Determination of trace amounts of morphine in human plasma by anodic adsorptive stripping differential pulse voltammetry

New adsorptive anodic differential pulse stripping voltammetry method for the direct determination of morphine at trace levels in human plasma of addicts is proposed.The procedure involves an adsorptive accumulation of morphine on a HMDE,followed by oxidation of adsorbed morphine by voltammetry scan using differential pulse modulation.The optimum conditions for the analysis of morphine are pH 10.5,Eacc of -100 mV（vs.Ag/AgCl）,and tacc of 120 s.The peak current is proportional to the concentration of morphine,and a Linear calibration graph is obtained at 0.01-3.10μg mL^-1.A relative standard deviation of 1.06%（n=5）was obtained,and the limit of detection was 3 ng mL^-1.The capabiLity of the method for the analysis of real samples was evaluated by the determination of morphine in spiked human plasma and addicts human plasma with satisfactory results.

Amperometric detection of gold by differential pulse voltammetry using a DNA biosensor

A DNA biosensor with [Ru（DA-bpy）3]Cl2（DA-bpy：4,4＇-diamino-2,2＇-bipyridine） （RuL） as the electrochemical probe was prepared on pyrolytic graphite electrode （PGE） through the supramolecular interaction between RuL complex and DNA template. Cyclic voltammetry of RuL-DNA film showed a pair of stable and reversible peaks corresponding to the Ru（Ⅲ）/Ru（Ⅲ） redox potential of-0.165 V versus AglAgCl in pa 7.4 0.1 mol·L^-1Tris-HCl. The electron transfer was expected across the double-strand DNA by an ＂electron tunneling＂ mechanism. When the DNA biosensor was immerged in gold （Ⅲ） buffer solution, the current peak signal （I） of the RuL-DNA supramolecular depressed and △I was linear in the concentration range of Au ion from 1×10^-7 to 2×10^-5 mol·L^-1 with a regression coefficient of 0.9879. The detection limit was 5×10^-8 mol·L^-1. The developed procedures were applied to the analysis of synthetic samples of real materials with good sensitivity and selectivity.

Electrochemical Determination of Alkaline Phosphatase in Human Serum by Differential Pulse Voltammetry

Differential pulse voltammetry(DPV) was applied to the determination of alkaline phosphatase(ALP) activity in human serum with phenyl phosphate as the substrate. Phenyl phosphate can enzymatically be hydrolyzed to produce phenol which is quantified by DPV at +660 mV(vs.Ag/AgCl) in the concentration range of 2.0_100 μmol/L. The standard curve for ALP is linear over the range from 0.06 to 1000 U/L with a relative standard deviation of 3.0%. The conditions for the enzymatic reaction and voltammetric detection were optimized and the kinetic constants were also examined.The human serum samples were tested by this method and the results were in good agreement with those obtained by the routine p-nitrophenyl phosphate spectrophotometric method.

Simultaneous determination of three 5-nitroimidazoles in foodstuffs by differential pulse voltammetry and chemometrics

The voltammetric behaviour of three 5-nitroimidazoles,metronidazole,tinidazole and ornidazole,was investigated,and a method was developed for the simultaneous determination of these compounds,based on their reduction at a hanging mercury drop electrode（HMDE） in pH 8.95 buffer with differential pulse voltammetric（DPV） approach.Well defined voltammetric waves with peak potentials of -692,-640 and -652 mV were observed for these compounds,respectively.It is difficult to determine them individually from their mixtures without preseparation,for their voltammetric peaks overlapped seriously,so the chemometrics were used to resolve the overlapped voltammogram and quantify the mixtures.The proposed method was successfully applied to the determination of three 5-nitroimidazoles in milk and honey samples.

Differential Pulse Voltammetric Simultaneous Determination of Paracetamol and Omnipaque on Boron Doped Diamond Electrode: Application to Natural Tomato, Carrot, Cucumber Juices and Wastewater

This article describes the use of a boron-doped diamond electrode (BDDE) as an electrochemical sensor for the simultaneous determination of omnipaque (OMP) and paracetamol (PCM) in perchloric acid medium (HClO4 0.1 M) and in complex matrices such as tomato, carrot and cucumber juices and waste water from the Treichville University Hospital. Voltammetric studies allowed us to have well-defined oxidation peaks at distinct potentials of OMP (E = 0.5 V/SCE) and PCM (E = 0.7 V/SCE). Under optimized conditions, well-defined quantities of OMP and PCM, introduced simultaneously by metered additions, gave linear responses in concentration ranges of 259.8 - 467.2 μM for OMP and 58.73 - 116.3 μM PCM. The detection limits obtained are 7.23 μΜ and 3.6 μΜ respectively for OMP and PCM with recovery rates between 85.8% ± 0.1% and 92.6% ± 0.1% for OMP and between 99.9% ± 0.1% and 101.2% ± 0.4% for the PCM. This technique has been successfully used to simultaneously detect these pharmaceuticals in these complex environments. It allows recovery of OMP and PCM respectively up to 97.5% ± 0.0% and 91.6% ± 0.3% in tomato juice;100.0% ± 0.0% and 95.2% ± 0.2% in carrot juice;101.4% ± 0.1% and 97.3% ± 0.3% in cucumber juice;100.1% ± 0.9% and 100.9% ± 0.1% in wastewater. The relevance of this technique for the simultaneous detection of OMP and PCM in tomato, carrot, cucumber juices and in waste water can be studied in the context of the contamination of certain fruits and vegetables by the substances organic pharmaceuticals released into the environment without prior treatment.

Indirect Differential Pulse Voltammetric Determination of Aluminum by a Pyrocatechol Violet-Modified Electrode

A PCV-modified electrode was simply prepared by dip-coating a pyrolytic graphite electrode in a NaAc-HAc buffer solution of PCV. The peak currents of differential pulse voltammograms (DPV) decrease with the addition of Al and the peak potentials remain the same. The decreasing of Delta i(p) is linear with Al concentration in the range of 1 x 10(-8) similar to 1 x 10(-7) mol/L. The detection limit is 5 x 10(-9) mol/L and the relative standard deviation for 4 x 10(-8) mol/L Al is 2.9% (n=8). No serious interference was found. The determination of Al in water samples is reported.

4-methoxy-2,6-bis(3,5-dimethylpyrazoyl)-1,3,5-triazine modified carbon paste electrode for trace Cu(Ⅱ) determination by differential pulse volt-ammetry

A differential pulse voltammetric method was developed for the sensitive andselective determination of Cu(II) at 4-methoxy-2,6-bis(3,5-dimethylpyrazoyl)-l,3,5-triazine modifiedcarbon paste electrode in 0.05 mol/L KHC_8H_4O_4 solution (pH = 4.02). The oxidation peak of Cu(II)was observed at 0.065 V(vs Ag/AgCl) by scanning the potential in positive direction. The analysisprocedure consisted of an open circuit accumulation step in stirred sample solution. It was followedby medium exchange to a clean solution and subsequently an anodic potential scan was affected toobtain the voltammetric peak. The current was proportional to the concentration of the Cu(II) ion ina range of 1 X 10^(-7) -1 X 10^(-4) mol/L for 6 min accumulation; the most of metal ions did notinterfere with the determination. The developed method was applied to Cu (II) determination incoal-ash sample, the results agreed with that of atomic adsorption spectroscopy (AAS).

Application of differential pulse stripping voltammetry and chemometrics for the determination of three antibiotic drugs in food samples

A reliable method for simultaneous determination of three antibiotic drugs（levofloxacin,gatifloxacin and lomefloxacin） by differential pulse stripping voltammetry（DPSV） in Britton-Robinson buffer（pH 7.96） was presented.The method is based on adsorptive accumulation of the antibacterial drugs on a hanging mercury dropping electrode（HMDE）,followed by the reduction of the adsorptive species by the technique of DPSV.Optimal conditions,the deposition time of 80 s,the deposition potential of—1250 mV,and the scan rate of 25 mV/s,were obtained.The linear concentration ranges of 0.010-0.080μg/mL were obtained for all these three antibiotic drugs,while the detection limits were 2.38,3.20 and 1.60ng/mL for levofloxacin,gatifloxacin and lomefloxacin,respectively.In this work,chemometrics methods,such as classical least squares（CLS）,partial least squares（PLS）, principle component regression（PCR） and radial basis function-artificial neural networks（RBF-ANN）,were used to quantitatively resolve the overlapping signals.It was found that PCR gave the best results with total relative prediction error（RPE_T） of 7.71%.The proposed method was applied to determine these three drugs in several commercial food samples with spiked method and yielded satisfactory recoveries.

Automated Determination of Cd^(2+) and Pb^(2+) in Natural Waters with Sequential Injection Analysis Device Using Differential Pulse Anodic Stripping Voltammetry

An electrochemical flow device has been developed for the determination of heavy metal ions(HMI)in water using multiwalled carbon nanotubes(MWCNTs)/Nafion(NA)/Hg electrode,by mean of diff erential pulse anodic stripping voltammetry coupled with sequential injection analysis.The accuracy of the determination was ensured by the great electrical conductivity of MWCNTs and the high adsorption capacity of Hg.NA was used for MWCNTs immobilization for the long-term application of the electrode.The mercury film was cleaned after determination and another one would form during deposition.A lower limit of detection and a wider determination range of Cd^(2+)and Pb^(2+)could be achieved using the automatically analytical device combining with the MWCNTs/NA/Hg-modified electrode.The real-time monitoring of Cd^(2+)and Pb^(2+)in fresh water using this device continued for 10 days.The results indicated that the method was potential for on-site and real-time determination of HMI in water samples.

Electrochemical study and application on rutin at chitosan/graphene films modified glassy carbon electrode

Graphene（G） was dispersed into 0.5% chitosan（Chit） solution,then the composite films were coated on glassy carbon electrode（GCE）,the electrochemical behavior of rutin on a Chit/G modified GCE was investigated and the electrochemical parameters of rutin were calculated.Rutin effectively accumulated on the Chit/G/GCE and caused a pair of redox peaks at around 408 mV and 482 mV（vs.SCE） in 0.1M phosphate buffer solution（pH 4.0）.Under optimized conditions,the anodic peak current was linear to the rutin concentration in the range of 5×107-1.04×105M.The regression equation was：y 9.9219x-0.0025,r=0.9958.The proposed method was successfully used for the determination of rutin content in tablet samples with satisfactory results.

Electrochemical Determination of Epinephrine with a Pyrolytic Graphite Electrode in the Presence of Ascorbic Acid and Dopamine

A method for determination of epinephrine（EP） in the presence of ascorbic acid （AA） and dopamine （DA） with bare pyrolytic graphite electrodes has been described for the first time. In pH 7.0 phosphate buffer solution, the linear relationship was observed between the reduction peak current of EP and its concentration over the range from 1×10^-4 to 5×10^-7 mol/L, the related coefficient is 0.9992 （N=8）.

A New Voltammetric Enzyme Immunoassay System for the Detection of Alkaline Phosphatase

A new voltammetric enzyme immunoassay system was investigated based on p-nitrophenyl phosphate (PNPP) as the substrate for alkaline phosphatase (ALP). PNPP is enzymatically hydrolyzed and the product p-nitrophenol (PNP) is detected by differential pulse voltammetry (DPV), which can be oxidized at +1.02 V (vs. Ag/AgCl) on bare glass carbon electrode (GCE). The conditions for enzymatic reaction and electrochemical detection were studied. According to this method, ALP can be detected with a detection limit of 2.8102 mU/L and a linear range of 4.0102 ~ 1.0106 mU/L.

Detection of Breast Cancer 1 (BRCA1) Gene Using an Electrochemical DNA Biosensor Based on Immobilized ZnO Nanowires

Herein we report an electrochemical DNA biosensor for the rapid detection of sequence (5’ AAT GGA TTT ATC TGC TCT TCG 3’) specific for the breast cancer 1 (BRCA1) gene. The proposed electrochemical genosensor is based on short oligonucleotide DNA probe immobilized onto zinc oxide nanowires (ZnONWs) chemically synthesized onto gold electrode via hydrothermal technique. The morphology studies of the ZnONWs, performed by field emission scanning electron microscopy (FESEM), showed that the ZnO nanowires are uniform, highly dense and oriented perpendicularly to the substrate. Recognition event between the DNA probe and the target was investigated by differential pulse voltammetry (DPV) in 0.1 M acetate buffer solution (ABS), pH 7.00;as a result of the hybridization, an oxidation signal was observed at +0.8 V. The influences of pH, target concentration, and non-complimentary DNA on biosensor performance were examined. The proposed DNA biosensor has the ability to detect the target sequence in the range of concentration between 10.0 and 100.0 μM with a detection limit of 3.32 μM. The experimental results demonstrated that the prepared ZnONWs/Au electrodes are suitable platform for the immobilization of DNA.

Simultaneous Voltammetric Determination of Three Herbicides in Food and Water Samples with the Aid of Chemometrics

Differential pulse stripping voltammetry method（DPSV） was applied to the determination of three herbicides, ametryn, cyanatryn, and dimethametryn. It was found that their voltammograms overlapped strongly, and it is difficult to determine these compounds individually from their mixtures. With the aid of chemometrics, classical least squares（CLS）, principal component regression（PCR） and partial least squares（PLS）, voltammogram resolution and quantitative analysis of the synthetic mixtures of the three compounds were successfully performed. The proposed method was also applied to the analysis of some real samples with satisfactory results.

Simultaneous electrochemical DNA hybridization assay for PAT and FMV 35S gene sequence using quantum dots as labels

An electrochemical method for the simultaneous detection of two different DNA sequences from PAT and FMV 35S gene sequence using CdS and PbS quantum dots （QDs） as labels was described. The QDs were readily functionalized with oligonucleotides as electrochemical DNA probes and selectively hybridized to the complementary sequences immobilized on the microplate. The QDs anchored on the hybrids were dissolved in the solution by the oxidation of HNO3 and further detected by a sensitive differential pulse anodic stripping voltammetric method （DPASV）. The DPASV signals of the oxidation of Cd^2＋ and Pb^2＋ ions present in the solution were different and reflected the identity of corresponding ssDNA targets sequences.

Electrochemical Determination of Trace Amounts of Lead (Ⅱ) and Cadmium (Ⅱ) at a Calix[6]arene Modified Carbon Paste Electrode

An electrochemical method for the simultaneous determination of lead(II) and Cadmium(II) with a calix[6]arene modified carbon paste electrode (CPE) has been developed. Pb2+ and Cd2+ were accumulated at the surface of the modified electrode via formation of chemical complexes with calix[6]arene, and reduced at 1.40 V. During the following anodic potential sweep, reduced lead and cadmium were oxidized, and two well-defined striping peaks appeared at about ?0.60 V and ?0.84 V. Compared with a bare carbon paste electrode, the calix[6]arene modified CPE greatly improves the sensitivity of determining lead and cadmium. The stripping peak currents change linearly with the concentration of Pb2+ 3.0×10?8–8.0×10?6 mol·L?1 and with that of Cd2+ 6.0×10?8–1.0×10?5 mol ·L?1. The detection limits of Pb2+ and Cd2+ are found to be 8.0×10?9 mol·L?1 and 2.0×10?8 mol·L?1, respectively. The modified carbon paste electrode was applied to determine trace levels of lead and cadmium in water samples. Comparing with that of atomic absorption spectrometry, the results suggests that the calix[6]arene modified CPE has great potential for the practical sample analysis. Key words lead(II) - cadmium(II) - calix[6]arene - differential pulse stripping voltammetry - chemically modified electrode CLC number O 657.15 Foundation item: Supported by the National Natural Science Foundation of China (60171023)Biography: JI Xiao-bo (1980-), male, Master, research direction: electroanalytical chemistry.

The Electrochemical Behavior and the Determination of Bavistin on Glassy Carbon Electrode

In this paper, the electrochendcal behavior of bavistin (MBC) on glassy carbon electrode is reported. In a base solution of pH=9.0 NH3-NH4Cl, a sensitive anodic peak was found by cyclic voltammetry. Differential pulse stripping voltanunetry was applied for determing MBC in grains. The detection limit is 4×10-8mo/L.The recovery is from 91.3% to 95.7%. The method has advantages of simplicity and high sensitivity.

Electrochemical Study and Application on Shikonin at Poly（diallyldimethylammonium chloride） Functionalized Graphene Sheets Modified Glass Carbon Electrode

The electrochemical behaviors of shikonin at a poly（diallyldimethylammonium chloride） functionalized graphene sheets modified glass carbon electrode（PDDA-GS/GCE） have been investigated. Shikonin could exhibit a pair of well-defined redox peaks at the PDDA-GS/GCE located at 0.681 V（Epa） and 0.662 V（Epc）[vs. saturated calo- mel electrode（SCE）] in 0.1 mol/L phosphate buffer solution（pH=2.0） with a peak-to-peak separation of about 20 mV, revealing a fast electron-transfer process. Moreover, the current response was remarkably increased at PDDA- GS/GCE compared with that at the bare GCE. The electrochemical behaviors of shikonin at the modified electrode were investigated. And the results indicate that the reaction involves the transfer of two electrons, accompanied by two protons and the electrochemical process is a diffusional-controlled electrode process. The electrochemical para- meters of shikonin at the modified electrode, the electron-transfer coefficient（a）, the electron-transfer number（n） and the electrode reaction rate constant（ks） were calculated to be as 0.53, 2.18 and 3.6 s^-1, respectively. Under the optimal conditions, the peak current of differential pulse voltammetry（DPV） increased linearly with the shikonin concentra- tion in a range from 9A72×10^-8 mol/L to 3,789×10^-6 mol/L with a detection limit of 3,157× 10^-8 mol/L. The linear regression equation was Ip=O.7366c＋0.7855（R=0.9978; lp： 10-7 A, c： 10-8 mol/L）. In addition, the modified glass carbon electrode also exhibited good stability, selectivity and acceptable reproducibility that could be used for the sensitive, simple and rapid determination of shikonin in real samples. Therefore, the present work offers a new way to broaden the analytical application of graphene in pharmaceutical analysis.

Direct and Simultaneous Determination of Phenol, Hydroquinone and Nitrophenol at Boron-Doped Diamond Film Electrode

The electrochemical characteristics of multi-component phenolic pollutants, such as phenol （Ph）, hydroquinone （HQ） and 4-nitrophenol （4-NP）, were investigated on boron-doped diamond （BDD） film electrode by differential pulse voltammetry （DPV） technique. A simple and feasible platform was accordingly established for the direct and simultaneous determination of these three phenolic pollutants. Results showed that, Ph, HQ and 4-NP gave obvious oxidation peaks on BDD electrode at the potential of 1.24, 0.76 and 1.52 V, respectively. Each of them displayed good linear relationship between their oxidation peak currents and their corresponding concentrations in a rather wide range coexisting with one or two of the other phenolic pollutants. The detection limits of Ph, HQ and 4-NP were estimated to be as low as 1.82×10^-6, 1.67×10^-6 and 1.44×10^-6 mol·L^-1, respectively. Therefore, a promising direct and simultaneous electrochemical determination method of multi-component phenolic pollutants in wastewater samples was constructed successfully on BDD electrode with advantages being rapid, simple, convenient, sensitive, in situ and inexpensive.

Fabrication of a Sensitive Electrochemical Biosensor for Detection of DNA Hybridization Based on Gold Nanoparti- cles/CuO Nanospindles Modified Glassy Carbon Electrode

In this work, a sensitive electrochemical DNA biosensor for the detection of sequence-specific target DNA was reported. Firstly, CuO nanospindles （CuO NS） were immobilized on the surface of a glassy carbon electrode （GCE）. Subsequently, gold nanoparticles （Au NPs） were introduced to the surface of CuO NS by the electrochemical deposition mode. Probe DNA with SH （HS-DNA） at the 5＇-phosphate end was covalently immobilized on the surface of the Au NPs through Au-S bond. Scanning electron microscopy （SEM） was used to elucidate the morphology of the assembled film, and electrochemical impedance spectroscopy technique （EIS） was used to investigate the DNA sensor assembly process. Hybridization detection of DNA was performed with differential pulse voltammetry （DPV） and the methylene blue （MB） was hybridization indicator. Under the optimal conditions, the decline of reduction peak current of MB （A/） was linear with the logarithm of the concentration of complementary DNA from 1.0 X 10-13 to 1.0× 10-6 mol·L l with a detection limit of 3.5 × 10 14 mol·L -1 （S/N=3）. In addition, this DNA biosensor has good selectivity, and even can distinguish single-mismatched target DNA.