| Transition metal complexes of amino acid derivative and Schiff base are widely used in the fields of material, medicine and catalysis etc. Thus, studies on the synthesis of novel complexes, studing their properties and application are significant the development of coordination chemistry.L-cysteine isα-amino Acids which has strong biological activity. It is widely used in medicine, food and cosmetic areas. It can prevent and treat the radioactivity. L-cysteine is an antidote of hepatotoxicity and stibialism. The study of synthetization and bioactivity of metal complex, which is derived from L-cysteine derivative, is an important research topic in life science.In this paper, three ligands derived from L-cysteine (L-cys) , vanillin(vani), o-vanillin(ovani), 3,4-dihydroxybenzaldehyde(3,4DHD) and a Schiff base ligand derived from 4,4`-diaminodiphenylmethane and o-vanillin were prepared. And twenty-one coordination compounds of transition metal were synthesized. Four crystals of these ligands or complexes were prepared. These ligands and complexes were characterized by elemental analysis, 1H NMR, IR spectroscopy, UV spectroscopy, single-crystal X-ray diffraction, TG-DTG analysis and molar conductance analysis. The binding mode of some complexes with DNA, anticancer activity and a fluorescent probe based on Schiff Base which derived from 4,4`-diaminodiphenylmethane and o-vanillin, for the detection of Zinc (Ⅱ) . The details of contents are as follow:(1) The ligand and 4 transition metal complexes derived from L-cysteine and o-vanillin were synthetized. The compositions of the complexes are confirmed to be [M2 (C)11H13NO4S) 2(CH3COO) 2] [M=Cu (Ⅱ), Co (Ⅱ), Zn (Ⅱ), Mn (Ⅱ)].(2) The ligand and 5 transition metal complexes derived from L-cysteine and vanillin were synthetized. The compositions of the complexes are confirmed to be [Cu (C)11H12NO4S) (CH3COO) (H2O)], [Co (C)11H12NO4S) (CH3COO) (H2O) 3], [Cd(C)11H12NO4S)(CH3COO)(H2O)]·2H2O,[Zn(C)11H12NO4S)(CH3COO)(H2O)]·2H2O, [Mn(C)11H12NO4S) (CH3COO) (H2O)2].(3) The ligand and 5 transition metal complexes derived from L-cysteine and 3,4-dihydroxybenzaldehyde were synthetized. The compositions of the complexes are confirmed to be [M (C10H11NO4S) 2] [M=Cu (Ⅱ), Co (Ⅱ), Cd (Ⅱ), Zn(Ⅱ), Mn(Ⅱ)].(4) The ligand and 7 transition metal complexes derived from 4,4`-diaminodiphenylmethane and o-vanillin were synthetized. The compositions of the complexes are confirmed to be [M2(C58H58N4O8)2], [M=Cu(Ⅱ), Co(Ⅱ), Ni(Ⅱ), Cd(Ⅱ), Zn(Ⅱ), Mn(Ⅱ), Fe(Ⅱ)]. The crystals of Schiff base and its Cu (Ⅱ) were obtained.X-ray crystallography shows that the crystal derived from 4,4`-diaminodiphenylmethane and o-vanillin [L] crystallizes in the orthorhombic, Fdd2 space group, molecular formula: C29H26N2O4, M= 466.5. Unit cell parameter: a = 24.433(2) (?), b=38.886(3) (?), c =4.7896(6) (?),α= 90°,β= 90°,γ= 90°, Z = 8, V=4736.8(8) (?)3, T = 293(2) K, Dc = 1.308 g·cm -3, R1 = 0.046, wR2 = 0.0712 for I>2σ(I), F(000) =1968. The crystal structure shows that the H atom of hydroxybenzene and N atom of Schiff base formed intramolecular hydrogen bond.The crystal of Cu(Ⅱ) complex with Schiff base ligand derived from4,4`-diaminodiphenylmethane and o-vanillin(Cu2L2) belongs to orthorhombic, Fdd2 space group, molecular formula: C)125H127Cu4N)11O25,M =2437.5.Unit cell parameter: a =13.697()13 (?),b=14.181(15) (?),c =18.6859(19)(?),α= 69.56°,β=70.07°,γ= 81.63°,Z = 1, V=3195.9(6)(?)3,T = 298 K,Dc = 1.267 g·cm-3,R1 =0.0756,wR2 = 0. 0.1920 for I>2σ(I),F(000) =)1270. The structure of Cu2L2 shows that the complex is bi-nuclear. The Cu (Ⅱ) ion is in a four-coordinate, located in center of a distorted tetrahedron.(5) Combinating Achar differential and Coats-Redfern integral method which fits the thirty kinetic equations, the calculating program of some step of thermal decomposition for complexes was designed. The kinetic equations of corresponding kinetic parameters were obtained. The kinetic parameters include E, A, order of reaction and correlation coefficient etc. The activation entropy△S≠and activation free-energy△G≠for some thermal decomposition steps were also calculated.The thermal decomposition kinetic function of [Cu (C)11H12NO4S)2(CH3COO)]·H2O in step(2) may be expressed as f(α)=1/4(1-α)[-ln(1-α)]-3, and the kinetic equation of thermal decomposition may be expressed as dα/dt = A·e-E/RT·f(α) = A·e-E/RT·1/4(1-α)[-ln(1-α)]-3,E = 349.5 kJ·mol-1, lnA = 73.74, r = 0.9901,△S≠= 363.6 J·mol-1·K,△G≠= 161.2 kJ·mol-1.The thermal decomposition kinetic function of [Zn2L2] in step(2) may be expressed as f(α) =(1-α)2, and the kinetic equation of thermal decomposition may be expressed as dα/dt = A·e-E/RT·f(α) = A·e-E/RT·(1-α)2, E = 390.5 kJ·mol-1, lnA = 66.68, r = 0.9884,△S≠= 242.2 J·mol-1·K,△G≠= 287.0 kJ·mol-1.TG-DTG analysis data of [Cu(C10H11NO4S)2] , [Cu2L2] , [Cd2L2] and [Cu2(C)11H13NO4S)2(CH3COO)2] were omitted.(6) The crystals of 4-[(E)-(2-Methoxyphenyl)iminomethyl]-N,N-dimethylaniline and 1,5-Dimethyl-2-phenyl-4-{[(E)-3,4,5-Tri methoxy benzylidene]amino}-1H -pyrazol-3(2H)-one were obtained. The measurement of crystal structure showed that:The crystal 4-[(E)-(2-Methoxyphenyl)iminomethyl]-N,N-dimethylaniline belongs to orthorhombic, Pna21 space group, molecular formula: C16 H18 N2 O, M =254.3.Unit cell parameter: a =15.182(8)(?),α=90.000(?),b=)11.756(6)(?) ,β= 90.000(?), c = 7.809(4)(?),γ= 90.000(?), V = )1393.8()13)(?)3, Z = 4, F(000) = 544.0, Dc = 1.2)12 Mg·m-3, R1 = 0.0433, wR2 = 0.1006 for I>2σ(I).The crystal 1, 5-Dimethyl-2-phenyl-4-{[(E)-3,4,5-Tri methoxy benzylidene] amino}-1H-pyrazol-3(2H)-one belongs to monoclinic, P21/cspace group, molecular formula: C21H23N3O4,M =381.4.Unit cell parameter: a =)12.3644 ()12)(?), b=14.0075(16)(?), c = )11.2682()11)(?),α=90.000(?),β= 90.000(?),γ= 90.000(?), V = 1393.813(?)3,Z = 4, F(000) = 544.0, Dc = 1.212 Mg·m-3, R1 = 0.0433, wR2 = 0.1006 for I>2σ(I).The crystals of 4-[(E)-(2-Methoxyphenyl)iminomethyl]-N,N-dime-thylaniline and 1,5-Dimethyl-2-phenyl-4-{[(E)-3,4,5-Tri methoxy benzylidene]-amino}-1H- Pyrazol-3(2H)-one were calculated using the density functional theory (DFT) with the gradient corrected B3LYP method. The crystal structure of the compound is totally optimized. The energies and components of molecular orbital (HOMO and LUMO), natural population, NBO and stabilization energy were calculated. All data obtained from the calculations are consistent with those gained from the determination, which means the calculation model is stabilized. The chemical property of two Schiff bases was illustrated.(7) In this paper, the character of fluorescent probe (L) derived from 4,4`-diaminodiphenylmethane and o-vanillin for detection of Zn (Ⅱ) cation was studied. The metal ion, negative ion, effect of pH and solution of the fluorescent probe (L) were studied.The results showed that: the Schiff base (L) derived from 4,4`-diaminodiphenylmethane and o-vanillin, has no fluorescence intensity in a range of 450-650 nm, but its fluorescence spectrum shows enhancement in the intensity of the signal at 525 nm on binding with the Zn(Ⅱ) cation. This Schiff base can be used in N, N-dimethylformamide (DMF), tetrahydrofuran (THF), toluene, and dimethylsulfoxide (DMSO), at pH 6 to 14, and Na(I), Mg(Ⅱ), Ca(Ⅱ), Al(Ⅲ), Cu(Ⅱ), Co(Ⅱ), Ni(Ⅱ), Cd(Ⅱ), Mn(Ⅱ), Sn(Ⅱ), Pb(Ⅱ), Cr(Ⅲ), Fe(Ⅲ), La(Ⅲ), Yb(Ⅲ), Er(Ⅲ) and Pr(Ⅲ) ion has no effect to the fluorescence intensity of Zn-L system. Dissolved in DMF, Fluorescence intensity is linear with concentration of Zn (Ⅱ) cation in a range from 1.0×10-7 mol·L-1 to 1.2×10-5 mol·L-1 atλem=538 nm. I=45.86c+18.12, R2=0.9991. [I: fluorescence intensity; c: concentration of Zn (Ⅱ)]. Schiff base derived from 4, 4`-diaminodiphenylmethane and o-vanillin, can be used as a fluorescent probe for detection of Zn (Ⅱ) cation.(8) The DNA binding modes of the four Cu (Ⅱ) complexes were investigated by electronic absorption spectra, EB-DNA displacement experiment and viscosity measurement. The experimental evidences indicated that: [Cu2(C)11H13NO4S)2(CH3COO)2], [Cu (C)11H12NO4S)2(CH3COO)]·H2O and [Cu2L2] could interact with DNA through intercalation, and [Cu(C10H11NO4S)2] binds to DNA through an electrostatic interaction mode.(9) In this paper, the anticancer activity of complexes was studied using protease for targets. 3 complexes were sifted from 18 complexes using MTT method. It was found that complexes of No.6 [Cu (Ⅱ) complex derived from L-cysteine and ovanillin], NO.14 [Cu (Ⅱ) complex derived from 4,4`-diaminodiphenylmethane and o-vanillin] and No.18 [Fe(Ⅱ) complex derived from 4,4`-diaminodiphenylmethane and o-vanillin] showed high anticancer activity. The study of the impact of complexes to CT-like (chymotrypsin-like activity) and Caspase-3 showed that No.18 complex could inhibit proteasome and activate Caspase-3 to induce apoptosis in prostate cancer PC-3.
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