A one-pot synthetic approach to prepare palladium nanoparticles embedded hierarchically porous TiO2 hollow spheres for hydrogen peroxide sensing

A simple one-step method to fabricate hierarchically porous TiO₂/Pd composite hollow spheres without any template was developed by using solvothermal treatment. Pd nanoparticles (2-5 nm) were well dispersed in the mesopores of the TiO₂ hollow spheres via in-situ reduction. In our experiment, polyvinylpyrrolidone played an important role in the synthetic process as the reducing agent and the connective material between TiO₂ and Pd nanoparticles. HF species generated from solvothermal reaction leaded to the formation of TiO₂ hollow spheres and Ostwald ripening was another main factor that affected the size and structure of the hollow spheres. The as-prepared TiO₂/Pd composite hollow spheres exhibited high electrocatalytic activity towards the reduction of H₂O₂. The sensitivity was about 226.72 μA mM⁻¹ cm⁻² with a detection limit of 3.81 μM at a signal-to-noise ratio of 3. These results made the hierarchically porous TiO₂/Pd composite a promising platform for fabricating new nonenzymic biosensors.     

Template free fabrication of hollow hematite spheres via a one-pot polyoxometalate-assisted hydrolysis process

Uniform hollow hematite (α-Fe₂O₃) spheres with diameter of about 600-700 nm and shell thickness lower than 100 nm are obtained by direct hydrothermal treatment of dilute FeCl₃ and tungstophosphoric acid H₃PW₁₂O₄₀ solution at 180 °C. The hollow spheres are composed of robust shells with small nanoparticles standing out of the surface and present a high-surface area and a weak ferromagnetic behavior at room temperature. The effect of concentration of H₃PW₁₂O₄₀, reaction time and temperature for the formation of the hollow spheres are investigated in series of experiments. The formation of the hollow spheres may be ascribed to a polyoxometalte-assisted forced hydrolysis and dissolution process.     

Preparation of gold nanoparticles on eggshell membrane and their biosensing application

A facile green biosynthesis method has been successfully developed to prepare gold nanoparticles (AuNPs) of various core sizes (25 ± 7 nm) using a natural biomaterial, eggshell membrane (ESM) at ambient conditions. In situ synthesis of AuNPs-immobilized ESM is conducted in a simple manner by immersing ESM in a pH 6.0 aqueous solution of HAuCl₄ without adding any reductant. The formation of AuNPs on ESM protein fibers is attributed to the reduction of Au(III) ions to Au(0) by the aldehyde moieties of the natural ESM fibers. Energy dispersive X-ray spectroscopy, scanning electron microscopy, X-ray photoelectron spectroscopy, and X-ray powder diffraction unambiguously identify the presence of AuNPs on ESM. The effect of pH on the in situ synthesis of AuNPs on ESM has been investigated in detail. The pH of the gold precursor (HAuCl₄) solution can influence the formation rate, dispersion and size of AuNPs on ESM. At pH ≤3.0 and ≥7.0, no AuNPs are observed on ESM while small AuNPs are homogeneously dispersed on ESM at pH 4.0-6.0. The optimal pH for AuNPs formation on ESM is 6.0. AuNPs/ESMs are used to immobilize glucose oxidase (GO_x) for glucose biosensing. AuNPs on ESM can increase the enzyme activity of GO_x. The linear response range of the glucose biosensor is 20 μM to 0.80 mM glucose with a detection limit of 17 μM (S/N = 3). The biosensor has been successfully applied to determine the glucose content in commercial glucose injections. Our work provides a very simple, non-toxic, convenient, and green route to synthesize AuNPs on ESM which is potentially useful in the biosensing field.     

Preparation of reversibly photo-cross-linked nanogels from pH-responsive block copolymers and use as nanoreactors for the synthesis of gold nanoparticles

Reversibly photo-cross-linkable pH-responsive block copolymer poly(ethylene oxide)-b-poly((2-(diethylamino)ethyl methacrylate-co-4-methyl-[7-(methacryloyl)oxyethyloxy] coumarin)) (PEO-b-P(DEA-co-CMA)) was synthesized via atom transfer radical polymerization (ATRP). Block copolymer nanogels could be easily prepared by first photo-cross-linking of the micelles at pH > 7 and then adjusting the solution to pH < 7. The photo-cross-linking was proved to be reversibly controlled under alternative irradiation of UV light at 365 nm and 254 nm. As a result, the cross-linking degrees and sizes of the nanogels can be easily controlled by alternatively UV light irradiation. Finally, the nanogels can serve as nanoreactors for the synthesis of gold nanoparticles. The protonated DEA units were first coordinated with HAuCl₄, and then the electrostatically bounded AuCl⁴⁻ anions were reduced to gold nanoparticles by NaBH₄. The nanogel-supported gold nanoparticles were used in chemical catalysis. The pH-responsive photo-cross-linked nanogels have been characterized using dynamic light scattering, transmission electron microscopy, UV-vis spectra and ¹H NMR spectroscopy measurements, respectively.     

Detection of polycyclic aromatic hydrocarbon (PAH) compounds in artificial sea-water using surface-enhanced Raman scattering (SERS)

This paper reports an accurate synthesis of surface-enhanced Raman scattering (SERS) active substrates, based on gold colloidal monolayer, suitable for in situ environmental analysis. Quartz substrates were functionalized by silanization with (3-mercaptopropyl)trimethoxysilane (MPMS) or (3-aminopropyl)trimethoxysilane (APTMS) and they subsequently reacted with colloidal suspension of gold metal nanoparticles: respectively, the functional groups SH and NH₂ bound gold nanoparticles. Gold nanoparticles were prepared by the chemical reduction of HAuCl₄ using sodium tricitrate and immobilized onto silanized quartz substrates. Active substrate surface morphology was characterized with scanning electron microscopy (SEM) measurements and gold nanoparticles presented a diameter in the range 40-100 nm. Colloidal hydrophobic films, allowing nonpolar molecule pre-concentration, were obtained. The surfaces exhibit strong enhancement of Raman scattering from molecules adsorbed on the films. Spectra were recorded for two PAHs, naphthalene and pyrene, in artificial sea-water (ASW) with limits of detection (LODs) of 10 ppb for both on MPMS silanized substrates.     

Amperometric hydrogen peroxide biosensor based on the immobilization of heme proteins on gold nanoparticles-bacteria cellulose nanofibers nanocomposite

A novel matrix, gold nanoparticles-bacterial cellulose nanofibers (Au-BC) nanocomposite was developed for enzyme immobilization and biosensor fabrication due to its unique properties such as satisfying biocompatibility, good conductivity and extensive surface area, which were inherited from both gold nanoparticles (AuNPs) and bacterial cellulose nanofibers (BC). Heme proteins such as horseradish peroxidase (HRP), hemoglobin (Hb) and myoglobin (Mb) were successfully immobilized on the surface of Au-BC nanocomposite modified glassy carbon electrode (GCE). The immobilized heme proteins showed electrocatalytic activities to the reduction of H₂O₂ in the presence of the mediator hydroquinone (HQ), which might be due to the fact that heme proteins retained the near-native secondary structures in the Au-BC nanocomposite which was proved by UV-vis and IR spectra. The response of the developed biosensor to H₂O₂ was related to the amount of AuNPs in Au-BC nanocomposite, indicating that the AuNPs in BC network played an important role in the biosensor performance. Under the optimum conditions, the biosensor based on HRP exhibited a fast amperometric response (within 1 s) to H₂O₂, a good linear response over a wide range of concentration from 0.3 μM to 1.00 mM, and a low detection limit of 0.1 μM based on S/N = 3. The high performance of the biosensor made Au-BC nanocomposite superior to other materials as immobilization matrix.     

ZnO hollow nanospheres via Laux-like oxidation of Zn0 nanoparticles

Zinc oxide hollow nanospheres were obtained via a Laux-like oxidation of zinc nanoparticles using nitrobenzene as oxidizing agent. The ZnO hollow nanospheres exhibit an outer diameter of 10.4 ± 1.3 nm and a well crystallized sphere wall with a thickness of 2.9 ± 0.4 nm. Laux-like oxidation and formation of the ZnO hollow nanospheres were performed instantaneously after sodium naphthalenide ([NaNaph]) driven reduction of ZnCl₂ to Zn⁰ nanoparticles in the liquid phase without any separation of the intermediate Zn⁰ nanoparticles. The diameter of the resulting ZnO hollow nanospheres (10.4 ± 1.3 nm) reflects the diameter of the intermediate Zn⁰ nanoparticles (10.1 ± 2.3 nm). In accordance with the small diameter of the ZnO sphere wall, quantum-size effects occur with a band gap that is blue-shifted by 0.2 eV in comparison to bulk-ZnO.     

Colorimetric detection of fluoride ion in an aqueous solution using a thioglucose-capped gold nanoparticle

The thioglucose-capped gold nanoparticles have been prepared by the chemical reduction of HAuCl₄ using thioglucose as the reducing and capping agent, which displays selective colorimetric detection of fluoride ion in 10 mM HEPES buffer at physiological pH.     

Localized surface plasmon resonance sensing detection of glucose in the serum samples of diabetes sufferers based on the redox reaction of chlorauric acid

In this paper, the formation of gold nanoparticles (Au NPs) as a result of the thermo-active redox reaction of chlorauric acid (HAuCl₄) and glucose in alkaline medium was identified by measuring the plasmon resonance absorption, localized surface plasmon resonance (LSPR), and transmission electron microscopy (TEM) images, for the formation of Au NPs displays characteristic plasmon resonance absorption bands and corresponding LSPR signals. It was found that the resulted LSPR signals could be easily detected with a common spectrofluorometer. With increasing glucose concentration, the LSPR intensity displays linear response with the glucose content over the range from 2.0 to 250.0 μmol l⁻¹. Thus, a novel assay of glucose was established with the limits of determination (3σ) being 0.21 μmol l⁻¹, and the detection of glucose could be made easily in the serum samples of diabetes sufferers. Mechanism investigations showed that the activation energy and molar ratio of the reaction were 34.8 kJ mol⁻¹ and 3:2, respectively.     

Shape-controlled synthesis of gold icosahedra and nanoplates using Pluronic P123 block copolymer and sodium chloride

Gold icosahedra with an average diameter of about 600 nm were easily prepared by heating an aqueous solution of the amphiphilic block copolymer, poly(ethylene oxide)₂₀-poly(propylene oxide)₇₀-poly(ethylene oxide)₂₀ (Pluronic P123), and hydrogen tetrachloroaurate(III) trihydrate (HAuCl₄·3H₂O) at 60 °C for 25 min. When sodium chloride (NaCl:HAuCl₄ molar ratio=10:1) was added to this aqueous solution, gold nanoplates were produced. The chloride ion was found to be a key component in the formation of the gold nanoplates by facilitating the growth of {111} oriented hexagonal/triangular gold nanoplates, because similar gold nanoplates were produced when LiCl or KCl was added to the aqueous solution instead of NaCl, while gold nanocrystals having irregular shapes were produced when NaBr or NaI was added.     

Ultra-trace level determination of hydroquinone in waste photographic solutions by UV-vis spectrophotometry

A simpler UV-vis spectrophotometric method was investigated for hydroquinone (HQ) determination using KMnO₄ as oxidizing agent for conversion of HQ to p-benzoquinone (BQ) as well as signal enhancer. Various parameters such as analytical wavelength, stability time, temperature, pH, solvent effect and interference of chemicals were checked and parameters optimized by using 1 μg ml⁻¹ standard solution of HQ. Beer's Law was applicable in the range of 0.07-2 μg ml⁻¹ and 0.005-0.05 μg ml⁻¹ at 245.5 nm and at 262 nm for aqueous standard solutions of HQ with linear regression coefficient value of 0.9978 and 0.9843 and detection limit of 0.021 μg ml⁻¹ and 0.0016 μg ml⁻¹ HQ, respectively. Standard deviation of 1.7% and 2.4% was true for 1 μg ml⁻¹ and 0.03 μg ml⁻¹ HQ solution (n = 11) run at respective wavelengths. The method was successfully applied to dilute waste photographic developer samples for free HQ determination.     

Adding sodium dodecylsulfate to the running electrolyte enhances the separation of gold nanoparticles by capillary electrophoresis

This paper describes employing capillary electrophoresis (CE) for the separation of gold colloids in nanometer-size regimes. Adding sodium dodecylsulfate (SDS) surfactant to the running buffer enhances the capability of CE to separate gold nanoparticles. We found that the optimized separation conditions involved SDS (70 mM), 3-cyclohexylamoniuopropanesulfonic acid (CAPS) buffer (10 mM), pH 10.0, and an applied voltage of 20 kV. We propose that the charged surfactants associate onto the surface of the gold nanoparticles and cause a change in the charge-to-size ratio of gold nanoparticle, which is a function of the surface area of nanoparticle and the surfactant concentration of running electrolyte. At high concentrations of the surfactant in the running electrolyte—i.e., when the surface of the gold nanoparticles is fully occupied with SDS—a linear relationship exists between the electrophoretic mobility and nanoparticles having diameters ranging from 5.3 to 38 nm. Based on the results of separating the 5.3 and 19 nm nanoparticles, we estimate that the size resolution (R_s=1.0) is 5.0 nm. The relative standard deviations of the electrophoretic mobilities of the 5.3 and 19 nm gold nanoparticles are 0.97 and 0.54%, respectively.     

Selective detection and recovery of gold at tannin-immobilized non-conducting electrode

A tannin-immobilized glassy carbon electrode (TIGC) was prepared via electrochemical oxidation of the naturally occurring polyphenolic mimosa tannin, which generated a non-conducting polymeric film (NCPF) on the electrode surface. The fouling of the electrode surface by the electropolymerized film was evaluated by monitoring the electrode response of ferricyanide ions as a redox marker. The NCPF was permselective to HAuCl₄, and the electrochemical reduction of HAuCl₄ to metallic gold at the TIGC electrode was evaluated by recording the reduction current during cyclic voltammetry measurement. In the mixed electrolyte containing HAuCl₄ along with FeCl₃ and/or CuCl₂, the NCPF remained selective toward the electrochemical reduction of HAuCl₄ into the metallic state. The chemical reduction of HAuCl₄ into metallic gold was also observed when the NCPF was inserted into an acidic gold solution overnight. The adsorption capacity of Au(III) on tannin-immobilized carbon fiber was 29 ± 1.45 mg g⁻¹ at 60 °C. In the presence of excess Cu(II) and Fe(III), tannin-immobilized NCPF proved to be an excellent candidate for the selective detection and recovery of gold through both electrochemical and chemical processes.     

Visual and fluorescent detection of acetamiprid based on the inner filter effect of gold nanoparticles on ratiometric fluorescence quantum dots

In this work, we develop a simple and rapid sensing method for the visual and fluorescent detection of acetamiprid (AC) based on the inner-filter effect (IFE) of gold nanoparticles (AuNPs) on ratiometric fluorescent quantum dots (RF-QDs). The RF-QDs based dual-emission nanosensor was fabricated by assembling green emissive QDs (QDs_539 nm, λ_em = 539 nm) on the surface of red emissive QDs (QDs_661 nm, λ_em = 661 nm)-doped silica microspheres. The photoluminescence (PL) intensity of RF-QDs could be quenched by AuNPs based on IFE. Acetamiprid can adsorb on the surface of AuNPs due to its cyano group that has good affinity with gold, which could induce the aggregation of AuNPs accompanying color change from red to blue. Thus, the IFE of AuNPs on RF-QDs was weakened and the PL intensity of RF-QDs was recovered accordingly. Under the optimized conditions, the PL intensity of the RF-QDs/AuNPs system was proportional to the concentration of AC in the range of 0.025–5.0 μg mL⁻¹, with a detection limit of 16.8 μg L⁻¹. The established method had been used for AC detection in environmental and agricultural samples with satisfactory results.     

Enhanced plasmon resonance light scattering signals of colloidal gold resulted from its interactions with organic small molecules using captopril as an example

Gold nanoparticles are known for their plasmon resonance absorption (PRA) depending on their size. Our this investigation shows that plasma resonance light scattering (PRLS) signals in the corresponding PRA region could be measured using a common spectrofluorometer, and be enhanced when aggregation of gold nanoparticles occurs due to their interaction with organic small molecules (OSMs). Using captopril (Cap) as an example, we investigated the interactions of gold nanoparticles with OSMs in order to propose a general method of OSMs such as typical clinic organic drugs. In aqueous medium of pH 2.09, there are about 2.2 × 10³ Cap molecules covalently binding to the surface of a 10-nm diameter gold nanoparticle through the thiol functional group of Cap, and thus forms a core-shell assembly of [(Au)₃₁₀₀₀]@[(Cap)₂₂₀₀], displaying strong enhanced PRLS signals in the PRA region of gold colloid. The PRLS intensities characterized at 553.0 nm were found to be proportional to the concentration of Cap over the range of 0.1-1.7 mg L⁻¹ with the determination limit (3σ) of 32.0 μg L⁻¹. With that, Cap in pharmaceutical preparations could be determined with the recovery of 97.0-104.5% and R.S.D. of less than 2.4%.     

Homogeneous, unmodified gold nanoparticle-based colorimetric assay of hydrogen peroxide

An unmodified gold nanoparticle-based colorimetric assay system in homogeneous format has been developed using hydrogen peroxide (H₂O₂) as a model analyte. H₂O₂ is added to o-phenylenediamine/horseradish peroxidase solution, and allowed to react for 10 min. Then, unmodified gold nanoparticles that serve as “reaction indicators” are added to the reaction solution. The resulting mixture color changes dramatically from red to blue. The reason is that azoaniline, a horseradish peroxidase-catalyzed oxidation product, induces the nanoparticle aggregation. Using this approach, H₂O₂ can be semiquantitatively determined over the concentration range of ∼4 orders of magnitude by the naked eye. If the observed peak intensity at 420 nm is used for the construction of the calibration plot, hydrogen peroxide can be accurately determined down to concentration levels of 1.3 × 10⁻⁶ M. Compared with the conventional electrochemical protocol, this sensing system offers several important advantages: (1) ability to be monitored by the naked eye, (2) avoiding the need of surface modification of electrodes or gold nanoparticles and (3) detection in homogeneous solution. It is worthy of note that this efficient and convenient strategy is also suitable for the detection of other species, such as glucose and cholesterol.     

Photochemical synthesis of gold nanoparticles in aqueous dispersions of carboxylated polystyrene

Photochemical synthesis of gold nanoparticles in aqueous dispersions of carboxylated polystyrene with microsphere sizes of 100, 300, 500, and 1410 nm under the action of monochromatic light with an excitation wavelength of 254 nm was studied. Preliminary irradiation of the polymer dispersion induces formation of gold particles under dark conditions. Dependences of gold nanoparticles formation on the duration of preliminary polymer irradiation and concentration of introduced HAuCl₄ aqueous solution were determined. A mechanism of the polystyrene-assisted formation of gold nanoparticles was proposed. The size and structure of gold nanoparticles were determined.     

Immobilization of gold nanoparticles on poly(methyl methacrylate) electrospun fibers exhibiting solid‐state surface plasmon effect

In this study, the surface plasmon effect of Au nanoparticles was successfully realized in the solid state by embedding the Au nanoparticles on the surface of the transparent polymer fibers for the first time. Electrospinning a poly(methyl methacrylate) (PMMA) and HAuCl₄ mixture followed by a wet chemical reduction, the gold nanoparticles were formed on the PMMA nanocomposite electrospun fibers in a well‐distributed manner to give photostable purple color. The Au nanoparticles were all sphere shaped with an average diameter of 12 nm. Specifically, simply adjusting HAuCl₄ salt concentration in the electrospinning solution, it is able to control the electrospun fiber diameter and gold nanoparticle content in the resulting PMMA/Au nanocomposite fibers. Therefore, the developed method described herein is simple and effective for the large volume production of PMMA/Au nanocomposite fibers. Copyright © 2011 John Wiley & Sons, Ltd.     

Estimating the thickness of hydrated ultrathin poly(o-phenylenediamine) film by atomic force microscopy

A novel method to measure ultrathin poly(o-phenylenediamine) (PPD) film electropolymerized on gold electrode in liquid was developed. It is based on the force versus distance curve (force curve) of atomic force microscopy (AFM). When 1-0.25 μm/s was chosen as the rising rate of the scanner, and 50% of the confidence interval (CI) as the qualifying threshold value, the thickness of the hydrated polymer film could be calculated. This result was compared with one obtained from an AFM image. A step-like electrode fabricated by a photolithographic process was used. The height difference of the electrode before and after the PPD coating was imaged in liquid, and then the real thickness, 19.6±5.2 nm, was obtained. The sample was also measured by estimating the transition range of the force curve of hydrated PPD film, and the thickness of the hydrated PPD film was determined to be 19.3±8.2 nm. However, the results calculated by integrating the electropolymerized charge for the oxidation process of o-phenylenediamine (o-PD) was only one-third as large as it was when using the two previously described methods. This indicated that the structure of hydrated PPD film might have been swollen.     

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.