含肽键（-CONH）芳酰腙、1，10-菲啰啉与稀土配合物的研究
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摘要
在水醇混合溶剂中，以2-羰基丙酸水杨酰腙(C_(10)H_(10)N_2O_4，H_3L)及1，10-菲啰啉(C_(12)H_8N_2，phen)与稀土(RE=La、Pr、Nd、Sm、Eu、Gd、Tb、Dy、Er、Yb、Lu和Y)的硝酸盐反应，合成了12种未见文献报道的配合物，经元素分析、IR、UV、FS、~1H NMR等表征并结合热分析确定了配合物的组成为RE_2(HL)_2(H_2L)_2·phen·nH_2O，探讨了配合物的成键特点及光谱性质。测定了4个配合物的晶体结构，X-单晶衍射结果表明，配合物[RE(H_2L)(HL)(H_2O)_3]_2·phen·4H_2O(RE=Sm、Eu、Gd)的每个单元均为两个结构相似的9配位配合物，每个配合物中有两个2-羰基丙酸水杨酰腙和三个水分子参与了配位，同时还有一个1，10-菲啰啉分子和四个水分子游离于晶格中，形成了三维网状的超分子化合物。镝配合物[Dy(HL)(phen)(NO_3)(H_2O)_2]·H_2O的晶体则有所不同，它是由2-羰基丙酸水杨酰腙、1，10-菲啰啉、硝酸根和两个水分子构成的9配位配合物，晶格中还存在一个游离的水分子。配合物在空间均呈扭曲的单帽四方反棱柱。
通过TG—DTG—DSC热分析研究了配合物RE_2(HL)_2(H_2L)_2·phen·nH_2O在4个升温速率下的热分解过程，利用Kissinger法和Ozawa法计算了各配合物主要分解阶段的表观活化能。对晶体[Eu(HL)(H_2L)(H_2O)_3]_2·phen·4H_2O在4个升温速率下的三个热分解阶段，分别采用三种积分法和两种微分法对非等温动力学数据进行了线性回归处理，得到了三个不同阶段的动力学方程、分解机理及动力学参数。
选取6个具代表性的稀土与2-羰基丙酸水杨酰腙、1，10-菲啰啉配合物，采用生长速率法和孢子萌发法对番茄灰霉病菌、烟草赤星病菌和小麦条锈病菌等3种菌进行了生物活性试验。结果表明，6种配合物均具有一定的抑菌活性，其中Y(H_2L)_3(H_3L)·5H_2O、Dy_2(H_2L)_2(HL)_2(phen)·2H_2O两种配合物的抑菌效果较为明显，在40ug·ml~(-1)时Y(H_2L)_3(H_3L)·5H_2O对番茄灰霉病菌抑菌率为100％，在80ug·ml~(-1)时对烟草赤星病菌的的抑菌率为100％，而Dy_2(H_2L)_2(HL)_2(phen)·2H_2O在0.05ug·ml~(-1)时对小麦条锈病菌孢子萌发的抑制率仍高达79.7％。
In mixed solution of aqua-ethanon, novel twelve rare earth (RE= La, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Er, Yb, Lu and Y) complexes with 2-oxo-propionic acid salicyloyl hydrazone(C10H10N2O4, H3L) and 1,10-phenanthroline(C12H8N2, phen) had been synthesized. The formulae RE2(HL)2(H2L)2.phen.nH2O were determined by elemental analysis, IR, UV, FS, 1H NMR and thermoanalysis. The bonding character and spectra properties were discussed. The crystals of four complexes (RE= Sm, Eu, Gd, Dy) were obtained and determined by X-ray single crystal diffraction. There were two similar 9-coordinated complexes in every crystal unit of [RE(HL)(H2L)(H2O)3]2.phen.4H2O (RE=Sm, Eu, Gd), in which RE(III) were coordinated by two tridentate H3L ligands and three water molecules. There were a free 1,10-phenanthroline and four water in the crystal cell. The complex formed a three-dimensional network supramolecular. For [Dy(HL)(phen)(NO3)(H2O)2].H2O monocrystal, the Dy atom was nine-coordinated by linking to one tridentate H3L ligand, one bident
ate phen, one bidentate nitrate and two water molecule. The coordination polyhedron around RE(III) (RE= Sm, Eu, Gd, Dy) was a distorted monocapped square antiprism.
The thermal decompositions of the complexes RE2(HL)2(H2L)2.phen.nH2O were carried out by TG-DTG-DSC curve. The Kissinger's method and Ozawa's method were used to calculate the activation energy value of two main decomposition stages. For [Eu(HL)(H2L)(H2O)3]2.phen.4H2O crystal, the non-isothermal kinetic data of three stages of the decompositions were analyzed by three integral methods and two differential methods. The most probable reaction mechanism and the kinetic equation were investigated by comparing the kinetic parameters.
The biologic activity of six complexes for three bacteria: Botrytis cirerea Pers.ex Tris., Alternaria alternata (Fries) keissler and wheat rust were carried out by growth rate method and spore sprout method. The result showed that all six complexes possessed a
certain bacteriostasis activity. It is obvious that Y(H2L)3(H3L).5H2O, Dy2(H2L)2(HL)2(phen).2H2O had good antimicrobial activities. The inhibitory rate of Y(H2L)3(H3L).5H2O for Botrytis cirerea Pers.ex Tris. is 100% at 80ug.ml-1, for Alternaria alternate (Fries) keissler is 100% at 40ug.m-1, and that of Dy2(H2L)2(HL)2(phen).2H2O for spore growth of wheat rust is still high of 79.7% at 0.05ug.ml-1.
Yang Rui (Chemistry) Directed by He Shuiyang and Wen Zhenyi
通过TG—DTG—DSC热分析研究了配合物RE_2(HL)_2(H_2L)_2·phen·nH_2O在4个升温速率下的热分解过程，利用Kissinger法和Ozawa法计算了各配合物主要分解阶段的表观活化能。对晶体[Eu(HL)(H_2L)(H_2O)_3]_2·phen·4H_2O在4个升温速率下的三个热分解阶段，分别采用三种积分法和两种微分法对非等温动力学数据进行了线性回归处理，得到了三个不同阶段的动力学方程、分解机理及动力学参数。
选取6个具代表性的稀土与2-羰基丙酸水杨酰腙、1，10-菲啰啉配合物，采用生长速率法和孢子萌发法对番茄灰霉病菌、烟草赤星病菌和小麦条锈病菌等3种菌进行了生物活性试验。结果表明，6种配合物均具有一定的抑菌活性，其中Y(H_2L)_3(H_3L)·5H_2O、Dy_2(H_2L)_2(HL)_2(phen)·2H_2O两种配合物的抑菌效果较为明显，在40ug·ml~(-1)时Y(H_2L)_3(H_3L)·5H_2O对番茄灰霉病菌抑菌率为100％，在80ug·ml~(-1)时对烟草赤星病菌的的抑菌率为100％，而Dy_2(H_2L)_2(HL)_2(phen)·2H_2O在0.05ug·ml~(-1)时对小麦条锈病菌孢子萌发的抑制率仍高达79.7％。
In mixed solution of aqua-ethanon, novel twelve rare earth (RE= La, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Er, Yb, Lu and Y) complexes with 2-oxo-propionic acid salicyloyl hydrazone(C10H10N2O4, H3L) and 1,10-phenanthroline(C12H8N2, phen) had been synthesized. The formulae RE2(HL)2(H2L)2.phen.nH2O were determined by elemental analysis, IR, UV, FS, 1H NMR and thermoanalysis. The bonding character and spectra properties were discussed. The crystals of four complexes (RE= Sm, Eu, Gd, Dy) were obtained and determined by X-ray single crystal diffraction. There were two similar 9-coordinated complexes in every crystal unit of [RE(HL)(H2L)(H2O)3]2.phen.4H2O (RE=Sm, Eu, Gd), in which RE(III) were coordinated by two tridentate H3L ligands and three water molecules. There were a free 1,10-phenanthroline and four water in the crystal cell. The complex formed a three-dimensional network supramolecular. For [Dy(HL)(phen)(NO3)(H2O)2].H2O monocrystal, the Dy atom was nine-coordinated by linking to one tridentate H3L ligand, one bident
ate phen, one bidentate nitrate and two water molecule. The coordination polyhedron around RE(III) (RE= Sm, Eu, Gd, Dy) was a distorted monocapped square antiprism.
The thermal decompositions of the complexes RE2(HL)2(H2L)2.phen.nH2O were carried out by TG-DTG-DSC curve. The Kissinger's method and Ozawa's method were used to calculate the activation energy value of two main decomposition stages. For [Eu(HL)(H2L)(H2O)3]2.phen.4H2O crystal, the non-isothermal kinetic data of three stages of the decompositions were analyzed by three integral methods and two differential methods. The most probable reaction mechanism and the kinetic equation were investigated by comparing the kinetic parameters.
The biologic activity of six complexes for three bacteria: Botrytis cirerea Pers.ex Tris., Alternaria alternata (Fries) keissler and wheat rust were carried out by growth rate method and spore sprout method. The result showed that all six complexes possessed a
certain bacteriostasis activity. It is obvious that Y(H2L)3(H3L).5H2O, Dy2(H2L)2(HL)2(phen).2H2O had good antimicrobial activities. The inhibitory rate of Y(H2L)3(H3L).5H2O for Botrytis cirerea Pers.ex Tris. is 100% at 80ug.ml-1, for Alternaria alternate (Fries) keissler is 100% at 40ug.m-1, and that of Dy2(H2L)2(HL)2(phen).2H2O for spore growth of wheat rust is still high of 79.7% at 0.05ug.ml-1.
Yang Rui (Chemistry) Directed by He Shuiyang and Wen Zhenyi
引文
1．杨频，高飞．生物无机化学原理 科学出版社，北京，2002，p4
2．谭钦德．生物无机化学导论．广东高等教育出版社，广州，1993，p284
3．计亮年，黄锦汪，莫庭焕等编著．生物无机化学导论．中山大学出版社，广州，2001
4. Frouin A., et al. C. R. Sos. Biol., 1913, (74), 990
5. Nath B. B. Indian J. Biochem. Biophys., 1982, 19, 32
6. Kramsch D. M., Aspen A. J., Rozler L. J.. Science, 1992, 213, 1151
7. Jansco N., Gabor A. Jansco. Naunyn-Schnieberg's Arch, Exp. Path. Pharmacol. 1960,
238, 83
8. Tweeddle M. E. Invest Radiol. 1992, 27(suppl. 1), S2
9．杨正银，李发伸，杨立，杨汝栋．α-酮戊二酸腙稀土配合物的合成、表征及驰豫性能研究(Ⅱ)—α-酮戊二酸苯甲酰腙Gd配合物的驰豫性能．科学通报，2000，45(9)，923-928
10．杨正银，杨汝栋，蔡利平．α-酮戊二酸2,4-二硝基苯腙稀土配合物的合成与表征．应用化学，2002，17(4)，371-374
11．郭柏生译．稀有金属(稀土农用专辑)，1982，2，22-24
12．郭柏生．稀有金属(稀土农用专辑)，1981，10，1
13．傅素冉，赵周文，王兰仙，吴相钰．小麦对稀土元素络合物的吸收．北京大学学报(自然科学版)，1987，2，61-64
14．黄春辉，徐光宪．今日稀土．大学化学，1991，6(1)，1-4
15. Mohan Katyal, Yag Dutt. Analytical applications of hydrazones. Talanta, 1975, 22,151-166
16．Marsh R．W．编．郑仲等译．内吸性杀菌剂．化学工业出版社，北京，1983
17．沙家骏，张敏恒，姜雅君．国外新农药品种手册．化学工业出版社，北京，1993
18. Johri R. B., Sharma R. C., Synthetic and biocidal studies of some bivalent metal complexes of benzal-dehyde-salicylcylhydrazones. J. Indian Chem. Soc. 1988, LXV, 793
19. Easmon, et al.. Int. J. Cancer, 2001, 94, 89-96
20. Hofrnann J., Scheran G., Easmon J., Puerstinger G., Musumarra G., Condorelli D. F., Scire S., Heinisch G. New hydrazones, a novel class of experimental antitumor agents. European J. of Cancer, 2002, 38, S96
21. Easmon J., F(?)rtinger S., Lackner G., Magreiter E., Hofmann J., Heinisch G., Puerstinger G.. Hydrazones derived from monosubstitued 2-acetylpyridines and 2-hydrazino-1-methylbenzimidazole: Synthesis and biological studies. European J. of Cancer, 2002, 38, S122
22．仉文升，李安良．药物化学．高等教育出版社，北京，1999，第三章
23．李振肃主编．药物化学．化学工业出版社，北京，1981
24．邓汝温，张仲生．稀土药物和药学性质．稀土，1987，(3)，36
25．张仲生，吴集贵，邓汝温．烟酸钆与邻菲哕啉三元配合物的研究．高等学校化学学报，1990，11(1)，7-9
26．黄仲贤．混合配位体络合物的结构稳定性及其生物学意义(下)．生物化学与生物物理进展，1985，(4)，23-29
27．何水样，曹文凯，陈军利，赵建社，史启祯，王汝贤，孙杰．铜(Ⅱ)与2-羰基丙酸水杨酰腙配合物的合成、晶体结构和抑菌活性．高等学校化学学报，2002，23(6)，991-995
28．何水样，曹文凯，杨锐，赵建社，史启祯，王哲明，严纯华．二水·2-羰基丙酸水杨酰腙合铜(Ⅱ)配合物的晶体结构及生物活性．无机化学学报，2003，19(7)，699-703
2．谭钦德．生物无机化学导论．广东高等教育出版社，广州，1993，p284
3．计亮年，黄锦汪，莫庭焕等编著．生物无机化学导论．中山大学出版社，广州，2001
4. Frouin A., et al. C. R. Sos. Biol., 1913, (74), 990
5. Nath B. B. Indian J. Biochem. Biophys., 1982, 19, 32
6. Kramsch D. M., Aspen A. J., Rozler L. J.. Science, 1992, 213, 1151
7. Jansco N., Gabor A. Jansco. Naunyn-Schnieberg's Arch, Exp. Path. Pharmacol. 1960,
238, 83
8. Tweeddle M. E. Invest Radiol. 1992, 27(suppl. 1), S2
9．杨正银，李发伸，杨立，杨汝栋．α-酮戊二酸腙稀土配合物的合成、表征及驰豫性能研究(Ⅱ)—α-酮戊二酸苯甲酰腙Gd配合物的驰豫性能．科学通报，2000，45(9)，923-928
10．杨正银，杨汝栋，蔡利平．α-酮戊二酸2,4-二硝基苯腙稀土配合物的合成与表征．应用化学，2002，17(4)，371-374
11．郭柏生译．稀有金属(稀土农用专辑)，1982，2，22-24
12．郭柏生．稀有金属(稀土农用专辑)，1981，10，1
13．傅素冉，赵周文，王兰仙，吴相钰．小麦对稀土元素络合物的吸收．北京大学学报(自然科学版)，1987，2，61-64
14．黄春辉，徐光宪．今日稀土．大学化学，1991，6(1)，1-4
15. Mohan Katyal, Yag Dutt. Analytical applications of hydrazones. Talanta, 1975, 22,151-166
16．Marsh R．W．编．郑仲等译．内吸性杀菌剂．化学工业出版社，北京，1983
17．沙家骏，张敏恒，姜雅君．国外新农药品种手册．化学工业出版社，北京，1993
18. Johri R. B., Sharma R. C., Synthetic and biocidal studies of some bivalent metal complexes of benzal-dehyde-salicylcylhydrazones. J. Indian Chem. Soc. 1988, LXV, 793
19. Easmon, et al.. Int. J. Cancer, 2001, 94, 89-96
20. Hofrnann J., Scheran G., Easmon J., Puerstinger G., Musumarra G., Condorelli D. F., Scire S., Heinisch G. New hydrazones, a novel class of experimental antitumor agents. European J. of Cancer, 2002, 38, S96
21. Easmon J., F(?)rtinger S., Lackner G., Magreiter E., Hofmann J., Heinisch G., Puerstinger G.. Hydrazones derived from monosubstitued 2-acetylpyridines and 2-hydrazino-1-methylbenzimidazole: Synthesis and biological studies. European J. of Cancer, 2002, 38, S122
22．仉文升，李安良．药物化学．高等教育出版社，北京，1999，第三章
23．李振肃主编．药物化学．化学工业出版社，北京，1981
24．邓汝温，张仲生．稀土药物和药学性质．稀土，1987，(3)，36
25．张仲生，吴集贵，邓汝温．烟酸钆与邻菲哕啉三元配合物的研究．高等学校化学学报，1990，11(1)，7-9
26．黄仲贤．混合配位体络合物的结构稳定性及其生物学意义(下)．生物化学与生物物理进展，1985，(4)，23-29
27．何水样，曹文凯，陈军利，赵建社，史启祯，王汝贤，孙杰．铜(Ⅱ)与2-羰基丙酸水杨酰腙配合物的合成、晶体结构和抑菌活性．高等学校化学学报，2002，23(6)，991-995
28．何水样，曹文凯，杨锐，赵建社，史启祯，王哲明，严纯华．二水·2-羰基丙酸水杨酰腙合铜(Ⅱ)配合物的晶体结构及生物活性．无机化学学报，2003，19(7)，699-703
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