A Facile Graphene Nanosheets‐based Electrochemical Sensor for Sensitive Detection of Honokiol in Traditional Chinese Medicine

The sensitive detection of honokiol was performed using a graphene nanosheets‐based electrochemical sensor by cyclic voltammogram and a differential pulse anodic stripping voltammogram. Several important parameters such as deposition cycle of reduced graphene oxide, the acidity of the running buffer, accumulation potential and accumulation time were investigated to acquire the optimum conditions. The sensor was further applied to quantification of honokiol in the concentration range from 0.005 to 10 µM with a low detection limit of 1.7 nM. Finally, the sensor successfully determined the content of honokiol in Ageratum Liquid with a satisfied recovery of 98.2 %～99.1 %.     

Highly Sensitive and Selective Fluorescence Probe for 2,4‐Dinitrophenylhydrazine Detection in Wastewater Using Water‐Soluble CdTe QDs

A simple, cheap, sensitive and selective probe for determination of DNPH in wastewater using thioglycolic acid (TGA)‐coated CdTe QDs (TGA‐QDs) as fluorescence probe has been established, and the properties of CdTe QDs were characterized by TEM, FT‐IR, DLS, XRD and zeta potentials. CdTe QDs fluorescence is highly efficiently quenched after adding DNPH on account of electron transfer effect, and the fluorescence quenching behavior of CdTe QDs interaction with DNPH is static quenching process. A good linear relationship is observed between the relative fluorescence intensity (F₀/F) and 0.06–10 ng mL^?1 of DNPH. As compared with some of reported methods, LOD of this method for analysis of DNPH (0.23 ng mL^?1) is the lowest. Masking agents of DDTC and NH₄OH can eliminate the interference of Cu²⁺, Ag⁺ and Hg²⁺. Hence, DNPH can be selectively and accurately detected and the established method was successfully used for detecting DNPH in wastewater with acceptable recovery of 90.6–102%.     

Electrochemiluminescence Based Enzymatic Urea Sensor Using Nanohybrid of Isoluminol‐gold Nanoparticle‐graphene Oxide Nanoribbons

This study evaluates on the possibility of using gold nanoparticles functionalized with the luminol derivative N‐(aminobutyl)‐N‐(ethylisoluminol) (ABEI) and hybridized with graphene oxide nanoribbons on a carbon based screen‐printed electrode (ABEI‐AuNP‐GONR/SPE) as an enzymatic electrochemiluminescence (ECL) urea sensor. The electrocatalytic activity and ECL intensity of ABEI‐AuNP‐GONR/SPE were found to increase proportionally with the concentration of urea in the analyte sample, owing to the rise in pH value. These phenomena are attributed to increased formation of luminol monoanion precursors for further electrochemical oxidation, which in turn produce either luminol radicals or excited 3‐amino‐phthalate molecules. The luminescence is most likely caused by the interaction of luminol radicals with superoxide radicals formed from dissolved oxygen. The sensitivity of our sensor was determined to be 170.58 mM⁻¹ and 16.23 mM⁻¹ for urea concentrations from 2 to 5.82 mM and from 5.82 to 30 mM, respectively, covering the normal urea level in human blood.     

A Sensitive and Selective Nitrite Detection in Water Using Graphene/Platinum Nanocomposite

A glassy carbon electrode modified with reduced graphene oxide and platinum nanocomposite film was developed simply by electrochemical method for the sensitive and selective detection of nitrite in water. The electrochemical reduction of graphene oxide (GO) efficiently eliminates oxygen‐containing functional groups. Pt nanoparticles were electrochemically and homogeneously deposited on the ErGO surface. Field emission scanning electron microscopy (FE‐SEM), Raman spectroscopy, attenuated total reflectance‐fourier transform infrared spectroscopy (ATR‐FTIR), electrochemical impedance spectroscopy (EIS), and cyclic voltammetry (CV) were used to examine the surface morphology and electrocatalytic properties of the Pt‐ErGO nanocomposite film‐modified electrode surface. The fabricated nitrite sensor showed good electrochemical performance with two linear ranges; one from 5 to 100 µM (R²=0.9995) and the other from 100 to 1000 µM (R²=0.9972) and a detection limit of 0.22 µM. The proposed sensor was successfully applied for the detection of nitrite in tap water samples which proves performance of the Pt‐ErGO nanocomposite films.     

A Novel L‐Cysteine Electrochemical Sensor Using Sulfonated Graphene‐poly(3,4‐Ethylenedioxythiophene) Composite Film Decorated with Gold Nanoparticles

By exploiting the electrostatic interaction between positively charged 3,4‐ethylenedioxythiophene cation radicals and negatively charged sulfonated graphene (SG) sheets, we prepared a poly(3,4‐ethylenedioxythiophene)‐sulfonated graphene (SG‐PEDOT) composite film by a one‐step electrochemical process. The composite was further decorated with gold nanoparticles (AuNPs) and employed as an electrode material for the detection of L ‐cysteine (Cys). The SG‐PEDOT composite film is shown to provide a rough surface for the electrodeposition of AuNPs and to improve substrate accessibility and interaction with Cys. Moreover, the AuNPs‐decorated composite exhibits better electrocatalytic performance than that of a SG‐PEDOT composite only. Under optimum experimental conditions, the amperometric current of the sensor is linearly related to the concentration of Cys in the 0.1 to 382 µM range, and the detection limit is 0.02 µM (at S/N=3). The modified electrode displays favorable selectivity, good stability and high reproducibility. The method was successfully applied to the detection of Cys in spiked human urine.     

Chemically‐reduced Graphene Oxide Sensor for Dipyrone Quantification in Pharmaceutical Samples Using Amperometric Detection

Dipyrone (metamizole sodium) is one of the most consumed drugs in the world. In this work a novel analytical method was developed for dipyrone sensing. This method involves the amperometric detection on a chemically‐reduced graphene‐oxide (CRGO)‐modified glassy carbon electrode. Raman spectroscopy and scanning electron microscopy revealed the presence of multilayer graphene layers that contributed to the electrocatalytic oxidation of dipyrone and increase in the electroactive area. Advantages of this sensor include elimination of previous separations, solvent extraction, or sample filtration, low detection limit (0.13 μmol L^?1) with a linear range from 48 to 246 μmol L^?1 and adequate recovery values (97–103 %). Applied to commercial pharmaceutical samples, this method showed results ranging from 451 to 541 mg of dipyrone per tablet, which agreed with the expected values. The results obtained by amperometry were compared statistically with the official method recommended by the Brazilian Pharmacopoeia (iodometric method), with no significant differences between them at 95 % confidence level. The proposed method is accurate for the monitoring of sodium dipyrone in pharmaceutical formulations, highlighting the lower reagent consumption and interferences in the analytical process.     

PSS功能化海绵状石墨烯电化学传感灵敏检测瑞香素的研究

通过绿色环保、简单易行的方法合成聚苯乙烯磺酸钠(PSS)功能化的海绵状石墨烯(3D-PSS-rGO),利用紫外-可见吸收光谱及扫描电镜对复合材料进行表征和分析,构筑了基于3D-PSS-rGO复合材料修饰玻碳电极检测瑞香素的电化学传感器。结果表明,3D-PSS-rGO/GCE对瑞香素有较强富集作用,对瑞香素表现出优异的电催化活性。在优化实验条件下,瑞香素浓度在0.08～10.0μmol/L和10.0～60.0μmol/L范围内与其氧化峰电流呈良好的线性关系,检出限(S/N=3)为0.04μmol/L。将该传感用于祖师麻粉中瑞香素含量的检测,回收率为90.0%～96.0%。该研究为中药材中瑞香素含量的测定提供了方法参考。     

固相微萃取/二氧化锡气体传感器联用技术对果蔬中有机磷农药残留的快速检测

研究了固相微萃取(SPME)和二氧化锡气体传感器的联用技术对果蔬中有机磷农药残留乐果、氧乐果、甲胺磷、乙酰甲胺磷、马拉硫磷、敌百虫等的快速检测。结果表明，在85℃下，解吸8min，二氧化锡气体传感器在2min内完成对有机磷农药残留的快速检测。零解吸时间测量的甲胺磷的动态响应曲线表明。SPME／二氧化锡气体传感器联用技术对分析SPME的解吸平衡非常有利。     

Electrochemical Sensor Based on a Novel Pt−Au Bimetallic Nanoclusters Decorated on Reduced Graphene Oxide for Sensitive Detection of Ofloxacin

Pt−Au nanoclusters decorated on the surface of reduced graphene oxide (rGO/Pt−Au) was facilely prepared by one‐pot electrochemical reduction. The morphology and composition of rGO/Pt−Au composites had been characterized by scanning electron microscopy (SEM) coupled with energy‐dispersive X‐ray spectrometry (EDX), fourier transform‐infrared spectroscopy (FT‐IR) and electrochemical methods. Ofloxacin is a member of synthetic quinolones which has been widely used for the treatment of common diseases in humans and animals. The performance of the rGO/Pt−Au nanocomposite toward the oxidation of ofloxacin was compared with the other similar nanostructures like rGO/Pt and rGO/Au. In the optimized conditions, two linear calibration curves were obtained, from 0.08 to 10 μM and 10 to 100 μM ofloxacin. A detection limit of 0.05 μM ofloxacin was observed at pH 5.7 for the GCE/rGO/Pt−Au. The proposed sensor was successfully applied to determine ofloxacin in tablets and human urine samples and the results were satisfactory.     

Highly Sensitive and Selective Amperometric Sensor for Iodate Based on 9,10-Phenanthrenequinone Derived Graphene

We reported on a new amperometric sensor for the sensitive and selective determination of iodate in table salt. The iodate sensor was constructed by the integration of a novel nanocomposite which was made from 9,10-phenanthrenequinone(PQ) and graphene(GP) with a glassy carbon electrode(GCE). The synthesized graphene and the nanocomposite were well characterized by X-ray diffraction(XRD), transmission electron microscopy(TEM), Fourier transform infrared(FTIR) spectroscopy and Raman spectroscopy. We fully studied the electrochemical behavior and kinetic characteristics of the PQ/GP nanocomposite at GCE. The PQ/GP electrode shows a good electrochemical catalytic activity towards the reduction of iodate, which makes itself a sensitive and selective electrochemical sensor for iodate. The iodate sensor displays a high sensitivity(1.04 mA·mmol·L^-1), a low detection limit(1.0×10^-8 mol/L), a rapid response(less than 2 s), and a broad linear range(from 5.0×10^-8 mol/L to 6.0×10^-3 mol/L ). In addition, the sensor is interference free. The practical application of the proposed sensor was tested by the detection of iodate in table salt.     

Electrochemical Sensor for Sensitive Determination of Capsaicin Using Pd Decorated Reduced Graphene Oxide

In this work, the reduced graphene oxide functionalized with poly dimethyl diallyl ammonium chloride (PDDA) modified palladium nanoparticles (PDDA‐rGO/Pd) had been facile synthesized and used as the sensing layer for sensitive determination of capsaicin. The prepared composite was characterized by transmission electron microscopy, UV‐visible absorption spectroscopy. The image demonstrated that Pd nanoparticles were uniformly distributed on the graphene surface. The electrochemical properties of the prepared sensor were investigated by cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). The results showed that the nanocomposite exhibits attractive electrocatalytic activity towards the oxidation of capsaicin. This attributed to the synergistic action of the excellent properties of Pd nanoparticles and graphene nanosheets. Under optimized conditions, the electrochemical sensor possessed a dynamic linear range from 0.32 μM to 64 μM with a detection limit of 0.10 μM (S/N=3) for capsaicin detection. Moreover, the cost‐effective and simple fabrication procedure, good reproducibility and stability as well as acceptable accuracy for capsaicin determination in actual samples are also the main advantages of this method, which might have broad application in other amide alkaloid detection.     

磁性石墨烯修饰辛基酚印迹传感器制备及应用研究

以辛基酚(4-OP)为模板分子,多巴胺为功能单体,采用电聚合技术在磁性石墨烯修饰碳电极表面制备对辛基酚具有高选择性与灵敏性的印迹电化学传感器。采用循环伏安法(CV)和差分脉冲伏安法(DPV)对此印迹传感器的电化学性能进行详细表征;采用扫描电子显微技术对修饰电极的形貌进行表征。结果表明,此印迹电化学传感器对辛基酚具有良好的特异识别性能。采用 DPV 法考察了孵化时间和洗脱溶剂对印迹传感器性能影响,结果表明,最佳孵化时间为14 min。此印迹电化学传感器的响应电流(△IR )与辛基酚在5.0×10-6~5.0×10-9 mol/ L 范围内浓度的负对数(-lgC)呈良好的线性关系,线性方程为△IR ( mA)=-0.25lgC(mol/ L)+2.35,检出限为3.64×10-10 mol/ L (S/ N=3)。此印迹电化学传感器对辛基酚具有良好的选择性和灵敏性,成功用于实际水样中辛基酚的检测,回收率为96.0%~104.0%。     

Application of Graphene as a Sorbent for Simultaneous Preconcentration and Determination of Trace Amounts of Cobalt and Nickel in Environmental Water and Vegetable Samples

A new method using a column packed with graphene as adsorbent was developed for the preconcentration of trace amounts of cobalt (Co) and nickel (Ni) prior to their determinations by flame atomic absorption spectrometry. Several factors influencing the extraction efficiency of Co and Ni and their subsequent determinations, such as pH, amounts of the chelating agent, flow rates of sample and eluent solution, eluent type and its volume, breakthrough volume, and adsorption capacity were established. Under the optimum conditions, the calibration graphs were linear in the range of 4.0‐200.0 μg L^?1 and 5.0‐200.0 μg L^?1 with detection limits of 0.36 μg L^?1 and 0.51 μg L^?1 for Co and Ni, respectively. Good relative standard deviations for ten determinations of 100.0 μg L^?1 of Co and Ni were 3.2 and 3.6%, respectively. The results for determination of Co and Ni in tap water, river water, sea water, vegetable and spiked samples have demonstrated the accuracy and applicability of the proposed method. To validate the proposed method, three certified reference materials of environment water (GSBZ 50030‐94 and GSB 07‐1186‐2000) and tomato leaf (GSBZ 51001‐94) were analyzed, and the determined values were in good agreement with the certified values.     

Graphene/polydopamine‐modified polytetrafluoroethylene microtube for the sensitive determination of three active components in Fructus Psoraleae by online solid‐phase microextraction with high‐performance liquid chromatography

Determination of bioactive compounds in traditional Chinese medicines and biological samples is usually interfered with by coexisting components in matrices. In this work, we prepared novel multilayer functional graphene/polydopamine‐modified polytetrafluoroethylene microtube for selective solid‐phase microextraction of three bioactive compounds in Fructus Psoraleae. Functional graphene/polydopamine‐modified polytetrafluoroethylene microtube showed good extraction efficiency toward bavachin, isobavachalcone, and bavachinin; enrichment from 357‐ to 737‐fold was obtained for these compounds. For qualitative analysis, an online solid‐phase microextraction with high‐performance liquid chromatography method was developed, which showed low limits of detection of 0.02 ng/mL by using UV detection, which is significantly more sensitive than previously reported methods. The proposed method has been used to determine bavachin, isobavachalcone, and bavachinin in Fructus Psoraleae, the contents of three compounds were quantified to be 64.0, 324.0, and 384.5 μg/g; recoveries were 93.4–101.1%. The proposed method has also been applied to determine bavachin, isobavachalcone, and bavachinin in rat plasma samples after oral administration of Fructus Psoraleae.     

Determination of Hg2+ in Tap Water Based on the Electrochemiluminescence of Ru(phen)32+ and Thymine at Bare and Graphene Oxide‐Modified Glassy Carbon Electrodes

The electrochemiluminescence (ECL) of the Ru(phen)₃²⁺/thymine (T) system at bare and graphene oxide (GO)‐modified glassy carbon (GC) electrodes was utilized to determine Hg²⁺ in tap water. The ECL intensity of Ru(phen)₃²⁺ was considerably enhanced by the addition of thymine because of the occurrence of ECL reaction between them. Subsequently, the ECL intensity of Ru(phen)₃²⁺/T system rapidly decreased with the addition of Hg²⁺ because of the formation of a T‐Hg²⁺‐T complex. A linear response (R²=0.9914) was obtained over a Hg²⁺ concentration range of 1.0×10^?9 mol/L to 1.0×10^?5 mol/L with a detection limit of 3.4×10^?10 mol/L at a bare GC electrode in 0.1 mol/L phosphate buffer (pH=8.0). The detection limit can be further reduced to 4.2×10^?12 mol/L after modification of the GC electrode by GO. To verify its applicability, the proposed method was utilized to determine Hg²⁺ in tap water and simulated wastewater. The method exhibited good reproducibility and stability and thus reveals the possibility of developing a novel ECL detection method for Hg²⁺.     

Water‐Soluble Polymer Functionalized CdTe/ZnS Quantum Dots: A Facile Ratiometric Fluorescent Probe for Sensitive and Selective Detection of Nitroaromatic Explosives

A ratiometric fluorescent probe based on dual luminescence QD/CPL for selective sensing of the nitroaromatic explosive picric acid (PA) was constructed. The observed ratiometric fluorescence intensity change allows the quantitative detection of PA with a detection limit of 9 nM .     

The Signal Amplification in Electrochemical Detection of Chloramphenicol Using Sulfonated Polyaniline‐chitosan Composite as Redox Capacitor

In this work, a novel redox capacitor was designed for signal amplification in electrochemical detection. It was fabricated by co‐electrodeposition of a conducting polymer, sulfonated polyaniline (SPAN) and chitosan on a glass carbon electrode, and its function was evaluated for being a localized source to transfer electron between FcCOOH (Fc) and Ru(NH₃)₆Cl₃ in solution via redox cycling. Furthermore, the electrochemical detection of chloramphenicol, a broad‐spectrum antibiotic was performed using the redox capacitor in the presence of Fc. A significant amplification in cathodic current response of chloramphenicol was obtained through a continuous redox‐cycling reaction. The performance of the amplifying signal responded linearly to chloramphenicol in a concentration range of 0.05 to 50.0 μmol L⁻¹ with a low detection limit of 0.01 μmol L⁻¹. The proposed approach exhibited good reproducibility and stability, and could be used for detection of chloramphenicol in eye drops by standard addition method with the recoveries from 96.5 % to 103.0 %.     

Magnetite Nanorods Stabilized by Polyaniline/Reduced Graphene Oxide as a Sensing Platform for Selective and Sensitive Non‐enzymatic Hydrogen Peroxide Detection

In this study, magnetite nanorods stabilized on polyaniline/reduced graphene oxide (Fe₃O₄@PANI/rGO) was synthesized via a wet‐reflux strategy. The possible formation of Fe₃O₄@PANI/rGO was morphologically and structurally verified by field emission scanning electron microscopy (FE‐SEM), Fourier transform infrared (FT‐IR) spectroscopy, Raman spectroscopy, X‐ray diffraction (XRD) and X‐ray photoelectron spectroscopy (XPS). Furthermore, the thermal stability of Fe₃O₄@PANI/rGO was measured by a thermogravimetric analyzer (TGA); the composite had good thermal stability owing to the ceramic nature of Fe₃O₄. The Fe₃O₄@PANI/rGO has been applied as a potential sensing platform for electrochemical detection of hydrogen peroxide (H₂O₂). By the combined efforts of extended active surface area, active carbon support, more catalytic active sites and high electrical conductivity, the Fe₃O₄@PANI/rGO exhibited an improved performance toward the non‐enzymatic detection of H₂O₂ in 0.5 M KOH with a fast response time (5 s), high sensitivity (223.7 μA mM^?1 cm^?2), low limit of detection (4.45 μM) and wide linear range (100 μM–1.5 mM). Furthermore, the fabricated sensor exhibited excellent recovery rates (94.2–104.0 %) during real sample analysis.