Researches Of Preparation And Characterization Of Ordered-films And Nanomaterials Basing On Metalloporphyrin Complexes

In this paper, ordered molecular films of four porphyrin complexes were prepared by Langmuir-Blodgett technology and their properties prepared at air/water interface were also systematically analyzed by Small angle X-ray scattering, UV-vis spectrophotometer, Atomic force microscopy (AFM) and water contact angle analysis. The interaction between porphyrin complexes LB films modified electrode with DNA bases was investigated by cyclic voltammetry. The main work are as follows:1.5-(m-hydroxyphenyl)-10,15,20-tir(p-chlorohenyl) porphyrin Cu(Ⅱ)(HPCPP Cu(Ⅱ))、5-(m-hydroxyphenyl)-10,15,20-tir(p-chlorohenyl) porphyrin Zn(Ⅱ)(HPCPP Zn(Ⅱ)) and5-(m-hydroxyphenyl)-10,15,20-tir(p-chlorohenyl)porphyrin Mn(Ⅱ)(HPCPPMn(Ⅱ)) were synthesized. The porphyrin (HPCPP) and its complexes of HPCPPCu(Ⅱ), HPCPPZn(Ⅱ) and HPCPPMn(Ⅱ) supermolecular organized films were prepared by Langmuir-Blodgett technique. The film-forming conditions of the four porphyrin complexes and their molecules behavior at air/water interface were studied by surface pressure-Area isotherms and the curve of static elastic modulus-surface pressure. The surface morphology and the arranged orientation of molecules in membrane were also analysed with Atomic force microscopy (AFM), UV-vis spectrophotometer, Small angle X-ray scattering and Static water contact angle methods.2. The study of the molecular orientation of porphyrin complexes in LB films:1) Results showed that whether the spreading solution was treated or not for HPCPP, the particles in LB films prepared had uniform size and smooth surface. But they had not presented the orientation arrangement of molecules in LB films. In the case of the HPCPPZn(Ⅱ), HPCPPMn(Ⅱ) and HPCPPCu(Ⅱ), the nano-film fabricated with the spreading solutions treated with ultrasonic showed significant orientation arrangement, which has the potential optical activity.2) It showed that the orientation of porphyrin ring can be controlled by adding metal ions in the subphase, showing that the orientation angles of the porphyrin with respect to the substrate were increased in LB film.3) The control of regular orientation of porphyrin ring could be achieved by ultrasonic treatment of the solution of film-forming materials, in which the orientation angles of the porphyrin with respect to the substrate in LB films were gradually direcased.3. The electrochemical behaviors of the four porphyrin complexes in DMF and modified electrode with porphyrin complexes LB films were investigated with cyclic voltammetry.1) The experiments showed that the interaction mechanism of electrode modified with the four porphyrins’ LB fim was difference from that in solution.2) In the studies of the molecular recognition behavior of electrode modified with porphyrin complexes LB films to the DNA bases, the four complexes had different ability to identify for DNA bases. HPCPP, HPCPPZn(Ⅱ) and HPCPPMn(Ⅱ) had extensive recognition to cytosine, while weaker identify guanine. However, HPCPPCu(Ⅱ) showed the better ability to identify guanine.