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Curcumin (Cur) is an acidic polyphenol with some effects on α-glucosidase (α-Glu), but Cur has disadvantages such as being a weak target, lacking passing the blood-brain barrier and having low bioavailability. To enhance the curative effect of Cur, the hybrid composed of ZnO nanoparticles decorated on rGO was used to load Cur (ZnO@rGO-Cur). The use of the multispectral method and enzyme inhibition kinetics analysis certify the inhibitory effect and interaction mechanism of ZnO@rGO-Cur with α-Glu. The static quenching of α-Glu with both Cur and ZnO@rGO-Cur is primarily driven by hydrogen bond and van der Waals interactions. The conformation-changing ability by binding to the neighbouring phenolic hydroxyl group of Cur increased their ability to alter the secondary structure of α-Glu, resulting in the inhibition of enzyme activity. The inhibition constant (K i, Cur  > K is,ZnO@rGO-Cur ) showed that the inhibition effect of ZnO@rGO-Cur on α-Glu was larger than that of Cur. The CCK-8 experiments proved that ZnO@rGO nanocomposites have good biocompatibility. These results suggest that the therapeutic potential of ZnO@rGO-Cur composite is an emerging nanocarrier platform for drug delivery systems for the potential treatment of diabetes mellitus., (© 2024 John Wiley & Sons Ltd.)

Transition bimetallic sulphides have emerged as important electrode materials for supercapacitors owing to their low toxicity, environmental friendliness, cost-effectiveness, multiple oxidation states, high natural abundance, flexible structure, and high theoretical specific capacitance. Herein, a porous nanosheet-nanosphere@nanosheet FeNi 2 -LDH@FeNi 2 S 4 (FNLDH@FNS) core-shell heterostructure was directly prepared on nickel foam (NF) via a two-step hydrothermal method. The prepared electrode material exhibits an outstanding electrochemical performance. The specific capacity ( C s ) values are 806 and 450 C g -1 at current density ( D c ) values of 1 and 6 A g -1 , respectively, revealing a satisfactory magnification performance. In addition, the FNLDH@FNS electrode exhibits a long cycle life with an supercapacitor (SC) retention rate of 92.3% after 5000 cycles at a D c of 6 A g -1 . The FNLDH@FNS//activated carbon (AC) asymmetric SC assembled with FNLDH@FNS (positive electrode) and activated carbon (AC, negative electrode) displays an energy density ( E d ) of 36.67 Wh kg -1 and a power density ( P d ) of 775.17 W kg -1 .

Based on the previous research, we found that the magnetic nanocomposite Fe 3 O 4 /rGO (reduced graphene oxide) has a good drug loading effect. Therefore, in this paper, we studied the positive role of Fe 3 O 4 /rGO as a drug carrier in the interaction between resveratrol (RES) and calf-thymus DNA (ct-DNA). The fluorescence experiment is used to evaluate by the Stern-Volmer equation, the quenching constant of RES - ct-DNA system with and without Fe 3 O 4 /rGO decreases with the increasing temperature. It was found the quenching mode of RES - ct-DNA and Fe 3 O 4 /rGO - RES - ct-DNA systems were all static quenching, but the binding constant of RES -ct-DNA increased from 4.14 ± 0.21 × 10 4 L mol -1 to 10.12 ± 0.02 × 10 4 L mol -1 . It was found that Fe 3 O 4 /rGO formed a ternary complex with RES and ct-DNA by ultraviolet spectrum (UV-vis), resonance light scattering experiments (RLS) and scanning electron microscope (SEM). Meanwhile, Fourier transform infrared (FT-IR) and circular dichroism (CD) experiments show that Fe 3 O 4 /rGO and Fe 3 O 4 /rGO loaded with RES have effect on the secondary structure of ct-DNA and change the conformation of ct-DNA. On the cellular level, the comet assay shows that Fe 3 O 4 /rGO and Fe 3 O 4 /rGO - RES could not cause DNA strand break to the mouse hepatocytes after 24 co-incubation. These results confirm that Fe 3 O 4 /rGO nanocomposites have good application potential, which can be used as a good drug carrier in a wide range of therapeutic methods., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 Elsevier B.V. All rights reserved.)

In this paper, a new Co3O4-Ni nanocomposite-modified glassy carbon electrode (Co3O4-NiNPs/GCE) was successfully constructed and used to detect glucose and hydrogen peroxide (H2O2). The morphologies and structures of the Co3O4 and Co3O4-Ni nanocomposites were characterized via transmission electron microscopy (TEM), scanning electron microscopy (SEM), and X-ray diffraction (XRD). The construction process of the modified electrode was characterized via electrochemical impedance spectroscopy (EIS) and cyclic voltammetry (CV) techniques. Co3O4-NiNPs/GCE shows more excellent electrocatalytic activity for the detection of glucose and H2O2 compared with Co3O4/GCE and NiNPs/GCE. The amperometric i-t method was used for the quantitative analysis of glucose and H2O2. The plots of current difference versus concentration of glucose and H2O2 were linear in the range of 0.3-550 μM and 0.5-89 μM, respectively. The corresponding limits of detection (LODs) were 0.086 μM and 0.23 μM for glucose and H2O2, respectively. This recommended sensor was successfully applied for the quantitative analysis of glucose in fruit and H2O2 in water samples.

Magnetic nanoparticles have been widely used in the field of nanomedicine as drug delivery vehicles for targeted imaging-guided and controlled drug uptake and release actions. In this work, the loading of curcumin on Fe 3 O 4 /rGO nanocomposites and their interaction mechanism were investigated by multispectral methods including resonance light scattering (RLS), atomic force microscopy (AFM), circular dichroism (CD) and Fourier transform infrared (FT-IR). Results revealed that the drug loading was a complex process which is not governed by a simple adsorption. The interactions of vitro human serum albumin (HSA) with free curcumin and/or curcumin-Fe 3 O 4 /rGO complex have been studied. Outcomes from the fluorescence quenching showed that the binding constant of curcumin to HSA increased significantly in the presence of Fe 3 O 4 /rGO, confirming the enhanced effect of Fe 3 O 4 /rGO besides its low toxicity towards HSA. Findings from this work verified that Fe 3 O 4 /rGO nanocomposite has a promising potential as a good drug loading carrier that can be used and broad range of therapies., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2021 Elsevier B.V. All rights reserved.)

In this study, molybdenum disulfide (MoS 2 ), polyaniline (PANI) and their composite (MoS 2 /PANI) were facilely prepared via a liquid-phase method and in situ polymerization. An MoS 2 /PANI/functionalized carbon cloth (MoS 2 /PANI/FCC) was facilely constructed by a drop-casting method. MoS 2 /PANI-10/FCC displays remarkable electrochemical performances, and its specific capacitances varied from 452.25 to 355.5 F g -1 at current densities ranging from 0.2 to 4 A g -1 , which were higher than those of MoS 2 /CC (from 56.525 to 7.5 F g -1 ) and pure PANI/CC (319.5 to 248.5 F g -1 ), respectively. More importantly, the MoS 2 -10/PANI/FCC electrode has a long cycling life, and a capacity retention of 87% was obtained after 1000 cycles at a large current density of 10 A g -1 . Moreover, the MoS 2 /PANI-10/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 72.8 F g -1 at a current density of 0.2 A g -1 and the capacitance retention of 85% is obtained after 1000 cycles., Competing Interests: Xiaoyun Lin declares that he has no conflict of interest. Yangfang Wang declares that she has no conflict of interest. Xinrong Lv declares that she has no conflict of interest. Yongnian Ni declares that he has no conflict of interest., (This journal is © The Royal Society of Chemistry.)

Adenine-stabilized carbon dots (A-CDs) are shown to be a viable fluorescent probe for highly sensitive detection and imaging of Cu 2+ . The probe has a linear fluorometric response in the 1-700 nM concentration range and a 0.3 nM detection limit. The probe, with excitation/emission maxima at 380/435 nm, is highly selective for Cu 2+ over other metal ions, anions, amino acids, and biomolecules. The fluorescence quenching mechanism of the A-CDs by Cu 2+ is investigated using transmission electron microscopy images coupled with elemental mapping, X-ray photoelectron spectroscopy, X-ray-excited Auger electron spectroscopy, fluorescence lifetime, UV-visible spectroscopy, and cyclic voltammetry. The experimental results show that the fluorescence quenching is caused by the combination of Cu 2+ -coordination-induced aggregation of the A-CDs, the reduction of Cu 2+ by the A-CDs, and the nonradiative photoinduced electron transfer process from the A-CDs to Cu 2+ or metallic Cu. The high sensitivity and high selectivity of the sensor are ascribed to the chemical interactions between the A-CDs and Cu 2+ , the photophysical process between the A-CDs and Cu 2+ , and the high fluorescence quantum yield of the A-CDs (44.6%). The A-CDs have excellent water solubility, good stability to variation of pH values, high photostability, fast response time, and low cytotoxicity. They are successfully employed for intracellular imaging of Cu 2+ in HepG2 cells and Cu 2+ detection in the tap water samples., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier B.V. All rights reserved.)

Foods generally contain special ingredients which easily to interact with drugs human intaking, thus affecting drug efficacy and excretion, and even cause adverse reactions. Vitamin C (Vit. C) is abundant in fresh fruits and vegetables. It plays a regulatory role in redox metabolism, and its absence can cause scurvy. Aspirin (ASP) can be used to treat many diseases, is the earliest, common and widely used as antipyretic, analgesic and antirheumatic medicine. Human serum albumin (HSA) is the most abundant protein in vertebrate plasma and has the property of combining and transporting endogenous and exogenous substances. In this paper, the effects of Vit. C on the combination of ASP and HSA were studied by multi-spectra and voltammetric approaches. Fluorescence spectra showed that the quenching mode between Vit. C and HSA is dynamic, and the main binding force is hydrophobic force. The quenching mode between ASP and HSA is static one, and the main binding force is hydrogen bond and van der Waals force. For ternary biological system of (HSA-ASP)-Vit. C, the binding constant decreases compared with HSA-Vit. C system. However, for (HSA-Vit. C)-ASP system, the binding constant does not change when compared with binary system of HSA-ASP. Based on the technology combination of voltammetry, infrared, three-dimensional fluorescence and circular dichroism (CD), it is proved that the existence of ASP will influence the binding process of Vit. C to HSA. It could be concluded that taking Vit. C first doesn't affect the absorption of ASP and may be good for health; in contrast, it is not good to take Vit. C immediately as one have just taken ASP, because the existence of ASP reduce the absorption of Vit. C for human body., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier B.V. All rights reserved.)

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 0.10-2.0 μg/mL and 0.02-0.40 μg/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.

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., (Copyright © 2019 Elsevier B.V. All rights reserved.)

A hydrothermal synthetic approach is developed for the preparation of graphitic carbon nitride quantum dots (g-C 3 N 4 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-C 3 N 4 QDs. The as-prepared g-C 3 N 4 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-C 3 N 4 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-C 3 N 4 QDs, which are transformed from the human bodily wastes, are promising in diverse chemical applications., (Copyright © 2018 Elsevier B.V. All rights reserved.)

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., (Copyright © 2018 Elsevier B.V. All rights reserved.)

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%. Graphical abstract Schematic presentation of an electrochemical sensor that was fabricated by electrodeposition of the metal-organic framework (MOF) of copper(II)-1,3,5-benzenetricarboxylic acid (Cu-BTC) onto the surface of electroreduced graphene oxide (ERGO) modified glassy carbon electrode (GCE). It was applied to sensitive and selective detection of 2,4,6-trinitrophenol (TNP).

In this paper, we constructed a novel label-free analytical strategy for highly sensitive and selective detection of nitrofurantoin (NFT) based on adenosine-stabilized copper nanoclusters (CuNCs) as nanoprobes. It was found that NFT caused a rapid decrease in the photoluminescence intensity of CuNCs. The photoluminescence quenching was likely attributed to the inner filter effect between NFT and CuNCs. The CuNCs exhibited a wide linear range of 0.05-4.0μM with the detection limit of 30nM (7.1ngmL -1 ) for detection of NFT. And it was successfully applied for NFT detection in lake water samples., (Copyright © 2017 Elsevier B.V. All rights reserved.)

We reported a sensitive and selective fluorescence "turn on-off" strategy for detection of Cu 2+ and hemin, respectively. The fluorescence "turn on" sensor for Cu 2+ 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 Cu 2+ 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 Cu 2+ 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 Cu 2+ in lake water samples and hemin in duck blood samples., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

A facile, one-pot synthetic method has been proposed to prepare water-soluble fluorescent copper nanoclusters (CuNCs) templated by nucleosides. The nucleoside-templated fluorescent CuNCs were further characterized by using various analytical techniques, such as transmission electron microscopy, X-ray photoelectron spectroscopy, Fourier transform infrared spectroscopy, and fluorescence spectroscopy. The role of various reactants such as ascorbic acid, nucleoside, and citrate buffer in the synthesis process of fluorescent CuNCs was explored. The results showed that nucleoside and ascorbic acid were very likey to respectively act as a stabilizer and a reductant to form nanoclusters, and citrate buffer acted as both pH regulator solution and a reducing agent. The fluorescence spectra of various nucleoside-templated CuNCs were finally combined with multivariate chemometrics analysis for discrimination of different nucleosides.

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 1.0μM with a detection limit of 0.3nM. Finally, the sensor was successfully used to detection of Hg 2+ in water and milk samples., (Copyright © 2016 Elsevier B.V. All rights reserved.)

A strong red fluorescent nanocomposite, consisting of graphite-like carbon nitride nanosheets (g-C 3 N 4 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-C 3 N 4 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 (F 0 - F)/F 0 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., (Copyright © 2016 Elsevier B.V. All rights reserved.)

In the present study, we demonstrated that the luminescent molybdenum disulfide (MoS2) 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 (H2O2) 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 MoS2/OPD/H2O2 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 MoS2/OPD/H2O2 sensor displayed enhanced sensitivity and selectivity toward Fe(2+) compared with the OPD/H2O2 sensor, suggesting that the MoS2 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 MoS2 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 MoS2/OPD/H2O2 sensor for Fe(2+) detection likely arose from its large reaction rate constant. Finally, the proposed MoS2/OPD/H2O2 sensor was successfully applied for detection of Fe(2+) in water samples., (Copyright © 2016 Elsevier B.V. All rights reserved.)

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., (Copyright © 2015 Elsevier B.V. All rights reserved.)

The work demonstrated that solid citric acid, one of the most common food additives, can be converted to graphene quantum dots (GQDs) under microwave heating. The as-prepared GQDs were further characterized by various analytical techniques like transmission electron microscopy, atomic force microscopy, X-ray diffraction, X-ray photoelectron spectroscopy, Fourier transform infrared spectroscopy, fluorescence and UV-visible spectroscopy. Cytotoxicity of the GQDs was evaluated using HeLa cells. The result showed that the GQDs almost did not exhibit cytotoxicity at concentrations as high as 1000 µg mL(-1). In addition, it was found that the GQDs showed good solubility, excellent photostability, and excitation-dependent multicolor photoluminescence. Subsequently, the multicolor GQDs were successfully used as a fluorescence light-up probe for live-cell imaging., (Copyright © 2015 John Wiley & Sons, Ltd.)

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.

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.

Near-infrared spectroscopy (NIRS) calibrations were developed for the discrimination of spectra of the jujube (Zizyphus jujuba Mill.) fruit samples from four geographical regions. Prediction models were developed for the quantitative prediction of the contents of jujube fruit, i.e., total sugar, total acid, total phenolic content, and total antioxidant activity. Four pattern recognition methods, principal component analysis (PCA), linear discriminant analysis (LDA), least squares-support vector machines (LS-SVM), and back propagation-artificial neural networks (BP-ANN), were used for the geographical origin classification. Furthermore, three multivariate calibration models based on the standard normal variate (SNV) pretreated NIR spectroscopy, partial least squares (PLS), BP-ANN, and LS-SVM were constructed for quantitative analysis of the four analytes described above. PCA provided a useful qualitative plot of the four types of NIR spectra from the fruit. The LS-SVM model produced best quantitative prediction results. Thus, NIR spectroscopy in conjunction with chemometrics, is a very useful and rapid technique for the discrimination of jujube fruit., (Copyright © 2015 Elsevier B.V. All rights reserved.)

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., (Copyright © 2015 Elsevier B.V. All rights reserved.)

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., (Copyright © 2015 Elsevier B.V. All rights reserved.)

Variations in the enzyme activity of acetylcholinesterase (AChE) in the presence of the nano-material, graphene oxide (GO), were investigated with the use of molecular spectroscopy UV-visible and fluorescence methods. From these studies, important kinetic parameters of the enzyme were extracted; these were the maximum reaction rate, Vm , and the Michaelis constant, Km . A comparison of these parameters indicated that GO inhibited the catalytic activity of the AChE because of the presence of the AChE-GO complex. The formation of this complex was confirmed with the use of fluorescence data, which was resolved with the use of the MCR-ALS chemometrics method. Furthermore, it was found that the resonance light-scattering (RLS) intensity of AChE changed in the presence of GO. On this basis, it was demonstrated that the relationship between AChE and GO was linear and such models were used for quantitative analyses of GO., (Copyright © 2015 John Wiley & Sons, Ltd.)

Carbon quantum dots (CQDs) have recently attracted significant attention for both their fundamental science and technological applications as a new class of fluorescent zero-dimensional nanomaterials with a size below 10 nm. However, the reported methods of synthesis were generally less suitable for the large-scale production of the CQDs with high-fluorescent quantum yield (QY). In the paper, a novel one-pot microwave-assisted drying synthesis approach was presented to prepare CQDs with high QY of 61.3 % for the first time. The production yield of CQDs was 35±3 % in weight. The as-prepared CQDs were characterized by various techniques such as TEM, AFM, XRD, XPS, FTIR spectroscopy, UV/Vis absorption spectroscopy, and fluorescence spectroscopy. The results showed that the high QY of CQDs was largely attributed to the dual doping of nitrogen and sulphur into CQDs. Such CQDs were then used as live-cell imaging reagents due to their high QY, good water dispersibility, fine biocompatibility, high photostability, and low cytotoxicity., (© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

A magnetic and fluorescent nano-composite was prepared. It comprised of a core of Fe3O4 nanoparticles (NPs), a silica shell and satellitic Au nano-clusters (AuNCs) capped with bovine serum albumin (BSA). This nano-composite has many desirable properties, e.g. magnetism, red emission, high water solubility, and high resistance to photo-bleaching. On addition of the analyte, 6-mercaptopurine (6-MP) or indeed other similar thiols, AuNCs formed aggregates because the existing cross-links within the Fe3O4 NPs@SiO2 and AuNC structure were broken in favor of the gold-thiol bonds. On suitable irradiation of such aggregates, red fluorescence was emitted at 613 nm. It decreased significantly as a function of the added 6-MP concentration, and the quenching ratio (F0 - F) / F0 was related linearly to the concentration of 6-MP in the range of 0.01 to 0.5 μmol L(-1). The detection limit was 0.004 μmol L(-1) (S/N=3). The method was strongly selective for 6-MP in the presence of oxidants, phenols, heavy-metal ions, and especially bio-thiols., (Copyright © 2015 Elsevier B.V. All rights reserved.)

The Chinese yam (Dioscorea opposita) is a basic food in Asia and especially China. Consequently, an uncomplicated, reliable method should be available for the analysis of the quality and origin of the yams. Thus, near-infrared (NIR) and mid-infrared (mid-IR) spectroscopic methods were developed to discriminate among Chinese yam samples collected from four geographical regions. The yam samples were analyzed also for total sugar, polysaccharides, and flavonoids. These three analytes were used to compare the performance of the analytical methods. Overlapping spectra were resolved using chemometrics methods. Such spectra were compared qualitatively using principal component analysis (PCA) and quantitatively using partial least squares (PLS) and least squares-support vector machine (LS-SVM) models. We discriminated among the four sets of yam data using PCA, and the NIR data performed somewhat better than the mid-IR data. We constructed the PLS and LS-SVM calibration models for the prediction of the three key variables, and the LS-SVM model produced better results. Also, the NIR prediction model produced better outcomes than the mid-IR prediction model. Thus, both infrared (IR) techniques performed well for the analysis of the three key analytes, and the samples were qualitatively discriminated according to their provinces of origin. Both techniques may be recommended for the analysis of Chinese yams, although the NIR technique would be preferred.

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)., (Copyright © 2015 Elsevier B.V. All rights reserved.)

A rapid and effective sensor for the analysis of nitrophenol-based explosive substances, represented by trinitrophenol (TNP), has been developed with the use of the blue luminescent graphene quantum dots (GQDs); these GQDs are derived from citric acid by a pyrolysis procedure. They emit strong blue fluorescence at 450 nm after excitation at 365 nm, and TNP can quench this fluorescence because a fluorescence resonance energy transfer occurs. The quenching ratio (F0-F)/F0 was related linearly to the concentration of TNP in the range of 0.1-15 μmol L(-1) with a detection limit of 0.091 μmol L(-1) (S/N=3). The developed method exhibits high sensitivity, good linearity and reliable reproducibility for the quantitative analysis of TNP in water samples. The GQDs were used directly without any further treatment or complicated modification., (Copyright © 2014 Elsevier B.V. All rights reserved.)

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 method was developed for the determination of clenbuterol in meat using stable-isotope-dilution gas chromatography with mass spectrometry coupled with solid-phase microextraction and on-fiber derivatization. The samples were first homogenized with hydrochloric acid followed by protein deposition. After headspace solid-phase microextraction and on-fiber derivatization, the content of clenbuterol was measured with the aid of stable-isotope dilution. The condition of solid-phase microextraction was optimized by central composite design. The relative standard deviations, limit of detection, and recoveries for clenbuterol were 4.2-9.2%, 0.48 μg/kg, and 96-104%, respectively. The proposed method was satisfactory for analysis of real samples as compared with the Chinese standard method., (© 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

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., (© 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

A novel combined near- and mid-infrared (NIR and MIR) spectroscopic method has been researched and developed for the analysis of complex substances such as the Traditional Chinese Medicine (TCM), Illicium verum Hook. F. (IVHF), and its noxious adulterant, Iuicium lanceolatum A.C. Smith (ILACS). Three types of spectral matrix were submitted for classification with the use of the linear discriminant analysis (LDA) method. The data were pretreated with either the successive projections algorithm (SPA) or the discrete wavelet transform (DWT) method. The SPA method performed somewhat better, principally because it required less spectral features for its pretreatment model. Thus, NIR or MIR matrix as well as the combined NIR/MIR one, were pretreated by the SPA method, and then analysed by LDA. This approach enabled the prediction and classification of the IVHF, ILACS and mixed samples. The MIR spectral data produced somewhat better classification rates than the NIR data. However, the best results were obtained from the combined NIR/MIR data matrix with 95-100% correct classifications for calibration, validation and prediction. Principal component analysis (PCA) of the three types of spectral data supported the results obtained with the LDA classification method., (Copyright © 2014 Elsevier B.V. All rights reserved.)

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 novel, highly selective resonance light scattering (RLS) method was researched and developed for the analysis of phenol in different types of industrial water. An important aspect of the method involved the use of graphene quantum dots (GQDs), which were initially obtained from the pyrolysis of citric acid dissolved in aqueous solutions. The GQDs in the presence of horseradish peroxidase (HRP) and H2O2 were found to react quantitatively with phenol such that the RLS spectral band (310 nm) was quantitatively enhanced as a consequence of the interaction between the GQDs and the quinone formed in the above reaction. It was demonstrated that the novel analytical method had better selectivity and sensitivity for the determination of phenol in water as compared to other analytical methods found in the literature. Thus, trace amounts of phenol were detected over the linear ranges of 6.00×10(-8)-2.16×10(-6)M and 2.40×10(-6)-2.88×10(-5)M with a detection limit of 2.20×10(-8)M. In addition, three different spiked waste water samples and two untreated lake water samples were analysed for phenol. Satisfactory results were obtained with the use of the novel, sensitive and rapid RLS method., (Copyright © 2014 Elsevier B.V. All rights reserved.)

The self-assembly of layered molybdenum disulfide-graphene (MoS2-Gr) and horseradish peroxidase (HRP) by electrostatic attraction into a novel hybrid nanomaterial (HRP-MoS2-Gr) is reported. The properties of the MoS2-Gr were characterized by X-ray diffraction (XRD), high-resolution transmission electron microscopy (TEM), electrochemical impedance spectroscopy (EIS) and cyclic voltammetry (CV). UV-vis and Fourier transform infrared spectroscopy (FT-IR) indicate that the native structure of the HRP is maintained after the assembly, implying good biocompatibility of MoS2-Gr nanocomposite. Furthermore, the HRP-MoS2-Gr composite is utilized as a biosensor, which displays electrocatalytic activity to hydrogen peroxide (H2O2) with high sensitivity (679.7 μA mM(-1)cm(-2)), wide linear range (0.2 μM-1.103 mM), low detection limit (0.049 μM), and fast amperometric response. In addition, the biosensor also exhibits strong anti-interference ability, satisfactory stability and reproducibility. These desirable electrochemical properties are attributed to the good biocompatibility and electron transport efficiency of the MoS2-Gr composite, as well as the high loading of HRP. Therefore, this biosensor is potentially suitable for H2O2 analysis in environmental, pharmaceutical, food or industrial applications., (Copyright © 2014 Elsevier B.V. All rights reserved.)

A novel electrochemical biosensor, DNA/hemin/nafion-graphene/GCE, was constructed for the analysis of the benzo(a)pyrene PAH, which can produce DNA damage induced by a benzo(a)pyrene (BaP) enzyme-catalytic product. This biosensor was assembled layer-by-layer, and was characterized with the use of cyclic voltammetry, electrochemical impedance spectroscopy (EIS) and atomic force microscopy. Ultimately, it was demonstrated that the hemin/nafion-graphene/GCE was a viable platform for the immobilization of DNA. This DNA biosensor was treated separately in benzo(a)pyrene, hydrogen peroxide (H2O2) and in their mixture, respectively, and differential pulse voltammetry (DPV) analysis showed that an oxidation peak was apparent after the electrode was immersed in H2O2. Such experiments indicated that in the presence of H2O2, hemin could mimic cytochrome P450 to metabolize benzo(a)pyrene, and a voltammogram of its metabolite was recorded. The DNA damage induced by this metabolite was also detected by electrochemical impedance and ultraviolet spectroscopy. Finally, a novel, indirect DPV analytical method for BaP in aqueous solution was developed based on the linear metabolite versus BaP concentration plot; this method provided a new, indirect, quantitative estimate of DNA damage., (Copyright © 2014 Elsevier B.V. All rights reserved.)

Interactions between the anti-carcinogens, bendamustine (BDM) and dexamethasone (DXM), with bovine serum albumin (BSA) were investigated with the use of fluorescence and UV-vis spectroscopies under pseudo-physiological conditions (Tris-HCl buffer, pH 7.4). The static mechanism was responsible for the fluorescence quenching during the interactions; the binding formation constant of the BSA-BDM complex and the binding number were 5.14×10(5)Lmol(-1) and 1.0, respectively. Spectroscopic studies for the formation of BDM-BSA complex were interpreted with the use of multivariate curve resolution - alternating least squares (MCR-ALS), which supported the complex formation. The BSA samples treated with site markers (warfarin - site I and ibuprofen - site II) were reacted separately with BDM and DXM; while both anti-carcinogens bound to site I, the binding constants suggested that DXM formed a more stable complex. Relative concentration profiles and the fluorescence spectra associated with BDM, DXM and BSA, were recovered simultaneously from the full fluorescence excitation-emission data with the use of the parallel factor analysis (PARAFAC) method. The results confirmed that on addition of DXM to the BDM-BSA complex, the BDM was replaced and the DXM-BSA complex formed; free BDM was released. This finding may have consequences for the transport of these drugs during any anti-cancer treatment., (Copyright © 2013 Elsevier B.V. All rights reserved.)

A simple, inexpensive and sensitive kinetic spectrophotometric method was developed for the simultaneous determination of three anti-carcinogenic flavonoids: catechin, quercetin and naringenin, in fruit samples. A yellow chelate product was produced in the presence neocuproine and Cu(I) - a reduction product of the reaction between the flavonoids with Cu(II), and this enabled the quantitative measurements with UV-vis spectrophotometry. The overlapping spectra obtained, were resolved with chemometrics calibration models, and the best performing method was the fast independent component analysis (fast-ICA/PCR (Principal component regression)); the limits of detection were 0.075, 0.057 and 0.063 mg L(-1) for catechin, quercetin and naringenin, respectively. The novel method was found to outperform significantly the common HPLC procedure., (Copyright © 2013 Elsevier B.V. All rights reserved.)

Phenols are well known noxious compounds, which are often found in various water sources. A novel analytical method has been researched and developed based on the properties of hemin-graphene hybrid nanosheets (H-GNs). These nanosheets were synthesized using a wet-chemical method, and they have peroxidase-like activity. Also, in the presence of H2O2, the nanosheets are efficient catalysts for the oxidation of the substrate, 4-aminoantipine (4-AP), and the phenols. The products of such an oxidation reaction are the colored quinone-imines (benzodiazepines). Importantly, these products enabled the differentiation of the three common phenols - pyrocatechol, resorcin and hydroquinone, with the use of a novel, spectroscopic method, which was developed for the simultaneous determination of the above three analytes. This spectroscopic method produced linear calibrations for the pyrocatechol (0.4-4.0 mg L(-1)), resorcin (0.2-2.0 mg L(-1)) and hydroquinone (0.8-8.0 mg L(-1)) analytes. In addition, kinetic and spectral data, obtained from the formation of the colored benzodiazepines, were used to establish multi-variate calibrations for the prediction of the three phenol analytes found in various kinds of water; partial least squares (PLS), principal component regression (PCR) and artificial neural network (ANN) models were used and the PLS model performed best., (Copyright © 2013 Elsevier B.V. All rights reserved.)

Study of the interactions between proteins and nanomaterials is of great importance for understanding of protein nanoconjugate. In this work, we choose human serum albumin (HSA) and citrate-capped gold nanoparticles (AuNPs) as a model of protein and nanomaterial, and combine UV-vis spectroscopy with multivariate curve resolution by an alternating least squares (MCR-ALS) algorithm to present a new and efficient method for comparatively comprehensive study of evolution of protein nanoconjugate. UV-vis spectroscopy coupled with MCR-ALS allows qualitative and quantitative extraction of the distribution diagrams, spectra and kinetic profiles of absorbing pure species (AuNPs and AuNPs-HSA conjugate are herein identified) and undetectable species (HSA) from spectral data. The response profiles recovered are converted into the desired thermodynamic, kinetic and structural parameters describing the protein nanoconjugate evolution. Analysis of these parameters for the system gives evidence that HSA molecules are very likely to be attached to AuNPs surface predominantly as a flat monolayer to form a stable AuNPs-HSA conjugate with a core-shell structure, and the binding process takes place mainly through electrostatic and hydrogen-bond interactions between the positively amino acid residues of HSA and the negatively carboxyl group of citrate on AuNPs surface. The results obtained are verified by transmission electron microscopy, zeta potential, circular dichroism spectroscopy and Fourier transform infrared spectroscopy, showing the potential of UV-vis spectroscopy for study of evolution of protein nanoconjugate. In parallel, concentration evolutions of pure species resolved by MCR-ALS are used to construct a sensitive spectroscopic biosensor for HSA with a linear range from 1.8 nM to 28.1 nM and a detection limit of 0.8 nM., (© 2013 Published by Elsevier B.V.)

In recent years, great efforts have focused on the exploration and fabrication of protein nanoconjugates due to potential applications in many fields including bioanalytical science, biosensors, biocatalysis, biofuel cells and bio-based nanodevices. An important aspect of our understanding of protein nanoconjugates is to quantitatively understand how proteins interact with nanomaterials. In this report, human serum albumin (HSA) and citrate-coated silver nanoparticles (AgNPs) are selected as a case study of protein-nanomaterial interactions. UV-visible spectroscopy together with multivariate curve resolution by alternating least squares (MCR-ALS) algorithm is first exploited for the detailed study of AgNPs-HSA interactions. Introduction of the chemometrics tool allows extracting the kinetic profiles, spectra and distribution diagrams of two major absorbing pure species (AgNPs and AgNPs-HSA conjugate). These resolved profiles are then analysed to give the thermodynamic, kinetic and structural information of HSA binding to AgNPs. Transmission electron microscopy, circular dichroism spectroscopy and Fourier transform infrared spectroscopy are used to further characterize the complex system. Moreover, a sensitive spectroscopic biosensor for HSA is fabricated with the MCR-ALS resolved concentration of absorbing pure species. It is found that the linear range for the HSA nanosensor was from 1.9 nM to 45.0 nM with a detection limit of 0.9 nM. It is believed that the proposed method will play an important role in the fabrication and optimization of a robust nanobiosensor or cross-reactive sensors array for the detection and identification of biocomponents.

A novel near-infrared spectroscopy (NIRS) method has been researched and developed for the simultaneous analyses of the chemical components and associated properties of mint (Mentha haplocalyx Briq.) tea samples. The common analytes were: total polysaccharide content, total flavonoid content, total phenolic content, and total antioxidant activity. To resolve the NIRS data matrix for such analyses, least squares support vector machines was found to be the best chemometrics method for prediction, although it was closely followed by the radial basis function/partial least squares model. Interestingly, the commonly used partial least squares was unsatisfactory in this case. Additionally, principal component analysis and hierarchical cluster analysis were able to distinguish the mint samples according to their four geographical provinces of origin, and this was further facilitated with the use of the chemometrics classification methods-K-nearest neighbors, linear discriminant analysis, and partial least squares discriminant analysis. In general, given the potential savings with sampling and analysis time as well as with the costs of special analytical reagents required for the standard individual methods, NIRS offered a very attractive alternative for the simultaneous analysis of mint 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.

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., (Copyright © 2013 Elsevier Ltd. All rights reserved.)

A novel modified electrode was constructed by the electro-polymerization of 4,5-dihydroxy-3-[(2-hydroxy-5-sulfophenyl)azo]-2,7-naphthalenedisulfonic acid trisodium salt (acid chrome blue K (ACBK)) at a graphene oxide (GO)-nafion modified glassy carbon electrode (GCE). The characterization of an electrochemically synthesized poly-ACBK/GO-nafion film was investigated by electrochemical impedance spectroscopy (EIS), cyclic voltammetry (CV), atomic force microscopy (AFM) and scanning electron microscopy (SEM) techniques, and the results were interpreted and compared at each stage of the electrode construction. Electrochemical oxidation of eight β-agonists - clenbuterol, salbutamol, terbutaline, ractopamine, dopamine, dobutamine, adrenaline, and isoprenaline, was investigated by CV at the different electrodes. At the poly-ACBK/GO-nafion/GCE, the linear sweep voltammetry peak currents of the eight β-agonists increased linearly with their concentrations in the range of 1.0-36.0 ng mL(-1), respectively, and their corresponding limits of detection (LODs) were within the 0.58-1.46 ng mL(-1) range. This electrode showed satisfactory reproducibility and stability, and was used successfully for the quantitative analysis of clenbuterol in pork samples., (Copyright © 2013 Elsevier B.V. All rights reserved.)

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).