Radiation, radicals formed

The radiation sensitivity of a substrate is measured in terms of its GR value or free radical yield, which is the number of free radicals formed per 100 eV energy absorbed per gram. The highest grafting yields will occur for polymer monomer combinations in which the free radical yield of the polymer is much greater than for the monomer. It also follows that the grafting yield will increase at a lower monomer concentration. 

The radiation sensitivity of polymers and monomers is characterized by a G value the number of radicals formed per 100 e.v. (16 aJ) absorbed. Radiation sensitive groups include -COOH, C-halogen, -S02-, -NH2 and -C=C, Radiation resistant groups are aromatic rings. It appears that the presence of aromatic moieties also offers some degree of radiation protection to the polymer chain as a whole. 

The chlorine-containing product species (HCl, CIONO2, HOCl) are "inert reservoirs" because they are not directly involved in ozone depletion however, they eventually break down by absorbing solar radiation or by reaction with other free radicals, returning chlorine to its catalytically active form. Ozone is formed fastest in the upper stratosphere at tropical latitudes (by reactions 1 and 2), and in those regions a few percent of the chlorine is in its active "free radical" form the rest is in the "inert reservoir" form (see Figure 3). 

Evidence indicates [28,29] that in most cases, for organic materials, the predominant intermediate in radiation chemistry is the free radical. It is only the highly localized concentrations of radicals formed by radiation, compared to those formed by other means, that can make recombination more favored compared with other possible radical reactions involving other species present in the polymer [30]. Also, the mobility of the radicals in solid polymers is much less than that of radicals in the liquid or gas phase with the result that the radical lifetimes in polymers can be very long (i.e., minutes, days, weeks, or longer at room temperature). The fate of long-lived radicals in irradiated polymers has been extensively studied by electron-spin resonance and UV spectroscopy, especially in the case of allyl or polyene radicals [30-32]. 

The kinetics of the various reactions have been explored in detail using large-volume chambers that can be used to simulate reactions in the troposphere. They have frequently used hydroxyl radicals formed by photolysis of methyl (or ethyl) nitrite, with the addition of NO to inhibit photolysis of NO2. This would result in the formation of 0( P) atoms, and subsequent reaction with Oj would produce ozone, and hence NO3 radicals from NOj. Nitrate radicals are produced by the thermal decomposition of NjOj, and in experiments with O3, a scavenger for hydroxyl radicals is added. Details of the different experimental procedures for the measurement of absolute and relative rates have been summarized, and attention drawn to the often considerable spread of values for experiments carried out at room temperature (-298 K) (Atkinson 1986). It should be emphasized that in the real troposphere, both the rates—and possibly the products—of transformation will be determined by seasonal differences both in temperature and the intensity of solar radiation. These are determined both by latitude and altitude. 

Radiolysis Effects. Radicals formed in solvent (SH) and trunk polymers (PH) are important in the grafting of monomers (MH) with gamma radiation. With polymers such as polyethylene, grafting sites are formed by direct bond rupture (Equation 1). Additional sites are also... 

Some time ago, an allyl-like radical was observed in irradiated crystals of 5 -dCMP [26]. This radical was thought to be a sugar radical, although no likely scheme was proposed for its formation. It now appears that this radical is formed on 5-methyl cytosine impurities in these crystals [27]. This radical forms by deprotonation at the methyl group of the cytosine cation, 5meCyt(Me—H) , and may have important consequences in the radiation chemistry of DNA since the ionization potential of 5-methyl cytosine is lower than that of either cytosine or thymine. 

Chemical and biological effects of ionizing radiation are thought to occur through two main mechanisms direct interaction of the radiation with food components and living cells in materials exposed to it, and indirect action from radiolytic products, such as the radicals formed from water molecules (see Chap. 12). 

Hutchinson, F. (1957). The distance that a radical formed by ionizing radiation and diffuse in a yeast cell. Radiat. Res. 7, 473-483. 

In addition to ESR spectroscopy, which is a general method for detecting radicals, Dole et al. (9, 10, 11, 12) have developed a method of ultraviolet spectroscopy at low temperatures, which is specific for allylic and polyenylic radicals. Numerous papers have dealt with changes in polymers on irradiation, and all of these conclude that the reactions, in one way or another, arise from the formation of free radicals. Only a few papers describe experiments in which the radicals have been observed directly by ESR or ultraviolet spectroscopy at low temperatures. This article merely summarizes the present knowledge of the nature of radicals formed in polyolefins by irradiation in vacuum (ionizing radiation and ultraviolet light) and discusses some new trends in studying these radicals. 

Polyethylene. Polyethylene is without doubt the polymer which has been studied most extensively by ESR spectroscopy. The irradiation has been carried out with all sorts of high energy radiation at different temperatures, in vacuo, and under air or other gases. Since reviews of this subject exist (19, 36), a comprehensive discussion of the radicals formed is not attempted, and emphasis is given here only to the more recent advances. From the reviews (19, 35) it is evident that the spectra mainly observed are caused by three different radicals. 

Polypropylene. In the reported studies of radicals formed in polypropylene by ionizing radiation, several different radical structures have been proposed—i.e., V to IX—but no agreement has been reached so far (13, 14, 28, 30, 31, 37, 41, 49, 50). Almost all ESR spectra seem to have an even number of lines, which is possible with all the radical structures proposed here. 

Although it is well established that polyisobutylene degrades under radiation, the main-chain scission radicals were never observed as primary radicals in any of these ESR studies. A possible explanation is that the two free radicals formed by chain scission are unable to migrate from the reaction site. The two end-group radicals are then likely to react with each other by either recombination or disproportionation. 

Poly (4-methyl-1-pentene). Poly(4-methyl-l-pentene) has not yet drawn much attention in radiation chemistry. As far as we know, only one study on high energy-irradiated poly(4-methyl-l-pentene) has been published (25), and this was in the form of a short communication. The ESR spectrum at liquid nitrogen temperature was a sextet with a hyper-fine splitting constant of 23 gauss. The radicals producing this spectrum were supposed to have structure XXI—i.e., radicals formed by side-chain scission. 

The poly (amino acid)s with aromatic side chains behave somewhat differently. In poly(phenylalanine) the a-carbon radical is the major radical species observed, but radicals formed by hydrogen atom addition to the ring are also found. Benzyl radicals formed by side-chain cleavage are present, but only in very low yield. In poly (tyrosine) the only radical species observed is the tyrosyl phenoxyl radical formed by loss of the hydroxyl hydrogen. There is no evidence for formation of significant concentrations of a-carbon radicals. Thus, the nature of the substituents can strongly influence the radiation sensitivity of the backbone chain. 

---