Iron(III) Complexes with Hydrogen Peroxide which Can Discriminate Two Reaction Types; Oxidation (H-Atom Abstraction) and Oxygenation Reaction

1995 ◽  
Vol 50 (3-4) ◽  
pp. 205-208 ◽  
Author(s):  
Yuzo Nishida ◽  
Sayo Ito
Keyword(s):  
Hydrogen Peroxide ◽  
Acid Solution ◽  
High Activity ◽  
Oxidative Degradation ◽  
Nitrilotriacetic Acid ◽  
Diacetic Acid ◽  
Experimental Conditions

Iron(III)-NTA (nitrilotriacetic acid) solution shows high activity for oxidative degradation of 2′-deoxyribose in the presence of hydrogen peroxide, whereas its activity of Fe(III)-TFDA (2-aminomethyltetrahydrofuran-N,N-diacetic acid) is negligible under the same experimental conditions; however the latter solution exhibits abnormally higher reactivity for oxygenation reaction at 8-position of 2′-deoxyguanosine than other iron(III) chelates examined. These results suggest that oxidative degradation of deoxyribose and the oxygenation of deoxyguanosine are caused by a different iron(III)-peroxide species.

Structural Variety of Copper(II)-Peroxide Adducts and Its Relevance to DNA Cleavage

1999 ◽  
Vol 54 (1-2) ◽  
pp. 94-99 ◽  
Author(s):  
Satoshi Nishino ◽  
Teruyuki Kobayashi ◽  
Mami Kunita ◽  
Sayo Ito ◽  
Yuzo Nishida
Keyword(s):  
Hydrogen Peroxide ◽  
High Activity ◽  
Dna Cleavage ◽  
Esr Spectroscopy ◽  
Spin Trapping ◽  
The Other ◽  
Experimental Conditions ◽  
Structural Variety ◽  
Supercoiled Form ◽  
Tetradentate Ligands

The reactivity of copper(II) compounds with several tetradentate ligands towards some spin-trapping reagents was studied in the presence of hydrogen peroxide. The compounds used in this study are roughly divided into two groups based on the reactivity towards 2 ,2 ,6 ,6 -tetramethyl-4-piperidinol(and also 2,2,6,6-tetramethyl-4-piperidone), which are trapping agents for singlet oxygen, 1O2 (1Δg); The A-group compounds exhibited a high activity to form the corresponding nitrone radical, which was detected by ESR spectroscopy, but corresponding activity of the B-group compounds was very low. The A-group compounds defined as above exhibited high activity for cleavage of DNA(supercoiled Form I) in the presence of hydrogen peroxide, yielding DNA Form II (relaxed circular) or Form III (linear duplex) under our experimental conditions ([Cu(II)]=0.1~0.5 mᴍ). On the other hand, the B-group compounds effected complete degradation of the DNA (double-strand scission) under the same experimental conditions, formation of Form II or Form III DNA was negligible. Two different DNA cleavage patterns observed for A-and B-group compounds were elucidated by the different structural property of the copper(II)-peroxide adducts, which is controlled by the interaction through both DNA and the peripheral group of the ligand system

Oxygenation of Nucleosides by Peroxide Adduct of Binuclear Iron(III) Complex with a μ-Oxo Bridge

1999 ◽  
Vol 54 (7-8) ◽  
pp. 554-561
Author(s):  
Sayo Ito ◽  
Yumiko Sasaki ◽  
Yasuyuki Takahashi ◽  
Shigeru Ohb ◽  
Yuzo Nishida
Keyword(s):  
Hydrogen Peroxide ◽  
High Activity ◽  
Structural Properties ◽  
Coordination Mode ◽  
Active Species ◽  
Diacetic Acid ◽  
Acid Hydroxylation ◽  
Binuclear Iron ◽  
Oxo Bridge

Abstract The (μ-oxo)(μ-carbonato)diiron(III) complex with H2(tfda) (H2(tfda) = 2-aminomethyl-tetrahydrofuran-N,N-diacetic acid) exhibited high activity for hydroxylation of 2′-deoxygua-nosine in the presence of hydrogen peroxide, giving 8-hydroxydeoxyguanosine, but its hy­ droxylation activity towards other nucleosides such as 2′-deoxyadenosine, adenosine or thym­ idine was found negligible. In the case of the Fe(III)-(ed a) complex (H2(eda) = 2-methoxyethylamine-N,N-diacetic acid), hydroxylation occurred mainly at the sugar site, con­verting 2′-deoxyguanosine to guanosine. Based on the spectroscopic and structural properties of these iron(III) compounds, it seems most likely that an intrinsic active species for hydrox­ylation should be an electrophilic peroxide adduct of the (μ-oxo)diiron(III) core with η1 coordination mode, while the contribution of OH· sides is ruled out.

High Activity of Binuclear Cobalt(II) Complex for Ethylene Evolution from 1-AminocycIopropane-1-carboxylic Acid in the Presence of Hydrogen Peroxide

1999 ◽  
Vol 54 (7-8) ◽  
pp. 534-541 ◽  
Author(s):  
Teruyuki Kobayashi ◽  
Yumiko Sasaki ◽  
Tetsuya Akamatsu ◽  
Toshihiro Ishii ◽  
Yoshiaki Oda ◽  
...  
Keyword(s):  
Hydrogen Peroxide ◽  
Carboxylic Acid ◽  
High Activity ◽  
Spectral Data ◽  
Cobalt Complex ◽  
Oxidative Degradation ◽  
Mass Spectral Data ◽  
Ethylene Evolution ◽  
Mass Spectral

Abstract The binuclear Co(II) and Mn(II) complexes with H5(HXTA). where H5(HXTA) repre­sents N,N′-(2-hydroxy-5-methyl-1,3-xylylene)bis(N-carboxymethylglycine), induced a strong ethylene evolution from 1-aminocyclopropane-l-carboxylic acid (ACC) in the presence of hydrogen peroxide, whereas activities of the corresponding Fe(III), Ni(II), and V(III) com­plexes were found negligible. Based on spectroscopic results and mass-spectral data it is proposed that a peroxide adduct of binuclear Co(II) (and Mn(II)) complex with η1-coordina­tion mode interacts with ACC, which is chelated to a binuclear cobalt complex leading to facile oxidative degradation of ACC and to evolution of ethylene.

Comparison on Reactivity of Fe(III) and AI(III) Compounds in the Presence of Hydrogen Peroxide: Its Relevance to Possible Origin for Central Nervous System Toxicity by Aluminum Ion

1995 ◽  
Vol 50 (7-8) ◽  
pp. 571-577 ◽  
Author(s):  
Yuzo Nishida ◽  
Sayo Ito
Keyword(s):  
Hydrogen Peroxide ◽  
Central Nervous System ◽  
Nervous System ◽  
High Activity ◽  
Furan Ring ◽  
Nitrilotriacetic Acid ◽  
Central Nervous System Toxicity ◽  
The Brain ◽  
System Toxicity

Abstract The iron(III) compounds with several aminocarboxylate chelates containing an aryl or furan substituent exhibit high activity in enhancement of the reactivity of hydrogen peroxide, leading to facile hydroxylation at benzene ring, and to degradation of furan ring, but no such activity was observed for the corresponding Al(III) compounds. These results were inter­preted in terms of the molecular orbital consideration, and lack of the activity of the Al(III) complexes was attributed to lack of electrophilic nature of the peroxide adduct due to the absence of a d-orbital: this may explain the fact that there were no tumors in Al-NTA (nitrilotriacetic acid)-treated rats. Based on the facts observed in this study, the decreased function of iron(III) ions for synthesizing neurotransmitters in the brain was assumed to be one of the possible origin for the neurotoxicity by injection of the Al(III) salts in vivo.

Xylenol-orange-assay-of-hydrogen-peroxide for Measuring Uricase Activity and Recognizing High-activity Uricase Mutant

2013 ◽  
Vol 19 (3) ◽  
pp. 523-527 ◽  
Author(s):  
Miaomiao LIU ◽  
Juan FENG ◽  
Hongbo LIU ◽  
Xiaolan YANG ◽  
Liping FENG ◽  
...  
Keyword(s):  
Hydrogen Peroxide ◽  
High Activity ◽  
Xylenol Orange ◽  
Uricase Activity

A review of lignin hydrogen peroxide oxidation chemistry with emphasis on aromatic aldehydes and acids

Holzforschung ◽  
2021 ◽  
Vol 0 (0) ◽  
Author(s):  
Ajinkya More ◽  
Thomas Elder ◽  
Zhihua Jiang
Keyword(s):  
Hydrogen Peroxide ◽  
Oxidative Degradation ◽  
Reaction Medium ◽  
Dicarboxylic Acids ◽  
Aromatic Aldehydes ◽  
Product Distribution ◽  
Reaction Conditions ◽  
Alkaline Conditions ◽  
The Stability ◽  
Oxidation Chemistry

Abstract This review discusses the main factors that govern the oxidation processes of lignins into aromatic aldehydes and acids using hydrogen peroxide. Aromatic aldehydes and acids are produced in the oxidative degradation of lignin whereas mono and dicarboxylic acids are the main products. The stability of hydrogen peroxide under the reaction conditions is an important factor that needs to be addressed for selectively improving the yield of aromatic aldehydes. Hydrogen peroxide in the presence of heavy metal ions readily decomposes, leading to minor degradation of lignin. This degradation results in quinones which are highly reactive towards peroxide. Under these reaction conditions, the pH of the reaction medium defines the reaction mechanism and the product distribution. Under acidic conditions, hydrogen peroxide reacts electrophilically with electron rich aromatic and olefinic structures at comparatively higher temperatures. In contrast, under alkaline conditions it reacts nucleophilically with electron deficient carbonyl and conjugated carbonyl structures in lignin. The reaction pattern in the oxidation of lignin usually involves cleavage of the aromatic ring, the aliphatic side chain or other linkages which will be discussed in this review.

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