Photodegradation in Encapsulated Silole‐Based Polymer: PCBM Solar Cells Investigated using Transient Absorption Spectroscopy and Charge Extraction Measurements

Light induced degradation has been observed in the performance of organic solar cells in the absence of oxygen and a detailed analysis of the effect of this photodegradation on optical and electrical features has been accomplished. This photodegradation study has been performed on encapsulated photovoltaic blend devices comprised of the silole‐based donor–acceptor polymer KP115 blended with [6,6]‐phenyl C61‐butyric acid methyl ester (PCBM). Photodegradation induces an almost 20% decrease in power conversion efficiency, primarily as a result of a reduction in short circuit current, J_SC. The initial burn‐in phase of the photodegradation has been examined using a combination of transient absorption spectroscopy and charge extraction measurements, including photo‐CELIV (charge extraction by linearly increasing voltage) and time‐resolved charge extraction using a nanosecond switch. These measurements reveal a bimodal KP115 polaron population, comprised of both delocalised and localised/trapped charge carriers. The photodegradation results are consistent with an alteration of this bimodal KP115 polaron population, with the polarons becoming trapped in a broader, deeper density of localised states. Under laser illumination and at open circuit conditions, this enhanced trapping after light soaking inhibits charges from undergoing bimolecular recombination, leading to higher extracted charge densities at long times. At the lower charge densities operating at short circuit conditions and under continuous white light illumination, where bimolecular recombination is much less significant, the J_SC decreases after light soaking due to a reduction in the efficiency of trapped charge carrier extraction.     

光降解在凋落物分解中的作用

近年来,越来越多的研究者认识到光降解可能在凋落物分解中发挥着重要作用.本文对光降解的作用机制,光降解在碳循环、养分循环中的作用,光降解与微生物分解的关系,以及影响光降解的因素进行了综述.光降解对凋落物分解过程同时具有正效应和负效应,正效应指光降解通过氧化有机质,或是改变凋落物自身理化性质使其更易淋溶和分解,负效应指高光辐射对分解者产生不利影响从而押制微生物分解.在光降解过程中光化学矿化产生CO2是生态系统碳流失的主要机制.除紫外光外,可见光中的蓝、绿光波段也对凋落物的降解产生影响.光降解作用的大小受到水分状况、凋落物化学性质和凋落物的暴露面积的影响.最后,讨论了该领域有待深入研究的方向,指出今后应当重点对光降解研究方法,光降解与环境因子的交互作用,光降解作用的空间差异,光降解与微生物分解的相互关系及其作用强度进行研究.     

Correlations between Photodegradation of Bisretinoid Constituents of Retina and Dicarbonyl Adduct Deposition

Non-enzymatic collagen cross-linking and carbonyl adduct deposition are features of Bruch''s membrane aging in the eye, and disturbances in extracellular matrix turnover are considered to contribute to Bruch''s membrane thickening. Because bisretinoid constituents of the lipofuscin of retinal pigment epithelial (RPE) cells are known to photodegrade to mixtures of aldehyde-bearing fragments and small dicarbonyls (glyoxal (GO) and methylglyoxal (MG)), we investigated RPE lipofuscin as a source of the reactive species that covalently modify protein side chains. Abca4^−/− and Rdh8^−/−/Abca4^−/− mice that are models of accelerated bisretinoid formation were studied and pre-exposure of mice to 430 nm light enriched for dicarbonyl release by bisretinoid photodegradation. MG protein adducts were elevated in posterior eyecups of mutant mice, whereas carbonylation of an RPE-specific protein was observed in Abca4^−/− but not in wild-type mice under the same conditions. Immunolabeling of cryostat-sectioned eyes harvested from Abca4^−/− mice revealed that carbonyl adduct deposition in Bruch''s membrane was accentuated. Cell-based assays corroborated these findings in mice. Moreover, the receptor for advanced glycation end products that recognizes MG and GO adducts and glyoxylase 1 that metabolizes MG and GO were up-regulated in Abca4^−/− mice. Additionally, in acellular assays, peptides were cross-linked in the presence of A2E (adduct of two vitamin A aldehyde and ethanolamine) photodegradation products, and in a zymography assay, reaction of collagen IV with products of A2E photodegradation resulted in reduced cleavage by the matrix metalloproteinases MMP2 and MMP9. In conclusion, these mechanistic studies demonstrate a link between the photodegradation of RPE bisretinoid fluorophores and aging changes in underlying Bruch''s membrane that can confer risk of age-related macular degeneration.     

The interaction between abiotic photodegradation and microbial decomposition under ultraviolet radiation

Elevated ultraviolet (UV) radiation has been demonstrated to stimulate litter decomposition. Despite years of research, it is still not fully understood whether the acceleration in litter degradation is primarily attributed to abiotic photodegradation or the combined effects of abiotic photodegradation and microbial decomposition. In this study, we used meta‐analysis to synthesize photodegradation studies and compared the effects of UV radiation on litter decomposition between abiotic and biotic conditions. We also conducted a microcosm experiment to assess the effects of UV radiation on litter biodegradability and microbial activity. Overall, our meta‐analysis found that under abiotic photodegradation, UV radiation reduced the remaining litter mass by 1.44% (95% CI: 0.85% to 2.08%), did not affect the remaining lignin and increased the dissolved organic carbon (DOC) concentration by 14.01% (1.49–23.67%). Under combined abiotic photodegradation and microbial decomposition, UV radiation reduced the remaining litter mass and lignin by 1.60% (0.04–3.58%) and 16.07% (9.27–24.23%), respectively, but did not alter DOC concentration. UV radiation had no significant impact on soil microbial biomass carbon (MBC), but it reduced microbial respiration by 44.91% (2.26–78.62%) and altered the composition of the microbial community. In addition, UV radiation reduced nitrogen (N) immobilization by 19.44% (4.77–37.92%). Our microcosm experiment further indicated that DOC concentration and the amount of respired C in UV‐treated litter increased with UV exposure time, suggesting that longer UV exposure resulted in greater biodegradability. Overall, our study suggested that UV exposure could increase litter biodegradability by increasing the microbial accessibility of lignin, as well as the labile carbon supply to microbes. However, the remaining litter mass was not different between the abiotic and biotic conditions, most likely because the positive effect of UV radiation on litter biodegradability was offset by its negative effect on microbial activity. Our results also suggested that UV radiation could alter the N cycle during decomposition, primarily by inhibiting N immobilization.     

Effects of ultraviolet radiation on litter decomposition depend on precipitation and litter chemistry in a shortgrass steppe ecosystem

We examined the effect of altered levels of ultraviolet (UV) radiation (280–400 nm) and different amounts of precipitation on the decomposition rates of litter of contrasting carbon to nitrogen ratio (C : N) in a 3-year field experiment in a shortgrass steppe (SGS) ecosystem. UV radiation was either blocked or passed under clear plastic tents where precipitation was applied to simulate a very dry or very wet year. These treatments minimized or maximized the abiotic component (UV) or the biotic component (biological activity of decomposer organisms) of decomposition to assess potential interactions between the two. Initial litter chemistry varied in response to having been grown under ambient or elevated atmospheric CO₂ concentrations. While precipitation and litter chemistry were the most important drivers in decomposition in this system, UV radiation increased decomposition rates under dry conditions in litter with higher C : N ratios. Exposure to UV radiation slightly increased the amount of holocellulose that was lost from the litter. UV exposure did not affect the decomposition of the lignin fraction. Increased decomposition with UV radiation was accompanied by a decrease in N immobilization over the summer months. These results suggest that the effects of UV radiation on decomposition rates may be primarily abiotic, caused by direct photochemical degradation of the litter. Our results demonstrate that the role of UV radiation in litter decomposition in semiarid systems depends on the aridity of the system and the chemistry of the litter.     

Evidence for the possible involvement of the superoxide radicals in the photodegradation of bilirubin

The photodecomposition of bilirubin follows first order kinetics with ak _B value of 12.5 × 10^-3 min^-1. In the presence of a model system generating superoxide anions, such as xanthine-xanthine oxidase, thek _B value was 103 × 10^-3 min^-1 This ten-fold enhancement ofk _B value by xanthine-xanthine oxidase was abolished when the reaction mixture was supplemented with a superoxide ion scavenger— superoxide dismustase. Further, known singlet oxygen quenchers like Β-carotene and bistidine did not prevent the enhancement of bilirubin oxidation by xanthine-xanthine oxidase, thereby ruling out the obligatory conversion of Superoxide anion to singlet oxygen. It is concluded that radical oxygen mediated bilirubin degradation might be a natural catabolic route for the bile pigment degradation during oxygen stress. deceased May 1977.     

Towards Long‐Term Photostability of Solid‐State Dye Sensitized Solar Cells

The solid‐state dye‐sensitized solar cell (DSSC) was introduced to overcome inherent manufacturing and instability issues of the electrolyte‐based DSSC and progress has been made to deliver high photovoltaic efficiencies at low cost. However, despite 15 years research and development, there still remains no clear demonstration of long‐term stability. Here, solid‐state DSSCs are subjected to the severe aging conditions of continuous illumination at an elevated temperature. A fast deterioration in performance is observed for devices encapsulated in the absence of oxygen. The photovoltaic performance recovers when re‐exposed to air. This reversible behavior is attributed to three related processes: i) the creation of light and oxygen sensitive electronic shunting paths between TiO₂ and the top metal electrode, ii) increased recombination at the TiO₂/organic interface, and iii) the creation of deep electron traps that reduce the photocurrent. The device deterioration is remedied by the formation of an insulating alumino‐silicate shell around the TiO₂ nanocrystals, which reduces interfacial recombination, and the introduction of an insulating mesoporous SiO₂ buffer layer between the top electrode and TiO₂, which acts as a permanent insulating barrier between the TiO₂ and the metal electrode, preventing shunting.     

有机污染物在表层土壤中光降解的研究进展

土壤是承载有机污染物的重要介质,而光降解是降解土壤表层有机污染物的一种非常重要的非生物转化途径。研究土壤表层有机物的光降解对认识污染物土壤环境行为有非常重要的意义。20世纪90年代以来对土壤中有机污染物的光降解研究有了大量报道。本文阐述了土壤组成和质地、土壤湿度、土壤pH值和土壤厚度等因素对光解影响的研究现状;介绍了目前研究土壤光降解所采用的研究方法：土壤表层直接光解、土壤悬浮液光解、溶剂萃取与光降解联合处理,及其研究土壤光降解应用的动力模型;对不同农药和其它有机污染物在土壤中的光降解研究进行了综述,并对今后的研究作了展望。     

区域生态风险评价指标体系

区域生态风险评价包含多种风险源、多种风险受体和多种评价终点,评价指标的选取较为复杂,成为区域环境管理研究中的一个热点问题.大量国内外相关领域的研究成果表明,区域生态风险评价包括3个关键环节：1）风险概率评价,用风险概率指数来度量;2）生态系统在区域中的生态地位和价值评价,用生态指数来度量;3）各生态系统遭受风险时的脆弱程度评价,用脆弱度指数来度量.区域生态风险评价指标体系构建存在的主要问题为主观性强和可比性差,鉴于此,应遵循客观性、整体性、层次性和可比性原则分层次构建指标体系,其中,构建受体生态地位和价值的评价指标体系最为复杂,可通过建立必选指标和可选指标来完善,以增强区域之间生态风险评价结果的可比性.