摘要
离子选择性电极测定离子的浓度(活度),一般可不经化学分离,设备简单,操作方便,适用于连续和自动分析,它已经广泛应用于化学研究、生物制药和工业生产监控方面。近年来电极载体的设计、合成以及开发离子选择电极的应用范围,是电分析化学和有机或有机金属化合物研究领域中的一个重要方向。本论文力求探索新型金属配合物的设计和合成,及其作为中性载体的离子选择性电极的基础研究,并将电极初步应用于环境中阴阳离子的检测。
本文研究内容如下:
1.甘氨酸Schiff碱三核铜(Ⅱ)配合物在硫氰酸根离子选择性电极的研究
研究了3-羧基水杨醛缩甘氨酸Schiff碱三核铜(Ⅱ)配合物[Cu(Ⅱ)-CGSBT]为中性载体的PVC膜阴离子电极,该电极对硫氰酸根离子(SCN~-)具有优良的电位响应特征并呈现出反Hofmeister序列行为,其选择性顺序为:SCN~-＞CIO_4~-＞I~-＞Sal~-＞NO_3~-＞NO_2~-＞F~-＞SO_4~-＞Br~-＞SO_3~-＞Cl~-。电极在pH5.0的磷酸盐缓冲溶液体系中对SCN~-在5.6×10~(-6)～1.0×10~(-1)mol/L浓度范围内呈现近能斯特响应,斜率为-56.3 mV/dec,检出限为2.0×10~(-6)mol/L。采用交流阻抗技术和红外光谱研究了阴离子与载体的作用机理。将电极应用于废水分析,其测定结果与液相色谱法测定结果基本一致。
2.钴(Ⅱ)三唑衍生物在碘离子选择性电极研究中的应用合成了2-氨基-5-巯基-1,2,4-三唑钴(Ⅱ)配合物[Co(Ⅱ)CMETR]。以该配合物作为中性载体制备的聚合膜电极对碘离子呈现出高选择性。研究了膜组成、pH值、离子添加剂、增塑剂对电极的影响。电极对碘离子在8.5×10~(-7)～1.0×10~(-1)mol/L浓度范围内呈现出近近能斯特响应,斜率为-56.6 mV/dec(25℃)。其检出限为5.1×10~(-7)mol/L。其pH应朋范围为2—8。采用交流阻抗研究了电极的响应机理,该电极应用于水中及药物中碘离子含量的测定。
3.有机纳米硅胶修饰的碳糊电极电位检测痕量铬(Ⅲ)
设计合成了以2-乙酰基吡啶纳米硅(APNSG)胶修饰的碳糊电极(CPE)用于对铬离子的检测。载体含量为7.5%时电极对铬离子在10×10~(-8)～1.0×10~(-3)mol/L浓度范围内呈现能斯特响应,斜率为19.8±0.21mV/dec(25℃),其检出限为8.0×10~(-9)mol/L,响应时间为55s。该电极有较长的寿命相对其它阳离子而言对铬离子呈现出良好的选择性。电极的pH应用范围为1.5—5.0。采用交流阻抗技术和紫外光谱研究了铬离子与载体的作用机理。该电极应用于食物中铬离子含量的测定。
The ion-selective electrode determine concentration of ions,it need not through chemical score.It is a kind of analytical method that can rapidly determine sample continuously with simple structure,simple handled,wide potentiometric response range and highly sensitive.It has been applied in many departments of industry and agriculture and science technology.In recent years,design,synthsis and application of highly selective and sensitive neutral carriers are main research subjects in the ion-selective electrode studies.It is one of the most important of the research area of the potentiometric methods of the electroanalysis and of the organic or organometallic chemistry.This thesis focuses on seeking design and synthsis of novel metallic complexes and its used as carriers in ion-selective electrode.The proposed electrode try to applied to direct determination for anions and cations in sample..
Part 1 Study on Thiocyanate Electrode Based on Glycine Schiff Base Trinuclear Copper(Ⅱ) Complex as Neutral Carriers
A new thiocyanate PVC membrane electrode based on 3-carboxysalicylidene glycine Schiff base trinuclear copper(Ⅱ) complex as neutral carrier is developed,which displays an anti-Hofmeister selectivity sequence:SCN~-＞ClO_4~-＞I~-＞Sal~-＞NO_3~-＞NO_2~-＞F~-＞SO_4~-＞Br~-＞SO_3~-＞Cl~-.The electrode exhibits Nernstian potential linear range to thiocyanate from 5.6×10~(-6) mol/L to 1.0×10~(-1) mol/L with a detection limit 2.0×10~(-6) mol/L and a slope of -56.3 mV/dec in phosphate buffer solusion(pH5.0) at 25℃.The response mechanism is discussed in view of the AC impedance and IR spectroscopic techniques.The electrode based on trinuclear copper(Ⅱ) compound was used to determine the thiocyanate content in waste water with satisfactory results.
Part 2 Potentiometric Iodide Selectivity of Polymer-Membrane Sensors Based on Co(Ⅱ) Triazole Derivative
The 2-amion-5-mercapto-1,2,4-triazole cobalt(Ⅱ)[Co(Ⅱ)AMETR]was used as a new carrier for preparing polymeric membrane selective sensor which exhibited high affinity for iodide ion.The effects of membrane composition,pH,the influence of lipophilic ion additives and plasticizer on the response characteristics of the sensor were investigated.The sensor showed a near Nernstian slope of -56.6 mV/decade for I~- ion over a wide concentration range from 8.5×10~(-7) to 1.0×10~(-1) mol/L with a low detection limit of 5.1×10~(-7) mol/L The sensor has a fast response time and could be used over a wide pH range of 2-8.The response mechanism is discussed in view of the A.C impedance technique.The sensor was successfully applied to direct determination of iodide content in environmental water samples and mouth wash samples.
Part 3 Potentiometric detection of trace Cr(Ⅲ) at a carbon paste electrode based on organically nanoporous silica gel
A novel carbon paste electrode(CPE) has been constructed with 2-acetylpyridine modified nanoporous silica gel(APNSG) acting as both the paste binder and a reactive material facilitating the electrocatalytic detection of chromium(Ⅲ).The electrode with APNSG proportions of 7.5%(W/W) exhibits linear response to Cr(Ⅲ) over a wide concentration range 1.0×10~(-8) to 1.0×10~(-3) mol/L with Nemstian slope of 19.8 mV/decade. The detection limit of this electrode is 8.0×10~(-9) mol/L.The electrode present a response time of～55s,relatively long life time,high sensitivity toward Cr~(3+) ion in comparison to other common cations.The potentiometric response are independent of the pH of the test solution in the pH range 1.5-5.0 for CPE.The response mechanism is discussed in view of the A.C.impedance technique.The proposed electrode was successfully applied to direct determination in food samples.
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