抑霉唑的毛细管电泳手性拆分及其在线富集
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摘要
采用毛细管电泳法对抑霉唑进行手性拆分,研究了手性选择剂β-环糊精(β-CD)、有机添加剂、NaH_2PO_4、NH_4H_2PO_4和分离电压对手性拆分的影响;同时,采用堆积法对抑霉唑进行在线富集,研究了进样压力和进样时间对在线富集的影响。结果表明:在分离电压为20 kV、β-CD浓度为5 mmol/L及缓冲体系为2.5%异丙醇+75 mmol/L NaH_2PO_4+5 mmol/L NH_4H_2PO_4时,抑霉唑获得最佳分离度,分离度可达3.0;在分离电压为20 kV、β-CD浓度为5 mmol/L、缓冲体系为75 mmol/L NaH_2PO_4+5 mmol/L NH_4H_2PO_4+50 mmol/L H_3PO_4及进样条件为13.8 kPa×99.9 s时获得最高富集倍数,富集倍数达91～92倍。
The enantioseparation of imazalil was conducted by capillary electrophoresis, and the effects of chiral selector β-cyclodextrin(β-CD), organic additives, NaH_2PO_4, NH_4H_2PO_4 and separation voltage on the resolution were studied. And the effects of the injection pressure and preconcentration times on the on-column preconcentration of imazalil were studied by the stacking method. The results showed that the best resolution was achieved under the following conditions: separation voltage 20 kV, β-CD5 mmol/L and a buffer system of 2.5 % isopropanol + 75 mmol/L NaH_2PO_4 + 5 mmol/L NH_4H_2PO_4.And the resolution was up to 3.0. The highest enrichment factor was obtained at the separation voltage of 20 kV using 5 mmol/L β-CD, a buffer system of 75 mmol/L NaH_2PO_4 + 5 mmol/L NH_4H_2PO_4 +50 mmol/L H_3PO_4, and the injection conditions of 13.8 kPa×99.9 s. And the enrichment factor was up to 91-92 times.
The enantioseparation of imazalil was conducted by capillary electrophoresis, and the effects of chiral selector β-cyclodextrin(β-CD), organic additives, NaH_2PO_4, NH_4H_2PO_4 and separation voltage on the resolution were studied. And the effects of the injection pressure and preconcentration times on the on-column preconcentration of imazalil were studied by the stacking method. The results showed that the best resolution was achieved under the following conditions: separation voltage 20 kV, β-CD5 mmol/L and a buffer system of 2.5 % isopropanol + 75 mmol/L NaH_2PO_4 + 5 mmol/L NH_4H_2PO_4.And the resolution was up to 3.0. The highest enrichment factor was obtained at the separation voltage of 20 kV using 5 mmol/L β-CD, a buffer system of 75 mmol/L NaH_2PO_4 + 5 mmol/L NH_4H_2PO_4 +50 mmol/L H_3PO_4, and the injection conditions of 13.8 kPa×99.9 s. And the enrichment factor was up to 91-92 times.
引文
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[6]NAGAI T, KUROSU A, MATSUSHIMA K, et al. Simultaneous identification of the enantiomers and diastereomers of N, O-ditrifluoroacetylated ephedrine and norephedrine in blood plasma using chiral capillary gas chromatography-mass spectrometry with selected ion monitoring[J]. J Anal Toxicol., 2012, 36(2):96-105.
[7]SCHURIG V, JUZA M. Analytical separation of enantiomers by gas chromatography on chiral stationary phases[M]//Advances in Chromatography. CRC Press, 2014:117-168.
[8]MORRISON C, SMITH F J, TOMASZEWSKI T, et al. Chiral gas chromatography as a tool for investigations into illicitly manufactured methylamphetamine[J]. Chirality, 2011, 23(7):519-522.
[9]PENG L M, JAYAPALAN S, CHANKVETADZE B, et al. Reversedphase chiral HPLC and LC/MS analysis with tris(chloromethylphenylcarbamate)derivatives of cellulose and amylose as chiral stationary phases[J]. J Chromatogr A, 2010, 1217(44):6942-6955.
[10]TSUTSUI H, FUJII S, SAKAMOTO T, et al. Chiral amines as reagents for HPLC-MS enantioseparation of chiral carboxylic acids[J]. J Sep Sci, 2012, 35(13):1551-1559.
[11]MENG L, WANG B, LUO F, et al. Application of dispersive liquidliquid microextraction and CE with UV detection for the chiral separation and determination of the multiple illicit drugs on forensic samples[J]. Forensic Sci Int, 2011, 209(1-3):42-47.
[12]WAGNER Z, TáBI T, JAKóT, et al. Chiral separation and determination of excitatory amino acids in brain samples by CE-LIF using dual cyclodextrin system[J]. Anal Bioanal Chem, 2012, 404(8):2363-2368.
[13]ZHANG H Z, QI L, QIAO J, et al. Determination of sodium benzoate by chiral ligand exchange CE based on its inhibitory activity in Damino acid oxidase mediated oxidation of D-serine[J]. Anal Chim Acta, 2011, 691(1-2):103-109.
[14]刘海兴,于爱民,刘凤芹,等.毛细管电泳在手性物质分离中的应用[J].化学试剂, 2005, 27(9):535-540.LIU H X, YU A M, LIU F Q, et al. Application of capillary electrophoresis in chiral separation[J]. Chem Reagents, 2005, 27(9):535-540.
[15]ALTRIA K D, ELDER D. Overview of the status and applications of capillary electrophoresis to the analysis of small molecules[J]. J Chromatogr A, 2004, 1023(1):1-14.
[16]KANG J W, WISTUBA D, SCHURIG V. Recent progress in enantiomeric separation by capillary electrochromatography[J].Electrophoresis, 2002, 23(22-23):4005-4021.
[17]RIZZI A. Fundamental aspects of chiral separations by capillary electrophoresis[J]. Electrophoresis, 2001, 22(15):3079-3106.
[18]QUIRINO J P, TERABE S. Exceeding 5000-fold concentration of dilute analytes in micellar electrokinetic chromatography[J]. Science,1998, 282(5388):465-468.
[19]YU L J, LI S F Y. Dynamic pH junction-sweeping capillary electrophoresis for online preconcentration of toxic pyrrolizidine alkaloids in Chinese herbal medicine[J]. Electrophoresis, 2005,26(22):4360-4367.
[20]卢玉超,王海燕,宋萍萍,等.毛细管电泳-场强放大样品堆积法检测染发剂中的7种苯胺类物质[J].色谱, 2011, 29(11):1122-1127.LU Y C, WANG H Y, SONG P P, et al. Determination of seven aromatic amines in hair dyes by capillary electrophoresis coupled with field-amplified sample stacking[J]. Chin J Chromatogr, 2011,29(11):1122-1127.
[21]LEVENT A, YARDIM Y, DEMIR C. Determination of trace metal and mineral levels in the tobacco and cigarette samples using by fass[J]. J Chem Soc Pakistan, 2013, 35(2):257-261.
[22]WANG X, MASSCHELEIN E, HESPEL P, et al. Simultaneous determination of nitrite and nitrate in human plasma by on-capillary preconcentration with field-amplified sample stacking[J].Electrophoresis, 2012, 33(2):402-405.
[23]T?MA P,?USTKOVá-FI?EROVáM, OPEKAR F, et al. Largevolume sample stacking for in vivo monitoring of trace levels ofγ-aminobutyric acid, Glycine and glutamate in microdialysates of periaqueductal gray matter by capillary electrophoresis with contactless conductivity detection[J]. J Chromatogr A, 2013, 1303:94-99.
[24]冯丹,孙学鹏,姜丽英,等.浙江衢州地区柑橘绿霉病菌对抑霉唑和多菌灵的抗性水平及其分子机制[J].农药学学报, 2011, 13(4):341-346.FENG D, SUN X P, JIANG L Y, et al. Resistance level and mechanism of Penicillium digitatum to imazalil and carbendazim in Quzhou, Zhejiang[J]. Chin J Pestic Sci, 2011, 13(4):341-346.
[25]CHAI T, YANG W, QIU J, et al. Direct enantioseparation of nitrogen-heterocyclic pesticides on cellulose-based chiral column by high-performance liquid chromatography[J]. Chirality, 2015, 27(1):32-38.
[26]LI R N, DONG F S, XU J, et al. Enantioseparation of imazalil and monitoring of its enantioselective degradation in apples and soils using ultrahigh-performance liquid chromatography-tandem mass spectrometry[J]. J Agric Food Chem, 2017, 65(16):3259-3267.
[27]KODAMA S, YAMAMOTO A, OHURA T, et al. Enantioseparation of imazalil residue in orange by capillary electrophoresis with 2-hydroxypropyl-β-cyclodextrin as a chiral selector[J]. J Agric Food Chem, 2003, 51(21):6128-6131.
[28]SHI J H, DING Z J, HU Y. Experimental and theoretical studies on the enantioseparation and chiral recognition of mandelate and cyclohexylmandelate on permethylatedβ-cyclodextrin chiral stationary phase[J]. Chromatographia, 2011, 74(3-4):319-325.
[29]FANALI S. Enantioselective determination by capillary electrophoresis with cyclodextrins as chiral selectors[J]. J Chromatogr A, 2000, 875(1-2):89-122.
[30]CHU B L, GUO B Y, PENG Z L, et al. Studies on degradation of imazalil enantiomers in soil using capillary electrophoresis[J]. J Sep Sci, 2007, 30(6):923-929.
[31]WREN S A C, ROWE R C. Theoretical aspects of chiral separation in capillary electrophoresis:I. Initial evaluation of a model[J]. J Chromatogr A, 1992, 603(1-2):235-241.
[32]SERA Y, MATSUBARA N, OTSUKA K, et al. Sweeping on a microchip:Concentration profiles of the focused zone in micellar electrokinetic chromatography[J]. Electrophoresis, 2001, 22(16):3509-3513.
[33]QUIRINO J P, TERABE S. Approaching a million-fold sensitivity increase in capillary electrophoresis with direct ultraviolet detection:cation-selective exhaustive injection and sweeping[J]. Anal Chem,2000, 72(5):1023-1030.
[2]GELLAD W F, CHOI P, MIZAH M, et al. Assessing the chiral switch:approval and use of single-enantiomer drugs, 2001 to 2011[J].Am J Manag Care, 2014, 20(3):e90-e97.
[3]BUSER H R, MüLLER M D, POIGER T, et al. Environmental behavior of the chiral acetamide pesticide metalaxyl:enantioselective degradation and chiral stability in soil[J]. Environ Sci Technol, 2002,36(2):221-226.
[4]CHEN S W, LIU W P. Enantioselective degradation of metalaxyl in anaerobic activated sewage sludge[J]. Bull Environ Contam Toxicol,2009, 82(3):327-331.
[5]诸平.手性分子研究的过去、现在与未来:2001年诺贝尔化学奖深远意义剖析[J].宝鸡文理学院学报(自然科学版), 2002, 22(1):70-74.ZHU P. Chiral molecules research:past, present, and future[J]. J Baoji Coll Arts Sci(Nat Sci Ed), 2002, 22(1):70-74.
[6]NAGAI T, KUROSU A, MATSUSHIMA K, et al. Simultaneous identification of the enantiomers and diastereomers of N, O-ditrifluoroacetylated ephedrine and norephedrine in blood plasma using chiral capillary gas chromatography-mass spectrometry with selected ion monitoring[J]. J Anal Toxicol., 2012, 36(2):96-105.
[7]SCHURIG V, JUZA M. Analytical separation of enantiomers by gas chromatography on chiral stationary phases[M]//Advances in Chromatography. CRC Press, 2014:117-168.
[8]MORRISON C, SMITH F J, TOMASZEWSKI T, et al. Chiral gas chromatography as a tool for investigations into illicitly manufactured methylamphetamine[J]. Chirality, 2011, 23(7):519-522.
[9]PENG L M, JAYAPALAN S, CHANKVETADZE B, et al. Reversedphase chiral HPLC and LC/MS analysis with tris(chloromethylphenylcarbamate)derivatives of cellulose and amylose as chiral stationary phases[J]. J Chromatogr A, 2010, 1217(44):6942-6955.
[10]TSUTSUI H, FUJII S, SAKAMOTO T, et al. Chiral amines as reagents for HPLC-MS enantioseparation of chiral carboxylic acids[J]. J Sep Sci, 2012, 35(13):1551-1559.
[11]MENG L, WANG B, LUO F, et al. Application of dispersive liquidliquid microextraction and CE with UV detection for the chiral separation and determination of the multiple illicit drugs on forensic samples[J]. Forensic Sci Int, 2011, 209(1-3):42-47.
[12]WAGNER Z, TáBI T, JAKóT, et al. Chiral separation and determination of excitatory amino acids in brain samples by CE-LIF using dual cyclodextrin system[J]. Anal Bioanal Chem, 2012, 404(8):2363-2368.
[13]ZHANG H Z, QI L, QIAO J, et al. Determination of sodium benzoate by chiral ligand exchange CE based on its inhibitory activity in Damino acid oxidase mediated oxidation of D-serine[J]. Anal Chim Acta, 2011, 691(1-2):103-109.
[14]刘海兴,于爱民,刘凤芹,等.毛细管电泳在手性物质分离中的应用[J].化学试剂, 2005, 27(9):535-540.LIU H X, YU A M, LIU F Q, et al. Application of capillary electrophoresis in chiral separation[J]. Chem Reagents, 2005, 27(9):535-540.
[15]ALTRIA K D, ELDER D. Overview of the status and applications of capillary electrophoresis to the analysis of small molecules[J]. J Chromatogr A, 2004, 1023(1):1-14.
[16]KANG J W, WISTUBA D, SCHURIG V. Recent progress in enantiomeric separation by capillary electrochromatography[J].Electrophoresis, 2002, 23(22-23):4005-4021.
[17]RIZZI A. Fundamental aspects of chiral separations by capillary electrophoresis[J]. Electrophoresis, 2001, 22(15):3079-3106.
[18]QUIRINO J P, TERABE S. Exceeding 5000-fold concentration of dilute analytes in micellar electrokinetic chromatography[J]. Science,1998, 282(5388):465-468.
[19]YU L J, LI S F Y. Dynamic pH junction-sweeping capillary electrophoresis for online preconcentration of toxic pyrrolizidine alkaloids in Chinese herbal medicine[J]. Electrophoresis, 2005,26(22):4360-4367.
[20]卢玉超,王海燕,宋萍萍,等.毛细管电泳-场强放大样品堆积法检测染发剂中的7种苯胺类物质[J].色谱, 2011, 29(11):1122-1127.LU Y C, WANG H Y, SONG P P, et al. Determination of seven aromatic amines in hair dyes by capillary electrophoresis coupled with field-amplified sample stacking[J]. Chin J Chromatogr, 2011,29(11):1122-1127.
[21]LEVENT A, YARDIM Y, DEMIR C. Determination of trace metal and mineral levels in the tobacco and cigarette samples using by fass[J]. J Chem Soc Pakistan, 2013, 35(2):257-261.
[22]WANG X, MASSCHELEIN E, HESPEL P, et al. Simultaneous determination of nitrite and nitrate in human plasma by on-capillary preconcentration with field-amplified sample stacking[J].Electrophoresis, 2012, 33(2):402-405.
[23]T?MA P,?USTKOVá-FI?EROVáM, OPEKAR F, et al. Largevolume sample stacking for in vivo monitoring of trace levels ofγ-aminobutyric acid, Glycine and glutamate in microdialysates of periaqueductal gray matter by capillary electrophoresis with contactless conductivity detection[J]. J Chromatogr A, 2013, 1303:94-99.
[24]冯丹,孙学鹏,姜丽英,等.浙江衢州地区柑橘绿霉病菌对抑霉唑和多菌灵的抗性水平及其分子机制[J].农药学学报, 2011, 13(4):341-346.FENG D, SUN X P, JIANG L Y, et al. Resistance level and mechanism of Penicillium digitatum to imazalil and carbendazim in Quzhou, Zhejiang[J]. Chin J Pestic Sci, 2011, 13(4):341-346.
[25]CHAI T, YANG W, QIU J, et al. Direct enantioseparation of nitrogen-heterocyclic pesticides on cellulose-based chiral column by high-performance liquid chromatography[J]. Chirality, 2015, 27(1):32-38.
[26]LI R N, DONG F S, XU J, et al. Enantioseparation of imazalil and monitoring of its enantioselective degradation in apples and soils using ultrahigh-performance liquid chromatography-tandem mass spectrometry[J]. J Agric Food Chem, 2017, 65(16):3259-3267.
[27]KODAMA S, YAMAMOTO A, OHURA T, et al. Enantioseparation of imazalil residue in orange by capillary electrophoresis with 2-hydroxypropyl-β-cyclodextrin as a chiral selector[J]. J Agric Food Chem, 2003, 51(21):6128-6131.
[28]SHI J H, DING Z J, HU Y. Experimental and theoretical studies on the enantioseparation and chiral recognition of mandelate and cyclohexylmandelate on permethylatedβ-cyclodextrin chiral stationary phase[J]. Chromatographia, 2011, 74(3-4):319-325.
[29]FANALI S. Enantioselective determination by capillary electrophoresis with cyclodextrins as chiral selectors[J]. J Chromatogr A, 2000, 875(1-2):89-122.
[30]CHU B L, GUO B Y, PENG Z L, et al. Studies on degradation of imazalil enantiomers in soil using capillary electrophoresis[J]. J Sep Sci, 2007, 30(6):923-929.
[31]WREN S A C, ROWE R C. Theoretical aspects of chiral separation in capillary electrophoresis:I. Initial evaluation of a model[J]. J Chromatogr A, 1992, 603(1-2):235-241.
[32]SERA Y, MATSUBARA N, OTSUKA K, et al. Sweeping on a microchip:Concentration profiles of the focused zone in micellar electrokinetic chromatography[J]. Electrophoresis, 2001, 22(16):3509-3513.
[33]QUIRINO J P, TERABE S. Approaching a million-fold sensitivity increase in capillary electrophoresis with direct ultraviolet detection:cation-selective exhaustive injection and sweeping[J]. Anal Chem,2000, 72(5):1023-1030.