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In this work, the binary nanocomposite of crosslinked polyaniline nanorods (CPANINRs) and molybdenum disulfide (MoS2) is first synthesized by in situ polymerization, and CPANINRs/MoS2 on functionalized carbon cloth (CPANINRs/MoS2/FCC) is facilely constructed by a drop-casting method. The composition, morphology, and structure of the CPANINRs, MoS2, and CPANINRs/MoS2 binary nanocomposite are characterized by transmission electron microscope (TEM), scanning electron microscope (SEM), X-ray diffraction (XRD), and thermogravimetric analysis (TGA). The electrochemical properties of the MoS2/FCC, CPANINRs/FCC, and CPANINRs/MoS2/FCC are tested by cyclic voltammetry (CV) and galvanostatic charge–discharge (GCD). The experiment results show that the CPANINRs/MoS2/FCC exhibits excellent stability and high specific capacitance, and its specific capacitance reaches 618.75 F g−1 at a current density of 0.5 A g−1. The CPANINRs/MoS2/FCC has a long cycling life and the capacity retention of 91.46% is obtained after 2000 cycles at a large current density of 10 A g−1. Moreover, the CPANINRs/MoS2/FCC-based symmetric supercapacitor also exhibits excellent rate performance and good cycling stability. The specific capacitance based on the total mass of the two electrodes is 106.4 F g−1 at a current density of 0.5 A g−1 and the capacitance retention of 93.6% is obtained after 2000 cycles.

A MoS2/PANI/functionalized carbon cloth (MoS2/PANI/FCC) was constructed by a drop-casting method. Its specific capacitances were higher than those of MoS2/CC and pure PANI/CC.

In this paper, an electrochemical sensor based on depositing acid chrome blue K on the surface of glassy carbon electrode was developed for detection of nitrofurazone. The obtained poly-ACBK film was characterised by atomic force microscope. The experimental results indicated that the Poly-ACBK/GCE showed good electrocatalytic activity to the redox reactions of nitrofurazone by differential pulse voltammetry and cyclic voltammetry in Britton-Robinson buffer solution, and the different redox peak currents were observed in different pH ranges (2.0–6.0, 7.0–12.0). Base on these, electrochemical reaction mechanism of nitrofurazone was presented in different pH ranges. Under the optimal conditions, a linear relationship between the reduction peak currents and concentrations for nitrofurazone is figured out in the range of 0.75‒192 μM, with detection limits of 0.25 µM (S/N = 3). This sensor produced satisfactory reproducibility and stability and was successfully applied to monitor of nitrofurazone in real samples (nasal drops).

Fluorescent tremella-like carbon nanosheets (TCNs) were hydrothermally synthesized using citric acid and adenosine as the starting materials. The resulting product had high quantum yield, water-sol...

In the work, water-soluble bovine serum albumin-protected fluorescent nickel nanoclusters (BSA-NiNCs) are used as fluorescent probes to construct a label-free fluorescence quenching sensor for sensitive and selective detection of tartrazine. The fluorescent BSA-NiNCs are synthesized in one pot using BSA as both the template and reducing agent, and hydrogen peroxide as the additive. The as-prepared NiNCs are characterized by using various analytical techniques like transmission electron microscopy, X-ray photoelectron spectroscopy, Fourier transform infrared spectroscopy, UV–Vis absorption spectroscopy, circular dichroism spectroscopy, and fluorescence spectroscopy. The synthesized BSA-NiNCs have a quantum yield of ca. 8% by using quinine sulfate as a standard. The sensor for tartrazine detection shows a wide linear range of 0.01–3.5 μM, with a low detection limit of 4 nM. The fluorescence quenching very likely results from the combination of the intermolecular interactions and the secondary inner filter effect between BSA-NiNCs and tartrazine. Then, the proposed sensor is successfully employed for tartrazine detection in drink samples, and the results are comparable with those based on a reference HPLC method.

In this paper, graphite phase carbon nitride (g-C3N4) was prepared by one-step high temperature thermal decomposition method, and layered g-C3N4 was prepared by protonation with concentrated hydrochloric acid. The morphology and composition of g-C3N4 were characterised by transmission electron microscope (TEM), energy dispersive spectroscopy (EDS) and X-ray powder diffraction (XRD). Furthermore, the AuNPs-g-C3N4/GCE was constructed by coating method and potentiostatic deposition method, and the construction process and resistance change of the electrodes were characterised by cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). The experimental results indicated that the AuNPs-g-C3N4/GCE has excellent electrocatalytic performance for bisphenol A (BPA) and 4-n-octylphenol (OP). Under optimized experimental conditions, BPA and OP were detected by differential pulse voltammetry (DPV) at the AuNPs-g-C3N4/GCE. The linear ranges were 0.1–6.5 µmol L−1 and 0.1–3.8 µmol L−1 for BPA and OP, wtih the detection limits of 0.0176 µmol L−1 and 0.0324 µmol L−1, respectively. In addition, the AuNPs-g-C3N4/GCE showed satisfactory reproducibility and stability and can be successfully applied to monitor of BPA and OP in baby formula samples.

A hydrothermal synthetic approach is developed for the preparation of graphitic carbon nitride quantum dots (g-C3N4 QDs) from human urine. The reported synthetic method is green, simple, low-cost, less time-consuming, and can be used for the large-scale production of the g-C3N4 QDs. The as-prepared g-C3N4 QDs possess a high quantum yield of 15.7% by using quinine sulfate as a reference, and display excitation-wavelength dependent fluorescent emission. In addition, the g-C3N4 QDs exhibit high photostability, low cytotoxicity. and are successfully used as fluorescent probes for cell multicolor imaging. It is believed that the valuable nanomaterials, g-C3N4 QDs, which are transformed from the human bodily wastes, are promising in diverse chemical applications.

Most of the conventional multidimensional differential sensors currently need at least two-step fabrication, namely synthesis of probe(s) and identification of multiple analytes by mixing of analytes with probe(s), and were conducted using multiple sensing elements or several devices. In the study, we chose five different nucleobases (adenine, cytosine, guanine, thymine, and uracil) as model analytes, and found that under hydrothermal conditions, sodium citrate could react directly with various nucleobases to yield different nitrogen-doped carbon nanodots (CDs). The CDs synthesized from different nucleobases exhibited different fluorescent properties, leading to their respective characteristic fluorescence spectra. Hence, we combined the fluorescence spectra of the CDs with advanced chemometrics like principle component analysis (PCA), hierarchical cluster analysis (HCA), K-nearest neighbor (KNN) and soft independent modeling of class analogy (SIMCA), to present a conceptually novel "synthesis-identification integration" strategy to construct a multidimensional differential sensor for nucleobase discrimination. Single-wavelength excitation fluorescence spectral data, single-wavelength emission fluorescence spectral data, and fluorescence Excitation-Emission Matrices (EEMs) of the CDs were respectively used as input data of the differential sensor. The results showed that the discrimination ability of the multidimensional differential sensor with EEM data set as input data was superior to those with single-wavelength excitation/emission fluorescence data set, suggesting that increasing the number of the data input could improve the discrimination power. Two supervised pattern recognition methods, namely KNN and SIMCA, correctly identified the five nucleobases with a classification accuracy of 100%. The proposed "synthesis-identification integration" strategy together with a multidimensional array of experimental data holds great promise in the construction of differential sensors.

Three-dimensional copper hydroxide nanosupercages and electrochemically reduced graphene oxide were used to modify the glassy carbon electrode for the selective determination of hydrogen peroxide. ...

A facile, simple, and relatively environment-friendly hydrothermal approach was developed for one-step synthesis of graphitic carbon nitride nanosheets (GCNNs) using melamine and sodium citrate as the precursors. The prepared GCNNs emit strong fluorescence with a high quantum yield of 48.3%. The GCNNs were then characterized by various techniques including transmission electron microscopy, atomic force microscopy, X–ray diffraction, Fourier transform infrared spectroscopy, and UV–Vis absorption spectroscopy. In addition, the fluorescence quenching behavior of the GCNNS by mercuric ions (Hg 2+ ) was exploited to fabricate a label-free fluorescence quenching sensor for sensitive and selective detection of Hg 2+ . The results showed that there existed a linear relationship between the fluorescence intensity and the concentration of Hg 2+ from 0.001 to 1.0 μM with a detection limit of 0.3 nM. Finally, the sensor was successfully used to detection of Hg 2+ in water and milk samples.

An electrochemical biosensor capable of direct detection of DNA damage induced by clenbuterol (CLB) has been developed. A glassy carbon electrode (GCE) was modified using reduced graphene oxide-Nafion and dsDNA to produce a dsDNA/RGO-Nafion/GCE sensor. The modified electrode was characterized by electrochemical impedance spectroscopy (EIS) and cyclic voltammetry (CV), and the results at each stage of the electrode construction were interpreted. They indicated that the electrochemical oxidation peak currents of guanine and adenine at the electrode (dsDNA/RGO-Nafion/GCE) significantly increased as compared with those at the untreated electrode (dsDNA/GCE). Based on this, the sensor was used to measure the change of the oxidation peak currents for guanine and adenine between the intact and damaged dsDNA in the sensor films, and the DNA damage was successfully detected. Furthermore, the plot of peak current decline for the guanine and adenine versus the concentration of CLB was linear in the range of 5.0 × 10−7 to 4.0 × 10−6 mol L−1, with a limit of detection (LOD) of 3.2 × 10−7 mol L−1, which provided a good method to determine CLB indirectly.

Lotus has been widely cultivated and consumed in Asia, Oceania and America, and it is not only used as an ornamental plant but also as a dietary staple. In this work, fingerprinting techniques based on NIR spectroscopy and HPLC chromatography were used to discriminate four important kinds of lotus seed cultivars, Xianglian, Jianlian, Ganlian and Hulian. By the use of the NIR spectra and the aid of genetic algorithm-partial least squares (GA-PLS) and principal component analysis (PCA), cored lotus seed samples were successfully discriminated into four cultivars. High performance liquid chromatographic (HPLC) characteristic peaks detected at different wavelengths can also be used for PCA analysis to differentiate the lotus seed cultivars. Furthermore, quantitative prediction analysis of total sugar, total polysaccharide, liensinine and rutin in cored lotus seed (liensinine and rutin are mainly in lotus plumule) can be successfully performed with the use of the combined data matrix of 30 common characteristic HPLC peaks and 37 GA-PLS selected NIR spectral variables (wavelengths). The results suggested that the combination of NIR and HPLC supported by chemometrics is suitable for the discrimination of the plant cultivars and quantitative prediction of the active constituents in lotus seed samples.

In this work, the electrochemical behavior of hydrochlorothiazide and pyridoxine on the ethylenediamine-modified glassy carbon electrode were investigated by differential pulse voltammetry. In pH 3.4 Britton-Robinson (B-R) buffer solution, both hydrochlorothiazide and pyridoxine had a pair of sensitive irreversible oxidation peaks, that overlapped in the 1.10 V to 1.20 V potential range. Under the optimum experimental conditions, the peak current was linearly related to hydrochlorothiazide and pyridoxine in the concentration range of 0.10&ndash, 2.0 &mu, g/mL and 0.02&ndash, 0.40 &mu, g/mL, respectively. Chemometrics methods, including classical least squares (CLS), principal component regression (PCR) and partial least squares (PLS), were introduced to resolve the overlapped signals and determine the two components in mixtures, which avoided the troublesome steps of separation and purification. Finally, the simultaneous determination of the two components in commercial pharmaceuticals was performed with satisfactory results.

A strong red fluorescent nanocomposite, consisting of graphite-like carbon nitride nanosheets (g-C3N4 NSs) and serum albumin-capped Au nanoclusters (AuNCs), was synthesized. Dopamine (DA) can quench the red fluorescence of the nanocomposite, based on the Forster resonance energy transfer (FRET) mechanism. In this quenching process, the energy is transferred from the fluorescent g-C3N4 NSs-AuNCs to the oxidized DA quinine molecules (DA is easily oxidated to form DA quinine in air). The red fluorescence emission at 420 nm decreases dramatically and the quenching ratio (F0 – F)/F0 is linearly related to the concentration of DA in the range of 0.05–8.0 μmol L−1 with a detection limit of 0.018 μmol L−1 (S/N = 3). Additionally, this sensor has a potential of application to assay the DA in the real samples, such as human serum and human urine.

In the present study, we demonstrated that the luminescent molybdenum disulfide (MoS 2 ) nanosheets, which were prepared hydrothermally by using sodium molybdate and thiourea as precursors, possessed peroxidase-like activity, and could catalyze the oxidation of peroxidase substrate o-phenylenediamine (OPD) in the presence of hydrogen peroxide (H 2 O 2 ) to produce a yellow color reaction. Further addition of Fe 2+ into the nanosheets led to peroxidase mimetics with greatly enhanced catalytic activity. The observation was exploited to develop a label-free colorimetric nanozyme sensor for detection of Fe 2+ . The fabricated MoS 2 /OPD/H 2 O 2 sensor showed a wide linear range of 0.01–0.8 µM with a detection limit of 7 nM. Moreover, it was found that the MoS 2 /OPD/H 2 O 2 sensor displayed enhanced sensitivity and selectivity toward Fe 2+ compared with the OPD/H 2 O 2 sensor, suggesting that the MoS 2 nanosheets could improve the performance of the Fe 2+ sensor. An advanced chemometrics algorithm, multivariate curve resolution by alternating least squares (MCR-ALS), was further applied to interpret the origin of enhancing sensitivity and selectivity in the Fe 2+ sensor with the MoS 2 nanosheets. The time-dependent UV–vis spectral data of the studied systems were collected, and submitted to the MCR-ALS. The results showed that the increased sensitivity and selectivity of the MoS 2 /OPD/H 2 O 2 sensor for Fe 2+ detection likely arose from its large reaction rate constant. Finally, the proposed MoS 2 /OPD/H 2 O 2 sensor was successfully applied for detection of Fe 2+ in water samples.

A novel 3D nano-flower-like Cu/multi-layer molybdenum disulfide composite (CuNFs/MoS2) modified glassy carbon electrode (GCE) has been successfully constructed. It was a highly sensitive and selective non-enzymatic hydrogen peroxide (H2O2) and glucose biosensor. The morphology of the obtained CuNFs-MoS2 nano-particles was investigated with the use of a scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD) and energy dispersive X-ray spectroscopy (EDS). The physicochemical properties of the modified electrode were characterized at each of the construction stages with the use of an electrochemical impedance spectroscopy (EIS) and cyclic voltammetry (CV) techniques. The new sensor combined the advantages of MoS2 and CuNFs, and exhibited high electro-catalytic activity toward H2O2 and glucose. Quantitative analysis of H2O2 and glucose was carried out with the use of the amperometric i-t method. Linear ranges were obtained between 0.04-1.88 μM and 1.88-35.6 μM for H2O2 and 1-20 μM and 20-70 μM for glucose, and their corresponding limits of detection (LOD) were 0.021 μM and 0.32 μM. This novel sensor was successfully applied for the quantitative analysis of H2O2 in tap water and glucose in human serum samples.

Fluorescent molybdenum disulfide (MoS2) nanosheets were synthesized hydrothermally by employing sodium molybdate and thiourea as the starting materials. Lead(II) ion was introduced as a chemical dopant into the fluorescent nanosheets for the first time, and it was found that the fluorescence of the doped MoS2 nanosheets showed a considerable enhancement compared with that of initial MoS2 nanosheets, implying that lead(II)-doping into the MoS2 nanosheets could result in an increase in the fluorescence quantum yield. In parallel, we exploited the lead(II)-induced fluorescence enhancement of MoS2 nanosheets to design a green and facile fluorescent “turn on” nanosensor for lead(II) detection. Moreover, we found that the fluorescent intensity of the doped MoS2 nanosheets was drastically quenched by the successive addition of sulfide ions. Hence, the “turn off” process was used to fabricate a green fluorescence quenching sensor for detection of sulfide ions. Finally, we elucidated the origin of the lead(II)-ind...

The interactions of the sugars glucose and lactose with the transport protein bovine serum albumin (BSA) were investigated using fluorescence, FT-IR and circular dichroism (CD) techniques. The results indicated that glucose could be bonded and transported by BSA, mainly involving hydrogen bonds and van der Waals interactions (ΔH = -86.13 kJ mol(-1)). The obtained fluorescence data from the binding of sugar and BSA were processed by the multivariate curve resolution-alternating least squares (MCR-ALS) method, and the extracted concentration profiles showed that the equilibrium constant, rglucose:BSA, was about 7. However, the binding of lactose to BSA did not quench the fluorescence significantly, and this indicated that lactose could not be directly transported by BSA. The binding experiments were further performed using the fluorescence titration method in the presence of calcium and BSA. Calcium was added so that the calcium/BSA reactions could be studied in the presence or absence of glucose, lactose or hydrolysis products. The results showed that hydrolyzed lactose seemed to enhance calcium absorption in bovine animals. It would also appear that for children, lactose provides better nutrition; however, glucose is better for adults.

Near-infrared (NIR) spectroscopy is a well-known, rapid and non-destructive technique suitable for analyses of many different food products. In this work, it was used to develop a novel method for the analysis of dehydrated tomato samples, collected from four different producers. The NIR spectra from such samples were discriminated according to the four production sources, with the use of principal component analysis (PCA). Also, hierarchical cluster analysis (HCA), linear discriminant analysis (LDA) and K-nearest neighbors (KNN) were successfully used for pattern recognition. The prediction rates were 100% for assigning producers to samples. Two multivariate calibration models—partial least squares regression (PLSR) and radial basis function neural networks (RBF-NN), were applied for quantitative analysis. NIRS calibration models were established for the determination of lycopene and total acid, sugar, phenols and antioxidant activity in dehydrated tomatoes. These calibrations were then used for prediction of unknown, dehydrated tomato samples with satisfactory results. The RBF-NN results were better than those obtained from the PLSR models, and the better predictions suggested that the novel NIR spectroscopic method supported by chemometrics, is suitable for the discrimination and prediction of the five quality parameters in the dehydrated tomato products.

Bulk graphitic carbon nitride (g-C3N4) was obtained by pyrolysis of urea at 600 °C. The material was then subjected to protonation and exfoliation to obtain strongly fluorescent g-C3N4 nanosheets. These nanosheets are representing a two-dimensional layered material that emits strong blue fluorescence peaking at 434 nm, and their quantum yield of up to 10.3 % is much higher than that of bulk g-C3N4 (6.0 %). It was found that Cu(II) ions quench the fluorescence of the nanosheets due to photo-induced electron transfer (PET), probably the result of the stronger binding affinity between Cu(II) and the nitrogen and oxygen functional groups of the nanosheets. The probe responds to Cu(II) in the 0.01 to 0.4 nM concentration range, with a 8 pM detection limit. The method was applied to the determination of Cu(II) in spiked water samples.

A simple, environmentally friendly hydrothermal method was used to prepare strongly luminescent, nitrogen-doped carbon dots (NCDs) with the use of Chinese yams as a source of carbon and nitrogen. Such NCDs have an average size of 2.7±1.4 nm; they emit blue light at 420 nm and have a quantum yield of up to 9.3%. Thus, carboxyfluorescein (FAM)-DNA macro-molecules were assembled on the surfaces of the NCDs, and stabilised by strong π-π stacking; the so formed hybrid nano-sensors were found to have an ultra-sensitive response to 6-mercaptopurine (6-MP). A strong emission and enhancement of yellow radiation was observed from FAM. Furthermore, due to the specific interactions between DNA and Hg(2+), which resulted in the formation of the T-Hg(2+)-T (T: thymine base) complex - a large, conjugated system, which formed between NCDs, DNA and 6-MP, was broken up. Thus, the fluorescence from FAM was quenched. The detection limits for 6-MP and Hg(2+) were 0.67 and 1.26 nM, respectively. The proposed method was applied for the determination of 6-MP in human serum and Hg(2+) in water samples with satisfactory results.

A metal organic framework (MOF) of the type copper(II)-1,3,5-benzenetricarboxylic acid (Cu-BTC) was electrodeposited on electroreduced graphene oxide (ERGO) placed on a glassy carbon electrode (GCE). The modified GCE was used for highly sensitive electrochemical determination of 2,4,6-trinitrophenol (TNP). The fabrication process of the modified electrode was characterized by scanning electron microscopy and electrochemical impedance spectroscopy. Differential pulse voltammetry (DPV) demonstrates that the Cu-BTC/ERGO/GCE gives stronger signals for TNP reduction than Cu-BTC/GCE or ERGO/GCE alone. DPV also shows TNP to exhibit three reduction peaks, the first at a potential of −0.42 V (vs. SCE). This potential was selected because the other three similarly-structured compounds (2-nitrophenol, 4-nitrophenol, 2,4-dinitrophenol) do not give a signal at this potential. Response is linear in the 0.2 to 10 μM TNP concentration range, with a 0.1 μM detection limit (at S/N = 3) and a 15.98 μA∙μM−1∙cm−2 sensitivity under optimal conditions. The applicability of the sensor was evaluated by detecting TNP in spiked tap water and lake water samples. Recoveries ranged between 95 and 101%.

Tungsten disulfide (WS2) is a two-dimensional transition metal dichalcogenide, which is of particular interest because it has highly anisotropic bonding, which leads to strongly anisotropic electrical and mechanical properties. Thus, in this work, a simple hydrothermal process was developed to produce photoluminescence from WS2 dots. This was achieved in the presence of sodium tungstate and reduced L-glutathione; the emitted fluorescence produced a quantum yield as high as 0.066. The WS2 dots and the associated fluorescence were investigated with the use of transmission electron microscopy, atomic force microscopy, X-ray photoelectron spectroscopy, Fourier transform infrared and UV-vis spectroscopies. The WS2 dots were used as a fluorescent probe to analyze nitrofurazone (NFZ). The associated fluorescence resonance energy transfer (FRET) mechanism was also investigated and the emitted fluorescence was found to be linear in the range of 0.17-166 μmol L(-1) with a detection limit of 0.055 μmol L(-1). The proposed method was successfully applied for analysis of NFZ in nasal drops and water samples.

This work demonstrates how near-infrared reflectance spectroscopy (NIR) in combination with chemometrics can be used to analyse and discriminate powdered, pure and adulterated sweet potato samples. Thus, the principal component analysis (PCA) method, which is able to produce diagrams of objects as a function of PC scores, was able to distinguish and group the NIRS from the many different types of potato sample. Other methods such as the radial basis function-partial least squares (RBF-PLS) as well the successive projection algorithm (SPA) combination, distinguished the purple and white sweet potato varieties from each other as well as, importantly, from the different adulterated purple sweet potato samples. Furthermore, the total anthocyanin (TA) and total antioxidant activity (TAA) parameters were also analysed quantitatively in these samples, and high residual prediction deviation (RPD) values were noted. Also, the two recognition methods, k-nearest neighbours (KNN) and linear discriminant analysis (LDA), were able to discriminate the sweet potato samples. Thus, overall this work demonstrated that NIRS combined with chemometrics methods can be employed for the identification of purple sweet potato, white sweet potato and their adulterated samples; in addition, quantitative analysis for TA and TAA in such samples can be successfully performed.

A new electrochemical sensor for H2O2 was constructed by depositing copper doped CuO nanosheets on a glassy carbon electrode (GCE). The morphology and composition of the modified electrode were characterized via scanning electron microscopy, energy dispersive X-ray spectroscopy and X-ray diffraction. The electrochemical properties of the electrode were studied using cyclic voltammetry and electrochemical impedance spectroscopy. The catalytic performance of the sensor was studied in 100 mM NaOH solution via differential pulse voltammetry and revealed the sensor to display significantly improved electrocatalytic activity with respect to the analysis of the H2O2 in comparison to a plain GCE or a GCE modified with copper only. The response to H2O2 at a working voltage of −0.46 V (vs. Ag/AgCl) is linear in the 0.003 – 8 mM concentration range, and the detection limit is 0.21 mM (at an S/N ratio of 3). Satisfactory results were obtained in the analysis of tap, rain and river waters spiked with H2O2. The analytical performance of this electrode compares favorably to the results obtained with other commonly used techniques for analysis of H2O2.

An electrochemical biosensor capable of indirect detection of DNA damage induced by any one of the three endocrine-disrupting compounds (EDCs) – bisphenol A (BPA), 4-nonylphenol (NP) and 4- t -octylphenol (OP), has been researched and developed. The methylene blue (MB) dye was used as the redox indicator. The glassy carbon electrode (GCE) was modified by the assembled dsDNA/graphene oxide-chitosan/gold nano-particles to produce a dsDNA/GO-CS/AuNPs/GCE sensor. It was characterized with the use of electrochemical impedance spectroscopy (EIS), cyclic voltammetry (CV) and scanning electron microscopy (SEM) techniques. The loading/release of the MB dye by the dsDNA/GO-CS/AuNPs film was investigated, and the results showed that the process was reversible. Based on this, the sensor was used to measure the difference between the loading capabilities of intact and damaged dsDNA in the films. The sensor was then successfully applied to detect DNA damage electrochemically. The differential pulse voltammetry (DPV) peak current ratio for MB, observed before and after DNA damage, increased linearly in the presence the BPA, NP or OP compounds; the treatment range was 10–60 min, and the respective damage rates were 0.0069, 0.0044 and 0.0031 min −1 , respectively. These results were confirmed by the binding constants: 2.09 × 10 6 M −1 (BPA-DNA), 1.28 × 10 6 M −1 (NP-DNA) and 9.33 × 10 5 M −1 (OP-DNA), all of which were obtained with the use of differential pulse stripping voltammetry (DPSV).

In this study, complex substances such as Mint (Mentha haplocalyx Briq.) samples from different growing regions in China were analyzed for phenolic compounds by high-performance liquid chromatography with diode array detection and for the volatile aroma compounds by gas chromatography with mass spectrometry. Chemometrics methods, e.g. principal component analysis, back-propagation artificial neural networks, and partial least squares discriminant analysis, were applied to resolve complex chromatographic profiles of Mint samples. A total of 49 aroma components and 23 phenolic compounds were identified in 79 Mint samples. Principal component analysis score plots from gas chromatography with mass spectrometry and high-performance liquid chromatography with diode array detection data sets showed a clear distinction among Mint from three different regions in China. Classification results showed that satisfactory performance of prediction ability for back-propagation artificial neural networks and partial least squares discriminant analysis. The major compounds that contributed to the discrimination were chlorogenic acid, unknown 3, kaempherol 7-O-rutinoside, salvianolic acid L, hesperidin, diosmetin, unknown 6 and pebrellin in Mint according to regression coefficients of the partial least squares discriminant analysis model. This study indicated that the proposed strategy could provide a simple and rapid technique to distinguish clearly complex profiles from samples such as Mint.

A novel electrochemical sensor was constructed by depositing copper/copper oxide nano-particles on a glassy carbon electrode (GCE) to produce a Cu@CuO/GCE. The morphology and composition of this modified electrode were characterized with the use of scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDS), and X-ray diffraction (XRD) techniques. The electrochemical properties of the novel modified GCE electrode were studied using various electrochemical techniques such as cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). The catalytic performance of the sensor was studied with the use of differential pulse voltammetry (DPV) under optimized conditions. The constructed Cu@CuO/GCE sensor showed significantly better electrocatalytic activity for the analysis of the H 2 O 2 in comparison to the Cu/GCE or GCE. The novel sensor produced a linear response for H 2 O 2 analysis in the range of 0.005–8 mM and the detection limit was 0.23 μM (S/N = 3). Satisfactory results were obtained for H 2 O 2 analyses of tap and lake waters. This performance compares very favorably with the results from several other commonly used techniques for analysis of H 2 O 2 .

Molybdenum disulfide (MoS2) is an emerging material with some unique physical and electronic properties somewhat comparable to those of graphene. It was prepared with the use of a simple hydrothermal process, and has a layered structure similar to that of graphene. Also, it has a peroxidase-like catalytic activity and is able to catalyze the oxidation of the colorless peroxidase substrate, 3,3',5,5'-tetramethylbenzidine (TMB), in the presence of H2O2 to produce a blue product. This reaction used MoS2 as a useful peroxidase, which involved a colorimetric method for trace analysis of H2O2 in water, e.g. lake waters. This method is uncomplicated, inexpensive and highly sensitive for H2O2 in the 0.125-1.75 μM range (LOD: 0.08 μM). It is also quite stable in the presence of many common inorganic and organic potentially interfering compounds, e.g. metal ions as well as amino acids and sugars.

A novel, uncomplicated method for the analysis of lead (Pb2+) and mercury (Hg2+) ions has been developed with the use of gold nano-rods (AuNRs), which were combined with ssDNA. The AuNR–ssDNA assembly was stabilized by electrostatic interactions. The ssDNA has a random coil structure, which was changed to G-quartet and hairpin-like structures after binding with Pb2+ and Hg2+ ions, respectively. The bonding with lead and mercury caused the ssDNA assembled AuNRs (ssDNA–AuNRs) to disperse, and this increased the surface plasmon resonance (SPR) absorption of the AuNRs. Changes in the UV-vis spectral intensities allowed the selective detection of Pb2+ and Hg2+ ions at concentrations as low as 19.8 nM and 3.2 nM, respectively. Linear correlations were observed between the UV-vis spectra and the Pb2+ and Hg2+ analytes in the concentration ranges of 25–250 nM (R2 = 0.9971) for Pb2+ and 4–40 nM (R2 = 0.9956) for Hg2+, respectively. The literature suggests that the novel method is another example in which the ssDNA–AuNR assembly has been used for trace analysis of Pb2+ and Hg2+.

Very recently, the interest in layered transition metal chalcogenides, especially molybdenum disulfide (MoS 2 ), has been growing as quickly as interest in two-dimensional graphene did a few years ago because they share many impressive physicochemical properties of graphene. For the first time, we herein attempted to exploit 32-mer homoadenine ssDNA oligonucleotides (A 32 ) and graphene as an effective anchoring block for attachment to the layered MoS 2 and the Au electrode, and then the MoS 2 binding with the Au electrode was electrochemically reduced to form the reduced MoS 2 (rMoS 2 ). The morphology and electrochemistry of the obtained rMoS 2 –graphene/A 32 /Au electrode were characterized by various techniques such as scanning electron microscopy, energy-dispersive X-ray spectroscopy, cyclic voltammetry, and electrochemical impedance spectroscopy. To show the electrochemical sensing performance of the modified electrode, riboflavin was selected as model target. The results displayed that the riboflavin sensor with the use of differential pulse voltammetry possessed a wide linear range from 0.025 to 2.25 μM, with a low detection limit of 20 nM. The sensor was then successfully employed for the detection of riboflavin in human urine samples.

We reported a sensitive and selective fluorescence “turn on–off” strategy for detection of Cu2+ and hemin, respectively. The fluorescence “turn on” sensor for Cu2+ detection had a wide linear range of 0.05–2.0 μM with a limit of detection (LOD) of 0.032 μM, and the fluorescence “turn off” sensor for hemin detection possessed a wide linear range of 0.05–4.0 μM with an LOD of 0.045 μM. The sensor for Cu2+ or hemin exhibited high selectivity over other possible substances. In addition, it was demonstrated by using various analytical characterization techniques that the fluorescence “turn on” sensor for Cu2+ was constructed on the basis of the formation of water-soluble fluorescent copper nanoclusters (CuNCs), and the fabrication of the fluorescence “turn off” sensor for hemin was predominately based on the inner filter effect of hemin on the fluorescence of the CuNCs. Finally, the proposed fluorescence “turn on–off” sensor system was successfully applied for detection of Cu2+ in lake water samples and hemin in duck blood samples.

A novel differential pulse voltammetry (DPV) method was developed for the simultaneous analysis of herbicides in water. A mixture of four herbicides, atrazine, simazine, propazine and terbuthylazine was analyzed simultaneously and the complex, overlapping DPV voltammograms were resolved by several chemometrics methods such as partial least squares (PLS), principal component regression (PCR) and principal component-artificial networks (PC-ANN). The complex profiles of the voltammograms collected from a synthetic set of samples were best resolved with the use of the PC-ANN method, and the best predictions of the concentrations of the analytes were obtained with the PC-ANN model (%RPET = 6.1 and average %Recovery = 99.0). The new method was also used for analysis of real samples, and the obtained results were compared well with those from the GC-MS technique. Such conclusions suggest that the novel method is a viable alternative to the other commonly used methods such as GC, HPLC and GC-MS.

Transition metal chalcogenides, especially molybdenum disulfide (MoS2), have recently attracted wide attention from researchers as graphene-analogous materials. However, until now, little literature has reported the synthesis of photoluminescent MoS2 materials and their applications in analytical chemistry. We herein presented a facile bottom-up hydrothermal route for the synthesis of photoluminescent MoS2 quantum dots (QDs) by using sodium molybdate and cysteine as precursors. The prepared MoS2 QDs were characterized by transmission electron microscopy, atomic force microscopy, X-ray photoelectron spectroscopy, Fourier transform infrared spectroscopy, photoluminescence spectroscopy, and UV-vis spectroscopy. The MoS2 QDs were then used as photoluminescent probes to construct a photoluminescence (PL) quenching sensor for detection of 2,4,6-trinitrophenol (TNP). The TNP sensor presented a wide linear range from 0.099 to 36.5 μM with a high detection limit of 95 nM. Furthermore, the sensor displayed a high sensitivity toward TNP over other structurally similar compounds like 2,4,6-trinitrotoluene, p-chlorophenol, phenol, and 2,6-di-tert-butyl-4-methylphenol. To understand the origin of the high sensitivity, we assessed the emission wavelength-dependent PL quenching behavior of MoS2 QDs by the above five compounds using Stem-Volmer equation in detail. The results showed that the novel approach we put forward can satisfactorily explain the interaction mechanisms between MoS2 QDs and the five compounds, and the high sensitivity for TNP very likely originated from a combination of the PL resonance energy transfer, electronic energy transfer, and electrostatic interactions between MoS2 QDs and TNP. Finally, the sensor was successfully applied for detection of TNP in water samples and test papers.

A simple one-step electrodeposition method was used to construct a glassy carbon electrode (GCE), which has been modified with Cu doped gold nanoparticles (GNPs), i.e. a Cu@AuNPs/GCE. This electrode was characterized with the use of scanning electron microscopy (SEM) and X-ray diffraction (XRD) techniques. The eugenol was electrocatalytically oxidized at the Cu@AuNPs/GCE. At this electrode, in comparison with the behavior at the GCE alone, the corresponding oxidation peak current was enhanced and the shift of the oxidation potentials to lower values was observed. Electrochemical behavior of eugenol at the Cu@AuNPs/GCE was investigated with the use of the cyclic voltammetry (CV) technique, and additionally, in order to confirm the electrochemical reaction mechanism for o-methoxy phenols, CVs for catechol, guaiacol and vanillin were investigated consecutively. Based on this work, an electrochemical reaction mechanism for o-methoxy phenols was suggested, and in addition, the above Cu@AuNPs/GCE was successfully employed for the analysis of eugenol in food samples.

A novel, uncomplicated and rapid method of analysis for organophosphorus (OP) pesticides was researched and developed using the important, common OP, dipterex, as a typical example. The basis of the method involved the citrate-capped silver nanoparticles (citrate-capped AgNPs) and Acetylthiocholine (ATCh). The latter compound can be catalyzed by Acetylcholinesterase (AChE) to form thiocholine (TCh), which induces the aggregation of AgNPs. Correspondingly, the color of AgNPs in solution changes from bright yellow to pink, and the UV–vis characteristic absorption peak of AgNPs at about 400 nm decreases; simultaneously, a new absorption band appears at about 520 nm. Irreversible inhibition of AChE activity caused by dipterex, prevents the aggregation of AgNPs. Thus, a UV–vis spectrophotometric method was developed for the analysis of dipterex. The absorbance ratio A396 nm/A520 nm was found to be linearly related to the concentration of dipterex in the range of 0.25–37.5 ng mL−1 with a detection limit of 0.18 ng mL−1. This method was used successfully to analyse dipterex in spiked, different water samples.

A novel kinetic spectrophotometric method was developed for the simultaneous determination of caffeine, theobromine and theophylline in food samples. This method was based on the different kinetic characteristics between the reactions of analytes with cerium sulphate in sulphuric acid and the associated change in absorbance at 320 nm. Experimental conditions, the effects of sulphuric acid, cerium sulphate and temperature, were optimised. Linear ranges (0.4–8.4 μg mL −1 ) for all three analytes were established, and the limits of detection were: 0.30 μg mL −1 (caffeine), 0.33 μg mL −1 (theobromine) and 0.16 μg mL −1 (theophylline). The recorded data were processed by partial least squares and artificial neural network, and the developed mathematical models were then used for prediction. The proposed, novel method was applied to determine the analytes in commercial food samples, and there were no significant differences between the results from the proposed method and those obtained by high-performance liquid chromatography.

A novel Prussian blue/copper-gold bimetallic nanoparticles hybrid film modified electrode was prepared by electrochemical deposition on a glassy carbon electrode (PB/Cu-AuNPs/GCE). Morphology and electrochemistry of this electrode were studied by UV-vis spectroscopy, scanning electron microscopy, X-ray diffraction, cyclic voltammetry and electrochemical impedance spectroscopy. The sensor showed significantly better electrocatalytic activity for the reduction of hydrogen peroxide in comparison with the single PB/GCE and PB/AuNPs/GCE. This was attributed to the synergistic effect of PB and Cu-Au bimetallic nanoparticles. Also, the sensor demonstrated an overall high level of performance for the analysis of H2O2 in the concentration range from 0.002 to 0.84 mM.

The effect of ionic surfactants, sodium dodecyl sulfate (SDS) and N-cetyl-N,N,N-trimethylammonium bromide (CTAB), on the interaction between β-agonist salbutamol (SAL) and bovine serum albumin (BSA) was investigated with the use of fluorescence spectroscopy (FLS) and chemometrics methods [multivariate curve resolution-alternating least-squares (MCR-ALS) and parallel factor analysis algorithm (PARAFAC)]. It was found that the binding constant of SAL to BSA in the presence of CTAB was much larger than that without this ligand. The ligand/BSA stoichiometry was 4:1, that is, (CTAB)4-BSA, and was 2:1 with the ligand, that is, (SAL)2-BSA. These results were obtained from the concentration profiles extracted by MCR-ALS for all three reactants. Quantitative information on the complex CTAB-BSA-SAL species was obtained with the resolution of the excitation-emission fluorescence three-way data matrices by PARAFAC. This research has implications for the analysis of SAL in food and might be performed in laboratories associated with organizations such as the U.S. Food and Drug Administration (FDA) and the International Olympic Committee (IOC).

Hydrogen peroxide is an important analyte in biochemical, industrial and environmental systems. Therefore, development of novel rapid and sensitive analytical methods is useful. In this work, a hemin-graphene nano-sheets (H-GNs)/gold nano-particles (AuNPs) electrochemical biosensor for the detection of hydrogen peroxide (H2O2) was researched and developed; it was constructed by consecutive, selective modification of the GCE electrode. Performance of the H-GNs/AuNPs/GCE was investigated by chronoamperometry, and AFM measurements suggested that the graphene flakes thickness was ∼1.3 nm and that of H-GNs was ∼1.8 nm, which ultimately indicated that each hemin layer was ∼0.25 nm. This biosensor exhibited significantly better electrocatalytic activity for the reduction of hydrogen peroxide in comparison with the simpler AuNPs/GCE and H-GNs/GCE; it also displayed a linear response for the reduction of H2O2 in the range of 0.3 μM to 1.8 mM with a detection limit of 0.11 μM (S N−1 = 3), high sensitivity of 2774.8 μA mM−1 cm−2, and a rapid response, which reached 95% of the steady state condition within 5 s. In addition, the biosensor was unaffected by many interfering substances, and was stable over time. Thus, it was demonstrated that this biosensor was potentially suitable for H2O2 analysis in many types of sample.

In this work, we developed a novel layered molybdenum disulfide (MoS2) nanosheet peroxidase mimetic-based fluorescent catalytic biosensor for the sensitive and selective detection of Fe(2+). It was found that Fe(2+) remarkably enhanced the catalytic activity of the MoS2 nanosheet for oxidation of OPD to form a highly fluorescent substance, 2,3-diaminophenazine (DAPN), and the MoS2/OPD/H2O2 biosensor displayed substantial fluorescence enhancement after addition of Fe(2+) in a concentration-dependent manner. The fluorescence intensity was proportional to the concentration of Fe(2+) over a range of 0.005-0.20 μM with a limit of detection of 3.5 nM (signal/noise = 3). When compared with the OPD/H2O2 biosensor, the MoS2/OPD/H2O2 biosensor provided a higher sensitivity and selectivity for Fe(2+), suggesting the validity of the use of the MoS2 nanosheets. To further demonstrate the feasibility of the MoS2/OPD/H2O2 biosensor for Fe(2+) detection in real water samples, we measured the three-dimensional excitation-emission spectra of the real system, and submitted the excitation-emission matrix (EEM) data to an advanced chemometrics model based on parallel factor analysis (PARAFAC). The results showed that the use of the PARAFAC model could further enhance the selectivity of the biosensor and determine Fe(2+) concentration in the presence of unexpected interferents from real water samples. This work opens up new opportunities for the use of the catalytic properties of the MoS2 nanosheets and advanced chemometrics models in the field of biosensors.

Enantioselective binding interaction of the pesticides, metolachlor (RAC-metolachlor) and its S-enantiomer (S-metolachlor), with bovine serum albumin (BSA) was investigated by fluorescence and UV-vis absorption spectroscopy. Both RAC- and S-metolachlors quenched the intrinsic fluorescence of BSA via a static mechanism, and various binding parameters indicated that electrostatic forces were involved in the binding of both of these compounds. Site marker competitive experiments demonstrated that S-metolachlor bound to site I of BSA, while R-metolachlor bound to site II, indicating the importance of enantiomeric factors for binding site selection. Further experiments showed that S-metolachlor had a higher binding affinity to BSA than R-metolachlor. The obtained spectral data were resolved with use of the multivariate curve resolution-alternating least squares method (MCR-ALS), and the extracted concentration profiles of the reacting species in the interaction were obtained. These profiles indicated that S-metolachlor was the main active constituent of RAC-metolachlor for binding with BSA, and these findings have significant implications in providing an explanation why S-metolachlor is the preferred herbicide in practice than RAC-metolachlor.

Chromatographic fingerprints of raw, wine-treated and braised rhubarb samples were obtained by liquid chromatography with a diode array detector (LC-DAD). Eight LC peaks were selected for fingerprint analysis, and six compounds were identified as gallic acid, emodin, chrysophanol, palmidin, rhein glucoside and desoxyrhaponticin. A data matrix of the chromatographic fingerprints from the three types of sample was submitted to principal component analysis (PCA) and this indicated that the three types of rhubarb were distinguished in the PC1versusPC2 space. Training, verification and prediction data sets of the three types of HPLC fingerprint were processed successfully by chemometrics data classification methods, K-nearest neighbor (KNN), linear discriminant analysis (LDA) and least squares support vector machines (LS-SVM), and these types of rhubarb sample were classified satisfactorily.

The interaction of 10-hydroxycamptothecine (HCPT) with DNA under pseudo-physiological conditions (Tris-HCl buffer of pH 7.4), using ethidium bromide (EB) dye as a probe, was investigated with the use of spectrofluorimetry, UV-vis spectrometry and viscosity measurement. The binding constant and binding number for HCPT with DNA were evaluated as (7.1 ± 0.5) × 104 M-1 and 1.1, respectively, by multivariate curve resolution-alternating least squares (MCR-ALS). Moreover, parallel factor analysis (PARAFAC) was applied to resolve the three-way fluorescence data obtained from the interaction system, and the concentration information for the three components of the system at equilibrium was simultaneously obtained. It was found that there was a cooperative interaction between the HCPT-DNA complex and EB, which produced a ternary complex of HCPT-DNA-EB. © 2011 Elsevier B.V.

A novel kinetic spectrophotometric method was developed for determination of pyrocatechol, resorcin, hydroquinone and phenol based on their inhibitory effect on the oxidation of Rhodamine B (RhB) in acid medium at pH=3.0. A linear relationship was observed between the inhibitory effect and the concentrations of the compounds. The absorbance associated with the kinetic reactions was monitored at the maximum wavelength of 557nm. The effects of different parameters such as pH, concentration of RhB and KBrO(3), and temperature of the reaction were investigated and optimum conditions were established. The linear ranges were 0.22-3.30, 0.108-0.828, 0.36-3.96 and 1.52-19.76μg mL(-1) for pyrocatechol, resorcin, hydroquinone and phenol, respectively, and their corresponding detection limits were 0.15, 0.044, 0.16 and 0.60μg mL(-1). The measured data were processed by several chemometrics methods, such as principal component regression (PCR), partial least squares (PLS) and artificial neural network (ANN), and a set of synthetic mixtures of these compounds was used to verify the established models. It was found that the prediction ability of PLS, PCR and RBF-ANN was similar, however, the RBF-ANN model did perform somewhat better than the other methods. The proposed method was also applied satisfactorily for the simultaneous determination of pyrocatechol, resorcin, hydroquinone and phenol in real water samples.

Interaction of chlorotetracycline (CTC) with bovine serum albumin (BSA) was investigated under simulated physiological conditions by spectroscopy with the aid of multivariate curve resolution-alternating least squares (MCR-ALS). Eosin Y was selected as an alternative site I marker on the BSA to study the above molecular interaction. The binding of Eosin Y and CTC to BSA showed that CTC was displaced from CTC-BSA complex by Eosin Y, and Eosin Y-BSA complex was formed. However, the recorded fluorescence spectra of Eosin Y and Eosin Y-BSA overlapped and MCR-ALS was applied to resolve the two-way fluorescence spectra. From the resolved equilibrium concentration profiles, it was observed that Eosin Y competed with CTC in the binding process with BSA; it was also shown that the binding site of CTC on BSA was site I, and this was further confirmed by the fluorescence polarization method. Compared with some common site I markers for BSA, the fluorescence and UV-vis spectral shapes of the Eosin Y-BSA complex were quite different from that of Eosin Y, and this feature facilitated the investigation of the small molecule-BSA interaction.

Interaction of a steroid drug, Ractopamine (RAC), and DNA was investigated by electroanalysis-differential pulse and cyclic voltammetry (DPV and CV), and UV-vis and fluorescence spectroscopy. DPV showed that RAC intercalated with DNA, and CV indicated that the reaction mechanism of RAC and dsDNA involved irreversible oxidation with the loss of two H+ and a transfer of two electrons. Reaction binding parameters were obtained. Pure spectra of RAC, DNA and the RAC-DNA complex, and their concentrations were extracted by multivariate curve resolution-alternating least squares method (MCR-ALS). Concentration profiles indicated quantitatively the course of the reaction.

To investigate the interaction between Ractopamine (RAC), an animal growth promoter, and bovine serum albumin (BSA), three spectroscopic approaches (fluorescence, UV–vis and FT-IR) and three different experiments (two mole-ratio and a Job's methods) were used to monitor the biological kinetic interaction procedure. The Stern–Volmer quenching constants K SV , the binding constants K a , and the number of binding sites n at 298, 301 and 304 K were evaluated by molecular spectroscopic approaches. The values of enthalpy (−13.47 kJ mol −1 ) and entropy (78.39 J mol −1 K −1 ) in the reaction indicated that RAC bound to BSA mainly by electrostatic and hydrophobic interaction. The site markers competitive experiments indicated that the binding of RAC to BSA primarily took place in site I. The spectra data matrix was further investigated with multivariate curve resolution-alternating least squares (MCR-ALS), and the concentration profiles and the pure spectra for three species (BSA, RAC and RAC-BSA) existed in the kinetic interaction procedure, as well as the apparent equilibrium constants, were obtained.