Study On The Synthesis, Characterization And Application Of Indole Carboxylic Acid

Marine active small molecules, due to their special chemical strucures andphysiological activities, have got more and more get attention. In the thesis, thederivatives of indole---3-indole carboxylic acid are regarded as ligands. Throughadding essential elements of human, new complexes are synthetized. By researchingthe structures, properties and bioactivities, they may offer theoretic basis fordeveloping anticancer drugs and marine resources.In the paper, three different3-indole carboxylic acid ligands are chosen tosynthetized three new series complexes and one single crystal is cultivated. Thepowder complexes are characterized by elemental analysis,1H NMR, IR spectrometry,UV-Vis spectrometry, molar conductance and TG-DTG and the possible chemicalstructures of them are inferred. The single crystal is measured by X-ray crystaldiffraction. Fluorescence properties of ligands and part complexes are tested. Themode of interaction between [Cu₂(C₁₀H8O₂N)4（CH3OH）2]·2CH3OH and CT-DNA isstudied. Moreover, the method of agarose gel electrophoresis is used to analyze theability of [Cu₂(C₁₀H8O₂N)4（CH3OH）₂]·2CH3OH to cleave pBR322plasmid DNA.Themain works of the thesis are shown as follows:（1） The metal complexes derived from3-indole acetic acid are synthesized. Onesingle crystal is obtained. The crystal data show that the crystal is a dinuclear complexwhich belongs to the monoclinic crystal system, space group p2（1）/c with the cellparameter a=12.0660（11），b=12.0660（11），c=18.8289（16），α=90，β=127.748（2），γ=90，V=2279.3（4）3，F（000）=988，Dc=1.387g/cm3, R1=0.0504，wR2=0.1492. The crystallographic structural analysis reveals that the Cu（II） complexis coordinated by four carboxylic oxygen atoms from four ligands, one oxygen atomfrom ethanol and the other Cu（II） ion. The two-dimensional network of molecule isformed by the interaction of the intramolecular and intermolecular hydrogen bonds （N —H…O）. The possible chemical structure of other are confirmed to be[M₂(C₁₀H₈O₂N)₄（H₂O）₂]·nH₂O （M=Zn（II）, Cr（Ⅲ）, Fe（Ⅲ））,[Cu(C₁₀H₈O₂N)₂(C₁₂H₈N₂)].（2） The metal complexes derived from3-indole propionic acid are synthetized.The possible chemical structure of other are confirmed to be[M₂(C₁₁H₁₀O₂N)4（H₂O）₂]·nH₂O （M=Cu（II）,Zn（II）, Cd（II）, Fe（Ⅲ）, Cr（Ⅲ））;[Cu(C₁₁H₁₀O₂N)2(C₁₂H₈N₂)].（3） The metal complexes derived from3-indole butyrate acid are synthetized.The possible chemical structure of other are confirmed to be[M₂(C₁₂H₁₂O₂N)₄（H₂O）₂]·nH₂O （M=Cu（II）, Cd（II）, Fe（Ⅲ）, Mn（II））;[Cu(C₁₂H₁₂O₂N)₂(C₁₂H₈N₂)].（4） Combinating Achar differential and Coats-Redfern integral method which fitsthe thirty kinetic equations, the calculating program of some step of thermaldecomposition for complexes is designed. The kinetic equations of correspondingkinetic parameters are obtained. The kinetic parameters include E, A, order of reactionand correlation coefficient etc. The activation entropy△S≠and activation free-energy△G≠for some thermal decomposition steps are also calculated.The thermal decomposition kinetic function of [Cu₂(C₁₀H₈O₂N)₄（CH₃OH）₂]·2CH₃OH in step two can be expressed as f（α）=1/2（1-α）[-ln（1-α）]-1, andthe kinetic equation of thermal decomposition can be expressed as dα/dt=A·exp（-E/RT）·f（α）=A·exp（-E/RT）·1/2（1-α）[-ln（1-α）]-1，E=243.43kJ·mol^-1, lnA=57.15, r=0.9858,△S≠=227.00J·mol^-1·K,△G≠=140.53kJ·mol^-1.The thermal decomposition kinetic function of [Cd₂(C₁₁H₁₀O₂N)₄（H₂O）₂]·2H₂Oin step two can be expressed as f（α）=1/3（1-α）[-ln（1-α）]-2, and the kinetic equation ofthermal decomposition may be expressed as dα/dt=A·exp（-E/RT）·f（α）=A·exp（-E/RT）·1/3（1-α）[-ln（1-α）]-2, E=371.22kJ·mol^-1, lnA=66.36, r=0.9817,△S≠=243.60J·mol^-1·K,△G≠=226.38kJ·mol^-1. TG-DTG analysis data of othercomplexes are omitted.（5） Fluorescence spectra of materials ligands and part of the matal complexes areresearched. The experimental results show that the raw material ligands have very strong fluorescence effects, while synthetic complexes fluorescence intensity enhancesignificantly. Besides, the excitation and emission peaks of these complexes haveshifted to some range.（6） The interaction of the [Cu2(C₁₀H8O₂N)4（CH3OH）2]·2CH3OH with CT-DNAhas been investigated by UV-Vis spectrometry, fluorescence spectrometry, EB-DNAexperiment and viscosity experiment. The results show that the interaction of complexand DNA is part intercalation. Moreover, agarose gel electrophoresis assaydemonstrates that the complex possesses the ability to cleave pBR322plasmid DNAinto FormII.（7） In the thesis, anticancer activity of part complexes is studied through MTTmethod. It is found that three ternary Cu（II） complexes had better inhibitory effect forbreast cancer cells. Further, antitumor activity of the one complex is furthe researched.The results show that the concentration and action time are positively correlated.