Peroxidase-Like Catalytic Activity of Anion-Exchange Resins Modified with Metal-Porphyrins in Oxidative Reaction of Hetrocyclic Amines with Hydrogen Peroxide

Abstract

Heterocyclic amines (HCAs, Fig. 1) are mutagenic factors that are predominantly ingested as pyrolysis products of meats and fishes.1) To adsorb the HCAs on ligands, a cellulose coupled with a Cu-phthalocyanine derivative (Cu-PC, a related compound metal-porphyrin), so-called "blue cotton," was developed, 2,3) which was reported to be beneficial for callbacks and determinations of HCAs in environmental waters 2) and air-born particules.4) The adsorption of HCAs on the blue cotton is caused by hydrophobic p-p interaction between HCAs and Cu-PC coupled with cotton fiber. Peroxidase (POD), of which active cite is Fe-protoporphyrin, was reported to catalyze oxidative reactions of a wide range of mutagens and carcinogens including HCAs, thereby decreasing the mutagenicity and carcinogenicity. 5,6) In the above cases, metal-porphyrin derivatives serve as an adsorbent of HCAs or a catalysis of oxidative reaction of mutagens.On the other hand, we previously reported that some anion-exchangers modified with metal-tetrakis(sulfophenyl)-porphines (M-TSPP r ) exhibited a peroxidase (POD)-like activity and was applicable to the determination of hydrogen peroxide as a solid-mimesis of horse radish POD. 7,8) In the present paper, we investigated the POD-like activity of M-TSPP r s in the oxidation of HCAs to elucidate the usefulness of M-TSPP r s as a POD-like catalyst in the oxidation of HCAs. We revealed that some M-TSPP r s exhibit a similar POD-like activity for HCAs to horse radish POD. In particular, Fe-and Mn-TSPP r s catalyze the oxidation of 2-amino-3-methyl-imidazo[4,5-f ]quinoline (IQ) with hydrogen peroxide. The resulting IQ-dimmer has no mutagenicity in umutest. We elucidated that M-TSPP r can decrease mutagenicity of HCAs in vitro through its POD-like catalytic activity. ExperimentalMaterials Tetrakis(sulfophenyl)porphine (H 2 -TSPP) was purchased from Wako Junyaku Co. Ltd. (Osaka, Japan). Mutagenic HCAs (see Fig. 1), IQ, MeIQ, MeIQx, TrpP-1 and TrpP-2, were purchased from Wako Junyaku Co. Ltd. GluP-1 and GluP-2 (Chemsyn Science Laboratories, Lenaxa, Kansas, U.S.A.) were kindly donated from Prof. Hikoya Hayatsu (Shujitsu University). They were used without further purification. An anion-exchange resin, Amberlite IRA 900 (24-42 mesh) in nitrate form, was a manufacture of Organo Chemical Co. Ltd. (Tokyo, Japan). Other reagents were of analytical or reagent grade. umu-Test kit was purchased from Japan Immunoresearch Laboratories Co. Ltd. (Takasaki, Japan).Apparatus Absorption (UV/V) spectra and absorbances (abbr. "A") were measured on a Shimadzu UV-180 or a JASCO V-570 spectrophotometer with 10 mm quartz cells. HPLC system was constructed with a Shimadzu pump (LC-6A), a Shimadzu photodiode array detector (SPD-M6A) and a To elucidate the peroxidase (POD)-like catalytic activity of anion-exchange resins modified with metaltetrakis(sulfophenyl)porphine (M-TSPP r s), an oxidative reaction of seven mutagenic heterocyclic amines (HCAs) with hydrogen peroxide, which reaction is catalyzed by horse radish POD, was investigate...

Silica gel-immobilized aluminum phthalocyanine complex as a heterogeneous catalyst for the synthesis of α-amino phosphonates

“…The same disadvan tage has electrostatic binding of phthalocyanines (involv ing COO -or Alk 3 N + groups on the periphery of macro cycle) at ion exchange resin or modified silica gels. 1, 11 These drawbacks deprived the physical incorporation of vinyl phthalocyanine derivatives into a macromolecular matrix, 12 however, on its turn, this method limited by the use of polystyrene as a matrix and has a number of disad vantages inherent for organic polymeric carries (e.g., low temperature limits of applicability and low mechanical stability).…”