(1)Journal of the Korean Chemical Society 2004, Vol

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(1)Journal of the Korean Chemical Society 2004, Vol. 48, No. 1 Printed in the Republic of Korea. A

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(3) (2003. 11. 3 ). †. Molecularly Imprinted Polymer for Adsorption of Bisphenol A Jae Chun Ryu, Jong-Hun Kim†, and Sang Hee Lee* Department of Chemistry, School of Natural Science, Kunsan National University, Kunsan 573-701, Korea † Department of Environmental Science and Technology, Jeonju University, Jeonju 560-759, Korea (Received November 3, 2003). : A, , Keywords: Bisphenol A, Solid Phase Extraction, Molecular imprinting Polymer. Bisphenol A(BPA) !" #$%&'() *+,- ./ 0( 123(4. ( *+,5 65 78 9:- ;<.= >?@A, ! B?

(4) , CDE, F G5 HI.8J KLM NO (lacquer)= (?@P QR >?@ SS TU3V BPAW ;XM Y4. Z[, BPA estrogenic \ ]^_(Endocrine Disruptors) = àb Yc 7 8, d3 e Î fgM BPAW hijk= l M

(5) mZ no( pq@ Y4. rs2- BPAW t2jk= lM

(6) muR vw hijk= xy M t( zj(4. {

(7) ?|W >?M} ~j k= (liquid-liquid extraction)M xyM n 5 65 - {

(8) ?|" ( @= %)$! W (?Z 3 (solid phase extraction) ( h ij(P J mu zM4. BPA j r( F= ~j %)$ != i( ! kP d3 : T- ( !_ ( X @c t2l c aJ

(9) BPAW &4 ¡jk= ¢M£ ¤ Y %)$!¥ q4. ¦+R § pq R BPA Z ¨©( ªZ %)$!- «¬ J mM} W UM Z4. 1-3. 4,5. 6-12. 13,14. 15. Fig. 1. Bisphenol A(BPA)..

(10) . (molecular 5 U 7$(recognition site) W o

(11) mZ n(4. J mM} 65 ª %®¯

(12) " °±

(13) - ionic ²³?J (?M !, - ÚJ (?Z µV àb Y 4. § pqR (hydrophobic) ²³? e BPA- ¶«-

(14) " >(- ÚJ (?M Z4. (·Z ¸J Scheme 1 V 7jk= ¹\º4. - 123=R (P »p´ ¼½J {!¤ Y divinylbenzene(DVB, 15.4 mmol) J >?M¾ °¿· BPA" ÚJ ¤ Y U^ N-vinylpyrolidone(NVP, 13.2 mmol)J >? M¾4. À fg MR ÁTU Âk=R B" G5 Ã Ä À¥ ;Å »p´ ÁTU3(crosslinked copolymer)W Æ M¾4. ; imprinting). 16-22. 23. 7.

(15) . 8. Scheme 1 Table 1. Conditions of polymerization polymer. II. condition Polymerization Template Porogenic solvent(eq)c. III. IV. V. VII. Suspension polymerizationa Solution polymerizationb 3 3 4 3 4 toluene (2.4) toluene (2.4) toluene (1.2) toluene (2.4) toluene (1.8) CH2Cl2 (1.8) toluene (1.8). a. polymerization was performed at 70 oC for 20 h. b) polymerization was performed at rt for 15 h under UV light. c) based on the amoumt of monomers (DVB+NVP).. Table 2. Recovery efficiency and composition of polymers Polymer Composition (mmole%)a. DVB NVP. Recovery efficiency(%). 74.3 25.7 7.1. II. III. IV. V. VI. VII. 73.2 26.8 15.5. 69.5 30.5 18.1. 66.0 34.0 17.4. 91.70 8.3 6.8. 96.4 3.6 20.7. 91.8 8.2 66.5. a. Determined by elemental analysis of polymers.. Å ÀW {

(16) ?|= Çc .ÈXk=R CW Æº4. C Ã Ä BPA-

(17) (-OH)¥ ÚJ ¤ Y %®&É

(18) (C=O)W jÊZ mQ Ë Y4. ¦+R Ì

(19) " ( jÊ Z - Ã" BPA- Í~A®¬ © Î$

(20) " %®&É

(21) - Úk= M} C BPA" |ª ÄtZ ^J À¤ YVÏ M¾4. ÐÑ TU(suspension polymerization)R 30~90 µm Ì

(22) - qÀ(granular bead) TU3W ÆJ Yc Î = %)$!- tk= >?M¾4. {

(23) ?|= tolueneJ >?Z ?Ò TU~Ó -M} Æ5 Ô>¬= Õ£ Í Ö×ØR nQM} Í {M sÙÚW .ÈM¾4. Û Úo T ÜÝ Ú 90 µm- sieveW (?u .ÈM 30~90 µm - Þ J Ë ÚW Æc >?M¾4. TU ~Ó / ßJ Table 1 àM¾4. ~Ó/ßR Æcá X{@c Y 123- /J âl ãÈM} ´tM¾ (W Table 2 ¹\º4. T U~Ó >?Z ¶ 123- i5 ¶ Gä! 24. TU~Ó- /ß e >?Z ?| ¦+ Æcá ;X ¶ 123- / »(W &¾4.

(24) . § pqR BPAW hjk = 7M

(25) mZ W UM

(26) muR >?uåM (j À5 BPA 3+ ¤ Y 4. Î· phenol æ5 +çè TU~ÓR TU w u.= ³?M= BPAW Àk= >?M é5 ê ¥¨M4. ëZ, TU~Ó ì í Í îï ¤ Y BPA t2l ¤ |ª ð»W { ¬¤ V Y4. ¦+R BPAW ñ¤ Y À =

(27) W °±

(28) = Q Z À 2¥ ´ UJ ¤ Yc vw d¤ Yk °± ò + çè TU~ÓJ wuM} TU~Ó( c! ä J ó °+ jk= Ät( ô° >?¤ ¥ õº4. ¦+R § pqR - Ì

(29) ¥ O!ö M! 3- ÷¥ õ Ú J ¤ Y À 3J >?M¾4. À 3J 123 (DVB e NVP)" øUZ í TU~Ó ù 70~80 C - úVR .¥ õºk úR TU~Ó û ¤ ?uV¥ ô° üZ ?Ò( oc! o. Journal of the Korean Chemical Society.

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(31) A . 9. Fig. 2. Structure of the templates.. Scheme 2. ! ä4. ¦+R wú TU~ÓR - {p J ý¥ þ ?uV .W u´M

(32) mM} À 4W >?M¾4. À 3 e 4- UtJ Scheme 2 ¹\º4. 5=Í para mQ ¡jk= nitration ù Yº kP, )=

(33) Pd/C ÿ| MR ~Ó þ °±k= M} 2W Æº4. °± 2 acetyl chloride ë valeroyl chloride" ~Ó Âk=R 3 e 4W ÆJ Yº4. BPA . - BPA Z i t´W Table 2 ¹\º4. }

(34) R i5 BPA(1.0 ng/ml)W X{Z ?Ò 300 mlW 1.0 g æ J BP- J %= . ¹ (4. BPAW {

(35) ?|= ? þ Î J GC/MS= t2M} ´tM¾4. Z[ BPA"- ©J (

(36) mM} ÀJ >?Z ª (II, III, IV, VI e VII)¥ ÀJ >?M! 5 (I e V) M} BPA Z i( ÐwM£ ý¥M¾4. (·Z h ÐÑTUR&4 ?ÒTU~ÓR hj(ºA, ( Fig. 3 ¹ " G( ¤ Y4. ÐÑTU~Ó(a)R ^J >?M=

(37) W Ë À" NVP 123¥

(38) - ^ UJ Xk=R À " NVP- U- tV¥ ô°! ~

(39) , ?ÒTU (b)R ^( õk= ¶

(40) - U( &4 ?(M

(41) k= 4.. Fig. 3. Interaction between template and monomer. 2004, Vol. 48, No. 1. 25.

(42) . 10. 4Á {V?|(porogenic solvent)= = toluene J >?M¾A >?2J $M} UZ (II " III)- i t´ »(W &(! ä4. úR TU~Ó û ª( VI) À 3( toluene ! äk= ?|W chloroform k= ºA, Î ¦+ i( À 4W > ?M ?|= tolueneJ >?Z VII&4 BPA i ( Ì£ ô°A, (·Z »( À- q/- » (&4 >?Z ?| e X{ NVP- X 2- »(R

(43) Z ék= &4. à NVPW j£ >?M

(44) ^( ÛM

(45) ¥ ca b ´jk= ?ÒT- ²® ^_( " ÿM

(46) ca! IV¥ |ª a_ é (4. ëZ Ú$¥ ÍM} ¨©( wM é(4. ~= ÜÝ 6( >?M

(47) ² ® ^_- ²³?( à@c ò ¨©( wM é(4. (·Z J aM} NVP e À- >?2 - j Z pq¥ T (4..

(48) 1. Borotons, J. A.; Olea-Serrano, M. F.; Villaloobos, M.; Fedraza, V.; Olea, N. Environmental Health Perspective 1995, 103, 608. 2. Kawamura, Y.;Inoue, K.; Nakazawa, H.; Yamada, T.; Maitani, T. J. Food Hygien. Soc. Japan. 2001, 42, 13. 3. Munguia-Lopez, E. M.; Soto-Valdez, H. J. Agricultural Food Chem. 2001, 49, 3666. 4. Krishnan, A. V.; Starhis, P.; Permuth, S. F.; Tokes, L.; Feldman, D. Endocrinology 1993, 132, 3. 5. Brotons, J. A.; Olea-Serrano, M. F.; Villalobos, M.; Pedreza, V.; Olea, N. Environ. Health Perspect. 1995, 105, 70. 6. Sajiki, J. J. Chromatogr. B, 2001, 755, 9. 7. Kang, J.-H.; Kondo, F. Research Veterinary Science, 2002, 73, 177. 8. Biles, J. E.; Mcneal, T. P.; Begley, T. H. J. Agricultural Food Chem. 1997, 45, 4697. 9. Horie, M.; Yoshida, T.; Ishii, R.; Nakazawa, H. Bunseki Kagaku 1999, 48, 579. 10. Imanaka, M.; Sasaki, K.; Nemoto, S.; Ueda, E.; Murakami, E.; Miyata, d.; Tonogai, Y. J. Food Hygien. Soc. Japan. 2001, 42, 71. 11. Inoue, K.; Kato, K.; Yoshimura, Y.; Makino, T.; Nakazawa, H. J. Chromatogr. B, 2000, 749, 17.. 12. Perderson, S. N.; Lindholst, C. J. Chromatogr. A, 1999, 864, 17. 13. Hankemeier, T.; van Leewen, S. P. J.; Vreuls, R. J. J.; Brinkman, U. A.Th. J. Chromatogr. A. 1998, 811, 117. 14. Verma, K. K.; Louter, A. H. H.; Jain, A.; Pocurull, E.; Vruels, J. J.; Brinkman, U. A. Th. Chromatographia, 1997, 44, 372. 15. Sellergren, B. Trends Anal. Chem. 1997, 16, 310. 16. Shea, K. J. Trends Polym Sci. 1994, 2, 166. 17. Wulff, G. Angew Chem, Int Ed Engl. 1995, 34, 1812. 18. Vidyasankar, S.; Arnold, F. H. Curr Opin Biotechnol. 1995, 6, 218. 19. Steinke, J.; Sherrington, D. C.; Dunkin, I. R. Adv Polym Sci. 1995, 123, 81. 20. Haupt, K.; Mosbach, K. Trends Biotechnol. 1998, 16, 468. 21. Takeuchi, T.; Haginaka, J. J. Chromatogr. B 1998, 728, 1. 22. Mayes, A. G.; Mosbach, K. Trends Anal. Chem. 1997, 16, 321. 23. Yu, C.; Mosbach, K. J. Org. Chem. 1997, 62, 4057. VII (solutionpolymerization). 24. 4(454.5 mg, 1.152 Borosilicate glass mmol) N-vinyl-2-pyrrolidinone(1.05 ml, 9.91 mmol) divinylbenzene(DVB-80, 80%, 2.04 ml, 11.52 mmol), toluene(2.2 ml) AIBN (58.6 mg, 0.35 mmol) ..

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(51) ! "#$ %&' () 5!* purge . +,) - . /0 1 15* 23 UV lamp(365 nm)) 456 . 78' !9 .9:; < =9 >? @ 30~100 µm AB CBD EFG. 100 ml flask EFH !9I CH OH(50 ml) J 10* 2 3 K5$ 10!* LM . NOH PQR glass filter) STUI CH OH CH Cl ) V!W XO 56 Y Z[\ "#$ 70 C1 20* 23 %& . %&' !9 Standard Sieve(90 µm)) ](^. !9 VII(1.722 g, 67.5%)(1.5 g, 58.8%, <90 µm) _` [) NG. a!b: C(88.83%), H (8.11%), 3. 3. 2. 2. o. N(0.88%): DVB-80(91.8 mole%), N-vinyl-2-pyrrolidinone (8.2 mole%). (solid-phase extraction methods): 25. (L95 D12 mm) (1:1) 10 ml CH2Cl2 10 ml . 0.01 µg/ml BPA antracene-d10 1 µg/l 300 ml 2 ml . BPA 1 antracene-d10 40 oC 20 ml CH2Cl2 0.2 ml vial . purge. 8 $ !9 :? cd e VHf I ghi STU ) jk XOG ? l Im noR( pq$ no !r sB) tu I < vw' !9 1 *23 %&f ) xy zU {|} ~) %& Q S;? < @ ) ' () Journal of the Korean Chemical Society.

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(53) A . $ GC-Mass) !b . GC-Mass . cd 0B 155 C1 1!* q$ !r 1 C 0B i 165 C1 1!* Rk , !r 6 C i 200 C1 1!* R k $ +.) !r 10 C 0B i 300 C1 0!b . :? : o. o. o. o. o. o. o. 2004, Vol. 48, No. 1. 11. 1 µl = , split ratio 14:1). . <2?[(carrier gas) (He, 99.999%) ? [ : , qs !r 1 ml) & :. . =(injector)I y?(detector) 0B l l 200 CI 250 C1 !b . o. o.

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