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Abstract  

The terpenes α-(+)-pinene, and α-(−)pinene have been radiolyzed at radiation doses of 150, 300 and 600 kGy. The radiolyzed samples have been analyzed by FT-IR spectroscopy and polarimetry. Both α-(+)-, α-(−)-pinenes show a linear trend to radioracemization as a function of the radiation dose administered ≈2.5·10−3 [α]D/kGy. The solvent fractionation and the liquid chromatographic analysis (HPLC) of the radiolyzed samples shows that both α-pinene enantiomers produce ocimene and dipentene together with minor quantities of other products and a resin. The kinetics of α-pinene decomposition under radiolytic conditions can be described by a pseudofirst order rate constant k∼5.3·10−7s−1 while the radiation chemical yield for the same reaction has a G = 5.0 molecules/100 eV, so that about 30% of the original α-pinene is converted into other products at 600 kGy.

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The degradation of a mixture of 18 different polycyclic aromatic hydrocarbons (PAHs) has been studied in acetonitrile solution by usingg-radiation at radiation doses of 100, 200 and 300 kGy. The mixture of radiolyzed PAHs was analyzed by liquid chromatography (HPLC) using a diode array detector. Radiolysis at 100 kGy total dose is already sufficient to cause the complete disappearance of all PAHs with the exception of fluorene and crysene which still survive in small amounts. They are known to be among the most radiation-resistant PAHs and can be completely eliminated from the radiolyzed solution by a treatment with ozone. Alternatively higher radiation dose (200 kGy) is needed to eliminate fluorene and crysene completely from the acetonitrile solution. PAHs can be degraded completely with an excess of ozone but the distribution of products is of course different from that obtained by radiolysis and radiolysis followed by ozonolysis.

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Abstract  

The radiolysis of β(−)pinene has been studied at five different radiation dose, namely at 50, 100, 150, 300 and 600 kGy with a dose rate of 2.2 kGy/h. At lower radiation dose, β(−)pinene showed a reduction of the optical activity, hence, the expected radioracemization appeared predominant. At higher radiation dose, an opposite and unexpected trend was observed: the optical activity increased almost linearly with the radiation dose. The increase of [α]D of radiolyzed β(−)pinene was due to the formation oligomers, mainly a dimer and/or a trimer of β(−)pinene which remain soluble in the monomer but which displayed a higher optical activity than the starting monomer, contributing to the increase in the specific optical rotation. Simultaneously to the formation of the dimer/trimer the radiolysis of β(−)pinene induced also its polymerization into a poly(β(−)pinene) resin which was insoluble in the monomer and which was characterized by a high structural order and by the preservation of the chiral centers so that it showed an enhanced specific optical rotation which is ≈2 times that of the monomer. It is shown that poly(β(−)pinene) radiopolymer can be easily racemized in presence of a Friedel-Crafts catalyst. The kinetics of β(−)pinene radiation-induced oligomerization and polymerization can be described by a pseudofirst order rate constant k = 1.9·10−7·s−1. The radiation chemical yield for the same reaction is G = 1.93·10−6 mol/J. The work shows that also the radiation-induced polymerization of chiral monomers may be a tool for the preservation and amplification of the optical activity of the monomer with implications for abiotic mechanisms of chiral amplification.

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Abstract  

A relatively heavy petroleum fraction called distillate aromatic extract (DAE) which has been proposed to be the carrier of the emission bands of certain astronomical objects like protoplanetary nebulae (PPNe) and the so-called unidentified infrared bands (UIBs), has been radiolyzed with -radiation to a total dose of 1 MGy. The stability of DAE toward radiation was assessed by FT-IR and electronic spectroscopy. The gases produced during radiolysis have been identified by GC. They were essentially H2 and CH4. A certain degree of crosslinking has been verified on the radiation-processed material by measuring the hexane insoluble fraction of DAE, which increased dramatically after the radiation treatment. Further analyses were conducted using high performance liquid chromatography (HPLC) on the radiation processed sample in comparison to the pristine sample.

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Abstract  

Anthracite coal and oil bitumen were submitted to γ-radiation at a total dose of 1 MGy and the radiation-processed samples were studied by FT-IR spectroscopy, thermogravimetric analysis (TGA) and differential thermal analysis (DTA). The coal samples were studied also by TGA coupled with FT-IR spectroscopy of the evolved gases. Thermal analysis has revealed a completely different behavior of the radiolyzed samples in comparison to the unirradiated samples. Both for coal and bitumen significantly less volatile fraction was released during the TGA and in both cases a significant increase in the amount of carbon coke produced at 800-900 °C was observed. The radiation processed bitumen increased significantly its ethyl acetate insolubles content. These results were interpreted in terms of extensive crosslinking and coalification of the samples under the action of γ-radiation. The results of this study have been applied to the carbonization process of terrestrial sedimentary organic matter which is commonly attributed to the action of heat flux from the depth of the Earth but which may be also due to the action of natural radiation. Other application of the results of the present study is to the complex organic matter present on the surfaces of comets and meteorites. This complex matter was formed by exposure of simple precursors to a field of high energy radiation for millions or billions of years and is consequently transformed into coal-like and bitumen-like matter. The same arguments apply to the carbon grains present in the interstellar and circumstellar medium.

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Abstract  

Three isomeric chiral terpenes, R(+)-limonene, S(-)-limonene and R(-)-a-phellandrene were γ-radiolyzed in sealed vials at room temperature with a total radiation dose of 317 kGy. The radiolyzed samples were analyzed by FT-IR, electronic absorption spectroscopy, liquid chromatography using a diode-array detector (HPLC-DAD) and by polarimetry. Despite a relatively high radiation dose used, all the chiral molecules selected have shown a low radioracemization rate. This fact and the role played by the impurities in the selective radio-degradation of one of the two enantiomers has been discussed in the context of the origin of chirality in prebiotic molecules and the chirality enhancement in a prebiotic world. The results were also discussed in the frame of the radiosterilization technique of chiral drugs, perfumes and food components.

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Abstract  

Triazines are a class of molecules which have been found in meteorites such as Orgueil meteorite. Despite their poor resistance to UV radiation, these molecules survived millions of years inside a meteorite. The present work is dedicated to the examination of the radiation resistance of the simplest sym-triazine: 1,3,5-triazine. The crystals of this molecule have been irradiated with γ-radiation at 50 and 350 kGy and were studied by electronic absorption spectroscopy, liquid chromatography, FT-IR spectroscopy and differential scanning calorimetry (DSC). All the data suggest the relatively low stability of this molecule to high energy radiation. The resulting products from radiolysis are formamidine together with triazine dimers and oligomers. Other radiolysis products are H2, CH4, HCN and other gases.

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Abstract  

Isoprene polymerizes under the action of γ-radiation from a 60Co source yielding a low molecular weight polyisoprene which remains soluble in the unreacted monomer. The electronic absorption spectrum of polyisoprene oligomer in isoprene monomer has been explained using squalene, a polyisoprene hexamer, as model compound. The radiation chemical yield for polyisoprene formation has been estimated from both gravimetric and spectrophotometric data pertaining the amount of polymer formed. An average G value of 35 molecules/100 eV has been determined suggesting that the polymerization mechanism involves free radicals. The chemical structure of the resulting polyisoprene radio-oligomer has been determined by FT-IR spectroscopy and found identical to that of a reference polyisoprene sample prepared by a chemically-initiated free radical polymerization process. The structure determination by FT-IR spectroscopy has been reported in detail.

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Abstract  

Poly(dimethylbutadiene) (PDMB) was synthesized through the inclusion polymerization technique, by γ-irradiation of a clathrate of 2,3-dimethyl-1,3-butadiene in deoxycholic acid (DOCA) at 75, 150, 320 and 430 kGy. The resulting inclusion complexes PDMB@DOCA were studied by FTIR spectroscopy and by thermal analysis (DTA, TGA and DTG). Pure PDMB was isolated by extracting the complex PDMB@DOCA with ethanol. The best sample in terms of purity was that prepared at 75 kGy, while the other samples prepared at higher doses suffered of DOCA grafting on PDMB chains. Pure PDMB isolated from PDMB@DOCA complex was studied by FT-IR spectroscopy and by thermal analysis in comparison to a reference highly crystalline and ≈=100% trans-1,4-PDMB prepared by inclusion polymerization in thiourea and in comparison to PDMB prepared by emulsion polymerization. A lower degree of regularity and crystallinity has been found on the PDMB sample prepared as inclusion compound in DOCA in comparison to the reference PDMB obtained by inclusion polymerization in thiourea.

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Abstract  

C60 fullerene was radiolyzed in toluene solution both in presence of air and in vacuum at four different radiation doses 12, 24, 36, 48 and 96 kGy. Clear evidences of the addition of benzyl radicals to the fullerene cage derive from FT-IR and C13-NMR spectra of the reaction product. In presence of air the interference of oxygen is evident in the FT-IR spectra and from the elemental analysis. A detailed analysis of the kinetics of the multiple addition of benzyl radicals to the fullerene cage was made spectrophotometrically with the determination of the addition rate constants at the each addition step and the average number of benzyl groups added to the fullerene cage as function of the radiation dose.

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