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1.
We describe a new method for the visualization of the activity of red-ox proteins on a gold interface. Glucose oxidase was selected as a model system. Surfaces were modified by adhesion of glucose oxidase on (a) electrochemically cleaned gold; (b) gold films modified with gold nanoparticles, (c) a gold surface modified with self-assembled monolayer, and (d) covalent immobilization of protein on the gold surface modified with a self-assembled monolayer. The simple optical method for the visualization of enzyme on the surfaces is based on the enzymatic formation of polypyrrole. The activity of the enzyme was quantified via enzymatic formation of polypyrrole, which was detected and investigated by quartz microbalance and amperometric techniques. The experimental data suggest that the enzymatic formation of the polymer may serve as a method to indicate the adhesion of active redox enzyme on such surfaces.
Figure
An optical method for the evaluation of activity and distribution of glucose oxidase on the different surfaces was described. The enzymatic synthesis of polypyrrole (black colour) was successfully applied for the visualization of active enzyme on the surfaces.  相似文献   

2.
A nanocomposite film is described that is composed of alternating layers of poly(diallydimethyl ammonium chloride) and gold nanoparticles that interact through electrostatic forces. The films of varying thickness were prepared by the layer-by-layer technique, and Au-NPs were generated by electrochemical reduction of hexachloroauric acid. The composite films were characterized by UV?Cvis spectroscopy, X-ray photoelectron spectroscopy, and cyclic voltammetry. Most nanocomposite films exhibit linear, uniform, and regular layer-by-layer growth during the process of formation. The films exhibit unique performance in terms of surface enhanced Raman scattering and electrocatalytic activitiy towards the oxidation of ascorbic acid.
Figure
A nanocomposite film was prepared by alternating layers of poly(diallydimethyl ammonium chloride) and gold nanoparticles, in which Au-NPs were generated by electrochemical reduction of hexachloroauric acid. The films exhibit unique performance in terms of surface enhanced Raman scattering and electrocatalytic activitiy towards the oxidation of ascorbic acid.  相似文献   

3.
Bioactivity of proteins is evaluated to test the adverse effects of nanoparticles interjected into biological systems. Surface plasmon resonance (SPR) spectroscopy detects binding affinity that is normally related to biological activity. Utilizing SPR spectroscopy, a concise testing matrix is established by investigating the adsorption level of bovine serum albumin (BSA) and anti-BSA on the surface covered with 11-mercaptoundecanoic acid (MUA); magnetic nanoparticles (MNPs) and single-walled carbon nanotubes (SWCNTs), respectively. The immunoactivity of BSA on MNPs and SWCNT decreased by 18?% and 5?%, respectively, compared to that on the gold film modified with MUA. This indicates that MNPs cause a considerable loss of biological activity of adsorbed protein. This effect can be utilized for practical applications on detailed biophysical research and nanotoxicity studies.
Figure
Schematic diagram of Ab-Ag interaction on MNPs confined Au surface (left) and SPR study on the immunoactivity of BSA adsorbed on MNPs (right).  相似文献   

4.
We show that the antigen CFP-10 (found in tissue fluids of tuberculosis patients) can be used as a marker protein in a surface-plasmon resonance (SPR) based method for early and simplified diagnosis of tuberculosis. A sandwich SPR immunosensor was constructed by immobilizing the CFP-10 antibody on a self-assembled monolayer on a gold surface, this followed by blocking it with bovine serum albumin. Following exposure of the sensor surface to a sample containing CFP-10, secondary antibody immobilized on nickel oxide nanoparticles are injected which causes a large SPR signal change. The method has a dynamic range from 0.1 to around 150 ng per mL of CFP-10, and a detection limit as low as 0.1 ng per mL. This is assumed to be due to the high amplification power of the NiO nanoparticles.
Figure
Schematic diagram of sensor chip configuration (left) and SPR study based on amplification strategy with NiO nanoparticles (right).  相似文献   

5.
We describe a method for the synthesis of gold nanoparticles in a stainless steel continuous flow tubular reactor using tetrachloroauric acid as a precursor but without using a classical reducing agent. Gold(III) ion is reduced by stainless steel to form gold nanoparticles which are collected at the end of the coil. A single-phase system is introduced that generates dispersed nanoparticles in the absence of reducing agents on their surface. By controlling flow rates and temperature, the size of the nanoparticles can be tuned in the range from 24 nm to 36 nm. The reproducibility of the preparation was investigated, relative standard deviation of both the wavelength of the peak and the intensity of the plasmonic absorption band were determined and found to vary by 0.15 % and 6.5 %, respectively. Flow synthesis is found to be an excellent alternative to chemical methods to produce stable gold nanoparticles of varying size in an efficiently way. The particles obtained also perform very well when used as a substrate in surface enhanced Raman scattering as shown by the characterization of carboxylated single walled carbon nanotubes.
Figure
Bare gold nanoparticles have been synthesized in a single-phase stainless steel continuous flow tubular reactor using tetrachloroauric acid as a precursor  相似文献   

6.
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.
Figure
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7.
A method was developed for the detection of the insecticide acetamiprid based on the strong interaction of the cyano group of acetamiprid with gold nanoparticles (AuNPs). The interaction results in the aggregation of gold nanoparticles and is accompanied by a color change from red to purple. The concentration of acetamiprid can be determined qualitatively and quantitatively by visually monitoring the color change or by using a spectrometer. Transmittance electron microscopy and UV-vis spectroscopy have been used to characterize the process. The experimental parameters were optimized with regard to the size of the AuNPs, pH, and incubation time. Under optimal experimental conditions, linear relationships between the logarithm of the concentration of acetamiprid and the absorbance were found over the range of 0.66 to 6.6???M for AuNPs with diameters of 22.0?±?1.0?nm and of 6.6?C66???M for AuNPs with diameters of 15.0?±?1.0?nm. This method was successfully applied to detect acetamiprid in vegetables.
Figure
A method was developed for the detection of acetamiprid based on the strong interaction of the cyano group of acetamiprid with gold nanoparticles. This method is rapid, sensitive and low-cost. It can be used for pesticide residues detection.  相似文献   

8.
Catalytic nanotubes made from titanium dioxide (TiO2-NTs) and covered with gold nanoparticles (Au-NPs) were prepared via galvanic deposition of the Au-NPs on the TiO2-NTs. The morphology and surface characteristics of the resulting electrodes were investigated using scanning electron microscopy and energy-dispersive X-ray spectroscopy. The results indicated that the Au-NPs were homogeneously deposited on the surface of TiO2-NTs which consist of individual tubes of about 40?C80?nm in diameter. The AuNPs with a size of 80?C100?nm are well-dispersed on the surface of the TiO2-NTs. The electro-catalytic activity of the electrodes towards the electro-oxidation of levodopa was studied by cyclic voltammetry, differential puls voltammetry. The results showed that the electrodes exhibit a considerably higher activity toward the oxidation of levodopa. The oxidation peak current linearly depends on the concentration of levodopa in the 10 to 70???M concentration range. Levodopa was determined by the method in pharmaceutical preparations, and results were found to be satisfactory.
Figure
Comparison of cyclic voltammograms of Au?\TiO2?\NTs/Ti and a flat gold electrode for determination levodopa.  相似文献   

9.
We report on the synthesis of a composite made from iridium oxide and gold that has a flower-like morphology. The ratio of iridium oxide to gold can be controlled by altering the concentrations of the metal precursors or the pH of the solution containing the reductant citrate. Scanning electron microscopy, transmission electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy, and laser confocal micro-Raman spectroscopy were applied to characterize the structures of the nanoflowers, and a mechanism of their formation was deduced. The nanoflowers display an electrocatalytic activity in an oxygen evolution reaction (OER) that is significantly enhanced compared to bare iridium oxide nanoparticles. The highest turnover frequency for the OER of the new nanoflowers is 10.9?s?1, which is almost one order of magnitude better than that of the respective nanoparticles. These attractive features are attributed to the high oxidation states of iridium in the nanoflowers which is caused by the transfer of electronic charge from metal oxides to gold, and also to the flower fractal structure which is thought to provide a much more accessible surface than suspensions of the respective nanoparticle.
Figure
Gold and iridium oxide composites with nanoflower shapes have been successfully prepared. The nanoflowers display an electrocatalytic activity for the oxygen evolution reaction, which is significantly enhanced compared to bare iridium oxide nanoparticles.  相似文献   

10.
The fabrication of highly dense gold nanoparticles (NPs)-coated sulfonated polystyrene (PS) microspheres and their application in surface-enhanced Raman spectroscopy (SERS) were reported. After the preparation of PS microsphere using dispersion polymerization and subsequent sulfonation, [Ag(NH3)2]+ ions were adsorbed on the surfaces of the sulfonated PS microspheres and then reduced to silver nanoseeds for further growth of gold NPs shell by seeded growth approach. Reaction conditions such as the concentration of the growth solution and growth time were adjusted to achieve nonspherical gold NPs-coated PS microspheres with different coverage degree. The application of the as-prepared spiky gold NPs-coated PS microsphere hybrid composite in SERS was finally investigated by using 4-aminothiophenol as probe molecules. The results showed that as-prepared gold NPs-coated PS microspheres could be used as functional hybrid materials to exhibit excellent enhancement ability in SERS.
Figure
High dense gold nanoparticle shell coated sulfonated polystyrene microspheres for SERS application  相似文献   

11.
Functionalized gold nanoparticles capped with polyoxometalates were prepared by a simple photoreduction technique where phosphododecamolybdates serve as reducing reagents, photocatalysts, and as stabilizers. TEM images of the resulting gold nanoparticles show the particles to have a relative narrow size distribution. Monolayer and multilayer structures of the negatively charged capped gold nanoparticles were deposited on a poly(vinyl pyridine)-derivatized indium-doped tin oxide (ITO) electrode via the layer-by-layer technique. The surface plasmon resonance band of the gold nanoparticles displays a blue shift on the surface of the ITO electrode. This is due to the substrate-induced charge redistribution in the gold nanoparticles and a change in the electromagnetic coupling between the assembled nanoparticles. The modified electrode exhibits the characteristic electrochemical behavior of surface-confined phosphododecamolybdate and excellent electrocatalytic activity. The catalysis of the modified electrode towards the model compound iodate was systematically studied. The heterogeneous catalytic rate constant for the electrochemical reduction of iodate was determined by chronoamperometry to be ca. 1.34?×?105 mol?1·L·s?1. The amperometric method gave a linear range from 2.5?×?10?6 to 1.5?×?10?3 M and a detection limit of 1.0?×?10?6 M. We believe that the functionalized gold nanoparticles prepared by this photoreduction technique are advantageous in terms of fabrication of sensitive and stable redox electrodes.
Figa
Functionalized gold nanoparticles (Au-NPs) capped with polyoxometalates were prepared by a simple photoreduction technique. The negatively charged capped Au-NPs were deposited on a poly(vinyl pyridine)-derivatized indium-doped tin oxide electrode via the layer-by-layer technique. The modified electrode exhibits the characteristic electrochemical behavior of surface-confined phosphododecamolybdate, and excellent catalytic activity.  相似文献   

12.
Cysteine and thioglycolic acid were immobilized on gold nanoparticles via established thiolgold surface chemistry. It is found that calcium ions rapidly induce the aggregation of the functional gold nanoparticles due to the complexation of Ca(II) by immobilized cysteine. It was also found that triethanolamine enhances the effect of calcium ions by decreasing the electrostatic repulsion between the gold nanoparticles. Transmission electron microscopy, electrophoresis, zeta potential measurements and absorptiometry were used to investigate the mechanism. Under the optimum experimental condition, the cysteine/thioglycolate/triethanolamine-modified nanoparticles were highly sensitive (the detection limit being 0.3 ??M) and selective towards calcium and magnesium ions, with a linear detection range between 1.0 ??M and 14 ??M. Based on these findings, a rapid and selective colorimetric method was developed for assaying Ca(II) ions in serum.
Figure
It was found that triethanolamine could be immobilize on the surface of GNPs by electrostatic adsorption with TGA and neutralize the negative charge of TGA, furthermore reduce the electrostatic repulsion and decrease the interparticle distance between aggregated GNPs (as showed in Scheme 1). These results indicated that TGA and cysteine could be successfully immobilized on the surface of the GNPs to improve the stability of the as-prepared functional GNPs for sensing Ca2+ ion  相似文献   

13.
We report on a novel hydrogen peroxide biosensor that was fabricated by the layer-by-layer deposition method. Thionine was first deposited on a glassy carbon electrode by two-step electropolymerization to form a positively charged surface. The negatively charged gold nanoparticles and positively charged horseradish peroxidase were then immobilized onto the electrode via electrostatic adsorption. The sequential deposition process was characterized using electrochemical impedance spectroscopy by monitoring the impedance change of the electrode surface during the construction process. The electrochemical behaviour of the modified electrode and its response to hydrogen peroxide were studied by cyclic voltammetry. The effects of the experimental variables on the amperometric determination of H2O2 such as solution pH and applied potential were investigated for optimum analytical performance. Under the optimized conditions, the biosensor exhibited linear response to H2O2 in the concentration ranges from 0.20 to 1.6?mM and 1.6 to 4.0?mM, with a detection limit of 0.067?mM (at an S/N of 3). In addition, the stability and reproducibility of this biosensor was also evaluated and gave satisfactory results.
Figure
A novel hydrogen peroxide biosensor was fabricated via layer-by-layer depositing approach. Thionine was first deposited on a glassy carbon electrode by electropolymerization to form a positively charged surface (PTH). Negatively charged gold nanoparticles (NPs) and positively charged horseradish peroxidase (HRP) were then immobilized onto the electrode via electrostatic adsorption.  相似文献   

14.
The dynamic and reversible switching behaviour of polyelectrolyte brushes of poly(2-(dimethylamino)ethyl methacrylate) (PDMAEMA) toward changes of the pH value was studied by in situ VIS-spectroscopic ellipsometry (SE). For this, PDMAEMA brushes with three different molecular weights were synthesized via the “grafting from” method using surface initiated atom transfer radical polymerization. In detail, the applicability of different SE data modelling to describe the optical properties of the different brush layers in the swollen and collapsed state was investigated. Especially for the PDMAEMA brushes with a high molecular weight, an improved optical modelling of the experimental data could be achieved and revealed an exponential distribution of the PDMAEMA fraction in the brush layer.
Figure
Analysis of the volume fraction-depth profile of pH responsive poly(2-(dimethylamino)ethyl methacrylate) (PDMAEMA) brushes attached to a gold substrate using VIS-spectroscopic ellipsometry.  相似文献   

15.
A novel glucose biosensor is presented as that based on a glassy carbon electrode modified with hollow gold nanoparticles (HGNs) and glucose oxidase. The sensor exhibits a better differential pulse voltammetric response towards glucose than the one based on conventional gold nanoparticles of the same size. This is attributed to the good biological conductivity and biocompatibility of HGNs. Under the optimal conditions, the sensor displays a linear range from 2.0?×?10?6 to 4.6?×?10?5?M of glucose, with a detection limit of 1.6?×?10?6?M (S/N?=?3). Good reproducibility, stability and no interference make this biosensor applicable to the determination of glucose in samples such as sports drinks.
Figure
A novel glucose biosensor was prepared based on glucose oxidase, hollow gold nanoparticles and chitosan modified glassy carbon electrode. The electrode showed a good response for the glucose. The sensor has been verified by the determination of glucose in sport drink  相似文献   

16.
We report on the modification of a graphene paste electrode with gold nanoparticles (AuNPs) and a Nafion-L-cysteine composite film, and how this electrode can serve as a platform for the construction of a novel electrochemical immunosensor for the detection of hepatitis B surface antigen (HBsAg). To obtain the immunosensor, an antibody against HBsAg was immobilized on the surface of the electrode, and this process was followed by cyclic voltammetry and electrochemical impedance spectroscopy. The peak currents of a hexacyanoferrate redox system decreased on formation of the antibody-antigen complex on the surface of the electrode. Then increased electrochemical response is thought to result from a combination of beneficial effects including the biocompatibility and large surface area of the AuNPs, the high conductivity of the graphene paste electrode, the synergistic effects of composite film, and the increased quantity of HBsAb adsorbed on the electrode surface. The differential pulse voltammetric responses of the hexacyanoferrate redox pair are proportional to the concentration of HBsAg in the range from 0.5–800?ng?mL?1, and the detection limit is 0.1?ng?mL?1 (at an S/N of 3). The immunosensor is sensitive and stable.
Figure
We report on the modification of a graphene paste electrode with gold nanoparticles and a Nafion-L-cysteine composite film, and how this electrode can serve as a platform for the construction of a novel electrochemical immunosensor for the detection of hepatitis B surface antigen. The immunosensor is sensitive and stable.  相似文献   

17.
The modification of electrodes with gold nanoparticles results in an increased electrode surface area, enhanced mass transport, and improved catalytic properties. We have extended this approach to indium tin oxide (ITO) electrodes to obtain optically transparent gold nanorod-modified electrodes which display enhanced electrochemical capabilities and have the additional advantage of showing a tunable surface plasmon resonance. The procedures for attaining high surface coverage (15 gold nanorods per square µm) of such electrodes were optimized, and the potential-dependent surface plasmon resonance was studied under controlled electrical potential. In an exemplary sensor application, we demonstrate the detection of mercury via potential-dependent formation of an Au-Hg amalgam.
Immobilization of gold nanorods on optically transparent ITO electrodes provides tunable surface plasmon resonance detection coupled with electrochemical potential control. These novel sensors are applied to the detection and quantification of mercury with a combined SPR-electrochemical technique  相似文献   

18.
The use of nanoparticles (NPs) can substantially improve the analytical performance of surface plasmon resonance imaging (SPRi) in general, and in DNA sensing in particular. In this work, we report on the modification of the gold surface of commercial biochips with gold nanospheres, silica-coated gold nanoshells, and silver nanoprisms, respectively. The NPs were tethered onto the surface of the chip and functionalized with a DNA probe. The effects of tethering conditions and varying nanostructures on the SPRi signals were evaluated via hybridization assays. The results showed that coupling between planar surface plasmons and electric fields, generated by localized surface plasmons of the NPs, is mandatory for signal enhancement. Silver nanoprisms gave the best results in improving the signal change at a target DNA concentration of <50 nM by +50 % (compared to a conventional SPRi chip). The limit of detection for the target DNA was 0.5 nM which is 5 times less than in conventional SPRi.
Figure
?  相似文献   

19.
Xiaoyu Cao 《Mikrochimica acta》2014,181(9-10):1133-1141
We have developed an ultra-sensitive electrochemical DNA biosensor by assembling probe ssDNA on a glassy carbon electrode modified with a composite made from molybdenum disulfide, graphene, chitosan and gold nanoparticles. A thiol-tagged DNA strand coupled to horseradish peroxidase conjugated to AuNP served as a tracer. The nanocomposite on the surface acts as relatively good electrical conductor for accelerating the electron transfer, while the enzyme tagged gold nanoparticles provide signal amplification. Hybridization with the target DNA was studied by measuring the electrochemical signal response of horseradish peroxidase using differential pulse voltammetry. The calibration plot is linear in the 5.0?×?10?14 and 5.0?×?10?9 M concentration range, and the limit of detection is 2.2?×?10?15 M. The biosensor displays high selectivity and can differentiate between single-base mismatched and three-base mismatched sequences of DNA. The approach is deemed to provide a sensitive and reliable tool for highly specific detection of DNA.
Figure
We have developed an ultra-sensitive electrochemical DNA biosensor by assembling probe (ssDNA) on a glassy carbon electrode modified with a composite made from molybdenum disulfide, graphene, chitosan and gold nanoparticles. The nanocomposite on the surface acts as relatively good electrical conductor for accelerating the electron transfer, while the enzyme tagged gold nanoparticles provide signal amplification. The biosensor displays high selectivity and can differentiate between single-base mismatched and three-base mismatched sequences of DNA  相似文献   

20.
The hepatotoxic microcystins, especially microcystin?CLR (MC?CLR), are causing serious problems to public health and fisheries. We describe here a label-free amperometric immunosensor for rapid determination of MC?CLR in water sample. The sensor was prepared by immobilizing antibody on a gold electrode coated with L-cysteine-modified gold nanoparticles. The stepwise self-assembly of the immunosensor was monitored and characterized by means of electrochemical impedance spectroscopy and differential pulse voltammetry. A 0.60?mmol L?1 solution of hydroquinone was used as the electron mediator. The immunosensor was incubated with MC?CLR at 25?°C for 20?min, upon which the differential pulse voltammetric current changed linearly over the concentration range from 0.05 to 15.00???g L?1, with a detection limit of 20?ng L?1. The developed biosensor was used to determine MC?CLR in spiked crude algae samples. The recovery was in the range from 95.6 to 105%. This method is simple, economical and efficient, this making it potentially suitable for field analysis of MC-LR in crude algae and water samples.
Figure
The present investigation combines SAM monolayer with gold nanoparticles monolayer to prepare a stable film to immobilize the antibody, and takes hydroquinone as electron mediator, establishes a miniature, economic, compatible and label-free amperometric immunosensor for the quick detection of MC-LR.  相似文献   

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