钨基纳米材料修饰碳糊电极的应用研究
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摘要
作为过渡金属的化合物，纳米WO_3具有可逆电致变色和良好的催化性能,还对NO_x、O_3、O_2、H_2S、NH3等多种气体有敏感性，在医药行业和过程控制、环境监测等领域可得到广泛的应用，但作为电极材料却研究甚少。本论文是利用溶剂热法以WCl6为主要原料在180℃持续16小时条件下得到钨基纳米电极材料，然后用其制作碳糊电极，主要研究了以下几个方面：
1．利用溶剂热法制备了WO_3纳米线，将其作为修饰剂制作出修饰碳糊电极。实验中，采用循环伏安法、脉冲差分法等对纳米WO_3修饰电极电化性能进行了研究，找出了测定丁香酚的最优测试条件，建立了线性范围方程，并对电极的重现性和回收率做了评估。
2．在WO_3制备过程中加入一定量的MnCl2，得到纳米MnWO_4，并成功制作了纳米MnWO_4修饰碳糊电极。实验表明，与纯WO_3修饰电极相比，MnWO_4修饰电极在测定丁香酚时富集时间缩短至60s，检测线性范围移向低浓度区，检测限低至8×10-9mol/L，线性效果较好，电极具有良好的重现性，并做了回收率评估。
3．在WO_3纳米线修饰的碳糊电极上，采用循环伏安法、脉冲差分法等对和厚朴酚的测定进行了研究，找出了WO_3最佳配比和最优的测试条件，建立了测定和厚朴酚浓度的线性范围方程，电极表现出良好重现性。同时，将该方法成功应用于测定厚朴中和厚朴酚，测定结果与高效液相色谱法（HPLC）相比较，相对偏差低于5%，回收率在96.5%~98.8%，数据一致性好。
本论文有助于人们把纳米WO_3新型材料作为测试电极来研究药物中主要活性成份的测定，建立一种简单、快速、准确的检测方法，为准确掌握药物中有效成份剂量的控制在临床医学实践中得到更好的利用提供参考。
As a chemical compound of transient metals, nano-WO_3not only has thecharacteristics of reversible electrochromism and catalytic properties, but also hasacute sensitivity to such gases as NO_x, O_3, O_2, H_2S, NH3, which can be widelyapplied to pharmaceutical industry, process control, environmental monitoring, etc.But little attention has been paid to its use as a kind of electrode material. The presentthesis conducts a series of research on the use of tungsten based material modifiedcarbon paste electrode, which is generated from WCl6as the main raw material byusing solvothermal method, lasting for16hours at the temperature of180℃. Themain aspects are as follows:
1. WO_3nanowire, synthesized using a simple hydrothermal technique, was usedto modify the carbon paste electrode (CPE). Determination of eugenol wasinvestigated under the methods of cyclic voltammetry and differentiation pulsevoltammetry. Therefore, optimal conditions have been discovered, on the basis ofwhich the linear equation for the determination of eugenol content has beenestablished and evaluation has been made on the reproducibility and recovery rate ofthe electrode.
2. Nano-MnWO_4was obtained by mixing a certain amount of MnCl2in thepreparation process of WO_3. Nano-MnWO_4was successfully modified the carbonpaste electrode.It shows that nano-MnWO_4modified carbon paste electrode canimprove the electrochemical properties of pure WO_3modified carbon paste electrode,the accumulation time of the determination of eugenol reduced to60seconds. It isalso displayed that the linear range moves towards the area of lower concentration andeven as low as8×10-9mol/L, which brings better linearity and reproducibility.Assessment recovery is also carried out.
3. The determination of honokiol is carried out under the methods of cyclicvoltammetry and pulse differentiation. WO_3nanowire is used to modify carbon pasteelectrode, the best ratio and optimal test conditions of which is discovered. Linearrange equation has been established to determine the density of honokiol and good reproducibility of electrode has been observed. Meanwhile, the same methods aresuccessfully applied to the determination of Magnolol and honokiol, the result ofwhich is consistent with the result of HPLC, relative deviation lower than5%and therecovery rate from96.5%to98.8%.
The thesis can contribute to the determination and study of the main activeingredients of medicine by using nano-WO_3as a new kind of testing electrode. Suchtesting method is simple, rapid and accurate, which can provide accurate reference tothe drug dose control of active ingredients so that it can be better used in clinicalpractice.
1．利用溶剂热法制备了WO_3纳米线，将其作为修饰剂制作出修饰碳糊电极。实验中，采用循环伏安法、脉冲差分法等对纳米WO_3修饰电极电化性能进行了研究，找出了测定丁香酚的最优测试条件，建立了线性范围方程，并对电极的重现性和回收率做了评估。
2．在WO_3制备过程中加入一定量的MnCl2，得到纳米MnWO_4，并成功制作了纳米MnWO_4修饰碳糊电极。实验表明，与纯WO_3修饰电极相比，MnWO_4修饰电极在测定丁香酚时富集时间缩短至60s，检测线性范围移向低浓度区，检测限低至8×10-9mol/L，线性效果较好，电极具有良好的重现性，并做了回收率评估。
3．在WO_3纳米线修饰的碳糊电极上，采用循环伏安法、脉冲差分法等对和厚朴酚的测定进行了研究，找出了WO_3最佳配比和最优的测试条件，建立了测定和厚朴酚浓度的线性范围方程，电极表现出良好重现性。同时，将该方法成功应用于测定厚朴中和厚朴酚，测定结果与高效液相色谱法（HPLC）相比较，相对偏差低于5%，回收率在96.5%~98.8%，数据一致性好。
本论文有助于人们把纳米WO_3新型材料作为测试电极来研究药物中主要活性成份的测定，建立一种简单、快速、准确的检测方法，为准确掌握药物中有效成份剂量的控制在临床医学实践中得到更好的利用提供参考。
As a chemical compound of transient metals, nano-WO_3not only has thecharacteristics of reversible electrochromism and catalytic properties, but also hasacute sensitivity to such gases as NO_x, O_3, O_2, H_2S, NH3, which can be widelyapplied to pharmaceutical industry, process control, environmental monitoring, etc.But little attention has been paid to its use as a kind of electrode material. The presentthesis conducts a series of research on the use of tungsten based material modifiedcarbon paste electrode, which is generated from WCl6as the main raw material byusing solvothermal method, lasting for16hours at the temperature of180℃. Themain aspects are as follows:
1. WO_3nanowire, synthesized using a simple hydrothermal technique, was usedto modify the carbon paste electrode (CPE). Determination of eugenol wasinvestigated under the methods of cyclic voltammetry and differentiation pulsevoltammetry. Therefore, optimal conditions have been discovered, on the basis ofwhich the linear equation for the determination of eugenol content has beenestablished and evaluation has been made on the reproducibility and recovery rate ofthe electrode.
2. Nano-MnWO_4was obtained by mixing a certain amount of MnCl2in thepreparation process of WO_3. Nano-MnWO_4was successfully modified the carbonpaste electrode.It shows that nano-MnWO_4modified carbon paste electrode canimprove the electrochemical properties of pure WO_3modified carbon paste electrode,the accumulation time of the determination of eugenol reduced to60seconds. It isalso displayed that the linear range moves towards the area of lower concentration andeven as low as8×10-9mol/L, which brings better linearity and reproducibility.Assessment recovery is also carried out.
3. The determination of honokiol is carried out under the methods of cyclicvoltammetry and pulse differentiation. WO_3nanowire is used to modify carbon pasteelectrode, the best ratio and optimal test conditions of which is discovered. Linearrange equation has been established to determine the density of honokiol and good reproducibility of electrode has been observed. Meanwhile, the same methods aresuccessfully applied to the determination of Magnolol and honokiol, the result ofwhich is consistent with the result of HPLC, relative deviation lower than5%and therecovery rate from96.5%to98.8%.
The thesis can contribute to the determination and study of the main activeingredients of medicine by using nano-WO_3as a new kind of testing electrode. Suchtesting method is simple, rapid and accurate, which can provide accurate reference tothe drug dose control of active ingredients so that it can be better used in clinicalpractice.
引文
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