The high-affinity binding site for manganese on the oxidizing side of Photosystem II

Electron donation to Photosystem II (PS II) by diphenylcarbazide (DPC) is interrupted by the presence of endogenous Mn in PS II particles. Removal of this Mn by Tris treatment greatly stimulates the electron transport with DPC as donor. Binding of low concentration of exogenous Mn(II) to Tris-treated PS II particles inhibits DPC photooxidation competitively with DPC. This phenomenon was used to locate a highly specific Mn(II) binding site on the oxidizing side of Photosystem II with dissociation constant about 0.15 μM. The binding of Mn(II) is electrostatic in nature. Its affinity depends not only on the ionic strength, but also on the anion species of the salt in the medium. The effectiveness in decreasing the affinity follows the order F⁻ > SO²⁻₄ > CH₃COO⁻ > CI⁻ > Br⁻ > NO₃⁻. This observation is interpreted as follows: smaller ions, like F⁻, CH₃COO⁻, and larger ions, like SO²⁻₄, have inhibitory effects on Mn(II) binding, whereas ions with optimal size, like Cl⁻, Br⁻ and NO₃⁻, can stabilize the binding, resembling the anion requirement for reactivation of Cl⁻-depleted chloroplasts. We suggest that the binding site for Mn(II) we observed is the site for the endogenous Mn in the O₂-evolving complex of PS II. This site remains after Tris treatment, which removes all the endogenous Mn as well as the three extrinsic proteins, indicating that it is on the intrinsic component(s) of PS II reaction centers. Furthermore, the Cl⁻ requirement for O₂ evolution may be attributed, at least partly to its stabilizing effect on Mn binding.     

Electron-acceptor loadings affect chloroform dechlorination in a hydrogen-based membrane biofilm reactor

Chloroform (CF) can undergo reductive dechlorination to dichloromethane, chloromethane, and methane. However, competition for hydrogen (H₂), the electron-donor substrate, may cause poor dechlorination when multiple electron acceptors are present. Common acceptors in anaerobic environments are nitrate (NO₃⁻), sulfate (SO₄²⁻), and bicarbonate (HCO₃⁻). We evaluated CF dechlorination in the presence of HCO₃⁻ at 1.56 e⁻ Eq/m²-day, then NO₃⁻ at 0.04–0.15 e⁻ Eq/m²-day, and finally NO₃⁻ (0.04 e⁻ Eq/m²-day) along with SO₄²⁻ at 0.33 e⁻ Eq/m²-day in an H₂-based membrane biofilm reactor (MBfR). When the biofilm was initiated with CF-dechlorination conditions (no NO₃⁻ or SO₄²⁻), it yielded a CF flux of 0.14 e⁻ Eq/m²-day and acetate production via homoacetogenesis up to 0.26 e⁻ eq/m²-day. Subsequent addition of NO₃⁻ at 0.05 e⁻ Eq/m²-day maintained full CF dechlorination and homoacetogenesis, but NO₃⁻ input at 0.15 e⁻ Eq/m²-day caused CF to remain in the reactor's effluent and led to negligible acetate production. The addition of SO₄²⁻ did not affect CF reduction, but SO₄²⁻ reduction significantly altered the microbial community by introducing sulfate-reducing Desulfovibrio and more sulfur-oxidizing Arcobacter. Dechloromonas appeared to carry out CF dechlorination and denitrification, whereas Acetobacterium (homoacetogen) may have been involved with hydrolytic dechlorination. Modifications to the electron acceptors fed to the MBfR caused the microbial community to undergo changes in structure that reflected changes in the removal fluxes.     

Circular dichroism of chromium(III) hexadentate edta-type complexes. Part II. Ethylenediaminetetra-3-propionatochromate(III) ion

The hexadentate Cr(III) complex with ethylenediaminetetra-3-propionate (edtp) ion has been prepared and resolved. Infrared, electronic absorption and CD spectra were used to characterize the [Cr(edtp)]⁻ complex. The CD data in the region of the d-d transitions are discussed in comparison with those of other edta-type Cr(III) complexes of known configuration. The (+)₅₈₉₋[Cr(edtp)]⁻ complex, having a positive (dominant) CD peak in the first spin-allowed d-d absorption band region, is tentatively assigned the Δ configuration.     

The significance of stemflow chemistry for epiphytic lichen diversity in a dieback-affected spruce forest on Mt Brocken,northern Germany

Epiphytic lichen diversity in a boggy stand of Norway spruce (Picea abies) was studied in the eastern Harz Mountains, northern Germany. Spruce trees at wet sites were affected by forest dieback, whereas trees on drier sites remained unaffected. Lichen diversity was higher on dieback-affected trees than on healthy ones. The foliose lichen Hypogymnia physodes was significantly more frequent on dead trees, whereas the crustose, extremely toxitolerant Lecanora conizaeoides occurred more frequently on healthy trees. Stemflow concentrations of NH₄⁺, NO₃⁻, PO₃⁻, and SO₄²⁻ were lower on affected trees. This is attributed to reduced interception from the atmosphere due to needle loss. Cover of H. physodes decreased with increasing mean SO₄²⁻ concentration in stemflow. The total of lichen species per sample tree also decreased with increasing SO₄²⁻ concentration in stemflow, indicating that most species reacted in a similar way as H. physodes. Cover of L. conizaeoides increased with increasing SO₄²⁻ concentration, but decreased at higher SO₄²⁻ concentrations. Bark chemistry had a minor influence on lichen diversity.     

Mechanistic Elucidation of Salicylic Acid and Sulphur-Induced Defence Systems,Nitrogen Metabolism,Photosynthetic, and Growth Potential of Mungbean (Vigna radiata) Under Salt Stress

The potential of plant nutrients (such as sulphur, S) and phytohormones (such as salicylic acid, SA) has been explored in isolated studies by researchers in controlling the impact of abiotic stresses such as salinity in plants. However, information is scanty on the major mechanisms underlying the role of S and/or SA in modulation of enzymes involved in nitrogen (N) assimilation, GOGAT cycle, and antioxidant defence system; the cellular status of N-containing osmolyte proline, glucose, S-containing compounds; and their cumulative role in photosynthesis functions and growth in crop plants. The present study aimed to assess the role of cumulative effect of SA and S (SO₄²⁻) mediated induction of N assimilatory enzymes, GOGAT cycle, N-osmolyte proline and its metabolizing enzymes, glyoxylase enzymes, and antioxidant capacity in mungbean (Vigna radiata L.) exposed to NaCl with or without SO₄²⁻ and SA. Salt-exposed V. radiate showed differential elevations in damage (O^.₂⁻, H₂O₂, lipid peroxidation; glucose) and defence (ascorbate peroxidase, APX; glutathione reductase, GR; superoxide dismutase, SOD; reduced GSH; proline) and inhibitions in the activities of NR and NiR; N content, photosynthesis, photosynthetic N-use-efficiency (NUE), and growth. The separate supplementation of SA and SO₄²⁻ to 50 mM NaCl almost equally strengthened the antioxidant machinery and diminished NaCl-accrued damages. However, combined supply of SA and SO₄²⁻ to NaCl-exposed cultivars led to significant improvements in NR and NiR activities, the accumulation of N, GSH, proline, enhanced activity of APX, GR, and reduced activity of SOD, and also decreases in O^.₂⁻, H₂O₂, lipid peroxidation and glucose. These observations were corroborated with SA, SO₄²⁻ and NaCl-mediated changes in the traits of photosynthesis and growth, stomatal behaviour, and the polypeptide patterns of Rubisco in V. radiata. Overall, in V. radiata, SA-mediated higher enhancements in the activity of N assimilatory enzymes (NR, NiR, and GS), increase in the N and proline, and GSH; and decreases in the contents of Na⁺ and Cl⁻ ions, and glucose (a photosynthesis repressor); maintenance of a fine tuning among SOD, APX, and GR enzymes; and higher minimization of ROS (O^.₂⁻, H₂O₂) and lipid peroxidation finally led to a higher promotion in photosynthesis and growth.

     

Low pH (6, 5 and 4) sulfate reduction during the acidification of sucrose under thermophilic (55 °C) conditions

The effect of a low pH (6, 5 and 4) and different COD/SO₄²⁻ ratios (9 and 3.5) on thermophilic (55 °C) sulfate reduction and acidification of sucrose was investigated using three upflow anaerobic sludge bed reactors fed with sucrose at an organic loading rate of 3.5 gCOD (l_reactor d)⁻¹. The three reactors showed nearly 100% acidification of sucrose for all pH values and COD/SO₄²⁻ ratios investigated. Sulfate reduction was complete at pH 6 and a COD/SO₄²⁻ ratio of 9. At pH 5, sulfate reduction efficiencies were 80–95% for both COD/SO₄²⁻ ratios (9 and 3.5). At pH 4, sulfate reduction efficiencies further dropped to 55–65% at a COD/SO₄²⁻ ratio of 9 and 30–40% at a COD/SO₄²⁻ ratio of 3.5. The pH decrease from 6 to 5 or 4 caused a shift in the acidification products from mainly acetate to butyrate, as well as a higher production of ethanol, especially at pH 4. At pH 4, propionate and methane were not formed and hydrogen concentrations in the biogas reached 50%, equivalent to a hydrogen yield of 1.3 mol H₂ (mol glucose)⁻¹. This study shows that sulfate reduction is possible in the acidification phase of anaerobic wastewater treatment at pH values as low as 6 till 4 and that the pH strongly affects both the acidification pathways and the sulfate reduction efficiencies.     

Sorption of caesium,iodine and sulphur in solution to the adaxial leaf surface of broad bean (Vicia faba L.)

The interception by crop canopies of radionuclides in rainfall can be important in determining radiation exposures to animals and man. Data were obtained on the sorption and desorption of radionuclides on the adaxial surfaces of fully expanded bean leaves by exposing them to ionic forms of caesium (Cs⁺), iodine (I⁻) or sulphur (SO₄²⁻) over a six order of magnitude concentration range. The accumulation of each element was determined as a time course over a 48 h period using radioactive labels (¹³⁷Cs, ¹²⁵I or ³⁵S, respectively). Time- and concentration-dependent sorption of each element to the leaf surface was analysed to determine: (a) the leaf surface-solution distribution coefficient (K_d) at equilibrium and (b) the sorption and desorption rate coefficients for each element over the range of concentrations investigated. It was expected that Cs⁺ would show a stronger tendency to sorb to the leaf surface than both I⁻ and SO₄²⁻ because of the cation exchange properties of the cuticular membrane. The K_d for Cs⁺ was approximately 90× greater than that for SO₄²⁻ but 5× less than that for I⁻. This is thought to be due to either (a) the highly organophilic nature of iodide and the relatively high iodine number of cuticular waxes on plant leaf surfaces or (b) the possible oxidation of I⁻ to I⁰ or IO₃⁻, with consequently enhanced leaf surface sorption. Based on data obtained in this study, ranges and best estimates of sorption and desorption rate coefficients are presented for Cs⁺, I⁻ and SO₄²⁻ for use in modelling the interception of radioactive Cs, I and S in rainfall by crops.     

Partitioning of amylase produced by Aspergillus niger in solid state fermentation using aqueous two-phase systems

Equilibrium data of aqueous two-phase systems composed of polyethylene glycol (4000 g mol⁻¹ or 6000 g mol⁻¹) and Li₂SO_4, (NH₄)₂SO₄ or Na₂SO₄ at pH 6.5 and 25 °C were obtained. The efficiency of these in the partition of amylases derived from Aspergillus niger was determined. The experimental data of binodal curves and tie lines were used to estimate the group interaction parameters using the UNIFAC model. Additionally, the influence of phases on the activity of the enzymes was investigated. The results indicate that the polymer molar mass did not influence the biphasic region size. However, the cations under study presented differences in induction to phase formation. It was verified that the systems formed with the Na⁺ presented a larger biphasic region. The increase in the molar mass of the polymer caused the increase in the exclusion volume from 3970.732 g mol⁻¹ to 5700.873 g mol⁻¹. The transfer Gibbs free energy of enzymes presented values between −1296.30 kJ mol⁻¹ and −2867.70 kJ mol⁻¹, that is, the process was spontaneous for all systems studied. The systems formed by (NH₄)₂SO₄ and PEG 4000 g mol⁻¹ presented the best K_e result (3.421) and theoretical recovery of 80.35 %.     

Effect of ligand congeniality on energy transfer reaction between photo-excited tris(bipyridine)ruthenium(II) and chromate(III) complexes in aqueous solutions

Energy-transfer rate-constants from photo-excited [Ru(N–N)₃]²⁺ (N–N = 2,2′-bipyridine (bpy), 4,4′-dimethyl-2,2′-bipyridine (4dmb), 5,5′-dimethyl-2,2′-bipyridine (5dmb)) to [Cr(O–O)₃]³⁻ (O–O²⁻ = ox²⁻ ((COO⁻)₂), mal²⁻ (CH₂(COO⁻)₂)) and [Cr(CN)₆]³⁻ in encounter complexes were evaluated in aqueous solutions containing alkali metal ion. The rate constant depends on the molecular size of the ruthenium(II) complex: 1.8 × 10⁸ s⁻¹ for [Ru(bpy)₃]²⁺ (molecular radius, r = 5.8 Å), 1.4 × 10⁸ s⁻¹ for [Ru(5dmb)₃]²⁺ (r = 6.1 Å) and 0.96 × 10⁸ s⁻¹ for [Ru(4dmb)₃]²⁺ (r = 6.7 Å) in the system of [Ru(N–N)₃]²⁺–[Cr(ox)₃]³⁻ in aqueous solution. However, the rate constant is much more sensitive to the chromate(III) complex than to ruthenium(II) complex; 1.8 × 10⁸ s⁻¹ and 0.43 × 10⁸ s⁻¹ for [Cr(ox)₃]³⁻ (r = 4.0 Å) and [Cr(mal)₃]³⁻ (r = 4.2 Å) in the [Ru(bpy)₃]²⁺–[Cr(O–O)₃]³⁻ systems, respectively. We conclude that the congeniality between the donor’s and acceptor’s ligands in encounter complex plays an important role in energy transfer in aqueous solution.     

Soil and tree chemistry reflected the cumulative impact of acid deposition in Pinus banksiana and Populus tremuloides stands in the Athabasca oil sands region in western Canada

The spatial variability of soil chemistry and Ca/Al ratios of soil solution and fine roots were investigated in jack pine (Pinus banksiana) and trembling aspen (Populus tremuloides, aspen) stands to assess the impact of chronic acid deposition on boreal forest ecosystems in the Athabasca oil sands region (AOSR) in Alberta, Canada. Available SO₄²⁻ (as the sum of soluble and adsorbed SO₄²⁻) accumulated in the soil near tree boles of both species, reflecting the influence of canopy intercepted SO₄²⁻. In jack pine stands, pH and soluble base cation concentrations decreased towards tree boles due to increased SO₄²⁻ leaching; the reverse was found in aspen stands due to deposition of base cations leached from the canopy. As a result, Ca/Al ratios in the soluble fraction in soils near jack pine boles were 5–20 times lower than that near aspen boles. The Ca/Al ratio did not reach the critical limits of 1.0 for soil solution (ranged from 1.0 to 4.1) or 0.5 for fine roots (0.7–7.9) in the studied watersheds. However, Alⁿ⁺ concentrations in the soil solution ranged from 0.2 to 4.1 mg L⁻¹ in NE7 and from 0.1 to 8.5 mg L⁻¹ in SM8 that can inhibit the growth of white spruce (Picea glauca) seedlings that commonly succeed aspen in upland sites in the AOSR. We suggest that the spatial variation caused by tree canopies/stems will affect forest regeneration and the effect of acid deposition on forest succession in the AOSR should be further studied.     

Structural and vibrational characteristics of the tetrasulfatodimolybdenum ions with MoMo bond orders of 3.5 and 4.0

The compound K₄[Mo₂(SO₄)₄]Br·4H₂O has been made and its crystal structure determined. Space group P4/mnc; unit cell dimensions, a = 11.903(2), c = 8.021(1) Å, V = 1136(1) ų. The compound is isomorphous with the analogous chloride whose structure has been reported. The MoMo and MoBr distances are 2.169(2) and 2.926(1) Å, respectively and the [Mo₂(SO₄)₄] ³⁻ ions reside on crystallographic special positions with 4/m symmetry. The Raman spectra of both the bromo and chloro compounds have been measured and the MoMo stretching frequency is 370 ± 1.5 cm⁻¹ in each, for the compounds containing the natural isotopic distribution of molybdenum. The chloro compound has been prepared containing the pure isotope ⁹²Mo as well, and the Raman spectra recorded. The v(MoMo) band is shifted by 6.8 ± 0.5 cm⁻¹. The compound K₄[Mo₂(SO₄)₄]·2H₂O has also been prepared with Mo at natural abundance and with the pure isotope ¹⁰⁰Mo, whereby a shift of 8.5 ± 0.5 cm⁻¹ was found. These and other results will be discussed with regard to the similarity of the Raman spectra of the Mo₂(S0₄)₄³⁻ and M0₂(S0₄)₄⁴⁻ species.     

Mechanisms for acceleration of halide anation reactions of platinum(IV) complexes. REOA versus ligand assistance and platinum(II) catalysis Without central ion exchange

Chloride anation of trans-Pt(CN)₄ClOH₂⁻ has been studied with and without Pt(CN)₄²⁻ present at 25.0°C by use of stopped-flow and conventional spectrophotometry and a 1.00 M perchlorate medium. The rate law in the absence of Pt(CN)₄²⁻ is Rate=(p₁ + p₂ [H⁺] ) [Cl⁻]² [complex]/(1 + q [Cl₋]) with p₁=(3.0 ± 0.1) × 10⁻⁵ M⁻²s⁻¹, p₂=(3.6 ± 0.1) × 10⁻⁵ M⁻³ s⁻¹ and q=(0.62 ± 0.02) M⁻¹. It is compatible with a chloride assistance via an intermediate of the type Cl-Cl-Pt(CN)₄···OH₂²⁻, in which the reactivity of the aqua ligand is enhanced due to a partial reduction of the platinum. This mechanism of halide assistance is in principle the same as the modified reductive elimination oxidative addition (REOA) mechanism proposed by Poë, in which the intermediate is not split into free halogen, platinum(II) and water, and in which electron transfer not necessarily involves complete reduction to platinum(II). To avoid confusion with complete reductive eliminations, reactions without split of the intermediates are here termed halide-assisted reactions. The pH-dependence indicates acid catalysis via a protonated intermediate ClClPt(CN)₄···OH₃⁻.The Pt(CN)₄²⁻accelerated path has the rate law Rate=

[Cl-] [Pt(CN)₄²⁻] [complex] where k=(39.9±0.5) M⁻² s⁻¹ and K_a=(4.0±0.2)10⁻² M is the protolysis constant of trans-Pt(CN)₄ClOH²⁻.Reaction between PtCl₅OH₂⁻ and chloride is accelerated by Pt(CN)₄²⁻ and gives PtCl₆²⁻ as the reaction product. The rate law is Rate=k [Cl⁻] [Pt(CN)₄²⁻] [PtCl₅OH₂⁻] with k=(5.6 ± 0.2)10⁻³ M⁻² s⁻¹ at 35.0°C and for a 1.50 M perchlorate acid medium. The reaction takes place without central ion exchange. Alternative mechanisms with two consecutive central ion exchanges can be excluded. The role of Pt(CN)₄²⁻ in this reaction is very similar to that of the assisting halide in the halide assisted anations. [p ]Reaction between trans-Pt(CN)₄ClOH₂⁻ and PtCl₄²⁻ gives Pt(CN)₄²⁻ and PtCl₅OH₂⁻ as products and has the rate law Rate=k[PtCl₄²⁻] [trans-Pt(CN)₄ClOH₂⁻] with k=(3.32 ± 0.02) M⁻¹ s⁻¹ at 25 °C for a 1.00 M perchloric acid medium. The formation of an aqua complex as the primary reaction product and the rate independent of [Cl⁻] shows that formation of a bridged intermediate of the type Pt(II)Cl₄ClPt(IV)(CN)₄OH₂³⁻ is formed in the initial reaction step, not five-coordinated PtCl₅³⁻.     

Synthesis and spectroscopic studies of platinum(II) complexes of N,N′-dicyclohexylethylenediamine

The platinum(II) complexes of the formula [Pt(DCHEDA)X₂], where DCHEDA is N,N′-dicyclohexylethylenediamine and X⁻ is CL⁻, Br⁻, I⁻, 0.5C₂O₄²⁻ (oxalate), 0.5C₃H₂O₄²⁻ (malonate), 0.5C₉H₄O₆²⁻ (4-carboxyphthalate), 0.5S₂O₃²⁻ or 0.5SO₄²⁻, have been synthesized and characterized by UVVis, IR, and ¹H NMR spectral techniques. All the above complexes are non-electrolytes in DMF/H₂O, except the sulphate complex which becomes a 1:1 electrolyte after incubation for 24 h at 28 °C. The halide complexes were also studied by X-ray photoelectron spectroscopy and these data suggest that there is π-bonding from platinum to halide in these complexes. The oxalate, malonate and sulphate bind in their complexes as bidentate ligands to platinum through two oxygen atoms whereas the thiosulphate in its complex binds as a bidentate ligand to platinum through one oxygen atom and one sulphur atom.     

Reactions of Cr(III) tetraphenylporphyrin complex with superoxide ion: ESR evidence for the formation of a new superoxide adduct of Cr(IV) porphyrinate and its reactive character

The electron spin resonance (ESR) spectrum of the reaction product of superoxide ion, O₂⁻, with chloro-5,10,15,20-tetraphenylporphyrinatochromium(III) [Cr(III)(TPP)Cl] shows strong hyperfine interactions with the metal nucleus and the metal ligand, indicating the formation of a superoxide adduct, Cr(IV)(TPP)(Cl)(O₂⁻). The formation of this superoxide adduct was also confirmed by UV-Vis spectroscopy. The reactive character of this superoxide adduct was investigated by ESR spectrometry. It was found that Cr(IV)(TPP)(Cl)(O₂⁻) can oxidize t-butylamine and triphenylphosphine to give the corresponding radical species, respectively, but not pyridine, 4-cyanopyridine or imidazole. These results indicate that the reactive character of Cr(IV)(TPP)- (Cl)(O₂⁻) resembles that of the free superoxide ion.     

Isotope effect on the nonradiative decay in mixed amminechromium(III) complexes

Mixed amminechromium(III) complexes of the general formula [Cr(NH₃)_6−nX_n]^m (X = H₂O, SCN⁻) have been prepared and deuterated in the presence of a base. Phosphorescence decay times have been measured at ca. 77 K and the isotope effect on the nonradiative deactivation is discussed using Kupka's theory.     

Oxidation of copper(II)-coordinated diethylenetriamine by hexacyanoferrate(III) ion. A kinetic investigation

The stoichiometry and kinetics of the reaction between [Cu(dien)(OH)]⁺ and [Fe(CN)₆]³⁻ in aqueous alkaline medium are described. The rate equation − (d[Fe(III)]/dt = {k₁[OH⁻]²[[Cu(dien)(OH)]⁺] + k₂[OH⁻] × [[Cu(dien)(OH)]⁺]²}([Fe(III)]/[Fe(II)]) (Fe(III) = [Fe(CN)₆]³⁻; Fe(II) = [Fe(CN)₆]⁴⁻, the 4:4:1 OH⁻/Fe(III)/[Cu(dien)(OH)]⁺ stoichiometric ratio and the nature of the ultimate products identified in the reaction solution suggest the fast formation of a doubly deprotonated Cu(III)-diamido complex which slowly undergoes an internal redox process where the ligand is oxidised to the Schiff base H₂NCH₂CH₂NCHCHNH.The [[Cu(dien)(OH)]⁺]² term in the rate equation is explained with the formation of a transient μ-hydroxo mixed-valence Cu dimer. A two-electron internal reduction of the Cu(III) complex yielding a Cu(I) intermediate is suggested to account for the presence of monovalent copper in a precipitate which forms at relatively high reactant concentrations and in the absence of dioxygen.     

Kinetics and mechanism of the anation reactions of aquocobaloximes containing bulky phosphine ligands

The anation reactions of phosphino-aquocobaloximes containing bulky P donor ligands with HSO₃⁻ lead through a multistep mechanism to the formation of SO₃Co(DH)₂SO₃³⁻; the first step leads to the water substitution. The successive steps involve the hydrolysis of the phosphine and the ligation of HSO₃⁻, the dissociation of phosphine being the rate determining step.The steric bulk of the P ligand appears to be the factor determining the phosphine lability.     

Storage of abnormal oxidants ‘∑1’, ‘∑2’ and ‘∑3’ in photosynthetic water oxidases inhibited by Cl−-removal

The Cl⁻ requirement of photosynthetic O₂ evolution was studied by thermoluminescence measurements with purified Photosystem II-containing membrane particles from chloroplast thylakoids. When Cl anions had been removed from the particles either by an alkaline shock in a Cl⁻-free medium, or by treatment with SO²⁻₄, the pattern of the thermoluminescence emission after illumination with increasing numbers of flashes suggested that the oxidant storage in the water oxidase could only proceed up to the final step. The final step itself. i.e., the advance to the water-oxidizing S₄ state, apparently was blocked. An upward shift of the emission temperatures of the thermoluminescence bands was seen both in the absence and in the presence of 3-(3′,4′-dichlorophenyl)-1,1-dimethyl urea, indicating that the stored oxidants had redox properties different from those of normal, Cl⁻-sufficient preparations. These properties were readily interconvertible by addition or removal of Cl⁻. We postulate that in Cl⁻-deficient water oxidases abnormal S₁, S₂ and S₃ states, symbolized as ∑₁, ∑₂ and ∑₃, respectively, are formed which are in a Cl⁻-dependent equilibrium with the corresponding normal S states. An oxidation of ∑₃ to a ∑₄ state is not possible. It is proposed that Cl⁻ controls the oxidation potential of the stored oxidants by regulating events associated with the binding and/or oxidative modification of water molecules at the water oxidase.     

The interaction of D-galactonic acid with CrVI and CrIII. Structure,stability and physical properties of CrIII—aldonate complexes

The redox reaction between D-galactonic acid and potassium chromate yields ((lyxonateH₋₁)(galactonateH₋₁)Cr(OH₂))K·H₂O_n, with both aldonate molecules acting as bidentate ligands with the carboxylate and one alkoxo function as the donor sites. The shift of the CO₂^{poststaggered−} stretching vibration towards lower frequencies upon coordination and the high value of Δv indicate that the carboxylate acts as a monodentate donor site. Magnetic susceptibility data for the compound in the temperature range 3–300 K exhibit a drop in the effective magnetic moment with temperature below 70 K, which is indicative of antiferromagnetic interactions between the Cr^III centres. The molar magnetic susceptibility versus temperature plot could be fitted with the Fisher Hamiltonian for the case of infinite chains, equation-modified for the presence of monomeric species. The EPR and UV-Vis spectroscopic studies reveal that, in solution, the complex retains the distorted octahedral local coordination geometry. The ((lyxonateH₋₁)(galactonateH₋₁)Cr(OH₂))K_n dissociates slowly in aqueous solution but faster at high [H⁺], because of the rapid protonation of the alkoxo bridges linking the monomeric units. The potentiometric evaluation of the closely related binary system Cr^III-d-galactonate shows that the (Cr(galactonateH_−n)₂)^{1 − 2n} complexes are the major species in the 4–12 pH range, when a 1:2 Cr^III:ligand ratio is used. ¹³C NMR reveals that theCO₂^{poststaggered−} group is one of the coordination sites of the ligand.     

Phallus impudicus loaded with γ-Fe2O3 as solid phase bioextractor for the preconcentrations of Zn(II) and Cr(III) from water and food samples

We investigated the application of fungus Phallus impudicus loaded γ-Fe₂O₃ nanoparticles as a biosorbent for magnetic solid phase extractions of trace levels of Zn(II) and Cr(III) ions from natural samples before their measurements by inductively coupled plasma optical emission spectrometry. The characterization of magnetized P. impudicus was performed using the scanning electron microscope, the energy dispersive X-ray and Fourier transform infrared spectroscopy. Important experimental factors were investigated. The experimental results fitted well to the Langmuir adsorption model and pseudo-second order kinetic model. Limit of detections of targeted ions by magnetic solid phase extraction method based on use of P. impudicus were found as 10.5 ngL⁻¹ and 12.6 ngL⁻¹ respectively for Cr(III) and Zn(II). The sorption capacities of the biosorbent were 22.8 mgg⁻¹ for Cr(III) and 25.6 mgg⁻¹ for Zn(II). The preconcentration factors were achieved as 100 for both of ions. RSDs for inter- and intraday precisions were found as lower than 2.0% and 2.1% respectively for both of targeted ions. The accuracy of the recommended process was tested by recovery measurements on the certificated reference materials and successfully applied for quantification recoveries of Cr(III) and Zn(II) ions from water and food samples.