血红蛋白修饰粉末微电极的电化学行为及其在NO检测中的应用

制备并研究了使用表面活性剂DDAB和血红蛋白(Hb)修饰的粉末微电极(DDAB Hb PME)的电化学行为.结果表明,Hb于该修饰电极表面的表观载量较之文献报道提高了近3个数量级.在DDAB Hb PME电极上,Hb的氧化/还原过程转移的质子数为1.NO能在DDAB Hb PME电极表面富集,利用DDAB Hb PME电极检测溶液中的NO,可以明显提高电极的输出性能,测量灵敏度为3.1mA/μmol·L-1cm2,明显大于文献报道值(0.001～0.02mA/μmol·L-1·cm2).相应的线性检测范围为9～100nmol·L-1,检测下限达到9nmol·L-1,并可完全消除溶液中共存的抗坏血酸和尿酸对检测的干扰.     

铜铂微粒修饰微电极测定一氧化氮

详细报道了金属铜，铂微粒微电极用于ＮＯ的检测，该修饰电极对ＮＯ具有催化氧化作用，当ＮＯ浓度在８．２×１０＾－８－４．５×１０＾－６ｍｏｌ／Ｌ内，浓度与峰电流呈线性关系，相关系数为０．９９７。     

Electrochemical Detection of Nitric Oxide on a SWCNT/RTIL Composite Gel Microelectrode

Single walled carbon nanotubes (SWCNT) and room temperature ionic liquid (RTIL) were used to make a gel microelectrode for studies of the oxidation of nitric oxide (NO). The Faraday response of the gel microelectrode was contributed from two components: an outside‐surface microdisk and a thin‐layer cell formed by inner porous electrode materials, and enhanced by the thin‐layer effect. An EC mechanism, electrochemical NO oxidation followed by a chemical oxidation, was proposed. The gel microelectrode with a Nafion coating eliminated interferences from nitrite and some biomolecules, improved stability, and had a linear response range from 100 nM to 100 μM.     

PVP/Pd/IrO_2/Nafion修饰微电极用于成纤维细胞中一氧化氮释放的研究

采用PVP/Pd/IrO_2/Nafion修饰电极对成纤维细胞中NO的释放情况进行了研究 。结果表明,在正常状态下,采用NO前体L-精氨酸和乙酰胆碱对成纤维细胞进行刺 激后没有NO的释放;当用脂多糖进行诱导后,则释放出高浓度的NO,加入L-精氨酸 和乙酰胆碱都促进了NO的合成,而L-NNA的加入则逆转了L-精氨酸和乙酰胆碱的作 用。     

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.     

用研磨电极研究Bi2O3的循环伏安行为

用研磨电极研究Bi2O3的循环伏安行为;微电极;氧化铋;循环伏安     

甲氨蝶呤与一氧化氮供体或一氧化氮合酶抑制剂组合物的合成

一氧化氮(nitric oxide,NO)在肿瘤病理生理过程中产生多方面的生化作用,诸如引起的某些核苷酸碱基的羟基化,参与免疫系统清除肿瘤细胞,促进肿瘤细胞凋亡和调节血管生成等．在此基础上,首次提出将NO供体(NO donor)或一氧化氮合酶(nitric oxide synthase,NOS)抑制剂分别连接到甲氨蝶呤(methotrexate,MTX,MTX本身就是NOS抑制剂)的α或γ位羧基上的设想,设计并合成出：(1)MTX-NO供体(3-羟甲基-4-苯基-1,2,5-噁二唑-2-氧化物,属于Furoxan衍生物,缩写为FU)：1a(MTX-α-FU),2a(MTX-γ-FU);(2)MTX-NOS抑制剂(L-N^ω-硝基精氨酸或L-N^ω-硝基精氨酸甲酯)：1b(MTX-α-L-N^ω-NO2-Arg),2b(MTX-γ-L-N^ω-NO2-Arg),1c(MTX-α-L-N^ω-NO2-Arg-OMe),2c(MTX-γ-L-N^ω-NO2-Arg-OMe)．在生物活性测试中,我们选择耐MTX细胞株K-562(慢性粒细胞性白血病急性病变细胞株),进行抗肿瘤活性测试,得到以下结果：(1)脂溶性差的MTX衍生物1b,2b抗肿瘤活性低于MTX,其它1a,2a;1c,2c均优于MTX;(2)连接有NO供体的MTX明显增强了MTX衍生物的抗肿瘤活性;(3)MTX中谷氨酸γ位组合物抗肿瘤活性均高于相应的α位异构体的活性．以上初步结果,将对进一步研究NO抗肿瘤作用以及新的抗肿瘤药物设计提供新的思路,对肿瘤临床化疗也有一定的参考价值．     

Recent Developments in Nitric Oxide Donors and Delivery for Antimicrobial and Anti-Biofilm Applications

The use of nitric oxide (NO) is emerging as a promising, novel approach for the treatment of antibiotic resistant bacteria and biofilm infections. Depending on the concentration, NO can induce biofilm dispersal, increase bacteria susceptibility to antibiotic treatment, and induce cell damage or cell death via the formation of reactive oxygen or reactive nitrogen species. The use of NO is, however, limited by its reactivity, which can affect NO delivery to its target site and result in off-target effects. To overcome these issues, and enable spatial or temporal control over NO release, various strategies for the design of NO-releasing materials, including the incorporation of photo-activable, charge-switchable, or bacteria-targeting groups, have been developed. Other strategies have focused on increased NO storage and delivery by encapsulation or conjugation of NO donors within a single polymeric framework. This review compiles recent developments in NO drugs and NO-releasing materials designed for applications in antimicrobial or anti-biofilm treatment and discusses limitations and variability in biological responses in response to the use of NO for bacterial eradiation.     

Performance of Amperometric Platinized‐Nafion Based Gas Phase Sensor for Determining Nitric Oxide (NO) Levels in Exhaled Human Nasal Breath

Nitric oxide (NO) levels in exhaled breath are a non‐invasive marker that can be used to diagnose various respiratory diseases and monitor a patient's response to given therapies. A portable and inexpensive device that can enable selective NO concentration measurements in exhaled breath samples is needed. Herein, the performance of an amperometric Pt‐Nafion‐based gas phase sensor for detection of NO in exhaled human nasal breath is examined. Enhanced selectivity over carbon monoxide and ammonia is achieved via an in‐line zinc oxide‐based filter. Exhaled nasal NO levels measured in 21 human samples with the sensor are shown to correlate well with those obtained using a chemiluminescence reference method (R²=0.9836).     

一氧化氮化学性质的研究进展

概括了由Louis J. Ignarro, Ferid Murad和Robert F. Furchgott三位诺贝尔奖获得者提出的一氧化氮作为血管内皮松弛因子(EDRF)的作用机制及生物学意义; 同时也总结了100多年来一氧化氮在化学本质的探讨方面做出的研究成就; 归纳了一氧化氮自由基在化学反应过程中的行为本质.     

一氧化氮荧光分子探针

一氧化氮（NO）在生物体中扮演重要的角色,对其选择性识别引起了人们极大的兴趣。本文综述了两类NO荧光分子探针的研究进展,即含金属离子的NO荧光分子探针：如Co(Ⅱ)、Fe(Ⅱ)、 Ru(Ⅱ)、Rh(Ⅱ)和Cu(Ⅱ)配合物作为荧光打开的NO分子探针;邻苯二胺类荧光分子探针：如2,3-二氨基萘（DAN）、二氨基荧光素衍生物（DAFs）、二氨基罗丹明衍生物（DARs）、硼二吡咯甲基衍生物（BODIPY）和三碳菁衍生物（DAC）等。     

The Catalytic Cycle of Oxidation of Iodide Ion in the Oxygen/Nitrous Acid/Nitric Oxide System and Its Potential for Analytical Applications

Abstract

The oxidation of iodide to iodine by nitrous acid in aqueous acidic medium takes place catalytically in the presence of dissolved oxygen and can be followed spectrophotometrically at 288 and 352 nm. An indirect molar absorptivity for nitrite on the basis of I₃ ^? formation can be as high as 8.5×10⁵ L mol^?1 cm^?1 at 288 nm. Analytical curves were established. The iodine released in the catalytic cycle can also be titrated with thiosulfate. The reaction is pseudo–second‐order in oxygen consumed, with t_1/2=15.7 min at 25°C. A rate determining step could be the NO · O₂ as the activated species. Measurements of the iodine formed at catalytic conditions was used to determine nitrite in meat extracts and NOx in car exhausts.     

Preparing of Iridium Oxide Film Modified Microelectrode as an Amperometric Detector in FIA for Determination of Epinephrine

Abstract

Iridium oxide film modified microelectrode with a tip diameter of 25 µm was constructed using anodically grown iridium oxide film. The iridium oxide film, which was formed at the tip of the iridium wire by cyclic voltammetry in dilute sulfuric acid, showed excellent catalytic activity towards the oxidation of epinephrine. The stability and electrochemical properties of iridium oxide film modified microelectrode along with catalytic oxidation of epinephrine was studied. An oxidation peak was observed at 0.28 V. The electron‐transfer number (n) was 2. The iridium oxide film modified microelectrode was used as a detector in flow injection system for determination of epinephrine. Under the optimized conditions, the calibration curve was linear in the concentration range of 1.0×10^?8 to 1.0×10^?5 mol/l for epinephrine, with a detection limit of 1.0×10^?9 mol/l. The iridium oxide film modified microelectrode was used for direct determination of the epinephrine in human serum samples. The flow injection analysis was precise detection method of epinephrine and time saving device.     

Nitric Oxide Photoreleasers with Fluorescent Reporting

Nitric oxide (NO) plays a multifaceted role in human physiology and pathophysiology, and its controlled delivery has great prospects in therapeutic applications. The light-activated uncaging of NO from NO caging compounds allows this free radical to be released with accurate control of site and dosage, which strictly determine its biological effects. Molecular constructs able to activate fluorescence concomitantly to NO release offer the important advantage of easy and real-time tracking of the amount of NO uncaged in a non-invasive fashion even in the cell environment. This contribution provides an overview of the advances in photoactivatable NO releasers bearing fluorescent reporting functionalities achieved in our and other laboratories, highlighting the rationale design and their potential therapeutic applications.     

Developing an Iridium Oxide Film Modified Microelectrode for Microscale Measurement of pH

Iridium oxide film modified microelectrode was fabricated by anodic oxidation method onto the tip of an etched iridium wire in diluted sulfuric acid solution by cyclic voltammetry. The iridium oxide film microelectrode exhibited very promising pH sensing performance, with an ideal Nernstian in the tested pH range of 0 to 14. This method for preparing microelectrode allowed accurately control of the deposited amount and the rate of the iridium oxide film growth. The electrodes demonstrated advantages of long lifetime, good selectivity and fast response with a relative time less than 0.2 s for pH changes in a large scale. The microelectrode was not interfered by a wide variety of inorganic ions and organic compounds. Furthermore, the electrodes were successfully applied to the measurement of pH in microscale of apples.     

Photoactivable Platforms for Nitric Oxide Delivery with Fluorescence Imaging

The multifaceted role nitric oxide (NO) plays in human physiology and pathophysiology has stimulated a massive interest on NO‐releasing compounds for therapeutic purposes. A main issue associated with use of NO donors is the precise spatiotemporal control of the NO release, as its effects are strictly site‐ and dose‐dependent. NO photochemical precursors permit surmounting this difficulty since triggering with light offers an exquisite control of location and timing of NO delivery. On the other hand, the combination of NO photodonors with fluorescent components remains an urgent need for image‐guided phototherapeutic treatments based on the use of NO. Fluorescence techniques permit not only an easy tracking of the photoprecursor in a biological environment but also the real‐time quantification of the NO photoreleased therein in a non‐invasive fashion. In this Focus Review we seek to provide an overview of recent advances in photoactivable platforms developed in our and other laboratories which combine the photoregulated release of NO with fluorescent functionalities. We shall focus attention on NO photoreleasing systems exhibiting 1) persistent fluorescence and 2) photoactivable fluorescence signals, highlighting their logical design and potential developments for phototheranostics.     

Standard Mixtures of Nitric Oxide

Abstract

Standard mixtures of nitric oxide may be prepared by converting NO₂ to NO in presence of a molybdenum catalyst. Quantitative conversion has been obtained in the concentration range 0–100 pnm at temperatures as low as 200°C.

It has been proved that this material is scarcely affected by poisoning when exposed to high levels of nitrogen oxides.     

一氧化氮在Nafion—钴席夫碱膜修饰电极上的电催化氧化及其测定

将一种杂环席夫碱N,N′－2,6－二乙酰吡啶缩双苯胺和Nafion修饰在铂电极上,然后与钴（Ⅱ）反应,得到Nafion－钴席夫碱膜修饰电极。实验结果表明,该修饰电极具有良好的机械、化学和电化学稳定性,对生物分子一氧化氮的电化学氧化有显著的催化作用。以1.5次微分线性扫描伏安法测定一氧化氮,当浓度在2.8×10     

Nafion修饰铂电极测定天然海水中一氧化氮

用Nafion修饰铂电极测定天然海水介质中的一氧化氮。确定了富集时间、电极修饰时间、修饰膜厚度等最佳实验条件,同时用线性扫描伏安法对海水中的NO进行测定,测得NO的浓度与其氧化峰电流之间有一定线性关系,线性范围1~77μmol/L,r=0.9916;检出限0.4μmol/L;相对标准偏差0.5%,探讨了Nafion对NO的富集机理,并用N-亚硝基-乙腈霉胺分解法(SNAP)对本方法进行了验证。