摘要
氨基酸是生命的内源物质，是生物体细胞生长所必需的生理活性物质。氨基酸希夫碱及其金属配合物在医药、催化、光学、材料等诸多领域具有广阔的应用前景，已成为当前配位化学的研究热点之一。因此，通过反应引入各类功能基团使其衍生化，合成新型的氨基酸希夫碱及其金属配合物，研究其分子结构、理化性质及实际应用，对配位化学的发展具有重要的意义。
本文合成了6个系列28种氨基酸希夫碱金属配合物，培养了三个配合物的单晶。通过元素分析、红外光谱、紫外可见光谱、摩尔电导率及热重分析等对配合物进行表征，推断出可能的化学结构。利用X-射线单晶衍射仪解析配合物的晶体得到其空间结构。对配合物进行了荧光光谱分析，研究了三元金属配合物与CT-DNA的作用方式。检测所有的金属配合物对乳腺癌细胞(MDA-MB~(-2)31)和前列腺癌细胞(PC~(-3))增殖的抑制能力，筛选出了具有抗肿瘤活性的配合物。以蛋白酶体为作用靶点，探讨了氨基酸希夫碱铜三元配合物通过抑制蛋白酶体活性诱导肿瘤细胞凋亡的作用机理。具体内容如下：
1.合成了2,4-二羟基苯甲醛缩L-天冬氨酸希夫碱(H_2L~1)配合物，其组成分别为：[M(L~1)(H_2O)_2]·nH_2O (M=Cu, Zn, n=2; M=Co, Mn, n=3),[M(L~1)(NO_3)(H_2O)_x]·nH_2O (M=La, x=3, n=2),[M(L~1)(Phen)]·nH_2O (M=Cu, n=1)。H_2L~1=C_(11)H_(11)NO_6,Phen:1,10-菲罗啉
2.合成了2,4-二羟基苯乙酮缩L-天冬氨酸希夫碱(H_2L~2)配合物，其组成分别为：[M(L~2)(H_2O)_2]·nH_2O (M=Cu, n=0; M=Co, n=2; M=Zn, n=3),[M(L~2)(NO_3)(H_2O)x]·nH_2O (M=Sm, x=2, n=2; M=La, x=3, n=3),[M(L~2)(Phen)]·nH_2O (M=Cu,n=3)。H_2L~2=C_(12)H_(15)NO_7
3.合成了2,4-二羟基苯甲醛缩L-缬氨酸希夫碱(H_2L~3)配合物，其组成分别为：[M(L~3)(H_2O)_2]·nH_2O (M=Zn, n=1; M=Co, n=2; M=Cu, n=3),[M(L~3)(NO_3)(H_2O)x]·nH_2O (M=Yb, x=2, n=1; M=Er, x=3, n=2),[M(L~3)(Phen)]·nH_2O (M=Cu,n=2)。H_2L~3=C_(12)H_(15)NO_4
4.合成了2,4-二羟基苯乙酮缩L-缬氨酸希夫碱(H_2L~4)配合物，其组成分别为：[M(L~4)(H_2O)_2]·nH_2O (M=Cu, n=1; M=Zn, Co, n=2),[M(L~4)(NO_3)(H_2O)x]·nH_2O(M=Er, x=2, n=3; M=La, x=3, n=2),[M(L~4)(Phen)]·nH_2O (M=Cu, n=4)。H_2L~4=C_(13)H_(17)NO_4
5.合成得到了邻香草醛缩L-甲硫氨酸-铜(II)-1,10-菲啰啉三元配合物，邻香草醛缩L-甲硫氨酸-铜(II)~(-2),2’-联吡啶三元配合物的单晶，其组成分别为：[Cu(L~5)(Phen)]·9H_2O,[Cu(L~5)(Bpy)]·3H_2O。H_2L~5=C_(13)H_(17)NO_4S, Bpy:2,2’-联吡啶
[Cu(L~5)(Phen)]·9H_2O属单斜晶系，空间点群C2,晶胞参数为a=22.510(2),b=21.479(2), c=14.8300(17), α=90°, β=92.7460(10)°, γ=90°, V=7162.0(13)3,F(000)=2888。配体H_2L~5以脱两个质子、三齿配体的形式与铜原子形成并列排布的五元、六元螯合环。配体中的羧基氧原子、亚胺氮原子与铜原子形成五元螯合环；酚羟基氧原子、亚胺氮原子与铜原子形成六元螯合环；1,10-菲啰啉的两个氮原子与铜原子形成另一个五元螯合环。配合物中的铜原子处在五配位、畸变的四角锥配位环境中。
[Cu(L~5)(Bpy)]·3H_2O属单斜晶系，空间点群P21/c,晶胞参数为a=11.0970(11)
, b=19.101(2), c=13.203(12), α=90°, β=114.1490(10)°, γ=90°, V=2553.7(4)3,F(000)=1156。[Cu(L~5)(Bpy)]·3H_2O中配体的配位方式与[Cu(L~5)(Phen)]·9H_2O的相似，只是2,2’-联吡啶代替1,10-菲啰啉与铜配位形成五元螯合环。这两个配合物均通过O-H…O氢键形成一维链状结构，链之间通过氢键形成二维网状结构。
6.合成了2-羟基-1-萘甲醛缩L-缬氨酸希夫碱(H_2L~6)铜的三元配合物，其组成分别为：[Cu(L~6)(Phen)]·3H_2O,[Cu(L~6)(Bpy)]·3H_2O。H_2L~6=C16H19NO4。得到了2-羟基-1-萘甲醛缩L-缬氨酸-铜(II)~(-2),2’-联吡啶三元配合物的单晶。
[Cu(L~6)(Bpy)]·3H_2O属三斜晶系，空间点群P-1,晶胞参数为a=9.2950(10),b=9.7861(11), c=14.3819(15), α=79.9710(10)°, β=74.7180(10)°, γ=85.745(2)°,V=1242.1(2)3, F(000)=566。配体中的氮、氧原子与铜原子配位形成五元、六元螯合环，配合物之间通过O-H…O氢键形成了梯子式的二维网状结构。
7.利用Achar的微分法和Coats-Redfern的积分法计算程序，对热分解动力学进行拟合，对部分配合物进行非等温热分解动力学处理，得出配合物的热分解反应机理、相应的动力学参数及活化熵变△S≠和吉布斯自由能变△G≠。其中，配合物3a相关步骤热分解反应的动力学函数符合反应方程：f(α)=(1-α)_2；配合物2e和3d的符合反应方程：f(α)=1/3(1-α)[-ln(1-α)]~(-2)；配合物2f、4e和5d的符合反应方程：f(α)=1/4(1-α)[-ln(1-α)]~(-3)；配合物4f的符合反应方程：f(α)=1/2(1-α)3。
8.测定了配合物的荧光光谱，比较其荧光特性。研究结果表明：与对应的配体相比，配合物[Cu(L~1)(H_2O)_2]·2H_2O、[Zn(L~1)(H_2O)_2]·2H_2O的激发峰均发生了一定程度的蓝移，发射峰一个发生了红移，一个发生了蓝移，荧光强度均明显增强；[Zn(L~2)(H_2O)_2]·3H_2O、[La(L~2)(NO_3)(H_2O)3]·3H_2O的激发峰和发射峰都发生了轻微的红移，且荧光强度有所降低；配合物[Zn(L~3)(H_2O)_2]·H_2O、[Yb(L~3)(NO_3)(H_2O)_2]·H_2O、[Zn(L~4)(H_2O)_2]·2H_2O、[Er(L~4)(NO_3)(H_2O)_2]·3H_2O的激发峰和发射峰都发生了一定程度的蓝移，且荧光强度有所减弱。
9.采用紫外可见光谱、荧光光谱和粘度测定等方法研究了氨基酸希夫碱铜的三元配合物与CT-DNA之间的作用方式。结果显示当第二配体为1,10-菲啰啉时，配合物[Cu(L~1)(Phen)]·H_2O、[Cu(L~2)(Phen)]·3H_2O、[Cu(L~3)(Phen)]·2H_2O、[Cu(L~5)(Phen)]·9H_2O都以插入方式与CT-DNA作用，[Cu(L~4)(Phen)]·4H_2O以部分插入方式与CT-DNA作用。当第二配体为2,2’-联吡啶时，配合物[Cu(L~5)(Bpy)]·3H_2O与CT-DNA之间则为静电作用。通过对[Cu(L~5)(Phen)]·9H_2O和[Cu(L~5)(Bpy)]·3H_2O的空间结构进行对比发现，配合物中配体的共平面性越好，越有利于其以插入方式与CT-DNA发生相互作用，配合物与CT-DNA结合的能力越强。
10.对配合物作为蛋白酶体抑制剂的抗肿瘤活性及作用机制进行了研究。
采用MTT法对28种氨基酸希夫碱金属配合物进行体外药物抗肿瘤实验，筛选出[Cu(L~1)(Phen)]·H_2O、[Cu(L~2)(Phen)]·3H_2O、[Cu(L~3)(Phen)]·2H_2O、[Cu(L~4)(Phen)]·4H_2O、[Cu(L~5)(Phen)]·9H_2O、[Cu(L~6)(Phen)]·3H_2O等具有抗肿瘤活性的三元配合物。检测筛选出的配合物对肿瘤细胞内蛋白酶体的抑制活性，确定配合物的作用靶点为蛋白酶体；利用浓度及动力学实验考察配合物抑制蛋白酶体活性与诱导肿瘤细胞凋亡的关系；利用细胞形态学变化检测技术对细胞凋亡的形态进行检测。研究发现，上述铜的三元配合物均能以浓度和时间依赖方式抑制人乳腺癌细胞(MDA-MB~(-2)31)和前列腺癌细胞(PC~(-3))蛋白酶体活性而诱导肿瘤细胞凋亡。
对某些不同第二配体的三元铜配合物抗肿瘤活性进行了分析对比，发现当1,10-菲啰啉(Phen)作为第二配体时具有显著的抗肿瘤活性，而当第二配体换为2,2’-联吡啶(Bpy)时，则抗肿瘤活性很小。如：邻香草醛缩L-甲硫氨酸-铜(II)-1,10-菲啰啉三元配合物、2-羟基-1-萘甲醛缩L-缬氨酸-铜(II)-1,10-菲啰啉三元配合物可以有效地抑制人乳腺癌细胞(MDA-MB~(-2)31)的增殖，而邻香草醛缩L-甲硫氨酸-铜(II)~(-2),2’-联吡啶三元配合物、2-羟基-1-萘甲醛缩L-缬氨酸-铜(II)~(-2),2’-联吡啶三元配合物的抗癌活性很小。这表明第二配体的选择对整个三元配合物的抗肿瘤活性有重要作用。
根据实验结果，结合分子模拟对接技术对配合物作为蛋白酶体抑制剂靶向诱导肿瘤细胞凋亡的作用机制进行了探讨。研究结果表明，当第二配体是1,10-菲啰啉时，所得到的配合物能顺利地到达20S蛋白酶体的β6位点，配合物中的铜离子可以与β6位点形成共价键，生物活性基团可以与β6位点内的氨基酸残基形成多种氢键。这些共价键和氢键将配合物牢牢地固定在β6位点，从而阻挡蛋白质分子通过β6位点通道进入具有类糜蛋白酶活性(CT-like)的β5位点，抑制20S蛋白酶体内的类糜蛋白酶活性，诱导肿瘤细胞凋亡。
Amino acids are endogenous substance of life and essential physiological activesubstances for organism cell growth. Amino acid Schiff base and their metalcomplexes have a wide application prospect in medicine, catalysis, optics, materialsand other fields, has become the focus in the field of coordination chemistry. Thesynthesis of many novel amino acid Schiff bases and their metal complexes throughthe reaction of various functional groups into the derivatization, and the studies ontheir molecular structures, physicochemical properties and practical application haveimportant significance for the development of coordination chemistry.
In this paper, six Schiff base ligands and twenty-eight corresponding metalcomplexes have been synthesized and the single crystals of three coordinationcompounds have been obtained. These complexes have been characterized byelemental analysis, IR spectrum, UV spectrum, fluorescence spectrum, molarconductivity and thermal gravimetric analysis. The suggested structures of the metalcomplexes have been concluded. The spatial structures of three single crystals havebeen detected using the X-ray diffraction analysis. Fluorescence properties of theSchiff base metal complexes and the interaction modes of ternary metal complexesand DNA have been studied. The proliferation inhibitory abilities of all the metalcomplexes on breast cancer cell (MDA-MB~(-2)31) and prostate cancer cells (PC~(-3))have been detected and the complexes which have antitumor activity have beenselected. The reaction mechanisms of the amino acid Schiff base copper ternarycomplexes induce cancer cells apoptosis through inhibiting proteasome activity havebeen discussed using proteasome as reaction target. The main works of the article areas follows:
1. The metal complexes with Schiff base ligand (H_2L~1) derived from2,4-Dihydroxybenzaldehyde and L-Aspartic acid were synthesized. The possible chemical compositions of these complexes are confirmed to be:[M(L~1)(H_2O)_2]·nH_2O(M=Cu, Zn, n=2; M=Co, Mn, n=3),[M(L~1)(NO_3)(H_2O)x]·nH_2O (M=La, x=3, n=2),[M(L~1)(Phen)]·nH_2O (M=Cu, n=1)。H_2L~1=C_(11)H_(11)NO_6, Phen:1,10-Phenanthroline
2. The metal complexes with Schiff base ligand (H_2L~2) derived from2,4-Dihydroxyacetophenone and L-Aspartic acid were synthesized. The possiblechemical compositions of these complexes are confirmed to be:[M(L~2)(H_2O)_2]·nH_2O(M=Cu, n=0; M=Co, n=2; M=Zn, n=3),[M(L~2)(NO_3)(H_2O)x]·nH_2O (M=Sm, x=2,n=2; M=La, x=3, n=3),[M(L~2)(Phen)]·nH_2O (M=Cu, n=3)。H_2L~2=C_(12)H_(15)NO_7
3. The metal complexes with Schiff base ligand (H_2L~3) derived from2,4-Dihydroxybenzaldehyde and L-Valine were synthesized. The possible chemicalcomposition of these complexes are confirmed to be:[M(L~3)(H_2O)_2]·nH_2O (M=Zn,n=1; M=Co, n=2; M=Cu, n=3),[M(L~3)(NO_3)(H_2O)x]·nH_2O (M=Yb, x=2, n=1; M=Er,x=3, n=2),[M(L~3)(Phen)]·nH_2O (M=Cu, n=2)。H_2L~3=C_(12)H_(15)NO_4
4. The metal complexes with Schiff base ligand (H_2L~4) derived from2,4-Dihydroxyacetophenone and L-Valine were synthesized. The possible chemicalcomposition of these complexes are confirmed to be:[M(L~4)(H_2O)_2]·nH_2O (M=Cu,n=1; M=Zn, Co, n=2),[M(L~4)(NO_3)(H_2O)x]·nH_2O (M=Er, x=2, n=3; M=La, x=3,n=2),[M(L~4)(Phen)]·nH_2O (M=Cu, n=4)。H_2L~4=C_(13)H_(17)NO_4
5. The single crystals of ternary copper complexes with Schiff base ligand (H_2L~5)derived from O-vanillin and L-Methionine were obtained. The chemical compositionsof these complexes are confirmed to be:[Cu(L~5)(Phen)]·9H_2O,[Cu(L~5)(Bpy)]·3H_2O.H_2L~5=C_(13)H_(17)NO_4S, Bpy:2,2’-Bipyridine
The crystal of [Cu(L~5)(Phen)]·9H_2O belongs to the monoclinic crystal system,space group C2with the cell parameter a=22.510(2), b=21.479(2), c=14.8300(17)
, α=90°, β=92.7460(10)°, γ=90°, V=7162.0(13)3, F(000)=2888. The ligand acts asa doubly deprotonated, tridentate form to coordinate with copper atom to formparatactic five-member and six-member chelated ring. In the ligand, the carbonyloxygen atom and Imine nitrogen atom coordinate with copper atom to formfive-member chelated ring, the phenol hydroxyl oxygen atom and Imine nitrogenatom coordinate with copper atom to form six-member chelated ring, the nitrogen atom of1,10-Phenanthroline coordinate with copper atom to form other five-memberchelated ring. The Cu atoms exhibit five-coordinate distorted square-pyramidconfigurations.
The crystal of [Cu(L~5)(Bpy)]·3H_2O belongs to the monoclinic crystal system,space group P21/c with the cell parameter a=11.0970(11), b=19.101(2), c=13.2031(12), α=90°, β=114.1490(10)°, γ=90°, V=2553.7(4)3, F(000)=1156. Thecoordination mode of ligand in [Cu(L~5)(Bpy)]·3H_2O is similar with [Cu(L~5)(Phen)]·9H_2O, except for the use of2,2’-bipyridineinstead of1,10-phenanthroline tocoordinate with copper atom to form five-member chelated ring. Both coppercomplexes are linked into one-dimensional chain structure through O-H…O hydrogenbonds, and the chains to form two-dimensional network also by hydrogen bonds.
6. The ternary copper complexes with Schiff base ligand (H_2L~6) derived from2-hydroxy-1-naphthaldehyde and L-Valine were synthesized. The possible chemicalcompositions of these complexes are confirmed to be:[Cu(L~6)(Phen)]·3H_2O,[Cu(L~6)(Bpy)]·3H_2O. H_2L~6=C16H19NO4. The crystals of [Cu(L~6)(Bpy)]·3H_2O were otained.
The crystal of [Cu(L~6)(Bpy)]·3H_2O belongs to the triclinic crystal system, spacegroup P-1with the cell parameter a=9.2950(10), b=9.7861(11), c=14.3819(15),α=79.9710(10)°, β=74.7180(10)°, γ=85.745(2)°, V=1242.1(2)3, F(000)=566. Theoxygen atom and nitrogen atom of the ligand coordinate with copper atom to formfive-member and six-member chelated ring. The complexes are linked into ladderform two-dimensional network structure through O-H…O hydrogen bonds.
7. A combination of Achar differential and Coats-Redfern method was used toprocess non-isothermal decomposition of kinetics of part of the complexes. Thethermal decomposition reaction mechanism, correspondent kinetic parameters,activation entropy change△S≠and gibbs free energy change△G≠of the complexes.Among them, the thermal decomposition kinetic functions of related steps of complex3a conforms to the reaction equation: f(α)=(1-α)_2; complexes2e and3d conforms tothe reaction equation: f(α)=1/3(1-α)[-ln(1-α)]~(-2); complexes2f,4e and5d conforms tothe reaction equation: f(α)=1/4(1-α)[-ln(1-α)]~(-3); complexes2f,4e and5d conforms tothe reaction equation: f(α)=1/2(1-α)3.
8. Fluorescence spectra of these complexes were detected and the related fluorescence properties were studied. The experimental results show that compared with thecorresponding ligand, the excitation and emission peaks of complexes [Cu(L~1)(H_2O)_2]·2H_2O,[Zn(L~1)(H_2O)_2]·2H_2O have shifted to blue for some degree and thefluorescence intensity enhanced obviously. The excitation and emission peaks ofcomplexes [Zn(L~2)(H_2O)_2]·3H_2O,[La(L~2)(NO_3)(H_2O)3]·3H_2O have shifted to redslightly and the fluores cence intensity Weakened for a little. The excitation andemission peaks of complexes [Zn(L~3)(H_2O)_2]·H_2O,[Er(L~3)(NO_3)(H_2O)3]·2H_2O,[Zn(L~4)(H_2O)_2]·2H_2O,[Co(L~4)(H_2O)_2]·2H_2O have shifted to blue for some degree andthe intensity weakened slightly.
9. The interaction modes between the ternery amino acid Schiff base coppercomplexes and DNA was studied by UV-Vis spectrium, fluorescent spectrium andviscosity method. The results show that when1,10-philippines was added as thesecond ligand, complexes [Cu(L~1)(Phen)]·H_2O,[Cu(L~2)(Phen)]·3H_2O,[Cu(L~3)(Phen)]·2H_2O,[Cu(L~5)(Phen)]·9H_2O can interact with CT-DNA as the insert mode, and[Cu(L~4)(Phen)]·4H_2O can interact with CT-DNA as the partly insert mode. When2,2'-bipyridyl was added as the second ligand, complex [Cu(L~5)(Bpy)]·3H_2O caninteract with CT-DNA as electrostatic mode. Comparison of [Cu(L~5)(Phen)]·9H_2Owith [Cu(L~5)(Bpy)]·3H_2O indicate that the complexes with better coplanar propertiesare more favorable to interact with DNA as the insert mode, and have better DNAbinding ability.
10. Antitumor activity and action mechanism of the complexes as the proteasomeinhibitor is studied. In vitro antitumor drug tests of28kinds of amino acids are carriedout using MTT method, from which some ternary complexes with antitumor activitieslike [Cu(L~1)(Phen)]·H_2O,[Cu(L~2)(Phen)]·3H_2O,[Cu(L~3)(Phen)]·2H_2O,[Cu(L~4)(Phen)]·4H_2O,[Cu(L~5)(Phen)]·9H_2O and [Cu(L~6)(Phen)]·3H_2O are screened out.Inhibition activities to proteasome in tumor cells of the complexes that have beenscreened out are tested to determine whether proteasome is the target or not. Therelevance between proteasome activity and tumor cells apoptosis induction isinvestigated using concentration experiments and kinetics experiments. Morphologies of the apoptotic cells are determined by the cell morphological changes testingtechnique. The results show that the above mentioned ternary complexes can inhibitthe proteasome activity of human breast cancer cells (MDA-MB~(-2)31) and prostatecancer cells (PC~(-3)) in concentration-dependent and time-dependent mode.
Antitumor activities of some ternary copper complexes using different secondligands are analyzed and compared. It is found that the complexes using1,10-Phenanthroline as the second ligands demonstrate dramatic antitomor activities while thecomplexes using2,2'-bipyridyl as the second ligands demonstrate weak antitomoractivities. For example, the ternary Cu(II) complexes derived from o-Vani llin,L-Methionine and1,10-Phenanthroline as well as2-Hydroxy-1-naphthaldehyde,L-Valine and1,10-Phenanthroline can effectively inhibit the proliferation of breastcancer cells. In contrast, the ternary Cu(II) complexes derived from o-Vanillin,L-Methionine and2,2'-bipyridyl as well as2-Hydroxy-1-naphthaldehyde, L-Valineand2,2'-bipyridyl exhibit weak antitumor activities. This indicates that the secondligands play key roles to the antitumor activities of the ternary complexes.
The mechanism of the complexes as proteasome inhibitor to induce the tumorcells apoptosis is discussed, according to the experimental results combined withmolecular simulation and docking technology. The results show that when1,10-Phenanthroline serve as second ligands, the obtained complexes can smoothly reach the β6target of20S proteasome. Then the copper ions can form covalent bonds with β6target and the bioactive radicals can form several hydrogen bonds with the residues inβ6target. These covalent bonds and hydrogen bonds can fix the complexes on β6target to block the protein molecules to go through β5target that has chymotrypsin-like avtiveity. Thus, the activity chymotrypsin-like in20S proteasome will beinhibited and the cell apoptosis will occur.
引文
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