Preparation and Function of Poly(acrylic acid)s Modified by Supramolecular Complex Composed of Porphinatoiron and a Cyclodextrin Dimer That Bind Diatomic Molecules (O2 and CO) in Aqueous Solution

被引:19
作者
Kano, Koji [1 ]
Ochi, Toshiro [1 ]
Okunaka, Sayuri [1 ]
Ota, Yusuke [1 ]
Karasugi, Keiichi [1 ]
Ueda, Takunori [1 ]
Kitagishi, Hiroaki [1 ]
机构
[1] Doshisha Univ, Dept Mol Chem & Biochem, Kyoto 6100321, Japan
关键词
bioinorganic chemistry; cyclodextrins; oxygen; polymers; supramolecular chemistry; IRON-PORPHYRIN; DIOXYGEN-BINDING; MYOGLOBIN; HEMOGLOBIN; SYSTEM; MODEL; IRON(III); PEROXIDE; BEHAVIOR;
D O I
10.1002/asia.201100354
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
Poly(acrylic acid) (PAA) is modified by 5-(4-beta-alanylaminophenyl)-10,15,20-tris(4-sulfonatophenyl) porphinatoiron(III) to yield iron porphyrin-bearing PAAs (FeP(n)s) through a condensation reaction. FeP(n)s were further functionalized by Py3CD, which is a per-O-methylated beta-cyclodextrin (CD) dimer with a pyridine linker and includes the porphyrin pendants to form ferric hemoCD-P(n) s. Ferrous hemoCD-P(3), having three porphyrin chromophores in a polymer chain, is shown to bind molecular oxygen (P-1/2 = 7.9 +/- 1.4 Torr) in aqueous solution at pH 7.0 and 25 degrees C, affording oxy-hemoCD-P(3). Oxy-hemoCD-P(3) is biphasically autoxidized to ferric hemoCD-P(3), with 27% of the dioxygen adducts being rapidly oxidized. The rate of autoxidation of oxy-hemoCD-P(15), having 15 porphyrin chromophores in a polymer chain, was much faster than that of oxy-hemoCD-P(3), thus suggesting self-catalyzed autoxidation of oxy-hemoCD-P(n)s. Oxy-hemoCD-P(n)s are markedly stabilized by catalase, thereby indicating that hydrogen peroxide generated from oxy-hemoCD-P(n) accelerates the autoxidation. Most of the hemoCD-P(3) molecules injected into the femoral vein of a rat remained in the body, though about 16% of the hemoCD-P(3) molecules were excreted in the urine as a carbon monoxide adduct.
引用
收藏
页码:2946 / 2955
页数:10
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