Pulse radiolytic investigation of the reaction of hydroxyl radicals with gentamycin

Hydroxyl radicals were generated radiolytically in N₂O-saturated aqueous solutions of the aminoglycoside antibiotic, gentamycin. Using the pulse radiolysis technique, the rate constant of OH radicals with gentamycin determined was 1.2·10⁹ dm³·mol⁻¹·s⁻¹. Upon^.OH attack a transient species with an absorption maximum at 270 nm is observed which decays by second-order kinetics within the solute concentration range of 3.2·10⁻⁵ to 1·10⁻³mol·dm⁻³. Transient species undergoes transformation to a permanent product absorbing between 260 and 340 nm with maximum absorption at 300 nm. Rate constant of the reaction of bimolecular decay of gentamycin radicals, k (Gen^.+Gen^.) was found to be ≈ 1.4·10⁷ dm³·mol⁻¹·s⁻¹.     

Nature of the transient species formed in pulse radiolysis of n-allylthiourea in aqueous solutions

Reactions of e⁻_aq, OH radicals and H atoms were studied with n-allylthiourea (NATU) using pulse radiolysis. Hydrated electrons reacted with NATU (k = 2.8×10⁹ dm³ mol⁻¹ s⁻¹) giving a transient species which did not have any significant absorption above 300 nm. It was found to transfer electrons to methyl viologen. At pH 6.8, the reduction potential of NATU has been determined to be −0.527 V versus NHE. At pH 6.8, OH radicals were found to react with NATU, giving a transient species having absorption maxima at 400–410 nm and continuously increasing absorption below 290 nm. Absorption at 400–410 nm was found to increase with parent concentration, from which the equilibrium constant for dimer radical cation formation has been estimated to be 4.9×10³ dm³ mol⁻¹. H atoms were found to react with NATU with a rate constant of 5 × 10⁹ dm³ mol⁻¹ s⁻¹, giving a transient species having an absorption maximum at 310 nm, which has been assigned to H-atom addition to the double bond in the allyl group. Acetoneketyl radicals reacted with NATU at acidic pH values and the species formed underwent reaction with parent NATU molecule. Reaction of Cl^.−₂ radicals (k = 4.6 × 10⁹ dm³ mol⁻¹ s⁻¹) at pH 1 was found to give a transient species with λ_max at 400 nm. At the same pH, reaction of OH radicals also gave transient species, having a similar spectrum, but the yield was lower. This showed that OH radicals react with NATU by two mechanisms, viz., one-electron oxidation, as well as addition to the allylic double bond. From the absorbance values at 410 nm, it has been estimated that around 38% of the OH radicals abstract H atoms and the remaining 62% of the OH radicals add to the allylic double bond.     

Rate constants for reactions of iodine atoms in solution

Laser flash photolysis (at 248 or 308 nm) or aryl iodides in water or water/methanol solutions produces iodine atoms and phenyl radicals. Iodine atoms react rapidly with added I^? to form I₂^? but do not react rapidly with O₂ (k ? 10⁷ L mol^?1 s^?1). Iodine atoms oxidize phenols to phenoxyl radicals, with rate constants that vary from 1.6 × 10⁷ L mol^?1 s^?1 for phenol to about 6 × 10⁹ L mol^?1 s^?1 for 4-methoxyphenol and hydroquinone. Ascorbate and a Vitamin E analogue are also oxidized very rapidly. N-Methylindole is oxidized by I atoms to its radical cation with a diffusion-controlled rate constant, 1.9 × 10¹⁰ L mol^?1 s^?1. Iodine atoms also oxidize sulfite and ferrocyanide ions rapidly but do not add to double bonds. The phenyl radicals, produced along with the I atoms, react with O₂ to give phenylperoxyl radicals, which react with phenols much more slowly than I atoms. © 1995 John Wiley & Sons, Inc.     

Reaktionen der H-Radikale mit aromatischen Halogenverbindungen in wäßriger Lösung

The spectroscopic and kinetic data of the short lived intermediates obtained by the attack of H-radicals on fluoro-, chloro-, bromobenzene, benzylchloride and phenethylchloride in aqueous solutions were studied by pulse radiolysis technique. The first three yield cyclohexadienylradicals (k=1–1.5×10⁹ dm³ mol^?1 s^?1) with characteristic absorption maxima in the region 220–330 nm. In the case of benzylchloride a quantitative abstraction of chlorine by the H-atoms is observed (k=9.5×10⁸ dm³ mol^?1 s^?1) leading to the formation of the benzylradical (λ_max=257, 303, 317.5nm). The attack of H-atoms on phenethylchloride can occur on the aromatic ring forming also a cyclohexadienylradical (k=2.0×10⁹ dm³ mol^?1 s^?1, λ_max=317, 323nm) as well as on the side chain (k=1.5×10⁸ dm³ mol^?1 s^?1) yielding H₂. The intermediates decay according to a second order reaction withk=2 to 4.6×10⁹ dm³ mol^?1 s^?1. To elucidate reaction mechanisms, steady state radiolysis experiments on the same systems were performed.     

PRIMARY INTERMEDIATES IN THE PULSED IRRADIATION OF RETINOIDS

Abstract Laser flash photolysis and pulse radiolysis have led to the characterisation of several shortlived intermediates formed after irradiation of retinoic acid and retinyl acetate in hexane or methanol. For retinoic acid, the triplet state, wavelength maximum 440 nm, extinction coefficient 7.3 × 10⁴ dm³ mol^?1 cm^?1, decay constant 6.2 × 10⁵ s^?1, is formed with a quantum yield of 0.012 for 347 nm excitation. The radical cation, absorption maximum 590 nm, extinction coefficient ～7 × 10⁴ dm³mol^?1 cm^?1, is formed in a biphotonic process. The radical anion, absorption maximum 510nm in hexane, 480 nm in methanol where its extinction coefficient is 1.2 × 10⁵ dm³mol^?1 cm^?1, appears to decay partially in methanol into another longer-lived neutral radical, wavelength maximum 420 nm, by loss of OH^?. For retinyl acetate, the triplet state, absorption maximum 395 nm, extinction coefficient 7.9 × 10⁴dm³mol^?1 cm^?1, decay constant 1.2 × 10⁶s^?1 is formed with a quantum yield of 0.025 for 347 nm excitation. Monophotonic photoelimination of OCOCH₃? in methanol produces the retinylic carbenium ion, wavelength maximum 590 nm, whose decay is enhanced by ammonia, k ～ 2 × 10⁶ dm³ mol^?1 s^?1 and retarded by water. The radical cation also has a wavelength maximum at 590 nm, its extinction coefficient being ～ 1.0 × 10⁵ dm³mol¹ cm^?1. The long-lived transient absorption with maximum at 385 nm, extinction coefficient 1.0 × 10⁵ dm³mol^?1 cm^?1, obtained from the reaction of the solvated electron with retinyl acetate in methanol may be due to either the radical anion itself or more likely the radical resulting from elimination of OCOCH₃? from this anion. These results suggest that skin photosensitivity caused by retinyl acetate might be greater than that due to retinoic acid.     

Mono-complex formation kinetics of iron(III) with nonsubstituted octane and nonane 2,4-dicarbonyl ligands in aqueous solution

The kinetics and mechanism of the reaction of complexation of iron(III) with 2,4-octanedione and 2,4-nonanedione have been investigated spectrophotometrically in aqueous solution at 10°C and ionic strength 0.5 mol dm^?3 NaClO₄. The equilibrium constants of the mono-complexes have been determined. The mechanism proposed to account for the kinetic data involves a double reversible pathway where both Fe³⁺ and Fe(OH)²⁺ react with the enol tautomer of the ligand. 2,4-Octanedione reacts with Fe³⁺ and Fe(OH)²⁺ with rate constants of 0.65 dm³ mol^?1 s^?1, and 14.07 dm³ mol^?1 s^?1, respectively. For 2,4-nonanedione complexation the rate constants determined are 0.49 dm³ mol^?1 s^?1, and 11.39 dm³ mol^?1 s^?1, respectively. Some discussions are made on the basis of Eigen-Wilkins theory considering the effect of solvent exchange on the complex formation. © 1993 John Wiley & Sons, Inc.     

The rate constants for the reaction of the hydroxyl radical with methyl,n-propyl,and n-butyl nitrites

The kinetics of the reaction of OH radicals with methyl, n-propyl, and n-butyl nitrite have been studied in a discharge flow system under pseudo first-order conditions. The OH radicals were generated by the reaction of H atoms with NO₂ and the concentration of OH; monitored by resonance fluorescence, was followed as a function of time in an excess of each nitrite. Values of k(CH₃ONO) = (0.6 ± 0.09) × 10⁹ dm³ mol^?1 s^?1 k(n – C₃H₇ONO) = (1.39 ± 0.20) × 10⁹ dm³ mol^?1 s^?1, and k(n – C₄H₉ONO) = (2.89 ± 0.43) × 10⁹ dm³ mol^?1 s^?1 at 295 K were obtained. These results agree with previous relative rate measurements from this laboratory but the value for k (CH₃ONO) is a factor of 7 greater than the value obtained by relative rate measurements elsewhere using a different OH source.     

Reactivity of OH radicals with chlorobenzoic acids—A pulse radiolysis and steady-state radiolysis study

The reactions of OH radicals with 2-, 3-, 4-chlorobenzoic acids (ClBzA) and chlorobenzene (ClBz), k(OH+substrates)=(4.5?6.2)×10⁹ dm³ mol^?1 s^?1, have been studied by pulse radiolysis in N₂O saturated solutions. The absorption maxima of the OH-adducts were in the range of 320?340 nm. Their decay was according to a second-order reaction, 2k=(1?9)×10⁸ dm³ mol^?1 s^?1. In the presence of N₂O/O₂ the formation of peroxyl radicals was detectable for 2-, 4-ClBzA and ClBz, k(OH-adduct+O₂)=(2?4)×10⁷ dm³ mol^?1 s^?1, while this reaction for 3-ClBzA was too slow to be registered. In the presence of N₂O the degradation rates induced by gamma radiation were very similar for all chlorobenzoic acids, yet the chloride formation was distinctly higher for 3-ClBzA. In the presence of oxygen the initial degradation of 2-and 4-ClBzA equaled the OH-radical concentration, whereas in case of 3-ClBzA only ～60% of OH led to degradation. The order for the efficiency of dehalogenation was 4->2->3-ClBzA. Several primary radiolytic products could be detected by HPLC. To evaluate the toxicity of final products a bacterial bioluminescence test was carried out.     

Polymerization of neat 2‐ethylhexyl acrylate induced by a pulsed electron beam

The bulk polymerization of 2‐ethylhexyl acrylate (2‐EHA), induced by a pulsed electron beam, was investigated with pulse radiolysis, gravimetry, and Fourier transform infrared spectroscopy. The roles of the dose rate, pulse frequency, and added acrylic acid (AA) in the polymerization of 2‐EHA were examined at ambient temperature. In the range of 12.6–71.2 Gy/pulse, the polymerization of 2‐EHA was dose‐rate‐dependent: at the same total dose, a lower dose rate yielded a higher conversion. Also, a lower pulse rate gave a higher conversion at the same total dose. The addition of up to 10 wt % AA showed no increase in the conversion of 2‐EHA at a low conversion (8 kGy), but at a higher conversion (16 kGy), a 20 wt % increase in the conversion of 2‐EHA was observed. The estimated values (1.6 ± 0.3) × 10^?3 (dm³ s)^3/2 mol^?1 s^?1/2 for k_p(G/2k_t)^1/2 and 2.6 ± 0.8 dm³ s J^?1 for 2k_tG (where k_p is the rate constant of propagation, k_t is the rate constant of bimolecular termination, and G is the yield of free radicals) were obtained at relatively low conversions. The reaction rate constant of the addition of 2‐EHA^· free radicals to the monomer was measured by pulse radiolysis and found to be 2.8 × 10² mol^?1 dm³ s^?1. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 196–203, 2003     

Reactions of melatonin with radicals in deoxygenated aqueous solution

Reactions of melatonin (N-acetyl-5-methoxytryptamine) with radiolytically generated radicals were studied. Reaction of melatonin with OH radicals is diffusion-controlled (k=1.2·10¹⁰ dm³ mol⁻¹·s⁻¹), the main (but not the only one) intermediate being the indolyl-type radical, while the rate constant for the reaction with hydrated electrons isk=4.3·10⁸ dm³·mol⁻¹·s⁻¹. Melatonin is capable of scavenging tert-butanol radicals, while its reactivity towards polymer radicals of poly(acrylic acid) and poly(vinyl pyrrolidone) is very low.     

Pulse radiolysis investigations on the reactions of primary radiolytic species of water with atropine

On pulse radiolysis of N₂O saturated aqueous solutions of atropine, an optical absorption band (_max at 320 nm,e=2.81·10³ dm³·mol^–1·cm^–1) was observed, which is assigned to the product of reaction of OH radicals with the solute. This absorption decayed following second order kinetics with a rate constant of 4.5·10⁸ dm³·mol^–1·s^–1. The rate constant for the reaction of OH radicals with atropine as estimated by following the build-up kinetics is 2.7·10⁹ dm³·mol^–1·s^–1. The H atoms also reacted with this compound to produce a transient absorption band behaving similarly to the one observed in the case of reaction with OH radicals. The transient species formed in both cases is assigned to a radical derived by H atom abstraction by H/OH radicals from the parent compound. This radical was unreactive towards 2-mercaptoethanol. e _aq ^– was found to react with atropine forming a transient band with _max at 310 nm (=3.55·10³ dm³·mol^–1). Its decay was also second order with a rate constant of 1.64·10⁹ dm³·mol^–1·s^–1. The bimolecular rate constant for the reaction of e _aq ^– with atropine as estimated from the decay of e _aq ^– absorption at 720 nm is 3.9·10⁹ dm³·mol^–1·s^–1. Specific one-electron oxidizing and reducing agents (such as Cl ₂ ^– , Tl²⁺, SO ₄ ^– and (CH₃)₂COH, CO ₂ ^– , respectively) failed to oxidize or reduce this compound in aqoues solutions. The radical anion of atropine formed by its reaction with e _aq ^– was found to reduce thionine and methyl viologen with bimolecular rate constant of 3.8·10⁹ and 3.2·10⁹ dm³·mol^–1·s^–1, respectively.     

Kinetics and mechanism of oxidation of aurate(I) by peroxydisulphate in aqueous hydrochloric acid

The reaction between Au(I), generated by reaction of thallium(I) with Au(III), and peroxydisulphate was studied in 5 mol dm^?3 hydrochloric acid. The reaction proceeds with the formation of an ion‐pair between peroxydisulphate and chloride ion as the Michealis–Menten plot was linear with intercept. The ion‐pair thus formed oxidizes AuCl₂^? in a slow two‐electron transfer step without any formation of free radicals. The ion‐pair formation constant and the rate constant for the slow step were determined as 113 ± 20 dm^?3 mol^?1 and 5.0 ± 1.0 × 10^?2 dm³ mol^?1 s^?1, respectively. The reaction was retarded by hydrogen ion, and formation of unreactive protonated form of the reductant, HAuCl₂, causes the rate inhibition. From the hydrogen ion dependence of the reaction rate, the protonation constant was calculated to be as 0.6 ± 0.1 dm³ mol^?1. The activation parameters were determined and the values support the proposed mechanism. © 2002 Wiley Periodicals, Inc. Int J Chem Kinet 34: 589–594, 2002     

Radical scavenging reactions of chlorogenic acid: A pulse radiolysis study

At near neutral pH (approx. 5.5), the OH-adduct of chlorogenic acid (CGA), formed on pulse radiolysis of N₂O-saturated aqueous CGA solutions (λ _max = 400 and 450 nm) with k = 9 × 10⁹ dm³ mol⁻¹ s⁻¹, rapidly eliminates water (k = 1 × 10³ s⁻¹) to give a resonance-stabilized phenoxyl type of radical. Oxygen rapidly adds to the OH-adduct of CGA (pH 5.5) to form a peroxyl type of radical (k = 6 × 10⁷ dm³ mol⁻¹ s⁻¹). At pH 10.5, where both the hydroxyl groups of CGA are deprotonated, the rate of reaction of · OH radicals with CGA was essentially the same as at pH 5.5, although there was a marked shift in the absorption maximum to approx. 500 nm. The CGA phenoxyl radical formed with more specific one-electron oxidants, viz., Br ₂ ^·− and N ₃ ^· radicals show an absorption maximum at 385 and 500 nm, k ranging from 1–5.5 × 10⁹ dm³ mol⁻¹ s⁻¹. Reactions of other one-electron oxidants, viz., NO ₂ ^· , NO^· and CCl₃OO^· radicals, are also discussed. Repair rates of thymidine, cytidine and guanosine radicals generated pulse radiolytically at pH 9.5 by CGA are in the range of (0.7–3) × 10⁹ dm³ mol⁻¹ s⁻¹.     

Spectral,kinetics, and redox properties of the transients formed on one‐electron oxidation of 4,4′‐thiodiphenol: A pulse radiolysis study

The transient absorption bands (λ_max = 330, 525 nm, k_f = 5 × 10⁹ dm³ mol⁻¹ s⁻¹) obtained on pulse radiolysis of N₂O‐saturated neutral aqueous solution of 4,4′‐thiodiphenol (TDPH) are due to the reaction of TDPH with ^·OH radicals and are assigned to phenoxyl radical formed on fast deprotonation of the solute radical cation. The reaction of specific one‐electron oxidants (Cl₂^·−, Br₂^·−, N₃^·, TI²⁺, CCl₃OO^·) with TDPH also produced similar transient absorption bands. The phenoxyl radicals are also produced on pulse radiolysis of N₂‐saturated solution of TDPH in 1,2‐dichloroethane. The nature of transient absorption spectrum obtained on reaction of ^·OH radicals with TDPH is not affected in acidic solutions, showing that OH‐adduct is not formed in neutral solutions. The oxidation potential for the formation of phenoxyl radical is determined to be 0.98 V. © 1999 John Wiley & Sons, Inc. Int J Chem Kinet 31: 603–610, 1999     

Rate constants for the gas‐phase reaction of CF3CF2CF2CF2CF2CHF2 with OH radicals at 250–430 K

The rate constants k₁ for the reaction of CF₃CF₂CF₂CF₂CF₂CHF₂ with OH radicals were determined by using both absolute and relative rate methods. The absolute rate constants were measured at 250–430 K using the flash photolysis–laser‐induced fluorescence (FP‐LIF) technique and the laser photolysis–laser‐induced fluorescence (LP‐LIF) technique to monitor the OH radical concentration. The relative rate constants were measured at 253–328 K in an 11.5‐dm³ reaction chamber with either CHF₂Cl or CH₂FCF₃ as a reference compound. OH radicals were produced by UV photolysis of an O₃–H₂O–He mixture at an initial pressure of 200 Torr. Ozone was continuously introduced into the reaction chamber during the UV irradiation. The k₁ (298 K) values determined by the absolute method were (1.69 ± 0.07) × 10^?15 cm³ molecule^?1 s^?1 (FP‐LIF method) and (1.72 ± 0.07) × 10^?15 cm³ molecule^?1 s^?1 (LP‐LIF method), whereas the K₁ (298 K) values determined by the relative method were (1.87 ± 0.11) × 10^?15 cm³ molecule^?1 s^?1 (CHF₂Cl reference) and (2.12 ± 0.11) × 10^?15 cm³ molecule^?1 s^?1 (CH₂FCF₃ reference). These data are in agreement with each other within the estimated experimental uncertainties. The Arrhenius rate constant determined from the kinetic data was K₁ = (4.71 ± 0.94) × 10^?13 exp[?(1630 ± 80)/T] cm³ molecule^?1 s^?1. Using kinetic data for the reaction of tropospheric CH₃CCl₃ with OH radicals [k₁ (272 K) = 6.0 × 10^?15 cm³ molecule^?1 s^?1, tropospheric lifetime of CH₃CCl₃ = 6.0 years], we estimated the tropospheric lifetime of CF₃CF₂CF₂CF₂CF₂CHF₂ through reaction with OH radicals to be 31 years. © 2003 Wiley Periodicals, Inc. Int J Chem Kinet 36: 26–33, 2004     

Pulse radiolysis of Triton X-100 aqueous solution

Pulse radiolysis of deaerated aqueous solutions of 4·10^–5–2.4·10^–3 mol dm^–3 Triton X-100 gives rise to a transient species originating from the reactions of OH radicals and H atoms. The rate constants of these reactions were found to be 8.8·10⁹ mol^–1·dm³·s^–1 and 1.25·10⁹ mol^–1·dm³·s^–1, respectively, for Triton X-100 concentrations below CMC. The corresponding transient species were found to decay according to second order kinetics. The mechanism of the reactions involved including concentration effects is discussed.     

Kinetics of the gas‐phase reaction of CF3OC(O)H with OH radicals at 242–328 K

The rate constants, k₁, of the reaction of CF₃OC(O)H with OH radicals were measured by using a Fourier transform infrared spectroscopic technique in an 11.5‐dm³ reaction chamber at 242–328 K. OH radicals were produced by UV photolysis of an O₃–H₂O–He mixture at an initial pressure of 200 Torr. Ozone was continuously introduced into the reaction chamber during UV irradiation. With CF₃OCH₃ as a reference compound, k₁ at 298 K was (1.65 ± 0.13) × 10^?14 cm³ molecule^?1 s^?1. The temperature dependence of k₁ was determined as (2.33 ± 0.42) × 10^?12 exp[?(1480 ± 60)/T] cm³ molecule^?1 s^?1; possible systematic uncertainty could add an additional 20% to the k₁ values. The atmospheric lifetime of CF₃OC(O)H with respect to reaction with OH radicals was calculated to be 3.6 years. © 2004 Wiley Periodicals, Inc. Int J Chem Kinet 36: 337–344 2004     

Scavenging of reactive oxygen radicals by resveratrol: antioxidant effect

Pulse radiolysis of resveratrol was carried out in aqueous solutions at pH ranging from 6.5 to 10.5. The one-electron oxidized species formed by the N^•₃ radicals at pH 6.5 and 10.5 were essentially the same with λ_max at 420 nm and rate constant varying marginally (k = (5−6.5) × 10⁹ dm³ mol⁻¹ s⁻¹). The nature of the transients formed by NO^•₂, NO^• radical reaction at pH 10.5 was the same as that with N^•₃, due to the similarity in decay rates and the absorption maximum. Reaction of ^•OH radical with resveratrol at pH 7 gives an absorption maximum at 380 nm, attributed to the formation of carbon centered radical. The repair rates for the thymidine and guanosine radicals by resveratrol were approx. 1 × 10⁹ dm³ mol⁻¹ s⁻¹, while the repair rate for tryptophan was lower by nearly an order of magnitude (k = 2 × 10⁸ dm³ mol⁻¹ s⁻¹). The superoxide radical anion was scavenged by resveratrol, as well as by the Cu–resveratrol complex with k = 2 × 10⁷ and 1.5 × 10⁹ dm³ mol⁻¹ s⁻¹, respectively. Its reduction potential was also measured by cyclic voltammetry.     

Rate constants for reactions of hydroxyl radicals with nitromethane and methyl nitrite vapours at 292 K

The variations of yields of CO₂ from the gas phase H₂O₂ + NO₂ + CO chain reaction system with added nitromethane or methyl nitrite have given rate constants for reactions of OH radicals with these substrates. At 292 K these are (5.5 ± 0.6) × 10⁸ and (8.0 ± 1.1) × 10⁸ dm³ mol^?1 s^?1 respectively.     

Pulse radiolysis study on one-electron oxidation of 1-naphthylamine-4-sulphonic acid in aqueous solutions

Reactions of 1-naphthylamine-1-sulphonic acid (NASA) with hydroxyl radicals and oneelectron oxidants such as N₃, Br₂ ^- and Cl₂ ^- radicals have been studied at various pHs using pulse radiolysis technique. Rate constants for the reaction of N₃ and Br₂ ^-. radicals with NASA at neutral pH were found to be 5 × 10⁹ and 4 × 10⁸ dm³ mol^-1 s^-1 respectively. These reactions led to the formation of a cation radical (semi-oxidized species). OH radical reaction with NASA (k = 7.2 × 10⁹ dm³ mol^-1 s^-1) at neutral pH gave a mixture of species, namely, a semi-oxidized species as well as an adduct species. Cl₂ ^-. radicals reacted with NASA rather slowly (k = 7 × 10⁷ dm³ mol^-1 s^-1) at pH 1 to give the semioxidised species. However, even at pH 1, OH radical reaction with NASA gave a mixture containing semi-oxidized as well as an adduct species. The OH-adduct species having _max at 340 nm decays at acidic pHs to give semi-oxidized species having _max at 370 nm. Electron adduct of NASA was found to be a strong reducing radical.