Pulse radiolysis rate constant

Re-examination of the radiolysis of aqueous solutions of alanine (absence of oxygen) shows that electrons react rapidly with the cationic form, less rapidly with the zwitterion, and much less rapidly with the anionic form. These conclusions have been confirmed by pulse radiolysis. Rate constants for amino acids, peptides, proteins, and numerous other substances have been obtained. Critical evaluation of these and correlation with molecular properties is now well under way. In living systems the reactions of the hydrated electron vary with the part of the cell concerned, with the developmental stage of the cell, and possibly with the nature of any experimentally added substances. 

Table I. Pulse Radiolysis Rate Constants for Methylene Blue...

The one-electron reduction of thiazole in aqueous solution has been studied by the technique of pulse radiolysis and kinetic absorption spectrophotometry (514). The acetone ketyl radical (CH ljCOH and the solvated electron e were used as one-electron reducing agents. The reaction rate constant of with thiazole determined at pH 8.0 is fe = 2.1 X 10 mole sec in agreement with 2.5 x 10 mole sec" , the value given by the National Bureau of Standards (513). It is considerably higher than that for thiophene (6.5 x 10" mole" sec" ) (513) and pyrrole (6.0 X10 mole sec ) (513). The reaction rate constant of acetone ketyl radical with thiazolium ion determined at pH 0.8 is lc = 6.2=10 mole sec" . Relatively strong transient absorption spectra are observed from these one-electron reactions they show (nm) and e... 

Elegant evidence that free electrons can be transferred from an organic donor to a diazonium ion was found by Becker et al. (1975, 1977a see also Becker, 1978). These authors observed that diazonium salts quench the fluorescence of pyrene (and other arenes) at a rate k = 2.5 x 1010 m-1 s-1. The pyrene radical cation and the aryldiazenyl radical would appear to be the likely products of electron transfer. However, pyrene is a weak nucleophile the concentration of its covalent product with the diazonium ion is estimated to lie below 0.019o at equilibrium. If electron transfer were to proceed via this proposed intermediate present in such a low concentration, then the measured rate constant could not be so large. Nevertheless, dynamic fluorescence quenching in the excited state of the electron donor-acceptor complex preferred at equilibrium would fit the facts. Evidence supporting a diffusion-controlled electron transfer (k = 1.8 x 1010 to 2.5 X 1010 s-1) was provided by pulse radiolysis. 

The reader can show that, with the steady-state approximation for [Tl2+], this scheme agrees with Eq. (6-14), with the constants k = k i and k = k j/k g. Of course, as is usual with steady-state kinetics, only the ratio of the rate constants for the intermediate can be determined. Subsequent to this work, however, Tl2+ has been generated by pulse radiolysis (Chapter 11), and direct determinations of k- and k g have been made.5... 

Some of the most conclusive studies of the mechanisms of chain reactions come from experiments in which some of the propagating steps have been independently measured directly. This measurement can sometimes be done by the use of flash photolysis and pulse radiolysis (Chapter 11). Such determinations can verify the occurrence of a certain reaction in the sequence and provide its rate constant. 

Pulse radiolysis. If one wishes to determine the rate constant for the reaction of e q with a substrate A, the approximate value of which is 107 LmoP1 s l, what is the lowest pH that can be used ... 

Meissner and coworkers36 studied the pulse radiolysis of aqueous solutions of dimethyl sulfoxide. It was found that hydrated electrons react with DMSO with a rate constant of... 

Tl(III) < Pb(IV), and this conclusion has been confirmed recently with reference to the oxythallation of olefins 124) and the cleavage of cyclopropanes 127). It is also predictable that oxidations of unsaturated systems by Tl(III) will exhibit characteristics commonly associated with analogous oxidations by Hg(II) and Pb(IV). There is, however, one important difference between Pb(IV) and Tl(III) redox reactions, namely that in the latter case reduction of the metal ion is believed to proceed only by a direct two-electron transfer mechanism (70). Thallium(II) has been detected by y-irradiation 10), pulse radiolysis 17, 107), and flash photolysis 144a) studies, butis completely unstable with respect to Tl(III) and T1(I) the rate constant for the process 2T1(II) Tl(III) + T1(I), 2.3 x 10 liter mole sec , is in fact close to diffusion control of the reaction 17). 

Measurements of absolute rate constants for the reduction and oxidation of metal ions by e, H- and OH- has been a prominent achievement of the technique of pulse radiolysis. This subject is too broad to be included in this review and is to be dealt with later in the series. A key reference is given, however, to help cover the interim period. 

Packer, J.E., Willson, R.L., Hahnemann, D. and Asmus, K.-D. (1980). Electron transfer reactions of halogenated aliphatic peroxyl radicals measurements of absolute rate constants by pulse radiolysis. J. Chem. Soc. Perkins Transact. II, 296-299. 

Studies have been carried out on the methylated complex [H3C-Niin(17)(H20)]2+, which is obtained from the reaction of methyl radicals (generated by pulse radiolysis) with [Ni(17)]2+. The volumes of activation are consistent with the coherent formation of Ni—C and Ni—OH2 bonds, as expected for the generation of a Ni111 complex from a square planar Ni11 precursor.152 The kinetics of reactions of [H3C-Niin(17)(H20)] + involving homolysis, 02 insertion and methyl transfer to Crn(aq) have been determined, and intermediates have been considered relevant as models for biological systems.153 Comparing different alkyl radicals, rate constants for the... 

The bimolecular rate constants were determined (Burke 2001) for the repair of carotenoid radical cations by trolox, ascorbic, ferrulic, and uric acids from the pulse radiolysis studies of carotenoids in aqueous micellar solutions (see Table 14.10). 

By employing an extinction coefficient for the anion radical obtained from the pulse radiolysis experiments, the concentration of the radical could be calculated, and plotted against /c. The straight line plot so obtained was taken as strong evidence for the ECE mechanism, i.e. the solution phase attack of C02 on C02, thus fully resolving the controversy over the identity and state of the intermediate. From the slope of the plot the authors obtained the rate constant k2 as 7.5 x I03dm3mol 1 s 1. 

J. Rabani, W.A. Mulac, and M.S. Matheson, The pulse radiolysis of aqueous tetranitromethane. I. Rate constants and the extinction coefficient [absorptivity] of aq-. II. Oxygenated solutions. J. Phys. Chem. 69, 53-70 (1965). 

G. Gzapski and L.M. Dorfman, Pulse radiolysis studies. V. Transient spectra and rate constants in oxygenated aqueous solutions. J. Phys. Chem. 68, 1169-1177 (1964). 

One striking prediction of the energy gap law and eq. 11 and 14 is that in the inverted region, the electron transfer rate constant (kjjj. = ket) should decrease as the reaction becomes more favorable (lnknr -AE). Some evidence has been obtained for a fall-off in rate constants with increasing -AE (or -AG) for intermolecular reactions (21). Perhaps most notable is the pulse radiolysis data of Beitz and Miller (22). Nonetheless, the applicability of the energy gap law to intermolecular electron transfer in a detailed way has yet to be proven. 

Rate Constants for Reaction of Superoxide with Flavonoids and Related Compounds (Pulse-Radiolysis Experiments)... 

Bors et al. [175] determined the rate constants and equilibrium constants for the reactions of flavonoids with ascorbate (Reaction (18)) by a pulse-radiolysis method and on their basis calculated the one-electron oxidation potentials of flavonoids (Table 29.9). 

In this mechanism, RNO and RNO+ are nitroxide radical and its oxoammonium cation. The rate constants for Reactions (5) and (6) determined by pulse radiolysis are equal to ... 

Using basic pH leads to higher plateau rate constants, indicating that the ratedetermining step is reaction 18. Reaction 17 must be at least as fast as the rate of 02 addition in the highest 02 concentration used, kn 8 x 105 s 1, which is the limit of the instrument measurement. The G of benzene in pulse radiolysis was found to be equal to that of the nitroform anion (1.6 x 10-7 molJ-1) as can be expected from reactions 17-19. Since the yield of the cyclohexadienylperoxyl radical is 2.9 x 10-7 mol. 1 1 it means that only a fraction (ca 60%) of the cyclohexadienylperoxyl radicals eliminates HO2. The H02 elimination occurs by H-transfer of the allylic hydrogen to the oxygen... 

X = 0, CH2, CHCOOH, C(COOH)2, NH, NCH3 N(CH2CH=CH2), N(CHs)2 Cl Bobrowski and Das published a series of papers on the transients in the pulse radiolysis of retinyl polyenes31-37, due to their importance in a variety of biomolecular processes. They studied32 the kinetics and mechanisms of protonation reaction. The protons were released by pulse radiolysis, on a nanosecond time scale, of 2-propanol air-saturated solutions containing, in addition to the retinyl polyenes, also 0.5 M acetone and 0.2 M CCI4. Within less than 300 ns, the electron beam pulse results in formation of HC1. The protonated products of retinyl polyenes were found to absorb optically with Xmax at the range of 475-585 nm and were measured by this absorption. They found that the protonation rate constants of polyene s Schiff bases depend on the polyene chain... 

Bobrowski and Das33 studied the transient absorption phenomena observed in pulse radiolysis of several retinyl polyenes at submillimolar concentrations in acetone, n -hexane and 1,2-dichloroethane under conditions favourable for radical cation formation. The polyene radical cations are unreactive toward oxygen and are characterized by intense absorption with maxima at 575-635 nm. The peak of the absorption band was found to be almost independent of the functional group (aldehyde, alcohol, Schiff base ester, carboxylic acid). In acetone, the cations decay predominantly by first-order kinetics with half life times of 4-11 ps. The bimolecular rate constant for quenching of the radical cations by water, triethylamine and bromide ion in acetone are in the ranges (0.8-2) x 105, (0.3-2) x 108 and (3 — 5) x 1010 M 1 s 1, respectively. 

The generation of HO by pulse radiolysis provides a way for investigating the kinetics of hydroxyl spin adduct formation. For PBN and some of its 4-substituted derivatives (ranging from 4-MeO to 4-N02), rate constants in the range of (5-9) X 109 dm3 mol 1 s 1 were determined (Greenstock and Wiebe, 1982). A study of the reaction of the water-soluble 2-, 3- and 4-PyBN[23] and HO showed that most of the hydroxyl radicals became attached to the heteroaromatic ring (Neta et al., 1980 Sridhar et al., 1986). Similar findings... 

Dopamine (10) has also been the subject of some study. Maity and coworkers17 have studied the pulse radiolysis or /-irradiation induced reduction of the protonated form. In this instance the addition of an electron affords the radical anion 11 with a bimolecular rate constant for the reaction of 2.5 x 108 M-1 s-1. 

TMPD (k = 5.2 x 108 M 1s 1), p-diaminobenzene (k = 5 x 107 M 1s 1) and diphenylamine (k = lx 107 M 1 s 1) can all be readily converted into the corresponding radical cation by oxidation with pulse radiolysis generated SC>3 . With higher redox potential amines such as aniline and A. /V-dimethylandinc the oxidation to the radical cation fails32. Rate constants have also been measured for conversion of the same amines... 

Other important aromatic amines such as chlorpromazine (26) have also been subjected to oxidation studies using oxidants produced by pulse radiolysis. Typical among these is the use of chloroalkylperoxyl radicals formed by pulse radiolysis in a variety of solvents. These oxidants yield the corresponding radical cation. The rate constants (Table 3) for these reactions were determined42. Other studies have determined the reactivity between chlorpromazine and BiV- in H2O/DMSO in varying proportions. The rate constants for the formation of the radical cation of chlorpromazine were similar in value to those obtained from the peroxy radical reactions4. 

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