The Decomposition of Aqueous Dithionite and its reactions with polythionates SnO2−6 (n = 3–5) studied by ion-pair chromatography

Aqueous dithionite decomposes at 20°C and pH values not far from 7.0 to give thiosulfate and sulfite from which trithionate may form. Addition of thiosulfate accelerates this reaction only at pH < 6. The pH dependence is explained by formation of HS₂O₃^? ions which are reduced by dithionite to HS^? and SO^2?₃. Sulfide destroys dithionite by nucleophilic cleavage, probably with formation of sulfoxylate and thiosulfite ions. The polythionates S_nO^2?₆ (n = 3–5) are reduced by dithionite at pH = 7.0 and 20°C according to S_nO^2?₆ + S₂O^2?₄ + 2 H₂O→S₂O₃^2? + S_n–3SO₃^2? + 4H¹ + 2SO₃^2? The reaction rate rapidly increases with the number n of sulfur atoms. In secondary reactions sulfite attacks S_nO₆^2? ions with thiosulfate formation.     

Type I Photosensitized Oxidation of Methionine†

Methionine (Met) is an essential sulfur‐containing amino acid, sensitive to oxidation. The oxidation of Met can occur by numerous pathways, including enzymatic modifications and oxidative stress, being able to cause relevant alterations in protein functionality. Under UV radiation, Met may be oxidized by direct absorption (below 250 nm) or by photosensitized reactions. Herein, kinetics of the reaction and identification of products during photosensitized oxidation were analyzed to elucidate the mechanism for the degradation of Met under UV‐A irradiation using pterins, pterin (Ptr) and 6‐methylpterin (Mep), as sensitizers. The process begins with an electron transfer from Met to the triplet‐excited state of the photosensitizer (Ptr or Mep), to yield the corresponding pair of radicals, Met radical cation (Met^?+) and the radical anion of the sensitizer (Sens^??). In air‐equilibrated solutions, Met^?+ incorporates one or two atoms of oxygen to yield methionine sulfoxide (MetO) and methionine sulfone (MetO₂), whereas Sens^?? reacts with O₂ to recover the photosensitizer and generate superoxide anion (O₂^??). In anaerobic conditions, further free‐radical reactions lead to the formation of the corresponding dihydropterin derivatives (H₂Ptr or H₂Mep).     

Spectrophotometric and Polarographic Studies on 9,10-Anthradione-2-Sodium Sulfonate

The effect of solvent structure on the rates of redox reactions in alcohol+water mixture was discussed by some authors. The rate of photoreduction of 9,10-anthraquinone-2-sulfonate was decreased by addition of H₂SO₄ but was unchanged by increase of ionic strengh with (NH₄)₂SO₄. The magnitude of the decrease in presence of acid was greater with ethanol or isopropanol than with N-ethylacetamide as substrate. The formation of semiquinone and carbonate radical anions was observed⁽⁴⁾ during the direct photoreaction. The electron transfer from the carbonate anion to sulfoanthraquinone in the first excited triplet state was the controlling step of this process. Therefore, anthraquinone β-sodium sulfonate is efficient sensitizers of the photooxidation of organic substrates in aqueous media.     

Investigation on the formation and decay of the N,N,N′,N′-tetramethylbenzidine radical cation using various oxidants and reductants by stopped-flow spectrophotometry

N,N,N′,N′-Tetramethylbenzidine (TMB) is an aromatic amine that undergoes oxidation by various oxidizing agents such as Ce⁴⁺, MnO⁻₄, Cr₂O²⁻₇; HSO⁻₅, S₂O⁻₈, H₂O₂, Cl₂, Br₂ and I₂, thereby serving as a reducing substrate. One-electron oxidation of TMB results in a radical cation (TMB^˙+), and on further oxidation leads to the product dication (TMB⁺⁺) were monitored by stopped-flow spectrophotometer at the absorption wavelength of TMB^˙+(λ_max; 460 nm). ESR data was also provided to confirm the formation of radical cation. The rates of both the formation and decay of TMB^˙+ have been followed by a total second-order kinetics, a first-order dependence each on [TMB] (or) [TMB^˙+] and [oxidant]. The kinetic and transition state parameters have been evaluated for the effects of pH and temperature on the formation and decay of TMB^˙+ and discussed with suitable reaction mechanisms. Also, the rate constants for the reactions of the radical cation with various reducing agents such as sulfite (SO²⁻₃), thiosulfate (S₂O²⁻₃), dithionite (S₂O²⁻₄) and disulfite (S₂O²⁻₅) and ascorbic acid (vitamin C, AH₂ were determined. Besides these, this article also explains how TMB acts as a better electron relay than unsubstituted benzidine, even though both of them undergo one-electron oxidation and are used in the chemical routes to solar energy conversions. The observed rate constants for electron transfer were correlated theoretically using Marcus theory. The observed and calculated rate constants have good correlation.     

Theoretical studies of electron and hydrogen transfer reactions between semiquinone radicals and oxygen

 To explore the interactions between ubiquinones and oxygen in living organisms, the thermodynamics of a series of electron and hydrogen transfer reactions between semiquinone radicals, as well as their corresponding protonated forms, and oxygen, singlet or triplet, were studied using the hybrid Hartree–Fock–density functional theory method Becke's three parameter hybrid method with the Lee, Yang, and Parr correlation functional. Effects of the solvent and of the isoprenyl tail on the electron and hydrogen transfer reactions were also investigated. It is found that semiquinone radicals (semiquinone anion radicals or protonated semiquinone radicals) cannot react with triplet oxygen to form the superoxide anion radical O₂ ⁻. In contrast, neutral quinones can scavenge O₂ ⁻ efficiently. In the gas phase, only protonated semiquinone radicals can react spontaneously with singlet oxygen to produce peroxyl radical (HO₂). However, both semiquinone anion radicals and protonated semiquinone radicals can react with singlet oxygen to produce harmful oxygen radicals (O₂ ^{− a l l b u l l} and HO₂, respectively) in aqueous and protein environments. The free-energy changes of the corresponding reactions obtained for different ubiquinone systems are very similar. It clearly shows that the isoprenyl tail does not influence the electron and hydrogen transfer reactions between semiquinone radicals and oxygen significantly. Results of electron affinities, vertical ionization potentials, and proton affinities also show that the isoprenyl tail has no substantial effect on the electronic properties of ubiquinones. Received: 3 July 2000 / Accepted: 6 September 2000 / Published online: 21 December 2000     

The reaction of carbanions with tert-Butyl radicals

The S_RN1 free radical chain reaction of Me₃CHgCl with nitronate (^?O₂NC(R₁)(R₂)) and phenone enolate (PHC(0^?)C(R₁)(R₂)) anions yields the C-alkylation products (Me₃CC(R₁)(R₂)N0₂, PhCOC(R₁)(R₂)CMe₃). Competitive reactions between pairs of anions demonstrate that as the basicity of the anion increases the reactivity toward Me₃C at first increases and then decreases. An inverted reactivity order is also observed with phenylacetonitrile anions. In early transition state reactions, the nucleophilic character of the $\text{tert}$-butyl radical apparently controls the reactivity by virtue of a transition state involving transfer of the electron from radical to the LUMO of the resonance stabilized anion.     

Negative Ion Formation by Thermal Surface Ionization of Sulfur Dioxide

The generation of negative ions from SO₂ in the gas phase was studied using the thermal surface ionization method. Six anion types were measured: O⁻, S⁻, SO⁻, and SO₂⁻ and anions with m/z=96 and m/z=128. The most abundant anion formed was S⁻ and the formation routes are discussed for each of the six anions. O⁻, S⁻, and SO⁻ are formed via dissociative electron attachment to the molecule, whereas the generation of SO₂⁻ and anions with m/z=96 and m/z=128 are probably associated with the formation of H₂SO₄ in the gas inlet system and the ion source. Using statistical thermodynamics the dissociation temperatures of SO₂ and SO in the gas phase are calculated and values of above 1800 °C are obtained for both molecules. We also estimated the optimal filament temperatures for the formation of all anions measured, indicating that for SO₂ the optimal temperature is related to the electron affinity of the molecules: the optimal temperature increases with decreasing value of the electron affinity for the molecule corresponding to the respective anion.     

Formation of cation–radical anion pairs derived from carboxybenzophenone–tetrabutylammonium salts. Pulse radiolysis studies

Pulse radiolysis of acetonitrile solutions of tetra-n-butyl ammonium salts of 2- and 4-carboxybenzophenones [BP-COO⁻···N⁺(C₄H₉)₄] were performed in order to generate directly the reduced forms of the benzophenone moieties within pre-formed ion pairs. In earlier studies on photochemical electron transfer reactions, ion pairs containing a tetraalkyl ammonium cation and a benzophenone radical anion were formed in an electron transfer to the triplet BP from a quencher consisting of a tetraalkyl ammonium salt of (phenylthio)acetic acid. In the current work, the [BP^•−COO⁻···N⁺(C₄H₉)₄] ion pairs were formed by direct reduction of the salts without the complication of a third moiety, i.e., the (phenylthio)acetic anion. The spectra and kinetic parameters of the radiolytically-reduced salts were compared to the behavior of reduced forms of the 2- and 4-COOH substituted benzophenones. The results from the pulse radiolysis and photochemistry were compared and explained in terms of the different structures of the ion pairs.     

Sulfonylation from sodium dithionite or thiourea dioxide

The cheap and easily available sodium dithionite and thiourea dioxide have been used as the source of sulfonyl group in the synthesis of sulfones and sulfonamides recently.Compared with other methods for the sulfonylation reactions,the strategies using sodium dithionite or thiourea dioxide provide an alternative and complementary route to diverse sulfonyl compounds.During the reaction process,sulfur dioxide anion radical is the key intermediate,which is usually generated from a single electron transfer under suitable conditions.The advantages using sodium dithionite or thiourea dioxide in the sulfonylation reactions include mild conditions and broad substrate scope with excellent functional group compatibility.Further applications by using sodium dithionite and thiourea dioxide in organic transformations will be anticipated.     

Single‐electron‐transfer/degenerative‐chain‐transfer mediated living radical polymerization of vinyl chloride catalyzed by thiourea dioxide/octyl viologen in water/tetrahydrofuran at 25 °C

The single‐electron‐transfer/degenerative‐chain‐transfer mediated living radical polymerization (SET–DTLRP) of vinyl chloride (VC) in H₂O/tetrahydrofuran at 25 °C catalyzed by thiourea dioxide [(NH₂)₂C?SO₂] is reported. This polymerization occurs only in the presence of a basic sodium bicarbonate (NaHCO₃) buffer and the electron‐transfer cocatalyst octyl viologen. The resulting poly(vinyl chloride) (PVC) has a number‐average molecular weight of 1500–7000 and a weight‐average molecular weight/number‐average molecular weight ratio of 1.5. This PVC does not contain detectable amounts of structural defects and has both active chloroiodomethyl and inactive chloromethyl chain ends. Because of possible side reactions caused by the primary sulfoxylate anion (SO), the catalytic activity of (NH₂)₂C?SO₂ in the SET–DTLRP of VC is lower than that of the single‐electron‐transfer agent sodium dithionite. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 287–295, 2005     

Laser study of photooxidation of chloranyl-sensitized 1,2,3,4-tetrachlorodibenzo-p-dioxine

The kinetics of quenching of the triplet state of chloranyl (CA) by 1,2,3,4-tetrachlorodibenzo-p-dioxine (TCD) in benzene and acetonitrile was studied by nanosecond laser flash photolysis. The reaction proceedsvia electron transfer (ET) with the rate constants of 1.5·10⁹ and 3.7·10⁹ L mol^?1 s^?1, respectively. In benzen ET results in the formation of short-lived triplet radical ion pairs (lifetime 100 ns). In acetonitrile, relatively long-lived (lifetime ≥10 μs) radical anion CA^.? and radical cation TCD^.? are formed and decay due to bimolecular reactions in the bulk of the solvent accompanied by the consumption of TCD.     

Activation of SO2 with [(η5‐C5Me5)2Ln(THF)2] (Ln=Eu,Yb) Leading to Dithionite and Sulfinate Complexes

The reaction of decamethylytterbocene [(η⁵‐C₅Me₅)₂Yb(THF)₂] with SO₂ at low temperature gave two new compounds, namely, the Yb^III dithionite/sulfinate complex [{(η⁵‐C₅Me₅)₂Yb(μ₃,1κ²O^1,3,2κ³O^2,2′,4‐S₂O₄)}₂{(η⁵‐C₅Me₅)Yb(μ,1κO,2κO′‐C₅Me₅SO₂)}₂] ( 1 ) and the Yb^III dithionite complex [{(η⁵‐C₅Me₅)₂Yb}₂(μ,1κ²O^1,3,2κ²O^2,4‐S₂O₄)] ( 2 ). After extraction of 1 , the mixture was heated to give the dinuclear tetrasulfinate complex [{(η⁵‐C₅Me₅)Yb}₂(μ,κO,κO’‐C₅Me₅SO₂)₄] ( 3 a ). In contrast, from the reaction of [(η⁵‐C₅Me₅)₂Eu(THF)₂] with SO₂ only the tetrasulfinate complex [{(η⁵‐C₅Me₅)Eu}₂(μ,κO,κO’‐C₅Me₅SO₂)₄] ( 3 b ) was isolated. Two major reaction pathways were observed: 1) reductive coupling of two SO₂ molecules to form the dithionite anion S₂O₄^2?; and 2) nucleophilic attack of one metallocene C₅Me₅ ligand on the sulfur atom of SO₂. The compounds presented are the first dithionite and sulfinate complexes of the f‐elements.     

Mechanisms of reactive oxygen species photogeneration by benzo[a]pyrene: A DFT study

Benzo[a]pyrene (BaP) possesses photosensitive activity and can photogenerate reactive oxygen species (ROS), which have been postulated to be involved in the BaP induced oxidative DNA damage. Therefore, in the present work, a thermodynamic analysis on the ROS-photogenerating mechanisms of BaP was performed on the basis of quantum chemical calculations. It was revealed that: (i) the ¹O₂-generating pathway involves direct energy transfer from triplet excited state BaP to ³O₂ both in benzene and water; (ii) BaP gives birth to O₂^? through two pathways in water, i.e., electron transfer from triplet excited state BaP or anion radical of BaP to ³O₂.     

ELECTRON TRANSFER REACTIONS OCCURRING UPON LASER FLASH PHOTOLYSIS OF PHOSPHOLIPID BILAYER SYSTEMS CONTAINING CHLOROPHYLL,BENZOQUINONE AND CYTOCHROME c-I. NEGATIVELY-CHARGED VESICLES*

Abstract— In negatively-charged lipid bilayer vesicles prepared in deionized water from egg phosphatidylcholine and 25 mol % of α-eleostearic acid, and containing chlorophyll a, benzoquinone, and cytochrome c, primary electron transfer after a laser flash occurred principally from chlorophyll triplet to benzoquinone, and to a smaller extent from chlorophyll triplet to oxidized cytochrome c. Several secondary electron transfer reactions occurred subsequent to this. The most rapid of these was electron transfer from reduced cytochrome c, which was bound to the outer surface of the negatively-charged vesicle, to chlorophyll cation radical (k= 3.9 times 10³ s^-1). Subsequent to this, the cation radical was reduced by benzoquinone anion radical (k= 1.6 times 10² s^-1>) and bound oxidized cytochrome c was reduced by the remaining anion radical which was expelled into the aqueous phase by the negative charge on the vesicle surface. This latter reaction occurred at the membrane-solution interface with an observed rate constant (k= 60 s^-1) two orders of magnitude smaller than cytochrome oxidation. Net reduced cytochrome c was produced in this process. The reduced cytochrome c was slowly reoxidized by benzoquinone (k= 17 s^-1) and the system was returned to its original state. When the vesicle system was made slightly basic by adding tris(hydroxymethyl)aminomethane, the rates of both the reverse electron transfer between chlorophyll cation radical and benzoquinone anion radical (k= 5 times 10² s^-1) and the oxidation of reduced cytochrome c by chlorophyll cation radical (k= 9.4 times 10³ s^-1) were accelerated. The rate of reduction of oxidized cytochrome c by benzoquinone anion radical remained approximately the same.     

Application of the pulse radiolysis technique to reactions of organic radical ions

The nanosecond pulse radiolysis technique has been applied to study the rate constants for charge transfer and substitution reactions of radical ions. Electron transfer from biphenyl anion to styrene derivatives shows a correlation with the reduction potential of the acceptors expected from the Marcus theory. The positive charge transfer from biphenyl cation to the same acceptors shows a much larger rate constant, suggesting a considerable shift of the free energy relationship to the positive side of G^o. The substitution reaction of fluorenone anion with organic halides shows an S_N2 character, while that of diethyl fumarate shows electron transfer nature. The dimerization of radical anions has been proven for benzophenone and fluorenone, when their lifetime of the parent anions are prolonged by countercations.     

EPR and Spectrophotometric Studies of Free Radicals (O2°−, °OH, BPD-MA°−) and Singlet Oxygen (1O2) Generated by Irradiation of Benzoporphyrin Derivative Monoacid Ring A

Abstract— Benzoporphyrin derivative monoacid ring A (BPD-MA), a chlorin-type molecule, is a new photosensitizer currently in phase II clinical trials for the treatment by pho-todynamic therapy of cancerous lesions, psoriasis and pathologic neovascularization. The photochemistry (type I and/or II) of BPD-MA has been studied in homogeneous solution and in aqueous dispersions of unilamellar liposomes of dipalmitoylphosphatidylcholine (DPPC) using electron paramagnetic resonance and spectrophotometric methods. When oxygen-saturated solutions of BPD-MA were illuminated with 690 nm light, singlet oxygen (¹O₂), superoxide anion radical (O₂^?), hydroxyl radical (OH) and hydrogen peroxide (H₂O₂) were formed. The BPD-MA generates ¹O₂ with a quantum yield of ca 0.81 in ethanolic solution. The quantum yield does not change upon incorporation of BPD-MA into liposomes of DPPC. The superoxide anion radical was generated by the BPD-MA anion radical (BPD-MA^?) via electron transfer to oxygen, and this process was significantly enhanced by the presence of electron donors. The rate of production of 0₂ was also dependent on the concentration of BPD-MA used (3-100 μM). The quantum yield of O₂^?was found to be 0.011 and 0.025 in aqueous solution and DPPC liposomes, respectively. Moreover, O₂^_upon dis-proportionation can generate H₂O₂ and ultimately the highly reactive OH via the Fenton reaction. In anaerobic homogeneous solution, BPD-MA^?was predominantly photoproduced via the self-electron transfer between the excited- and ground-state species. The presence of an electron donor significantly promotes the reduced form of BPD-MA. These findings suggest that the photodynamic action of BPD-MA may proceed via both type I and type II mechanisms.     

Simple Ion–Gas Mixtures as a Source of Key Molecules Relevant to Prebiotic Chemistry

Very simple chemistry can result in the rapid and high-yield production of key prebiotic inorganic molecules. The two reactions investigated here involve such simple systems, (a) carbon disulfide (CS₂) and acetate (CH₃COO¯) and (b) sulfur dioxide (SO₂) and formate (HCOO¯). They have been carried out under non-aqueous conditions, either in an organic solvent or with a powdered salt exposed to the requisite gas. Under such dry conditions the first reaction generated the thioacetate anion [CH₃COS]¯ while the second produced the radical [SO₂^·]¯anion. Anhydrous conditions are not rare and may have arisen on the early earth at sites where an interface between different phases (liquid/gas or solid/gas) could be generated. This is one way to rationalize the formation of molecules and ions (such as we have produced) necessary in the prebiotic world. Interpretation of our results provides insight into scenarios consistent with the more prominent theories of abiogenesis.     

Synthesis and X-ray and Spectral Study of the Compounds [Q4N]2[Fe2(S2O3)2(NO)4] (Q = Me,Et, n-Pr,n-Bu)

Iron nitrosyl complexes with general formula [Q₄N]₂[Fe₂(S₂O₃)₂(NO)₄] (Q = Me, Et, n-Pr, n-Bu) were synthesized by the exchange reaction of K₂[Fe₂(S₂O₃)₂(NO)₄] with tetraalkylammonium bromides. The molecular and crystal structure of [(CH₃)₄N]₂[Fe₂(S₂O₃)₂(NO)₄] were studied by X-ray diffraction analysis. The iron atom in the four-membered cycle of the [2Fe–2S] anion is bound to another Fe atom and to two sulfur atoms and is coordinated by two nonequivalent NO groups, each bridging sulfur atom being bound to the SO₃group. The structurally equivalent iron atoms are in the state Fe^1–(S= 1/2). The Mössbauer spectroscopy method shows that the complexes are diamagnetic due to the strong Fe–Fe bond. It is found that the SO₃group provides higher stability of the thiosulfate anion than the anion in Roussin's red salt [Fe₂S₂(NO)₄]^2–.     

Mechanism of Back Electron Transfer in an Intermolecular Photoinduced Electron Transfer Reaction: Solvent as a Charge Mediator

Back electron transfer (BET) is one of the important processes that govern the decay of generated ion pairs in intermolecular photoinduced electron transfer reactions. Unfortunately, a detailed mechanism of BET reactions remains largely unknown in spite of their importance for the development of molecular photovoltaic structures. Here, we examine the BET reaction of pyrene (Py) and 1,4‐dicyanobenzene (DCB) in acetonitrile (ACN) by using time‐resolved near‐ and mid‐IR spectroscopy. The Py dimer radical cation (Py₂^.+) and DCB radical anion (DCB^.?) generated after photoexcitation of Py show asynchronous decay kinetics. To account for this observation, we propose a reaction mechanism that involves electron transfer from DCB^.? to the solvent and charge recombination between the resulting ACN dimer anion and Py₂^.+. The unique role of ACN as a charge mediator revealed herein could have implications for strategies that retard charge recombination in dye‐sensitized solar cells.     

Mechanisms of interactions involving formation and rupture of S-S bonds in inorganic sulphur OXO-derivative systems

Mechanisms of ten redox interactions involving inorganic sulphur oxo-derivative systems thiosulphate (S_bS_aO₃ ^2-) and polythionate (O₃ ^-S_a(S_b)_nS_aO₃ ^-) have been investigated where S_a is a sulphur centre directly coordinated by oxygens and one sulphur-b (S_b); S_b is a sulphur atom either directly bonded to S_a or any one of the others catenated to one adjacent to S_a. The degree of lability of the S-S bonds of these systems towards the hydroxyl anion is a function of its concentration and also of other species in the medium. In a weak concentration of hydroxyl anion medium, iodine effects only breakage of the π(S_a-S_b) bond of S_bS_aO₃ ^2-. One electron from this bond migrates to S_a and another to S_b to give S^* _bS^* _aO₃ ^2-. An electron from one anionic oxygen reduces the oxidant. Then one electron from this oxygen pairs with the S_a unpaired electron to form a new π(S_a-O) bond and highly reactive S^* _bS_aO₃ ^- radicals, two of which couple to form the S_b-S_b bond of the tetrathionate anion (O₃ ^-S_a(S_b)₂S_aO₃ ^-). However, above a minimum OH^- concentration for some interactions, the S_a=S_b bond completely breaks to yield S_aO₃ ^2- and S_b such that in the presence of iodine, nascent oxygen (O) and H^- from OH^- oxidizes S_aO₃ ^2-/S_b to S_aO₄ ^2-/S_bO₄ ^2- and reduces iodine respectively. In the absence of an oxidant, OH^- reduces two-thirds of S_b to S^b _2- with a concomitant yield of *OH which oxidizes a third of S_b to S_bO³ _2- leaving S_aO₃ ^2- intact.