Gudkov Sergey V, Astashev Maxim E, Bruskov Vadim I, Kozlov Valeriy А, Zakharov Stanislav D, Bunkin Nikolai F
Institute of Theoretical and Experimental Biophysics, Russian Academy of Sciences, Pushchino, Institutskaya 3, Moscow Region, 142290, Russia.
Pushchino State Natural Scientific Institute Pushchino, Nauki prospekt 1, Moscow Region, 142290, Russia.
Entropy (Basel). 2014 Nov 21;16(11):6166-6185. doi: 10.3390/e16116166.
Samples of water inside and outside an exclusion zone (EZ), created by Nafion swollen in water, were irradiated at the wavelength l = 1264 nm, which stimulates the electronic transition of dissolved oxygen from the triplet state to the excited singlet state. This irradiation induces, after a long latent period, chemiluminescence self-oscillations in the visible and near UV spectral range, which last many hours. It occurs that this effect is EZ-specific: the chemiluminescence intensity is twice lower than that from the bulk water, while the latent period is longer for the EZ. Laser irradiation causes accumulation of HO, which is also EZ-specific: its concentration inside the EZ is less than that in the bulk water. These phenomena can be interpreted in terms of a model of decreasing O content in the EZ due to increased chemical activity of bisulfite anions (HSO), arisen as the result of dissociation of terminal sulfonate groups of the Nafion. The wavelet transform analysis of the chemiluminescence intensity from the EZ and the bulk water gives, that self-oscillations regimes occurring in the liquid after the latent period are the determinate processes. It occurred that the chemiluminescence dynamics in case of EZ is characterized by a single-frequency self-oscillating regime, whereas in case of the bulk water, the self-oscillation spectrum consists of three spectral bands.
对由在水中溶胀的全氟磺酸膜形成的禁区(EZ)内外的水样,在波长λ = 1264 nm下进行辐照,该波长能激发溶解氧从三重态到激发单重态的电子跃迁。这种辐照在经过很长的潜伏期后,会在可见光和近紫外光谱范围内引发化学发光自振荡,且持续数小时。结果发现这种效应是EZ特有的:化学发光强度比本体水低两倍,而EZ的潜伏期更长。激光辐照会导致羟基自由基(HO)的积累,这也是EZ特有的:其在EZ内的浓度低于本体水中的浓度。这些现象可以用一个模型来解释,即由于全氟磺酸末端磺酸根基团解离产生的亚硫酸氢根阴离子(HSO)化学活性增加,导致EZ中氧含量降低。对EZ和本体水的化学发光强度进行小波变换分析表明,潜伏期后液体中出现的自振荡状态是确定性过程。结果发现,EZ情况下的化学发光动力学以单频自振荡状态为特征,而在本体水的情况下,自振荡光谱由三个光谱带组成。