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Water-soluble metalloporphyrins as models of hemoproteins and peroxynitrite decomposition catalysts.

Record Type:	Electronic resources : Monograph/item
Title/Author:	Water-soluble metalloporphyrins as models of hemoproteins and peroxynitrite decomposition catalysts.
Author:	Zhou, Huchen.
Description:	155 p.
Notes:	Adviser: John T. Groves.
Notes:	Source: Dissertation Abstracts International, Volume: 64-08, Section: B, page: 3833.
Contained By:	Dissertation Abstracts International64-08B.
Subject:	Chemistry, Organic.
Online resource:	http://pqdd.sinica.edu.tw/twdaoapp/servlet/advanced?query=3103024
ISBN:	0496505939

Water-soluble metalloporphyrins as models of hemoproteins and peroxynitrite decomposition catalysts.
Zhou, Huchen.

Water-soluble metalloporphyrins as models of hemoproteins and peroxynitrite decomposition catalysts. [electronic resource] - 155 p.

Adviser: John T. Groves.

Thesis (Ph.D.)--Princeton University, 2003.

A highly sensitive fluorescent probe, 6A-N-dansyl-permethylated-beta-cyclodextrin, formed 2:1 complexes with manganese(III) meso-tetrakis(4-carboxyphenyl) porphyrin (Mn(III)TCPP), manganese(III) meso-tetrakis(4-sulfonatophenyl) porphyrin (Mn(III)TPPS) and manganese(III) meso-tetrakis(2,3,5,6-tetrafluoro-N,N,N-trimethyl-4-aniliniumyl) porphyrin with binding constants of 6.1 x 109 M-2, 7.1 x 1010 M-2 , and 1.6 x 1011 M-2 as determined by fluorescence titrations. This made possible the reliable measurement of weak binding constants. As shown by 1H-NMR and UV-Vis, a novel PEGylated cyclodextrin, Heptakis(2,3,6-tri-O-2-(2-(2-methoxyethoxy)ethoxy)ethyl)-beta-cyclodextrin formed 1:1 complexes with Mn(III)TCPP and H2TCPP (meso -tetrakis(4-carboxyphenyl) porphyrin) with binding constants of 1.2 x 106 M-1 and ≥108 M-1 that was the highest for a monomeric cyclodextrin. On the contrary, heptakis(2,6-di-O-methyl-3-O-2-(2-(2-methoxyethoxy)ethoxy)ethyl)-beta-cyclodextrin bound porphyrins with a 2:1 mode. Based on the successful control of binding mode, Hemodextrin, a self-assembled construct between Fe(III)TPPS and py-PPCD (2A-O-(3-pyridylmethyl)-perPEGylated beta-cyclodextrin) has been built. The binding constant was 2 x 106 M -1 and the pyridyl nitrogen of py-PPCD was shown to ligate to iron by 1H-NMR and UV-Vis. This hemodextrin ensemble has been shown to bind dioxygen reversibly and to form a stable ferryl species. This is the first self-assemble synthetic functional hemoprotein model compound.

ISBN: 0496505939Subjects--Topical Terms:

193634
Chemistry, Organic.

Water-soluble metalloporphyrins as models of hemoproteins and peroxynitrite decomposition catalysts.
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245 1 0 $a Water-soluble metalloporphyrins as models of hemoproteins and peroxynitrite decomposition catalysts. $h [electronic resource]
300 $a 155 p.
500 $a Adviser: John T. Groves.
500 $a Source: Dissertation Abstracts International, Volume: 64-08, Section: B, page: 3833.
502 $a Thesis (Ph.D.)--Princeton University, 2003.
520 # $a A highly sensitive fluorescent probe, 6A-N-dansyl-permethylated-beta-cyclodextrin, formed 2:1 complexes with manganese(III) meso-tetrakis(4-carboxyphenyl) porphyrin (Mn(III)TCPP), manganese(III) meso-tetrakis(4-sulfonatophenyl) porphyrin (Mn(III)TPPS) and manganese(III) meso-tetrakis(2,3,5,6-tetrafluoro-N,N,N-trimethyl-4-aniliniumyl) porphyrin with binding constants of 6.1 x 109 M-2, 7.1 x 1010 M-2 , and 1.6 x 1011 M-2 as determined by fluorescence titrations. This made possible the reliable measurement of weak binding constants. As shown by 1H-NMR and UV-Vis, a novel PEGylated cyclodextrin, Heptakis(2,3,6-tri-O-2-(2-(2-methoxyethoxy)ethoxy)ethyl)-beta-cyclodextrin formed 1:1 complexes with Mn(III)TCPP and H2TCPP (meso -tetrakis(4-carboxyphenyl) porphyrin) with binding constants of 1.2 x 106 M-1 and ≥108 M-1 that was the highest for a monomeric cyclodextrin. On the contrary, heptakis(2,6-di-O-methyl-3-O-2-(2-(2-methoxyethoxy)ethoxy)ethyl)-beta-cyclodextrin bound porphyrins with a 2:1 mode. Based on the successful control of binding mode, Hemodextrin, a self-assembled construct between Fe(III)TPPS and py-PPCD (2A-O-(3-pyridylmethyl)-perPEGylated beta-cyclodextrin) has been built. The binding constant was 2 x 106 M -1 and the pyridyl nitrogen of py-PPCD was shown to ligate to iron by 1H-NMR and UV-Vis. This hemodextrin ensemble has been shown to bind dioxygen reversibly and to form a stable ferryl species. This is the first self-assemble synthetic functional hemoprotein model compound.
520 # $a As a nitric oxide synthase model, iron(III) tetrakis(N-methyl-2-pyridyl)porphyrin (Fe(III)P) catalyzed the unprecedented aerobic oxidation of NG-Hydroxy-L-Arginine in buffers at 25°C. N-nitrosoarginine and Ndelta-cyanoornithine were produced at pH 7.4, while Ndelta-cyanoornithine and nitrite/nitrate were the major products at pH 11. At pH = 3 or 5, there was no significant reaction. A new species at 420 nm appeared upon mixing NHA with Fe(III)P at pH 9 or 11 and was tentatively assigned to Fe(III)P-NHA complex. The oxidation is proposed to be initiated by a homolytic cleavage of the Fe-O bond.
520 # $a The second generation of cationic porphyrinic peroxynitrite decay catalysts have been synthesized. The atropisomer-free iron(III) meso-tetrakis(N,N-di-(2-(2-methoxyethoxy)ethyl)-imidazol-2-yl)porphyrin and iron(III) meso-tetrakis(N,N-dicarboxymethyl)-imidazol-2-yl)porphyrin are of great pharmacological significance as potent peroxynitrite decomposition catalysts in vitro and in vivo.
590 $a School code: 0181.
650 # 0 $a Chemistry, Organic. $3 193634
710 0 # $a Princeton University. $3 212488
773 0 # $g 64-08B. $t Dissertation Abstracts International
790 $a 0181
790 1 0 $a Groves, John T., $e advisor
791 $a Ph.D.
792 $a 2003
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