4 3 3 Vol 43 No 3 2 0 1 4 6 Journal of Shanghai Normal UniversityNatural Sciences Jun 2 0 1 4 DOI10 3969 /J 1SSN 100-5137 2014 03 011 - -2 6-1 1 2 1 1 1 1 2002342 200234 1- -3- -4- -5-2 6- X - TEM Na CuPMBPPDA CT - DNA DNA DNA O 641 4 O 614 33 A 1000-5137201403-0285-07 60 1-3 4-6 Cu 7-8 9-13 14-15 1- -3- -4- -5- O N 16-18 18-19 2 6- N O 19-21 2 6-19 23-25 DNA 1 1 1 CuCl 2 2H 2 O 2 6-1- -3- -4- -5- N N- 2014-05-14 DEL124 DZL123 SK201235 SK201048 100 200234 E-mailxdf@ shnu edu cn 100 200234 E-mailjrlin@ shnu edu cn
286 2014 DMF NaOH 8099 ATCC6538P 1 2 Elementar Vario EL III Nicolet AVATAR 380 FT - IR KBr 4000 ~ 400 cm - 1 Perkin-Elmer17 Varian VIS- TA-MPXICP-OES Ulvac-Phi PHI - 5000 VersaProbe X - PerkinElmer Pyris Diamond TG /DTA JEM - 2010 XRD Rigaku D /Max - 2200 X - Cu - Kα 1 54056 kv 80 Ma 0 3 /s Varian Gray 4000E 1 3 2 mmol 1- -3- -4- -5- PMBP ph 6 5 2 mmol CuCl 2 60 1 h 2 mmol 2 6- H 2 PDA 3h 61% 2 2 1 C N H ICP 11 C H N Cu 4 NaCuPMBP PDA PMBP H HPMBP 1- -3- -4- -5- PDA H 2 PDA 2 - COOH 2 H 2 6-1 NaCuPMBP PDA N C H M % 8 027 94 54 5254 45 3 083 02 12 2412 05 HPMBP H 2 PDA DMSO DMF 2 2 KBr 4000!400 cm - 1 2 M - O M - N Cu 26 3058 cm - 1 HPMBP - OH HPMBP ν C = O 1599 cm - 1 1620 cm - 1 C = O HPMBP ν C = C 1495 cm - 1 1575 cm - 1 ν C - O 1281 cm - 1 1000 cm - 1 HPMBP 27 H 2 PDA ν c = o ν as COOH ν C = N H 2 PDA 1573 cm - 1 H 2 PDA N H 2 PDA C = N Δν ν as COO - - ν s COO -
3 - -2 6-287 200 cm - 1 H 2 PDA Δν 285 cm - 1 H 2 PDA C = O 28 - H 2 PDA COOH 30 O COOH - OH O 2 cm - 1 ν O - H ν c = o ν C = C ν C - O ν s COO - ν as COO - ν C = N ν M - O ν M - N HPMBP 3058 1599 1495 1281 - - - - - H 2 PDA - 1700 - - 1415 1700 1573 - - NaCuPMBP PDA - 1600 1570 1068 1375 1600 1510 420 570 2 3 DMF 1 HPMBP 240 nm 278 nm H 2 PDA 270 nm 276 nm 400 ~ 500 nm 2 4 XRD 2 XRD 2 NaCuPMBP PDA HPMBP H 2 PDA CuCl 2 2H 2 O NaCuPMBP PDA NaCuPMBP PDA 1 NaCuPMBP PDA UV 2 NaCuPMBP PDA XRD 2 5 XPS 3 HPMBP O 531 37 ev H 2 PDA - COOH O 532 04 ev O HPMBP H 2 PDA O HPMBP O H 2 PDA - OH O Cu 2 + 2 O H 2 PDA N 399 09 ev N N NaCuPMBP PDA Cu CuCl 2 2H 2 O Cu
288 2014 3 ev N O La Sm Er Y Cu HPMBP - 531 37 - - - - - H 2 PDA 399 09 532 04 - - - - - CuCl 2 2H 2 O - - - - - - 934 59 954 19 NaCuPMBP PDA 400 94 530 01 - - - - 934 74 954 74 2 6 TG - DTA 100 ml min - 1 25 ~ 1000 10 min - 1 4 TG - DTA / / / /% NaCuPMBP PDA - 285 520 656 85 3182 91 4 NaCuPMBP PDA 270 3 4 Na Cu PMBP PDA 285 NaCuPMBP PDA 470 ~ 625 645 ~ 670 NaCu PMBP PDA CuO Na 2 O 2 7 TEM 4 NaCuPMBP PDA TEM 3 NaCuPMBP PDA - DNA DNA 31 4 NaCuPMBP PDA TEM 2 8 DMF
3 - -2 6-289 5 5 1 E c S a 2 HPMBP H 2 PDA Cu 2 + 5 MIC /mol L - 1 /mm MIC /10-6 CuCl 2 2H 2 O 0 005 9 10 > 500 > 500 HPMBP 0 005 8 7 > 500 > 500 H 2 PDA 0 005 7 6 > 500 > 500 NaCuPMBP PDA 0 005 11 12 300 260 2 9 DNA 2 9 1 1 0 10-5 2 5 10-5 5 0 10-5 10 0 10-5 CT-DNA 30 min DNA 5 NaCu PMBP PDACT - DNA UV NaCuPMBP PDA DNA TEM DNA 2 9 2 32-33 300 nm E x = E m = 10 nm 450 V 400 ~ 800 nm EB CT - DNA CT - DNA EB 2 10-4 mol L - 1 CT - DNA 1 5 10-4 mol L - 1 6 EB - DNA 1 0 10-5 mol L - 1 + EB - DNA 2 5 10-5 mol L - 1 + EB - DNA 5 0 10-5 mol L - 1 + EB - DNA 10 0 10-5 mol L - 1 + EB - DNA 15 0 10-5 mol L - 1 + EB - DNA 30 min NaCuPMBP PDA DNA 6 NaCuPMBP PDA 34 - CT - DNA 35 5 NaCuPMBP PDADNA UV 6 NaCuPMBP PDA DNA
290 2014 3 1 IR UV XRD XPS TG - DTA TEM NaCuPMBP PDA 2 Cu 2 + NaCuPMBP PDAS a E c 3 DNA 1 J 2008 1412 77-80 2 M 1986 3 M 1995 4 J 1995 113 219-227 5 M 1987 6 M 2006 7 M 1991 8OLIVARES M UAUY R Copper as an essential nutrient J A J Clin Nutr 1996 63791S - 796S 9SUKSRICHAVALIT T PRACHAYASITTIKUL S NANTASENAMAT C et al Copper complexes of pyridine derivatives with superoxide scavenging and antimicrobial activities J Eur J Med Chem 2009 443259-3265 10CHOHAN Z H ARIF M SARFRAZ M Metal-based antibacterial and antifungal amino acid derived Schiff basestheir synthesis characterization and in vitro biological activity J Appl Organomet Chem 2007 214 294-302 11SASMAL P K PATRA A K NETHAJI M et al DNA cleavage by new oxovanadiumivcomplexes of N-salicylidene α- amino acids and phenanthroline bases in the photodynamic therapy windowj J Inorg Biochem 2007 4611112-11121 12 DNA J 2004 10 1159-1164 13 IⅡ J 1997551198-1206 14XU D F SHEN Z H YANG S et al Synthesis Characterization Crystal Structure and Biological Activity of the Copper Complex J Russ J Coord Chem 2010 366 458-462 15 M 2003 16ZHOU D LI QHUANG C et al Room - temperature fluorescence phosphorescence and crystal structure of 4-acyl pyrazolone lanthanide complexeslnl 3 2H 2 O J Polyhedron 1997 168 1381-1389 17XU H Z ZHANG X YU G S 3-1Z-3-Methyl-5-oxo-1-phenyl-1 5-dihydropyrazol-4-ylidene phenylmethylaminopropionic acid J Acta Cryst 2005 E61456-458 18 J 2007 2310 1723-1728 19 β - D 2012 20LAINE P GOURDON A LAUNAY J P Chemistry of iron with dipicolinic acid1 M ononuclear complexes of ironiior iron Ⅲ J Inorg Chem 1995 3421 5129-5137 21YANG L CRANS D C MILLER S M et a1 CobaltIIand cobaltⅢdipicolinate complexessolid state solution and in vivo insulin-like properties J Inorg Chem 2002 4119 4859-4871 22TANG T RAJAN K S GRECZ N Mixed chelates of CaII- pyridine-2 6-dicarboxylate with some amino acids related to
3 - -2 6-291 bacterial spores J Biophys J 1968 812 1458-1474 23MARKEES D G DEWEY V C KIDDER G W The synthesis and biological activity of substituted 2 6-diaminopyridines J J Med Chem 1968 111 126-129 24GROVES J T KADY I O Sequence-specific cleavage of DNA by oligonucleotide-bound metal complexes J Inorg Chem 1993 3218 3868-3872 25-2 6-2 6- J 2010 366 786-791 26ALY H F KERIM F M A KANDIL A T IR spectra of lanthanide 8-hydroxyquinoline complexes J J Inorg Nucl Chem 1971 3312 4340-4344 27 D 2008 28XU D F XU Y M CHENG N et al Synthesis characterization and biological studies of lanthanide complexes with 2 6- pyridine dicarboxylic acid and a - picolinic acid J J Coord Chem 2010 632360-2369 29DEMESSENCEA ROGEZ G RABU P Grafting of thiophenecarboxylates into magnetic transition metal hydroxide layer J Chem Mater 2006 183005-3015 30NAKAMOTO K Infrared and Raman Spectra of Inorganic and Coordination CompoundsM New YorkWiley 1986 31COLAK A T COLAK F Synthesis spectroscopic thermal voltammetric studies and biological activity of crystalline complexes of pyridine-2 6-dicarboxylic acid and 8 - hydroxy quinoline J J Mol Struct 2009 93667-74 32 D 2011 33 D 2011 34 DNA D 2006 35BAGULEY B C LEBRET M Quenching of DNA-ethidium fluorescence by amsacrine and other antitumor agentsa possible electron-transfer effect J Biochem 1984 235 937-943 36 Rubpy 2 PNT 2 + DNA J 2008 2912 2496-2501 Synthesis characterization and properties of some rare earth complexes with pyrazolone and 2 6-pyridinecarboxylic acid CHEN Jing 1 CHENG Ningning 1 YU Hui 2 XU Dongfang 1 LIN Jingrong 1 HE Qizhuang 1 1 College of Life and Environmental Sciences Shanghai Normal University Shanghai 200234 China 2 Interdisciplinary Research Centre Shanghai Normal University Shanghai 200234 China AbstractA new solid ternary complex of copper with 1 - phenyl-3-methyl-4-acetyl - pyrazolone - 5 and 2 6-pyridinecarboxylic acid NaCuPMBP PDAhas been synthesized and characterized by elemental analysis FT - IR UV - Vis XRD TG - DTA and XPS The antibacterial test indicated that the complex exhibited moderate antibacterial ability against Escherichia coli and- Staphylococcus aureus The interactions of the complex with calf thymus DNA CT DNAwas investigated by employing florescence spectroscopic studies and ultraviolet spectrum spectrom etries The results indicated that the complex can intercalate between DNA base pairs Key wordscoppercomplexantibacterialdna