38 2010 10 FENXI UAXUE Chinese Journal of Analytical Chemistry 10 1400 ~ 1404 DOI 10. 3724 /P. J. 1096. 2010. 01400 - - * 442700 442000 - FO-DLLME - 3 24 1-200 μl 300 μl 1. 2 g NaCl 1 mol /L 3 PO 4 200 μl 8. 0 ml 3 min 3 0. 05 ~ 6. 0 mg /L 20 ~ 38 μg /L 90. 11% ~ 107. 7% 3. 5% ~ 4. 6% - 1-1 1 2 Lai 3-5 4-3 - 5 6 7 DLLME 8 9 ~ 11 - FO-DLLME 12 DLLME DLLME FO-DLLME 24 1-2- 2-CP 2 6-2 6-DCP 2 4-2 4-DCP 2 2. 1 1100 Agilent Agilent 802 2-2 6-2 4- ACRO 1. 0 g /L 1. 0 ml 2-1. 0 ml 2 6-0. 4 ml 2 4-1 L 4 1- V V = 2 1 NaCl 1 mol /L 3 PO 4 TEDIA 2010-03-23 2010-04-22 No. Q20096001 * E-mail dzqyx@ yahoo. cn
10 - - 1401 2. 2 Tc-C 18 150 mm 4. 6 mm 5 μm Agilent V V = 70 30 1. 0 ml /min 245 nm 30 20 μl 2. 3 10 ml 8. 0 ml 1. 2 g NaCl 200 μl 1 mol /L 3 PO 4 300 μl 1a 200 μl - 2 1 V /V 3 min 1b 3000 r /min 2 min 1c 0 3 min 1d 50 μl 20 μl 3 3. 1 DLLME 13 1- mp 11 1-1 - mp 24 1- mp 38 Fig. 1 Photograph of different steps in dispersive mp 18 liquid-liquid microextraction base on solidification 1- of floating organic FO-DLLME 1- a. Water sample b. 1- Emulsion of water sample after 1- injection of mixture of extraction and disperser solvent 1- - 2 1 V /V 2 c. After centrifuging floating extraction solvent droplet d. olidification of floating organic drop 200 μl 200 μl 200 μl 3. 2 3 300 μl 300 μl 3. 3 14 NaCl 1. 2 g NaCl 1. 2 g NaCl 15 1 mol /L 3 PO 4 3 PO 4 200 μl
1402 38 2 Fig. 2 Optimization of extractant volume 1. 0 mg /L 2-chlorophenol 2-CP 1. 0 mg /L 2-6-dichlorophenol 2- CP 2 6-DCP 0. 4 mg /L 2 4-DCP. 300 μl methanol 1. 2 g NaCl 200 μl 1 mol /L 3 PO 4 8. 0 ml Mixed standard solution. 3 Fig. 3 Optimization of dispersive solvent 2 Experimental conditions are same as in Fig. 2 3 PO 4 p 16 200 μl 1 mol /L 3 PO 4 p = 1. 34 3. 4 10 ml 8. 0 ml 8. 0 ml 3 min 3 min 3. 5 LOD /N = 3 1. 0 mg /L 6 1 1 3 Table 1 Linear equation limit of detection RD and enrichment factor for three kinds of chlorophenols RD % Linear range Analyte Linear equation r 2 Detection limit Enrichment mg /L factor Intra-day Inter-day 2-CP y = 0. 05581c + 7. 906 0. 05 ~ 6. 0 0. 9985 38 38. 2 3. 7 4. 6 2 6-DCP y = 0. 2875c - 6. 22 0. 05 ~ 6. 0 0. 9989 22 46. 5 3. 5 3. 8 2 4-DCP y = 0. 3379c - 5. 48 0. 05 ~ 6. 0 0. 9995 20 47. 4 2. 2 3. 5 3. 6 -LPME 17 2 -LPME 2-CP 2 6-DCP -LPME 2 - Table 2 Comparison of FO-DLLME method and -LPME method Analyte Extraction time min Detection limit Linear range RD Intra-day RD % Inter-day RD % 2-CP 6 38 0. 05 ~ 2. 0 0. 05 ~ 6. 0 4. 6 3. 7 5. 4 4. 6 2 6-DCP 20 3 12 22 0. 05 ~ 2. 0 0. 05 ~ 6. 0 3. 3 3. 5 6. 8 3. 8 2 4-DCP 23 20 0. 05 ~ 2. 0 0. 05 ~ 6. 0 2. 4 2. 2 8. 8 3. 5 eadspace liquid-phase microextraction -LPME - Dispersive liquid-liquid microextraction based on solidification of floating organic FO-DLLME
10 - - 1403 3. 7 0. 45 μm 3 90. 1% ~ 107. 7% 4 4 Fig. 4 Chromatograms of sample determination A. Blank water sample B C. piked water sample B 0. 375 mg /L C 0. 5 mg /L 1. 2-CP 2. 2 6-DCP 3. 2 4- DCP R olvent peak 10 min 3 Table 3 Analytical results of samples ample Tap water Water of anjiang river Added mg /L ND. Not detected 2-CP Found mg /L 2 6-DCP 2 4-DCP 2-CP Recovery % n = 5 2 6-DCP 2 4-DCP 0. 00 0. 129 ND ND 0. 375 0. 527 0. 391 0. 366 106. 2 104. 2 97. 5 0. 500 0. 655 0. 518 0. 498 105. 2 103. 6 99. 7 0. 00 0. 041 ND ND 0. 500 0. 520 0. 517 0. 451 95. 8 103. 4 90. 1 1. 00 0. 962 1. 005 1. 077 92. 1 100. 5 107. 7 References 1 Tsuji N irooka T Nagase irata K Miyamoto K. Biotechnol. Lett. 2003 25 3 241 ~ 244 2 Feng Q Z Zhao L X Yan W Ji F. Anal. Bioanal. Chem. 2008 391 3 1073 ~ 1079 3 Lai B W Liu B M Malik P K Wu F. Anal. Chim. Acta 2006 576 1 61 ~ 66 4 CAI Min WANG Wei XING Jun FENG Yu-Qi WU Cai-Ying. Chinese J. Anal. Chem. 2006 34 1 91 ~ 94 5 Tor A Cengeloglu Y Aydin M E Wichmann Bahadir M. Fresenius Environmental Bulletin 2004 13 11B 1329 ~ 1333 6 Portillo M Prohibas N alvado V imonet B M. J. Chromatogr. A 2006 1103 1 29 ~ 34 7 ZANG Xiao-uan WU Qiu-ua ZANG Mei-Yue XI Guo-ong WANG Zhi. Chinese J. Anal. Chem. 2009 37 2 161 ~ 168 8 Rezaee M Assadi Y Milani M R Aghaee E Ahmadi F Berijani. J. Chromatogr. A 2006 1116 1-2 1 ~ 9 9 ZANG Yan-Jie BAI Xiao-ong LI Li-ua WANG Quan-De. Chinese J. Anal. Chem. 2009 37 12 1805 ~ 1809 10 DING Zong-Qing LIU Guang-Dong. Chinese J. Anal. Chem. 2009 37 1 119 ~ 122 11 Chiang J uang D. Talanta 2008 75 1 70 ~ 75 12 Leong M I uang D. J. Chromatogr. A 2008 1211 1-2 8 ~ 12 13 Wei G Li Y Y Wang X D. J. ep. ci. 2007 30 18 3262 ~ 3267 14 Basheer C Lee K Obbard J P. J. Chromatogr. A 2004 1022 1-2 161 ~ 169 15 Zhao L M Lee K. J. Chromatogr. A 2001 931 1-2 95 ~ 105
1404 38 16 Buchholz K D Pawliszyn J. Anal. Chem. 1994 66 1 160 ~ 167 17 Xu Liao Y Yao J R. J. Chromatogr. A 2007 1167 1 1 ~ 8 Dispersive Liquid-Liquid Microextraction Based on olidification of Floating Organic Drop Combined with igh Performance Liquid Chromatography for Determination of Chlorophenols in Aqueous amples DING Zong-Qing * 1 ZANG Qiong-Yao 2 1 Department of Chemistry Yunyang Teachers College Danjiangkou 442700 2 Department of Comment Medicinal Chemistry ubei Medical College hiyan 442000 Abstract Using the method of dispersive liquid liquid microextraction based on solidification of floating organic DLLME-FO combined with PLC three kinds of chlorophenols in aqueous samples were determined. The DLLME method with 1-dodecanol whose density was less than water and freezing point was 24 utilized as extractant and methanol as dispersive solvent was applied to analyze water samples. After the mixture was centrifugaled the floated extractant that was solidified in ice bath was easily removed from water phase. When the solidified extractant droplet was redissolved it was injected into the PLC for analysis. The optimal experiment conditions were as follows extractant solvent 200 μl dispersive solvent 300 μl NaCl 1. 2 g 1 mol /L 3 PO 4 200 μl sample volume 8. 0 ml extraction time 3 min. The calibration curve was linear in the range of 0. 05-6. 0 mg /L of the three kinds of chlorophenols and the detection limits were 20-38 μg /L. This method has been applied to the determination of real water samples the recovery of standard additions were from 90. 11% to 107. 7% and the inter-day RDs were between 3. 5% and 4. 6%. The method extended the range of choosing the extractant in DLLME it was proven to be simple rapid accurate and environment friendly. Keywords Dispersive liquid liquid microextraction based on solidification of floating organic igh performance liquid chromatography Chlorophenol 1-Dodecanol eparation and enrichment Received 23 March 2010 accepted 22 April 2010 櫞櫞櫞櫞櫞櫞櫞櫞櫞櫞櫞櫞櫞櫞櫞櫞櫞櫞櫞櫞櫞櫞櫞櫞櫞櫞櫞櫞櫞櫞櫞櫞櫞櫞櫞櫞櫞櫞櫞櫞櫞櫞櫞櫞 " " 9 3 9 2010 6 78. 00