPs aggregation in the presence of 2,6‐pyridinedicarboxylic acid (PDCA) and H₂O₂ induced fluorescence quenching of 11‐MUA?Au NDs. PDCA‐Hg²⁺‐MPA coordination is responsible for Au NPs aggregation, while the formation of 11‐MUA disulfide compounds that release into the bulk solution is responsible for H₂O₂‐induced fluorescence quenching. In addition to providing information about the chemical structures, SALDI‐MS is also selective and sensitive for the detection of Hg²⁺ ions and H₂O₂. The limits of detection (LODs) for Hg²⁺ ions and H₂O₂ by SALDI‐MS were 300 nM and 250 µM, respectively. The spot‐to‐spot variations in the two studies were both less than 18% (50 sample spots). Our results reveal that SALDI‐MS can be used to study analyte‐induced changes in the surface properties of nanoparticles. Copyright © 2010 John Wiley & Sons, Ltd.     

Nonenzymatic Hydrogen Peroxide Electrochemical Sensor Based on Au‐HS/SO3H‐PMO (Et) Nanocomposite

A newly nonenzymatic sensor for hydrogen peroxide (H₂O₂) based on the (Au‐HS/SO₃H‐PMO (Et)) nanocomposite is demonstrated. The electrochemical properties of the as‐prepared nanocomposite were studied. It displayed an excellent performance towards H₂O₂ sensing in the linear response range from 0.20 µM to 4.30 mM (R=0.9999) with a sensitivity of 6.35×10² µA µM^?1 cm^?2 and a low detection limit of 0.0499 µM. Furthermore, it was not affected by electroactive interference species. These features proved that the modified electrode was suitable for determination of H₂O₂.     

Electrochemical nanostructured biosensors: carbon nanotubes versus conductive and semi-conductive nanoparticles

The aim of this work was to demonstrate that various types of nanostructures provide different gains in terms of sensitivity or detection limit albeit providing the same gain in terms of increased area. Commercial screen printed electrodes (SPEs) were functionalized with 100 µg of bismuth oxide nanoparticles (Bi₂O₃ NPs), 13.5 µg of gold nanoparticles (Au NPs), and 4.8 µg of multi-wall carbon nanotubes (MWCNTs) to sense hydrogen peroxide (H₂O₂). The amount of nanomaterials to deposit was calculated using specific surface area (SSA) in order to equalize the additional electroactive surface area. Cyclic voltammetry (CV) experiments revealed oxidation peaks of Bi₂O₃ NPs, Au NPs, and MWCNTs based electrodes at (790 ± 1) mV, (386 ± 1) mV, and (589 ± 1) mV, respectively, and sensitivities evaluated by chronoamperometry (CA) were (74 ± 12) µA mM^?1 cm^?2, (129 ± 15) ±A mM^?1 cm^?2, and (54 ± 2) ±A mM^?1 cm^?2, respectively. Electrodes functionalized with Au NPs showed better sensing performance and lower redox potential (oxidative peak position) compared with the other two types of nanostructured SPEs. Interestingly, the average size of the tested Au NPs was 4 nm, under the limit of 10 nm where the quantum effects are dominant. The limit of detection (LOD) was (11.1 ± 2.8) ±M, (8.0 ± 2.4) ±M, and (3.4 ± 0.1) ±M for Bi₂O₃ NPs, Au NPs, and for MWCNTs based electrodes, respectively.     

Efficient chemiluminescence by aptamer – reactant platform combination with activated Ag–Au alloy nanoparticles for cobalt detection

This article deals with the detection of Co(II) in real water sample using aptamer – reactant platform combination with activated Ag–Au alloy nanoparticles (NPs) by chemiluminescence (CL) method. CL is attributed to a catalytically enhanced decomposition of H₂O₂ by aptamer conjugated Ag–Au alloy NPs to produce reactive oxygen species. The Ag–Au alloy NPs were prepared by chemical method using double reducing agent (i.e. trisodium citrate and polyethylenimine) and used for detection of Co(II) from water by CL method. CL experiments were carried out with the variation of different parameters such as pH, concentration of luminol, concentration of H₂O₂ and Ag–Au alloy NPs. We found that Ag–Au alloy NPs have very good efficiency towards Co(II) detection. Analytical parameters and kinetics were studied in detail to know the nature and mechanism of CL in presence of aptamer conjugated Ag–Au alloy NPs. The linear range of the CL sensor of Co(II) is covered concentration from 0.01 to 10 µg/L with detection limit of 0.001 µg/L. The relative standard deviation for determination of Co(II) was 6.65 in 10 replicated measurements. CL method is first time applied to detect the Co(II) in real water samples at very low level using aptamer conjugated Ag–Au NPs as a catalyst.     

Palladium Nanoparticles Embedded into Graphene Nanosheets: Preparation,Characterization, and Nonenzymatic Electrochemical Detection of H2O2

A novel nonenzymatic H₂O₂ sensor based on a palladium nanoparticles/graphene (Pd‐NPs/GN) hybrid nanostructures composite film modified glassy carbon electrode (GCE) was reported. The composites of graphene (GN) decorated with Pd nanoparticles have been prepared by simultaneously reducing graphite oxide (GO) and K₂PdCl₄ in one pot. The Pd‐NPs were intended to enlarge the interplanar spacing of graphene nanosheets and were well dispersed on the surface or completely embedded into few‐layer GN, which maintain their high surface area and prevent GN from aggregating. XPS analysis indicated that the surface Pd atoms are negatively charged, favoring the reduction process of H₂O₂. Moreover, the Pd‐NPs/GN/GCE could remarkably decrease the overpotential and enhance the electron‐transfer rate due to the good contact between Pd‐NPs and GN sheets, and Pd‐NPs have high catalytical effect for H₂O₂ reduction. Amperometric measurements allow observation of the electrochemical reduction of H₂O₂ at 0.5 V (vs. Ag/AgCl). The H₂O₂ reduction current is linear to its concentration in the range from 1×10^?9 to 2×10^?3 M, and the detection limit was found to be 2×10^?10 M (S/N=3). The as‐prepared nonenzymatic H₂O₂ sensor exhibits excellent repeatability, selectivity and long‐term stability.     

Gold‐Nanoparticle‐Loaded Carbonate‐Modified Titanium(IV) Oxide Surface: Visible‐Light‐Driven Formation of Hydrogen Peroxide from Oxygen

Gold nanoparticle‐loaded rutile TiO₂ with a bimodal size distribution around 10.6 nm and 2.3 nm (BM‐Au/TiO₂) was prepared by the deposition precipitation and chemical reduction (DP‐CR) technique. Visible‐light irradiation (λ>430 nm) of the BM‐Au/TiO₂ plasmonic photocatalyst yields 35 μm H₂O₂ in aerated pure water at irradiation time (t_p)=1 h, and the H₂O₂ concentration increases to 640±60 μm by the addition of 4 % HCOOH as a sacrificing electron donor. Further, a carbonate‐modified surface BM‐Au/TiO₂ (BM‐Au/TiO₂‐CO₃^2?) generates a millimolar level of H₂O₂ at t_p=1 h with a quantum efficiency (Φ) of 5.4 % at λ=530 nm under the same conditions. The recycle experiments confirmed the stable performance of BM‐Au/TiO₂.     

Direct Electrochemistry and Application in Electrocatalysis of Hemoglobin in a Polyacrylic Resin‐Gold Colloid Nanocomposite Film

A novel nanocomposite integrating the good biocompatibility of polyacrylic resin nanoparticles (PAR) and the good conductivity of colloidal gold nanoparticles was proposed to construct the matrix for the immobilization of hemoglobin (Hb) on the surface of a glassy carbon electrode (GCE). UV‐vis spectra demonstrated that Hb preserved its native structure after being entrapped into the composite film. The direct electrochemistry of hemoglobin (Hb) in this nanocomposite films showed a pair of well‐defined and quasi‐reversible cyclic voltammetric peaks with a formal potential of ?0.307 mV and a constant electron transfer rate of 2.51±0.2 s^?1. The resultant amperometric biosensor showed fast responses to the analytes with excellent detection limits of 0.2 µM for H₂O₂ and 0.89 µM for TCA (S/N=3), and high sensitivity of 1108.6 for H₂O₂ and 77.14 mA cm^?2 M^?1 for TCA, respectively. The linear current response was found in the range from 0.59 to 7.3 µM (R²=0.9996) for H₂O₂ and from 5 to 85 µM (R²=0.9996) for TCA, while the superior apparent Michaelis–Menten constant was 0.012 mM for H₂O₂ and 0.536 mM for TCA, respectively. Therefore, the PAR‐Au‐Hb nanocomposite as a novel matrix opens up a possibility for further study on the direct electrochemistry of other proteins.     

Visible‐Light‐Induced Electron Transport from Small to Large Nanoparticles in Bimodal Gold Nanoparticle‐Loaded Titanium(IV) Oxide

A key to realizing the sustainable society is to develop highly active photocatalysts for selective organic synthesis effectively using sunlight as the energy source. Recently, metal‐oxide‐supported gold nanoparticles (NPs) have emerged as a new type of visible‐light photocatalysts driven by the excitation of localized surface plasmon resonance of Au NPs. Here we show that visible‐light irradiation (λ>430 nm) of TiO₂‐supported Au NPs with a bimodal size distribution (BM‐Au/TiO₂) gives rise to the long‐range (>40 nm) electron transport from about 14 small (ca. 2 nm) Au NPs to one large (ca. 9 nm) Au NP through the conduction band of TiO₂. As a result of the enhancement of charge separation, BM‐Au/TiO₂ exhibits a high level of visible‐light activity for the one‐step synthesis of azobenzenes from nitrobenzenes at 25 °C with a yield greater than 95 % and a selectivity greater than 99 %, whereas unimodal Au/TiO₂ (UM‐Au/TiO₂) is photocatalytically inactive.     

Sensitive and Selective Sensing of Hydrogen Peroxide with Iron‐Tetrasulfophthalocyanine‐Graphene‐Nafion Modified Screen‐Printed Electrode

We developed a novel iron‐tetrasulfophthalocyanine‐graphene‐Nafion (FeTSPc‐GR‐Nafion) modified screen‐printed electrode to determine hydrogen peroxide (H₂O₂) with high sensitivity and selectivity. The nanocomposite film (FeTSPc‐GR‐Nafion) exhibits an excellent electrocatalytic activity towards oxidation of H₂O₂ at a potential of +0.35 V in the absence of enzyme. A comparative study reveals that the FeTSPc‐GR complexes play a dual amplification role. Amperometric experiment indicates that the sensors possess good sensitivity and selectivity, with a linear range from 2.0×10^?7 M to 5.0×10^?3 M and a detection limit of 8.0×10^?8 M. This sensor has been successfully used to develop the glucose biosensor and has also been applied to determine H₂O₂ in sterile water.     

Size‐Dependence of the Activity of Gold Nanoparticle‐Loaded Titanium(IV) Oxide Plasmonic Photocatalyst for Water Oxidation

Mesoporous TiO₂ nanocrystalline film was formed on fluorine‐doped tin oxide electrode (TiO₂/FTO) and gold nanoparticles (NPs) of different sizes were loaded onto the surface with the loading amount kept constant (Au/TiO₂/FTO). Visible‐light irradiation (λ>430 nm) of the Au/TiO₂/FTO photoanode in a photoelectrochemical cell with the structure of photoanode|0.1 m NaClO4 aqueous solution|Ag/AgCl (reference electrode)|glassy carbon (cathode) leads to the oxidation of water to oxygen (O₂). We show that the visible‐light activity of the Au/TiO₂/FTO anode increases with a decrease in Au particle size (d) at 2.9≤d≤11.9 nm due to the enhancement of the charge separation and increasing photoelectrocatalytic activity.     

Controlling the Selectivity of the Surface Plasmon Resonance Mediated Oxidation of p‐Aminothiophenol on Au Nanoparticles by Charge Transfer from UV‐excited TiO2

Although catalytic processes mediated by surface plasmon resonance (SPR) excitation have emerged as a new frontier in catalysis, the selectivity of these processes remains poorly understood. Here, the selectivity of the SPR‐mediated oxidation of p‐aminothiophenol (PATP) employing Au NPs as catalysts was controlled by the choice of catalysts (Au or TiO₂‐Au NPs) and by the modulation of the charge transfer from UV‐excited TiO₂ to Au. When Au NPs were employed as catalyst, the SPR‐mediated oxidation of PATP yielded p,p‐dimercaptobenzene (DMAB). When TiO₂‐Au NPs were employed as catalysts under both UV illumination and SPR excitation, p‐nitrophenol (PNTP) was formed from PATP in a single step. Interestingly, PNTP molecules were further reduced to DMAB after the UV illumination was removed. Our data show that control over charge‐transfer processes may play an important role to tune activity, product formation, and selectivity in SPR‐mediated catalytic processes.     

Direct electrochemical behavior of hemoglobin at surface of Au@Fe3O4 magnetic nanoparticles

Nanoparticles (NPs) consisting of an Fe₃O₄ core and a thin gold shell (referred to as Au@Fe₃O₄ NPs) were self-assembled on the surface of a glassy carbon electrode modified with ethylenediamine. Following adsorption of hemoglobin, its interaction with the NPs was studied by UV–Vis spectroscopy, electrochemical impedance spectroscopy, and cyclic voltammetry. Stable and well-defined redox peaks were observed at about ?350 mV and ?130 mV in pH 6.0 buffer. The modified electrode was used as a mediator-free sensor for hydrogen peroxide (H₂O₂), with a linear range from 3.4 µM to 4.0 mM of H₂O₂, and with a 0.67 µM detection limit (at an S/N of 3). The apparent Michaelis-Menten constant is 2.3 mM.     

Simple Electrodeposition of Dendritic Pd Without Supporting Electrolyte and Its Electrocatalytic Activity Toward Oxygen Reduction and H2O2 Sensing

Metallic palladium (Pd) electrocatalysts for oxygen reduction and hydrogen peroxide (H₂O₂) oxidation/reduction are prepared via electroplating on a gold metal substrate from dilute (5 to 50 mM) aqueous K₂PdCl₄ solution. The best Pd catalyst layer possessing dendritic nanostructures is formed on the Au substrate surface from 50 mM Pd precursor solution (denoted as Pd‐50) without any additional salt, acid or Pd templating chemical species. The Pd‐50 consisted of nanostructured dendrites of polycrystalline Pd metal and micropores within the dendrites which provide high catalyst surface area and further facilitate reactant mass transport to the catalyst surface. The electrocatalytic activity of Pd‐50 proved to be better than that of a commercial Pt (Pt/C) in terms of lower overpotential for the onset and half‐wave potentials and a greater number of electrons (n) transferred. Furthermore, amperometric i–t curves of Pd‐50 for H₂O₂ electrochemical reaction show high sensitivities (822.2 and ?851.9 µA mM^?1 cm^?2) and low detection limits (1.1 and 7.91 µM) based on H₂O₂ oxidation H₂O₂ reduction, respectively, along with a fast response (<1 s).     

Multiple plasmonic effect on photocurrent generation of metal‐loaded titanium dioxide composite/dye films on gold grating surface

We demonstrate the multiple plasmonic effect on the photocurrent properties of photoanodes containing Ag or Au nanoparticles (NPs) loaded onto titanium dioxide film (Ag–TiO₂ or Au–TiO₂) on Au grating surfaces. Ag–TiO₂ or Au–TiO₂ nanocomposite particles are prepared by a flame spray pyrolysis route. The structures and morphologies of the prepared products are characterized by high‐resolution transmission electron microscopy. The Ag–TiO₂ or Au–TiO₂ composite NPs are deposited by spin coating onto the Au grating surfaces. The photoanode electrode is a layered structure of blu‐ray disc‐recordable grating substrate/Au/Ag (or Au)–TiO₂/dye/electrolyte/indium‐tin oxide. The plasmonic effect is induced when Ag or Au NPs are located within the propagating surface plasmon (SP) field on the Au grating surface. The short‐circuit photocurrent is increased by exciting the grating‐coupled propagating SP on the Au gratings and is further enhanced by positioning the Ag or Au NPs within the grating‐coupled SP field. Copyright © 2014 John Wiley & Sons, Ltd.     

Electrochemical Fabrication of Prussian Blue Nanocube‐decorated Electroreduced Graphene Oxide for Amperometric Sensing of NADH

In this study, Prussian blue (PB) film on the electroreduced graphene oxide (ERGO)‐modified Au electrode surface (ERGO/PB) is easily prepared by means of cyclic voltammetric technique in the mixture of K₃Fe(CN)₆ and FeCl₃. Its electrochemical behaviors for NADH biosensor are studied. The structural and morphological characters of modified electrode material are analyzed with using of XPS, XRD, Raman, EDS, and SEM techniques. ERGO/PB hybrid nanocomposite for NADH biosensor is exhibited to the higher catalytic effect (linear range from 1.0 to 100 μM, detection limit of 0.23 μM at S/N=3) compared to naked Au, ERGO‐modified Au, and PB‐modified Au electrodes. In addition to, ERGO/PB electrode was used to voltammetric and amperometric detection of H₂O₂. ERGO/PB electrodes also showed the same behavior as the NADH sensor. This ERGO/PB‐modified electrode supplied a simple, new, and low‐cost route for amperometric sensing of both NADH and H₂O₂.     

A New Enzyme Immobilization Technique Based on Thionine‐Bovine Serum Albumin Conjugate and Gold Colloidal Nanoparticles for Reagentless Amperometric Biosensor Applications

A novel enzyme immobilization technique based on thionine‐bovine serum albumin conjugate (Th‐BSA) and gold colloidal nanoparticles (nano‐Au) was developed. Thionine was covalently bound onto the BSA film with glutaraldehyde(GA) as cross‐linker to achieve Th‐BSA conjugate. The free amino groups of thionine were then used to attach nano‐Au for the immobilization of horseradish peroxidase (HRP). Such nano‐Au/Th‐BSA matrix shows a favorable microenvironment for retaining the native activity of the immobilized HRP and thionine immobilized in this way can effectively shuttle electrons between the electrode and the enzyme. The proposed biosensor displays excellent catalytic activity and rapid response for H₂O₂. The linear range for the determination of H₂O₂ is from 4.9×10^?7 to 1.6×10^?3 M with a detection limit of 2.1×10^?7 M at 3σ and a Michaelies‐Menten constant K value of 0.023 mM.     

Correlation of the Catalytic Activity for Oxidation Taking Place on Various TiO2 Surfaces with Surface OH Groups and Surface Oxygen Vacancies

Three catalytic oxidation reactions have been studied: The ultraviolet (UV) light induced photocatalytic decomposition of the synthetic dye sulforhodamine B (SRB) in the presence of TiO₂ nanostructures in water, together with two reactions employing Au/TiO₂ nanostructure catalysts, namely, CO oxidation in air and the decomposition of formaldehyde under visible light irradiation. Four kinds of TiO₂ nanotubes and nanorods with different phases and compositions were prepared for this study, and gold nanoparticle (Au‐NP) catalysts were supported on some of these TiO₂ nanostructures (to form Au/TiO₂ catalysts). FTIR emission spectroscopy (IES) measurements provided evidence that the order of the surface OH regeneration ability of the four types of TiO₂ nanostructures studied gave the same trend as the catalytic activities of the TiO₂ nanostructures or their respective Au/TiO₂ catalysts for the three oxidation reactions. Both IES and X‐ray photoelectron spectroscopy (XPS) proved that anatase TiO₂ had the strongest OH regeneration ability among the four types of TiO₂ phases or compositions. Based on these results, a model for the surface OH group generation, absorption, and activation of molecular oxygen has been proposed: The oxygen vacancies at the bridging O^2? sites on TiO₂ surfaces dissociatively absorb water molecules to form OH groups that facilitate adsorption and activation of O₂ molecules in nearby oxygen vacancies by lowering the absorption energy of molecular O₂. A new mechanism for the photocatalytic formaldehyde decomposition with the Au/TiO₂ catalysts is also proposed, based on the photocatalytic activity of the Au‐NPs under visible light. The Au‐NPs absorb the light owing to the surface plasmon resonance effect and mediate the electron transfers that the reaction needs.     

Gold Nanoparticles Electrodeposited on Ordered Mesoporous Carbon as an Enhanced Material for Nonenzymatic Hydrogen Peroxide Sensor

A facile and controllable electrodeposition method was developed to directly attach gold nanoparticles (GNPs) on ordered mesoporous carbon (OMC). The GNPs on OMC substrate were characterized by scanning electron microscopy (SEM), X‐ray diffraction (XRD) and X‐ray photoelectron spectrometer (XPS), respectively. A nonenzymatic hydrogen peroxide (H₂O₂) sensor was fabricated on GNPs‐OMC/GCE. The sensor demonstrated a fast amperometric response (2.5 s), a wide linear range toward H₂O₂ concentrations between 2.0×10^?6 and 3.92×10^?3 M (R=0.999), and a low detection limit of 0.49 µM (S/N=3). Moreover, it exhibited good reproducibility and long‐term stability. The excellent electrocatalytical activity might be attributed to the synergistic effect of OMC and GNPs.     

Probing the Catalytic Activity of Reduced Graphene Oxide Decorated with Au Nanoparticles Triggered by Visible Light

Hybrid materials in which reduced graphene oxide (rGO) is decorated with Au nanoparticles (rGO–Au NPs) were obtained by the in situ reduction of GO and AuCl₄^?_(aq) by ascorbic acid. On laser excitation, rGO could be oxidized as a result of the surface plasmon resonance (SPR) excitation in the Au NPs, which generates activated O₂ through the transfer of SPR‐excited hot electrons to O₂ molecules adsorbed from air. The SPR‐mediated catalytic oxidation of p‐aminothiophenol (PATP) to p,p′‐dimercaptoazobenzene (DMAB) was then employed as a model reaction to probe the effect of rGO as a support for Au NPs on their SPR‐mediated catalytic activities. The increased conversion of PATP to DMAB relative to individual Au NPs indicated that charge‐transfer processes from rGO to Au took place and contributed to improved SPR‐mediated activity. Since the transfer of electrons from Au to adsorbed O₂ molecules is the crucial step for PATP oxidation, in addition to the SPR‐excited hot electrons of Au NPs, the transfer of electrons from rGO to Au contributed to increasing the electron density of Au above the Fermi level and thus the Au‐to‐O₂ charge‐transfer process.     

pH‐Switchable Redox Reactions and Bioelectrocatalytic Processes Using Au Nanoparticles‐Modified Electrodes

Boronate ester complexes generated between methylene blue (MB⁺)‐functionalized Au nanoparticles (NPs) and electrode surfaces are implemented to stimulate the bioelectrocatalyzed reduction of H₂O₂ in the presence of horseradish peroxidase (HRP). Two kinds of Au NPs are prepared: Class I includes MB⁺/phenylboronic acid as a modifying layer, whereas Class II includes MB⁺/dithiothreitol as a mixed capping layer. The Class I or II NPs form boronate ester complexes with a dithiothreitol‐ or phenylboronic acid‐functionalized Au electrodes, respectively. By the cyclic loading of the NPs on the electrodes (pH 8.1), and the removal of the NPs (pH 1.5), switchable bioelectrocatalyzed reduction of H₂O₂ is demonstrated.