全固态酸度微电极组的设计与应用
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摘要
以木犀草素为pH特性敏感物,碳纤维为导电基质,固体石蜡为粘合剂制成了木犀草素碳纤维酸度微电极,将该电极与自制导电凝胶型全固态微型Ag/AgCl电极和铂丝微电极联用,构成全固态酸度微电极组。采用循环伏安法研究了该电极组对pH值为2. 00～10. 00的磷酸盐缓冲溶液有效酸度的响应,结果表明,循环伏安曲线上有一对可逆氧化还原峰,两峰的峰电势均随pH值呈线性变化,据此建立了方波伏安法测定溶液酸度的方法,氧化峰的峰电势(E_(pa))与pH的线性回归方程为:E_(pa)(V)=-0. 0567pH+0. 603(r=0. 999),体液中常见离子及蛋白质等不干扰测定。该电极组微型、无毒、抗干扰能力强,应用于微量体表唾液和汗液酸度的测定,取得了令人满意的结果,为微量体液的实时、在体、现场检测提供了技术基础。
A micro-luteolin carbon fiber acidity microelectrode( Lu/CFME) was made with luteolin as a pH sensitive substance,carbon fiber as conductive matrix and solid paraffin as a binder. An all solid state acidity microelectrode set was combinated by Lu/CFME as working electrode,a self-made conductive gel type all-solid micro Ag/AgCl as reference electrode and a platinum wire microelectrode as auxiliary electrode. The response of the electrode set to the effective acidity was studied in the solution of phosphate buffer solution at pH 2. 00 ～ 10. 00 by cyclic voltammetry. The results show that there is a pair of reversible redox peaks on the cyclic voltammetry curve. Their peak potentials( E_(pa)) were all linear with pH. Based on this,a method for determining the acidity of solution was established by square wave voltammetry,and the linear regression equation for peak potential of oxidation peak and pH is E_(pa)( V) =-0. 0567 pH + 0. 603( r = 0. 999). The electrode set is micro,non-toxic and anti-interference. It is applied to acidity measurement of trace saliva and sweat on the skin surface,and satisfactory results have been obtained. Therefore,this result provides a technical basis for real-time,in-vivo detection of body fluids.
A micro-luteolin carbon fiber acidity microelectrode( Lu/CFME) was made with luteolin as a pH sensitive substance,carbon fiber as conductive matrix and solid paraffin as a binder. An all solid state acidity microelectrode set was combinated by Lu/CFME as working electrode,a self-made conductive gel type all-solid micro Ag/AgCl as reference electrode and a platinum wire microelectrode as auxiliary electrode. The response of the electrode set to the effective acidity was studied in the solution of phosphate buffer solution at pH 2. 00 ～ 10. 00 by cyclic voltammetry. The results show that there is a pair of reversible redox peaks on the cyclic voltammetry curve. Their peak potentials( E_(pa)) were all linear with pH. Based on this,a method for determining the acidity of solution was established by square wave voltammetry,and the linear regression equation for peak potential of oxidation peak and pH is E_(pa)( V) =-0. 0567 pH + 0. 603( r = 0. 999). The electrode set is micro,non-toxic and anti-interference. It is applied to acidity measurement of trace saliva and sweat on the skin surface,and satisfactory results have been obtained. Therefore,this result provides a technical basis for real-time,in-vivo detection of body fluids.
引文
[1]Jawed M,Khan R N,Shahid S M,et al. Protective Effects of Salivary Factors in Dental Caries in Diabetic Patients of Pakistan[J]. J Diabetes Res,2012,(1):1-5.
[2]Pradhan D,Jain D,Gulati A,et al. Effect of the Presence of Dental Plaque on Oral Sugar Clearance and Salivary pH:An in vivo Study[J]. J Contemp Dent Pract,2012,13(6):753-755.
[3]WANG Shuangxi,ZHANG Hui. Analysis and Investigation of the Influence of Salivary pH and Personal Living Habits on Caries[J]. China Foreign Med Treat,2014,25:41-42(in Chinese).汪双喜,张辉.分析探讨唾液pH值及个人生活行为习惯对患龋的影响[J].中外医疗,2014,25:41-42.
[4]Schmid-Wendtner M H,Korting H C. The pH of the Skin Surface and Its Impact on the Barrier Function[J]. Skin Pharmacol Physiol,2006,19(6):296-302.
[5]MA Huijun,ZHU Wenyuan. Skin Surface pH and Its Measurement[J]. J Clin Dermatovenereol,2004,33(7):448-450(in Chinese).马慧军,朱文元.皮肤表面酸碱度及其测定方法[J].临床皮肤科杂志,2004,33(7):448-450.
[6]Mackiewiczwysocka M,Araszkiewicz A,Niedzwiedzki P,et al. Skin pH is Lower in Type 1 Diabetes Subjects and is Related to Glycemic Control of the Disease[J]. Diabetes Technol Ther,2015,17(1):16-20.
[7]MAN Maoqiang,XIN Shujun,Peter M E. Skin Surface pH and Its Clinical Implication[J]. Chinese J Dermatol,2007,21(8):503-505(in Chinese).蔄茂强,辛淑君,Peter M Elias.皮肤表面pH值及其临床意义[J].中国皮肤性病学杂志,2007,21(8):503-505.
[8]Liu C C,Bocchicchio D B,Overmyer P A,et al. A Palladium-Palladium Oxide Miniature pH Electrode[J]. Science,1980,207(4427):188-189.
[9]XU Xiaojuan,LIU Luchuan,YUAN Ruo,et al. Preparation of pH Microelectrode and Its Application in Plaque pH Measurement[J]. Stomatology,2006,26(4):290-292(in Chinese).徐小娟,刘鲁川,袁若,等.微型pH电极的制备及其在牙菌斑pH检测中的应用[J].口腔医学,2006,26(4):290-292.
[10]Zhang X J,Ogorevc B,Wang J. Solid-State pH Nanoelectrode Based on Polyaniline Thin Film Electrodeposited onto Ion-Beam Etched Carbon Fiber[J]. Anal Chim Acta,2002,452(1):1-10.
[11]Kurzweil P. Metal Oxides and Ion-Exchanging Surfaces as pH Sensors in Liquids:State-of-the-Art and Outlook[J].Sensors,2009,9(6):4955-4985.
[12]Manjakkal L,Cvejin K,Kulawik J,et al. Fabrication of Thick Film Sensitive Ru O2-Ti O2,and Ag/Ag Cl/KCl Reference Electrodes and Their Application for pH Measurements[J]. Sens Actuators B,2014,204:57-67.
[13]Manjakkal L,Djurdjic E,Cvejin K,et al. Electrochemical Impedance Spectroscopic Analysis of Ru O2,Based Thick Film pH Sensors[J]. Electrochim Acta,2015,168:246-255.
[14]Manjakkal L,Cvejin K,Bajac B,et al. Microstructural,Impedance Spectroscopic and Potentiometric Analysis of Ta2O5Electrochemical Thick Film pH Sensors[J]. Electroanalysis,2015,27(3):770-781.
[15]Manjakkal L,Cvejin K,Kulawik J,et al. Sensing Mechanism of Ru O2-Sn O2,Thick Film pH Sensors Studied by Potentiometric Method and Electrochemical Impedance Spectroscopy[J]. J Electroanal Chem,2015,759:82-90.
[16]Dai C,Chan C W I,Barrow W,et al. A Route to Unbuffered pH Monitoring:A Novel Electrochemical Approach[J].Electrochim Acta,2016,190:879-886.
[17]Braiek M,Barhoumi H,Maaref A,et al. Elaboration and Characterization of pH Sensor Based on Polypyrrole Nanowires[J]. Sens Lett,2011,9(6):2154-2157.
[18]ZHOU Shuang,GUO Yushi,YAN Yu,et al. Study on a High Acidity and Wide Range and All-Solid-State Acidity Electrochemical Sensor[J]. Chinese J Anal Chem,2018,46(1):81-87(in Chinese).周爽,郭煜石,颜宇,等.一种测定高酸度水溶液有效酸度的固态电化学传感器[J].分析化学,2018,46(1):81-87.
[19]Lin Y,Shi R,Wang X,et al. Luteolin,A Flavonoid with Potential for Cancer Prevention and Therapy[J]. Curr Cancer Drug Targets,2008,8(7):634-646.
[20]Jang S,Kelley K W,Johnson R W. Luteolin Reduces IL-6 Production in Microglia by Inhibiting JNK Phosphorylation and Activation of AP-1[J]. Proc Natl Acad Sci USA,2008,105(21):7534-7539.
[21]Liu A,Zhang S,Huang L,et al. Electrochemical Oxidation of Luteolin at a Glassy Carbon Electrode and Its Application in Pharmaceutical Analysis[J]. Chem Pharm Bull,2008,56(6):745-748.
[22]YIN Nana,LI Mingqian,DAI Xin,et al. Preparation and Property of Electrographic Gel Style All-State-Ag/Ag Cl Reference Electrode[J]. Chinese J Inorg Anal Chem,2018,8(3):60-65(in Chinese).尹娜娜,李明谦,代鑫,等.导电凝胶型Ag/Ag Cl参比电极的制备及性能[J].中国无机与分析化学,2018,8(3):60-65.
[23]Bard A J,Faulkner L R. Electrochemical Methods Fundamentals and Applications[M]. GU Linying,LV Mingxiang,SONG Shizhe,et al. Trans. 1nd Ed. Trans. Beijing:Chemical Industry Press,1986:232-233(in Chinese).巴德A J,福克纳L R.电化学方法原理和应用[M].谷林瑛,吕鸣祥,宋诗哲,等译.第1版.北京:化学工业出版社,1986:232-233.
[2]Pradhan D,Jain D,Gulati A,et al. Effect of the Presence of Dental Plaque on Oral Sugar Clearance and Salivary pH:An in vivo Study[J]. J Contemp Dent Pract,2012,13(6):753-755.
[3]WANG Shuangxi,ZHANG Hui. Analysis and Investigation of the Influence of Salivary pH and Personal Living Habits on Caries[J]. China Foreign Med Treat,2014,25:41-42(in Chinese).汪双喜,张辉.分析探讨唾液pH值及个人生活行为习惯对患龋的影响[J].中外医疗,2014,25:41-42.
[4]Schmid-Wendtner M H,Korting H C. The pH of the Skin Surface and Its Impact on the Barrier Function[J]. Skin Pharmacol Physiol,2006,19(6):296-302.
[5]MA Huijun,ZHU Wenyuan. Skin Surface pH and Its Measurement[J]. J Clin Dermatovenereol,2004,33(7):448-450(in Chinese).马慧军,朱文元.皮肤表面酸碱度及其测定方法[J].临床皮肤科杂志,2004,33(7):448-450.
[6]Mackiewiczwysocka M,Araszkiewicz A,Niedzwiedzki P,et al. Skin pH is Lower in Type 1 Diabetes Subjects and is Related to Glycemic Control of the Disease[J]. Diabetes Technol Ther,2015,17(1):16-20.
[7]MAN Maoqiang,XIN Shujun,Peter M E. Skin Surface pH and Its Clinical Implication[J]. Chinese J Dermatol,2007,21(8):503-505(in Chinese).蔄茂强,辛淑君,Peter M Elias.皮肤表面pH值及其临床意义[J].中国皮肤性病学杂志,2007,21(8):503-505.
[8]Liu C C,Bocchicchio D B,Overmyer P A,et al. A Palladium-Palladium Oxide Miniature pH Electrode[J]. Science,1980,207(4427):188-189.
[9]XU Xiaojuan,LIU Luchuan,YUAN Ruo,et al. Preparation of pH Microelectrode and Its Application in Plaque pH Measurement[J]. Stomatology,2006,26(4):290-292(in Chinese).徐小娟,刘鲁川,袁若,等.微型pH电极的制备及其在牙菌斑pH检测中的应用[J].口腔医学,2006,26(4):290-292.
[10]Zhang X J,Ogorevc B,Wang J. Solid-State pH Nanoelectrode Based on Polyaniline Thin Film Electrodeposited onto Ion-Beam Etched Carbon Fiber[J]. Anal Chim Acta,2002,452(1):1-10.
[11]Kurzweil P. Metal Oxides and Ion-Exchanging Surfaces as pH Sensors in Liquids:State-of-the-Art and Outlook[J].Sensors,2009,9(6):4955-4985.
[12]Manjakkal L,Cvejin K,Kulawik J,et al. Fabrication of Thick Film Sensitive Ru O2-Ti O2,and Ag/Ag Cl/KCl Reference Electrodes and Their Application for pH Measurements[J]. Sens Actuators B,2014,204:57-67.
[13]Manjakkal L,Djurdjic E,Cvejin K,et al. Electrochemical Impedance Spectroscopic Analysis of Ru O2,Based Thick Film pH Sensors[J]. Electrochim Acta,2015,168:246-255.
[14]Manjakkal L,Cvejin K,Bajac B,et al. Microstructural,Impedance Spectroscopic and Potentiometric Analysis of Ta2O5Electrochemical Thick Film pH Sensors[J]. Electroanalysis,2015,27(3):770-781.
[15]Manjakkal L,Cvejin K,Kulawik J,et al. Sensing Mechanism of Ru O2-Sn O2,Thick Film pH Sensors Studied by Potentiometric Method and Electrochemical Impedance Spectroscopy[J]. J Electroanal Chem,2015,759:82-90.
[16]Dai C,Chan C W I,Barrow W,et al. A Route to Unbuffered pH Monitoring:A Novel Electrochemical Approach[J].Electrochim Acta,2016,190:879-886.
[17]Braiek M,Barhoumi H,Maaref A,et al. Elaboration and Characterization of pH Sensor Based on Polypyrrole Nanowires[J]. Sens Lett,2011,9(6):2154-2157.
[18]ZHOU Shuang,GUO Yushi,YAN Yu,et al. Study on a High Acidity and Wide Range and All-Solid-State Acidity Electrochemical Sensor[J]. Chinese J Anal Chem,2018,46(1):81-87(in Chinese).周爽,郭煜石,颜宇,等.一种测定高酸度水溶液有效酸度的固态电化学传感器[J].分析化学,2018,46(1):81-87.
[19]Lin Y,Shi R,Wang X,et al. Luteolin,A Flavonoid with Potential for Cancer Prevention and Therapy[J]. Curr Cancer Drug Targets,2008,8(7):634-646.
[20]Jang S,Kelley K W,Johnson R W. Luteolin Reduces IL-6 Production in Microglia by Inhibiting JNK Phosphorylation and Activation of AP-1[J]. Proc Natl Acad Sci USA,2008,105(21):7534-7539.
[21]Liu A,Zhang S,Huang L,et al. Electrochemical Oxidation of Luteolin at a Glassy Carbon Electrode and Its Application in Pharmaceutical Analysis[J]. Chem Pharm Bull,2008,56(6):745-748.
[22]YIN Nana,LI Mingqian,DAI Xin,et al. Preparation and Property of Electrographic Gel Style All-State-Ag/Ag Cl Reference Electrode[J]. Chinese J Inorg Anal Chem,2018,8(3):60-65(in Chinese).尹娜娜,李明谦,代鑫,等.导电凝胶型Ag/Ag Cl参比电极的制备及性能[J].中国无机与分析化学,2018,8(3):60-65.
[23]Bard A J,Faulkner L R. Electrochemical Methods Fundamentals and Applications[M]. GU Linying,LV Mingxiang,SONG Shizhe,et al. Trans. 1nd Ed. Trans. Beijing:Chemical Industry Press,1986:232-233(in Chinese).巴德A J,福克纳L R.电化学方法原理和应用[M].谷林瑛,吕鸣祥,宋诗哲,等译.第1版.北京:化学工业出版社,1986:232-233.
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