Radiation-Induced Methods

Three types of radiation-induced procedures have been used including (a) recoil tritiation, (b) Wilzbach gas irradiation7 with its modifications, and (c) radiation synthesis.8 All these methods utilize high-energy ionizing radiation to achieve tritium incorporation. Wilzbach exchange7 is the most satisfactory of the three and has been the most widely used. Radiation synthesis is a relatively recent development of limited but valuable specificity. 

For tritiating heterocyclic compounds the recoil method has been used to label nicotinic acid (l)11-18 and also reserpine.14,15 

Technically, any organic molecule containing a C-H bond can be labeled in one step by this procedure7 which involves exposure of an organic compound to tritium gas. The (8 radiation from the tritium 

The main limitation of the technique is the problem of achieving radiochemical, as distinct from chemical, purification of the final labeled product. Purification of the irradiated sample is necessary to remove radiation-induced degradation products and labile tritium. Many of the degradation products are not only chemically similar to the parent compound, but also possess much higher specific activities. For complete purification it is necessary to use multistage processes, such as gas and column chromatography, countercurrent distribution, and fractional distillation. Distribution of isotope within a molecule is generally random and nonuniform however, in some circumstances useful specificity can be achieved.17 

Although organic gases can be labeled by the present technique, for heterocyclic systems the most useful application is in condensed phases. Under these conditions, three principal mechanisms have been proposed.18-20 

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The radiation-induced method, in the y- or pulse regime [19,20] and, to a certain extent, the photo-induced method [21], provide a particularly powerful means to produce in condensed media, metal, and semiconductor clusters from monomers as precursors, to study their properties and to understand the exotic phenomena which occur whenever a new phase of oligomeric particles is formed in the bulk of a homogeneous mother phase [22-26], phenomena which are therefore rather frequent in physics and chemistry. Unlike a recent review concerning semiconductor clusters [19], the present chapter is specifically focused on metal clusters, induced by ionizing radiation or ultraviolet (UV)-visible photons. 

The radiation-induced method, in the y- or pulse regime, provides a particularly powerful means to understand the exotic phenomena which occur any time a new phase of oligomeric particles is formed in the bulk of a homogeneous mother phase, phenomena which are thus rather frequent in physics and chemistry. 

Isocyanates polymerize through the carbon-to-nitrogen double bonds by anionic mechanism. Reactions can be catalyzed by sodium or potassium cyanide at-58 °C. N,N -dimethylformamide is a good solvent for this reaction. Other anionic catalysts, ranging from alkali salts of various carboxylic acids to sodium-naphthalene, are also effective. In addition, polymerizations can be carried out by cationic, thermal, and radiation-induced methods. 

Over a wide range of monomer mixtures and using typical free-radical initiators or radiation-induced methods, a-methylstyrene 73 (R = CH3, X = none) will copolymerize with MA to give 1 1 alternating materials. Copolymerizations may occur even without... 

The production of tritium-labelled organic compounds was enormously facilitated by K. E. Wilz-bach s discovery in 1956 that tritium could be introduced merely by storing a compound under tritium gas for a few days or weeks the radiation induces exchange reactions between the hydrogen atoms in the compound and the tritium gas. The excess of gas is recovered for further use and the tritiated compound is purified chro-matographically. Another widely used method of... 

The creation of active sites as well as the graft polymerization of monomers may be carried out by using radiation procedures or free-radical initiators. This review is not devoted to the consideration of polymerization mechanisms on the surfaces of porous solids. Such information is presented in a number of excellent reviews [66-68]. However, it is necessary to focus attention on those peculiarities of polymerization that result in the formation of chromatographic sorbents. In spite of numerous publications devoted to problems of composite materials produced by means of polymerization techniques, articles concerning chromatographic sorbents are scarce. As mentioned above, there are two principle processes of sorbent preparation by graft polymerization radiation-induced polymerization or polymerization by radical initiators. We will also pay attention to advantages and deficiencies of the methods. 

Radiation-induced modification or processing of a polymer is a relatively sophisticated method than conventional thermal and chemical processes. The radiation-induced changes in polymer materials such as plastics or elastomers provide some desirable combinations of physical and chemical properties in the end product. Radiation can be applied to various industrial processes involving polymerization, cross-linking, graft copolymerization, curing of paints and coatings, etc. 

Radiation Treatment NVP, 2-hydroxyethylmethacrylate (HEMA), and acrylamide (AAm) have been grafted to the surface of ethylene-propylene-diene monomer (EPDM) rubber vulcanizates using the radiation method (from a Co 7 source) to alter surface properties such as wettability and therefore biocompatibility [197]. Poncin-Epaillard et al. [198] have reported the modification of isotactic PP surface by EB and grafting of AA onto the activated polymer. Radiation-induced grafting of acrylamide onto PE is very important... 

Radiation Induced Reactions. Graft polymers have been prepared from poly(vinyl alcohol) by the irradiation of the polymer-monomer system and some other methods. The grafted side chains reported include acrylamide, acrylic acid, acrylonitrile, ethyl acrylate, ethylene, ethyl methacrylate, methyl methacrylate, styrene, vinyl acetate, vinyl chloride, vinyl pyridine and vinyl pyrrolidone (13). Poly(vinyl alcohols) with grafted methyl methacrylate and sometimes methyl acrylate have been studied as membranes for hemodialysis (14). Graft polymers consisting of 50% poly(vinyl alcohol), 25% poly(vinyl acetate) and 25% grafted ethylene oxide units can be used to prepare capsule cases for drugs which do not require any additional plasticizers (15). 

Elastin-mimetic protein polymers have been fabricated into elastic networks primarily via y-radiation-induced, radical crosslinking of the material in the coacervate state [10]. Although effective, this method cannot produce polymers gels of defined molecular architecture, i.e., specific crosslink position and density, due to the lack of chemoselectivity in radical reactions. In addition, the ionizing radiation employed in this technique can cause material damage, and the reproducibility of specimen preparations may vary between different batches of material. In contrast, the e-amino groups of the lysine residues in polymers based on Lys-25 can be chemically crosslinked under controllable conditions into synthetic protein networks (vide infra). Elastic networks based on Lys-25 should contain crosslinks at well-defined position and density, determined by the sequence of the repeat, in the limit of complete substitution of the amino groups. 

Of course other methods of radiation enhancement may take place with reoxygenation of hypoxic tumor cells that may be increased with the use of chemotherapies like paclitaxel or gemcitabine (41,42), improved drug access to the tumor cells after radiotherapy, or a lowering of the threshold for radiation-induced apoptosis as has been described with the use of gemcitabine (43). 

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