A Novel Amperometric Nitric Oxide Sensor Based on Polythionine / Nation Modified Glassy Carbon Electrode

A novel amperometric sensor for the determination of nitric oxide was developed by coating polythionine / nafion on a glassy carbon electrode. This sensor exhibited a great enhancement to the oxidation of nitric oxide. The oxidation peak currents were linear to the concentration of nitric oxide over the wide range from 3.6×10-7 to 6.8×10-5 mol.L-1, and the detection limit was 7.2×10-8 mol.L-1. Experimental results showed that this nitric oxide sensor possessed excellent selectivity and longer stability. NO releasing from rat kidney was monitored by this sensor.     

A New Nitric Oxide Gas Sensor Based on Reticulated Vitreous Carbon/Nafion and Its Applications

Reticulated vitreous carbon (RVC), and Nafion membrane are used to fabricate a composition electrode to measure nitric oxide (NO) concentration amperometrically in the gas phase. Limit of detection was found to be 6 ppb at an applied voltage of 0.66 V (vs. mercury sulfate reference electrode) with average response time of less than 30 seconds. The response of the sensor was linearly dependent on the concentration over the whole tested range from 19 ppb‐50 ppm of NO. Simplicity in electrode fabrication and consistent performance between individual sensors make RVC and Nafion attractive materials for detecting very low levels of nitric oxide gas in routine analysis.     

Graphene‐Nafion Composite Film Modified Electrode for Voltammetric Sensor for Determination of Dihydromyricetin

A simple but highly snesitive electrochemical sensor for the determination of dihydromyricetin (DMY) based on graphene‐Nafion nanocomposite film modified Glassy carbon electrode (GCE) was reported. The characteristic of the sensor was examined by scanning electron microscopic (SEM) and electrochemical impedance spectroscopy (EIS). Compares with bare GCE, pre‐anodized glassy carbon electrode (GCE(ox)) and Nafion modified electrode, the sensor exhibited the more superior ability of detecting DMY, due to the synergetic graphene and Nafion. Other, the dependence of the current on pH, instrumental parameters, accumulation time and potential were investigated to optimize the experimental conditions in the determination of DMY. Under the selected conditions, the response peak currents were linear relationship with the DMY concentrations in the range of 8.0 × 10^?8 ～ 2.0 × 10^?5 mol L^?1 with a detection limit of 2.0 × 10^?8 mol L^?1. And, the method was also applied successfully to detect DMY in Ampelopsis grossedentata samples.     

Myoglobin‐Clay Electrode for Nitric Oxide (NO) Detection in Solution

Sodium montmorillonite was prepared via a colloidal chemical approach and deposited onto glassy carbon electrodes (GCE). Myoglobin was immobilized on the clay membrane modified electrode by spontaneous adsorption. Characterization of the myoglobin/clay/glassy carbon electrode (Mb/clay/GCE) showed a quasi‐reversible, electrochemical redox behavior of the adsorbed protein with a formal potential of ?0.380±0.010 V (vs. Ag/AgCl). The heterogeneous electron transfer rate constant was found to be strongly influenced by the buffer concentration. The Mb/clay/GCE was stable for several days in solution. The interaction of the immobilized Mb with nitric oxide (NO) is characterized by coordination chemistry. The reaction was found to be reversible and could be applied for NO detection in the nanomolar concentration range by a voltammetric analysis. In addition a mixed protein electrode with co‐immmobilized myoglobin (Mb) and cytochrome c (Cyt.c) was developed. By choice of the electrode potential both proteins can be addressed independently.     

一氧化氮响应性高分子荧光探针的构筑及其细胞内成像应用

一氧化氮(NO)是一种普遍存在的生理信号分子,但利用NO作为触发方法来精细调节仿生聚合物的自组装行为的研究却很少.本工作报道一种独特的具有一氧化氮(NO)反应特性的新型pH响应双亲水性嵌段共聚物(doublehydrophilicblockcopolymer,DHBC),其中NO可以自发地触发聚(寡聚乙二醇甲醚甲基丙烯酸酯)-嵌段-聚(NO响应性基元-共-7-硝基苯并呋咱衍生物)(POEGMA-b-P(APUEMA-co-NBD))双亲水嵌段共聚物,分别在酸性和中性环境中发生自组装和形态转变.在引入荧光团之后,这些转变还可以和NO存在下光致诱导电子转移过程被阻断导致荧光增强相关联,从而提供了观察细胞内NO的机会.     

The Nitric Oxide (NO) Donor Sodium Nitroprusside (SNP) and Its Potential for the Schizophrenia Therapy: Lights and Shadows

Schizophrenia is a severe psychiatric disorder affecting up to 1% of the worldwide population. Available therapy presents different limits comprising lack of efficiency in attenuating negative symptoms and cognitive deficits, typical features of schizophrenia and severe side effects. There is pressing requirement, therefore, to develop novel neuroleptics with higher efficacy and safety. Nitric oxide (NO), an intra- and inter-cellular messenger in the brain, appears to be implicated in the pathogenesis of schizophrenia. In particular, underproduction of this gaseous molecule is associated to this mental disease. The latter suggests that increment of nitrergic activity might be of utility for the medication of schizophrenia. Based on the above, molecules able to enhance NO production, as are NO donors, might represent a class of compounds candidates. Sodium nitroprusside (SNP) is a NO donor and is proposed as a promising novel compound for the treatment of schizophrenia. In the present review, we intended to critically assess advances in research of SNP for the therapy of schizophrenia and discuss its potential superiority over currently used neuroleptics.     

纳米金-卟啉复合传感阵列快速识别肺癌患者呼气中的有机小分子

合成了小粒径纳米金作为卟啉保护剂,以纳米金-卟啉化合物和p H指示剂共同构建6×6传感阵列,将其用于可视化检测12种肺癌患者呼出气体中的有机小分子(OSMs),设置了3个浓度梯度且每个样品重复5次.实验结果显示,纳米金的引入可显著提高阵列的稳定性和灵敏度;聚类分析结果表明,5次平行实验的结果优先聚为一簇,结构相似的目标物随后聚在一起;差谱图显示该方法对不同种类、不同浓度的OSMs具有良好的定性及半定量分析能力.该方法可快速识别OSMs且具有肺癌筛查的潜在应用前景.     

Ni(II)cyclam Catalyzed Reduction of CO2 – Towards a Voltammetric Sensor for the Gas Phase

The detection of CO₂ in the gas phase is possible in presence of oxygen with an amalgamated Au‐poly(tetrafluoroethylene) gas diffusion electrode and an internal electrolyte solution containing Ni(II)cyclam. For concentrations between 0.1 to 1% the electrochemical cell has a sensitivity of 3.58 mA %^?1 and the detection limit is 500 ppm. In preliminary experiments at rotating disk electrodes the optimum pH‐range was found to be between 3.5 to 6 and a selectivity ratio of the catalyst for CO₂/H⁺ of 5 : 1 could be determined. The relationship between reduction current and the square root of the angular speed is linear, indicating that the electrochemical process is limited by diffusion of CO₂. Tl and Pb are presented as alternative electrode materials at which the Ni(II)cyclam catalyzed reduction of CO₂ can be observed. Problems arise from fouling effects at the sensing electrode and a non‐linearity of the calibration plot at higher concentrations.     

A Novel Electrogenerated Chemiluminescence (ECL) Sensor Based on Ru(bpy)32+‐Doped Titania Nanoparticles Dispersed in Nafion on Glassy Carbon Electrode

A novel electrogenerated chemiluminescence (ECL) sensor based on Ru(bpy)₃²⁺‐doped titania (RuDT) nanoparticles dispersed in a perfluorosulfonated ionomer (Nafion) on a glassy carbon electrode (GCE) was developed in this paper. The electroactive component‐Ru(bpy)₃²⁺ was entrapped within the titania nanoparticles by the inverse microemulsion polymerization process that produced spherical sensors in the size region of 38±3 nm. The RuDT nanoparticles were characterized by electrochemical, transmission electron and scanning microscopy technology. The Ru(bpy)₃²⁺ encapsulation interior of the titania nanoparticles maintains its ECL efficiency and also reduces Ru(bpy)₃²⁺ leaching from the titania matrix when immersed in water due to the electrostatic interaction. This is the first attempt to prepare the RuDT nanoparticles and extend the application of electroactive component‐doped nanoparticles into the field of ECL. Since a large amount of Ru(bpy)₃²⁺ was immobilized three‐dimensionally on the electrode, the Ru(bpy)₃²⁺ ECL signal could be enhanced greatly, which finally resulted in the increased sensitivity. The ECL analytical performance of this ECL sensor for tripropylamine (TPA) was investigated in detail. This sensor shows a detection limit of 1 nmol/L for TPA. Furthermore, the present ECL sensor displays outstanding long‐term stability.     

Nickel Hexacyanoferrate‐Based Sensor Electrode for the Detection of Nitric Oxide at Low Potentials

Recently transition metal hexacyanoferrates, analogues of Prussian Blue, have found application in electroanalysis for the detection of biologically relevant species. Our study describes the development of a novel electrode based on nickel hexacyanoferrate (NiHCF) for the sensorial NO determination. A NiHCF layer was deposited on platinum by cyclic voltammetry in a solution of nickel (II) chloride and potassium hexacyanoferrate (III). The electrode was found to be active for NO reduction. The interaction with the radical was studied voltammetrically within the range from 0 V up to +0.4 V vs. Ag/AgCl/1 M KCl. The most appropriate potential for an amperometric detection was determined to be +0.25 V due to the advantageous signal/noise ratio. The sensitivity of the electrodes was found to be 2.0–2.3 A M^?1 cm^?2. The sensor response of the most important interferents for NO analysis, hydrogen peroxide, ascorbic acid and nitrite, was measured and determined to be sufficiently low.     

Titanium Dioxide-Yttrium(III)-Oxide Composite Based Cataluminescence Gas Sensor for Fast Detection of Propylene Oxide

By using nano TiO₂-Y₂O₃ as catalyst, cataluminescence (CTL) phenomenon of propylene oxide (PO) was studied, and it was found that the sensor has high sensitivity and good selectivity for the detection of propylene oxide. The common volatile organic compounds (VOCs) such as acetone, acetaldehyde and benzene show no response to the catalysis of TiO₂-Y₂O₃. Based on this phenomenon, a propylene oxide CTL sensor was designed. The ratio of TiO₂ and Y₂O₃ and the annealed temperatures of the composites were optimized. It was found that when the mass ratio of TiO₂ and Y₂O₃ was 1:3 and the annealed temperature was 500 °C, the catalytic materials showed the best performance. 0.3 L min^?1 of carrier gas flow rate, 490 nm of detection wavelength and 197 °C of working temperature were selected as the optimal working conditions, and under the optimized conditions, the quantitative analysis was performed and CTL intensity was linearly correlated with PO concentration from 4.5 mg L^–1 to 1375 mg L^–1 with a detection limit (3σ) of 1.25 mg L^–1. The sensor was used for quantitative analysis and real-time monitoring of propylene oxide residues in fumigation cereals. The result was consistent with that analyzed by gas chromatography. The CTL sensor proposed here had many merits such as high sensitivity, rapidity and simple operation and had potential application prospects in the rapid detection of propylene oxide in food. At last, the mechanism of catalytic oxidation of PO was discussed as well.     

Sensor System Based on Acetylcholinesterase in Homogenous Phase for Analysis of Paraoxon

Abstract

An amperometric sensor system based on acetylcholinesterase (AChE) was used for a paraoxon assay. Paraoxon-inhibited AChE resulted in the decrease of acetylthiocholine hydrolysis and the further oxidation of thiocholine on a platinum electrode. Thus described, the system allows for the detection of 1.2 ppb of paraoxon responding to absolute 12 pg. The sensor system functionality was verified on spiked beverages. The practical impact of system was summarized and future implementation is expected.     

Synthesis and Properties of a pH‐Insensitive Fluorescent Nitric Oxide Cheletropic Trap (FNOCT)

The synthesis and properties of the new fluorescent nitric oxide cheletropic trap (FNOCT) 14 , designed for the trapping and quantification of nitric oxide (NO) production in chemical and biological systems, is described (Scheme 3). The dicarboxylic acid 14 and the corresponding bis[(acetyloxy)methyl] ester derivative 15 of the FNOCT contain a 2‐methoxy‐substituted phenanthrene group as fluorophoric unit. The fluorescence of the reduced NO adduct of this FNOCT (λ_exc 320 nm, λ_em 380 nm) is pH‐independent. Trapping experiments were carried out in aqueous buffer solution at pH 7.4 with nitric oxide being added as a bolus as well as being released from the NO donor compound MAHMA NONOate (= (1Z)‐1‐{methyl[6‐(methylammonio)hexyl]amino}diazen‐1‐ium‐1,2‐diolate), indicating a trapping efficiency of ca. 50%. In a biological application, nitric oxide was scavenged from a culture of lipopolysaccharide‐stimulated rat alveolar macrophages. Under the applied conditions, a production of 11.1 ± 1.5 nmol of NO per hour and per 10⁵ cells was estimated.     

A Novel Enzymatic Glucose Biosensor and Nonenzymatic Hydrogen Peroxide Sensor Based on (3‐Aminopropyl) Triethoxysilane Functionalized Reduced Graphene Oxide

In the present study, a novel enzymatic glucose biosensor using glucose oxidase (GOx) immobilized into (3‐aminopropyl) triethoxysilane (APTES) functionalized reduced graphene oxide (rGO‐APTES) and hydrogen peroxide sensor based on rGO‐APTES modified glassy carbon (GC) electrode were fabricated. Nafion (Nf) was used as a protective membrane. For the characterization of the composites, Fourier transform infrared spectroscopy (FTIR), X‐ray powder diffractometer (XRD), and transmission electron microscopy (TEM) were used. The electrochemical properties of the modified electrodes were investigated using electrochemical impedance spectroscopy, cyclic voltammetry, and amperometry. The resulting Nf/rGO‐APTES/GOx/GC and Nf/rGO‐APTES/GC composites showed good electrocatalytical activity toward glucose and H₂O₂, respectively. The Nf/rGO‐APTES/GC electrode exhibited a linear range of H₂O₂ concentration from 0.05 to 15.25 mM with a detection limit (LOD) of 0.017 mM and sensitivity of 124.87 μA mM⁻¹ cm⁻². The Nf/rGO‐APTES/GOx/GC electrode showed a linear range of glucose from 0.02 to 4.340 mM with a LOD of 9 μM and sensitivity of 75.26 μA mM⁻¹ cm⁻². Also, the sensor and biosensor had notable selectivity, repeatability, reproducibility, and storage stability.     

Microfluidic Device Using a Gold Pillar Array and Integrated Electrodes for On‐chip Endothelial Cell Immobilization,Direct RBC Contact,and Amperometric Detection of Nitric Oxide

We describe a microfluidic device that can be used to detect interactions between red blood cells (RBCs) and endothelial cells using a gold pillar array (created by electrodeposition) and an integrated detection electrode. Endothelial cells can release nitric oxide (NO) via stimulation by RBC‐derived ATP. These studies incorporate on‐chip endothelial cell immobilization, direct RBC contact, and detection of NO in a single microfluidic device. In order to study the RBC‐EC interactions, this work used a microfluidic device made of a PDMS chip with two adjacent channels and a polystyrene base with embedded electrodes for creating a membrane (via gold pillars) and detecting NO (at a glassy carbon electrode coated with platinum‐black and Nafion). RBCs were pharmacologically treated with treprostinil in the absence and presence of glybenclamide, and ATP release was determined as was the resultant NO release from endothelial cells. Treprostinil treatment of RBCs resulted in ATP release that stimulated endothelial cells to release on average 1.8±0.2 nM NO per endothelial cell (average±SEM, n=8). Pretreatment of RBCs with glybenclamide inhibited treprostinil‐induced ATP release and, therefore, less NO was produced by the endothelial cells (0.92±0.1 nM NO per endothelial cell, n=7). In the future, this device can be used to study interactions between many other cell types (both adherent and non‐adherent cell lines) and incorporate other detection schemes.     

Calix[4]arene‐Based Bis(Nitric Oxide) Complexes: Synthesis,Physical Properties,and Structural Characterization

Calix[4]arene‐based molecules hold great promise as candidate sensors and storage materials for nitric oxide (NO), owing to their unprecedented binding affinity for NO. However, the structure of calix[4]arene is complicated by the availability of four possible conformers: 1,3‐alternate, 1,2‐alternate, cone, and partial cone (paco). Whilst complexes of NO with several of these conformers have previously been established, the 1,2‐alternate conformer complex, that is, [1,2‐alter ? NO]⁺, has not been previously reported. Herein, we determine the crystal structure of the NO complex with the 1,2‐alternate conformer for the first time. In addition, we have also found that the 1,2‐alternate and 1,3‐alternate conformers can combine with two NO molecules to form stable bis(nitric oxide) complexes. These new complexes, which exhibit remarkable binding capacity for the construction of NO‐storage molecules, were characterized by using X‐ray crystallography and NMR, IR, and UV/Vis spectroscopy. These findings will extend our understanding of the interactions between nitric oxide and cofacially and non‐cofacially arrayed aromatic rings, and we expect them to aid in the design and development of new supramolecular sensors and storage materials for NO with high capacity and efficacy.     

The Relationship of Glutathione-S-Transferase and Multi-Drug Resistance-Related Protein 1 in Nitric Oxide (NO) Transport and Storage

Nitric oxide is a diatomic gas that has traditionally been viewed, particularly in the context of chemical fields, as a toxic, pungent gas that is the product of ammonia oxidation. However, nitric oxide has been associated with many biological roles including cell signaling, macrophage cytotoxicity, and vasodilation. More recently, a model for nitric oxide trafficking has been proposed where nitric oxide is regulated in the form of dinitrosyl-dithiol-iron-complexes, which are much less toxic and have a significantly greater half-life than free nitric oxide. Our laboratory has previously examined this hypothesis in tumor cells and has demonstrated that dinitrosyl-dithiol-iron-complexes are transported and stored by multi-drug resistance-related protein 1 and glutathione-S-transferase P1. A crystal structure of a dinitrosyl-dithiol-iron complex with glutathione-S-transferase P1 has been solved that demonstrates that a tyrosine residue in glutathione-S-transferase P1 is responsible for binding dinitrosyl-dithiol-iron-complexes. Considering the roles of nitric oxide in vasodilation and many other processes, a physiological model of nitric oxide transport and storage would be valuable in understanding nitric oxide physiology and pathophysiology.     

Development of a Ruthenium(II) Complex Based Luminescent Probe for Imaging Nitric Oxide Production in Living Cells

A unique ruthenium(II) complex, bis(2,2′‐bipyridine)(4‐(3,4‐diaminophenoxy)‐2,2′‐bipyridine)ruthenium(II) hexafluorophosphate ([(Ru(bpy)₂(dabpy)][PF₆]₂), has been designed and synthesized as a highly sensitive and selective luminescence probe for the imaging of nitric oxide (NO) production in living cells. The complex can specifically react with NO in aqueous buffers under aerobic conditions to yield its triazole derivative with a high reaction rate constant at the 10¹⁰ M ^?1 s^?1 level; this reaction is accompanied by a remarkable increase of the luminescence quantum yield from 0.13 to 2.2 %. Compared with organic probes, the new Ru^II complex probe shows the advantages of a large Stokes shift (>150 nm), water solubility, and a wide pH‐availability range (pH independent at pH>5). In addition, it was found that the new probe could be easily transferred into both living animal cells and plant cells by the coincubation method, whereas the triazole derivative was cell‐membrane impermeable. The probe was successfully used for luminescence‐imaging detection of the exogenous NO in mouse macrophage cells and endogenous NO in gardenia cells. The results demonstrated the efficacy and advantages of the new probe for NO detection in living cells.