Contribution of the photo-Fenton reaction to hydroxyl radical formation rates in river and rain water samples.

The hydroxyl radical (OH radical) formation rates from the photo-Fenton reaction in river and rain water samples were determined by using deferoxamine mesylate (DFOM), which makes a stable and strong complex with Fe(III), resulting in a suppression of the photo-Fenton reaction. The difference between the OH radical formation rates with and without added DFOM denotes the rate from the photo-Fenton reaction. The photoformation rates from the photo-Fenton reaction were in the range of 0.7 - 45.8 x 10(-12) and 2.7 - 32.3 x 10(-12) M s(-1) in river and rain water samples, respectively. A strong positive correlation between the OH radical formation rate from the photo-Fenton reaction and the amount of fluorescent matter in river water suggests that fluorescent matter, such as humic substances, plays an important role in the photo-Fenton reaction. In rain water, direct photolysis of hydrogen peroxide was an important source of OH radicals as well as the photo-Fenton reaction. The contributions of the photo-Fenton reaction to the OH radical photoformation rates in river and rain water samples were in the ranges of 2 - 29 and 5 - 38%, respectively. Taking into account the photo-Fenton reaction, 33 - 110 (mean: 80) and 42 - 110 (mean: 84)% of OH radical sources in river and rain water samples, respectively, collected in Hiroshima prefecture were elucidated.     

New insight into photochemistry of ferrioxalate

Optical spectroscopy and nanosecond flash photolysis (Nd:YAG laser, 355 nm, pulse duration 5 ns, mean energy 5 mJ/pulse) were used to study the photochemistry of Fe(III)(C2O4)3(3-) complex in aqueous solutions. The main photochemical process was found to be intramolecular electron transfer from the ligand to Fe(III) ion with formation of a primary radical complex [(C2O4)2Fe(II)(C2O4(*))](3-). The yield of radical species (i.e., CO2(*-) and C2O4(*-)) was found to be less than 6% of Fe(III)(C2O4)3(3-) disappeared after flash. [(C2O4)2Fe(II)(C2O4(*))](3-) dissociates reversibly into oxalate ion and a secondary radical complex, [(C2O4)Fe(II)(C2O4(*))](-). The latter reacts with the initial complex and dissociates to Fe(II)(C2O4) and oxalate radical. In this framework, the absorption spectra and rate constants of the reactions of all intermediates were determined.     

Evidence of the hydroxyl radical formation upon the photolysis of an iron-rich clay in aqueous solutions

With the use of laser flash photolysis, the formation of hydroxyl radicals upon the photolysis of an iron-rich clay (montmorillonite KSF) was demonstrated. The ^•OH radical was shown to be formed by the photolysis of the Fe(OH)_aq ²⁺ complex that escaped from the clay into the solution bulk.     

Electron spin resonance study of radicals generated in cellulose/N-methylmorpholine solutions after flash photolysis at 77 K

The processes of radical formation in N-methylmorpholine-N-oxide monohydrate (NMMO) and cellulose/NMMO solutions were studied by ESR at 77 K under high-power UV (lambda = 248 nm) excimer laser flash photolysis. Radicals mainly generated were attributed to the nitroxide type radicals -CH2-NO*-CH2- and -CH2-NO*-CH3 at the first step and methyl *CH3 and formyl *CHO radicals at the second step of the photoreaction. Kinetic studies of these radicals revealed that formation and recombination rates of the radicals depend on the cellulose concentration in cellulose/NMMO solutions and the concentration of additional ingredients, e.g. Fe(II) and propyl gallate. Even at frozen state temperature, acceleration or quenching of radical reaction processes was found. The proposed scheme of UV light-induced NMMO degradation during irradiation based on ESR data correlates well with independently obtained results based on high-performance liquid chromatography (HPLC). The analysis of degradation products by HPLC, e.g. aminoethanol and acetaldehyde, supports the assumption concerning a radical-initiated ring opening of NMMO.     

Photochemical oxidation of halide ions by a nitratochromium(III) complex. Kinetics, mechanism, and intermediates

The 266 nm laser flash photolysis of the title complex in the presence of halide ions X(-) (X = I, Br, and Cl) generates halogen atoms on nanosecond time scales, followed by the known X(*)/X(-) reactions to yield dihalide radical anions, X2(*-). Plots of k(obs) against the concentration of X(-) were linear with zero intercepts, but the yields of X2(*-) increased with increasing concentrations of [X(-)]. This result suggests that a short-lived, strongly oxidizing intermediate reacts with X(-) to generate X(*) in parallel with the decomposition to Cr(aq)O(2+) and (*)NO2, both of which were identified in steady-state photolysis experiments in the presence of selective trapping agents. Bromide was oxidized quantitatively to bromine, and a combination of molecular oxygen and methanol channeled the reaction toward superoxochromium(III) ion, Cr(aq)OO(2+). In the absence of scavengers, nitrite and chromate were produced. The proposed reaction scheme draws additional support from the good agreement between the experimental product yields and those predicted by kinetic simulations.     

Reactions of Cl*/Cl2*- radicals with the nanoparticle silica surface and with humic acids: model reactions for the aqueous phase chemistry of the atmosphere

Reactions of chlorine radicals might play a role in aqueous aerosols where a core of inorganic components containing insulators such as SiO2 and dissolved HUmic-LIke Substances (HULIS) are present. Herein, we report conventional flash photolysis experiments performed to investigate the aqueous phase reactions of silica nanoparticles (NP) and humic acid (HA) with chlorine atoms, Cl*, and dichloride radical anions, Cl2*-. Silica NP and HA may be taken as rough models for the inorganic core and HULIS contained in atmospheric particles, respectively. Both Cl* and Cl2*- were observed to react with the deprotonated silanols on the NP surface with reaction rate constants, k +/- sigma, of (9 +/- 6) x 10(7) M(-1) s(-1) and (7 +/- 4) x 10(5) M(-1) s(-1), respectively. The reaction of Cl* with the surface deprotonated silanols leads to the formation of SiO* defects. HA are also observed to react with Cl* and Cl2*- radicals, with reaction rate constants at pH 4 of (3 +/- 2) x 10(10) M(-1) s(-1) and (1.2 +/- 0.3) x 10(9) M(-1) s(-1), respectively. The high values observed for these constants were discussed in terms of the multifunctional heterogeneous mixture of organic molecules conforming HA.     

Kinetics of the reaction C2H5 + HO2 by time-resolved mass spectrometry

The overall rate constant for the radical-radical reaction C2H5 + HO2 --> products has been determined at room temperature by means of time-resolved mass spectrometry using a laser photolysis/flow reactor combination. Excimer laser photolysis of gas mixtures containing ethane, hydrogen peroxide, and oxalyl chloride was employed to generate controlled concentrations of C2H5 and HO2 radicals by the fast H abstraction reactions of the primary radicals Cl and OH with C2H6 and H2O2, respectively. By careful adjustments of the radical precursor concentrations, the title reaction could be measured under almost pseudo-first-order conditions with the concentration of HO2 in large excess over that of C2H5. From detailed numerical simulations of the measured concentration-time profiles of C2H5 and HO2, the overall rate constant for the reaction was found to be k1(293 K) = (3.1 +/- 1.0) x 10(13) cm3 mol(-1) s(-1). C2H5O could be confirmed as a direct reaction product.     

Photochemistry of Fe(III) complex with glyoxalic acid in aqueous solution

Nanosecond laser flash photolysis technique was used to study photochemistry of Fe(III) complex with glioxalic acid. The primary photochemical process was found to be inner-sphere electron transfer in the excited complex leading to formation of the long-lived radical complex [Fe^II … ^·OOC-C(O)H]²⁺. A number of important spectral-kinetic parameters of this species were determined and mechanism of photolysis of Fe(III)-glioxalate complex was proposed. 1 The article was translated by the authors.     

One-electron oxidation of alcohols by the 1,3,5-trimethoxybenzene radical cation in the excited state during two-color two-laser flash photolysis

One-electron oxidation of alcohols such as methanol, ethanol, and 2-propanol by 1,3,5-trimethoxybenzene radical cation (TMB*+) in the excited state (TMB*+*) was observed during the two-color two-laser flash photolysis. TMB*+ was formed by the photoinduced bimolecular electron-transfer reaction from TMB to 2,3,5,6-tetrachlorobenzoquinone (TCQ) in the triplet excited-state during the first 355-nm laser flash photolysis. Then, TMB*+* was generated from the selective excitation of TMB*+ during the second 532 nm laser flash photolysis. Hole transfer rate constants from TMB*+* to methanol, ethanol, and 2-propanol were calculated to be (5.2 +/- 0.5) x 10(10), (1.4 +/- 0.3) x 10(11), and (3.2 +/- 0.6) x 10(11) M-1 s-1, respectively. The order of the hole transfer rate constants is consistent with oxidation potentials of alcohol. Formation of TCQH radical (TCQH*) with a characteristic absorption peak at 435 nm was observed in the microsecond time scale, suggesting that deprotonation of the alcohol radical cation occurs after the hole transfer and that TCQ radical anion (TCQ*-), generated together with TMB*+ by the photoinduced electron-transfer reaction, reacts with H+ to give TCQH*.     

Viologen-modified platinum clusters acting as an efficient catalyst in photocatalytic hydrogen evolution

A highly efficient photocatalytic system for hydrogen evolution with dihydronicotinamide coenzyme (NADH) as a sacrificial agent in an aqueous solution has been constructed by using water-soluble platinum clusters functionalized with methyl viologen-alkanethiol (MVA2+) and a simple electron-donor dyad, 9-mesityl-10-methylacridinium ion (Acr+-Mes), which is capable of fast photoinduced electron transfer but extremely slow back electron transfer. The mean diameter of the platinum core was determined as R(CORE) = 1.9 nm with a standard deviation sigma = 0.5 nm by transmission electron microscopy (TEM). As a result, the hydrogen-evolution rate of the photocatalytic system with MVA2+-modified platinum clusters (MVA2+-PtC) is 10 times faster than the photocatalytic system with the mixture of the same amount of MVA2+ and platinum clusters as that of MVA2+-PtC under otherwise the same experimental conditions. The radical cation of NADH has been successfully detected by laser flash photolysis experiments. The decay of the absorbance due to NAD*, produced by the deprotonation from NADH*+, coincides with the appearance of the absorption band due to Acr*-Mes. This indicates electron transfer from NAD* to Acr+-Mes to give Acr*-Mes, which undergoes the electron-transfer reduction of MVA2+-PtC, leading to the efficient hydrogen evolution.     

Photochemical organic oxidations and dechlorinations with a mu-oxo bridged heme/non-heme diiron complex

Steady state and laser flash photolysis studies of the heme/non-heme mu-oxo diiron complex [((6)L)Fe(III)-O-Fe(III)-Cl](+) (1) have been undertaken. The anaerobic photolysis of benzene solutions of 1 did not result in the buildup of any photoproduct. However, the addition of excess triphenylphosphine resulted in the quantitative photoreduction of 1 to [((6)L)Fe(II)...Fe(II)-Cl](+) (2), with concomitant production by oxo-transfer of 1 equiv of triphenylphosphine oxide. Under aerobic conditions and excess triphenylphosphine, the reaction produces multiple turnovers (approximately 28) before the diiron complex is degraded. The anaerobic photolysis of tetrahydrofuran (THF) or toluene solutions of 1 likewise results in the buildup of 2. The oxidation products from these reactions included gamma-butyrolactone (approximately 15%) for the reaction in THF and benzaldehyde (approximately 23%) from the reaction in toluene. In either case, the O-atom which is incorporated into the carbonyl product is derived from dioxygen present under workup or under aerobic photolysis conditions. Transient absorption measurements of low-temperature THF solutions of 1 revealed the presence of an (P)Fe(II)-like [P = tetraaryl porphyrinate dianion] species suggesting that the reactive species is a formal (heme)Fe(II)/Fe(IV)=O(non-heme) pair. The non-heme Fe(IV)=O is thus most likely responsible for C-H bond cleavage and subsequent radical chemistry. The photolysis of 1 in chlorobenzene or 1,2-dichlorobenzene resulted in C-Cl cleavage reactions and the formation of [[((6)L)Fe(III)-Cl...Fe(III)-Cl](2)O](2+) (3), with chloride ligands that are derived from solvent dehalogenation chemistry. The resulting organic products are biphenyl trichlorides or biphenyl monochlorides, derived from dichlorobenzene and chlorobenzene, respectively. Similarly, product 3 is obtained by the photolysis of benzene-benzyl chloride solutions of 1; the organic product is benzaldehyde (approximately 70%). A brief discussion of the dehalogenation chemistry, along with relevant environmental perspectives, is included.     

Formation of Tryptophan Radicals in Irradiated Aqueous Solutions of Hexachloroplatinate(IV): A Flash Photolysis Study

The oxidation of tryptophan photosensitized by PtCl6(2-) has been investigated in aqueous solutions at different pH using nanosecond laser flash photolysis. Cationic and neutral radicals of tryptophan were detected at pH 2.8 and 8.5, respectively. The generation of the radical was attributed to oxidation by Cl2- that was formed from the homolytic bond cleavage in the excited state of PtCl6(2-). The bimolecular rate constant derived from the kinetics analysis, 2.8 +/- 0.2 x 10(9) M-1 s-1, is in good agreement with the value obtained in earlier pulse radiolysis studies. Both the cationic and neutral radicals decayed by second-order kinetics, consistent with the dimerization process.     

Photophysical and photochemical processes of riboflavin (vitamin B_2) by means of the transient absorption spectra in aqueous solution

Using time-resolved techniques of 337 and 248 nm laser flash photolysis, the photo-physical and photochemical processes of riboflavin (RF, vitamin B2) were studied in detail in aqueous solution. The excited triplet state of riboflavin (3RF*) was produced with 337 nm laser, while under 248 nm irradiation, both 3RF* and hydrated electron (eaq) formed from photoionizationcould be detected. Photobiological implications have been inferred on the basis of reactivity of 3RF* including energy transfer, electron transfer and hydrogen abstraction. The RF.+ was generated by oxidation of SO4.- radical with the aim of confirming the results of photolysis.     

Competitive decay pathways of the radical ions formed by photoinduced electron transfer between quinones and 4,4'-dimethoxydiphenylmethane in acetonitrile

The reactivity of the cation radical of (4-MeOC6H4)2CH2 photosensitized by 1,4-benzoquinone (BQ), 2,5-dichloro-1,4-benzoquinone (Cl2BQ), and tetrachloro-1,4-benzoquinone (chloranil, CA) was investigated in acetonitrile. The main photoreaction products obtained by steady-state irradiation were identified to be: (4-MeOC6H4)2-CHOC6H4OH, sensitized by BQ; (4-MeOC6H4)2CHCl, sensitized by Cl2BQ; (4-MeOC6H4)2CHOH, sensitized by CA. The mechanism of their formation was investigated by nanosecond laser flash photolysis that allowed transient species (radical ions, neutral radicals, and ions) to be detected and characterized in terms of absorption spectra, formation quantum yields, and decay rate constants. For all systems, the interaction between the triplet quinone (Q) and (4-MeOC6H4)2CH2 produced the corresponding radical ions (quantum yield phi > or = 0.72) which mainly decay by back electron transfer processes. Less efficient reaction routes for the radical ions Q*- and (4-MeOC6H4)2CH2*+ were also: i) the proton-transfer process with the formation of the radical (4-MeOC6H4)2CH* by use of Cl2BQ; ii) the hydrogen-transfer process with the formation of the cation (4-MeOC6H4)2CH+ in the case of CA. Instead. BQ sensitized a much higher yield of BOH* and (4-MeOC6H4)2CH*, mainly by the direct interaction of triplet BQ with (4-MeOC6H4)2CH2. It was also shown that the presence of salts decreases significantly the rate of the back electron transfer process and enhances the quantum yields of formation of the neutral radicals and ions when Cl2BQ and CA are used, respectively. The behavior of BQ*-, Cl2BQ*-, and CA*- appears to be mainly determined by the Mulliken charges on the oxygen atom obtained from quantum mechanical calculations with the model B3LYP/6-311G(d,p). Spin densities seem to be much less important.     

Preliminary study on the photoproduction of hydroxyl radicals in aqueous solution with Aldrich humic acid, algae and Fe(III) under high-pressure mercury lamp irradiation

Under a high-pressure mercury lamp (HPML) and using an exposure time of 4 h, the photoproduction of hydroxyl radicals (*OH) could be induced in an aqueous solution containing humic acid (HA). Hydroxyl radicals were determined by high-performance liquid chromatography using benzene as a probe. The results showed that *OH photoproduction increased from 1.80 to 2.74 microM by increasing the HA concentration from 10 to 40 mg L(-1) at an exposure time of 4 h (pH 6.5). Hydroxyl radical photoproduction in aqueous solutions of HA containing algae was greater than that in the aqueous solutions of HA without algae. The photoproduction of *OH in the HA solution with Fe(III) was greater than that of the solution without Fe(III) at pH ranging from 4.0 to 8.0. The photoproduction of *OH in HA solution with algae with or without Fe(III) under a 250 W HPML was greater than that under a 125 W HPML. The photoproduction of *OH in irradiated samples was influenced by the pH. The results showed that HPML exposure for 4 h in the 4-8 pH range led to the highest *OH photoproduction at pH 4.0.     

The "somersault" mechanism for the p-450 hydroxylation of hydrocarbons. The intervention of transient inverted metastable hydroperoxides

A series of model theoretical calculations are described that suggest a new mechanism for the oxidation step in enzymatic cytochrome P450 hydroxylation of saturated hydrocarbons. A new class of metastable metal hydroperoxides is described that involves the rearrangement of the ground-state metal hydroperoxide to its inverted isomeric form with a hydroxyl radical hydrogen bonded to the metal oxide (MO-OH --> MO....HO). The activation energy for this somersault motion of the FeO-OH group is 20.3 kcal/mol for the P450 model porphyrin iron(III) hydroperoxide [Por(SH)Fe(III)-OOH(-)] to produce the isomeric ferryl oxygen hydrogen bonded to an *OH radical [Por(SH)Fe(III)-O....HO(-)]. This isomeric metastable hydroperoxide, the proposed primary oxidant in the P450 hydroxylation reaction, is calculated to be 17.8 kcal/mol higher in energy than the ground-state iron(III) hydroperoxide Cpd 0. The first step of the proposed mechanism for isobutane oxidation is abstraction of a hydrogen atom from the C-H bond of isobutane by the hydrogen-bonded hydroxyl radical to produce a water molecule strongly hydrogen bonded to anionic Cpd II. The hydroxylation step involves a concerted but nonsynchronous transfer of a hydrogen atom from this newly formed, bound, water molecule to the ferryl oxygen with a concomitant rebound of the incipient *OH radical to the carbon radical of isobutane to produce the C-O bond of the final product, tert-butyl alcohol. The TS for the oxygen rebound step is 2 kcal/mol lower in energy than the hydrogen abstraction TS (DeltaE() = 19.5 kcal/mol). The overall proposed new mechanism is consistent with a lot of the ancillary experimental data for this enzymatic hydroxylation reaction.     

Transient spectroscopy of ninhydrin

The photochemistry of ninhydrin in benzene and water was studied by laser flash photolysis and electron paramagnetic resonance. Its photochemistry was shown to be dependent on the solvent. In benzene, a triplet excited state was observed, which underwent hydrogen abstraction reactions or reduction to the radical anion. In water, the radical anion of ninhydrin was formed within the laser pulse (15 ns) at neutral pH, whereas the neutral ketyl radical was formed by protonation of the radical anion at low pH. A pKa of 0.77 was determined for the protonation equilibrium. The formation of hydrindantin is proposed to occur through the dimerization of the ketyl radical or the radical anion (or both). In addition, ninhydrin was shown to be a poor precursor for the photogeneration of hydroxyl radicals.     

A laser flash photolysis and pulse radiolysis study of primary photochemical processes of flumequine

The 355 nm laser flash photolysis of argon-saturated pH 8 phosphate buffer solutions of the fluoroquinolone antibiotic flumequine produces a transient triplet state with a maximum absorbance at 575 nm where the molar absorptivity is 14,000 M(-1) cm(-1). The quantum yield of triplet formation is 0.9. The transient triplet state is quenched by various Type-1 photodynamic substrates such as tryptophan (TrpH), tyrosine, N-acetylcysteine and 2-deoxyguanosine leading to the formation of the semireduced flumequine species. This semireduced form has been readily identified by pulse radiolysis of argon-saturated pH 8 buffered aqueous solutions by reaction of the hydrated electrons and the CO2*- radicals with flumequine. The absorption maximum of the transient semireduced species is found at 570 nm with a molar absorptivity of 2,500 M(-1) cm(-1). In argon-saturated buffered solutions, the semireduced flumequine species formed by the reaction of the flumequine triplet with TrpH stoichiometrically reduces ferricytochrome C (Cyt Fe3+) under steady state irradiation with ultraviolet-A light. In the presence of oxygen, O2*- is formed but the photoreduction of Cyt Fe3+ by O2*- competes with an oxidizing pathway which involves photo-oxidation products of TrpH.     

Study of the Reactions of Platinum Macrocyclic Complex Ions with Free Radicals Formed by Pulse Radiolysis of Aqueous Media

The near-diffusion-controlled reactions of hydroxyl radical, hydrated electron, and hydrogen atom with platinum macrocyclic complex ions in aqueous media have been studied using pulse radiolysis in conjunction with UV-visible absorption and conductivity detection. The hydrated electron and hydrogen atom react with trans-[Pt(cyclam)(Cl)(2)](2+) where cyclam is 1,4,8,11-tetraazacyclotetradecane to yield platinum(III) transients that exhibit intense absorption peaks in the 280-300 nm region; however in the case of the H-atom, the reaction involves a competition between chloride abstraction and a minor process, suggested to be attack on the organic ligand. The platinum(III) products are kinetically labile toward loss of chloro ligands, but these reactions are reversible in the presence of added KCl. The reactions of hydroxyl radical with [Pt(cyclam)](2+) and with [Pt(tmc)](2+), where tmc is 1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane, lead to platinum(III) intermediates absorbing in the 250-300 nm region. Depending on the presence or absence of added KCl and on the pH, the platinum(III) cyclam systems can react to form a product(s) exhibiting absorption peaks near 330 and 455 nm, and this species is proposed to be a long-lived amidoplatinum(III) complex. In support of this proposal is the observation that the tmc system does not give rise to a similar visible-absorbing product. The interrelations of the cyclam-based transients through acid-base, chloro-substitution and water-elimination processes are discussed.     

Reductive PET cycloreversion of oxetanes: singlet multiplicity, regioselectivity, and detection of olefin radical anion

Cycloreversion of 2-(p-cyanophenyl)-4-methyl-3-phenyloxetane (1) is achieved using 1-methoxynaphthalene (2) as electron-transfer photosensitizer. The experimental results are consistent with the reaction taking place from the singlet excited state of the sensitizer. Ring splitting of the radical anion 1*- occurs with cleavage of O-C2 and C3-C4 bonds, leading to products (acetaldehyde and p-cyanostilbene) different from the reagents used in the Paterno-Büchi synthesis of 1. The olefin radical anion involved in the electron-transfer process has been detected by means of laser flash photolysis.