Radiolysis detection

Fig. 5. Schematic of a computer-aided pulse radiolysis detection apparatus.

The overall time resolution 8t of a picosecond pulse radiolysis detection system is approximately expressed as ... 

Pulse-probe pulse radiolysis detection techniques are very powerful, however to obtain kinetic profiles of fast reactions they all rely to... 

Many experimental methods may be distinguished by whether and how they achieve time resolution—directly or indirectly. Indirect methods avoid the requirement for fast detection methods, either by detemiining relative rates from product yields or by transfonuing from the time axis to another coordinate, for example the distance or flow rate in flow tubes. Direct methods include (laser-) flash photolysis [27], pulse radiolysis [28]... 

In addition to the stable I2O5 and moderately stable I4O9 and I2O4, several short-lived radicals have been detected and characterized during y-radiolysis and flash photolysis of iodates in aqueous alkali ... 

UV photolysis [958] of NH Os yields N20, H20, N2, 02, and traces of NO, while the same products, with the exception of 02 were detected in gases evolved during 7-radiolysis [959]. No N02 was detected in the irradiated salt. 

Veltwisch and colleagues45 studied the reaction of OH with several sulfoxides by pulse radiolysis using electrical conductivity for the detection of formation or disappearance of ions. Pulse radio lysis of N20-saturated aqueous solution of DMSO (10-3m) leads to a decrease in conductivity at basic pH (pH = 9.0) and an increase in conductivity at acidic pH (pH = 4.4). This is explained by the reactions... 

They measured the formation of ionic species in the pulse radiolysis of a 10"3 m MTMSO aqueous solution saturated by N20 gas at pH 5.6 by conductivity detection and found an increase in conductivity. Assuming the molar conductivity of CH3SCH2S02 to be the same as that measured for CH3S02- 45, it is found that G(CH3SCH2S02") = 2.7. 

In the radiolysis of diphenyl sulfone, the yield of S02 shows marked deviation from linearity as a function of the dose. For higher doses it appears that S02 yield is 2-3 times less than the biphenyl yield of 0.05. The authors suggested that not all of the S02 was detected and that a significant amount was trapped in the irradiated crystals. After... 

In dibenzothiophene-S,S-dioxide the S atom is in a ring, and hence more constrained. The yield of SOz in the radiolysis is linear with the dose to about 13 Mrad after which it levels off as in p,p -ditolyI sulfone. However, the yield of S02 in this case is much lower (a factor of 25) than in the case of p,p -ditolyl sulfone (G = 0.002 compared to G = 0.05). This stability of the dibenzothiophene sulfone could be partially due to back reaction to reform the parent sulfone and partially due to more efficient energy delocalization. The expected biphenylene product was not detected due to limitations of the analytical method. Bowmer and O Donnell70 studied the volatile products in y-radiolysis of dialkyl, alkyl aryl and diaryl sulfones. Table 2 gives the radiolytic yields of S02 and of the hydrocarbon products of the alkyl or aryl radicals. The hydrocarbon products are those obtained either by H atom abstraction or by radical combination. The authors69 suggested the mechanism... 

As seen before, the radical cation of dimethyl sulfoxide (CH3)2SO has been detected by ESR spectroscopy among other radicals when DMSO glasses at 77 K are submitted to y-irradiation28. It has also been reported in pulse radiolysis experiments30 (Table 6). Constant current electrochemical oxidation of bis(dialkylamino)sulfoxides (R2N)2SO gives rise to radical cations which have been detected by ESR spectroscopy33. 

Field and Lampe (23) established the occurrence of the hydride transfer reaction in the gas phase in 1958 by detecting secondary ions of mass one unit lower than the parent compound. Subsequently, Futrell (24, 25) attempted to account for most lower hydrocarbon products formed in the radiolysis of hexane and pentane by assuming that hydride transfer reactions play a dominant role in radiolysis. More recently, Ausloos and Lias (2) presented experimental evidence which indicated that some of the products in the radiolysis of propane are, in... 

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). 

It is pertinent that S20g accepts an electron generated by pulse radiolysis of water to give optically detectable S04 within 1.5 x 10 sec . ... 

A precursor of the studies on electron transfer reactions between short-lived radicals and colloidal particles was the development of a fast pulse radiolysis method to measure. the polarograms of radicals in the 10 s range . After considerable information had been acquired about the electron transfer reactions of a few dozen radicals at the mercury electrode, this compact electrode was replaced by metal colloids somewhat later, by semiconductor colloids These studies led to the detection of the electron-storing properties of certain colloids and of reactions of the stored electrons. 

Grootveld et al. (1994) employed this technique to investigate radiolytic, damage to biomolecules present in human body fluids. 7-Radiolysis of healthy or rheumatoid human serum (5.00 kGy) in the presence of atmospheric O2 gave rise to reproducible elevations in the concentration of NMR-detectable acetate, which are predominantly ascribable to the prior oxidation of lactate to pyruvate by OH radical followed by oxidative decarboxylation of pyruvate by radiolytically generated H2O2 and/or further OH radicals (Equations 1.7 and 1.8). 

Typical spectra obtained are shown in Fig. 1.2. Moreover, substantial radiolytically-mediated elevations in the concentration of serum formate, arising from the oxidation of carbohydrates present by OH radical, were also detectable. In addition to the above modifications, 7-radiolysis of inflammatory knee-joint synovial fluid generated an oligosaccharide species of low molecular mass derived from the radiolytic fragmentation of hyaluronate as outlined in the previous section dealing with oxidative damage to carbohydrates. The... 

A very interesting technique for radical generation is flash photolysis, which employs a very intense pulse of radiation (visible or u.v.) of very short duration. This produces a very high immediate concentration of radicals, which may be detected—and whose fate may be followed—by spectroscopy through one or more subsequent pulses of lower intensity radiation of suitable wavelength. This is, of course, primarily a technique for the study of radicals rather than for their use in preparative procedures. Radicals may also be generated, in suitable cases, by irradiation of neutral molecules with X-rays or with y-rays radiolysis. 

The radical cations of urazole-annelated azoalkanes 65 were generated by pulse radiolysis and the transients characterized spectrally and kinetically by time-resolved optical monitoring. The initial distonic 1,3 radical cations 66 were detected, and the methyl-substituted 66 further deprotonates to radical 67 (Scheme 1) <1997JA10673>. 

Group VIA (Cr, Mo, W). y-Radiolysis studies have been carried out for the simple hexacarbonyls (31,32) and for certain carbonyl iodides (33) and cyclopentadienyl carbonyl iodides (34). In the case of the hexacarbonyls (31,32), two free-radical products have been detected and characterized for Cr(C0)6, weak unidentified EPR signals have been observed for Mo(C0)6, but irradiated W(C0)6 apparently contains no detectable paramagnetic centres. 

Another intermediate in the radiolysis of iron carbonyls is probably Fe(C0)4, a species which has been detected by infra-red spectroscopy (55) and by magnetic circular dichroism (56). Observation by the latter technique implies a triplet electronic ground-state for the radical, yet it has eluded detection by EPR in spite of careful searches from 0 to 25 kG at X-band (32). 

Perhaps the most fruitful of these studies was the radiolysis of HCo(C0)4 in a Kr matrix (61,62). Free radicals detected in the irradiated material corresponded to processes of H-Co fission, electron capture, H-atom additions and clustering. Initial examination at 77 K or lower temperatures revealed the presence of two radicals, Co(C0)4 and HCo(C0)4 , having similar geometries (IV and V) and electronic structures. Both have practically all of the unpaired spin-density confined to nuclei located on the three-fold axis, in Co 3dz2, C 2s or H Is orbitals. Under certain conditions, a radical product of hydrogen-atom addition, H2Co(C0)3, was observed this species is believed to have a distorted trigonal bipyramidal structure in which the H-atoms occupy apical positions. 

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