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1.
Hans Nohl 《Free radical research》1990,8(4):307-315
In most tissues mitochondria consume more than 90% of cellular oxygen. Although the greatest part of it undergoes tetravalent reduction thereby conserving free energy changes in the form of ATP. a great deal of evidence exists in the literature that also univalently reduced dioxygen is released during respiration. Redox-cycling ubiquinone was considered most frequently to be involved in this univalent e- transfer to oxygen out of sequence however, other components of the respiratory chain could not be excluded. Our investigations on this problem questioned the role of redox-cycling ubiquinone in mitochondrial O-2 formation while H2O2 is supposed to accept e- from this source. The paper provides experimental evidence that H2O2 in fact may operate as an oxidant of ubisemiquinone while dioxygen requires protons for such a reaction which are not available in the phospholipid bilayer where ubiquinone undergoes one e-redox-cycling 相似文献
2.
The aim of the present study was to elucidate the role of mitochondria in the development of heart failure following ischemia/reperfusion. Although mitochondria were increasingly assumed to be responsible for the establishment of an oxidative stress situation the lack of suitable methods to prove it required new concepts for an evaluation of the validity of this hypothesis. The principal idea was to expose isolated mitochondria to metabolic conditions which are developed during ischemia/reperfusion in the cell (anoxia, lactogenesis) and study how they respond. Heart mitochondria treated in that way responded with an incomplete collaps of the transmembraneous proton gradient, thereby impairing respiration-linked ATP generation. The membrane effect affected also the proper control of e- transfer through redox-cycling ubisemiquinone. Electrons were found to leak at this site from its normal pathway to O2- suggesting that ubisemiquinone becomes an active O2- generator. It was concluded from these observations that mitochondria are likely to play a pathogenetic role in the reperfusion injury of the heart both, by an impairment of energy conservation and their transition to a potent O2--radical generator. Furthermore, there is considerable evidence that the exogenous NADH-dehydrogenase of heart mitochondria is mainly responsible for functional changes of these organelles during ischemia/reperfusion. 相似文献
3.
Filipe P Morlière P Patterson LK Hug GL Mazière JC Freitas JP Fernandes A Santus R 《Free radical research》2004,38(3):295-301
The 1:1 complex of copper (II) and human serum albumin (HSA) slowly reacts with radiolytically generated •O2- radical-anion at a rate constant of 6.1×106 M-1 s-1. Absorbance and fluorescence spectroscopies demonstrate that addition of an equimolar portion of quercetin (QH2) to the solution of the copper (II)-HSA complex induces a relocalization of the copper resulting in a ternary copper (II)-QH2-HSA complex. This form of quercetin slowly oxidizes in air-saturated solutions. A 10-fold excess urate, a plasma antioxidant, cannot displace copper (II) bound to HSA. In N2O-saturated solutions the ternary complex form of QH2 can repair the urate radical with a rate constant of 2.7×106 M-1 s-1 by an electron transfer reaction similar to that observed in the absence of copper (II). In O2-saturated solutions and in the absence of copper, HSA-bound QH2 fails to repair the urate radical because of the fast competitive reaction of •O2- with urate radicals. However, addition of equimolar copper (II) restores the electron transfer from QH2 to the urate radical. These contrasting results are tentatively explained either by an enhanced reactivity of copper (II) with •O2- in the ternary complex or by direct production of quercetin radicals via a copper-catalyzed reduction of the •O2- radicals by QH2. 相似文献
4.
Ryusei Konaka Motoko Kawai Hiroyuki Noda Masahiro Kohno Ryuji Niwa 《Free radical research》1995,23(1):15-25
The spin traps substituted with some groups at the 4-position of dimethyl-1-pyrroline N-oxide(DMPO) were compared with DMPO itself regarding their abilities as spin traps and their physical properties. 4,5,5-Trimethyl-l-pyroHine N-oxide (4MDMPO) and 5,5-dimethyl- 4-phenyl-l-pyrolline N-oxide (4PDMPO) were synthesized by the Bonnett method, and 5,5-dimethyl-4-hydroxymethyl-l-pyrolline N-oxide (4HMDMPO) was made by a unique method from 2(5H)-furanone. The melting points of 4MDMPO, 4PDMPO and 4HMDMPO were higher than that of DMPO. The magnitude of hydrophilicity was in the order of 4HMDMPO, DMPO, 4MDMPO, and 4PDMPO based on the partition coefficient experiments in a 1-octanol-water system. Several radicals, O2, HO-, -CH3, -CH2OH, -CH(CH3)OH, (CH3)3 CO and H radicals, were trapped with these DMPO derivatives for comparison with the trapping by DMPO itself. Spin adducts of O J with the three DMPO derivatives showed ESR spectra similar to that of DMPO. In spite of the formation of diastereomers arising from spin trapping, the line-width enlargement was very small. The intensities and the decay rates of the spectra of 4MDMPO-O2-, 4PDMPO-O2- 4HMDMPO-O2- and DMPO-O2- were almost equal. In the trapping of the OH radical by 4MDMPO, 4PDMPO and 4HMDMPO, the eight-line ESR spectra observed were different from the well-known four-line spectrum of DMPO-OH. 相似文献
5.
The production of singlet oxygen by H2O2 disproportionation and via the oxidation of H2O2 by NaOCl in a neutral medium was monitored by spin trapping with 2,2,6,6 tetramethyl-4-piperidone (TMPone). The singlet oxygen formed in both reactions oxidized 2,2,6,6 tetramethyl-4-piperidone to give nitroxide radicals. However the production of nitroxide radicals was relatively small considering the concentrations of H2O2 and NaOCl used in the reaction systems. Addition of electron donating agents: ascorbate, Fe2+ and desferrioxamine leads to an increase in the production of nitroxide radicals. We assumed that a very slow step of the reaction sequence, the homolytic breaking of the O-O bond of N-hydroperoxide (formed as an intermediate product during the reaction of 1O2 with TMPone) could be responsible for the relatively small production of nitroxide radicals. Electron donating agents added to the reaction system probably raise the rate of the hydroperoxide decomposition by allowing a more rapid heterolytic cleavage of the O-O bond leading to a greater production of nitroxide radicals. The largest effect was observed in the presence of desferrioxamine. Its participation in this process is proved by the concomitant appearance of desferrioxamine nitroxide radicals. The results obtained demonstrate that the method proposed by several authors and tested in this study to detect singlet oxygen is not convenient for precise quantitative studies. The reactivity of TMPone towards O2-7HO2' and 'OH has been also investigated. It has been found that both O2-7HO2' and 'OH radicals formed in a phosphate buffer solution (pH 7.4, 37°C), respectively by a xanthine-oxidase/hypoxanthine system and via H2O2 UV irradiation, do not oxidize 2,2,6,6 tetramethyl-4-piperidone to nitroxide radicals. 相似文献
6.
C. Guarnieri G. Zucchelli F. Bernardi M. Scheda A. F. Valentini M. Calandriello 《Free radical research》1991,15(1):11-16
In the gingival crevicular fluid (GCF) of control and chronic adult periodontitis (CAP) patients there is a spontaneous release of O2- radicals from polymorphonuclear leukocytes (PMN). The addition of the exogenous stimuli phorbol myrystate acetate (PMA) decreased the O2- formation in control GCF, while in CAP patients produced a marked enhancement of O2- generation.
The circulating PMN of control subjects did not show a spontaneous O2- formation, differently from CAP patients. On the contrary, a similar O2- production was measured when the circulating PMN were stimulated with PMA.
Moreover, the antioxidant activity measured in 10μl of cell free gingival supernatant (GS) of control and CAP patients had the same values by inhibiting 12.6% and 18.9% respectively of the O2- formation supported by a xanthine/xanthine oxidase system.
Probably, the protective or destructive effect of PMN in GCF of CAP patients depends on the variations of the rate of O2- formation in respect to the intrinsic antioxidant property of GS. 相似文献
The circulating PMN of control subjects did not show a spontaneous O2- formation, differently from CAP patients. On the contrary, a similar O2- production was measured when the circulating PMN were stimulated with PMA.
Moreover, the antioxidant activity measured in 10μl of cell free gingival supernatant (GS) of control and CAP patients had the same values by inhibiting 12.6% and 18.9% respectively of the O2- formation supported by a xanthine/xanthine oxidase system.
Probably, the protective or destructive effect of PMN in GCF of CAP patients depends on the variations of the rate of O2- formation in respect to the intrinsic antioxidant property of GS. 相似文献
7.
Shigemichi Iha Kunzo Orita Tomoko Kannoh Toshihiko Utsumi Eisuke F. Sato Masayasu Inoue Kozo Utsumi 《Free radical research》1996,25(6):489-498
Effect of nitric oxide (NO) on the respiratory burst of neutrophils was examined under different oxygen tensions. Phorbol myristate acetate (PMA) stimulated oxygen consumption and superoxide (O2-) generation in neutrophils by a mechanism which was inhibited reversibly by NO. The inhibitory effect of NO increased significantly with a decrease in oxygen tension in the medium. The inhibitory effect of NO was suppressed in medium containing oxyhemoglobin (HbO2), a NO scavenging agent. In contrast, 3-morpholinosydnonimine (SIN-1), a compound that rapidly generates peroxynitrite (ONOO-) from the released NO and O2-, slightly stimulated the PMA-induced respiratory burst. These results suggested that NO, but not ONOO, might reversibly inhibit superoxide generation by neutrophils especially at physiologically low oxygen tensions thereby decreasing oxygen toxicity particularly in and around hypoxic tissues. 相似文献
8.
The multiple functions of coenzyme Q 总被引:11,自引:0,他引:11
The coenzyme function of ubiquinone was subject of extensive studies in mitochondria since more than 40 years. The catalytic activity of ubiquinone (UQ) in electron transfer and proton translocation in cooperation with mitochondrial dehydrogenases and cytochromes contributes essentially to the bioenergetic activity of ATP synthesis. In the past two decades UQ was recognized to exert activities which differ from coenzyme functions in mitochondria. From extraction/reincorporation experiments B. Chance has drawn the conclusion that redox-cycling of mitochondrial ubiquinone supplies electrons for univalent reduction of dioxygen. The likelihood of O2(.-) release as normal byproduct of respiration was based on the existence of mitochondrial SOD and the fact that mitochondrial oxygen turnover accounts for more than 90% of total cellular oxygen consumption. Arguments disproving this concept are based on results obtained from a novel noninvasive, more sensitive detection method of activated oxygen species and novel experimental approaches, which threw light into the underlying mechanism of UQ-mediated oxygen activation. Single electrons for O2(.-) formation are exclusively provided by deprotonated ubisemiquinones. Impediment of redox-interaction with the bc1 complex in mitochondria or the lack of stabilizing interactions with redox-partners are promotors of autoxidation. The latter accounts for autoxidation of antioxidant-derived ubisemiquinones in biomembranes, which do not recycle oxidized ubiquinols. Also O2(.-)-derived H2O2 was found to interact with ubisemiquinones both in mitochondria and nonrecycling biomembranes when ubiquinol was active as antioxidant. The catalysis of reductive homolytic cleavage of H2O2, which contributes to HO. formation in biological systems was confirmed under defined chemical conditions in a homogenous reduction system. Apart from dioxygen and hydrogen peroxide we will provide evidence that also nitrite may chemically interact with the ubiquinol/bc1 redox couple in mitochondria. The reaction product NO was reported elsewhere to be a significant bioregulator of the mitochondrial respiration and O2 activation. Another novel finding documents the bioenergetic role of UQ in lysosomal proton intransport. A lysosomal chain of redox couples will be presented, which includes UQ and which requires oxygen as the terminal electron acceptor. 相似文献
9.
John M. C. Gutteridge Melinda West Kent Eneff Robert A. Floyd 《Free radical research》1990,10(3):159-165
Bleomycin, in the presence of ferric salts, oxygen and a suitable reductant, degrades DNA with the release of base propenals, detected as thiobarbituric acid (TBA) reactivity, and the formation of 8-hydroxydeo-xyguanosine (80HdG) detected by HPLC. When xanthine oxidase is added to the incubated mixture of DNA degradation products, TBA-reactivity is destroyed but 80HdG formation is increased. EPR Spin trapping experiments show that hydroxyl radicals (OH) are formed in the reaction mixture and can be inhibited by the inclusion of either superoxide dismutase or catalase. These findings suggest that the base propenals and possibly malondialdehyde, formed from them, are aldehydic substrates for xanthine oxidase and, the product of this reaction is superoxide (O2-) and hydrogen peroxide (H2O2). Thus, TBA reactivity is destroyed in the formation of O2- and H2O2 which stimulate further oxidative damage to DNA resulting in increased 8OHdG formation. 相似文献
10.
Pholasin, the photoprotein of the common piddock Pholas dactylus, emits an intense luminescence upon oxidation. The contribution of superoxide anion radicals and myeloperoxidase (MPO) to Pholasin luminescence in stimulated neutrophils was investigated. Data on Pholasin luminescence were compared with results of superoxide anion radical generation detected by the cytochrome c test as well as with the release of elastase and MPO. In N-formyl-methionyl-leucyl-phenylalanine (fMLP) stimulated neutrophils, most of the luminescence is caused by superoxide anion radicals, whereas MPO shows only a small effect as shown by coincubation with superoxide dismutase (SOD) as well as potassium cyanide (KCN), an inhibitor of MPO. However, both, O2- and MPO contribute to light emission in fMLP/cytochalasin B and phorbol myristoyl acetate (PMA) stimulated cells. Thus, the kinetics of O2- generation and MPO release can be very well detected by Pholasin luminescence in stimulated neutrophils.
Degranulation of azurophilic granules was assessed using an ELISA test kit for released MPO or detection of elastase activity with MeO-Suc-Ala-Ala-Pro-Val-p-nitroanilide in the supernatant of stimulated cells. Both approaches revealed concurrently similar results concerning the amount and kinetics of enzyme release with data of Pholasin luminescence. Both, cytochrome c measurements and Pholasin luminescence indicate that fMLP/cytochalasin B and PMA stimulated neutrophils produce more O2- than fMLP stimulated cells. Thus, Pholasin luminescence can be used to detect, sensitively and specifically, O2- production and MPO release from stimulated neutrophils. 相似文献
Degranulation of azurophilic granules was assessed using an ELISA test kit for released MPO or detection of elastase activity with MeO-Suc-Ala-Ala-Pro-Val-p-nitroanilide in the supernatant of stimulated cells. Both approaches revealed concurrently similar results concerning the amount and kinetics of enzyme release with data of Pholasin luminescence. Both, cytochrome c measurements and Pholasin luminescence indicate that fMLP/cytochalasin B and PMA stimulated neutrophils produce more O2- than fMLP stimulated cells. Thus, Pholasin luminescence can be used to detect, sensitively and specifically, O2- production and MPO release from stimulated neutrophils. 相似文献
11.
Thioctic Acid and Dihydrolipoic Acid are Novel Antioxidants Which Interact With Reactive Oxygen Species 总被引:7,自引:0,他引:7
Thioctic acid (TA) and its reduced form dihydrolipoic acid (DHLA) have recently gained somc recognition as useful biological antioxidants. In particular, the ability of DHLA to inhibit lipid peroxidation has been reported. In the present study, the effects of TA and DHLA on reactive oxygen species (ROS) generated in the aqueous phase have been investigated. Xanthine plus xanthine oxidase-generated superoxide radicals (O2), detected by electron spin resonance spectroscopy (ESR) using DMPO as a spin trap. were eliminated by DHLA but not by TA. The sulhydryl content of DHLA, measured using Ellman's reagent decreased subsequent to the incubation with xanthine plus xanthine oxidase confirming the interaction between DHLA and O2-. An increase of hydrogen peroxide concentration accompanied the reaction between DHLA and O2x, suggesting the reduction of O2- by DHLA. Competition of O2- with epinephrine allowed us to estimate a second order kinetic constant of the reaction between O2- and DHLA, which was found to be a 3.3 × 105 M-1 s-1. On the other hand, the DMPO signal of hydroxyl radicals (HO ·) generated by Fenton's reagent were eliminated by both TA and DHLA. Inhibition of the Fenton reaction by TA was confirmed by a chemiluminescence measurement using luminol as a probe for HO ·. There was no electron transfer from Fe2+ to TA or from DHLA to Fe3 + detected by measuring the Fe2+ -phenanthroline complex. DHLA did not potentiate the DMPO signal of HO · indicating no prooxidant activity of DHLA. These results suggest that both TA and DHLA possess antioxidant properties. In particular. DHLA is very effective as shown by its dual capability by eliminating both O2-; and HO ·. 相似文献
12.
Short-term thermal acclimation induces adaptive changes in the inner mitochondrial membranes of fish skeletal muscle 总被引:1,自引:0,他引:1
In the oxidative muscles (musculi laterales superficiales) of crucian carp Carassius carassius acclimated for 6 weeks to either 5 or 25° C, the volume density and the surface density of fibres per tissue did not differ significantly between the control and experimental groups. The correlation ratio (μ2 ) for these values was below 50, 39·3 and 43·9 respectively. After acclimation to 5° C, the surface density of outer mitochondrial membrane per fibre increased significantly from 0·93 to 1·23m2 cm−3 in the summer population but dropped from 0·94 to 0·67 m2 cm−3 in the winter population. The surface density of outer mitochondrial membrane per mitochondrion increased from 3·24 to 4·52 m2 cm−3 in summer fish. After acclimation to 25° C, the surface density of inner mitochondrial membranes per muscle fibre decreased from 4·04 to 1·79 m2 cm−3 in summer fish and from 3·86 to 1·07 m2 cm−3 in winter fish. The surface density of inner mitochondrial membranes per mitochondrion increased from 14·17 to 15·60 m2 cm−3 in summer fish but dropped from 13·91 to 10·67 m2 cm−3 in winter fish. Correlation matrices demonstrate a negative correlation of the surface density of outer mitochondrial membrane per mitochondrion with the volume density of mitochondria per fibre and temperature, suggesting cold-induced proliferation of small mitochondria. It was concluded that short-term cold acclimation increased surface area of the inner mitochondrial membranes in summer fish. 相似文献
13.
《Free radical research》2013,47(4-6):307-315
In most tissues mitochondria consume more than 90% of cellular oxygen. Although the greatest part of it undergoes tetravalent reduction thereby conserving free energy changes in the form of ATP. a great deal of evidence exists in the literature that also univalently reduced dioxygen is released during respiration. Redox-cycling ubiquinone was considered most frequently to be involved in this univalent e? transfer to oxygen out of sequence however, other components of the respiratory chain could not be excluded. Our investigations on this problem questioned the role of redox-cycling ubiquinone in mitochondrial O?2 formation while H2O2 is supposed to accept e? from this source. The paper provides experimental evidence that H2O2 in fact may operate as an oxidant of ubisemiquinone while dioxygen requires protons for such a reaction which are not available in the phospholipid bilayer where ubiquinone undergoes one e?redox-cycling 相似文献
14.
Eduardo L pez-Huertas Luisa M. Sandalio Manuel G mez Luis A. Del Rí d 《Free radical research》1997,26(6):497-506
Peroxisomes were isolated from pea (Pisum sativum L.) leaves and the peroxisomal membranes were purified by treatment with Na2CO3. The production of superoxide radicals (O2-) induced by NADH was investigated in peroxisomal membranes from intact organelles incubated with proteases (pronase E and proteinase K). Under isoosmotic conditions, in the presence of pronase E, the production of O2- radicals was inhibited by 80%. SDS-PAGE of peroxisomal membranes after protease treatment demonstrated a decrease in the 18-kDa PMP. This suggests that this polypeptide has a small fragment exposed to the cytosolic side of the peroxisomal membrane which is essential for O2-production. The 18-kDa PMP was purified by preparative SDS-PAGE and in the reconstituted protein the NADH-driven production of O2- radicals was investigated. The isolated polypeptide showed a high generation rate of superoxide (about 300 nmol O2- × mg-1 protein × min-1) which was completely inhibited by 50 mM pyridine. The 18-kDa PMP was recognized by a polyclonal antibody against Cyt b5 from human ery-throcytes. The presence of b-type cytochrome in peroxisomal membranes was demonstrated by difference spectroscopy. Results obtained show that in the NADH-dependent O2- radical generating system of peroxisomal membranes, the 18-kDa integral membrane polypeptide, which appears to be Cyt b5, is clearly involved in superoxide radical production. 相似文献
15.
G Lenaz 《FEBS letters》2001,509(2):151-155
The function of the coenzyme Q (CoQ) pool in the inner mitochondrial membrane is reviewed in view of recent findings suggesting a supramolecular organization of the mitochondrial respiratory complexes. In spite of the structural evidence for preferential aggregations of the inner membrane components, most kinetic evidence is in favor of a dispersed organization based on random collisions of the small connecting redox components, in particular CoQ, with the individual complexes. The shape of the CoQ molecule in the pool, suggested to be a folded one, is in agreement with its very rapid lateral diffusion mobility in the membrane midplane. Since the structural evidence in favor of specific supercomplexes is rather strong, it cannot be excluded that electron transfer may follow either pool behavior or preferential channeling depending on the physiological conditions. Another function ascribed to the CoQ pool is the antioxidant action of the reduced CoQ molecules; although it cannot be excluded that protein-bound ubisemiquinones may be a source of oxygen radicals, particularly at the level of complex III, the available evidence suggests that the mitochondrial pool only behaves as an antioxidant under physiological conditions. 相似文献
16.
M. Kuwabara Y. Nishimura F. Sato T. Takahashi M. Tajima K. Takahashi H. Nagahata 《Free radical research》1993,18(5):309-318
The ability of neutrophils from a Holstein-Friesian calf with bovine leukocyte adhesion deficiency (the proband with a genetic deficiency of the Mac-1 (CD11b/CD18) glycoprotein corresponding to the receptor of complement iC3b) to generate oxygen radicals was examined using electron spin resonance spectrometry (ESR) combined with a spin-trapping technique and luminol-dependent chemiluminescence spectrometry. When the neutrophils were stimulated with phorbol 12-myristate 13-acetate (PMA), an ESR spectrum confirming the generation of superoxide anions (O2-) was clearly observed in both healthy and diseased calves. However, when the neutrophils were stimulated by opsonized zymosan, appearance of the ESR spectrum was recognized in the healthy calves but not in the diseased calf. Similar results were obtained from chemiluminescence experiments. 相似文献
17.
18.
The mitochondrial site of superoxide formation 总被引:6,自引:0,他引:6
Ubiquinone and cytochrome b566 have both been postulated to cause mitochondrial O2 formation by autoxidation of their reduced forms. The present investigation was made to evaluate capabilities of the two candidates to transfer electrons to molecular oxygen out of sequence of the normal pathway of respiration. The results show that electron transfer from ubisemiquinone to oxygen depends on the availability of protons. In agreement with this finding autoxidation of redox cycling ubiquinone could not be observed due to its location in an aprotic environment of the mitochondrial membrane. However, O2 release from mitochondria was found to be related to the existence of low potential cytochrome b566. The transfer of this b type cytochrome to more positive values caused a concomitant decrease and finally inhibition of univalent electron transfer to oxygen out of sequence. Our findings suggest a role of cytochrome b 566 in mitochondrial O2 formation. A contribution by ubiquinone is unlikely as long as protons are deprived from penetrating into the domain where ubiquinone is operating. 相似文献
19.
以盐敏感型甜瓜品种‘一品天下208’为试材,用80 mmol·L-1 Ca(NO3)2模拟设施土壤盐渍化,采用深液流水培,研究外源 γ-氨基丁酸(GABA)对Ca(NO3)2胁迫下甜瓜幼苗硝态氮(NO3--N)同化的影响.结果表明: Ca(NO3)2胁迫显著降低了甜瓜幼苗体内硝酸还原酶(NR)、谷氨酰胺合酶(GS)和谷氨酸合酶(GOGAT)活性,增强了谷氨酸脱氢酶(GDH)、谷草转氨酶(GOT)和谷丙转氨酶(GPT)活性,导致铵态氮(NH4+-N)和游离氨基酸含量增加,NO3--N和可溶性蛋白质含量下降,植株生长和光合作用受到严重抑制.Ca(NO3)2胁迫下,外源喷施GABA有效促进了甜瓜根系对NO3--N的吸收及其向地上部的转运,并通过增强NR、GS和GOGAT活性提高了甜瓜幼苗对NH4+的同化力;通过抑制GDH脱氨作用减少了甜瓜幼苗体内NH4+的释放量,从而缓解了盐诱导产生的NH4+-N积累所造成的氨毒害作用;外源喷施GABA也能调节甜瓜组织中氨基酸代谢途径,促进蛋白质的合成.表明外源GABA能增强甜瓜幼苗对NO3--N的同化能力,调控氨基酸代谢,进而有效缓解Ca(NO3)2胁迫对甜瓜幼苗的盐伤害作用. 相似文献
20.
The ability of various iron(II)-complexes of biological, clinical and chemical interest to reduce molecular oxygen to reactive oxy-radicals has been investigated using complementary oxygen-uptake studies and e.s.r. techniques. It is demonstrated that although the rate of oxygen reduction by a given iron complex is directly related to its redox potential [thus complexes with low values of E0 for the Fe(III)/Fe(II) couple are the most effective reductants of oxygen], the overall ability of an iron(II) complex to induce oxidative biomolecular damage is also determined by its ability to undergo redox-cycling reactions with reducing radicals formed following the reaction of hydroxyl radicals with organic substrates present in the system (e.g. metal-ion chelators and organic buffers). Evidence is presented to suggest that the “Good” buffer MOPS forms a reducing radical following attack by -OH, and hence encourages the autoxidation of iron with the generation of oxy-radicals (as also observed for some of the chelates studied); this may have important implications for the use of such buffers in free-radical studies. 相似文献