Mechanistic studies on peroxide activation by a water-soluble iron(III)-porphyrin: implications for O-O bond activation in aqueous and nonaqueous solvents

The reactions of a water-soluble iron(III)-porphyrin, [meso-tetrakis(sulfonatomesityl)porphyrinato]iron(III), [Fe(III)(tmps)] (1), with m-chloroperoxybenzoic acid (mCPBA), iodosylbenzene (PhIO), and H(2)O(2) at different pH values in aqueous methanol solutions at -35 degrees C have been studied by using stopped-flow UV/Vis spectroscopy. The nature of the porphyrin product resulting from the reactions with all three oxidants changed from the oxo-iron(IV)-porphyrin pi-cation radical [Fe(IV)(tmps(*+))(O)] (1(++)) at pH<5.5 to the oxo-iron(IV)-porphyrin [Fe(IV)(tmps)(O)] (1(+)) at pH>7.5, whereas a mixture of both species was formed in the intermediate pH range of 5.5-7.5. The observed reactivity pattern correlates with the E degrees' versus pH profile reported for 1, which reflects pH-dependent changes in the relative positions of E degrees'(Fe(IV)/Fe(III) ) and E degrees'(P(*+)/P) for metal- and porphyrin-centered oxidation, respectively. On this basis, the pH-dependent redox equilibria involving 1(++) and 1(+) are suggested to determine the nature of the final products that result from the oxidation of 1 at a given pH. The conclusions reached are extended to water-insoluble iron(III)-porphyrins on the basis of literature data concerning the electrochemical and catalytic properties of [Fe(III)(P)(X)] species in nonaqueous solvents. Implications for mechanistic studies on [Fe(P)]-catalyzed oxidation reactions are briefly addressed.     

Role of Pd(0) particles in oxidation of lower olefins in the catalytic system Fe(III)_Pd/ZrO<Subscript>2</Subscript>

Oxidation of metallic Pd(0) particles applied onto an oxide support with Fe(III) ions in a concentration not exceeding 0.06 M at 70°C was studied. In contrast to palladium black, with the supported catalyst Pd/ZrO₂ Pd(II) is formed in the solution in the concentration corresponding to the thermodynamic equilibrium. With an increase in the initial Fe(III) concentration, the equilibrium yield of Pd(II) increases. The initial reaction rate grows with an increase in the weight of the initial Pd-containing catalyst and in the initial Fe(III) concentration. The revealed kinetic relationships of the dissolution of Pd(0) in the reaction with Fe(III) aqua ions allow a conclusion that, in oxidation of lower olefins C₂-C₄ in the catalytic system Fe(III)_Pd/ZrO₂ in aqueous solution, Pd(II) is regenerated in the catalytic cycle by oxidation of Pd(I) species, rather than of Pd(0), with Fe(III) aqua ions.     

Role of oxygen in the degradation of atrazine by UV/Fe(III) process

In this study, the role of oxygen in the regeneration of Fe(III) during the degradation of atrazine in UV/Fe(III) process was studied. The degradations of atrazine in UV/Fe(III) and UV-photolysis processes in the presence and absence of oxygen were compared. The results showed that the degradations of atrazine in these processes followed the pseudo-first-order kinetics well. The process exhibiting the highest rate constant (k) was UV/Fe(III)/air process, because k-value for UV/Fe(III)/air process was about 1.47, 2.23 and 2.56 times of those for UV/Fe(III)/N₂, UV/air and UV/N₂ processes, respectively. The degradation of atrazine was enhanced by oxygen in UV/Fe(III) process and the enhancement was more remarkable at higher initial concentrations of Fe(III). The investigation into the changes of Fe(III) concentrations demonstrated that the presence of oxygen led to the regeneration of Fe(III), which resulted in the enhancement of atrazine degradation. With air bubbling, the ferric ions were 25% more than those with N₂ bubbling. The experimental data showed the regeneration of Fe(III) required the excited organic molecules and oxygen and on the basis of these results, the regeneration mechanism of Fe(III) was proposed. It was also found that due to the oxidation of Fe(II), the degradation of atrazine in UV/Fe(II)/air process was effective at a low Fe(II) concentration of 7 mg/L, similar to that in UV/Fe(III)/air process. This study makes clear the role of oxygen in the regeneration of Fe(III), and thus it provides a guide to reduce the input of Fe(III) and is helpful to the application of UV/Fe(III) process in practice.     

Fe (III)‐grafted Bi2MoO6 nanoplates for enhanced photocatalytic activities on tetracycline degradation and HMF oxidation

Fe (III)‐grafted Bi₂MoO₆ nanoplates (Fe (III)/BMO) with varying small quantity of Fe (III) clusters modification were fabricated through a simple hydrothermal and impregnation process. The characterization results indicate that the modification of Fe (III) clusters on the surface of Bi₂MoO₆ nanoplates with intimate interfacial contact is beneficial to the expansion of visible light absorption range and the separation of photoinduced carriers during the interface charge transfer process. The photocatalytic properties of the samples were studied by degradation of tetracycline (TC) and selective aerobic oxidation of biomass‐derived chemical 5‐hydroxymethylfuraldehyde (HMF) under visible light. The 1.5 wt% Fe (III) clusters‐grafted Bi₂MoO₆ nanoplates exhibited optimum photocatalytic activity, which is the TC degradation kinetic rate constant is 5.3 times higher than that of bare BMO, and the highest HMF conversion of 32.62% can be obtained with a selectivity of 95.30%. Furthermore, a possible visible light photocatalysis mechanism over Fe (III)/BMO sample has been proposed. This study may supply some insight for the development of visible‐light‐driven Bi₂MoO₆‐based photocatalysts applicable to both environmental remediation and biomass‐derived chemical transformation.     

Indirect determination of Fe(III) in synthetic samples and iron dextran tablets by capillary electrophoresis with ultraviolet detection

A capillary electrophoresis method based on the oxidation of ascorbic acid is proposed for the indirect determination of Fe(III). Fe(III) concentration corresponds to the decrease in ascorbic acid peak area. The calibration graph was linear in the range of 1.68-112 mg/L for Fe(III), which was easily detected at a concentration of 1.12 mg/L at 3 times the standard deviation of the blank divided by the slope of the calibration graph. The lack of interferences from Fe(II) in synthetic samples and 3 excipients (starch, magnesium strearate, and microcrystalline cellulose) in dextran tablets in the determination of Fe(III) confirmed the high selectivity of the proposed method. Its application to the determination of Fe(III) in several synthetic samples and iron dextran tablets produced excellent results.     

Fe(III)/Fe(II) separation by solvent extraction for the determination of oxygen stoichiometry in yttrium barium copper oxide superconductor materials

Summary Oxygen stoichiometry is a critical parameter defining the T_c of cuprate superconductors (e.g. YBa₂Cu₃O₇). On dissolution excess or deficiency of oxygen can be converted into shifts of the Fe(II)/Fe(III) concentration ratio of an aqueous solution. For small samples a solvent extraction technique for the separation of Fe(III) from Fe(II) was developed, to make use of the superior sensitivity of atomic spectrometry (AAS, ICP-AES). The system n-benzoylphenylhydroxylamine (BPHA)/CHCl₃ was chosen because it is relatively inactive as a redox partner. Despite the catalytic effect of Cu(II) on the oxidation of Fe(II), oxidation blanks can be kept down at negligible levels. Less than 0.55% of residual Fe(II) is converted to Fe(III) during the extraction procedure (argon atmosphere). In the presence of air, oxidation levels are still practical (3%). Extraction is from 0.3 mol/l HBr providing excellent recovery of Fe(III) (e.g. 98.8%). All Fe(II), Y, Ba (including BaSO₄ precipitate) and 99.4% of the Cu remain in the aqueous phase. Fe(III) is rapidly back-extracted into an aqueous phase by 6 mol/l HCl for dilution and aspiration into the flame or ICP. Recovery of Fe(III) after the two extraction steps is still 98.3%.     

Simultaneous kinetic determination of Fe(II) and Fe(III) based on their reactions with NQT4S in micellar media by using PLS and PCR methods

Simultaneous determination of Fe(II) and Fe(III) was studied using partial least squares regression (PLS) and principal component regression (PCR) methods. The models were based on the difference observed in the rates of the complex formation of iron in its two oxidation states with 1,2-naphthaquinone-2-thiosemicarbazone-4-sulphonic acid (NQT4S) at pH 4.0 in cetyltrimethylammoniumbromide (CTAB) as micellar media. The results showed that simultaneous determination of Fe(II) and Fe(III) could be performed in their concentration ranges of 0.10-2.10 and 0.25-2.25 μg/ml, respectively. The models used can proceed the data with low percent relative error of prediction (i.e. <5.5%). The procedure was successfully applied for the simultaneous determination of Fe(II) and Fe(III) in some environmental samples. The method would allow the transformation of the two oxidation states of iron to be monitored overtime in a water sample.     

Amorphous iron-(hydr) oxide networks at liquid/vapor interfaces: In situ X-ray scattering and spectroscopy studies

Surface sensitive X-ray reflectivity (XR), fluorescence (XF), and grazing incidence X-ray diffraction (GIXD) experiments were conducted to determine the accumulation of ferric iron Fe (III) or ferrous iron Fe (II) under dihexadecyl phosphate (DHDP) or arachidic acid (AA) Langmuir monolayers at liquid/vapor interfaces. Analysis of the X-ray reflectivity and fluorescence data of monolayers on the aqueous subphases containing FeCl(3) indicates remarkably high levels of surface-bound Fe (III) in number of Fe(3+) ions per molecule (DHDP or AA) that exceed the amount necessary to neutralize a hypothetically completely deprotonated monolayer (DHDP or AA). These results suggest that nano-scale iron (hydr) oxide complexes (oxides, hydroxides or oxyhydroxides) bind to the headgroups and effectively overcompensate the maximum possible charges at the interface. The lack of evidence of in-plane ordering in GIXD measurements and strong effects on the surface-pressure versus molecular area isotherms indicate that an amorphous network of iron (hydr) oxide complexes contiguous to the headgroups is formed. Similar experiments with FeCl(2) generally resulted with the oxidation of Fe (II)-Fe (III) which consequently leads to ferric Fe (III) complexes binding albeit with less iron at the interface. Controlling the oxidation of Fe (II) changes the nature and amount of binding significantly. The implications to biomineralization of iron (hydr) oxides are briefly discussed.     

Substrate-triggered activation of a synthetic [Fe2(μ-O)2] diamond core for C-H bond cleavage

An [Fe(IV)(2)(μ-O)(2)] diamond core structure has been postulated for intermediate Q of soluble methane monooxygenase (sMMO-Q), the oxidant responsible for cleaving the strong C-H bond of methane and its hydroxylation. By extension, analogous species may be involved in the mechanisms of related diiron hydroxylases and desaturases. Because of the paucity of well-defined synthetic examples, there are few, if any, mechanistic studies on the oxidation of hydrocarbon substrates by complexes with high-valent [Fe(2)(μ-O)(2)] cores. We report here that water or alcohol substrates can activate synthetic [Fe(III)Fe(IV)(μ-O)(2)] complexes supported by tetradentate tris(pyridyl-2-methyl)amine ligands (1 and 2) by several orders of magnitude for C-H bond oxidation. On the basis of detailed kinetic studies, it is postulated that the activation results from Lewis base attack on the [Fe(III)Fe(IV)(μ-O)(2)] core, resulting in the formation of a more reactive species with a [X-Fe(III)-O-Fe(IV)═O] ring-opened structure (1-X, 2-X, X = OH(-) or OR(-)). Treatment of 2 with methoxide at -80 °C forms the 2-methoxide adduct in high yield, which is characterized by an S = 1/2 EPR signal indicative of an antiferromagnetically coupled [S = 5/2 Fe(III)/S = 2 Fe(IV)] pair. Even at this low temperature, the complex undergoes facile intramolecular C-H bond cleavage to generate formaldehyde, showing that the terminal high-spin Fe(IV)═O unit is capable of oxidizing a C-H bond as strong as 96 kcal mol(-1). This intramolecular oxidation of the methoxide ligand can in fact be competitive with intermolecular oxidation of triphenylmethane, which has a much weaker C-H bond (D(C-H) 81 kcal mol(-1)). The activation of the [Fe(III)Fe(IV)(μ-O)(2)] core is dramatically illustrated by the oxidation of 9,10-dihydroanthracene by 2-methoxide, which has a second-order rate constant that is 3.6 × 10(7)-fold larger than that for the parent diamond core complex 2. These observations provide strong support for the DFT-based notion that an S = 2 Fe(IV)═O unit is much more reactive at H-atom abstraction than its S = 1 counterpart and suggest that core isomerization could be a viable strategy for the [Fe(IV)(2)(μ-O)(2)] diamond core of sMMO-Q to selectively attack the strong C-H bond of methane in the presence of weaker C-H bonds of amino acid residues that define the diiron active site pocket.     

Arsenate uptake and arsenite simultaneous sorption and oxidation by Fe-Mn binary oxides: influence of Mn/Fe ratio, pH, Ca2+, and humic acid

Arsenate retention, arsenite sorption and oxidation on the surfaces of Fe-Mn binary oxides may play an important role in the mobilization and transformation of arsenic, due to the common occurrence of these oxides in the environment. However, no sufficient information on the sorption behaviors of arsenic on Fe-Mn binary oxides is available. This study investigated the influences of Mn/Fe molar ratio, solution pH, coexisting calcium ions, and humic acids have on arsenic sorption by Fe-Mn binary oxides. To create Fe-Mn binary oxides, simultaneous oxidation and co-precipitation methods were employed. The Fe-Mn binary oxides exhibited a porous crystalline structure similar to 2-line ferrihydrite at Mn/Fe ratios 1:3 and below, whereas exhibited similar structures to δ-MnO(2) at higher ratios. The As(V) sorption maximum was observed at a Mn/Fe ratio of 1:6, but As(III) uptake maximum was at Mn/Fe ratio 1:3. However, As(III) adsorption capacity was much higher than that of As(V) at each Mn/Fe ratio. As(V) sorption was found to decrease with increasing pH, while As(III) sorption edge was different, depending on the content of MnO(2) in the binary oxides. The presence of Ca(2+) enhanced the As(V) uptake under alkaline pH, but did not significantly influence the As(III) sorption by 1:9 Fe-Mn binary oxide; whereas the presence of humic acid slightly reduced both As(V) and As(III) uptake. These results indicate that As(III) is more easily immobilized than As(V) in the environment, where Fe-Mn binary oxides are available as sorbents and they represent attractive adsorbents for both As(V) and As(III) removal from water and groundwater.     

Preparation of iron amido complexes via putative Fe(IV) imido intermediates

The isolation and characterization of monomeric Fe(III) amido complexes with hybrid ureate/amidate ligands is described. An aryl azide serves as the source of the amido ligand in preparing the complexes from trigonal monopyramidal Fe(II) precursors. Aryl azides more commonly react with transition metal complexes by a two-electron oxidation process to yield imido complexes, suggesting that the Fe(III) amido complexes may be formed from high valent species by hydrogen atom abstraction from an external species. The mechanistic basis for formation of the amido complexes is investigated using substrates that readily donate hydrogen atoms. Results from these experiments suggest that the Fe(III) amido complexes are generated from Fe(IV) imido intermediates that can facilitate homolytic X-H bond cleavage. The Fe(III) amido complexes are high spin (S = 5/2) with a strong absorbance band at lambdamax approximately 600 nm and extinction coefficients between 2000 and 3000 M-1 cm-1. These complexes are hygroscopic, reacting with 1 equiv of water to produce the corresponding Fe(III)-OH complexes and p-toluidine.     

Colorimetric method for enzymatic screening assay of ATP using Fe(III)-xylenol orange complex formation

In hygiene management, recently there has been a significant need for screening methods for microbial contamination by visual observation or with commonly used colorimetric apparatus. The amount of adenosine triphosphate (ATP) can serve as the index of a microorganism. This paper describes the development of a colorimetric method for the assay of ATP, using enzymatic cycling and Fe(III)-xylenol orange (XO) complex formation. The color characteristics of the Fe(III)-XO complexes, which show a distinct color change from yellow to purple, assist the visual observation in screening work. In this method, a trace amount of ATP was converted to pyruvate, which was further amplified exponentially with coupled enzymatic reactions. Eventually, pyruvate was converted to the Fe(III)-XO complexes through pyruvate oxidase reaction and Fe(II) oxidation. As the assay result, yellow or purple color was observed: A yellow color indicates that the ATP concentration is lower than the criterion of the test, and a purple color indicates that the ATP concentration is higher than the criterion. The method was applied to the assay of ATP extracted from Escherichia coli cells added to cow milk.     

Coulometric determination of uranium in presence of iron/plutonium using a platinum working electrode

A controlled potential coulometric method for the determination of uranium in the presence of iron or plutonium using a platinum working electrode has been developed. The method consists of reduction of uranium in 8M H₂SO₄ by Ti(III) followed by destruction of excess Ti(III) and selective oxidation of Fe(II) or Pu(III) to Fe(III) or Pu(IV), respectively, by sodium nitrite. The U(IV) is subsequently determined by electrolytic oxidation at Pt electrode using Fe(III) as an intermediate. The method was employed for the determination of uranium in synthetic mixtures of U+Fe and U+Pu containing varying ratios of U/Fe or U/Pu. The precision obtained for uranium results was ±0.25%.     

Simultaneous determination of Fe(II) and Fe(III) by kinetic spectrophotometric H-point standard addition method

The H-point standard addition method (HPSAM) for simultaneous determination of Fe(II) and Fe(III) is described. The method is based on the difference in the rate of complex formation of iron in two different oxidation states with Gallic acid (GA) at pH 5. Fe(II) and Fe(III) can be determined in the range of 0.02–4.50 μg ml⁻¹ and 0.05–5.00 μg ml⁻¹, respectively, with satisfactory accuracy and precision in the presence of other metal ions, which rapidly form complexes with GA under working conditions. The proposed method was successfully applied for simultaneous determination of Fe(II) and Fe(III) in several environmental and synthetic samples with different concentration ratios of Fe(II) and Fe(III).     

Redox-conjugated reversible isomerization of ferrocenylazobenzene with a single green light

A new reversible isomerization cycle for meta-ferrocenylazobenzene accomplished by combination of a single green light (546 nm) and redox change between Fe(II) and Fe(III) was discovered. In the Fe(II) state, trans-to-cis isomerization proceeded upon the green light irradiation exciting the metal-to-ligand charge transfer (MLCT) in a high quantum yield (Phit-->c = 0.51) which exceeds that of azobenzene (Phit-->c = 0.12 (313 nm excitation)). The cis molar ratio reached 35% in the photostationary state. The oxidation to the Fe(III) state followed by irradiation with the same green light led to the cis-to-trans back-reaction to recover almost all of the trans-form. The "on-off switching" of the MLCT character played an important role in the redox-dependent response to the green light for the isomerization. The photoisomerization behavior of ferrocenylazobenzenes was strongly dependent on the substitution position of the ferrocenyl moiety on the benzene ring. The MLCT excitation was not effective for the trans-to-cis conversion in para-ferrocenylazobenzene. Time-dependent density functional theory (TD-DFT) calculations for meta- and para-ferrcenylazobenzene showed that the origin of the visible band (MLCT band) is different. The initial orbital for the MLCT in meta-ferrocenylazobenzene is delocalized over Fe and the Cp ring, while that in para-ferrocenylazobenzene is localized on the iron.     

Redox-responsive gel-sol/sol-gel transition in poly(acrylic acid) aqueous solution containing Fe(III) ions switched by light

Redox-responsive gel-sol/sol-gel transition in aqueous PAA system containing Fe(III)-citrate complex was realized by switching the redox states of Fe(III)/F(II) ions conjugated with photoreduction and oxidation. This reversible transition can be indicated chromatically by the Fe(III) ions and repeated many times as long as there is sufficient citric acid.     

Fe(III)-ion-catalysed non-enzymatic transformation of adenosine diphosphate into adenosine triphosphate part II. Evidence of catalytic nature of Fe ions

Non-enzymatic phosphorylation of adenosine diphosphate (ADP) to adenosine triphosphate (ATP) in aqueous solutions using acetyl phosphate has been studied extensively. The reaction proceeds in the presence of Fe(III) ions. Normally, the yield of ATP never exceeds the amount of Fe ions but, when a sufficient amount of Mg(II) ions is added to the reaction system, the yield of ATP increases beyond the amount of Fe ions. This is because the Fe(III) ion is tightly bound to not only ADP but also ATP, the phosphorylation product. When, however, the Fe(III) ion is liberated from ATP by exchanging with an Mg(II) ion, it regains catalytic activity and contributes to the surplus production of ATP. The Fe(II) ion with either a single molecule of 1,10-phenanthroline or 2,2′-bipyridyl exhibits a remarkably high catalytic activity. This suggests that the Fe(II) aquo ion should also be an excellent catalyst.     

紫外光诱导氧合型肌红蛋白氧化反应及机理

肌红蛋白通常在无光条件下可进行输氧、储氧等重要功能,实验中我们发现紫外光照射可促进氧合肌红蛋白(MbO₂)的氧化反应,证实其在光照时部分生理功能会发生变化。紫外-可见(UV-Vis)吸收光谱数据显示,光照射时MbO₂的Soret带最大吸收波长蓝移、Q吸收带544和580 nm处还原峰强度下降,说明紫外光光照促进O₂解离, MbFe(Ⅱ)可被氧化至MbFe(Ⅲ)。四种波长光对光照氧化的影响程度为254 nm > 280 nm >430 nm > 409 nm;通入CO气体时氧合肌红蛋白较难发生光照氧化反应,即Fe的第六配位强度影响反应程度;溶液中的H⁺或OH^-对光照氧化反应有促进作用; 254、280 nm波长光照射时,苯丙氨酸(Phe)、酪氨酸(Tyr)、色氨酸(Trp)三种游离氨基酸均促进光照氧化反应的进行,而409、430 nm波长光照射时三种游离氨基酸对光照氧化反应的影响较小。以上数据表明体内光诱导MbO₂氧化反应过程中蛋白质内的Fe(Ⅱ)能否被光照激发形成未成对电子处于激发态是O₂离去和二价铁被氧化的关键。     

钴(Ⅲ)络合物氧化对苯二胺类化合物的动力学与机理的研究

本文通过监测氧化中间体半醌(S~+)的吸光度变化跟踪反应进程。用初始速率法处理得到了HAc-NaAc介质中Fe(CN)_6~(3-)(Ox′)催化[CO~Ⅲ(NH_3)_5Cl]~(2+)(Ox)氧化CD-4遵循下列动力学方程: d[S~+]/dt=k_(obs).[Ox′]~(0.90)[Ox]~(0.85)认为Fe(CN)_6~(3-)的再生过程是整个反应的决速步骤。估算了决速步的速率常数k(298K)、活化焓△H~(0≠)和活化熵分别为1.92dm~3·mol~(-1)s~(-1)、23.1kcal/mol和20.5cal/mol.K。以TEPPD代替CD-4、以Fe(CN)_6~(4-)代替Fe(CN)_6~(3-)的实验结果支持了所提出的再生机理的合理性。 实验也得到了[Co~Ⅲen_2Cl_2]~+直接氧化CD-4或TEPPD的动力学方程。测定了反应的活化能。认为PPD氧化为半醌是反应的决速步骤。[Co~Ⅲ(NH_3)_6]~(3+)、[Co~Ⅲ(NH_3)_5Cl]~(2+),[CoⅢen_3]~(3+)、[CoⅢen_2Cl_2]~+氧化PPD的实验结果表明,钴(Ⅲ)络合物的取代活性增加,氧化活性亦增加。     

Flash-induced blocking of the high-affinity manganese-binding site in photosystem II by iron cations: dependence on the dark interval between flashes and binary oscillations of fluorescence yield

Incubation of Fe(II) cations with Mn-depleted PSII membranes (PSII(-Mn)) under weak continuous light is accompanied by blocking of the high-affinity, Mn-binding (HAZ) site with ferric cations (Semin, B.K. et al. Biochemistry 2002, 41, 5854-5864). In this study we investigated the blocking yield under single-turnover flash conditions. The flash-probe fluorescence method was used to estimate the blocking efficiency. We found that the yield of blocking increases with flash number and reaches 50% after 7 flashes. When the dark interval between the flashes (Delta t) was varied, we found that the percentage of blocking decreases at Delta t < 100 ms (t 1/2, 4-10 ms). No inhibition of the blocking yield was found at longer time intervals (as with photoactivation). This result shows the necessity of a dark rearrangement during the blocking process (the dual-site hypothesis described in the text) and indicates the formation of a binuclear iron center. During the blocking experiments, we found a binary oscillation of the Fmax elicited during a train of flashes. The oscillations were observed only in the presence of Fe(II) cations or other electron donors (including Mn(II)) but not in the presence of Ca2+. Chelators had no effect on the oscillations. Our results indicate that the oscillations are due to processes on the acceptor side of PSII and to the appearance of "acceptor X" after odd flashes. Acceptor X is reduced by QA- at very high rate (<2 ms), is not sensitive to DCMU, and is rather stable in the dark (t l/2 approximately 2 min). These properties are similar to those of nonheme Fe(III) (Fe(III)NHI). When Fe(II)NHI was oxidized with ferricyanide (Fe(CN)6), the fluorescence decay kinetics and yield of fluorescence were identical to those observed when the sample was exposed to 1 flash prior to the fluorescence measurement. We suggest that acceptor X is Fe(III)NHI, oxidized by the semiquinone form of QB-. This is similar to the mechanism of "reduction-induced oxidation of Fe(II)NHI" by exogenous quinones reported in the literature. We suggest that involvement of QB- in the oxidation of Fe(II)NHI in PSII(-Mn) membranes is due to the modification of the QB-binding site and increase of its redox potential resulting from extraction of the functional Mn cluster.