二丙酮酸缩对苯二甲双酰腙稀土配合物的合成、表征和生物活性研究
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摘要
以二丙酮酸缩对苯二甲双酰腙(C_(14)H_(14)N_4O_6,H_4L)和稀土硝酸盐(RE(NO_3)_3·n H_2O)为原料,在水-乙醇混合溶剂中,制备了13种二丙酮酸缩对苯二甲双酰腙稀土配合物。采用元素分析、摩尔电导率、红外光谱、紫外光谱、X-射线粉末衍射和热重分析等手段对目标产物的结构进行了表征和测试,确定出配合物的组成为RE_2(H_2L)_3·n H_2O(RE=Y、La、Ce、Pr、Nd、Sm、Eu、Gd、Tb、Dy、Er、Yb、Lu,n=1、2、3、4、5),推测配合物中稀土离子与配体按照2∶3的物质的量比进行配位,稀土离子的配位数为九,配合物分子中配体的化学环境相同,稀土离子的化学环境相同,配合物的外界无其它离子存在,晶格中含有一定数目的结晶水。采用孢子萌发法测试了部分配合物对小麦条锈病菌的生物活性,结果显示:配合物对小麦条锈病菌的生物活性随浓度的减小而降低,在浓度为2500 mg/L时,Nd_2(H_2L)_3·2H_2O、Dy_2(H_2L)_3·2H_2O和Y_2(H_2L)_3·4H_2O对小麦条锈病菌孢子萌发的抑制率为100%,La_2(H_2L)_3·4H_2O和Eu_2(H_2L)_3·3H_2O的抑制率分别为83. 8%和84. 1%,说明选取配合物Nd_2(H_2L)_3·2H_2O、Dy_2(H_2L)_3·2H_2O和Y_2(H_2L)_3·4H_2O对小麦条锈病孢子的萌发有较强的抑制作用,La_2(H_2L)_3·4H_2O和Eu_2(H_2L)_3·3H_2O的性能稍差。
Thirteen lanthanide complexes constructed from multidentate ligand bi-[N-( propionic acid) ]terephthalal diacythydrazon( C_(14)H_(14)N_4O_6,H_4 L) were synthesized in water and ethanolmixture solvent. The structures of target products were characterized by elemental analysis,IR spectra,UV spectra,X-ray diffraction,TG and molar conductance. The compositions of the complexes were determined to be RE_2( H_2L)_3·n H_2O( RE = Y,La,Ce,Pr,Nd,Sm,Eu,Gd,Tb,Dy,Er,Yb,Lu,n = 1,2,3,4,5) and the structures of the complexes were speculated. The molar ratio of rare earth ions to ligands is 2 ∶ 3.The coordination number of each rare earth ions is nine. The chemical environments of ligands and rare earth ions in the complexes are the same. There are no other ions present in the complexes. The lattice of the complexes contains a certain amount of crystalline water molecule. The biological activity of some complexes against wheat rust was tested by spore germination method. The results showed that the inhibition rates of the complexes decreased with the decrease of the concentration. The inhibition rates of Nd_2( H_2L)_3·2 H_2O,Dy_2( H_2L)_3·2 H_2O and Y_2( H_2L)_3·4 H_2O are 100%,and inhibition rates of La_2( H_2L)_3·4 H_2O and Eu_2( H_2L)_3·3 H_2O are 83. 8% and 84. 1% respectively,which indicated that Nd_2( H_2L)_3·2 H_2O,Dy_2( H_2L)_3·2 H_2O and Y_2( H_2L)_3·4 H_2O had strong inhibitory effects on wheat rust,while the properties of La_2( H_2L)_3·4 H_2O and Eu_2( H_2L)_3·3 H_2O were slightly lower.
Thirteen lanthanide complexes constructed from multidentate ligand bi-[N-( propionic acid) ]terephthalal diacythydrazon( C_(14)H_(14)N_4O_6,H_4 L) were synthesized in water and ethanolmixture solvent. The structures of target products were characterized by elemental analysis,IR spectra,UV spectra,X-ray diffraction,TG and molar conductance. The compositions of the complexes were determined to be RE_2( H_2L)_3·n H_2O( RE = Y,La,Ce,Pr,Nd,Sm,Eu,Gd,Tb,Dy,Er,Yb,Lu,n = 1,2,3,4,5) and the structures of the complexes were speculated. The molar ratio of rare earth ions to ligands is 2 ∶ 3.The coordination number of each rare earth ions is nine. The chemical environments of ligands and rare earth ions in the complexes are the same. There are no other ions present in the complexes. The lattice of the complexes contains a certain amount of crystalline water molecule. The biological activity of some complexes against wheat rust was tested by spore germination method. The results showed that the inhibition rates of the complexes decreased with the decrease of the concentration. The inhibition rates of Nd_2( H_2L)_3·2 H_2O,Dy_2( H_2L)_3·2 H_2O and Y_2( H_2L)_3·4 H_2O are 100%,and inhibition rates of La_2( H_2L)_3·4 H_2O and Eu_2( H_2L)_3·3 H_2O are 83. 8% and 84. 1% respectively,which indicated that Nd_2( H_2L)_3·2 H_2O,Dy_2( H_2L)_3·2 H_2O and Y_2( H_2L)_3·4 H_2O had strong inhibitory effects on wheat rust,while the properties of La_2( H_2L)_3·4 H_2O and Eu_2( H_2L)_3·3 H_2O were slightly lower.
引文
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[4] Rosi N L,Eckert J,Eddaoudi M,et al. Hydrogen storage in microporous metal-organic frameworks[J]. Science,2003,300,1127-1129.
[5] Chae H K,Siberio-Prez D Y,Kim J,et al. A route to high surface area,porosity and inclusion of large molecules in crystals[J]. Nature,2004,427:523-527.
[6] Zhan S J,Sun Y,Li S P,et al. Syntheses,crystal structures and luminescent properties of three metal coordination polymers based on aromatic carboxylic acids and2-(pyridine-4-yl)-(1H)-benzoimidazole[J]. Polyhedron,2017,121(1):252-263.
[7] Mala N,Neelam S,Sharma C L. Studies on some organotin(IV)complexes of semicarbazones and thiosemicarbazones[J]. Synth React Inorg Met-Org Chem,1989,19(4):339-356.
[8] Williams D R. Metals,ligands,and cancer[J]. Chem Rev,1972,72(3):203-213.
[9]陈凤英,何水样,刘峰,等.配合物[RE2(H2L)2(HL)2(2,6-H2PDA)(H2O)2]·2H2O的合成、晶体结构及其与DNA作用方式初探[J].化学学报,2009,67(6):555-563.Chen Fe Y,He S Y,Liu F,et al. Synthesis,crystal structure and preliminary DNA-binding studies of[RE2(H2L)2(HL)2(2,6-H2PDA)(H2O)2]·2H2O[J]. Acta Chimica Sinica,2009,67(6):555-563.
[10] Syamal A,Maurya M R. Coordination chemistry of schiff base complexes of molybdenum[J]. Coord Chem Rev,1989,95(2):183-238.
[11]戴寰,耿志明,韩志坚. 2,6一二乙酰吡啶类双希夫碱配合物的研究——1 VO(ll)、Mn(ll)、Fe(II)和Fe(III)配合物的合成和表征[J].无机化学学报,1989,5(3):75-81.Dai H,Geng Z M,Han Z J. Studies on complexes of schiff bases derived from 2, 6-diacetylpyridine——I synthesis and characterization of VO(II),Mn(II),Fe(II)and Fe(III)complexes[J]. Chinese Journal of Inorganic Chemistry,1989,5(3):75-81.
[12]仉文升,李安良.药物化学[M].北京:高等教育出版社,1999.Zhang W H,Li A L. Pharmaceutical Chemistry[M].Beijing:Higher Education Press,1999.
[13] Chen F Y,Wu W T,Li H X,et al. Molecular structure and properties of a novel acylhydrazone(C14H14O6N4)·HCON(CH3)2·2H2O[J]. Chemical Research in Chinese Universities,2012,28(3):524-528.
[14] Geary W J. The use of conductivity measurements in organic solvents for the characterisation of coordination compounds[J]. Coord Chem Rev,1971,7(1):81-122.
[15]常建华,董绮功.波谱原理及解析[M].北京:科学出版社,2001.Chang J H,Dong Q G. Principle and Analysis of Spectrum[M]. Beijing:Science Press,2001.