Thiophene Rings Improve the Device Performance of Conjugated Polymers in Polymer Solar Cells with Thick Active Layers

Developing novel materials that tolerate thickness variations of the active layer is critical to further enhance the efficiency of polymer solar cells and enable large‐scale manufacturing. Presently, only a few polymers afford high efficiencies at active layer thickness exceeding 200 nm and molecular design guidelines for developing successful materials are lacking. It is thus highly desirable to identify structural factors that determine the performance of semiconducting conjugated polymers in thick‐film polymer solar cells. Here, it is demonstrated that thiophene rings, introduced in the backbone of alternating donor–acceptor type conjugated polymers, enhance the fill factor and overall efficiency for thick (>200 nm) solar cells. For a series of fluorinated semiconducting polymers derived from electron‐rich benzo[1,2‐b:4,5‐b′]dithiophene units and electron‐deficient 5,6‐difluorobenzo[2,1,3]thiazole units a steady increase of the fill factor and power conversion efficiency is found when introducing thiophene rings between the donor and acceptor units. The increased performance is a synergistic result of an enhanced hole mobility and a suppressed bimolecular charge recombination, which is attributed to more favorable polymer chain packing and finer phase separation.     

Fast further purification of diastereomeric salts of a nonracemic acid by gas antisolvent fractionation

A novel, green possibility of the further purification of the diastereomeric salt of 4‐chloromandelic acid and 1‐phenylethane‐1‐amine was developed. Gas antisolvent method using supercritical carbon dioxide was applied for the first time to precipitate the diastereomeric salts with increased purity followed by the supercritical fluid extraction of the dissolved diastereomers. The RR ‐salt can be purified to >99%, while fractionation‐based purification of the SR ‐salt is limited to ~80%. The limiting initial diastereomeric excess correlates strongly with the atmospheric melting eutectic composition of the same salts, which suggests that despite the fast precipitation, the diastereomeric excess of the solid product is not kinetically determined. The efficiency of the diastereomeric enrichment is in the same range as that of the atmospheric reference experiments; however, technological advantages provided by the antisolvent precipitation method such as fast processing and dry product obtained suggest that this novel procedure is a promising alternative to the atmospheric methods.     

土壤病毒生态学研究方法

病毒是地球上最丰富的生物实体,每克土壤中可包含数以亿计的病毒,它不仅影响土壤中其它微生物的群落组成、土壤元素的生物地球化学循环,还会影响土壤微生物的物种进化,甚至影响植物、动物和人体健康。目前人们对土壤中病毒的种类及丰度、分布特征以及功能引起的生态环境效应还知之甚少。在概述病毒生态学研究方法的基础上,对土壤病毒的提取、纯化、定量及分子生态学方法等基本流程进行了比较分析,以期建立一套快速简便、高效稳定的适用于土壤病毒研究的方法,并用于研究土壤病毒的多样性及分布特征,探讨病毒在环境中的生存和传播机制,为土壤病毒的防控及开发利用提供支撑。     

采用稳定碳同位素法分析白羊草在不同干旱胁迫下的水分利用效率

本研究以黄土高原乡土草种白羊草(Bothriochloa ischaemum(L.)Keng.)为研究对象,采用盆栽控制实验,比较白羊草在3个水分处理(CK80%FC、MS60%FC和SS 40%FC)下的生物量积累和分配模式、瞬时水分利用效率(WUE)、不同部位(新叶、老叶、茎、细根、粗根)的稳定碳同位素组成(δ~(13)C)和碳同位素分辨率(Δ~(13)C)及其相互关系,以及干旱胁迫下影响水分利用效率的主导环境因子。结果表明:1)重度干旱胁迫显著降低植物整体生物量,显著增加根冠比和细根生物量比例;2)随着干旱胁迫加剧,白羊草各器官的δ~(13)C均呈上升趋势,Δ~(13)C呈减小趋势,SS处理不同器官δ~(13)C和Δ~(13)C没有显著差异,CK和MS处理的各器官δ~(13)C均值表现分别为细根粗根老叶新叶茎、细根新叶老叶粗根茎,CK和MS处理Δ~(13)C的值总体呈根叶茎。3)新叶的δ~(13)CNL和Δ~(13)CNL与WUE的相关系数均最大,说明利用稳定碳同位素方法测定白羊草水分利用效率具有可行性。4)不同水分处理的WUE的主导影响因子不同,CK、MS、SS水分处理WUE分别受到叶面温度、大气水汽压亏缺和空气温度的影响最大。为采用稳定碳同位素方法指示白羊草水分利用效率可行性及阐明植物的胁迫响应机制提供理论依据。     

松嫩平原苏打盐渍化旱田土壤表观电导率空间变异

在松嫩平原西部吉林省大安市乐胜乡,于2013年4月20日选择盐碱程度不均一的典型盐渍化旱田地块,面积为4.8 hm~2作为研究样地。利用EM38大地电导率仪测定结合田间定点采样,并通过经典统计和地统计相结合的方法研究了盐渍化旱田土壤表观电导率空间变异特征,分析了土壤表观电导率与土壤盐碱指标之间的关系。结果表明,盐渍化旱田土壤水平方向表观电导率(EC_h)经对数转换后具有强空间自相关,其变异特征主要是与地形地貌和水文状况等结构性因素有关。垂直方向表观电导率(EC_v)经对数转换后具有中等空间自相关性,其变异特征受结构性因素和随机因素共同作用。EC_h和EC_v半方差模拟的最优模型分别为球状模型和指数模型。Pearson分析表明土壤表观电导率(EC_h和EC_v)与土壤盐碱指标EC_(1∶5)、pH_(1∶5)、SAR、SC、Na~+、CO_3~(2-)、HCO_3~-呈正相关关系(P0.05),EC_h与土壤盐碱指标相关系数均大于EC_v。在实际应用中可以用EC_h来指示土壤的盐碱程度。回归分析表明土壤表观电导率(EC_h和EC_v)与土壤盐碱指标呈线性相关,且EC_h回归模型的决定系数均大于EC_v回归模型的决定系数,可用水平方向土壤表观电导率(EC_h)来计算土壤盐碱指标,进行土壤盐渍化的快速评估。     

Analysis and assessment of heavy metals pollution in soils around a Pb and Zn smelter in Baoji City,Northwest China

Soil heavy metal pollution from mining activities is potentially harmful to human health through the food chain. In this study, a total of 43 soil samples were collected from a depth of 0–20 cm from fields close to a Pb and Zn smelter. The samples were used to: 1) analyze the pollution level of heavy metals (Pb, Zn, Cr, and Cu) and spatial distribution pattern; 2) evaluate the degree of accumulation and enrichment, potential ecological risk, and human health risk; and 3) perform source apportionment in Fengxiang County, Shaanxi Province of China. The results showed that the concentration ranged from 43.67 to 189.55, 131.43 to 239.53, 74.77 to 112.25, and 24.69 to 37.71 mg·kg^?1 for Pb, Zn, Cr, and Cu, respectively, and the mean concentration for Pb, Zn, Cr, and Cu was 129.46, 192.85, 91.98 and 31.67 mg·kg^?1, respectively. The concentrations were greater than the Shaanxi Province background values, while they were lower than the second-level limits of Environmental Quality Standard for Soils of China (EQSS). The spatial distribution of heavy metal contents showed a banded in soil except Cu. The spatial distribution pattern and pollution assessment indexes (I_geo, EF) indicated that the investigated metals had been accumulated in the study areas, and implied significant influences from anthropogenic activities, local meteorological situation, and soil properties. The ecological risk assessment showed that the risks were relatively low (RI<150). Compared with the exposure risk for adults, that for children was significantly greater. The ingestion of heavy metals in the soils by humans was the main exposure pathway compared with the dermal exposure. There may be a risk of noncarcinogenic adverse health effects (HQ < 1, 0.377 ≤ HI≤1.553) on children, but the adults were unlikely to experience obvious adverse health effects (HQ < 1, HI < 1). The carcinogenic risk of Cr for adults and children was at an unacceptable level. The carcinogenic and noncarcinogenic risks were in the order of children > adults. The correlation analysis showed that Pb, Cr, and Cu have identical anthropogenic and natural sources, while Zn has another identical source. This study could provide a basis for the sustainable management of this region by reducing metal inputs and to protect soils from long-term heavy metal accumulation.     

Ultrafine Metal Nanoparticles/N‐Doped Porous Carbon Hybrids Coated on Carbon Fibers as Flexible and Binder‐Free Water Splitting Catalysts

By employing in situ reduction of metal precursor and metal‐assisted carbon etching process, this study achieves a series of ultrafine transition metal‐based nanoparticles (Ni–Fe, Ni–Mo) embedded in N‐doped carbon, which are found efficient catalysts for electrolytic water splitting. The as‐prepared hybrid materials demonstrate outstanding catalytic activities as non‐noble metal electrodes rendered by the synergistic effect of bimetal elements and N‐dopants, the improved electrical conductivity, and hydrophilism. Ni/Mo₂C@N‐doped porous carbon (NiMo‐polyvinylpyrrolidone (PVP)) and NiFe@N‐doped carbon (NiFe‐PVP) produce low overpotentials of 130 and 297 mV at a current density of 10 mA cm^?2 as catalysts for hydrogen evolution reaction and oxygen evolution reaction, respectively. In addition, these binder‐free electrodes show long‐term stability. Overall water splitting is also demonstrated based on the couple of NiMo‐PVP||NiFe‐PVP catalyzer. This represents a simple and effective synthesis method toward a new type of nanometal–carbon hybrid electrodes.     

Loss of CpSRP54 function leads to a truncated light-harvesting antenna size in Chlamydomonas reinhardtii

The Chlamydomonas reinhardtii truncated light-harvesting antenna 4 (tla4) DNA transposon mutant has a pale green phenotype, a lower chlorophyll (Chl) per cell and a higher Chl a/b ratio in comparison with the wild type. It required a higher light intensity for the saturation of photosynthesis and displayed a greater per chlorophyll light-saturated rate of oxygen evolution than the wild type. The Chl antenna size of the photosystems in the tla4 mutant was only about 65% of that measured in the wild type. Molecular genetic analysis revealed that a single plasmid DNA insertion disrupted two genes on chromosome 11 of the mutant. A complementation study identified the “chloroplast signal recognition particle 54” gene (CpSRP54), as the lesion causing the tla4 phenotype. Disruption of this gene resulted in partial failure to assemble and, therefore, lower levels of light-harvesting Chl-binding proteins in the C. reinhardtii thylakoids. A comparative in silico 3-D structure-modeling analysis revealed that the M-domain of the CpSRP54 of C. reinhardtii possesses a more extended finger loop structure, due to different amino acid composition, as compared to that of the Arabidopsis CpSRP54. The work demonstrated that CpSRP54 deletion in microalgae can serve to generate tla mutants with a markedly smaller photosystem Chl antenna size, improved solar energy conversion efficiency, and photosynthetic productivity in high-density cultures under bright sunlight conditions.     

Computational study on the structural and optoelectronic properties of a carbazole-benzothiadiazole based conjugated oligomer with various alkyl side-chain lengths

The effect of the alkyl side-chain length on the structural and optoelectronic properties of poly[N-9′-heptadecanyl-27-carbazole-alt-55-(4′,7′-di-2-thienyl-2′,1′,3′-benzothiadiazole)] (PCDTBT) conjugated oligomers have been studied by density functional theory (DFT) and time-dependent density functional theory (TD-DFT). The study was carried out by varying the length of alkyl side-chain attached to the nitrogen atom of the carbazole unit of the PCDTBT oligomers. The structural properties of the optimised oligomers were then studied by determining the bond-length alternation and dihedral angles (Φ) for various side-chain lengths. Total energy calculations for the determination of HOMO energy (E_HOMO), LUMO energy (E_LUMO), and fundamental energy gap (E_Gap) were performed using DFT at the B3LYP/6-31G(d), while the first singlet excitation energies (E_Opt) were calculated by TD-DFT also at the same level of theory. It was observed that there are no significant structural changes occurring as the alkyl chain lengths are varied. For the electronic properties, very small differences (i.e. ~0.01 eV) were observed for E_Gap and E_Opt while the exciton binding energies (E_B) were virtually the same. The results suggest that using shorter alkyl side-chains do not significantly affect the structural and optoelectronic properties of the carbazole-benzothiadiazole based polymer. The observations can aid future computational design studies of analogous systems by reducing large structures thus decreasing computational costs.