Enzyme-free colorimetric assay of serum uric acid

A nonenzymatic method for the selective detection and quantification of serum uric acid (UA) using 2-thiouracil (2-TU) tailored Au nanoparticles is developed. The H-bonding interaction of UA with functionalized Au nanoparticles brings instantaneous visible color change and paves the way for the visible sensing of UA.     

Rapid detection of melamine with 4-mercaptopyridine-modified gold nanoparticles by surface-enhanced Raman scattering

A surface-enhanced Raman scattering (SERS) strategy based on 4-mercaptopyridine (MPY)-modified gold nanoparticles (AuNPs) was developed for the rapid and sensitive detection of melamine in milk powder. The SERS measurement of melamine strongly relied on the “hotspot” effect, in which AuNPs immediately aggregated upon the addition of melamine, leading to significantly enhanced Raman intensity of the reporter molecule MPY and a color change for the solution from red to blue-gray. The limit of detection based on a signal to noise of 3 (S/N = 3) was found to be as low as 0.1 ppb of melamine, with an excellent linearity of 0.5–100 ppb, demonstrating a higher sensitivity and a wider quantitation range than direct SERS sensing methods based on enhanced substrate. An impressive specificity for melamine detection over various common metal ions and excipients in dairy products, even at concentrations of 100-fold higher than melamine, was achieved. Good recoveries of 88.5% and 111.7% were obtained from milk samples spiked to 20 and 100 ppb levels, respectively. The proposed method is potentially applicable for the rapid in situ determination of melamine in complex matrices.     

Colorimetric recognition of melamine in milk using novel pincer zinc complex stabilized gold nanoparticles

A convenient colorimetric approach for visual detection of melamine in raw milk was realized by using gold nanoparticles (AuNPs) stabilized by an unsymmetrical terpyridyl zinc complex with a thymine fragment at one terminal and a quaternary ammonium salt at the other. Even without pre-addition of melamine or relative additives, obvious color change from red to blue was observed by naked eye in the presence of trace amount of melamine, which was attributed to the alternation of aggregation state of AuNPs caused by the selective binding between the thymine fragment and melamine via triple hydrogen-bonding interactions. Remarkably, the detection limit for melamine was as low as 2.4 ppb, providing a highly sensitive and efficient approach for the visual detection of melamine.     

Visual detection of melamine in milk products by label-free gold nanoparticles

A simple, rapid, field-portable colorimetric method for the detection of melamine based on melamine-induced color change of label-free gold nanoparticles (Au NPs) was developed in this study. Melamine can induced the aggregation of Au NPs and results in the color change from wine-red to purple, which provided a platform for rapid and field-portable colorimetric detection of melamine. The proposed method can be used to detect melamine in liquid milk and infant formula with a detection limit of 1.0 and 4.2 ppm, respectively, within 30 min by naked eyes observation without the aid of any advanced instrument and the need of any complex pretreatment, and detect as low as 0.15 ppm of melamine in liquid milk and 2.5 ppm of melamine in infant formula with UV-vis-spectroscopy. The proposed method is promising for on-site screening of melamine adulterant in milk products.     

Colorimetric recognition and sensing of nitrite with unmodified gold nanoparticles based on a specific diazo reaction with phenylenediamine

A colorimetric sensor for nitrite ion with high selectivity and sensitivity by unmodified citrate-capped gold nanoparticles (Au NPs) is presented. Recognition of nitrite is developed on the basis of a highly specific diazo reaction between nitrite and phenylenediamine (PDA). PDA caused the Au NPs to aggregate owing to the strong covalent NH-Au bond, with a clear color change of solution from red to blue being visualized. In the presence of phosphoric acid and nitrite, the amines of PDA would readily be converted to diazo bonds, and a red solution was observed after the subsequent addition of Au suspension due to the much less strength of electrostatic interaction between the positive diazo groups and the negative citrate-capped Au NPs. With this colorimetric "light-up" method, <1 ppm of nitrite can be easily detected within 5 min at room temperature without instrumentation. Since the diazo reaction and the colorimetric response are separate, this approach features the use of pristine Au NPs in an assay where acidic environment is a necessity, making it a more convenient and cost-effective method for the sensing of nitrite when compared with those utilizing chemically modified Au NPs.     

Au nanoparticle decorated silicate network for the amperometric sensing of isoniazid

Au nanoparticle (nAu) based electrochemical platform for the amperometric sensing of isoniazid at sub-nanomolar level is developed. The sol-gel derived 3-dimensional silicate network pre-assembled on a conducting substrate is chemically decorated with nAu of 70-100 nm by seed-mediated growth approach. The Au nanoseeds are first chemisorbed onto the thiol functional groups of the silicate network and their size was enlarged by hydroxylamine seeding. The nanoparticles efficiently catalyze the oxidation of isoniazid at less positive potential. Large decrease in the overpotential and significant enhancement in the anodic peak current with respect to the polycrystalline Au electrode are observed. The nanoparticle based platform is highly sensitive (4.03 ± 0.01 nA/nM) and it linearly responds to isoniazid up to the concentration of 1 mM. It could detect as low as 0.1 nM (S/N = 5) of isoniazid at the potential of 10 mV in aqueous solution without any redox mediator. The catalytic response of the sensing platform depends on the amount of nanoparticles loaded onto the silicate network. Very interestingly, the sensing platform could simultaneously detect isoniazid and hydrazine in their coexistence without compromising the sensitivity. Well separated individual voltammetric response is obtained for both analytes. The sensing platform is highly stable and it can be repeatedly used for 7 days.     

Membrane sampling with microdialysis coupled to HPLC/UV for on-line simultaneous determination of melamine and cyanuric acid in non-dairy coffee creamer

An on-line microdialysis/high-performance liquid chromatography method was developed for the simultaneous determination of melamine and cyanuric acid in non-dairy coffee creamer. To collect these analytes from aqueous samples, the microdialysis system featured a microdialysis probe incorporating a polyarylethersulfone membrane and employed 0.05 M HCl in 0.1% (v/v) MeOH as the perfusate, with optimal efficiency obtained at a flow rate of 1 μL min(-1). The chromatographic conditions were optimized when using a reverse-phase phenyl column and a mobile phase of phosphate buffer solution in 10% (v/v) MeOH, buffered at pH 3.0. Good linearity relationship (r(2) > 0.9987), intra- and inter-day precisions (RSDs < 6.6%), recoveries (96.9 - 105.0%), and limits of detection (melamine, 3 ppb; cyanuric acid, 150 ppb) were observed for the two analytes. This method has been successfully applied to simultaneous determination of melamine and cyanuric acid in commercial creamers with the recoveries in the range of 97.5 to 102.6%.     

Deposition of gold nanoparticles on β-FeOOH nanorods for detecting melamine in aqueous solution

This study demonstrates a facile but efficient approach to deposit metallic (gold) nanoparticles on β-FeOOH nanorods to obtain Au/β-FeOOH nanocomposites without the assistance of any polymers or surfactants at ambient conditions. In this method, a strong reducing agent (NaBH(4)) can be used to extensively produce Au nanoparticles, converting β-FeOOH into Fe(3)O(4) and depositing gold particles onto magnetic Fe(3)O(4) simultaneously. The microstructure, composition, and chemical properties of the obtained nanocomposites are characterized by various advanced techniques, including transmission electron microscopy (TEM), scanning electron microscopy (SEM), X-ray diffraction (XRD), and UV-vis spectroscopy. Moreover, the Au/β-FeOOH nanocomposite can be used to detect trace melamine using UV spectrum in the ultraviolet wavelength range (190-260 nm), in which the nanocomposites show a higher sensitivity toward melamine due to the promotion of symmetry-forbidden bands (n→π(*)) of melamine molecules and also avoid the disturbance of commercial products containing solid colloids or food colorings that distort visual spectrum during the detection of chemical sensing. The deposition mechanisms and their sensing detection toward melamine are discussed.     

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).     

Determination of melamine in food contact materials using an electrode modified with gold nanoparticles and reduced graphene oxide

We describe an electrochemical sensor for melamine based on a glassy carbon electrode (GCE) modified with reduced graphene oxide that was decorated with gold nanoparticles (AuNP/rGO). The AuNPs/rGO nanocomposite was synthesized by co-reduction of Au(III) and graphene oxide and characterized by transmission electron microscopy, Raman spectroscopy, X-ray diffraction and X-ray photoelectron spectroscopy. The response of the modified GCE to melamine was investigated by using hexacyanoferrate as an electrochemical reporter. It is found that the electrochemical response to hexacyanoferrate is increasingly suppressed by increasing concentration of melamine. This is attributed to competitive adsorption of melamine at the AuNP/rGO composite through the interaction between the amino groups of melamine and the AuNPs. The presence of rGO, in turn, provides a platform for a more uniform distribution of the AuNPs and enhances the electron transfer rate of the redox reaction. The findings were used to develop a sensitive method for the determination of melamine. Under optimized conditions, the redox peak current of hexacyanoferrate at a working voltage of 171 mV (vs. SCE) is linearly related to the concentration of melamine in 5.0 to 50 nM range. The method was successfully applied to the determination of melamine in food contact materials.

A simple electrochemical sensor based on gold nanoparticles decorated reduced graphene oxide was developed for highly sensitive measurement of melamine in food contact materials.

     

A displacement principle for mercury detection by optical waveguide and surface enhanced Raman spectroscopy

A novel displacement principle of metal nanoparticles for target analysis, differing from the usual target-induced aggregation principle, was proved feasible by the use of para-aminothiophenol coupled Au nanoparticles (PATP-Au) multilayer as probes to detect Hg(2+). The PATP-Au multilayer was fabricated through layer-by-layer assembly of Au nanoparticles on optical waveguide (OWG) chip surface using para-aminothiophenol (PATP) as coupling molecules. The localized surface plasmon resonance (LSPR) extinction from Au nanoparticles and the PATP as a Raman reporter enable to easily capture changes in PATP-Au multilayer by OWG and of surface enhanced Raman spectroscopy, respectively. The introduction of the Hg(2+), which has a higher binding affinity to the thiol group of PATP, greatly destroyed the multilayer structure, and produced a large change, several folds higher than the noise, in LSPR features and Raman signals of PATP-Au multilayer probes, and resulted in an excellent selectivity for Hg(2+) detection at a low level of 1nM. This investigation provides us more ideas on the future development of surface analysis techniques for the detection of various target analytes.     

Selective melamine detection in multiple sample matrices with a portable Raman instrument using surface enhanced Raman spectroscopy-active gold nanoparticles

Melamine adulteration of food and pharmaceutical products is a major concern and there is a growing need to protect the public from exposure to contaminated or adulterated products. One approach to reduce this threat is to develop a portable method for on-site rapid testing. We describe a universal and selective method for the detection of melamine in a variety of solid matrices at the 100–200 μg L⁻¹ level by surface enhanced Raman spectroscopy (SERS) with gold nanoparticles. With minimal sample preparation and the use of a portable Raman spectrometer, this work will lead to field-based screening for melamine adulteration. Citrate coated gold nanoparticles (Au NPs) were investigated for both colorimetric and Raman-based responses. Several non-hazardous solvents were evaluated in order to develop a melamine extraction procedure safe for field applications. Au NP agglomerates formed by the addition of isopropanol (IPA) prior to sample introduction enhanced the Raman signal for melamine and eliminated matrix interference for substrate formation. The melamine Raman signal resulted in a 10⁵ enhancement through the use of Au NP agglomerates. To our knowledge, we have developed the first portable SERS method using Au NPs to selectively screen for the presence of melamine adulteration in a variety of food and pharmaceutical matrices, including milk powder, infant formula, lactose, povidone, whey protein, wheat bran and wheat gluten.     

Gold-Titanium(IV) Oxide Plasmonic Photocatalysts Prepared by a Colloid-Photodeposition Method: Correlation Between Physical Properties and Photocatalytic Activities

Colloidal gold (Au) nanoparticles were prepared and successfully loaded on titanium(IV) oxide (TiO(2)) without change in the original particle size using a method of colloid photodeposition operated in the presence of a hole scavenger (CPH). The prepared Au nanoparticles supported on TiO(2) showed strong photoabsorption at around 550 nm due to surface plasmon resonance (SPR) of Au and exhibited a photocatalytic activity in mineralization of formic acid in aqueous suspensions under irradiation of visible light (>ca. 520 nm). A linear correlation between photocatalytic activity and the amount of Au loaded, that is, the number of Au nanoparticles, was observed, indicating that the activity of Au/TiO(2) plasmonic photocatalysts can be controlled simply by the amount of Au loading using the CPH method and that the external surface area of Au nanoparticles is a decisive factor in mineralization of formic acid under visible light irradiation. Very high reaction rates were obtained in samples with 5 wt % Au or more, although the rate tended to be saturated. The CPH method can be widely applied for loading of Au nanoparticles on various TiO(2) supports without change in the original size independent of the TiO(2) phase. The rate of CO(2) formation also increased linearly with increase in the external surface area of Au. Interestingly, the TiO(2) supports showed different slopes of the plots. The slope is important for selection of TiO(2) as a material supporting colloidal Au nanoparticles.     

Determination of melamine in milk powder based on the fluorescence enhancement of Au nanoparticles

We have developed a new analytical method to detect melamine (MA) in milk powder based on the fluorescence enhancement of Au nanoparticles (AuNPs). AuNPs with the average diameter of ～16 nm can emit stable fluorescence at 370 nm when the excitation wavelength was selected at 252 nm. The AuNPs could assemble with melamine to form larger aggregates (AuNPs-MA) through electrostatic interaction and coordinating interaction in acidic conditions, which led to the significant enhancement of the fluorescence intensity. Under the optimized conditions, the enhancement of the fluorescence intensity exhibited a good linear dependence on melamine concentration in the range from 8.0 × 10(-10) to 8.0 × 10(-8) M, and the detection limit is 6.1 × 10(-10) M (3σ). This proposed method showed high precision and accuracy when applied to the real sample analyses. In conclusion, a simple, rapid, accurate and sensitive method to detect melamine has been suggested.     

Using unmodified Au nanoparticles as colorimetric probes for TNT based on their competitive reactions with melamine

Gold nanoparticles(Au NPs) can serve as visualized colorimetric probes for various targets and modification-free sensing strategies are preferred.The donor–acceptor interaction between the electron-rich melamine(MA) and the electron-deficient trinitrotoluene(TNT) allows formation of a supramolecule in aqueous solution.Melamine alone makes the initially individual reddish Au NPs aggregate into gray/blue Au NP assemblies due to melamine forming multiple ligand sites toward the Au NPs.Interestingly,the preformed supramolecule of MA–TNT disenables aggregation of the Au NPs.Therefore the unmodified Au NPs provide facile colorimetric probes for TNT detection in aqueous solution.Rapid identification of TNT is established by naked eye inspection.By using spectrophotometer tools,quantification of TNT is accomplished with a linear range of 80 mmol Là1to 1.2 mmol Là1and a limit of detection(LOD) of 27 mmol Là1.In contrast to previous strategy with surface-modified Au NPs,here a modification-free sensing strategy for TNT assay has been developed with greater convenience,rapidity,and cost-effectiveness.     

Label free colorimetric sensing of thiocyanate based on inducing aggregation of Tween 20-stabilized gold nanoparticles

Based on inducing the aggregation of gold nanoparticles (AuNPs), a simple colorimetric method with high sensitivity and selectivity was developed for the sensing of thiocyanate (SCN(-)) in aqueous solutions. Citrate-capped AuNPs were prepared following a classic method and Tween 20 was subsequently added as a stabilizer. With the addition of SCN(-), citrate ions on AuNPs surfaces were replaced due to the high affinity between SCN(-) and Au. As a result, Tween 20 molecules adsorbed on the AuNPs surfaces were separated and the AuNPs aggregated. The process was accompanied by a visible color change from red to blue within 5 min. The sensing of SCN(-) can therefore be easily achieved by a UV-vis spectrophotometer or even by the naked eye. The potential effects of relevant experimental conditions, including concentration of Tween 20, pH, incubation temperature and time, were evaluated to optimize the method. Under optimized conditions, this method yields excellent sensitivity (LOD = 0.2 μM or 11.6 ppb) and selectivity toward SCN(-). Our attempt may provide a cost-effective, rapid and simple solution to the inspection of SCN(-) ions in saliva and environmental aqueous samples.     

Full-color tuning of surface plasmon resonance by compositional variation of Au@Ag core-shell nanocubes with sulfides

In the present study, we demonstrate the precise tuning of surface plasmon resonance over the full visible range by compositional variation of the nanoparticles. The addition of sulfide ions into the Au@Ag core-shell nanocubes generates stable Au@Ag/Ag(2)S core-shell nanoparticles at room temperature, and the plasmon extinction maximum shifts to the longer wavelength covering the entire visible range of 500-750 nm. Based on the optical property, the Au@Ag core-shell nanocubes are employed as a colorimetric sensing framework for sulfide detection in water. The detection limit is measured to be 10 ppb by UV-vis spectroscopy and 200 ppb by naked eyes. Such nanoparticles would be useful for decoration and sensing purposes, due to their precise color tunability and high stability.     

Development and characterization of Au-YSZ surface plasmon resonance based sensing materials: high temperature detection of CO

Au-YSZ nanocomposite films exhibited a surface plasmon resonance absorption band around 600 nm that underwent a reversible blue shift and narrowed upon exposure to CO in air at 500 degrees C. A linear dependence of the sensing signal was observed for CO concentrations ranging between 0.1 and 1 vol % in an air carrier gas. This behavior of the SPR band, upon exposure to CO, was not observed when using nitrogen as the carrier gas, indicating an oxygen-dependent reaction mechanism. Additionally, the SPR band showed no measurable signal change upon exposure to CO at temperatures below approximately 400 degrees C. The oxygen and temperature-dependent characteristics, coupled with the oxygen ion formation and conduction properties of the YSZ matrix, are indicative of charge-transfer reactions occurring at the three-phase boundary region between oxygen, Au, and YSZ, which result in charge transfer into the Au nanoparticles. These reactions are associated with the oxidation of CO and a corresponding reduction of the YSZ matrix. The chemical-reaction-induced charge injection into the Au nanoparticles results in the observed blue shift and narrowing of the SPR band.     

Au纳米粒子负载的ZnO空心球复合材料的光生电荷转移行为及光催化活性

通过简单的两步法合成了不同负载量的Au/ZnO空心球。采用扫描电子显微镜(SEM),X射线衍射(XRD),X射线光电子能谱(XPS)及紫外-可见漫反射光谱(UV-Vis DRS)对样品的形貌、结构、组成和晶相等进行一系列的表征。以罗丹明B (RhB)为目标降解物,探究了Au/ZnO空心球的光催化活性。结果表明,适量Au修饰的ZnO光催化剂在混合光下20 min内对RhB的降解率达到73%。利用表面光电压谱(SPS)和瞬态光电压(TPV)技术,探讨了Au修饰后对ZnO光诱导电荷转移行为与光催化性能之间的关系。结果表明,混合光照下Au/ZnO空心球光降解性能的提高主要归因于作为电子受体的Au纳米粒子与ZnO之间形成的强的电子相互作用。适量Au纳米粒子的负载能够提高ZnO空心球中光生载流子的分离效率,相应地延长载流子的传输时间,增加光生电荷的寿命,从而促进其光催化活性的提高。     

Monolayer Two‐dimensional Molecular Crystals for an Ultrasensitive OFET‐based Chemical Sensor

The sensitivity of conventional thin‐film OFET‐based sensors is limited by the diffusion of analytes through bulk films and remains the central challenge in sensing technology. Now, for the first time, an ultrasensitive (sub‐ppb level) sensor is reported that exploits n‐type monolayer molecular crystals (MMCs) with porous two‐dimensional structures. Thanks to monolayer crystal structure of NDI3HU‐DTYM2 (NDI) and controlled formation of porous structure, a world‐record detection limit of NH₃ (0.1 ppb) was achieved. Moreover, the MMC‐OFETs also enabled direct detection of solid analytes of biological amine derivatives, such as dopamine at an extremely low concentration of 500 ppb. The remarkably improved sensing performances of MMC‐OFETs opens up the possibility of engineering OFETs for ultrasensitive (bio)chemical sensing.