Electrochemical Behaviors of Single Gold Nanoparticles

In this paper, the electrochemical behaviors of a single gold nanoparticle attached on a nanometer sized electrode have been studied. The single nanoparticle was characterized by using electrochemical methods. Since there is only one nanoparticle on the electrode, unarguable information for that sized particle could be obtained. Our preliminary results show that it becomes more difficult to oxidize gold nanoparticle or reduce gold nanoparticle oxide as the radius of the particle becomes smaller. Also, the peak potential of the reduction of gold nanoparticle oxide is proportional to the reciprocal of the radius of the particle.     

Determination of Norepinephrine Alone and in the Presence of Ascorbic and Uric Acids Using a Gold Electrode Modified with Gold Nanoparticles and Self‐Assembled Layers of meso‐2,3‐Dimercaptosuccinic Acid

This paper reports on the modification of gold electrodes with self‐assembled layers (SAMs) composed of meso‐2,3‐dimercaptosuccinic acid, cysteamine and gold nanoparticles, respectively and their application to quantitative determination of norepinephrine alone and in the presence of ascorbic and uric acids in solution at pH 7. The modification was carried out on two kinds of templates: a bare gold electrode (2D electrode) and a gold electrode coated in the first step with gold nanoparticles (3D electrode). Cyclic voltammograms reveal an enhancement of the norepinephrine electrooxidation in comparison to a bare, (non‐modified) gold electrode. The oxidation peaks for norepinephrine, ascorbic acid and uric acid have a peak‐to‐peak separation that enables their selective determination even in a complex mixture.     

Voltammetric Determination of Sophoridine Based on Gold Nanoparticles/L‐cysteine/ Graphene Modified Glassy Carbon Electrode

A new strategy to make the electrochemical sensor was presented, through combining gold nanoparticles (GNPs) with reduced graphene oxide (rGO) via L‐cysteine (L‐cys) as crosslinker. The resulting electrodes were characterized by scanning electron microscopy (SEM) and electrochemical methods. And it was applied to develop a high‐sensitive electrochemical sensor for determination of sophoridine. Compared with the bare GCE and reduced graphene oxide modified electrode, the resulting electrodes exhibited excellent response toward the oxidation of sophoridine by significantly enhancing the oxidation peak currents and decreasing the overpotential of sophoridine. Under the selected conditions, there exist the linear relation between the oxidation peak currents and sophoridine concentration in the range of 1.0 x 10^‐6～1.0 x 10^‐4 mol L^‐1, with detection limit of 4.0 x 10^‐7 mol L^‐1. At the same time, the method can be successfully applied to the quantitative determination of sophoridine in injection samples and its result is satisfactory.     

Gold Surface Functionalization with S‐containing Organic Compounds and Gold Nanoparticles for Ethylene Glycol Electrooxidation

In this work a gold electrode modified with self‐assembled layers (SAMs) composed with organic S‐containing compound and gold nanoparticles was prepared. The electrode with SAMs endowed with gold nanoparticles gave the high catalytic effect for ethylene glycol (EG) electrooxidation in solution at pH 7. For this novel sensor a linear relationship between the current response of EG at the potential of peak maximum (j_p) and the concentration of this compound in solution (c_EG) was found over the range 0.1 µM to 0.7 M with the detection sensitivity j_p/c_EG equal to about 5 A cm^?2 mol^?1 dm³ (at v=0.1 V s^?1) and the detection limit of 0.046 µM.     

Comparative Studies on the Quick Recognition of Melamine Using Unmodified Gold Nanoparticles and p‐Nitrobenzenesulfonic Grafted Silver Nanoparticles

Both unmodified gold nanoparticles (AuNPs) and p‐nitrobenzenesulfonic (p‐NBS) grafted silver nanoparticles (AgNPs) were prepared by chemical synthesis, respectively. They could be used for visual detection via the interaction with the twelve amide compounds including melamine. These color changes could be seen with the naked eye directly and monitored by ultraviolet visible (UV‐Vis) absorbance spectra. The recognition mechanism for both nanoparticles was comparatively investigated by the addition of glutathione (GSH) in the presence of melamine, respectively. The triple hydrogen bonding recognition and the attractive van der Waals interactions between melamine (0.5 mg/L) and AuNPs were responsible for the color change during its aggregation (red‐to‐purple or blue), whilst the electron donor‐acceptor interaction between melamine (0.2 mg/L) and p‐NBS modified on the surface of AgNPs resulted in the color changes (yellow‐to‐grey or dark green).     

Fabrication of a Sensitive Impedance Biosensor of DNA Hybridization Based on Gold Nanoparticles Modified Gold Electrode

In this work, we report on the preparation of a simple, sensitive DNA impedance sensor. Firstly gold nanoparticles were electrodeposited on the surface of a gold electrode, and then probe DNA was immobilized on the surface of gold nanoparticles through a 5′‐thiol‐linker. Electrochemical impedance spectroscopy (EIS) was used to investigate probe DNA immobilization and hybridization. Compared to the bare gold electrode, the gold nanoparticles modified electrode could improve the density of probe DNA attachment and the sensitivity of DNA sensor greatly. The difference of electron transfer resistance (ΔR_et) was linear with the logarithm of complementary oligonucleotides sequence concentrations in the range of 2.0×10^?12 to 9.0×10^?8 M, and the detection limit was 6.7×10^?13 M. In addition, the DNA sensor showed a fairly good reproducibility and stability during repeated regeneration and hybridization cycles.     

Liquid‐Crystalline Thiol‐ and Disulfide‐Based Dendrimers for the Functionalization of Gold Nanoparticles. Preliminary Communication

Liquid‐crystalline dendrons carrying either a thiol or disulfide function which display nematic, smectic A, columnar, or chiral nematic phases have been synthesized. Their mesomorphic properties are in agreement with the nature of the mesogenic units and structure of the dendrons. The first‐generation poly(aryl ester) dendron containing two cyanobiphenyl mesogenic units was used to functionalize gold nanoparticles. For full coverage, a smectic‐like supramolecular organization on the nanometer scale is observed, when the gold nanoparticles are spread onto carbon‐coated copper grids. This result indicates that the dendritic ligands reported here act as self‐organization promoters.     

A Sensitive Hydrogen Peroxide Sensor Based on Hemoglobin Immobilized on Gold Nanoparticles and 1,6-hexanedithiol Modified Gold Electrode

Hemoglobin (Hb) was successfully immobilized on a gold electrode modified with gold nanoparticles (AuNPs) via a molecule bridge 1,6-hexanedithiol (HDT). The AFM images suggested that the HDT/gold electrode could adsorb more AuNPs. UV-vis spectra indicated that Hb on AuNPs/HDT film retained its near-native secondary structures. The electrochemical behaviors of the sensor were characterized with cyclic voltammetric techniques. The resultant electrode displayed an excellent electrocatalytical response to the reduction of hydrogen peroxide (H₂O₂). The linear relationship existed between the catalytic current and the H₂O₂ concentration ranging from 5.0 × 10^?8 to 1.0 × 10^?6 mol · L^?1. The detection limit (S/N = 3) was 1.0 × 10^?8 mol · L^?1.     

Electrochemical Deposition of Gold Nanoparticles on Pencil Graphite by Fast Scan Cyclic Voltammetry

Gold nanoparticles (AuNPs) were electrodeposited on the surface of pencil graphite (PG) by fast scan cyclic voltammetry without using any additives in acidic medium. The effect of deposition time on the size of electrodeposited AuNPs was investigated in sulfuric acid as a supporting electrolyte. The deposition time was varied by varying the scan rate, number of cycles and applied potential range. Scanning electron microscopy (SEM), transmission electron microscopy (TEM) and X‐ray diffraction (XRD) were used for characterization of PG and electrodeposited AuNPs. The results confirmed that nanosized gold particles (20 ± 8 nm) were deposited on the PG substrate with almost spherical geometry.     

Immobilization of a Monolayer of Bovine Serum Albumin on Gold Nanoparticles for Stereo‐specified Recognition of Dansyl‐norvaline

The assembly strategy to prepare a monolayer of bovine serum albumin on the surface of silica gel supported gold nanoparticles is described. The stereo‐specific recognition ability of this material was evaluated by enantioresolution of Dansyl‐norvaline. For enantiomeric separation, the influences of buffer concentration and the concentration of organic modifier on the separation performance were investigated. A better separation in terms of enantioresolution and peak shape was found with the phosphate concentration at 30 mM. Moreover, the peak shape and resolution can be improved by the addition of methanol solution. Enantioresolution of Dansyl‐norvaline was obtained from this material at optimized conditions. It appears that the immobilization of a monolayer of bovine serum albumin on gold nanoparticles as the chiral selector of Dansyl‐derivative amino acid is promising.     

Electroanalysis of Norepinephrine at Bare Gold Electrode Pure and Modified with Gold Nanoparticles and S‐Functionalized Self‐Assembled Layers in Aqueous Solution

Gold nanoparticles (Au‐NPs), cystamine (CA) and 3,3′‐dithiodipropionic acid (DTDPA) modified gold bare electrodes were applied in voltammetric sensors for simultaneous detection of norepinephrine (NEP), ascorbic (AA) and uric (UA) acids. A linear relationship between norepinephrine concentration and current response was obtained in the range of 0.1 μM to 600 μM M with the detection limit ≤0.091 μM for the electrodes modified at 2D template and in the range of 0.1 μM to 700 μM M with the detection limit ≤0.087 μM for the electrodes modified at 3D template The results have shown that using modified electrodes it is possible to perform electrochemical analysis of norepinephrine without interference of ascorbic and uric acids, whose presence is the major limitation in norepinephrine determination at a bare gold electrode. The modified SAMs electrodes show good selectivity, sensitivity, reproducibility and high stability.     

Phenylboronic Acid‐Gold Nanoparticles for Potentiometric Detection of Saccharides

We propose a concept for the analytical application of gold nanoparticles modified by mercaptophenylboronic acid as a receptor of saccharides in a potentiometric sensor based on a conducting polymer.     

Electrochemical Study and Direct Determination of Adenosine‐5′‐Monophosphate Coupled to 6‐Thioguanosine and a Glassy Carbon Modified Electrode with Gold Nanoparticles

The direct accumulation of 6‐thioguanosine (6‐TG) and its electrochemistry has been studied by cyclic voltammetry in different conditions physical and chemical. In a first moment the surface of electrode was modified with gold nanoparticles. This modification was realized by electrodeposition on the active surface of a glassy carbon electrode with a HAuCl₄ solution. The nucleotide 6‐thioguanosine was deposited in this gold nanoparticles monolayer. The study of accumulation of other nucleotide, adenosine 5′‐monophosphate (AMP), was realized by the direct reaction with 6‐TG deposited. The conditions of the reaction and its electrochemical response were tested to fix the ideal conditions of its determination. The ideal conditions of formation of the monolayer and its electrochemical response were studied; the possibility of preconcentration of 6‐TG nucleotide in gold nanoparticles, the possibility of catalysis and limits of identification and quantification were also determined. The method proposed can be applied in direct determination of oligonucleotides. In this respect we applied it in the determination of AMP in a commercial product of infantile nutrition.     

NADH Electrocatalytic Oxidation on Gold Nanoparticle‐Modified PVC/TTF‐TCNQ Composite Electrode. Application as Amperometric Sensor

We herein report on the electrocatalytic activity towards the oxidation of NADH of a PVC/TTF‐TCNQ composite electrode modified with gold nanoparticles. This electrocatalytic property allows proposing this system as a new alternative for amperometric determination of NADH, without need to add another mediator. The sensor shows a linear response to NADH over a concentration range from 5.0×10^?6 M up to 5.0×10^?4 M, with a sensitivity of 11.22±0.5 mA M^?1 and a detection limit (S/N=3) of 4.0×10^?6 M for measurements in batch and similar data in FIA.     

Gold Nanoparticles Modified Electrode for the Determination of an Antihypertensive Drug

The nature of binding between Terazosin (TR) and gold nanoparticles (Au‐Nps) is investigated using UV‐vis and fluorescence spectroscopies, cyclic voltammetry, SEM, and EIS. The results suggest that Au‐Nps are effective carriers for TR. An electrochemical sensor for TR is introduced using Au‐Nps electrodeposited on carbon paste electrode. The effect of parameters including pH and scan rate on the response was investigated. A linear range from 8.0×10^?9 to 5.4×10^?5 mol L^?1 with correlation coefficient of 0.9995 and detection limit of 1.2×10^?10 mol L^?1 was obtained. This sensor was used for determining TR spiked in urine, and excellent recovery results are achieved.     

Protein‐Directed In Situ Synthesis of Gold Nanoparticles on Reduced Graphene Oxide Modified Electrode for Nonenzymatic Glucose Sensing

A novel nonenzymatic glucose sensor was developed based on well‐dispersed gold nanoparticles, which were in situ grown under direction of protein on a reduced graphene oxide modified electrode. This electrode exhibited high electrocatalytic activity towards glucose oxidation without use of any enzyme or mediator. In application for the amperometric detection of glucose, a wide linear range of 0.02–16.6 mM, low detection limit of 5 µM and good selectivity were obtained. The attractive analytical performances of the proposed glucose sensor, coupled with the facile preparation method, provide a promising electrochemical platform for the development of effective nonenzymatic sensors.     

Gold and Nanogold Electrodes Modified with Gold Nanoparticles and meso‐2,3‐Dimercaptosuccinic Acid for the Simultaneous,Sensitive and Selective Determination of Dopamine and Its Biogenic Interferents

Gold and nanogold electrodes modified with self‐assembled layers composed of gold nanoparticles and organic sulfur compounds were applied for quantitative determination of dopamine and its biogenic interferents like: ascorbic and uric acids. For the novel sensor a linear relationship between the current response of dopamine at the potential of peak maximum and the concentration was found over a wide analyte concentration range in solution with a very good detection sensitivity and detection limit. It was proved that current peaks of dopamine and both ascorbic and uric acids were clearly separated from each other enabling selective detection of these compounds coexisting in a mixture in solution of pH 7.     

Selective Electrochemical Determination of Dopamine with Molecularly Imprinted Poly(Carbazole‐co‐Aniline) Electrode Decorated with Gold Nanoparticles

Dopamine (DA) is a significant neurotransmitter in the central nervous system, coexisting with uric acid (UA) and ascorbic acid (AA). UA and AA are easily oxidizable compounds having potentials close to that of DA for electrochemical analysis, resulting in overlapping voltammetric response. In this work, a novel molecularly imprinted (MI) electrochemical sensor was proposed for selective determination of DA (in the presence of up to 80‐fold excess of UA and AA), relying on gold nanoparticles (Au_nano)‐decorated glassy carbon (GC) electrode coated with poly(carbazole (Cz)‐co‐aniline (ANI)) copolymer film incorporating DA as template (DA imprinted‐GC/P(Cz‐co‐ANI)‐Au_nano electrode, DA‐MIP‐Au_nano electrode). The DA recognizing sensor electrode showed great electroactivity for analyte oxidation in 0.2 mol L^?1 pH 7 phosphate buffer. Square wave voltammetry (SWV) was performed within 10^?4–10^?5 mol L^?1 of DA, of which the oxidation peak potential was observed at 0.16 V. The limit of detection (LOD) and limit of quantification (LOQ) were 2.0×10^?6 and 6.7×10^?6 mol L^?1, respectively. Binary and ternary synthetic mixtures of DA‐UA, DA‐AA and DA‐UA‐AA yielded excellent recoveries for DA. Additionally, DA was quantitatively recovered from a real sample of bovine serum spiked with DA, and determined in concentrated dopamine injection solution. The developed SWV method was statistically validated against a literature potentiodynamic method using a caffeic acid modified‐GC electrode.     

A Reagentless Amperometric Immunosensor for Alpha‐Fetoprotein Based on Gold Nanoparticles/TiO2 Colloids/Prussian Blue Modified Platinum Electrode

A novel reagentless amperometric immunosensor for the determination of alpha‐fetoprotein (AFP) was prepared by immobilizing TiO₂ colloids on Prussian blue (PB) modified platinum electrode, which yielded a positively charged interface with strong adsorption to deposit gold nanoparticles for immobilization of alpha‐fetoprotein antibody (anti‐AFP). The factors influencing the performance of the proposed immunosensors were studied in detail. Under the optimized conditions, cyclic voltammograms determination of AFP showed a specific response in two concentration ranges from 3.0 to 30.0 ng/mL and from 30.0 to 300.0 ng/mL with a detection limit of 1.0 ng/mL at a signal‐to‐noise ratio of 3. The proposed immunosensor exhibited high selectivity, good reproducibility, long‐term stability (>2 months) and good repeatability.