Resonance Rayleigh Scattering Spectra of Interaction of Aminoglycoside Antibiotics with Trypan Red and Their Analytical Applications
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1 , ACTA CHIMICA SINICA Vol 61, 2003 No 8, a Ξ, a, b a Ξ ( a ) ( b ), (TR) ( KANA) (NEO) ( GEN) (TOB) (RRS), RRS RRS, nm, 400 nm, g ml - 1 RRS, (3 ) ng ml - 1, KANA > NEO > TOB > GEN,, RRS RRS, Resonance Rayleigh Scattering Spectra of Interaction of Aminoglycoside Antibiotics with Trypan Red and Their Analytical Applications HU, Xiao2Li a LIU, Shao2Pu Ξ a, b LUO, Hong2Qun a ( a School of Chemistry and Chemical Engineering, Southwest China Normal University, Chongqing ) ( b Institute of Environmental Chemistry, Southwest China Normal University, Chongqing ) Abstract In weak acid medium, some aminoglycoside antibiotics, such as kanamycin ( KANA), gentamicin ( GEN), tobramycin (TOB) and neomycin (NEO), or acid bisazo dye trypan red (TR) alone can only produce very weak resonance Rayleigh scattering ( RRS) signals However, when one of the antibiotics and TR react with each other to form the ion association complexes, the RRS intensity can be enhanced greatly and a new RRS spectrum and a significant enhancement of the RRS intensity in the wavelength range from 400 to 535 nm can be observed The maximum scattering peak is at 400 nm and there is a linear relationship between the RRS intensity and the antibiotics concentration in the range of g ml - 1 An RRS method for the determination of aminoglycoside antibiotics at trace amounts of levels has been developed The detection limits (3 ) of the four antibiotics, whose order of sensitivity from high to low ranks as KANA > NEO > TOB > GEN, are ng ml - 1 This method has good selectivity and has been successfully applied to the quick determination of antibiotics not only for injections and ear drips, but also for clinic serum samples as well In addition, the reaction mechanism by using quantum chemistry method and the influencing factors of the RRS spectra and the enhancement reasons of RRS have been discussed Keywords resonance Rayleigh scattering, aminoglycoside antibiotics, trypan red, determination, ( Polyhydroxy antibiotics), [1] Ξ E2mail : edu cn Received November 7, 2002 ; revised February 12, 2003 ; accepted March 25, 2003 (Nos , )
2 1288 Vol 61, 2003 ( Kanamycin) ( Gentamicin) ( Tobramycin) (Neomycin) (Streptomycin), mol L - 1, ,, mol L - 1 BR :0104 mol L - 1 H 3 PO 4,, H 3 BO 3 HAc 012 mol L - 1 NaOH,,, ph, ph,, (MA) [2,3] ( HPLC) [4,5] 1 2 (UV2vis) [6,7] ( IA) [8,9] MA 10 ml 110 ml, ph BR 110 ml, 110 ml, ;HPLC,,, ex = ;UV, ; IA, em, RRS,,, RRS I RRS I 0, I = I - I , [10] [11] RRS 2 1 [12 16] [17 20], RRS, (,trypan red,,, TR) RRS,,, RRS,, RRS,, 400 nm, nm RRS, RRS, RRS KANA > NEO > TOB > GEN 2 KANA TR2 RRS RRS, KANA RRS, RRS KANA, RRS,, 2 2, 2 2 1, 3 BR ph,ph RRS,, RRS RRS ( TR, Switzerland, Fluka ) : RF2540 (, ), :, 5, 5 nm ; UV28500 (, ) ;phs23c (, ) ( Kanamycin Sulphate, KANA ; Sigma ) (Neomycin Sulphate, NEO ; Sigma ) ( Gentamicin Sulphate, GEN ; Sigma ) (Tobramycin Sulphate, TOB ; ) : g ml - 1 ; 2010 g ml - 1, 1010 g ml TR2 RRS Figure 1 RRS spectra of TR2aminoglyside antibiotics 1, TR ; 2, KANA ; 3, TR2GEN ; 4, TR2TOB ; 5, TR2NEO ; 6, TR2KANA Antibiotics concentration : 316 g ml - 1 ; TR : mol L - 1 ; ph 312
3 No 8 : TR2KANA RRS Figure 2 RRS spectra of TR2KANA 1, TR ; 2, KANA ; 3, TR2KANA (212 g ml - 1 ) ; 4, TR2KANA (312 g ml - 1 ) ; 5, TR2KANA (412 g ml - 1 ) ; TR : mol L - 1 ; ph Figure 4 Effect of ionic strength on I RRS Antibiotics concentration : 410 g ml - 1 ; TR : mol L Figure 3 Effect of acidity on I RRS Antibiotics concentration : 410 g ml - 1 ; TR : mol L RRS, KANA, TR NEO, TOB, GEN ph , KANA 2 +, TR 610, , , KANA (ph 2), SO 3 H,,, ; ph (ph 6), H + ( CT), AM1 TR, 5 - KANA I RRS 2 +, TR , KANA NaCl, I RRS ( 4),, I RRS, KANA, 200 nm, Na +, Cl - ; TR 505 nm,,, 2 3 ph 312,, 5 Na +,, TR, RRS TR, n ( KANA) n ( TR) = 1 1 TR, AM1 TR KANA 5 TR 5-5, SO 3 -, 3 KANA,, KANA 2 +, 3, 6 TR 5 - KANA RRS RRS ,, max 570 nm, = 65 nm, CT, E
4 1290 Vol 61, TR 5 - Figure 5 TR 5 - charge distribution at ground state 6 KANA Figure 6 KANA charge distribution at ground state 7 TR 5 - KANA 2 + Figure 7 Diagram sketch of ion association complex of TR 5-2 KANA RRS Figure 8 RRS and absorption spectra,,, nm, RRS RRS nm nm -, RRS, 400 nm, RRS ( 8) RRS,, 535 nm RRS, RRS, RRS,,, 470 nm RRS, RRS ( (1), - ), RF2540, -,
5 No 8 : 1291 (2), 3 Na +, Mg 2 +, Ca 2 +, Sr 2 +, Mn 2 + NH 4 +, RRS, Rayleigh [21] TritonX2100 C, I RRS = KcMI 0 I RRS, I 0, c, K, M, 3 1, , RRS, (3),,, 4, 3 2, RRS ml, 210 mol L ml,,3000 r min min,, [27] 0150 ml, I RRS, I RRS, TR 0150 ml ph 312 BR 0150 ml,, 1, , 5100 ml, 5, 5, KANA, 1219 ng ml - 1 5, (4 12 g KANA, NEO, TOB, GEN ml - 1 ) [28], 113 % 215 % ;, 2, Sn 2 +, Pb 2 + Cu 2 + 3, 9910 % % 2 6,, 1, Table 1 Correlation coefficient, linear ranges and detection limits for standard curves / nm ( r) ( c, g ml - 1 ) / ( g ml - 1 ) (3, ng ml - 1 ) TR2KANA 400 I = c TR2NEO 400 I = c TR2TOB 400 I = c TR2GEN 400 I = c Table 2 Comparison of the sensitivities of RRS with other methods for the determination of aminoglycoside antibiotics / ( g ml - 1 ) (3, ng ml - 1 ) 421 nm Cu nm HPLC2IPD 268 nm ph nm
6 1292 Vol 61, 2003 / ( mol L - 1 ) 3 Table 3 Effects of coexistent substances / % / ( mol L - 1 ) / % Na NO Zn SiO Ba HAsO UO SO NH EDTA C 2 O SLS Cu TritonX PO Mal Sn Lac Cr SDS Co Mg Ca Pb a Be 2 + a Sr a Mn L Al Fe Cl C H 2 PO a g ml Table 4 Results for the determination of commercial aminoglycoside antibiotics / (mg ml - 1 ) / (mg ml - 1 ), n = 5 / %, n = 5 RSD/ %, n = Table 5 Results for the determination of serum samples / ( g ml - 1 ), n = 5 / / ( g ml - 1 ) ( g ml - 1 ), n = 5 / % n = 5 RSD/ % n = References 1 Zhao, M Chin J Antibiotics 1999, 24, 319 (in Chinese) (,, 1999, 24, 319 ) 2 Barnes, W G In The Aminoglycoside Antibiotic : A Guide to Therapy, 1st ed, Ed : Barnes, W G, CRC Press Inc, Boca Raton Florida, 1984, p The Pharmacopoeia Committee of the People s Republic of China, The Pharmacopoeia of the People s Republic of China, 2nd Version [ S ], Chemical Industry Press, Beijing, 2000, p 312 ( in Chinese) (,,
7 No 8 : , [ S],,, 2000, p 312 ) 4 Gambardella, P ; Punziano, R ; Gionti, M J Chromatogr 1985, 348, Stead, D A ; Richards, R M E J Chromatogr B : Biomed Sci Appl 1997, 693, Zakhari, N A Anal Lett 1990, 23, Al2Ghabsha, T S Microchem J 1987, 36, Kubo, H ; Huang, Y2S ; Kinoshita, T Bunseki Kagaku 1989, 38, 215 (in Japanese) 9 Cai, W2M ; Cheng, G ; Tan, H2S Chin J Pharm 1990, 25, 25 (in Chinese) (,,,, 1990, 25, 25 ) 10 Pasternack, R F ; Collings, P J Science 1995, 269, Liu, S2P ; Liu, Z 2F Spectrochim Acta, Part A 1995, 51A, Pasternack, R F ; Bustamarte, C ; Collings, P J J Am Chem Soc 1993, 115, Huang, C2Z ; Li, K2A ; Tong, S2Y Anal Chem 1996, 68, Huang, C2Z ; Li, K2A ; Tong, S2Y Anal Chem 1997, 69, Liu, S2P ; Hu, X2L ; Luo, H2Q ; Fan, L Sci China, Ser B 2002, 32, 18 (in Chinese) (,,,, (B ), 2002, 32, 18 ) 16 Liu, S2P ; Luo, H2Q ; Li, N2B ; Liu, Z 2F ; Zheng, W2 X Anal Chem 2001, 73, Liu, S2P ; Liu, Z 2F ; Zho, G2M Anal Lett 1998, 31, Liu, S2P ; Liu, Q ; Liu, Z2F Anal Chim Acta 1999, 379, Liu, S2P ; Liu, Z2F ; Huang, C2Z Anal Sci 1998, 14, Liu, S2P ; Liu, Z2F ; Luo, H2Q Anal Chim Acta 2000, 407, Editorial Committee of Chinese Macropaedia, Chinese Macropaedia ( Biology ), Chinese Macropaedia Press, Beijing, 1991, p 1374 (in Chinese) (, ),,, 1991, p 1374 ) 22 Mukhamedzyanov, R M ; Lihoded, V A Antibiot Khimioter 1991, 36, Xi, Y2Y ; Lang, H2Y ; Xie, Z2H ; Zhang, Q2D J Xi An Jiaotong Univ 1996, 30, 104 (in Chinese) (,,,,, 1996, 30, 104) 24 Yuan, C ; Jia, N ; Wang, J 2X ; Liu, S2F Chin J Pharm Anal 1999, 19, 108 (in Chinese) (,,,,, 1999, 19, 108) 25 Fang, B ; Hu, S2S ; Li, P2B ; Zhao, Z2F Chin J Anal Chem 1989, 17, 636 (in Chinese) (,,,,, 1989, 17, 636 ) 26 Naveh, A J Appl Bacteriol 1984, 56, The Medical Executive Department of Sanitation Ministry of the People s Repulic of China, National Clinic Analysis Procedure, 2nd ed, Southeast University Press, Nanjing, 1997, p 193 (in Chinese) ( ( ),,,,, 1997, p 193) 28 Wu, L2W Curative Medicine Monitoring, People s Sanitation Press, Beijing, 1989, pp (in Chinese) (,,,, 1989, pp ) (A LU, Y J ; DONG, L J )
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