摘要
综述了化学发光分析法测定铬、锰的进展,较为详细地介绍了化学发光法的分析原理及常用化学发光试剂,讨论了影响化学发光强度的因素,归纳了化学发光在分析领域中的应用。
基于Cr(Ⅵ)—8-羟基喹啉对鲁米诺—H_2O_2化学发光体系的催化作用,建立了测定Cr(Ⅵ)的新方法。选择鲁米诺5.0×10~(-4)mol/L、H_2O_2为0.25mol/L、8-羟基喹啉为1.0×10~(-4)mol/L、Cr(Ⅵ)试液pH4.0、最终化学发光反应溶液pH12,可获得最大化学发光信号。Cr(Ⅵ)浓度在3.0×10~(-6)—4.0×10~(-5)mg/mL范围与发光强度呈线性响应,回归方程为I_(CL)=3.6+1.68×10~6×c(mg/mL),检测下限C_(LD)为3.0×10~(-6)mg/mL;Cr~(3+)、Mn~(2+)、Co~(2+)、I~-、丙酸等离子、分子干扰测定,可用掩蔽剂EDTA或阳离子交换树脂去除阳离子干扰。HNO_3消化法去除I~-和丙酸的干扰。将该法应用于生物化工产品丙酸钙、动物蛋白粉等中痕量铬的测定,相对标准偏差4.3%,加标回收率105%。5次测定平均值与苯二碳酰二肼光度法相比较,相对偏差2.7%;并探讨了化学发光的机理。
基于Mn(Ⅱ)—邻菲罗啉对鲁米诺—KIO_4化学发光体系的催化作用建立了测定Mn(Ⅱ)的新方法。当鲁米诺浓度为5.0×10~(-4)mol/L、KIO_4浓度为2.5×10~(-4)mol/L、邻菲罗啉2.5×10~(-4)mol/L、Mn(Ⅱ)试液pH4.0时,发光信号最强,Mn(Ⅱ)浓度在2.0×10~(-6)—5.0×10~(-5)mg/mL范围与发光强度呈线性响应,线性回归方程为I_(CL)=0.6+1.39×10~6×c(mg/mL),检测限为2.0×10~(-6)mol/L。Cr~(3+)、Fe~(2+)、Co~(2+)、Au~(3+)等离子有干扰,使用EDTA、F~-、8-羟基喹啉等为掩蔽剂可消除或降低干扰。将该法应用于生物化工产品丙酸钙、动物蛋白粉等中痕量锰的测定,加标回收率105%,10次测定RSD为4.6%。将测定的结果与原子吸收法比较,相对偏差为8.3%,结果令人满意。此外还探讨了鲁米诺—KIO_4—Mn(Ⅱ)—邻菲罗啉化学发光的反应机理。
The development on determination of trace chromium and manganese by chemiluminescence reaction is reviewed, The analysis principle of chemiluminescence reaction and chemiluminescent reagent in common use is intrduced detailly. the factors which influence a chemiluminescent intensity are investigated and Application of Chemiluminescence reaction in analytical chemistry is discribed.
A sensitive and selective analytical method has been developed for determination of trace chromium. The method is based on the catalysis of 8-hydroxyquinoline -Cr ( VI ) for Luminol - H2O2 reaction system. When choose luminol concentration 5- 0×10~4 mol/L, the H2O2 act as 0. 25mol/L,8-hydroxyquinoline is 1.0×10-4mol/L, pH of Cr ( VI )test solution is 4.0 and the fina liquor pH is 12 in the chemiluminescene reaction solution, the largest chemiluminescence emission intensity may be obtained. The linear range of the working curves is 3.0×10-6 - 4.0×10-5mg/mL and the linear regression equation is an ICL = 0. 6 + 1. 39×106×c (mg/mL). Adetection limit of Cr (VI) is 3.0×10~6mg/mL. Several metal ions such as Cr3+, Mn2+, Co2+, gave heavy interference on Cr ( VI ) determination. In the presence of 1. 0×10-5mol/LEDTA, Cr2+, Mn2+and Co2+gave on interference. The method was applied to determination of trace chromium ( VI ) in some biochemical products with a satisfactry results. RSD is 4. 3%. The recovery rate of standard addition is 105%. Compared with absorptionmetric analysis of sym-diphenyl carbazide, the ralative deviation is 2.7%.
A mew method has been established for determination of trace manganese, which is based on the catalysis of Mn(o -phen. )32+ for luminol-KIO4 chemiluminescent reaction. Greatest chemiluminescence emission intensity would be obtained when the concentra-
tion of luminol is 5. 0×10 4mol/L, KIO4 2. 5×10~4mol/L, o -phenanthroline 2. 5×10~4mol/L, pH of Mn ( II) test solution 4.0 and the final pH in KOH reaction medium 12. The linear range is obtained from 2.0×10~6to 5.0×10~5mg/mL and the linear regression equation is an ICL = 0. 6 + 1.39×106×c (mg/mL). the detection limit of Mn ( II)is 2. 0×10~6 (mg/mL). Some coexist metal ions such as Cr3+, Fe2+, Co2+and Au3+ gave interference in Mn( II) determination. Added some screening agent such as EDTA, F-or 8-hydroxyquinoline, the interference may be remove or cut down. This method was applied to determination of trace manganese in some biochemical products with a satisfactory results. The recovery rate of standard addition is 105% and the RSD is 4.6%. Compared with atomic absorption spectrophotometry (AAS), the relative deviation is 8. 3%. The reaction mechanism of Luminol - KIO4-Mn (II ) -0 - phenanthroline system was discussed.
引文
[1] G.L.瓦尔德博特著.胡汉升,洪传洁译.环境污染物对人体健康的影响[M].北京:人民卫生出版社,1984:115-122.
[2] 王连生.环境健康化学[M].北京:科学出版社,1994:52-61.
[3] 郝平.快速氧化还原滴定法测定铬铜中间合金中铬[J].理化检验—化学分册,2001,37(7):327,329.
[4] 梁玉珍,黄静,邬洪缘,等.过氧化氢氧化罗丹明B催化动力学光度法测定痕量络(Ⅵ)[J].理化检验—化学分册,2002,38(11):579-580.
[5] 俞善辉,吴继魁,王麟生,等.铬的吸光光度法测定研究进展[J].化学试剂,2002,24(5):276-279,289.
[6] 李文最,盛丽娜,李一丹.极谱法测定自来水中六价铬[J].中国公共卫生,2000,16(10):946.
[7] 董学芝,赵海兰,艾天宗,等.催化电位滴定法测定铬鞣剂中铬(Ⅲ)[J].分析化学,2001,29(1):77-79.
[8] 张小林,曹槐,杨丽霞,等.不同样液制备方法电感耦合等离子体原子发射光谱测定人血清铁、铜、铬、镉、铅的比较[J].光谱学与光谱分析,1999,19(3):364-366.
[9] Harnly J M, Patterson K Y, Veillon C, et al. Comparison of electrothermal atomic absorption spectrometry and atomicemission spectrometry for determination of chromium in urine[J] Anal. chem.,1983,55:1417—1419.
[10] 刘云派,刘小珍,吴莉宇.革制红菇营养成分分析[J].光谱实验室,2001,18(5):637—639.
[11] 田松柏.离子对色谱测定碱性样品溶液中铬的方法研究[J].岩矿测试,1999,18(3):193—197.
[12] 高岐.尿液中痕量铬的化学发光分析法[J].理化检验—化学分册,1999,35(4):162—163.
[13] 张萍,曹文立.高氯酸.氧化容量法测定钢铁及合金中锰[J].冶金分析,1999,19(5):50—51.
[14] 杨秀英,冯尚彩.催化动力学光度法测定茶叶中的痕量锰[J].光谱实验室,2002,19(2):282—284.
[15] 周南.锰的光度试剂综述(上、下)[J].上海化工,2001,(13,14):20—23,17—21.
[16] 刘家欣,段有构.示波极谱法测定微量锰[J].理化检验—化学分册,1998,34(2):66—67.
[17] 金米聪,于笑宇,颜金良,等.还原溶出计时电位法测定水中痕量锰[J].理化检验—化学分析,2000,36(4):153—154.
[18] 余碧钰,程玉龙,王正霖,等.等离子发射光谱法同时测定鸡蛋中的矿物营养素[J].中国家禽,1999,21(11):13—14.
[19] 宋雅茹,王尚芝,徐建平,等.火焰原子吸收光度法测定何首鸟中锰的研究[J].光谱学与光谱分析,2002,22(3):483—484.
[20] 邓世林,李新凤,郭小林,等.饲料添加剂中铜和锰的原子吸收光谱直接测定方法[J].分析测试学报,2002,21(5):71—72.
[21] 张香荣.炉渣和原材料的X射线荧光光谱快速分析[J].冶金分析,2002,22(11):11—13.
[22] 郭明,孔亮,历欣,等.微波衍生—离子对高效液相色谱—磺化四苯基叶啉光度法同时测定痕量镍、铜、锰和锌[J].色谱,2002,20(2):137—139.
[23] 周延秀,朱果逸.痕量铁和锰的化学发光检测[J].岩矿测试,1997,16(3):221—228.
[24] 李梦耀,李绍卿.化学发光分析法测定金的进展[J].贵金属,2002,23(4):58—63,70.
[25] 章竹君,吕九如.发光分析[J].分析试验室,1901,10(4):102—115.
[26] 李光浩,于振安.化学发光分析法的进展[J].环境科学与技术,1990,(2):15—18.
[27] 吴风武,何治柯,罗庆尧,等.化学发光分析新进展[J].分析测试学报,2000,19(1):81—88.
[28] 耿征.中国化学发光分析进展[J].化学通报,1992,(11):1—5.
[29] 章竹君.发光分析[J].分析试验室,1989,8(4):35—51.
[30] 张帆,陈玉龙.化学发光分析法(Ⅰ)[J].分析试验室,1987,6(2):58—66.
[31] 张帆,陈玉龙,化学发光分析法(Ⅱ).化学发光体系的新进展及其在分析化学中的应用(一)[J].分析试验室,1987,6(3):52—58.
[32] 张帆,陈玉龙.化学发光分析法(Ⅲ).化学发光体系的新进展及其在分析化学中的应用(二)[J].分析试验室,1987,6(4):44—54.
[33] 张帆,陈玉龙.化学发光分析法(Ⅳ).液相化学发光的测量仪器和技术[J].分析试验室,1987,6(7):51—57,50.
[34] 张帆,陈玉龙.化学发光分析法(Ⅴ)气相化学发光和电生化学发光[J].分析试验室,1987,6(9):53—59.
[35] 梁肃臣,吕建华.国外化学发光物研究的进展[J].低温与特气,1998,(2):18—19.
[36] 韩鹤友,崔华,林祥钦.化学发光分析法应用新进展[J].光谱实验室,2002,19(1):39—45.
[37] 周延秀,朱果逸.流动注射化学发光检测法的进展[J].分析化学,1997,25(2):222—230.
[38] 段群章.化学发光分析在矿冶物料中的实际应用[J].有色矿冶,1998,(6):48—53.
[39] 李晓燕,何治柯,曾云鹗.化学发光分析法在环境分析中的应用[J].分析科学学报,1999,15(3):258—262.
[40] 张帆,刘振鸣.胶束在化学发光分析中的应用和发展[J].分析化学,1989,17(11):1051—1056.
[41] 李志良,彭平,石乐明,等.增效试剂在无机发光分析中的应用[J].岩矿测试,1990,9(1):57—65.
[42] 章竹君,吕九如,张新荣.鲁米诺化学发光反应及其在分析化学中的应用[J].化学试剂,1987,9(3):149—156.
[43] 章竹君.能量转移发光分析[J].分析试验室,1993,12(1):25—29.
[44] 方国桢,谯斌宗.表面活性剂在化学发光分析中的应用[J].化学试剂,1996,18(6):333—336.
[45] 吕小虎,陆明刚,武进.化学发光法在水分析中的应用[J].环境科学丛刊,1992,13(6)78—81.
[46] 李绍卿,张小燕.化学发光分析技术[M].西安:西安地图出版社,2000:1—142.
[47] 张帆,陈玉龙,周雄,等.槲皮素化学发光新体系在分析上的应用[J].分析化学,1991,19(2):147—151.
[48] D. B. Paul. Recent analytical developments using chemiluminescence in solution[J]. Talanta, 1978,25(7): 377—382.
[49] C. Dodeigne, L. Thunus,R. Lejeune. Chemiluminescence as a diagnostic tool. A review [J]. Talanta,2000,51(3): 415—439.
[50] Alan Townshencl. Solution chemiluminescence—some recent analytical development. plenary lecture[J]. Analyst,1990,115(5):495—500.
[51] Revin Robards,Paul J. Worsfold. Analytical applications of liquid—phase chemiluminescence[J]. Anal. chim. Acta, 1992,266(2): 147—173.
[52] Rosario Escobar, Qing Xing Lin, Alfonso Guiraum,et al. Flow injection chemiluminescence method for the selection determination of chromium(Ⅲ)[J]. Analyst, 1993, 118(6).-643—647.
[53] 段建平.流动注射化学发光检测血清和头发中的铬[J].福州大学学报(自然科学版),2001,29(5):100—103.
[54] 杨孙楷,郁建栓,王莉莉.海水中铬的化学发光分析[J].海洋学报,1994,16(1):131—135.
[55] 董文宾,强西怀.皮革及鞣液中铬的化学发光法测定[J].中国皮革,1998,27(6):14—16.
[56] 程占胜,周玲,唐棣,等.流动注射—化学发光法测定啤酒中痕量铬的研究[J].西安医科大学学报,1997,18(1):46—48.
[57] 程占胜,周玲,胡森科,等.流动注射—化学发光法测定车间空气中铬的研究[J].中国公共卫生,1996,12(7):324—326.
[58] Cheng A. Chang,Howard H. Patterson. Halide ion enhancement of chromium(Ⅲ), Iron(Ⅱ)and coblt(Ⅱ) catalysis of luminol chemiluminescence[J]. Anal. chem., 1980,52(4).-653—656.
[59] C. Allen Chang,Howard H. Patterson. Determination of trivalent chromium in seawater hy chemiluninescence [J]. Anal. Chem., 1980,52(8):1264—1267.
[60] Daniel E. Bause, Howard H. Patterson. Enhancement of luminol chemiluminescence with halide ions[J]. Anal. Chem., 1979,51(13): 2288—2289.
[61] 万国桢,汪丹丹.化学发光流动注射—胶束增敏连续测定钴铬研究[J].分析测试学报,1997,16(2):27—32.
[62] 李光浩,于振安.ABEI-H_2O_2-Cr(Ⅲ)体系反相流动注射化学发光法测定水中Cr(Ⅲ)[J].环境科学,1991,12(2):52—55.
[63] Allan MacDonald, Kenneth W. Chan, Timothy A. Nieman. Lophine Chemiluminescence for metal ion determination[J]. Anal. chem.,1979,51(13):2077—2082.
[64] 吕九如,张新荣,章竹君,等.铬(Ⅵ)-亚铁氰化钾-鲁米诺体系化学发光反应的研究[J].分析化学,1992,20(1):61—63.
[65] 胡森科,李林,周玲,等.FIA-化学发光法测定血铬的研究[J].中国卫生检验杂志,2000,10(4):422—423.
[66] 韩鹤友,何治柯,罗庆尧,等.流动注射化学发光法测定淮河水中痕量Cr(Ⅵ)[J].环境污染与防治,1998,20(6):34—35.
[67] 韩鹤友,何治柯,罗庆尧,等.在线氧化-流动注射-化学发光法测定痕量Cr(Ⅲ)/Cr(Ⅵ)[J].理化检验—化学分册,1998,34(7):295—296,299.
[68] D. F. Marino, J. D. Ingle. Determination of chromium(Ⅵ)in water by lophine chemi
luminescence[J]. Anal. chem., 1981,53(2):294—298.
[69] 张帆,梅英华,陈恒.水体中价态铬的化学发光测定[J].中国环境科学,1989,9(1):75—79.
[70] 张帆,陈玉龙.环境水样中六价铬的化学发光测定新方法[J].分析试验室,1986,5(6):1—3.
[71] 李梦耀,张小燕,李绍卿.化学发光分析法测定生化产品中铬的含量[J].西北大学学报(自然科学版),2002,32(增):85—87.
[72] 康新平,刘洪海,陈竖.液体样品中铬的价态和微量分析方法的研究进展[J].理化检验—化学分册,1999,35(3):139—142.
[73] 韩鹤友,何治柯,罗庆尧,等.流动注射-化学发光法同时测定痕量Cr(Ⅵ)/Cr(Ⅲ)[J].湖北三峡学院学报,1998,20(1):72—75.
[74] J. L. Burguera,Alan Townshend. Determination of manganese(Ⅱ) by a chemiluminescence reaction[J]. Talanta, 1981,28(10): 731—735.
[75] 吕小虎,陆明刚.化学发光分析法测定锰(Ⅱ)与锰(Ⅶ)[J].光谱学与光谱分析.1992,12(5):121—122,127.
[76] Eiichire Nakayams, Kenji—lsshiki, Yoshiki sohrin, et al. Automated determination of manganese in seawater by electrolytic concentration and chemiluminescence detection[J]. Anal. Chem., 1989,61(13): 1392—1396.
[77] 郑朱梓,王尊本.化学发光法在环保中的应用Ⅱ.矿泉水及污水中Mn(Ⅱ)测定[J].分析化学.1985,13(7):510—514.
[78] Kalinichenko I E. Chemiluminescent method for determination nanogram amounts of manganese. Ukr Khim Zh. 1969,35(7):755—757.
[79] 伍莉萍,杨秀岑,金靓,等.流动注射化学发光法同时测定Mn~(2+)和Co~(2+)[J].华西医学杂志,1999,14(4):245—247.
[80] QingXiong Lin, Alfonso Guiraum, Rosario Escobar. Flow-injection chemiluminescence determination of cobalt(Ⅱ) and manganese(Ⅱ)[J]. Anal. chim. Acta, 1993,283:379—385.
[81] 耿征,张志琪,边六交.鲁米诺-锰(Ⅱ)-高碘酸钾化学发光体系测定痕量锰的研究[J].高等学校化学学报.1988,9(11):1114—1117.
[82] 李绍卿,郭强,张新成,等.Mn(1,10—phen.)_3~(2+)-鲁米诺-KIO_4化学发光体系与应用[J].建材地质,1997,(6):38—40.
[83] 吕小虎,陆明刚,史文岩.化学发光法测定工业废水中Mn~(2+)[J].环境科学与技术,
1990,(2):20—22.
[84] 申金山,周清泽,王昕,等.液相化学发光法测定人发中的锰[J].分析化学,1998,26(1):121.
[85] Andrew R. Bowie, Peter R. Fielden, Roger D. lowe,et al. Sensitive determination of Manganeses Using Flow Injection and Chemiluminescent Detection [J]. Analyst, 1995,120(8): 2119—2127.
[86] 朱昌青,王伦,李永新,等.籍高锰酸钾氧化双乙酰的化学发光反应测定微量锰[J].分析化学,1997,25(4):387—390.
[87] Zhang Fan, Lin QingXiong. A new chemiluminescence system: MnO_4~--Na_2CO_3-KOH and its application in the determination of manganese [J]. Talanta. 1993,40(10):1557—1561.
[88] 林守麟,刘永庆.没食子酸-过氧化氢-甲醛体系中Co(Ⅱ)和Mn(Ⅱ)的化学发光同时测定[J].高等学校化学学报,1990,11(11):1199—1202.
[89] 朱霞石,江祖成,李杉,等.以8-羟基喹啉为化学改进剂石墨炉原子吸收光谱测定水和空气尘粒物中铬的研究[J].分析试验室,2002,21(4):13—15.