化学振荡反应在药物分析中的应用
|
摘要
近年来非线性热力学和化学振荡现象已成为许多科技工作者研究的热点问题。化学振荡反应具有特别的宏观现象及特殊的机理，因此成为分析化学进行微量检测的有效工具。本文利用化学振荡反应首次建立了巴比妥酸、茚三酮、海洛因的动力学检测方法，结果满意。论文由四部分组成。
第一部分：化学振荡反应在药物分析中的应用
阐述了化学振荡反应的基本概念及FKN机理，研究了与之有关的热力学基本理论和化学振荡反应具备的条件。对几类化学振荡反应，特别是B-Z振荡反应在分析检测中的应用进行了详细介绍。系统地列举了1978-2003年间化学振荡反应在药物分析检测应用中取得的进展。
第二部分：巴比妥酸对B-Z振荡反应的影响及其应用
研究了巴比妥酸对B-Z振荡反应的影响，结果表明，巴比妥酸的加入明显改变了振荡体系的周期和振幅，且巴比妥酸的浓度与振荡周期改变值ΔT及振幅改变值ΔA均呈现良好的线性关系，线性范围为6.4×10~(-7)～3.1×10~(-3)mol／L，相关系数分别为0.9921和0.9954，对其扰动机理进行了初步探讨。
第三部分：茚三酮对B-Z振荡反应的影响及其应用
研究了茚三酮对B-Z振荡体系的影响，考察了振幅和周期的改变值与茚三酮浓度的关系。结果表明，在6.9×10~(-7)～4.2×10~(-2)mol／L范围内，第一振幅改变值与茚三酮浓度有良好的线性关系，相关系数为0.9977。依据FKN模型，对此反应机理进行了初步探讨。
第四部分：利用APP技术及H_2O_2-CuSO_4-KSCN振荡反应测定海洛因
首次报道了利用Cu(Ⅱ)催化过氧化氢氧化硫氢化钠的敞开振荡体系测定海洛因的新方法。加入海洛因的浓度与振荡周期的改变值具有良好线性关系，检测下限达1.2×10~(-6)mol／L，浓度范围6.0×10~(-6)～1.2×10~(-4)M，相关系数为0.9971。对温度、流速、反应各组分浓度对扰动的影响，及其作用的可能机理进行了探讨。
The subject of "nonlinear dynamics" and the phenomenon of oscillating chemical reaction, in particular, have become of great interest across of wide range of scientific research in recent years. Oscillating chemical reactions exhibit exotic behavior and unusual mechanisms. Consequently, they have been considered a useful tool for the determination of trace amounts of chemical compounds. This work develops new methods using oscillating chemical reaction for quantitative analytical determinations of barbituric acid, ninhydrin, and heroin for the first time; the accuracy and selectivity of these methods are well pleasing. The main content consists of four parts:
Part I. Oscillating chemical reactions and applications for pharmaceutical
analysis
In this part, we describe the basic concepts of oscillating chemical reactions and FKN mechanism, studies some basic thermodynamic theory related, and gives the conditions of occurring oscillating chemical reactions. Some oscillating chemical reactions that were used in analytical determinations, especially B-Z chemical oscillation, are reported in details. The research progress in applications for pharmaceutical analysis from 1978 to 2003 is discussed systematically through representative examples.
Part II. Effect of barbituric acid on the B-Z the oscillating chemical
reaction and its analytical application
The effect of barbituric acid on the B-Z oscillating chemical reaction was studied. Results show that the adding of heroin can perturb both the oscillating period and amplitude, the changes of the oscillating period or the amplitude are linearly proportional to the concentration of barbituric acid, which over the range of 6.4×10-7-3.1×10-3 mol/L, and the related coefficient to be 0.9921 and 0.9954, respectively. The possible reaction mechanism has been explained using the FKN mode.
Part III. Effect of ninhydrin on the B-Z oscillating reaction
The effect of ninhydrin on the B-Z oscillating chemical reaction was studied. The dependence of the period and the amplitude change on the injected concentration was reported. Results show that the change of the first oscillation period is linearly proportional to the concentration of ninhydrin, which over the range of 6.9×10-7 ~ 4.2×10-2mol/L, and the related coefficient is 0.9977. The possible reaction mechanism has been studied as well as Field-K6r6s-Noyes (FKN) mechanism.
Part IV . Determination of heroin using H2O2-CuSO4-KSCN oscillating chemical reaction by the analyze pulse perturbation technique (APP)
A new analytical method for the determination of heroin by the sequential perturbation caused by different amounts of heroin on the chemical oscillating system involving the Cu (Il)-catalyzed reaction between hydrogen peroxide and sodium thioyanate in an alkaline medium with the aid of continuous-flow stirred tank reactor (CSTR) is proposed. The method relies on the linear relationship between the changes in the oscillation period of the chemical system and the concentration of heroin, with a detecting limit of 1.2×10-6M. The calibration curve fits a linear equation very well when the concentration of heroin over the range 6.0×10~6 to 1.2×10-4 M (r=0.9971). Influence of temperature, injection points, flow rate and reaction variables are investigated and the possible mechanism of the action of heroin in the chemical oscillating system is discussed. .
第一部分：化学振荡反应在药物分析中的应用
阐述了化学振荡反应的基本概念及FKN机理，研究了与之有关的热力学基本理论和化学振荡反应具备的条件。对几类化学振荡反应，特别是B-Z振荡反应在分析检测中的应用进行了详细介绍。系统地列举了1978-2003年间化学振荡反应在药物分析检测应用中取得的进展。
第二部分：巴比妥酸对B-Z振荡反应的影响及其应用
研究了巴比妥酸对B-Z振荡反应的影响，结果表明，巴比妥酸的加入明显改变了振荡体系的周期和振幅，且巴比妥酸的浓度与振荡周期改变值ΔT及振幅改变值ΔA均呈现良好的线性关系，线性范围为6.4×10~(-7)～3.1×10~(-3)mol／L，相关系数分别为0.9921和0.9954，对其扰动机理进行了初步探讨。
第三部分：茚三酮对B-Z振荡反应的影响及其应用
研究了茚三酮对B-Z振荡体系的影响，考察了振幅和周期的改变值与茚三酮浓度的关系。结果表明，在6.9×10~(-7)～4.2×10~(-2)mol／L范围内，第一振幅改变值与茚三酮浓度有良好的线性关系，相关系数为0.9977。依据FKN模型，对此反应机理进行了初步探讨。
第四部分：利用APP技术及H_2O_2-CuSO_4-KSCN振荡反应测定海洛因
首次报道了利用Cu(Ⅱ)催化过氧化氢氧化硫氢化钠的敞开振荡体系测定海洛因的新方法。加入海洛因的浓度与振荡周期的改变值具有良好线性关系，检测下限达1.2×10~(-6)mol／L，浓度范围6.0×10~(-6)～1.2×10~(-4)M，相关系数为0.9971。对温度、流速、反应各组分浓度对扰动的影响，及其作用的可能机理进行了探讨。
The subject of "nonlinear dynamics" and the phenomenon of oscillating chemical reaction, in particular, have become of great interest across of wide range of scientific research in recent years. Oscillating chemical reactions exhibit exotic behavior and unusual mechanisms. Consequently, they have been considered a useful tool for the determination of trace amounts of chemical compounds. This work develops new methods using oscillating chemical reaction for quantitative analytical determinations of barbituric acid, ninhydrin, and heroin for the first time; the accuracy and selectivity of these methods are well pleasing. The main content consists of four parts:
Part I. Oscillating chemical reactions and applications for pharmaceutical
analysis
In this part, we describe the basic concepts of oscillating chemical reactions and FKN mechanism, studies some basic thermodynamic theory related, and gives the conditions of occurring oscillating chemical reactions. Some oscillating chemical reactions that were used in analytical determinations, especially B-Z chemical oscillation, are reported in details. The research progress in applications for pharmaceutical analysis from 1978 to 2003 is discussed systematically through representative examples.
Part II. Effect of barbituric acid on the B-Z the oscillating chemical
reaction and its analytical application
The effect of barbituric acid on the B-Z oscillating chemical reaction was studied. Results show that the adding of heroin can perturb both the oscillating period and amplitude, the changes of the oscillating period or the amplitude are linearly proportional to the concentration of barbituric acid, which over the range of 6.4×10-7-3.1×10-3 mol/L, and the related coefficient to be 0.9921 and 0.9954, respectively. The possible reaction mechanism has been explained using the FKN mode.
Part III. Effect of ninhydrin on the B-Z oscillating reaction
The effect of ninhydrin on the B-Z oscillating chemical reaction was studied. The dependence of the period and the amplitude change on the injected concentration was reported. Results show that the change of the first oscillation period is linearly proportional to the concentration of ninhydrin, which over the range of 6.9×10-7 ~ 4.2×10-2mol/L, and the related coefficient is 0.9977. The possible reaction mechanism has been studied as well as Field-K6r6s-Noyes (FKN) mechanism.
Part IV . Determination of heroin using H2O2-CuSO4-KSCN oscillating chemical reaction by the analyze pulse perturbation technique (APP)
A new analytical method for the determination of heroin by the sequential perturbation caused by different amounts of heroin on the chemical oscillating system involving the Cu (Il)-catalyzed reaction between hydrogen peroxide and sodium thioyanate in an alkaline medium with the aid of continuous-flow stirred tank reactor (CSTR) is proposed. The method relies on the linear relationship between the changes in the oscillation period of the chemical system and the concentration of heroin, with a detecting limit of 1.2×10-6M. The calibration curve fits a linear equation very well when the concentration of heroin over the range 6.0×10~6 to 1.2×10-4 M (r=0.9971). Influence of temperature, injection points, flow rate and reaction variables are investigated and the possible mechanism of the action of heroin in the chemical oscillating system is discussed. .
引文
[1]李如生，非平衡现象和涨落化学，化学通报，1984，5，41
[2]Scott,E.S., Schreiner, R., Sharpe,L.R., Shakhashiri,B.Z., and Dirreen,G.E., Oscillating chemical Reactions, The university of wisconsin press, Madison wl, USA, 1985
[3]李如生，局域平衡假设和反应扩散过程，物理化学学报，1994，10，38
[4]Prigogine,I., Introduction to Thermodynamics of Irreversible Process, New York Interscience, 1955
[5]Rongming Guan, Non-Linear Phenomenon in chemical Reactions, shandong Qinggongye Xue Yuan Xuebao, 1996,10,15
[6]董小梅，刘剑波，徐功骅，B-Z振荡反应，大学化学，1996，11，35
[7]Ferino,I., and Rombi,E., Oscillatireaction, Catalysis Taday, 1999,52,291.
[8]李祥云，化学振荡反应研究简史，化学通报，1986，11，56
[9]Zongxiao Li, Chunlan Yuan, and chiming Tai, Study on the Energy in the chemical Oscillation, Baojj; wenli xueyuan xuebao, 1997,17,42
[10]李如生，非平衡态热力学和耗散结构[M]，北京：清华大学出版社，1986，248-285
[11]尼科利斯G，普里戈京I，非平衡系统的自组织[M]，北京：科学出版社，1986，51-64，377-393
[12]Guofang He and Maoju zheng, Oscrllotmg chemrcol reactron, Taran shizhuan xuebao, 2001,23,68.
[13]Chenxin Cui and Cuihong Huang, Oscillating chemical Reaetion, Nanjin shida xuebao, 1999,23,43
[14]Keizer,J., Statistical Thermodynamies of Monequilibrium Process. New York. Springer. 1987
[15]贺占博，化学振荡的研究方向，化学通报，1992,2．57
[16]许海涵，化学振荡，化学通报，1991．1．26
[17]徐济维，倪诗圣，汪明华，B-Z振荡反应一个中级无机化学实验，大学化学，1986．4．36
[18]Jintian Yang, Asurvey on the Theory of the Dissipative Structure and Its philosophical Meaning in the chemical Field.Huzhou shifan Xueyuan xuebao,2000.22.26
[19]Tikhonova, L.P., Zakrevskaya, L.N. and Yatsimirskii, K.B., Catalytic determination of ruthenium based on an oscillating chemical reaction, J. Anal. Chem. USSR, 1978, 33, 1991; CA 1979, 90:47852
[20]Jimenez-Prieto, R., Silva, M. and Perez-Bendito, D., Analyte pulse perturbation technique: A tool for analytical determination in far-from-equilibrium dynamic systems, Anal. Chem., 1995, 67, 729-734
[21]Yatsimirskii, K.B., Strizhak, P.E., and Ivaschenko, T.S., Potential of chaotic chemical systems in nanotraee analysis based on the Belousov-Zhabotinskii reaction (BrO3-malonic acid-ferroin)determination of manganese(II), Talanta, 1993, 40(8), 1227-1232
[22]高锦章，化学振荡现象在分析化学中的应用，西北师范大学学报自然科学版。2002，38(3)：100-105
[23]李湘如，刘之定，化学振荡实验和理论研究，自然杂志，1983，6，471
[24]刘秀辉、杨华、高锦章，任杰，氟对别洛李夫-扎鲍系斯基振荡反应的影响[J]，分析化学，2001，29(11)：1318-1321
[25]Irving R. Epstein, The role of flow systems in far-from-equilibrium dynamics, J. Chem. Edu., 1989, 66, 191-195
[26]Field, R.J., and Schneider, F.W., Oscillating chemical reactions and nonlinear dynamics, J. Chem. Edu., 1989, 66, 195-204
[27]李奇志，刘秀辉，任杰，柯华，杨武，高锦章，邓华陵，二苯胺酸钠对B-Z振荡反应的影响，西北师范大学学报(自学科学报)，2002，38(1)：51-54
[28]安从俊，甘南琴，刘义，蔡汝秀。乙酰丙酮-BrO_3~—Mn~(2+)-H_2SO_4的非线性化学反应特征，武汉大学学报(自然科学版)，1997，45(4)：411-414
[29]安从俊，甘南琴，刘义，李俊峰，林智信，DL-苹果酸。丙酮-BrO_3~—-Mn~(2+)-H_2SO_4化学振荡反应诱导期的新特征及其动力学研究，化学快报，1998，56：973-978
[30]安从俊，言贤要，刘义，林智信，蔡汝秀，碘离子对B-Z振荡反应的影响及其应用，武汉大学学报(自然科学版)，1993，4：56-60
[31]Orban M., KrsE., Chemical osoillotion during the uncatalyzed reaction of aromatic cpmpouuds with bromate I.search for chemical oscillators. J.phys.chem., 1978,82(14): 1672-1674.
[32]Field R J, KtrtsE, Noyes R M., Oscillotions in chemical systems. Ⅱ. Thorough analysis of temporal oscillation in the bromote-cedum-malonic acid system, J Am them soc, 1972,94(25):8649-8664.
[33]Field R.J., Noyes R.M., Oscillations in chemical systems. Part 4. Limit cycle behavior in a model of real chemical reaction. J.Chem.Phys., 1974, 60:1877-1889
[34]Richard J.Field and Naria Burger. Oscillations and Travelling waves in chemical systems. Wiley, New York, 1985, 55-75
[35]R.J. Field and F.W.Schneider. Oscillating Chemical Reactions and Nonelinear Dynamics., J.Chem.Educ., 1989, 66:195-204
[36]Richard J.Field and Naria Burger., Oscillations and Travelling waves in chemical systems. Wiley, New York, 1985, 60-62
[37]Richard J.Field and Naria Burger. Oscillations and travelling waves in chemical systems. Wiley, New York, 1985, 55-60
[38]Rafael Jimtnez-Pdeto, Manuel Silva and Dolores Ptrez-Bendito., Approaching the use of oscillating reactions for analytical monitoring. Analyst, 1998, 123: 1R-8R
[39]Mikls Orbán and Irving R.Epstein. Chemical Oscillators in Group VIA: The Cu(Ⅱ)-Catalyzed Reaction between Thiosulfate and Peroxodisulfate Ions. J. Amer. Chem. Sot., 1989, 111:2891-2896
[40]Mikls Orbán and Irving R.Epstein. Chemical Oscillators in Group VIA: The Cu(Ⅱ)-Catalyzed Reaction between Hydrogen Peroxide and Thiosulfate Ion. J. Amer. Chem. Sot., 1987, 109:101-106
[41]Mikls Orbán. Oscillations and Bistability in the Cu(Ⅱ)-Catalyzed Reaction between H_2O_2 and KSCN. J.Amer.Chem.Soc., 1986, 108, 6895-6898
[42]高庆宇，林娟娟，马克勤，臧雅茹，蔡遵生，赵学庄．CSTR中H_2O_2-KSCN-CuSO_4非线[56性反应体系的研究．物理化学学报，1995，111：488-491
[43]Simeen Scatter and Irving R.Epstein. Interaction of luminol with the Oscillating System H_2O_2-KSCN-CuSO4-NaOH.,.J.Phys.Chem., 1990, 94:275-277
[44]J.Amrehn, P.Resch and F.W.Sehneider. Oscillating Chemiluminesecence with luminol in the Continuous Flow Stirred Tank Reactor. J.Amer.Chem.Soc., 1988, 92: 3318-3320
[45]Orban, M., Oscillations and Bistability in the Cu(Ⅱ)-catalyzed reaction between H_2O_2 and KSCN, J. Am. Chem. Sot., 1986, 108, 6893-6898
[46]Luo, Y., Orban, M., Kustin, K., and Epstein, I.R., Mechanistic study of oscillating and bistability in the Cu(II)-catalyzed reaction between H202 and KSCN, J. Am. Chem. Sot., 1989, 111, 4541-4548
[47]Orban, M., and Epstein, I.R., The Cu(Ⅱ)-catalyzed reaction between thiosulfate and peroxodisulfate ions, J. Am. Chem. Soc., 1989, 111, 2891-2896
[48]Baltazer D.Aguda and Raima Latter. Sustained Oscillations and Bistability in a Detailed Mechanism of the Peroxidase-Oxidase Reaction. J.Amer.Chem.Soc., 1990, 112:2167-2174
[49]Dean L. Olson and Alexander Scheeline. The peroxidase-NADH biochemical oscillator: experimental system, control variables, and oxygen mass transport. Anal.Chim.Acta., 1993, 283:703-707
[50]李冬梅，贺占博，Marangoni效应与液漠振荡，化学进展，2003，15(1)：1-3
[51]贺占博，液膜振荡器，大学化学，1992，7，29
[52]贺占博，油水界面的自发振荡，化学通报，1990，2，54
[53]王寿祥，邱志新，陈森，穿过液膜的自发电势振荡，物理化学学报，1993，9，273
[54]李和兴，陆靖，李鹏宏，生物表面活性剂和氨基酸或多肽构成的界面振荡，科学通报，1998，43，265
[55]王文军，王文华，黄亚冰，张学林，生物膜的研究进展，环境科学进展，1999，7，43
[56]贺占博，阎喜龙，聂玉敏，赵著禄，新型液膜振荡器(Ⅱ)，化学工业与工程，2001，18，130
[57]赵国玺，表面活性剂物理化学，北京大学出版社
[58]贺占博，黄智，顾惕人，聚乙二醇对振荡反应的影响，物理化学学报，1995，8，741
[59]Zhanbo He, Application of Surfactants in the Study of Nonlinear Chemical Kinetics.Huaxue Gongcheng, 2001,18,93
[60]Kenichi Yoshikawa, Shoji M, Nakata S. An Excitable Liquid Membrane Possibily Mimicking the Sensing Mechanism of Taste., Langmuir, 1988,4(3):759-762
[61]Yoshikawak, K., and Matsubara, Y., Spontaneous Oscillation of PH and Electrical Potentialin an Oil-Water System, J.Am.Chem.Soc.,1983，105，267
[62] Toshifum Yoshidome, Toshifumi Higashi, Mitsushio M.Detection of Zinc(Ⅱ) Ion by Using Self-Osillation of the Electrical Potential across the Water-Oil-Water Liquid Membrane.Chem.Lett., 1998,(6):855-856
[63]Toshifum Yoshidome, Toshifumi Higashi, Satsuo Kamata. Application of Self-Oscillation of the Electrical Potential across the Water-Oil-Water Liquid Membrane to Quantitative Analysis of Aluminum Nitrate.Chem.Lett.2000, (5): 550-551
[64]金利通，宋丰斌，柏竹平，味觉电化学传感器的研究，分析实验室，1994，13，15
[65]刘文英，张亮，药物分析，分析实验室，2003，19(3)：91-108
[66]李修禄，李云华，药物分析，分析实验室1996，15(2)：90-110
[67]范少华，安从俊，庄林，甘南琴，林智信．维生素B_1对B-Z振荡反应的及反应动力学．物理化学学报，1999，15(2)：178-181
[68]Jinzhang Gao, Hua Yang, Xiuhui Liu, Jie Ren, Xiaoquan Lu, Jingguo Hou, Jingwan Kang. Kinetic determination of ascorbic acid by the B-Z oscillating chemical system. Talanta, 2001, 55:99-107
[69]Jinzhang Gao, Jie Ren, Wu Yang, Xiuhui Liu, Hua Yang, Qizhi Li, Hualing Deng. Kinetic Determination of Hydroquinone by Belousov-Zhabotinskii Oscillating Chemical Reaction., J.Electroanal.Chem., 2002, 520:157-162
[70]Jinzhang Gao, Jie Ren, Wu Yang, Xiuhui Liu, Hua Yang. Determination of Caffeine Using Oscillating Chemical Reaction in a CSTR, J.Pham.Bio.Anal, 32(2), (2003), 393-400
[71]Jinzhang Gao, Qizhi Li, Wu Yang, Xiuhui Liu, Jie Ren, Hua Yang and Jingwan Kang. Determination of L-valine based on an Oscillating chemical Reaction. Electroanatysrs, 14(17),(2002), 1191-1196
[72]Jinzhang Gao, Hua Yang, Xiuhui Liu, Jie Ren, Qizhi Li and Jingwan Kang. Determination of glutamic acid by an oscillating chemical reaction using the analyte pulse perturbation technique. Talanta, 2002, 57:105-114
[73]Rafael Jiménez-Prieto, Manuel Silva and Dolores Pérez-Bendito. Determination of Trace Amounts of Reduced Glutathione by a Chemical Oscillating Reaction. Analyst, 1996, 121:563-566
[74]Rafael Jiménez-Prieto, Manuel Silva and Dolores Pérez-Bendito. Determination of gallic acid by an oscillating chemical reaction using the analyte pulse perturbation technique., Anal.Chim.Acta, 1996, 321:53-60
[75]Rafael Jiménez-Prieto,Manuel Silva and Dolores Pérez-Bendito. Application of Oscillating Reaction-based Determinations to the Analysis of Real Samples. Analyst, 1997, 122:287-292
[76]Rafael Jiménez-Prieto, Manuel Silva and Dolores Pérez-Bendito. Simultaneous determination of gallic acid and resorcinol based on an oscillating chemical reaction by the analyte pulse perturbation technique. Anal.Chim.Acta., 1996, 334: 232-330
[77]沈振文，蒋萍初，李和兴，金艳，徐元昌．化学振荡用于临床检验的探索．上海师范大学学报(自然科学版)．1994，23：57-61
[78]任杰，杨武，刘秀辉，杨华，李奇志，高锦章．尿液对化学振荡的扰动作用．西北师范大学学报(自然科学版)，2002，38(1)：55-57
[79]G.Maya, P.V.Lattha and R.Ramaswamy. The oscillatory Belousov-Zhabotinskii reaction with flavones in batch systems using aqueous-DMF medium. Can.J.Chem., 1994, 72:1537-1540
[80]张珂，蔡汝秀，马万红，林智信，甘南琴．超痕量H_2O_2对MnSO_4-KBrO_3．乙酰丙酮化学振荡体系的扰动．高等学校化学学报．2000，21(3)：377-379
[2]Scott,E.S., Schreiner, R., Sharpe,L.R., Shakhashiri,B.Z., and Dirreen,G.E., Oscillating chemical Reactions, The university of wisconsin press, Madison wl, USA, 1985
[3]李如生，局域平衡假设和反应扩散过程，物理化学学报，1994，10，38
[4]Prigogine,I., Introduction to Thermodynamics of Irreversible Process, New York Interscience, 1955
[5]Rongming Guan, Non-Linear Phenomenon in chemical Reactions, shandong Qinggongye Xue Yuan Xuebao, 1996,10,15
[6]董小梅，刘剑波，徐功骅，B-Z振荡反应，大学化学，1996，11，35
[7]Ferino,I., and Rombi,E., Oscillatireaction, Catalysis Taday, 1999,52,291.
[8]李祥云，化学振荡反应研究简史，化学通报，1986，11，56
[9]Zongxiao Li, Chunlan Yuan, and chiming Tai, Study on the Energy in the chemical Oscillation, Baojj; wenli xueyuan xuebao, 1997,17,42
[10]李如生，非平衡态热力学和耗散结构[M]，北京：清华大学出版社，1986，248-285
[11]尼科利斯G，普里戈京I，非平衡系统的自组织[M]，北京：科学出版社，1986，51-64，377-393
[12]Guofang He and Maoju zheng, Oscrllotmg chemrcol reactron, Taran shizhuan xuebao, 2001,23,68.
[13]Chenxin Cui and Cuihong Huang, Oscillating chemical Reaetion, Nanjin shida xuebao, 1999,23,43
[14]Keizer,J., Statistical Thermodynamies of Monequilibrium Process. New York. Springer. 1987
[15]贺占博，化学振荡的研究方向，化学通报，1992,2．57
[16]许海涵，化学振荡，化学通报，1991．1．26
[17]徐济维，倪诗圣，汪明华，B-Z振荡反应一个中级无机化学实验，大学化学，1986．4．36
[18]Jintian Yang, Asurvey on the Theory of the Dissipative Structure and Its philosophical Meaning in the chemical Field.Huzhou shifan Xueyuan xuebao,2000.22.26
[19]Tikhonova, L.P., Zakrevskaya, L.N. and Yatsimirskii, K.B., Catalytic determination of ruthenium based on an oscillating chemical reaction, J. Anal. Chem. USSR, 1978, 33, 1991; CA 1979, 90:47852
[20]Jimenez-Prieto, R., Silva, M. and Perez-Bendito, D., Analyte pulse perturbation technique: A tool for analytical determination in far-from-equilibrium dynamic systems, Anal. Chem., 1995, 67, 729-734
[21]Yatsimirskii, K.B., Strizhak, P.E., and Ivaschenko, T.S., Potential of chaotic chemical systems in nanotraee analysis based on the Belousov-Zhabotinskii reaction (BrO3-malonic acid-ferroin)determination of manganese(II), Talanta, 1993, 40(8), 1227-1232
[22]高锦章，化学振荡现象在分析化学中的应用，西北师范大学学报自然科学版。2002，38(3)：100-105
[23]李湘如，刘之定，化学振荡实验和理论研究，自然杂志，1983，6，471
[24]刘秀辉、杨华、高锦章，任杰，氟对别洛李夫-扎鲍系斯基振荡反应的影响[J]，分析化学，2001，29(11)：1318-1321
[25]Irving R. Epstein, The role of flow systems in far-from-equilibrium dynamics, J. Chem. Edu., 1989, 66, 191-195
[26]Field, R.J., and Schneider, F.W., Oscillating chemical reactions and nonlinear dynamics, J. Chem. Edu., 1989, 66, 195-204
[27]李奇志，刘秀辉，任杰，柯华，杨武，高锦章，邓华陵，二苯胺酸钠对B-Z振荡反应的影响，西北师范大学学报(自学科学报)，2002，38(1)：51-54
[28]安从俊，甘南琴，刘义，蔡汝秀。乙酰丙酮-BrO_3~—Mn~(2+)-H_2SO_4的非线性化学反应特征，武汉大学学报(自然科学版)，1997，45(4)：411-414
[29]安从俊，甘南琴，刘义，李俊峰，林智信，DL-苹果酸。丙酮-BrO_3~—-Mn~(2+)-H_2SO_4化学振荡反应诱导期的新特征及其动力学研究，化学快报，1998，56：973-978
[30]安从俊，言贤要，刘义，林智信，蔡汝秀，碘离子对B-Z振荡反应的影响及其应用，武汉大学学报(自然科学版)，1993，4：56-60
[31]Orban M., KrsE., Chemical osoillotion during the uncatalyzed reaction of aromatic cpmpouuds with bromate I.search for chemical oscillators. J.phys.chem., 1978,82(14): 1672-1674.
[32]Field R J, KtrtsE, Noyes R M., Oscillotions in chemical systems. Ⅱ. Thorough analysis of temporal oscillation in the bromote-cedum-malonic acid system, J Am them soc, 1972,94(25):8649-8664.
[33]Field R.J., Noyes R.M., Oscillations in chemical systems. Part 4. Limit cycle behavior in a model of real chemical reaction. J.Chem.Phys., 1974, 60:1877-1889
[34]Richard J.Field and Naria Burger. Oscillations and Travelling waves in chemical systems. Wiley, New York, 1985, 55-75
[35]R.J. Field and F.W.Schneider. Oscillating Chemical Reactions and Nonelinear Dynamics., J.Chem.Educ., 1989, 66:195-204
[36]Richard J.Field and Naria Burger., Oscillations and Travelling waves in chemical systems. Wiley, New York, 1985, 60-62
[37]Richard J.Field and Naria Burger. Oscillations and travelling waves in chemical systems. Wiley, New York, 1985, 55-60
[38]Rafael Jimtnez-Pdeto, Manuel Silva and Dolores Ptrez-Bendito., Approaching the use of oscillating reactions for analytical monitoring. Analyst, 1998, 123: 1R-8R
[39]Mikls Orbán and Irving R.Epstein. Chemical Oscillators in Group VIA: The Cu(Ⅱ)-Catalyzed Reaction between Thiosulfate and Peroxodisulfate Ions. J. Amer. Chem. Sot., 1989, 111:2891-2896
[40]Mikls Orbán and Irving R.Epstein. Chemical Oscillators in Group VIA: The Cu(Ⅱ)-Catalyzed Reaction between Hydrogen Peroxide and Thiosulfate Ion. J. Amer. Chem. Sot., 1987, 109:101-106
[41]Mikls Orbán. Oscillations and Bistability in the Cu(Ⅱ)-Catalyzed Reaction between H_2O_2 and KSCN. J.Amer.Chem.Soc., 1986, 108, 6895-6898
[42]高庆宇，林娟娟，马克勤，臧雅茹，蔡遵生，赵学庄．CSTR中H_2O_2-KSCN-CuSO_4非线[56性反应体系的研究．物理化学学报，1995，111：488-491
[43]Simeen Scatter and Irving R.Epstein. Interaction of luminol with the Oscillating System H_2O_2-KSCN-CuSO4-NaOH.,.J.Phys.Chem., 1990, 94:275-277
[44]J.Amrehn, P.Resch and F.W.Sehneider. Oscillating Chemiluminesecence with luminol in the Continuous Flow Stirred Tank Reactor. J.Amer.Chem.Soc., 1988, 92: 3318-3320
[45]Orban, M., Oscillations and Bistability in the Cu(Ⅱ)-catalyzed reaction between H_2O_2 and KSCN, J. Am. Chem. Sot., 1986, 108, 6893-6898
[46]Luo, Y., Orban, M., Kustin, K., and Epstein, I.R., Mechanistic study of oscillating and bistability in the Cu(II)-catalyzed reaction between H202 and KSCN, J. Am. Chem. Sot., 1989, 111, 4541-4548
[47]Orban, M., and Epstein, I.R., The Cu(Ⅱ)-catalyzed reaction between thiosulfate and peroxodisulfate ions, J. Am. Chem. Soc., 1989, 111, 2891-2896
[48]Baltazer D.Aguda and Raima Latter. Sustained Oscillations and Bistability in a Detailed Mechanism of the Peroxidase-Oxidase Reaction. J.Amer.Chem.Soc., 1990, 112:2167-2174
[49]Dean L. Olson and Alexander Scheeline. The peroxidase-NADH biochemical oscillator: experimental system, control variables, and oxygen mass transport. Anal.Chim.Acta., 1993, 283:703-707
[50]李冬梅，贺占博，Marangoni效应与液漠振荡，化学进展，2003，15(1)：1-3
[51]贺占博，液膜振荡器，大学化学，1992，7，29
[52]贺占博，油水界面的自发振荡，化学通报，1990，2，54
[53]王寿祥，邱志新，陈森，穿过液膜的自发电势振荡，物理化学学报，1993，9，273
[54]李和兴，陆靖，李鹏宏，生物表面活性剂和氨基酸或多肽构成的界面振荡，科学通报，1998，43，265
[55]王文军，王文华，黄亚冰，张学林，生物膜的研究进展，环境科学进展，1999，7，43
[56]贺占博，阎喜龙，聂玉敏，赵著禄，新型液膜振荡器(Ⅱ)，化学工业与工程，2001，18，130
[57]赵国玺，表面活性剂物理化学，北京大学出版社
[58]贺占博，黄智，顾惕人，聚乙二醇对振荡反应的影响，物理化学学报，1995，8，741
[59]Zhanbo He, Application of Surfactants in the Study of Nonlinear Chemical Kinetics.Huaxue Gongcheng, 2001,18,93
[60]Kenichi Yoshikawa, Shoji M, Nakata S. An Excitable Liquid Membrane Possibily Mimicking the Sensing Mechanism of Taste., Langmuir, 1988,4(3):759-762
[61]Yoshikawak, K., and Matsubara, Y., Spontaneous Oscillation of PH and Electrical Potentialin an Oil-Water System, J.Am.Chem.Soc.,1983，105，267
[62] Toshifum Yoshidome, Toshifumi Higashi, Mitsushio M.Detection of Zinc(Ⅱ) Ion by Using Self-Osillation of the Electrical Potential across the Water-Oil-Water Liquid Membrane.Chem.Lett., 1998,(6):855-856
[63]Toshifum Yoshidome, Toshifumi Higashi, Satsuo Kamata. Application of Self-Oscillation of the Electrical Potential across the Water-Oil-Water Liquid Membrane to Quantitative Analysis of Aluminum Nitrate.Chem.Lett.2000, (5): 550-551
[64]金利通，宋丰斌，柏竹平，味觉电化学传感器的研究，分析实验室，1994，13，15
[65]刘文英，张亮，药物分析，分析实验室，2003，19(3)：91-108
[66]李修禄，李云华，药物分析，分析实验室1996，15(2)：90-110
[67]范少华，安从俊，庄林，甘南琴，林智信．维生素B_1对B-Z振荡反应的及反应动力学．物理化学学报，1999，15(2)：178-181
[68]Jinzhang Gao, Hua Yang, Xiuhui Liu, Jie Ren, Xiaoquan Lu, Jingguo Hou, Jingwan Kang. Kinetic determination of ascorbic acid by the B-Z oscillating chemical system. Talanta, 2001, 55:99-107
[69]Jinzhang Gao, Jie Ren, Wu Yang, Xiuhui Liu, Hua Yang, Qizhi Li, Hualing Deng. Kinetic Determination of Hydroquinone by Belousov-Zhabotinskii Oscillating Chemical Reaction., J.Electroanal.Chem., 2002, 520:157-162
[70]Jinzhang Gao, Jie Ren, Wu Yang, Xiuhui Liu, Hua Yang. Determination of Caffeine Using Oscillating Chemical Reaction in a CSTR, J.Pham.Bio.Anal, 32(2), (2003), 393-400
[71]Jinzhang Gao, Qizhi Li, Wu Yang, Xiuhui Liu, Jie Ren, Hua Yang and Jingwan Kang. Determination of L-valine based on an Oscillating chemical Reaction. Electroanatysrs, 14(17),(2002), 1191-1196
[72]Jinzhang Gao, Hua Yang, Xiuhui Liu, Jie Ren, Qizhi Li and Jingwan Kang. Determination of glutamic acid by an oscillating chemical reaction using the analyte pulse perturbation technique. Talanta, 2002, 57:105-114
[73]Rafael Jiménez-Prieto, Manuel Silva and Dolores Pérez-Bendito. Determination of Trace Amounts of Reduced Glutathione by a Chemical Oscillating Reaction. Analyst, 1996, 121:563-566
[74]Rafael Jiménez-Prieto, Manuel Silva and Dolores Pérez-Bendito. Determination of gallic acid by an oscillating chemical reaction using the analyte pulse perturbation technique., Anal.Chim.Acta, 1996, 321:53-60
[75]Rafael Jiménez-Prieto,Manuel Silva and Dolores Pérez-Bendito. Application of Oscillating Reaction-based Determinations to the Analysis of Real Samples. Analyst, 1997, 122:287-292
[76]Rafael Jiménez-Prieto, Manuel Silva and Dolores Pérez-Bendito. Simultaneous determination of gallic acid and resorcinol based on an oscillating chemical reaction by the analyte pulse perturbation technique. Anal.Chim.Acta., 1996, 334: 232-330
[77]沈振文，蒋萍初，李和兴，金艳，徐元昌．化学振荡用于临床检验的探索．上海师范大学学报(自然科学版)．1994，23：57-61
[78]任杰，杨武，刘秀辉，杨华，李奇志，高锦章．尿液对化学振荡的扰动作用．西北师范大学学报(自然科学版)，2002，38(1)：55-57
[79]G.Maya, P.V.Lattha and R.Ramaswamy. The oscillatory Belousov-Zhabotinskii reaction with flavones in batch systems using aqueous-DMF medium. Can.J.Chem., 1994, 72:1537-1540
[80]张珂，蔡汝秀，马万红，林智信，甘南琴．超痕量H_2O_2对MnSO_4-KBrO_3．乙酰丙酮化学振荡体系的扰动．高等学校化学学报．2000，21(3)：377-379