LUO, Hong2Qun LIU, Shao2Pu Ξ LI, Nian2Bing
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- Δανάη Ζάρκος
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1 , ACTA CHIMICA SINICA Vol 61, 2003 No 3, ΞΞ ( ), 2, 2, 2, 3/ 2 2,, 2,, Ne w Methods for the Determination of the Inclusion Constant between Procaine Hydrochloride and 2Cyclodextrin by Resonance Nonlinear Scattering Technology LUO, Hong2Qun LIU, Shao2Pu Ξ LI, Nian2Bing ( School of Chemistry and Chemical Engineering, Southwest China Normal University, Chongqing ) Abstract The resonance nonlinear scattering intensity of procaine hydrochloride solution is weak When 2 cyclodextrin was added to the procaine hydrochloride solution and formed an inclusion complex, the nonlinear scattering intensity was enhanced greatly The intensity of the resonance nonlinear scattering increased with an increase in 2cyclodextrin concentration In this work, the interaction of 2cyclodextrin and procaine hydrochloride in aqueous solution was studied by the resonance nonlinear scattering technology The new methods for the determination of the inclusion constant of 2cyclodextrin have been developed by using the frequency doubling scattering, second2 order scattering, frequency tripling scattering and 3/ 2 multiple frequency scattering technology The determination results were in correspondence with those of the spectrophotometric, fluorescence and resonance Rayleigh scattering methods Therefore, the resonance nonlinear scattering can be used as a new technology for the determination of the 2 cyclodextrin inclusion constant Keywords procaine hydrochloride, 2cyclodextrin, inclusion constant, resonance nonlinear scattering technology ( 2Cyclodextrin, CD) (CGT) CD 2, 2 2CD 6 8 CD,, [1,,2] CD CD, CD,, CD Ξ E2mail : edu cn Received August 8, 2002 ; revised October 18, 2002 ; accepted November 19, 2002 (No ) (No )
2 436 Vol 61, 2003, CD CD,G CD [20 ] ( ),,, 2 [3] : CD [4] ( I - I 0 ) / ( I - I) = K f [ CD] (3) [5] [6] [7] [8] [9] [10] [11] ( I SOS - I 0 SOS) / ( ISOS - I SOS ) = K f [ CD] (4) ( I FDS - I 0 FDS) / ( IFDS - I FDS ) = K f [ CD] (5) ( I FTS - I 0 FTS) / ( IFTS - I FTS ) = K f [ CD] (6) ( I (3/ 2) MFS - I 0 (3/ 2) MFS) / ( I (3/ 2) MFS - I 3/ 2MFS ) =, 3/ 2 K f [ CD] (7), (4) (7) : ( I - I 0 ) / ( I - I) [ CD] ( I I SOS, I FDS, I FTS I (3/ 2) MFS ) ( I - I 0 ) / ( I - I), [ CD] K f :,, CD, CD (SOS) C CD [ CD], (FDS) (FTS) 3/ 2 (3/ 2MFS), 2 : CD, 1 SOS, FDS, FTS 3/ 2MFS 2CD I = rc G rk f C G [ CD], 2CD 1 1 [20], 2CD :, 2CD, 1/ I SOS = 1/ ( rc G ) + 1/ ( rk f C G [ CD]) (9) 1/ I FDS = 1/ ( rc G ) + 1/ ( rk f C G [ CD]) (10) 1/ I FTS = 1/ ( rc G ) + 1/ ( rk f C G [ CD]) (11) 1, I s ex [21] : C G,1/ I 1/ [ CD] ( CD I s (, ex ) = Kcbf ( d) f ( ) E M ( ) E X ( ex ) K, ex 2, d, E X ( ex ), E M ( ), c, b 2 1 ex = 1/ 2, 2, 3 3/ 2 I s 2 F22500 ( ) 3/ 2 I SOS = Kbcf ( d) f ( ) E x (1/ 2 ) E M ( ) I FDS = Kbcf ( d) f ( ) E x (2 ) E M ( ) I FTS = Kbcf ( d) f ( ) E x (3 ) E M ( ) I (3/ 2) MFS = Kbcf ( d) f ( ) E x (3/ 2 ) E M ( ) 25 ml,,5 min,, SOS, FDS, FTS (3/ 2) MFS 3/ 2 c I 1 1 : SOS, I FDS, I FTS I (3/ 2) MFS, I SOS, I FDS, I FTS I (3/ 2) MFS, SOS, FDS, FTS CD + G CD2G (1) K f = [ CD2G]/ [ CD] [ G] (2) 1/ I (3/ 2) MFS = 1/ ( rc G ) + 1/ ( rk f C G [ CD]) (12) r (9) (12),, CD C CD [ CD]), K f, ( ), mol L - 1 ; 2 (Aldrich ), mol L ml 25 ml, 2, (3/ 2)2MFS,, 2 I SOS, I FDS, I FTS I (3/ 2) MFS
3 No 3 : ( nm), ( 2 ex ) ;, 1/ 2 [ em = (1/ 2) ex ] ; 1/ 3, 2/ 3 em = 3/ nm, 10 nm 5 nm, ( 1A) 2 (720, 730, 740 nm), nm 2, 1/ 2 (360, nm), 1/ 3 (240, nm) 2/ 3 (480, nm) 3/ 2, nm, 10 nm 5 nm (A), 3/ 2 (B) 2CD : a 0 mol L 3A - 1, b mol L - 1 : CD ( - 5 mol L - 1 EX : 5 0 nm ; EM : 5 0 nm ; PMT 3/ 2 ) : 400 V Figure 1 Diagram of second2order scattering scanning (A) and 1 3 : (1) second2order scattering spectra (B) of 2CD2procaine hydrochloride 3/ 2 ; (2) system 3/ 2 Concentration of 2CD : a 0 mol L - 1, b mol L - 1 ; (3) Concentration of procaine hydrochloride : mol L - 1 EX slit : 5 0 3/ 2, nm ; EM slit : 5 0 nm ; PMT voltage : 400 V 2 720, nm, nm 2CD : a 0 mol L - 1, b mol L - 1 : mol L - 1 EX : 20 0 nm ; EM : 20 0 nm ; PMT : 700 V Figure 2 The scattering scanning diagram in the wavelength range of nm when the wavelengths at 720, 730 and 740 nm were applied as the incident wavelengths Concentration of 2CD : a 0 mol L - 1, b mol L - 1 Concentration of procaine hydrochloride : mol L - 1 EX slit : 20 0 nm ; EM slit : 20 0 nm ; PMT voltage : 700 V
4 438 Vol 61, / 2 ISOS, IFDS, IFTS I (3/ 2) MFS ( I SOS - I 0 SOS) / ( ISOS - I SOS ) C 2CD, ( I FDS - I 0 FDS) / ( IFDS - I FDS ) C 2CD, ( I FTS - I 0 FTS) / ( IFTS - I FTS ) C 2CD ( I (3/ 2) MFS - I 0 (3/ 2) MFS) / ( I (3/ 2) MFS - I (3/ 2) MFS ) C 2CD ( 4), K f 1/ I SOS 1/ C 2CD, 1/ I FDS 1/ C 2CD, 1/ I FTS 1/ C 2CD 1/ I (3/ 2) MFS 1/ C 2CD ( 5), K f 1 3/ 2 2CD [20], [ 10 ],, (A) (B) 2CD : a 0 mol L - 1, b mol L - 1 : mol L - 1 EX : 20 0 nm ; EM : 20 0 nm ; PMT : 400 V Figure 3 Frequency tripling scattering scanning diagram (A) and frequency tripling scattering spectra ( B ) of 2CD2procaine hydrochloride system Concentration of 2CD : a 0 mol L - 1, b mol L - 1 Concentration of procaine hydrochloride : mol L - 1 EX slit : 2010 nm ; EM slit : 20 0 nm ; PMT voltage : 400 V 2CD, 4 ( I - I 0 ) / ( I - I) C 2CD 3/ 2, FDS; SOS; FTS; (3/ 2) MFS, 3/ 2 ( 1B 3B ), 3/ nm, 390 nm, 247 nm 484 nm, 2CD, 3/ 2, 2CD : 2CD 1 1, 3/ 2 2CD 3/ 2 5 1/ I 1/ C 2CD I SOS, I FDS, I FTS I (3/ 2) MFS, 2CD 3/ 2 I 0 SOS, I 0 FDS, I 0 FTS I 0 (3/ 2) MFS, 2CD Figure 4 Plots of ( I - I 0 ) / ( I - I) versus C Figure 5 Curves of 1/ I versus C 2CD FDS; SOS; FTS; (3/ 2) MFS 2CD
5 No 3 : CD Table 1 Inclusion constants of procaine hydrochloride2 2CD complex with different determination methods / nm K f / (10 2 L mol - 1 ) (UV2vis) a [20 ] (Flu) a [20 ] (RRS) 251, b, 1 23 c 1 21 b, 1 15 c [20 ] 1 37 [10 ] (SOS) This work ( FDS) This work ( FTS) This work 3/ 2 [ (3/ 2) MFS] This work n = 4 a b, Benesi2Hildebrand c 251 nm 332 nm 4 (,,,, 1995, 53, 1178 ) 3/ 2 13 Liu, S2P ; Liu, Z2F Chem J Chin Univ 1996, 17, (in Chinese), (,,, 1996, 17, 1213 ), 14 Liu, S2P ; Liu, Z2F ; Luo, H2Q J Southwest China Normal Univ ( Nat Sci ) 2000, 25, 408 (in Chinese),, (,,, ( References 5 Jiang, Y2B Spectrochim Acta 1995, 51A, Hui, Y2Z ; Gu, J 2H Acta Chim Sinica 1981, 39, 309 (in Chinese) (,,, 1981, 39, 309 ) 7 Inoue, Y ; Miyata, Y Bull Chem Soc Jpn 1981, 54, Higuchi, T ; Connors, K A Anal Chem Instrum 1965, 4, Uekama, K ; Hirayama, K ; Irie, T Chem Lett 1978, 7, Gu, J ; Pan, J 2H Talanta 1999, 50, Bersier, P M ; Bersier, J ; Klingert, B Electroanalysis ( N Y ) 1991, 3, Liu, S2P ; Liu, Z2F ; Li, M Acta Chim Sinica 1995, 53, 1178 (in Chinese) ), 2000, 25, 408 ) 15 Liu, S2P ; Liu, Z2F Chem J Chin Univ 1996, 17, 887 (in Chinese) 1 Szente, L ; Szejtli, J Analyst 1998, 123, 735 (,,, 1996, 17, 887 ) 2 Connors, K A Chem Rev 1997, 97, Liu, S2P ; Liu, Z2F ; Li, M Chin J Anal Chem 1996, 3 Zhang, H2C New Application of 120 Kinds of Old Drug in Clinic, People s Surgeon Press, Beijing, 1996, p 79 (in Chinese) 24, 501 (in Chinese) (,,,, 1996, 24, 501 ) (, 120,,, 17 Liu, S 2P ; Yang, R ; Liu, Z2F Chin J Anal Chem 1996, p 79 ) 1998, 26, 1432 (in Chinese) 4 Benesi, H A ; Hildebrand, J J Am Chem Soc 1949, 71, (,,,, 1998, 26, 1432 ) Liu, S2P ; Liu, Z2F ; Jiang, Z2L ; Li, M ; Long, X2F Acta Chim Sinica 2001, 59, 1864 (in Chinese) (,,,,,, 2001, 59, 1864 ) 19 Liu, S2P ; Liu, Z2F ; Li, M Chin J Anal Chem 1996, 24, 665 (in Chinese) (,,,, 1996, 24, 665 ) 20 Li, N2B ; Luo, H2Q ; Liu, S2P ; Chen, G2N Spectrochim Acta 2002, 58A, Jiang, Z2L ; Feng, Z2W ; Liu, Q2Y ; Jiang, Y2M ; Liang, H Chin J Inorg Chem 2001, 17, 355 ( in Chinese) (,,,,,, 2001, 17, 355 ) (A SHEN, H1)
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