DITHIONITE TREATMENT OF FLAVINS: SPECTRAL EVIDENCE FOR COVALENT ADDUCT FORMATION and EFFECT ON in vitro BACTERIAL BIOLUMINESCENCE

Intrigued by the apparent requirement of dithionite for FMN reduction (as opposed to photoreduction or catalytic hydrogenation) in the H2O2-initiated bacterial bioluminescence reaction, we chose 5-ethyl-3-methyllumiflavinium cation I as a model to investigate possible flavin adduct formation by treatment with dithionite or (bi)sulfite. In the range of pH 5-8, the reaction of dithionite with 5-ethyl-3-methyllumiflavinium cation, which is in equilibrium with the 5-ethyl-4a-hydroxy-3-methyl-4a, 5-dihydrolumiflavin pseudobase II (X = OH), is not limited to the formation of flavosemiquinone and dihydroflavin following two one-electron steps. Several parallel and sequential reactions may take place involving the intermediacy of covalent flavin adducts. Addition of (bi)sulfite gave a 4a-sulfiteflavin adduct II (X = SO3-). Consistent with the S2O4(2-) in equilibrium with 2 SO2-. equilibrium, the reaction of dithionite and II (X = OH; SO3-) gave rise to two flavin adducts in competitive nucleophilic displacements: a 4a-sulfoxylate-flavin radical (II, X = SO2.) and a 4a-dithioniteflavin adduct (II, X = S2O4-), respectively. On increasing the (S2O4(2-), SO2.-)/flavin ratio under N2, the formation of the 4a-sulfoxylate-flavin radical became predominant. The II (X = SO2.) so formed was in equilibrium with the flavosemiquinone and bisulfate and can be trapped by reacting with hydroxylamine. In the initial presence of oxygen, II (X = SO2.) was highly reactive toward O2, giving a fast oxidation to II (X = SO3-) and effectively suppressing the formation of the flavosemiquinone.(ABSTRACT TRUNCATED AT 250 WORDS)     

Kinetics and mechanism of the oxidation of tetrathionate by iodine in a slightly acidic medium

The iodine-tetrathionate reaction has been reinvestigated spectrophotometrically at T = 25.0 +/- 0.1 degrees C and at an ionic strength of 0.5 M adjusted by sodium acetate as a buffer component in both the absence and presence of the iodide ion in the pH range of 4.25-5.55. The reaction was found to be independent of pH within the range studied, and it was clearly demonstrated that the reaction proceeds via an intermediate S4O6I- formed in a pre-equilibrium. Iodide dependence of the kinetic curves strongly suggests that the iodide ion has to be involved in this equilibrium. Further reactions of the intermediate, including its hydrolysis and reaction with iodide, leads to the strict stoichiometry characterized by S4O62- + 7I2 + 10H2O --> 4SO42- + 14I- + 20H+. A seven-step kinetic model with three fitted kinetic parameters is suggested and discussed. A rate equation is also derived from which a sound explanation of the iodide dependence of the apparent rate coefficient is presented. Furthermore, it has also been pointed out that formation of the triiodide ion alone is not sufficient to take the retardation effect of the iodide ion into account quantitatively.     

Stoichiometries and thermodynamic stabilities for aqueous sulfate complexes of U(VI)

The formation constants of UO2SO4 (aq), UO2(SO4)2(2-), and UO2(SO4)3(4-) were measured in aqueous solutions from 10 to 75 degrees C by time-resolved laser-induced fluorescence spectroscopy (TRLFS). A constant enthalpy of reaction approach was satisfactorily used to fit the thermodynamic parameters of stepwise complex formation reactions in a 0.1 M Na(+) ionic medium: log 10 K 1(25 degrees C) = 2.45 +/- 0.05, Delta r H1 = 29.1 +/- 4.0 kJ x mol(-1), log10 K2(25 degrees C) = 1.03 +/- 0.04, and Delta r H2 = 16.6 +/- 4.5 kJ x mol(-1). While the enthalpy of the UO2(SO4)2(2-) formation reaction is in good agreement with calorimetric data, that for UO2SO4 (aq) is higher than other values by a few kilojoules per mole. Incomplete knowledge of the speciation may have led to an underestimation of Delta r H1 in previous calorimetric studies. In fact, one of the published calorimetric determinations of Delta r H1 is here supported by the TRLFS results only when reinterpreted with a more correct equilibrium constant value, which shifts the fitted Delta r H1 value up by 9 kJ x mol(-1). UO2(SO 4) 3 (4-) was evidenced in a 3 M Na (+) ionic medium: log10 K3(25 degrees C) = 0.76 +/- 0.20 and Delta r H3 = 11 +/- 8 kJ x mol(-1) were obtained. The fluorescence features of the sulfate complexes were observed to depend on the ionic conditions. Changes in the coordination mode (mono- and bidentate) of the sulfate ligands may explain these observations, in line with recent structural data.     

Mechanisms of NO release by N1-nitrosomelatonin: nucleophilic attack versus reducing pathways

A new type of physiologically relevant nitrosamines have been recently recognized, the N(1)-nitrosoindoles. The possible pathways by which N(1)-nitrosomelatonin (NOMel) can react in physiological environments have been studied. Our results show that NOMel slowly decomposes spontaneously in aqueous solution, generating melatonin as the main organic product (k = (3.7 +/- 1.1) x 10(-5) s(-1), Tris-HCl (0.2 M) buffer, pH 7.4 at 37 degrees C, anaerobic). This rate is accelerated by acidification (k(pH 5.8) = (4.5 +/- 0.7) x 10(-4) s(-1), k(pH 8.8) = (3.9 +/- 0.6) x 10(-6) s(-1), Tris-HCl (0.2 M) buffer at 37 degrees C), by the presence of O(2) (k(o) = (9.8 +/- 0.1) x 10(-5) s(-1), pH 7.4, 37 degrees C, [NOMel] = 0.1 mM, P(O(2)) = 1 atm), and by the presence of the spin trap TEMPO (2,2,6,6-tetramethylpiperidine 1-oxyl; k(o) = (2.0 +/- 0.1) x 10(-4) s(-1), pH 7.4, 37 degrees C, [NOMel] = 0.1 mM, [TEMPO] = 9 mM). We also found that NOMel can transnitrosate to l-cysteinate, producing S-nitrosocysteine and melatonin (k = 0.127 +/- 0.002 M(-1) s(-1), Tris-HCl (0.2 M) buffer, pH 7.4 at 37 degrees C). The reaction of NOMel with ascorbic acid as a reducing agent has also been studied. This rapid reaction produces nitric oxide and melatonin. The saturation of the observed rate constant (k = (1.08 +/- 0.04) x 10(-3) s(-1), Tris-HCl (0.2 M) buffer, pH 7.4 at 37 degrees C) at high ascorbic acid concentration (100-fold with respect to NOMel) and the pH independence of this reaction in the pH range 7-9 indicate that the reactive species are ascorbate and melatonyl radical originated from the reversible homolysis of NOMel. Taking into account kinetic and DFT calculation data, a comprehensive mechanism for the denitrosation of NOMel is proposed. On the basis of our kinetics results, we conclude that under physiological conditions NOMel mainly reacts with endogenous reducing agents (such as ascorbic acid), producing nitric oxide and melatonin.     

Kinetics and mechanism of the oxidation of sulfite by chlorine dioxide in a slightly acidic medium

The sulfite-chlorine dioxide reaction was studied by stopped-flow method at I = 0.5 M and at 25.0 +/- 0.1 degrees C in a slightly acidic medium. The stoichiometry was found to be 2 SO(3)(2-) + 2.ClO(2) + H(2)O --> 2SO(4)(2) (-) + Cl(-) + ClO(3)(-) + 2H(+) in *ClO(2) excess and 6SO(3)(2-) + 2*ClO(2) --> S(2)O(6)(2-) + 4SO(4)(2-) + 2Cl(-) in total sulfite excess ([S(IV)] = [H(2)SO(3)] + [HSO(3)(-)] + [SO(3)(2-)]). A nine-step model with four fitted kinetic parameters is suggested in which the proposed adduct *SO(3)ClO(2)(2-) plays a significant role. The pH-dependence of the kinetic traces indicates that SO(3)(2-) reacts much faster with *ClO(2) than HSO(3)(-) does.     

Ligand substitution behavior of a simple model for coenzyme B12

The ligand substitution reactions of trans-[CoIII(en)2(Me)H2O]2+, a simple model for coenzyme B12, were studied for cyanide and imidazole as entering nucleophiles. It was found that these nucleophiles displace the coordinated water molecule trans to the methyl group and form the six-coordinate complex trans-[Co(en)2(Me)L]. The complex-formation constants for cyanide and imidazole were found to be (8.3 +/- 0.7) x 10(4) and 24.5 +/- 2.2 M-1 at 10 and 12 degrees C, respectively. The second-order rate constants for the substitution of water were found to be (3.3 +/- 0.1) x 10(3) and 198 +/- 13 M-1 s-1 at 25 degrees C for cyanide and imidazole, respectively. From temperature and pressure dependence studies, the activation parameters delta H++, delta S++, and delta V++ for the reaction of trans-[CoIII(en)2(Me)H2O]2+ with cyanide were found to be 50 +/- 4 kJ mol-1, 0 +/- 16 J K-1 mol-1, and +7.0 +/- 0.6 cm3 mol-1, respectively, compared to 53 +/- 2 kJ mol-1, -22 +/- 7 J K-1 mol-1, and +4.7 +/- 0.1 cm3 mol-1 for the reaction with imidazole. On the basis of reported activation volumes, these reactions follow a dissociative mechanism in which the entering nucleophile could be weakly bound in the transition state.     

Hydration of Cm3+ in aqueous solution from 20 to 200 degrees C. A time-resolved laser fluorescence spectroscopy study

Time-resolved laser fluorescence spectroscopy (TRLFS) is used to study the hydration of the Cm3+ ion in acidified (0.1 M perchloric acid) H2O and D2O from 20 to 200 degrees C. Strong temperature dependency is found for several of the spectroscopic quantities associated with the 6D'(7/2) --> 8S'(7/2) photoemission spectra, with similar relative changes in both solvents. The emission band shifts to lower energy with increasing temperature, which is attributed to an equilibrium between hydrated Cm3+ ions with different numbers of water molecules in the first coordination sphere, namely [Cm(H2O)9]3+ and [Cm(H2O)8]3+. Comparison with crystalline reference compounds and the analysis of hot bands corroborates the assignment of these species. The molar fraction of the octahydrated species increases from approximately 10% at room temperature to approximately 40% at 200 degrees C, indicating an entropy driven reaction. The corresponding thermodynamic parameters are obtained as Delta H degrees = + 13.1 +/- 0.4 kJ mol(-1), Delta S degrees = + 25.4 +/- 1.2 J mol(-1) K(-1), and Delta G298 = + 5.5 +/- 0.6 kJ mol(-1). Both the emission intensity and lifetime decrease with increasing temperature. The temperature dependency of the nonradiative decay rate of the emitting 6D'(7/2) level follows an Arrhenius equation with the activation energy 26.5 kJ mol(-1) (2250 cm(-1)) in both H2O and D2O, which is somewhat lower than the energy gap between 6D'(7/2) and 6P'(5/2) exited state levels.     

The reaction of S-nitroso-N-acetyl-D,L-penicillamine (SNAP) with the angiotensin converting enzyme inhibitor, captopril--mechanism of transnitrosation

Kinetic studies involving the use of both stopped-flow and diode array spectrophotometers, show that the reaction between SNAP and captopril in the presence of the metal ion sequestering agent, EDTA, occurs in two well-defined stages. The first stage is a fast reaction while the second stage is slow. The first stage has been postulated to be transnitrosation, and the second stage involves the decay of the newly formed RSNO to effect nitric oxide (NO) release. Both stages are found to be dependent on captopril and H+ concentration. The rates of the transnitrosation increased drastically with increasing pH in the first stage, signifying that the deprotonated form of captopril is the more reactive species. In the case of the second stage the variation in pH showed an increase in rate up to pH 8 after which the rate remained unchanged. Both stages were clearly distinguishable and easily monitored separately. Transnitrosation is a reversible reaction with the tendency for the equilibrium to break down at high thiol concentration. Second-order rate constants were calculated based on the following derived expressions: -d[SNAP]/dt=k(f)((K(SHCapSH)[CapSH](t))/(K(SHCapSH)+[H+]))[SNAP]. k(f) is the second-order rate constant for the forward reaction of the reversible transnitrosation process. At 37 degrees C, k(f)= 785 +/- 14 M(-1) s(-1), activation parameters [Delta]H(f)++= 49 +/- 2 kJ mol(-1), (Delta)S(f)++=-32 +/- 2 J K(-1) mol(-1). The activation parameters demonstrate the associative nature of the transnitrosation mechanism. The second stage has been found to be very complex, as a variety of nitrogen products form as predicted before. However, the following expression was derived from the initial kinetic data: rate =k1K[SNOCap][CapS-]/(K[CapS-]+ 1) to give k1= 13.3 +/- 0.4 x 10(-4) s(-1) and K= 5.59 +/- 0.53 x 10(4) M(-1), at 37 degrees C, where k1 is the first-order rate constant for the decay of the intermediate formed during the reaction between SNOCap and the remaining excess CapSH present at the end of the first stage reaction. Activation parameters are (Delta)H1++= 37 +/- 1 kJ mol(-1), (Delta)S1++=-181 +/- 44 J K(-1) mol(-1).     

Hydrolysis of gadolinium(III) in light and heavy water

The hydrolysis constants of Gd(3+) and the solubility products of Gd(OH)(3) and Gd(OD)(3) in nitrate solutions at 25 and 70 degrees in H(2)O and D(2)O have been determined because of their importance in nuclear technology. The constants are defined (charges omitted for clarity) as *K(11) = a(GdOH)a(H)/a(Gd), *K(21) = a(Gd(OH)(2))a(2)(H)/a(Gd), *K(SO) = a(Gd)/a(3)(H). The values for the H(2)O system were p*K(11) = 7.87 +/- 0.02, p*K(21) = 15.I6 +/- 0.09, p*K(SO) = -19.32 +/- 0.03 at 25 degrees and p*K(11) = 7.55 +/- 0.03, p*K(21) = 13.04 +/- 0.03, p*K(SO) = -16.16 +/- 0.04 at 70 degrees . For the D(2)O system they were p*K(D)(11) = 8.17 +/- 0.01, p*K(D)(21) = 16.00 +/- 0.09, p*K(D)(SO) = -21.18 +/- 0.04 at 25 degrees and p*K(D)(11) = 7.84 +/- 0.02, p*K(D)(21) = 13.95 +/- 0.02, p*K(D)(SO) = -17.34 +/- 0.04 at 70 degrees . The mean enthalpy changes of the reactions were also calculated.     

Interaction of Al2O3 and CeO2 surfaces with SO2 and SO2 + O2 studied by X-ray photoelectron spectroscopy

The interaction of Al2O3 and CeO2 thin films with sulfur dioxide (2.5 mbar) or with mixtures of SO2 with O2 (5 mbar) at various temperatures (30-400 degrees C) was studied by X-ray photoelectron spectroscopy (XPS). The analysis of temperature-induced transformations of S2p spectra allowed us to identify sulfite and sulfate species and determine the conditions of their formation on the oxide surfaces. Sulfite ions, SO3(2-), which are characterized by the S2p(3/2) binding energy (BE) of approximately 167.5 eV, were shown to be formed during the interaction of the oxide films with pure SO2 at temperatures < or =200 degrees C, whereas sulfate ions, SO4(2-), with BE (S2p(3/2)) approximately 169 eV were produced at temperatures > or =300 degrees C. The formation of both the sulfite and sulfate species proceeds more efficiently in the case of CeO2. The addition of oxygen to SO2 suppresses the formation of the sulfite species on both oxides and facilitates the formation of the sulfate species. Again, this enhancement is more significant for the CeO2 film than for the Al2O3 one. The sulfation of the CeO2 film is accompanied by a reduction of Ce(IV) ions to Ce(III) ones, both in the absence and in the presence of oxygen. It has been concluded that the amount of the sulfates on the CeO2 surface treated with the SO2 + O2 mixture at > or =300 degrees C corresponds to the formation of a 3D phase of the Ce(III) sulfate. The sulfation of Al2O3 is limited by the surface of the oxide film.     

Homolysis of the peroxynitrite anion detected with permanganate

The reaction of peroxynitrite with violet-colored MnO4- leads to the formation of green MnO42-. The rate constant for the reaction at pH 11.7, 5.5 mM ionic strength, and 25 degrees C, 0.020 +/- 0.001 s(-1), is independent of the MnO4- concentration; homolysis of ONOO- to NO* and O2*- is the rate-determining step. Both NO* and O2*- react with MnO4- with rate constants of (3.5 +/- 0.7) x 10(6) M(-1)s(-1) and (5.7 +/- 0.9) x 10(5) M(-1)s(-1), respectively. The activation volume and activation energy for breaking the N-O bond are 12.6 +/- 0.8 cm(3)mol(-1) and 102 +/- 2 kJ mol(-1), respectively. In combination with the known standard Gibbs energies of formation of NO* and O2*-, the rate of the reaction of NO* and O2*-, and the pKa of ONOOH, we find a standard Gibbs energy of formation of ONOO- of +68 +/- 1 kJ mol(-1), and of ONOOH of +31 +/- 1 kJ mol(-1).     

Crystallographic evidence for oxygen acceptor directionality in oxyanion hydrogen bonds.

A survey of 2632 D-H...O-A hydrogen bonds in crystal structures (where D is any atom and A is the central atom of a trigonal planar (A = C, N) or tetrahedral (A = P, S, Cl, As, Se, Cr, Mo) oxyanion, has established the existence of a distinct directionalities at the oxygen atom acceptors. The directionality depends primarily on the geometry of the oxyanion. With the trigonal planar oxyanions NO3-, HCO3-, and CO32-, the average H...O-A angle is 115 +/- 12 degrees and there is a clear preference for the hydrogen to lie within the plane of the anion. With the tetrahedral oxyanions H2PO4-, HPO42-, HSO4-, SO42-, ClO4-, H2AsO4-, HAsO42-, AsO43-, HSeO4-, SeO42-, CrO42-, and MoO42-, the average H...O-A angle is 122 +/- 12 degrees , and there is a weak preference for eclipsed H...O-X-O dihedral angles. The observed directionality closely coincides with minima on electrostatic potential surfaces calculated for the anions.     

三维超分子化合物[H_2(C_4H_(10)N_2)](SO_4)(H_2O)的制备、晶体结构及差热-热重性质研究

用MnSO4H2O和哌嗪在水-甲醇混合溶剂中反应得到了1个超分子化合物[H2(C4H10N2)](SO4)(H2O) (C4H14N2O5S)。 该晶体属单斜晶系, 空间群为P21/n, 晶胞参数为: a = 6.386(1), b = 11.695(2), c = 11.680(2) ? = 101.06(3), V = 856.1(3) 3, Z = 4, Mr =202.23 , Dc = 1.569 g/cm3, F(000) = 432, ?= 0.368 mm-1。 该化合物是由[H2(C4H10N2)]2+、SO42-、H2O通过氢键自组装而形成的。 其中[H2(C4H10N2)]2+存在2种椅式构象:一种[H2(C4H10N2)]2+与4个SO42-、2个H2O通过氢键相连, 另一种[H2(C4H10N2)]2+则与6个SO42-相连。 它们分别沿着b、c方向交替排列展开, 通过SO42-桥联成二维的层状结构;层与层之间在NH…O、CH…O、OH…O氢键的作用下互相连接, 形成了具有网状结构的三维超分子化合物。 差热及热重测试表明:该化合物从92℃开始分解,首先失去1个H2O, 然后再失去[H2(C4H10N2)]2+和SO4 2-。     

Crystal Structure and Spectroscopic Characterization of K(6)(VO)(4)(SO(4))(8) Containing Mixed-Valent Vanadium(IV)-Vanadium(V)

Pleochroistic crystals (dark green to colorless) of a mixed-valence V(IV)-V(V) compound, K(6)(VO)(4)(SO(4))(8), suitable for X-ray determination have been obtained from the catalytically important K(2)S(2)O(7)-V(2)O(5)/SO(2)-O(2)-SO(3)-N(2) molten salt-gas system, at approximately 400 degrees C. The compound crystallizes in the monoclinic space group P2(1) (No. 4) with a = 8.931(2) ?, b = 18.303 (3) ?, c = 9.971(2) ?, beta = 90.11(2) degrees, and Z = 2. It contains two rather similar V(IV)-V(V) pairs of VO(6) octahedra distorted as usual having a short V-O bond of around 1.57 ?, a long bond of around 2.40 ? trans to this, and four equatorial bonds around 2.00 ?. The bond lengths of the V(V)O(6) octahedra are significantly shorter than those found for the V(IV)O(6) octahedra. The eight different SO(4)(2)(-) groups are all bridging bidentate between the V(IV) and V(V) atoms; a third oxygen is coordinated to a vanadium atom of a neighboring chain trans to the short V=O bond, and the fourth oxygen remains uncoordinated. The measured bond distances and angles show a considerable distortion of the SO(4) tetrahedra. This is confirmed by the IR spectra of the compound, where large shift and splitting of the sulfate nu(3) bands up to wave numbers of around 1300 cm(-)(1) is observed. The ESR spectra of the compound exhibit weak anisotropy with g(iso) = 1.972 +/- 0.002 and DeltaB(pp) = 65 +/- 2 G. The compound may cause the deactivation for industrial sulfuric acid catalysts observed around 400 degrees C in highly converted SO(2)-O(2)-N(2) gas mixtures.     

Coupled-cluster study of isomers of H2SO2

A theoretical study has been made on six isomers of H2SO2 using coupled-cluster singles and doubles with noniterative triple excitations (CCSD(T)). The isomers studied are sulfoxylic acid (S(OH)2; C2 and Cs conformers), sulfinic acid (HS(=O)OH; 2 C1 conformers), dihydrogen sulfone (H2SO2; C2v), sulfhydryl hydroperoxide (HSOOH; C1), thiadioxirane (Cs), and dihydrogen persulfoxide (H2SOO; Cs). Molecular geometries, harmonic vibrational frequencies, and infrared intensities of all species were obtained using the CCSD(T) method and the 6-311++G(2d,2p) basis set. All aforementioned species were found to be local minima, with the exception of thiadioxirane, which has one imaginary frequency. A prior possible infrared observation of sulfinic acid was reassessed on the basis of the present data. In agreement with previous MP2 results, the present CCSD(T) data provide support for at most 4 of the 8 observed frequencies. The CCSD(T) frequencies and intensities should be of assistance in future identification of H2SO2 isomers by vibrational spectroscopy. Relative energies were calculated using the CCSD(T) method and several larger basis sets. As found previously, the lowest energy species is C2 S(OH)2, followed by Cs S(OH)2, HS(=O)OH, H2SO2, HSOOH, thiadioxirane, and H2SOO. Expanding the basis set significantly reduces the relative energies of HS(=O)OH and H2SO2. The CCSD(T) method was used with extended basis sets (up to aug-cc-pV(Q+d)Z) and basis set extrapolation in two reaction schemes to calculate the DeltaH degrees t (25 degrees C) of C2 S(OH)2. The two reaction schemes gave -285.8 and -282.7 kJ mol-1, which are quite close to a prior theoretical estimate (-290 kJ mol-1).     

Oxidation of vanadium(III) by hydrogen peroxide and the oxomonoperoxo vanadium(V) ion in acidic aqueous solutions: a kinetics and simulation study

The reaction between vanadium(III) and hydrogen peroxide in aqueous acidic solutions was investigated. The rate law shows first-order dependences on both vanadium(III) and hydrogen peroxide concentrations, with a rate constant, defined in terms of -d[H(2)O(2)]/dt, of 2.06 +/- 0.03 L mol(-)(1) s(-)(1) at 25 degrees C; the rate is independent of hydrogen ion concentration. The varying reaction stoichiometry, the appreciable evolution of dioxygen, the oxidation of 2-PrOH to acetone, and the inhibition of acetone formation by the hydroxyl radical scavengers, dimethyl sulfoxide and sodium benzoate, point to a Fenton mechanism as the predominant pathway in the reaction. Methyltrioxorhenium(VII) does not appear to catalyze this reaction. A second-order rate constant for the oxidation of V(3+) by OV(O(2))(+) was determined to be 11.3 +/- 0.3 L mol(-)(1) s(-)(1) at 25 degrees C. An overall reaction scheme consisting of over 20 reactions, in agreement with the experimental results and literature reports, was established by kinetic simulation studies.     

Efficient low-temperature oxidation of carbon-cluster anions by SO2

Carbon-cluster anions, CN-, are very reactive toward SO2 (sticking probability of 0.012 +/- 0.005 for C27- at 25 degrees C), in contrast to their inertness toward other common atmospheric gases and pollutants. In flow reactor experiments at ambient temperature and near atmospheric pressure, primary adsorption of SO2 by the carbon cluster anions, N = 4-60, yields CNSO2- or CN-1S-. The inferred elimination of neutral CO2 is also detected as meta-stable decay in collision-induced dissociation. At higher temperatures, the reaction of SO2 with nascent carbon clusters yields CN-1SO- as well as undetected CO. The size-dependent initial reactivity reflects the previously established structural transitions (i.e., from chain to cyclic to cage structures). Such carbon clusters are formed in sooting flames and may act as nuclei for the formation of primary soot particles and serve as models for the local structural features of active soot particle sites for black-carbon soot. The facile generation of reactive carbon-sulfide and -sulfinate units may therefore have implications for understanding the health and environmental effects attributed to the coincidence of soot and SO2.     

Kinetics and mechanisms of aqueous ozone reactions with bromide, sulfite, hydrogen sulfite, iodide, and nitrite ions

Reactions of ozone with Br(-), SO(3)(2-), HSO(3)(-), I(-), and NO(2)(-), studied by stopped-flow and pulsed-accelerated-flow techniques, are first order in the concentration of O(3)(aq) and first order in the concentration of each anion. The rate constants increase by a factor of 5 x 10(6) as the nucleophilicities of the anions increase from Br(-) to SO(3)(2-). Ozone adducts with the nucleophiles are proposed as steady-state intermediates prior to oxygen atom transfer with release of O(2). Ab initio calculations show possible structures for the intermediates. The reaction between Br(-) and O(3) is accelerated by H(+) but exhibits a kinetic saturation effect as the acidity increases. The kinetics indicate formation of BrOOO(-) as a steady-state intermediate with an acid-assisted step to give BrOH and O(2). Temperature dependencies of the reactions of Br(-) and HSO(3)(-) with O(3) in acidic solutions are determined from 1 to 25 degrees C. These kinetics are important in studies of annual ozone depletion in the Arctic troposphere at polar sunrise.     

Interference in the kinetic determination of ascorbic acid by sulphide and sulphite

The reduction of 2,6-dichlorophenolindophenol (DCPI) by sulphides and sulphites has been studied kinetically by the stopped-flow technique. The reaction is first-order with respect to each of the reactants. From the distribution diagrams for the species DH(+)(2), DH and D(-) for DCPI and H(2)Q, HQ(-) and Q(2-) for sulphides or sulphites, a mechanism is proposed which suggests partial reactions of all possible combinations of the reacting species at any pH. An equation for calculation of the second-order reaction rate constants k at any pH is derived, which gives k as a function of [H(+)], the partial reaction rate constants and the dissociation constants of DCPI and H(2)S or H(2)SO(3). Values of the overall reaction rate constants over a wide pH-range have been determined, together with values of k for all possible partial reactions. For particular pH-values the second-order reaction rate constant was determined by four different methods. Mean values of k = 251 +/- 1 and 240 +/- 1 l.mole(-1).sec(-1) were obtained for pH 3.15 and 4.17, respectively, for the DCPI-Na(2)S reaction and k = 137 +/- 1, 127 +/- 1 and 136 +/- 1 l.mole(-1).sec(-1) for pH 2.02, 4.25 and 5.10, respectively, for the DCPI-Na(2)SO(3) reaction. From the slopes of the linear Arrhenius plots activation energies of 6.6 +/- 0.2 and 4.0 +/- 0.1 kcal/mole for the DCPI-Na(2)S and DCPI-Na(2)SO(3) reactions, respectively were calculated. The effect of ionic strength on the reactions supports the proposed mechanism.     

Cobalamin reduction by dithionite. Evidence for the formation of a six-coordinate cobalamin(II) complex

Evidence for the formation of a unique, six-coordinate cobalamin(II) complex with the anion-radical SO(2)(-) during the reduction of aquacobalamin(III) by sodium dithionite, was obtained from spectrophotometric and EPR measurements. The pK(a) value of the weakly coordinated dimethylbenzimidazole group was found to be 4.8 ± 0.1 at 25 °C.