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.     

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。     

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.     

广西不同林龄杉木、马尾松人工林根系生物量及碳储量特征

为了解不同林龄杉木、马尾松人工林地地下根系生物量及碳储量特征,以广西杉木、马尾松主产区5个不同林龄阶段(幼龄林、中龄林、近熟林、成熟林、过熟林)的人工林为研究对象,采用全根挖掘法和土钻法获取标准木根系生物量、灌草根系生物量和林分细根生物量,并测定其碳含量,分析其不同林龄阶段地下根系生物量和碳储量分配特征。结果表明:杉木、马尾松林地下根系总生物量分别在9.06—31.40Mg/hm~2和7.91—53.40Mg/hm~2之间,各林龄阶段根系总生物量总体上呈现随林龄增加而增加的趋势,杉木林细根生物量随林龄的增加呈现出先减后增的趋势,马尾松呈现出逐渐减小的趋势;林分各层次根系碳含量表现为乔木灌木草本、细根;杉木、马尾松地下根系碳储量变化趋势与生物量变化趋势相同,杉木、马尾松林不同林龄阶段各层次根系和土壤细根总碳储量分别在7.56—21.97Mg/hm~2和8.86—29.95Mg/hm~2之间;地下根系碳储量总体上以乔木根系占优势,且随林龄的增大其比例呈增加的趋势。     

Tropical soils degraded by slash‐and‐burn cultivation can be recultivated when amended with ashes and compost

In many tropical regions, slash‐and‐burn agriculture is considered as a driver of deforestation; the forest is converted into agricultural land by cutting and burning the trees. However, the fields are abandoned after few years because of yield decrease and weed invasion. Consequently, new surfaces are regularly cleared from the primary forest. We propose a reclamation strategy for abandoned fields allowing and sustaining re‐cultivation. In the dry region of south‐western Madagascar, we tested, according to a split‐plot design, an alternative selective slash‐and‐burn cultivation technique coupled with compost amendment on 30–year‐old abandoned fields. Corn plants (Zea mays L.) were grown on four different types of soil amendments: no amendment (control), compost, ashes (as in traditional slash‐and‐burn cultivation), and compost + ashes additions. Furthermore, two tree cover treatments were applied: 0% tree cover (as in traditional slash‐and‐burn cultivation) and 50% tree cover (selective slash‐and‐burn). Both corn growth and soil fertility parameters were monitored during the growing season 2015 up to final harvest. The amendment compost + ashes strongly increased corn yield, which was multiplied by 4–5 in comparison with ashes or compost alone, reaching 1.5 t/ha compared to 0.25 and 0.35 t/ha for ashes and compost, respectively. On control plots, yield was negligible as expected on these degraded soils. Structural equation modeling evidenced that compost and ashes were complementary fertilizing pathways promoting soil fertility through positive effects on soil moisture, pH, organic matter, and microbial activity. Concerning the tree cover treatment, yield was reduced on shaded plots (50% tree cover) compared to sunny plots (0% tree cover) for all soil amendments, except ashes. To conclude, our results provide empirical evidence on the potential of recultivating tropical degraded soils with compost and ashes. This would help mitigating deforestation of the primary forest by increasing lifespan of agricultural lands.     

Change of liver metabolism of 1,2-dibromoethane during simultaneous treatment with carbon tetrachloride

The combination of carbon tetrachloride (CCl₄) and 1,2-dibromoethane (DBE) in isolated rat hepatocytes led to a significant potentiation of both lipid peroxidation and of plasma membrane damage observed after a single treatment with CCl₄. Such a synergistic effect appeared to be related to the CCl₄-induced shift of DBE metabolism from the cytosolic conjugation with glutathione towards the microsomal transformation into toxic intermediates. In fact, CCl₄ significantly inactivated hepatocyte total GSH-transferase, i.e. the DBE detoxification pathway. Furthermore, while the microsomal metabolism of CCl₄ was not affected by the simultaneous presence of DBE, the amount of DBE reactive metabolities covalently bound to hepatocyte protein was significantly enhanced in the presence of CCl₄.     

Aphid Herbivory Drives Asymmetry in Carbon for Nutrient Exchange between Plants and an Arbuscular Mycorrhizal Fungus

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