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Radiation-Induced Chemical Reactions in Hydrogel of Hydroxypropyl Cellulose (HPC): A Pulse Radiolysis Study

机译:羟丙基纤维素(HPC)水凝胶中辐射诱导的化学反应:脉冲辐解研究

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摘要

We performed studies on pulse radiolysis of highly transparent and shape-stable hydrogels of hydroxypropyl cellulose (HPC) that were prepared using a radiation-crosslinking technique. Several fundamental aspects of radiation-induced chemical reactions in the hydrogels were investigated. With radiation doses less than 1 kGy, degradation of the HPC matrix was not observed. The rate constants of the HPC composing the matrix, with two water decomposition radicals [hydroxyl radical ((OH)-O-center dot) and hydrated electron (e(aq)(-))] in the gels, were determined to be 4.5 x 10(9) and 1.8 x 10(7) M-1 s(-1), respectively. Direct ionization of HPC in the matrix slightly increased the initial yield of e(aq)(-), but the additionally produced amount of e(aq)(-) disappeared immediately within 200 ps, indicating fast recombination of e(aq)(-) with hole radicals on HPC or on surrounding hydration water molecules. Reactions of e(aq)(-) with nitrous oxide (N2O) and nitromethane (CH3NO2) were also examined. Decay of e(aq)(-) due to scavenging by N2O and CH3NO2 were both slower in hydrogels than in aqueous solutions, showing slower diffusions of the reactants in the gel matrix. The degree of decrease in the decay rate was more effective for N2O than for CH3NO2, revealing lower solubility of N2O in gel than in water. It is known that in viscous solvents, such as ethylene glycol, CH3NO2 exhibits a transient effect, which is a fast reaction over the contact distance of reactants and occurs without diffusions of reactants. However, such an effect was not observed in the hydrogel used in the current study. In addition, the initial yield of e(aq)(-), which is affected by the amount of the scavenged precursor of e(aq)(-), in hydrogel containing N2O was slightly higher than that in water containing N2O, and the same tendency was found for CH3NO2. (C) 2016 by Radiation Research Society
机译:我们对使用辐射交联技术制备的高度透明且形状稳定的羟丙基纤维素(HPC)的水凝胶进行脉冲辐解进行了研究。研究了水凝胶中辐射诱导的化学反应的几个基本方面。辐射剂量小于1 kGy时,未观察到HPC基质的降解。确定在凝胶中具有两个水分解自由基[羟基自由基((OH)-O-中心点)和水合电子(e(aq)(-))]的HPC的速率常数为4.5 x 10(9)和1.8 x 10(7)M-1 s(-1)。 HPC在基质中的直接电离稍微增加了e(aq)(-)的初始产率,但额外产生的e(aq)(-)量在200 ps内立即消失,表明e(aq)(-)的快速重组)在HPC或周围的水合水分子上带有空穴自由基。还检查了e(aq)(-)与一氧化二氮(N2O)和硝基甲烷(CH3NO2)的反应。在水凝胶中,由于被N2O和CH3NO2清除,e(aq)(-)的衰减都比水溶液中的慢,这表明反应物在凝胶基质中的扩散较慢。衰减速率的降低程度对N2O而言比对CH3NO2更为有效,这表明N2O在凝胶中的溶解度低于在水中的溶解度。已知在粘性溶剂如乙二醇中,CH 3 NO 2表现出瞬时作用,其在反应物的接触距离上是快速反应,并且在没有反应物扩散的情况下发生。但是,在当前研究中使用的水凝胶中未观察到这种作用。此外,在含N2O的水凝胶中,受e(aq)(-)清除的前体的量影响的e(aq)(-)的初始产率略高于在含N2O的水中的产率。对于CH 3 NO 2也发现了相同的趋势。 (C)放射研究学会2016年

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