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The Study Of Synthesis And Application Of Porphrin Derivatives

Posted on:2009-06-14Degree:DoctorType:Dissertation
Country:ChinaCandidate:D S MaFull Text:PDF
GTID:1101360275998826Subject:Applied Chemistry
Abstract/Summary:PDF Full Text Request
Porphyrin derivates are a class of cyclotetrapyrrolic compounds,which have 18~22 conjugate electrons and then have unique light sensitivity and unique biochemical properties due to the macro conjugation.These derivates were used in various fields. Photodynamic therapy and catalysis are two important application fields of porphyrin derivates.In this dissertation,a rounded project route involving the extraction of haemin,the synthesis of porphyin derivates with haemin as starting material and the catalytic application of porphin derivates was designed.In this dissertation,the extraction process 1 was put forward on the basis of references and improved to process 2.At last,haemolysis in process 2 was carried out by ultrasonic excitation and the optimum ultrasonic haemolysis conditions were obtained. The optimum ultrasonic haemolysis conditions were:8 mL water per 50 mg erythrocyte, and 10 min haemolysis.The used water was pure.Under the optimum haemolysis conditions,compared with traditional stirring haemolysis,the application of ultrasonic exctiting in haemolysis decreased haemolisis time from 18 h under 50℃to 10 min under roomtemperature,and increased the yield of heamin from about 40 of the method of acidic acetone to 94.78%with a high haemin purity of 95.38%.At the same time,the using of ultrasonics simplified the process and saved the reagent(no NaOH was needed for haeomolysis,and the amount of HCl for the following process was decreased)。A series of photo sensitizers were designed and synthesized with haemin as starting material,and the synthesized photo sensitizers were characterized in structure and photophysical property.The results indicated that the structures and performance indexes of the products met to the design requirements.The designed synthesis routes were reasonable and feasible.The results also showed that,by saturating of 2-cyclic olefinic bond in porphyrin,the absorbance of porphyrins in photodynamicl therapy window (600~900 nm)was successfully improved.The synthesized photo sensitizers have a good prospect for further development and application.Metallodeuteroporphyrin-Ⅸ-dimethylesters(MDP-Ⅸ-DMEs)were used successflly for the first time to catalyze the selective aerobic oxidation of cyclohexane without any cocatalysts or solvents.The results were exciting.Under the conditions of 150℃and 0.8 MPa,deuteropor-phyrin-Ⅸ-dimethylester cobalt(Ⅱ)(DP-Ⅸ-DMCo)had the best catalytic activity with cyclohexane conversion of 18.6%,selectivity of cyclohexanol and cyclohexanone of 84.6%and catalyst turnover number of 8.5×10~4.Compared with ther system catalyzed by supported tetraphenylporphyrin cobalt(Ⅱ),The cyclohexane conversion catalyzed by DP-Ⅸ-DMCo was enhanced by 6~7%,and the catalyst turnover number was enhanced by 1 times.The kinetics of the oxidation of cyclohexane catalyzed by MDP-Ⅸ-DMEs was studied preliminarily.In the aspect of kineties,the reasons of high catalytic activities of metallodeuteroporphyrins compared with metallotetraporphrins as well as the reasons of high catalytic activities of cobalt porphyrins compared with other metalloporphyrines were gave explanation.The kinetics study indicated that the oxidation-reduction potential of complex ion inside the ring of porphyrin was the key factor which affected the catalytic activity of the porphyrin.So the focus of the study on catalytic oxidation of cyclohexane should been put on changing the potential of the complex ion.At last,the prospective mechanism of cyclohexane oxidation catalyzed by MDP-Ⅸ-DMEs was proposed referring to the mechanism of oxidation of hydrocarbon oxidation catalyzed by cytochrome P-450.
Keywords/Search Tags:porphyrin, chlorin, photo sensitizer, haemin, cyclohexane, synthesis, catalysis, selective oxidation
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