27 7 2011 7 CHINESE JOURNAL OF INORGANIC CHEMISTRY Vol.27 No.7 1239-1244 1,2 1 *,2 ( 1, 363000) ( 2, 361005) :,, 0.206 0(2) nm 0.206 8(2) nm [Co(Hlact) 2 (H 2 O) 2 ] (2) [Co(Hlact) 2 (phen)] 2H 2 O (4) (BSA=Bovine Serum Albumin), BSA, BSA : ; ; ; : O641.4 : A : 1001-4861(2011)07-1239-06 Syntheses of a Series of Lactato Cobalt Complexes and Their Interaction with Bovine Serum Albumin LIN Hai-Bin 1,2 WANG Qing-Xiang 1 ZHOU Zhao-Hui *,2 ( 1 Department of Chemistry, Zhangzhou Teachers College, Zhangzhou, Fujian 363000, China) ( 2 Department of Chemistry and State Key Laboratory for Physical Chemistry of Solid Surfaces, Xiamen University, Xiamen, Fujian 361005, China) Abstract: A series of lactate cobalt complexes are synthesized and characterized by spectral and structural analyses, including [Co(Hlact) 2 (H 2 O) 2 ] H 2 O (1), [Co(Hlact) 2 (H 2 O) 2 ] (2), [Co(Hlact)(phen)(H 2 O) 2 ]Cl (3) and [Co(Hlact) 2 (phen)] 2H 2 O (4) (Lactic acid=h 2 lact; 1,10-phenanthroline=phen). Their interactions with Bovine Serum Albumin (BSA) are investigated with infra-red spectra. CCDC: 819899. Key words: cobalt; lactic acid; phenanthroline; bovine serum albumin (BSA) 0 [5],, [6-8],, [9-12], -, BSA [Co(Hlact) 2 (H 2 O) 2 ], H 2 O (1),[Co(Hlact) 2 (H 2 O) 2 ] (2),[Co(Hlact)(phen)(H 2 O) 2 ]Cl [1-4] (3) [Co(Hlact) 2 (phen)] 2H 2 O (4)( =H 2 lact;1,10-, =phen), 2 4 BSA :2011-01-05 :2011-03-02 (No.20805041) (No.2010CB126504) * E-mail:zhzhou@xmu.edu.cn,Tel:0592-2181646
1240 27 H,4.3;N,7.0% IR (KBr,cm 1-1 ):as(coo) 1 590vs;1 524 s;s(coo) 1 423s,1 384m;δ phen (C-H) 850s;s(Co-O) 730 1.1 s,641w;s(co-n) 602w. (±) (C.P., ); 1.2.4 [Co(Hlact) 2 (phen)] 2H 2 O (4) (A.R., ); 20.0 mmol 10 ml, (C.P., ); ph 2.0 mol L -1 6~7, (A.R., ); 20.0 ml (A.R., ); (10.0 mmol) 1,10- (10.0 mmol), (A.R., );, Perkin Elmer UV3200 ; [Co (Hlact) 2 (phen)] 2H 2 O (4) [Co (Hlact) 2 Nicolet FTIR360 ; (phen)] 2H 2 O (4), : Bruker Apex CCD C,47.9;H,4.8;N,6.4% :C 18 N 2 O 8 H 22 Co:C,47.7; 1.2 H,4.9;N,6.2% IR (KBr,cm -1 ):as(coo) 1 590vs;s(COO) 1.2.1 [Co(Hlact) 2 (H 2 O) 2 ] H 2 O (1) 1 423s,1 388s;δ phen (C-H) 851s;s (Co-O) 726m,676w, 20.0 mmol 10 ml, 641w,540w;s(Co-N) 602w ph 2.0 mol L -1 6~ 1.2.5 [Co(Hlact) 2 (H 2 O) 2 ] (2) BSA 7, 20.0 ml (10.0 mmol), 0.305 g [Co(Hlact) 2 (H 2 O) 2 ] ph= [Co(Hlact) 2 (H 2 O) 2 ] H 2 O (1) 6.85, 0.504 g BSA,, :C,25.4;H,5.5%. :C 6 H 16 O 9 Co:C,25.3;H,5.3% IR(KBr,cm -1 ):as (COO) 1 592vs;s(COO) 1 433s;s(Co-O) 759m,673m, 562m 1.2.6 Co(lact) 2 2H 2 O(2) BSA 1.2.2 [Co(Hlact) 2 (H 2 O) 2 ] (2) 20.0 mmol 10 ml, 5.00mL 2.00g L -1 BSA 0.1 0.5 ph 2.0 mol L -1 6~7, 1.0 3.0 ml 0.02 mol L -1 Co(Lac) 2 2H 2 O 20.0 ml, ph=6.85 10 ml, (10.0 mmol), 80 20 min, :C,26.4;H,5.5%. :C 6 H 14 O 8 Co:C,26.6;H,5.2% IR (KBr,cm -1 ):as (COO) 1 582vs;s(COO) 1 462m,1 431s;s(Co-O) 769m, 45.4;H,4.8;N,7.1% :C 15 N 2 O 5 H 17 ClCo:C,45.1;, ; KBr, Nicolet360,,, [Co(Hlact) 2 (H 2 O) 2 ] [Co(Hlact) 2 (H 2 O) 2 ] (2) 1.2.7 [Co(Hlact) 2 (phen)] 2H 2 O (4) BSA 0.254 g [Co (Hlact) 2 (phen)] 2H 2 O ph=6.85, 0.386 g BSA, 680m,559m, ; 1.2.3 [Co(Hlact)(phen)(H 2 O) 2 ]Cl (3) KBr, 10.0 mmol 10 ml, Nicolet360 ph 2.0 mol L -1 6~7, 1.2.8 BSA [Co(lact) 2 (phen)] 2H 2 O(4) 20.0 ml (10.0 mmol) 1,10- (10.0 mmol), 2.00 ml 0.04 mmol L -1 [Co(lact) 2 (phen)] 2H 2 O, 0.50 1.00 2.00 3.00 ml 0.040 g [Co(Hlact)(phen)(H 2 O) 2 ]Cl [Co(Hlact)(phen) L -1 BSA, ph=6.85 (H 2 O) 2 ]Cl (3), :C, 25 ml,,
7 : 1241 -, 1.2.9 [Co(Hlact) 2 (H 2 O) 2 ] (2), 0.35 mm 0.18 mm 0.15 mm 2, Bruker, ), Co(Hlact) 3 Smart Apex CCD (Mo K,λ=0.701 7, nm, ), 2.24 ~28.29 7 904 [Co(Hlact) 2 (H 2 O) 2 ] (2) - -, I 3σ(I) 7 770,,, Lp [Co(Hlact)(phen)(H 2 O) 2 ]Cl (3) [Co(Hlact) 2 [12] (phen)] 2H 2 O (4), 2 [Co(Hlact) 2 (H 2 O) 2 ] H 2 O (1) [11] ( X- X-, 2.2 2 XRD 2.1 2 2, (1)~(4) 1 1 2, CCDC:819899 1 3 [Co(L) 3 ](L=phen ox; = H 2 ox) [13-16],,, [Co(Hlact) 2 (H 2 O) 2 ] 2, [Co(Hlact) 2 (H 2 O) 2 ] H 2 O [11], 1, [Co(Hlact) 2 (H 2 O) 2 ] Co-O [Co(Hlact) 2 1 (1)~(4) (H 2 O) 2 ] H 2 O Co-O Fig.1 Syntheses and transformations of complexes (1)~(4), [Co(Hlact) 2 (H 2 O) 2 ] H 2 O 1 [Co(Hlact) 2 (H 2 O) 2 ] (2) Table 1 Crystal data summaries of intensity data collection and structure refinement for complex (2) Empirical formula C 6H 14O 8Co D c / (g cm -3 ) 1.791 Formula weight 273 Z 13 Crystal color Carnation F(000) 564 Crystal dimension / mm 0.35 0.18 0.15 Diffractometer Bruker Apex CCD Crystal system Orthorhombic Radiation Mo K (λ=0.071 07 nm) a / nm 0.599 9(1) GOF on F 2 0.964 b / nm 1.178 1(2) Final R indices [I>2σ(I)] R 1=0.036 5, wr 2=0.090 9 c / nm 1.4329(3) R indices (all data) R 1=0.037 2, wr 2=0.091 5 V / nm 3 1.0127(3) Largest diff. peak and hole / (e nm -3 ) 1 209 and -482 Space group P2 12 12 1 Fig.2 2 [Co(Hlact) 2 (H 2 O) 2 ] Perspective view of the molecular structure for [Co(Hlact) 2 (H 2 O) 2 ]
1242 27 2 Table 2 [Co(Hlact) 2 (H 2 O) 2 ] H 2 O (1) [Co(Hlact) 2 (H 2 O) 2 ] (2) Selected interatomic bond lengths (nm) and angles ( ) in [Co(Hlact) 2 (H 2 O) 2 ] (2) [Co(Hlact) 2(H 2O) 2] H 2O (1) [Co(Hlact) 2(H 2O) 2] (2) Co-O(2) 0.207 0(3) 0.205 5(2) Co-O(3) 0.212 9(3) 0.206 9(2) Co-O(5) 0.210 5(3) 0.208 1(2) Co-O(6) 0.205 5(3) 0.205 2(2) Co-O(1w) 0.206 1(3) 0.208 7(2) Co-O(2w) 0.201 8(4) 0.204 9(2) (a) [Co(Hlact) 2(H 2O) 2] (2); (b) BSA; (c) [Co(Hlact) 2(H 2O) 2] (2)+BSA O(2)-Co-O(3) 77.1(1) 76.88(7) O(2)-Co-O(5) 95.7(1) 92.37(8) O(2)-Co-O(6) 164.2(2) 92.00(8) O(2)-Co-O(1w) 91.7(1) 87.73(8) 3, [Co(Hlact) 2 (H 2 O) 2 ] (2)( O(2)-Co-O(2w) 93.1(1) 174.33(8) a) BSA( b) 1 600 cm -1 O(3)-Co-O(5) 91.2(1) 99.44(8), [Co(Hlact) 2 (H 2 O) 2 ] (2) BSA O(3)-Co-O(6) 89.2(1) 167.95(8) O(3)-Co-O(1w) 91.7(1) 91.28(9), O(3)-Co-O(2w) 90.2(2) 98.36(8) 1 600 cm -1 O(5)-Co-O(6) 76.4(1) 76.10(8), a b, c 1 000 O(5)-Co-O(1w) 172.6(2) 169.02(8) cm -1 a b O(5)-Co-O(2w) 88.2(2) 91.44(8), c a b O(6)-Co-O(1w) 96.4(2) 92.92(8) [Co(Hlact) 2 (H 2 O) 2 ] (2) BSA O(6)-Co-O(2w) 100.2(2) 92.99(8), BSA O(2w)-Co-O(1w) 91.7(2) 89.33(9), Co 2+ -BSA,, 2 R ; Co 2+ -BSA 1 600 cm -1 [Co(Hlact) 2 (H 2 O) 2 ], 2 ; Co 2+ BSA, S,R, BSA 1 200 cm -1 [Co(Hlact) 2 (H 2 O) 2 ],2, (O3 O6) 2 2.4 Co(Hlact) 2 2H 2 O BSA, ; [Co(Hlact) 2 (H 2 O) 2 ] H 2 O, 2 2, 1 (O23) Co(Hlact) 2 2H 2 O BSA 1 (O11), 4, 6 Co(Hlact) 2 2H 2 O 278 nm,, BSA, 2 2.3 [Co(Hlact) 2 (H 2 O) 2 ] (2) BSA BSA, Co(Hlact) 2 2H 2 O,BSA Nicolet360 BSA [Co (Hlact) 2 (H 2 O) 2 ] (2) BSA [Co(Hlact) 2 (H 2 O) 2 ] (2), BSA,BSA 3 3 [Co(Hlact) 2 (H 2 O) 2 ] (2) BSA Fig.3 IR for the complex interaction between [Co(Hlact) 2 (H 2 O) 2 ] (2) and BSA Co(Hlact) 2 (H 2 O) 2 2.3, Co(Hlact) 2 (H 2 O) 2 (2) Co 2+
7 : 1243 Co 2+ -BSA 4 [Co(Hlact) 2 (H 2 O) 2 ] BSA 2.6 BSA [Co(Hlac) 2 (phen)] 2H 2 O (4) Fig.4 UV of BSA with different densities of, Co(Hlact) 2 2H 2 O BSA [Co(Hlac) 2 (phen)] 2H 2 O (4), Co 2+ BSA, 6 BSA, Co(Hlact) 2 (H 2 O) 2 (2), 278 nm 2.5 [Co(Hlact) 2 (phen)] 2H 2 O (4) BSA Nicolet360 BSA, [Co(Hlact) 2 (phen)] 2H 2 O (4) BSA [Co(Hlact) 2 (phen)] 2H 2 O (4), 5 (a) [Co(Hlact) 2(phen)] 2H 2O; (b) BSA; (c) [Co(Hlact) 2(phen)] 2H 2O + BSA] 5 [Co(Hlact) 2 (phen)] 2H 2 O (4) BSA Fig.5 IR spectra for the interaction between [Co(Hlact) 2 (phen)] 2H 2 O (4) and BSA 5, [Co(Hlact) 2 (phen)] 2H 2 O (4) ( a) BSA( b) [Co(Hlact) 2 (H 2 O) 2 ] (2) BSA [Co(Hlact) 2 (H 2 O) 2 ] (2), a, [Co(Hlact) 2 (phen)] 2H 2 O (4) 850 cm -1, [Co(Hlact) 2 (phen)] 2H 2 O (4) BSA ( c), 2.3, [Co(Hlact) 2 (phen)] 2H 2 O (4) BSA, BSA, 6 Fig.6 BSA [Co(Hlact) 2 (phen)] 2H 2 O UV of [Co(Hlact) 2 (phen)] 2H 2 O with different densities of BSA [Co(Hlact) 2 (phen)] 2H 2 O (4) 278 nm, BSA, BSA, 6, [Co(Hlact) 2 (phen)] 2H 2 O (4) BSA, 278 nm, BSA, 2.5, [Co(Hlact) 2 (phen)] 2H 2 O (4) BSA,BSA Co 2+,, Co 2+ BSA
1244 27 Co(Hlact) 2 (phen)] 2H 2 O (4), Kun-Yao ( ). Acta Sci. Nat. Univ. Sunyatseni: Nat. BSA, Sci. Ed.(Zhongshan Daxue Xuebao), 1996,35(2):1-4 [9] Zhou H Z, Ye J J, Zhong H, et al. Acta Cryst., 2002,E58: 278 nm m326-m327 3 [10]Carballo R, Castieiras A, Balboa S, et al. Polyhedron, 2002, 21:2811-2818 (1)~(4) [11]Carballo R, Covelo B, Vázquez-López E M, et al. Z. Anorg. Allg. Chem., 2002,628:468-472 [Co(Hlact) 2 (H 2 O) 2 ] (2) [Co(Hlact) 2 (phen)] [12]Covelo B, Carballo R, Vázquez-López E M, et al. 2H 2 O (4) BSA, : CrystEngComm, 2006,8:167-177 [Co (Hlact) 2 (H 2 O) 2 ] (2) [Co (Hlact) 2 (phen)] [13]Okazaki H, Kushi Y, Yoneda H. J. Am. Chem. Soc., 1985, 107:4183-4189 2H 2 O (4) BSA, [14]Coronado E, Gimenez-Lopez M C, Gimenez-Saiz C, et al. ( ) BSA Polyhedron, 2003,22:2375-2380 BSA [15]Geraghty M, Mcann M, Devereux M, et al. Inorg. Chim. [17-25], BSA Acta, 1999,293:160-166,, [16]Burns M C, Tershansy M A, Ellsworth J M, et al. Inorg., BSA Chem., 2006,45:10437-10439 [17]YANG Chang-Ying( ), LIU Yi( ), ZHU Jun-Cheng ( ), et al. Chin. J. Anal. Chem.(Fenxi Huaxue), 2008, : [1] Baroni S, Mattu M, Vannini A, et al. Eur. J. Biochem, 2001, 268:6214-6220 [2] Lin Y L, Lin S R, Wu T. Biochem. Biophy. Res. Commun., 2004,319(3):720-724 [3] LIU Xue-Feng( ), XIA Yong-Mei( ), FANG Yun ( ), et al. Acta Chim. Sinica(Huaxue Xuebao), 2004,62 (16):1484-1488 [4] YANG Pin( ), YANG Bin-Sheng ( ). Prog. Biochem. Biophys (Shengwu Huaxue Shengwu Wuli Jinzhang), 1992, 19(2):110-112 [5] FU Chun-Mei( ), HE Cui-Lian( ), LI Hong-Ying ( ), et al. Med. Recapitul.(Yixue Zongshu), 2005,11(3): 249-251 [6] GOU Jing( ). J. Chongqing Institute Technol.: Nat. Sci. Ed. (Chongqing Ligong Daxue Xuebao, Ziran Kexueban), 2002,16(5):62-64 [7] HAN De-Qiang( ), DING Hong-Biao( ), QIAO Yu( ). Biotechnol. Bull.(Shengwu Jishu Tongbao), 2005, 5:35-38 [8] ZHENG Chen-Mou( ), LUO Yu-Ji( ), HUANG 36(4):473-477 [18]WANG Xing-Ming( ), DONG Fa-Qin( ), DING Li-Sheng( ). Chemistry(Huaxue Tongbao), 2005,4:309-313 [19]WANG Xing-Ming( ), DONG Fa-Qin( ), DING Li-Sheng ( ), et al. Chinese J. Inorg. Chem. (Wuji Huaxue Xuebao), 2004,20(8):920-924 [20]LIU Hai-Ping( ), WANG Xing-Ming( ), DAI Ya-Tang ( ). Chinese J. Inorg. Chem. (Wuji Huaxue Xuebao), 2005,21(9):1422-1426 [21]HUANG Yu-Ting( ), REN Xiang-Xiang( ), LIU Hai-Feng( ). Chem. Res.(Huaxue Yanjiu), 2009,20(2): 37-40 [22]LIU Shao-Pu( ), LIU Zhong-Fang( ). Chin. J. Anal. Chemi.(Fenxi Huaxue), 1996,24(6):665-668 [23]LI Hua-Cen ( ), GAO Jian-Hua ( ). Chin. J. Spectrosc. Lab.(Guangpu Shiyanshi), 2004,1:112-114 [24]FENG Su-Ling( ), SHI Hui-Miu( ), FAN Jing ( ). Chin. J. Anal. Chem. (Fenxi Huaxue), 2006,34 (8): 1157-1160 [25]YU Ying( ), LIAO Jian( ), HUANG Fa-De( ). Spectrosc. Spectr. Anal. (Guangpuxue Yu Guangpu Fenxi), 2002,6:1067-1072