Photoactive Blend Morphology Engineering through Systematically Tuning Aggregation in All‐Polymer Solar Cells

Polymer aggregation plays a critical role in the miscibility of materials and the performance of all‐polymer solar cells (APSCs). However, many aspects of how polymer texturing and aggregation affect photoactive blend film microstructure and photovoltaic performance are poorly understood. Here the effects of aggregation in donor–acceptor blends are studied, in which the number‐average molecular weights (M_ns) of both an amorphous donor polymer, poly[4,8‐bis(5‐(2‐ethylhexyl)thiophen‐2‐yl)benzo[1,2‐b;4,5‐b′]dithiophene‐2,6‐diyl‐alt‐(4‐(2‐ethylhexyl)‐3‐fluorothieno[3,4‐b]thiophene‐)‐2‐carboxylate‐2‐6‐diyl)] ( PBDTT‐FTTE ) and a semicrystalline acceptor polymer, poly{[N,N′‐bis(2‐octyldodecyl)naphthalene‐1,4,5,8‐bis(dicarboximide)‐2,6‐diyl]‐alt‐5,5′‐(2,2′‐bithiophene)} ( P(NDI2OD‐T2) ) are systematically varied. The photovoltaic performance is correlated with active layer microstructural and optoelectronic data acquired by in‐depth transmission electron microscopy, grazing incidence wide‐angle X‐ray scattering, thermal analysis, and optical spectroscopic measurements. Coarse‐grained modeling provides insight into the effects of polymer aggregation on the blend morphology. Notably, the computed average distance between the donor and the acceptor polymers correlates well with solar cell photovoltaic metrics such as short‐circuit current density (J_sc) and represents a useful index for understanding/predicting active layer blend material intermixing trends. Importantly, these results demonstrate that for polymers with different texturing tendencies (amorphous/semicrystalline), the key for optimal APSC performance, photovoltaic blend morphology can be controlled via both donor and acceptor polymer aggregation.     

The insect metalloproteinase inhibitor gene of the lepidopteran Galleria mellonella encodes two distinct inhibitors

The insect metalloproteinase inhibitor (IMPI) from the greater wax moth, Galleria mellonella, represents the first and to date only specific inhibitor of microbial metalloproteinases reported from animals. Here, we report on the characterization including carbohydrate analysis of two recombinant constructs encoded by impi cDNA either upstream or downstream of the furin cleavage site identified. rIMPI-1, corresponding to native IMPI purified from hemolymph, is encoded by the N-terminal part of the impi sequence, whereas rIMPI-2 is encoded by its C-terminal part. rIMPI-1 is glycosylated at N48 with GlcNAc2Man3, showing fucosylation to different extents. Similarly, rIMPI-2 is glycosylated at N149 with GlcNAc2Man3, but is fully fucosylated. rIMPI-1 represents a promising template for the design of second-generation antibiotics owing to its specific activity against thermolysin-like metalloproteinases produced by human pathogenic bacteria such as Vibrio vulnificus. In contrast, rIMPI-2 does not inhibit bacterial metalloproteinases, but is moderately active against recombinant human matrix metalloproteinases (MMPs). Both microbial metalloproteinases and MMPs induce expression of the impi gene when injected into G. mellonella larvae. These findings provide evidence that the impi gene encodes two distinct inhibitors, one inhibiting microbial metalloproteinases and contributing to innate immunity, the other putatively mediating regulation of endogenous MMPs during metamorphosis.     

西南地区道路建设对植被净初级生产力的影响

道路建设促进区域社会经济发展的同时,通过直接改变原有生态系统、间接增强人类活动进而改变原有生态系统的途径对周围生态系统产生影响。定量评估道路建设对植被净初级生产力(Net Primary Productivity,NPP)的影响对掌握线性工程生态环境影响,进行社会经济发展与生态安全权衡具有一定现实意义。基于西南地区2016年道路和2015年NPP数据,利用核密度(Kernel Density,KD)表征道路影响域和影响强度,借助ArcGIS平台,分析不同土地覆被和经济发展强度下道路建设与NPP的关系。结果表明:(1)搜索半径为0.5km时,道路KD (km/km²)范围为[0.0,47.3],其中道路KD为零的区域约占研究区总面积的79.8%,这些未受道路干扰区域大部分位于西藏、青海、四川西部、贵州和云南的西北部;道路KD为(0.0,5.0\]的区域约占道路KD非零区域面积的88.4%,除成都、重庆、贵阳、南宁、昆明等城市外,区域大部分地区道路密度仍处于较低水平。(2)从不同土地覆被下道路KD与NPP的关系来看,中低道路干扰条件下,林地、耕地和人工表面稳定性更强,道路KD小于4.1时NPP相对稳定,而草地、湿地和其他土地覆被在道路KD大于2.1后,NPP出现急剧变化。随道路KD增大NPP趋于发散,这可能是由道路密度增加后其两侧人类干扰类型多样化引起。(3)以县级行政区划为单位,按单位面积道路KD由小到大的顺序,将研究区分成5个部分:分区1-分区5。在分区1,NPP随道路KD增大呈先波动升高,相对稳定变化后降低再发散;在分区2-分区5,NPP随道路KD增大总体呈降低趋势,且变异性逐渐增加,经历了相对稳定阶段、线性变化阶段、发散阶段。根据研究结果,道路建设需重点关注生态敏感脆弱区的植被保护,如草地和湿地,应尽量避免较高密度道路建设带来的生态系统退化问题,同时应根据不同的地区制定适宜的保护方案。     

New anaerobic, ammonium-oxidizing community enriched from peat soil

Anaerobic ammonium-oxidizing (anammox) bacteria have been recognized as an important sink for fixed nitrogen and are detected in many natural environments. However, their presence in terrestrial ecosystems has long been overlooked, and their contribution to the nitrogen cycling in natural and agricultural soils is currently unknown. Here we describe the enrichment and characterization of anammox bacteria from a nitrogen-loaded peat soil. After 8 months of incubation with the natural surface water of the sampling site and increasing ammonium and nitrite concentrations, anammox cells constituted 40 to 50% of the enrichment culture. The two dominant anammox phylotypes were affiliated with "Candidatus Jettenia asiatica" and "Candidatus Brocadia fulgida." The enrichment culture converted NH(4)(+) and NO(2)(-) to N(2) with the previously reported stoichiometry (1:1.27) and had a maximum specific anaerobic ammonium oxidation rate of 0.94 mmol NH(4)(+)·g (dry weight)(-1)·h(-1) at pH 7.1 and 32°C. The diagnostic anammox-specific lipids were detected at a concentration of 650 ng·g (dry weight)(-1), and pentyl-[3]-ladderane was the most abundant ladderane lipid.     

Proteins and protein complexes involved in the biochemical reactions of anaerobic ammonium-oxidizing bacteria

It has been less than two decades since anammox (anaerobic ammonium oxidation) coupled to nitrite reduction has been discovered. Already, this process has been recognized as an important sink for fixed nitrogen in the natural environment and has been implemented as a cost-effective ammonium removal technology. Still, little is known about the molecular mechanism of this remarkable reaction. In this mini review, we present an insight into how ammonium and nitrite are combined to form dinitrogen gas.     

Anammox bacteria disguised as denitrifiers: nitrate reduction to dinitrogen gas via nitrite and ammonium

Anaerobic ammonium-oxidizing (anammox) bacteria oxidize ammonium with nitrite and produce N(2). They reside in many natural ecosystems and contribute significantly to the cycling of marine nitrogen. Anammox bacteria generally live under ammonium limitation, and it was assumed that in nature anammox bacteria depend on other biochemical processes for ammonium. In this study we investigated the possibility of dissimilatory nitrate reduction to ammonium by anammox bacteria. Physically purified Kuenenia stuttgartiensis cells reduced (15)NO(3) (-) to (15)NH(4) (+) via (15)NO(2) (-) as the intermediate. This was followed by the anaerobic oxidation of the produced ammonium and nitrite. The overall end-product of this metabolism of anammox bacteria was (15)N(15)N dinitrogen gas. The nitrate reduction to nitrite proceeds at a rate of 0.3 +/- 0.02 fmol cell(-1) day(-1) (10% of the 'normal' anammox rate). A calcium-dependent cytochrome c protein with a high (305 mumol min(-1) mg protein(-1)) rate of nitrite reduction to ammonium was partially purified. We present evidence that dissimilatory nitrate reduction to ammonium occurs in Benguela upwelling system at the same site where anammox bacteria were previously detected. This indicates that anammox bacteria could be mediating dissimilatory nitrate reduction to ammonium in natural ecosystems.     

Complexome analysis of the nitrite-dependent methanotroph Methylomirabilis lanthanidiphila

The atmospheric concentration of the potent greenhouse gases methane and nitrous oxide (N₂O) has increased drastically during the last century. Methylomirabilis bacteria can play an important role in controlling the emission of these two gases from natural ecosystems, by oxidizing methane to CO₂ and reducing nitrite to N₂ without producing N₂O. These bacteria have an anaerobic metabolism, but are proposed to possess an oxygen-dependent pathway for methane activation. Methylomirabilis bacteria reduce nitrite to NO, and are proposed to dismutate NO into O₂ and N₂ by a putative NO dismutase (NO-D). The O₂ produced in the cell can then be used to activate methane by a particulate methane monooxygenase. So far, the metabolic model of Methylomirabilis bacteria was based mainly on (meta)genomics and physiological experiments. Here we applied a complexome profiling approach to determine which of the proposed enzymes are actually expressed in Methylomirabilis lanthanidiphila. To validate the proposed metabolic model, we focused on enzymes involved in respiration, as well as nitrogen and carbon transformation. All complexes suggested to be involved in nitrite-dependent methane oxidation, were identified in M. lanthanidiphila, including the putative NO-D. Furthermore, several complexes involved in nitrate reduction/nitrite oxidation and NO reduction were detected, which likely play a role in detoxification and redox homeostasis. In conclusion, complexome profiling validated the expression and composition of enzymes hypothesized to be involved in the energy, methane and nitrogen metabolism of M. lanthanidiphila, thereby further corroborating their unique metabolism involved in the environmentally relevant process of nitrite-dependent methane oxidation.     

Proton Nuclear Magnetic Resonance-Spectroscopic Discrimination of Wines Reflects Genetic Homology of Several Different Grape (V. vinifera L.) Cultivars

Background and Aims

Proton nuclear magnetic resonance spectroscopy coupled multivariate analysis (¹H NMR-PCA/PLS-DA) is an important tool for the discrimination of wine products. Although ¹H NMR has been shown to discriminate wines of different cultivars, a grape genetic component of the discrimination has been inferred only from discrimination of cultivars of undefined genetic homology and in the presence of many confounding environmental factors. We aimed to confirm the influence of grape genotypes in the absence of those factors.

Methods and Results

We applied ¹H NMR-PCA/PLS-DA and hierarchical cluster analysis (HCA) to wines from five, variously genetically-related grapevine (V. vinifera) cultivars; all grown similarly on the same site and vinified similarly. We also compared the semi-quantitative profiles of the discriminant metabolites of each cultivar with previously reported chemical analyses. The cultivars were clearly distinguishable and there was a general correlation between their grouping and their genetic homology as revealed by recent genomic studies. Between cultivars, the relative amounts of several of the cultivar-related discriminant metabolites conformed closely with reported chemical analyses.

Conclusions

Differences in grape-derived metabolites associated with genetic differences alone are a major source of ¹H NMR-based discrimination of wines and ¹H NMR has the capacity to discriminate between very closely related cultivars.

Significance of the Study

The study confirms that genetic variation among grape cultivars alone can account for the discrimination of wine by ¹H NMR-PCA/PLS and indicates that ¹H NMR spectra of wine of single grape cultivars may in future be used in tandem with hierarchical cluster analysis to elucidate genetic lineages and metabolomic relations of grapevine cultivars. In the absence of genetic information, for example, where predecessor varieties are no longer extant, this may be a particularly useful approach.     

Insight into the Ebola virus nucleocapsid assembly mechanism: crystal structure of Ebola virus nucleoprotein core domain at 1.8 ? resolution

Ebola virus (EBOV) is a key member of Filoviridae family and causes severe human infectious diseases with high morbidity and mortality. As a typical negative-sense single-stranded RNA (-ssRNA) viruses, EBOV possess a nucleocapsid protein (NP) to facilitate genomic RNA encapsidation to form viral ribonucleoprotein complex (RNP) together with genome RNA and polymerase, which plays the most essential role in virus proliferation cycle. However, the mechanism of EBOV RNP formation remains unclear. In this work, we solved the high resolution structure of core domain of EBOV NP. The polypeptide of EBOV NP core domain (NP_core) possesses an N-lobe and C-lobe to clamp a RNA binding groove, presenting similarities with the structures of the other reported viral NPs encoded by the members from Mononegavirales order. Most strikingly, a hydrophobic pocket at the surface of the C-lobe is occupied by an α-helix of EBOV NP_core itself, which is highly conserved among filoviridae family. Combined with other biochemical and biophysical evidences, our results provides great potential for understanding the mechanism underlying EBOV RNP formation via the mobility of EBOV NP element and enables the development of antiviral therapies targeting EBOV RNP formation.