Kinetics and Thermodynamics of Copper(I)/Dioxygen Interaction

Karlin, Kenneth D.; Kaderli, Susan; Zuberbühler, Andreas D.

doi:10.1021/ar950257f

Cited by 410 publications

(401 citation statements)

References 37 publications

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“…4). This binding mode is quite different from the JX-TI 2^2 and n-1,2 bridgings between the coupled Cu(II) site in oxyhemocyanin (12) and many model-compounds (13). According to the results of X-ray crystallography of ascorbate oxidase doped with peroxide (14), a hydroperoxide ion is terminally coordinated to one of the type 3 Cus, indicating that the end-on,, binding of a hydroperoxide ion is possible in the case of multicopper oxidases.…”

Section: Resultsmentioning

confidence: 72%

A Novel Mixed Valence Form of Rhus vernicifera Laccase and Its Reaction with Dioxygen to Give a Peroxide Intermediate Bound to the Trinuclear Center

Zoppellaro¹,

Sakurai²,

Huang³

2001

Journal of Biochemistry

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Multicopper oxidase belongs to the class of enzyme containing four or more Cu centers in a protein molecule (1). The minimum functional unit of multicopper oxidase comprises a set of one type 1 Cu, one type 2 Cu, and a pair of type 3 Cus. The type 1 Cu functions as the electron mediator from a substrate to the trinuclear center composed of the type 2 Cu and type 3 Cus, where dioxygen is bound and reduced to two water molecules. All these copper sites are indispensable for the four-electron reduction of dioxygen without the release of activated oxygen species as intermediates.When lacquer tree laccase, the best studied multicopper oxidase, was reduced fully and reacted with dioxygen, the three-electron reduced form of dioxygen appeared within 15 ms with a life-time of s to min order depending on the pH (2, 3). We spectroscopically and magnetically characterized this species as the oxygen-centered racial bound to the trinclear copper center, finding that it decayed on accepting the final electron from type 2 Cu under the control of proton transfer gating (4). In order to detect the preceding inter-1 This study was supported by Grants-in-Aid for Scientific Research, C 11640558 and B 13440194, from the Ministry of Education, Science, Sports and Culture of Japan, and the Joint Studies Program of the Institute for Molecular Science 1 To whom correspondence should be addressed. E-mail: tsO513@ kenroku.kanazawa-u.ac.jp Abbreviations: TloxT23red, type 1 Cu as Cu(II), and type 2 and 3 Cus as Cud); TloxT3red, type 2 Cu-depleted laccase in which type 1 Cu is Cu(II) and type 3 Cus are reduced; T12oxT3red, type 1 and 2 Cus as Cu(ll), and type 3 Cus as Cu(D; EPR, electron paramagnetic resonance; CD, circular dichroism; T, tesla (1 T = 10,000 G); TlHg, mercury derivative of laccase at the type 1 Cu site; FTTR, Fouriertransform infrared; DPPH, diphenylpicrylhydrazyl.© 2001 by The Japanese Biochemical Society. mediate, such as the two-electron reduced form of dioxygen, we investigated the earlier reaction process of the reduced laccase with dioxygen by means of stopped-flow spectroscopy (2). However, it was impossible to detect the two-electron reduced form of dioxygen because the diffusion of dioxygen towards the active site was too slow (ms order) compared with the rate of the electron transfer from type 1 Cu to the putative peroxide intermediate (the two-electron reduced form) (|xs or less order). The content of the two-electron reduced species has been estimated to be a few percent and only the formation of the metastable three-electron reduced form of dioxygen (the radical intermediate) could be observed insofar as the reactions of the native enzyme were studied (3).The type 2 Cu in laccase has been selectively depleted through the action of potassium hexacyanoferratefll) CK,-[Fe(CN) 6 ]) on the resting enzyme under anaerobic conditions, followed by the action of dimethylglyoxime and EDTA (5). In the type 2 Cu-depelted laccase the type 1 Cu is cupric and the coupled type 3 Cus are cuprous (TloxT3red, which has been simply ab...

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Section: Resultsmentioning

confidence: 72%

A Novel Mixed Valence Form of Rhus vernicifera Laccase and Its Reaction with Dioxygen to Give a Peroxide Intermediate Bound to the Trinuclear Center

Zoppellaro¹,

Sakurai²,

Huang³

2001

Journal of Biochemistry

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“…Various types of Cu n -O 2 complexes have been developed. [1][2][3][4] Some of the complexes, such as trans-"-1,2-peroxo-dicopper(II),…”

Section: à1 (788 CMmentioning

confidence: 99%

Dioxygen Reactivity of Copper(I) Complexes with Tetradentate Tripodal Ligands Having Aliphatic Nitrogen Donors: Synthesis, Structures, and Properties of Peroxo and Superoxo Complexes

Komiyama¹,

Furutachi²,

Nagatomo³

et al. 2004

Bulletin of the Chemical Society of Japan

127

112

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Oxygenation of copper(I) with tetradentate tripodal ligands (L) comprised of a tris(aminoethyl)amine (tren) skeleton having sterically bulky substituent(s) on the terminal nitrogens has been investigated, whereAll the copper(I) complexes reacted with dioxygen at low temperatures to produce superoxocopper(II) and/ or trans-("-1,2-peroxo)-dicopper(II) complexes depending on the steric bulkiness of the terminal nitrogens and the reaction conditions. The reaction of a copper( þ ($0:24 mM) and higher dioxygen concentration (P(O 2 ) = $1 atm), the superoxo species is predominantly formed, whereas at a higher concentration of [Cu(L Me,Bn )] þ ($1 mM) and lower dioxygen concentration (P(O 2 ) = $0:02 atm) the formation of the peroxo species is observed.

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“…Copper complexes have occupied a major place in oxidation chemistry because of their abundance and relevance in biological chemistry. [29][30][31][32][33] of 8.7, 9.2 and 15.4 μg L -1 respectively. 34,35 Several other methods have also been reported based on the luminol-DPC-CL reaction in an alkaline medium for the determination of chlortetracycline, cholesterol, ergometrine maleate, lincomycin, cefazoline, N-(4-aminobutyl)-N-ethylisoluminol and mitoxantrone [36][37][38][39][40][41][42] in pharmaceutical and biological fluids.…”

Section: Introductionmentioning

confidence: 96%

Flow-Injection Determination of Thiabendazole Fungicide in Water Samples Using a Diperiodatocuprate(III)-Sulfuric Acid-Chemiluminescence System

et al. 2016

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A limited number of FI-CL methods have been reported based on the use of the Cu(III) complex in aqueous phosphoric acid and sulfuric acid solutions for the determination of ofloxacin, levofloxacin and enrofloxacin in pharmaceutical preparations, urine and veterinary preparations with detection limits (S/N = 3) 2016 © The Japan Society for Analytical Chemistry † To whom correspondence should be addressed. E-mail: yaqoob2001@hotmail.com Chemiluminescence (CL) with a flow-injection method is reported for the determination of thiabendazole (TBZ) fungicide based on its enhancement effect on diperiodatocuprate(III) (DPC)-sulfuric acid-CL system. The calibration graph was linear in the concentration range of 1 -2000 μg L -1 (R 2 = 0.9999, n = 8) with a limit of detection (S/N = 3) of 0.3 μg L -1 . The injection throughput was 160 h -1 with relative standard deviations (RSD, n = 4) of 1.1 -2.9% in the concentration range studied. The experimental variables e.g., reagents concentrations, flow rates, sample volume, and PMT voltage were optimized, and the potential interferences were investigated individually. The method was successfully applied to the determination of TBZ in water samples showing good agreement and recovery in the range of 92 ± 2.2 -108 ± 3% (n = 3) using dispersive liquid-liquid micro-extraction (DLLME). The possible CL reaction mechanism for DPC-sulfuric acid-TBZ is also discussed.Keywords Flow injection analysis, DPC, chemiluminescence, thiabendazole, water samples

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Kinetics and Thermodynamics of Copper(I)/Dioxygen Interaction

Cited by 410 publications

References 37 publications

A Novel Mixed Valence Form of Rhus vernicifera Laccase and Its Reaction with Dioxygen to Give a Peroxide Intermediate Bound to the Trinuclear Center

A Novel Mixed Valence Form of Rhus vernicifera Laccase and Its Reaction with Dioxygen to Give a Peroxide Intermediate Bound to the Trinuclear Center

Dioxygen Reactivity of Copper(I) Complexes with Tetradentate Tripodal Ligands Having Aliphatic Nitrogen Donors: Synthesis, Structures, and Properties of Peroxo and Superoxo Complexes

Flow-Injection Determination of Thiabendazole Fungicide in Water Samples Using a Diperiodatocuprate(III)-Sulfuric Acid-Chemiluminescence System

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