Amperometric detection of catecholamines with liquid chromatography at a novelly constructed prussian blue chemically modified electrode

A novel Prussian blue chemically modified electrode (CME) was constructed and characterized for liquid chromatography electrochemical detection (LCEC) of catecholamines. Both anodic and cathodic peaks could be obtained by monitoring at constant applied potential at anodic and slightly cathodic potential ranges (0.3-0.7 and -0.2-0.1 V vs. SCE), respectively. When arranged in a series configuration, using the modified electrodes as generating and collecting detectors, extremely high effective collection efficiencies of 0.91 (for norepinephrine) and 0.58 (for dihydroxyphenylacetic acid) were achieved in dual-electrode LCEC for catecholamines; and a linear response range over 3 orders of magnitude and a detection limit of 10 pg were obtained with a downstream CME as the indicating detector.     

Direct Electrochemical Oxidation of DNA on Polycrystalline Gold Electrodes

Electrochemical CV and SWV studies were performed with double stranded DNA from salmon testes (dsDNA) and single stranded DNAs, containing 25 nucleotides (ssDNA) directly adsorbed at polycrystalline Au electrodes. A distinct oxidation peak at +730 mV (SWV, scan rate 0.248 V s^?1) or at +730 – +780 mV (CV, scan rate from 0.3 to 1 V s^?1) was obtained with DNA‐modified Au electrodes after a time‐dependent prepolarization step at a positive potential value, i.e., at +500 mV (vs. Ag|AgCl), performed with the DNA‐modified Au electrodes dipped in a blank buffer solution. No electrochemical activity was detected when ssDNA, containing no guanines, was used for adsorptive modification of the Au electrodes. Electrochemical impedance measurements registered a possible reorganization of the adsorbed DNA layer in the course of the prepolarization, accompanied by decreasing in‐phase impedance. The results enable us to relate the oxidation process observed at the DNA‐modified Au electrodes with the oxidation of guanine residues in DNA.     

Adsorptive Stripping Voltammetric Detection of Single‐Stranded DNA at Electrochemically Modified Glassy Carbon Electrode

Electrochemically modified glassy carbon electrode (GCE) was used to study the electrochemical oxidation and detection of denatured single‐stranded (ss) DNA by means of adsorptive stripping voltammetry. The modification of GCE, by electrochemical oxidation at +1.75 V (vs.SCE) for 10 min and cyclic sweep between +0.3 V and ?1.3 V for 20 cycles in pH 5.0 phosphate buffer, results in 100‐fold improvement in sensitivity for ssDNA detection. We speculated that the modified GCE has a high affinity to single‐stranded DNA through hydrogen bond (specific static adsorption). Single‐stranded DNA can accumulate at the GCE surface at open circuit and produce a well‐defined oxidation peak corresponding to the guanine residues at about +0.80 V in pH 5.0 phosphate buffer, while the native DNA gives no signal under the same condition. The peak currents are proportional to the ssDNA concentration in the range of 0–18.0 μg mL^?1. The detection limit of denatured ssDNA is ca. 0.2 μg mL^?1 when the accumulation time is 8 min at open circuit. The accumulation mechanism of ssDNA on the modified GCE was discussed.     

Tetrahydrofuran Activates Fluorescence Resonant Energy Transfer from a Cationic Conjugated Polyelectrolyte to Fluorescein‐Labeled DNA in Aqueous Media

A cationic water‐soluble conjugated polyelectrolyte, poly[9,9‐bis(6′′‐(N,N,N‐trimethylammonium)hexyl)fluorene‐co‐alt‐2,5‐bis(6′‐(N,N,N‐trimethylammonium)hexyloxyphenylene) tetrabromide], was synthesized. Fluorescence resonant energy transfer (FRET) experiments between the polymer and fluorescein‐labeled single‐stranded DNA (ssDNA‐Fl) were conducted in aqueous buffer and THF/buffer mixtures. Weak fluorescence emission in aqueous buffer was observed upon excitation of the polymer, whereas addition of THF turned on the fluorescence. Fluorescence self‐quenching of ssDNA‐Fl in the ssDNA‐Fl/polymer complexes as well as electron transfer from the polymer to fluorescein may account for the low fluorescence emission in buffer. The improved sensitization of fluorescence by the polymer observed in THF/buffer could be attributed to the weaker binding between the polymer and ssDNA‐Fl and a decrease in dielectric constant of the solvent mixture, which disfavors electron transfer. THF‐assisted signal sensitization was also observed for the polymer and fluorescein‐labeled double‐stranded DNA (dsDNA‐Fl). These results indicate that the use of cosolvent provides a strategy to improve the detection sensitivity for biosensors based on the optical amplification provided by conjugated polymers.     

Investigation of Metal Ion Effect on Specific DNA Sequences and DNA Hybridization

In this article, we investigated the sequence specific interaction of single (ssDNA) and double stranded (dsDNA) with silver ions (Ag⁺) with electrochemical methods. We, for the first time, examined the effect of base sequences, base content and physiochemical properties of different DNA sequences on interaction with Ag⁺ in detail. We used different base contents to show how the composition of nucleic acid influences the electrochemical signals. We first immobilized ssDNA probes on bare graphite electrodes. Then, we showed the sequence effect on oxidation signals of AgDNA complex by sensing Ag⁺ to the probe coated surfaces to interact with different ssDNA sequences. Furthermore, we investigated the effect of Ag⁺ on dsDNA. We measured the oxidation signals obtained from Ag⁺‐ssDNA and Ag⁺‐dsDNA complex at approximately 0.2 V and 1.0 V (vs Ag/AgCl), respectively with Differential Pulse Voltammetry (DPV). We showed that the oxidation signals of the AgDNA complex obtained from dsDNA‐modified electrodes is higher than the electrodes modified with ssDNA. More importantly, we showed that Ag⁺‐ssDNA and Ag⁺ ion‐dsDNA exhibit different electrochemical behaviors.     

Fabrication of Nano Flower‐shaped Platinum on Glassy Carbon Electrode as a Sensitive Sensor for Lead Electrochemical Analysis

Platinum nanoflowers modified glassy carbon electrodes (PtNFs/GCE) was fabricated simply for lead determination in water samples. The modified electrodes were prepared by electrodeposition in hexachloroplatinic acid solution at constant potential. The influence of deposition time and potential on surface morphology, chemical composition, electrochemical properties of electrode were investigated. At ?0.2 V of potential and 150 s of deposition duration, platinum developed as nanoflower shape and scattered densely all over the glassy carbon surface, producing the largest electrochemically active surface areas. The highest differential pulse stripping voltammetry (DPSV) signal of lead was obtained by using the prepared electrode. Under optimized experimental condition of electrolyte, accumulation potential and time, the peak current was found to be linear proportion to lead concentration in range of 1 to 100 μg L^?1 (slope=0.371) with a limit of detection of 0.398 μg L^?1. The method has good repeatability and reproducibility with relative standard deviations of 1.47 % and 4.83 %, respectively. The modified PtNFs/GCE also demonstrated an excellent long‐term stability with only 9 % decrease in Pb peak current over 30 days. Moreover, the performance of the modified PtNFs/GCE in determination of Pb(II) in two industrial wastewaters was good agreement with data obtained by a graphite furnace atomic absorption spectrometry (GFAAS) method.     

DNA修饰电极的研究: VIII. 1, 10-菲咯啉存在时钴离子在ssDNA 修饰金电极上 的电化学行为及痕量钴的检测

发现在过量1,10-菲咯啉存在时,Co^3^+^/^2^+在单链DNA(ssDNA)修饰金电极上的电化学响应显著增强。采用紫外光谱和循环伏安法考察了Co^3^+^/^2^+/1,10-菲咯啉体系与sSDNA的相互作用,并利用Co^3^+^/^2^+在1,10-菲咯啉存在时在ssDNA修饰金电极上的高灵敏电化学响应对痕量钴离子进行了测定。     

多金属氧簇阴离子[Mo6O19]2-/PAMAM超分子化合物的制备、表征及性能

采用树状聚酰胺-胺(PAMAM)大分子化合物与同多酸阴离子[Mo6O19]2-,基于静电作用合成了同多金属氧酸盐/树型分子超分子化合物。用元素分析、FTIR、UV-V is、TG/DTA、荧光光谱等测试技术分别对样品进行了结构表征及性能测试。并利用其作为电极修饰剂,制得化学体修饰的碳糊电极(CMCPE),用循环伏安法研究了同多金属氧酸盐/树型分子超分子化合物修饰碳糊电极在1 mol/L H2SO4水溶液中的电化学行为。结果表明,该化合物具有良好的荧光性能和可逆光致变色性能;用该化合物修饰的碳糊电极与[Mo6O19][N(C4H9)2]2修饰的电极相比,在-0.2~0.2 V范围内多了1对氧化还原峰;当扫描速率低于100 mV/s时,该电极过程为表面控制过程,而当扫描速率高于100 mV/s时,电极过程变为扩散控制过程;且该电极在室温下具有很好的稳定性。     

Topography changes of rhodium electrodes induced by the application of fast periodic potential routines

The surface structure of polycrystalline rhodium electrodes in contact with aqueous sulfuric acid was modified by chemical etching with hot concentrated acid or by applying fast square waves with an upper potential equal to 1.55 V and a lower potential within the –0.75 V to –0.35 V range. Polycrystalline rhodium and chemical etched electrodes were characterized by voltammetry, Cu underpotential deposition (upd) and X-ray diffraction. For electrofaceted surfaces were used voltammetry, Cu upd and SEM, revealing that two modified rhodium electrodes exhibit similar voltammetric characteristics as those found for Rh(111) and Rh(110) single crystals, and a third surface with an equal distribution of (110) and (111) planes. In addition, the upd of Cu on those surfaces corroborated the existence of those crystallographic planes. SEM micrographs show surface structures with a high density of terraces and steps. A mechanism of faceting is proposed. Electronic Publication     

Frequency-domain measurement of the photodegradation process of fluorescein

The frequency-domain technique is applied to measure the photodegradation rate of fluorescein in aqueous solutions. The illuminating light is modulated, and the changes in fluorescence from the illuminated region are detected synchronously. A constant flow rate is imposed on the fluorescein solution to control the mass transport of fluorescein into the illuminated region. The fluorescence response is described by a model that assumes that photodegradation occurs from the triplet excited state. The predictions of the model are consistent with the observed variations in the fluorescence response with flow rate, modulation frequency and incident power. We discuss in this article how the dependence of the model parameters on experimental conditions can be used to infer the photodegradation rate as well as some of the details of the photodegradation mechanism. The results are consistent with the known mechanism of photodegradation of fluorescein. The frequency-domain technique gives a photodegradation rate of 53 s(-1) in an air-saturated solution and 37 s(-1) in solutions purged with argon gas.     

铂电极上吸附芳香分子的表面增强红外光谱研究

应用衰减全反射表面增强红外吸收光谱法分别研究了0.1 mol•L^－1 HClO₄中对硝基苯甲酸(PNBA)和0.1 mol•L^－1 KClO₄中吡啶(Py)在铂电极上的吸脱附. 结果表明在较高电位下(0.3～0.7 V vs. SCE) PNBA是通过其羧基脱质子后羧酸根的两个氧原子等位吸附在Pt电极表面, 而随着电位的负移, 除PNBA逐步脱附外, 还呈现出单个氧原子吸附的谱学特征. 光谱强度与电位的关系表明PNBA在铂电极表面吸脱附的中间电位约为0.2 V vs. SCE. 吡啶的吸附主要是通过氮原子的孤对电子及脱氢后的α碳原子与Pt电极表面键合. 在较宽的电位区间(0.4～－0.4 V vs. SCE)吡啶的吸附方式和取向基本维持不变.     

MWNT-modified electrodes for voltammetric determination of lipophilic vitamins

Multi-walled carbon nanotube modified graphite electrodes (MWNT-GEs) have been created for the voltammetric determination of α-tocopherol and retinol. The electrode surface was characterized by atomic force microscopy. The MWNT-GEs presented structured surfaces and a significant (26-fold) increase in roughness over unmodified graphite electrodes (8.2 vs. 0.32?nm for MWNT-GEs and GEs, respectively). Their surfaces consisted of aggregates with a highly regular “thorn-like” structure. α-Tocopherol and retinol were oxidized on the bare GEs and the MWNT-GEs in 0.1?M HClO₄ in acetonitrile. Decreases in the overpotential of 0.2 and 0.04?V for α-tocopherol and retinol, respectively, and increased oxidation currents were observed on the MWNT-GEs in comparison with the unmodified electrodes. The calibration graphs were linear in the range 0.065–2.00?mM for α-tocopherol and 0.05–1.50?mM for retinol. The detection limits were found to be 0.05 and 0.04?mM for α-tocopherol and retinol, respectively. The developed electrodes were applied to determine α-tocopherol and retinol in pharmaceuticals. The results obtained agreed well with coulometric titration data.     

Electrochemical behavior of methyl viologen at graphite electrodes modified with Nafion sol–gel composite

Electrodes were prepared by spin-coating spectroscopic graphite rods with a Nafion doped sol. Coating solutions consisting of Nafion:TEOS (tetraethoxysilane) ratios of 3:1 and 4:1 gave smooth films on the electrode surface. These modified electrodes were evaluated and compared with Nafion modified and bare spectroscopic graphite electrodes using methyl viologen (MV²⁺) as a representative cationic electroactive probe. Substantial partitioning of MV²⁺ into the Nafion:sol–gel matrix to the electrode surface was observed by cyclic voltammetry and square wave voltammetry. Cyclic voltammograms of MV²⁺ in 0.1 M NaCl at Nafion:sol–gel 4:1 modified electrodes showed a reversible reduction to MV⁺ with E^0′=−0.695 V vs. Ag/AgCl. Results of scan rate variation showed the wave to be characterized by semi-infinite diffusion for scan rates in the range 50–500 mV/s. Slowing the scan rate below 50 mV/s resulted in a transition to thin-layer behavior. MV²⁺ partitioned much more quickly into the sol–gel-Nafion modified electrodes compared to pure Nafion modified electrodes. Reversibility of the MV²⁺-loaded modified Nafion-doped sol–gel coatings on electrodes was obtained by soaking in 1 M NaCl solution. Concentration calibration plots for MV²⁺ at the sol–gel-Nafion modified electrodes were nonlinear. Substantial enhancement of current signal at low concentrations was observed by square wave voltammetry.     

天青I修饰电极的电化学性质及对血红蛋白的电催化还原

天青I修饰电极在pH=5.5的HAc-NaAc缓冲溶液中,在0.3～-0.7V电位范围内表现出可逆的氧化还原行为,其表面式量电位E^0'=-0.21V,表观电极反应速率常数k_s'=0.69s^-1,该电极对血红蛋白的还原过程具有良好的催化作用。实验结果表明,由电沉积构成的修饰电极较吸附法制备的修饰电极具有更好的稳定性。     

Simultaneous observation of current oscillations and porous film growth during anodization of InP

The observation of spontaneous oscillations in current during the anodization of InP in relatively high concentrations of KOH electrolytes is reported. Oscillations were observed under potential sweep and constant potential conditions. Well-defined oscillations are observed during linear potential sweeps of InP in 5 mol dm(-)(3) KOH to potentials above approximately 1.7 V (SCE) at scan rates in the range of 50 to 500 mV s(-)(1). The oscillations observed exhibit an asymmetrical current versus potential profile, and the charge per cycle was found to increase linearly with potential. More complex oscillatory behavior was observed under constant potential conditions. Periodic damped oscillations are observed in high concentrations of electrolyte whereas undamped sinusoidal oscillations are observed in relatively lower concentrations. In both cases, the anodization of InP results in porous InP formation, and the current in the oscillatory region corresponds to the cyclical effective area changes due to pitting dissolution of the InP surface with the coincidental growth of a thick porous In(2)O(3) film.     

Voltammetric studies of indigo adsorbed on pre-treated carbon paste electrodes

The adsorptive behaviour of indigo on the surface of pre-treated carbon paste electrodes (CPE) has been studied in various aqueous media at different pH, by cyclic (CV) and alternating current voltammetry (ACV). Cyclic voltammograms of this molecule are characterised by two main electrodic processes in the potential range from −0.7 V to +0.9 V (vs. Ag/AgCl/sat. KCl), which are reversible in the pH range of 3–11, these being irreversible when both are recorded at pH 1. The first one at pH 1 becomes purely reversible when the applied potential range is from −0.2 V to +0.2 V and constitutes the best analytical signal. Due to these electrodic features a significant increase in sensitivity was achieved when the signal was recorded by alternating current voltammetry. Indigo was quantified by CV and ACV, in 0.1 M HClO₄ pH 1 and 0.1 M Tris-HCl pH 7.2 solutions. Limits of detection in the sub-nanomolar range were achieved for a 5-min accumulation time by ACV. These data provides useful information about the suitability of this electrodic process as a detection scheme in the development of alkaline phosphatase (AP) based voltammetric affinity devices, in which indigo is generated by the enzymatic hydrolysis of the 3-indoxyl phosphate substrate.     

Preparation, Electrochemical Behavior and Electrocatalytic Activity of a Copper Hexacyanoferrate Modified Ceramic Carbon Electrode

A copper hexacyanoferrate modified ceramic carbon electrode （CuHCF/CCE） had been prepared by two-step sol-gel technique and characterized using electrochemical methods. The resulting modified electrode showed a pair of well-defined surface waves in the potential range of 0.40 to 1.0 V with the formal potential of 0.682 V （vs. SCE） in 0.050 mol·dm^-3 HOAc-NaOAc buffer containing 0.30 mol·dm^-3 KCl. The charge transfer coefficient （a） and charge transfer rate constant （ks） for the modified electrode were calculated. The electrocatalytic activity of this modified electrode to hydrazine was also investigated, and chronoamperometry was exploited to conveniently determine the diffusion coefficient （D） of hydrazine in solution and the catalytic rate constant （kcat）. Finally, hydrazine was determined with amperometry using the resulting modified electrode. The calibration plot for hydrazine determination was linear in 3.0 × 10^-6--7.5 × 10^-4 mol·dm^-3 with the detection limit of 8.0 × 10^-7 molodm^-3. This modified electrode had some advantages over the modified film electrodes constructed by the conventional methods, such as renewable surface, good long-term stability, excellent catalytic activity and short response time to hydrazine.     

A sensitive fluorescence turn-on assay of bleomycin and nuclease using WS2 nanosheet as an effective sensing platform

As an important antitumor drug, bleomycin (BLM) is widely used in the treatment of a variety of cancers. In addition, nucleases play a crucial role in DNA replication, recombination and repair which are associated with cancer development. Thus, the development of BLM and nuclease detection methods is of great significance in cancer therapy and related biological mechanism research. Here, a WS₂ nanosheet-based turn-on fluorescent sensing platform for simple, fast and sensitive detection of BLM and nuclease was reported. WS₂ nanosheet exhibits different affinity toward ssDNA with different length and excellent fluorescence quenching ability. A fluorescein (FAM)-labeled long ssDNA could be adsorbed on the surface of WS₂ nanosheet and the fluorescence was therefore quenched. In the presence of BLM·Fe(II) or S1 nuclease (a ssDNA-specific nuclease which was used as a model enzyme), an irreversible scission of long ssDNA was underwent through the BLM-induced oxidation cleavage or S1 nuclease-induced enzymatic hydrolysis. Short FAM-linked oligonucleotide fragments which could not be adsorbed on the nanosheet surface were then produced, resulting in a weak fluorescence quenching after mixing WS₂ nanosheets. Thus, the fluorescence signal was restored. The proposed sensor displays a wide linear range and a high sensitivity with a detection limit of 0.3 nM for BLM and 0.01 U mL⁻¹ for S1 nuclease. It also exhibits a good performance in complex biological samples. This method not only provides a strategy for BLM or S1 nuclease assay but also offers a potential application in biomedical and clinical study.     

Amperometric Biosensors for Glucose Based on Layer‐by‐Layer Assembled Functionalized Carbon Nanotube and Poly (Neutral Red) Multilayer Film

Abstract

Multiwalled carbon nanotubes (MWNTs) were treated with a mixture of concentrated sulfuric and nitric acid to introduce carboxylic acid groups to the nanotubes. Conducting polymer film was prepared by electrochemical polymerization of neutral red (NR). By using a layer‐by‐layer method, homogeneous and stable MWNTs and poly (neutral red) (PNR) multilayer films were alternately assembled on glassy carbon (GC) electrodes. With the introduction of PNR, the MWNTs/PNR multilayer film system showed synergy between the MWNTs and PNR, with a significant improvement of redox activity due to the excellent electron‐transfer ability of carbon nanotubes (CNTs) and PNR. The electropolymerization is advantageous, providing both prolonged long‐term stability and improved catalytic activity of the resulting modified electrodes. The MWNTs/PNR multilayer film modified glassy carbon electrode allows low potential detection of hydrogen peroxide with high sensitivity and fast response time. As compared to MWNTs and PNR‐modified GC electrodes, the magnitude of the amperometric response of the MWNTs/PNR composite‐modified GC electrode is more than three‐fold greater than that of the MWNTs modified GC electrode, and nine‐fold greater than that of the PNR‐modified GC electrode. With the immobilization of glucose oxidase onto the electrode surface using glutaric dialdehyde, a biosensor that responds sensitively to glucose has been constructed. In pH 6.98 phosphate buffer, nearly interference‐free determination of glucose has been realized at ?0.2 V vs. SCE with a linear range from 50 µM to 10 mM and response time <10s. The detection limit was 10 µM glucose (S/N=3).     

Electrochemical Oxidation and Detection of Morphine at Ordered Mesoporous Carbon Modified Glassy Carbon Electrodes

In this work, three ordered mesoporous carbons (OMCs) with different structural parameters were synthesized by a simple variation of the hydrothermal temperature of the silica templates (SBA‐15). X‐ray diffraction and nitrogen adsorption‐desorption results show these OMCs exhibit an ordered 2D hexagonal mesostructure with tunable pore diameter. OMC‐modified glassy carbon electrodes exhibit efficient electrocatalytic reactivity toward oxidation of morphine (MO). The amperometric detection of MO in pH 7.0 phosphate buffered saline at +0.39 V versus Ag/AgCl is the lowest potential reported to‐date. A linear range from 0.2 to 197.6 μM and a detection limit of 0.03 μM MO were obtained.