Li Zao-ying

Synthesis of Novel Tailed Porphyrins with Covalently Linked Saccharide

The reaction of 5-(p-hydroxyphenyl)-10, 15, 20- (p-methoxy phenyl) porphyrin with Br(CH2)4 Br produced monobromo substituted porphyrin 1. The tailed porphyrins 2–4 were synthesized by the reactions of 1 with small molecular offering biological activities such as D-glucose, D-glucuronic acid. These new compounds were confirmed by1H NMR, IR, UV-vis and element analyses.

Synthesis of Novel Chiral Binaphthalene-Bridged Diporphyrins

Abstract Reactions of chiral 2,2′-biamino-1,1′-binaphthalene (R or S) with mono-substituted porphyrin 1a, 2b-c afforded novel chiral diporphyrins 3a-c and 4a-c which possess different linkers between the binaphthalene and porphyrin ring. Their structures have been identified by MS, IR, UV-visible and 1H NMR spectra, and elemental analysis.

Synthesis of novel diporphyrins

The novel diporphyrin ligands in which the two porphyrin ring units attached via a rigid aromatic linker were prepared. Their structures have been identified by IR, UV-visible,1H NMR spectra and elemental analysis.

Electrochemical behavior of novel bis (aliphatic amine) ruthenium (II) and osmium (II) porphyrins

Bis (aliphatic amine) ruthenium (II) and osmium (II) porphyrins, M (Por)-(H2NR)2 and M(Por)(HNR′2)2, [M=Ru and Os; Por=meso-tetrakis (p-tolyl) porphyrinato (TTP), meso-tetrakis (4-chlorophenyl) porphyrinato (4-Cl-TPP), meso-tetrakis (3, 5-dichlorophenyl) porphyrinato (3, 5-Cl-TPP) and meso—tetraphenyl porphyrinato(TPP); R=methyl, ethyl, iso-propyl and t-butyl; R′=methyl and ethyl] were synthesized by us. The electrochemical behavior of these complexes in 1, 2-dichloroethane with TBABF4 as supporting electrolyte, has been studied by cyclic voltammetry and controlled potential electrolysis. Bis (aliphatic amine) ruthenium (II) porphyrins under go reversible one-electron oxidation and one-electron reduction processes in 1,2-dichloroethane solution. The osmium (II) analogues is shown two oxidation couples III and V, an additional small wave IV. The redox potentials of these complexes are markedly dependent on the nature of the substituent bound to the phenyl group of the porphyrin ring. It is obvious that redox potentials increases the electron-withdrawing power of the substituents increases. The couple I was found at −0.34, −0.23 and −0.15 V vs Cp2 Fe+/0 (Cp2Fe=ferrocene) for Ru(TPP)(H2NBu-t)2, Ru(4-Cl-TPP) (H2NBu-t)2 and Ru(3,5-Cl-TPP)(H2NBu-t)2 respectively.

Synthesis and structure determination of ruthenium and osmium complexes with 2,6-bis-(diphenylphosphinomethyl) pyridine

Abstract2,6-Bis (diphenylphosphinomethyl) pyridine (PNP) reaction with Na2OsCl6 · 6H2O to give the five coordinated, sixteen-electron complex Os (PNP)Cl2. In the presence of formaldehyde, the reaction between Na2OsCl6· 6H2O and PNP proceeds rapidly in boiling ethanol to give the coordinately saturated Os(PNP)Cl2(CO). The IR spectrum of Os(PNP)Cl2(CO) shows a strong absorption band at 1 970 cm−1 assignable tov∞ stretch. PNP reacts with RuCl2(PPh3)3 and RuCl2(DMSO)4 (DMSO=dimethyl sulfoxide) to give Ru(PNP)Cl2 (PPh3) and Ru(PNP)Cl2 (DMSO) respectively. The average Ru−Cl, Ru−P and Ru−N bond distance in Ru(PNP)Cl2(PPh3) determineby X-ray crystallography are 0.242, 0.236 and 0.216 nm, respectively.

Synthesis and characterization of novel bridged porphyrins

The reaction of 5-(4-hydroxyphenyl)-10,15,20-triphenyl porphyrin with 2,6-dibromomethylpyridine and 4,4′-dicarboxyl-2,2′-bipyridine respectively gave 2,6-bis-[5,10,15-triphenyl-20-(4-phenoxymethyl)-porphyrin-yl]-pyridine(3) and 4,4′-di-[5,10,15-triphenyl-20-(p-phenoxycarbonyl)-porphyrin-yl]-2,2′-bipyridine (4). 5-[4-(4′- Bromobutoxy) phenyl]-10,15,20-triphenyl porphyrin reacted with 2,6-dihydroxymethylpyridine to give 2,6-bis-[5,10,15-triphenyl-20-(4-(p-phenoxy)-butoxymethyl)-porphyrin-yl]-pyridine(5). Those new compounds have been identified by1H NMR, IR, MS and UV-visible spectra, and elemental analysis.

Active testing of ruthenium porphyrins as mimic of enzyme

Three ruthenium(Ⅱ) porphyrin complexes [Ru Ⅱ(4-Cl-TPP)(CO)](1),[Ru Ⅱ(4-MeO-TPP)(CO)](2), [Ru Ⅱ(3,4,5-MeO-TPP)(CO)](3) and three ruthenium(Ⅵ) porphyrin complexes[Ru Ⅵ(4-Cl-TPP)(O) 2](4), [Ru Ⅵ(4-MeO-TPP)(O) 2 ](5),[Ru Ⅵ(3,4,5-MeO-TPP)(O) 2](6) were synthesized and their biological activities as bifunctional mimic of superoxide dismutase (SOD) and catalase (CAT) were tested. Their catalytic effects on depleting O -· 2 and decomposing H 2O 2 have been measured by riboflavin-methionine photoreduction method and spectrophotometry method respectively. The antioxidative activities of them were also studied, and the results showed these porphyrin complexes can indeed restraint the lipid peroxidation. The possible mechanism of ruthenium porphyrins catalyzing dismutation of superoxide radical and decomposition of hydrogen peroxide was put forward. In addition, the catalytic effects of different functional groups on the porphyrin rings were discussed.

Synthesis and Electrochemical Behavior of Poly N, N′- Dithiobis(1,3- Phenylenediamine)

A novel organic disulfide, N, N′-dithiobis(3-nitroaniline)(1) was prepared by the reaction of 3-nitroaniline with sulfur monochloride in chloroform. Compound 1 was reduced by zinc powder to give N, N′-dithiobis(1,3-phenylenediamine) (2). Poly N, N′-dithiobis (1,3-phenylenediamine) (3) was prepared by electrochemical polymerization of compound 2 and its basic electrochemical behavior is discussed.

Study on Synthesis and Biological Activities of Novel Water-Soluble Metalloporphyrins

The synthesis and characterization of a series of metal porphyrins, MII(Por), {Por=dianionic of 5, 10, 15, 20-tetrakis [4-(4′-bromobutyloxy) phenyl]porphyrinato and 5, 10, 15, 20-tetrakis [4-(4′-butyloxypyridine bromide)phenyl]porphyrinato, M=Zn, Cu, Mn, Co, Ni, Ru-CO} were described. The complexes 3a-3e were prepared from the reactions of compound 2 with metal acetates in chloroform, and the treatment of 3a-3f with excess of pyridine gave corresponding complexes 4a-4f. These new compounds were identified by absorption spectroscopies,1H-NMR and elemental analyses. The results of biological activity testing for 4a-4f revealed that 4a and 4c had stronger inhibiting action on the growth metabolism ofEsche richia coli.

Study on synthesis and deplete harmful radical of cobalt prophyrins as the mimic of enzyme

The four cobalt porphyrins [Co (3, 4, 5-MeO-TPP) (1); Co (TTP) (2); Co (4-Cl-TPP) (3); Co (4-HSO3-TPP) (4)] were synthesized and considered as two mimic of superoxide dismutaes (SOD) and catalase (CAT). The catalytic efficiency of them on deplete the harmful radical have been proved using riboflavin-methionine photoreduction method in the concentration range of 10−6∼10−5 mol/L. The catalytic efficiency of them at decomposing H2O2 has been performed by spectrophotometer. The percentage of decomposing H2O2 while the increasing the concentration of the imitating compounds. The lipid peroxidation produced in liver homogenated of mice was determined by spectrophotometer detecting the content of MDA.