Sequentially Deposited versus Conventional Nonfullerene Organic Solar Cells: Interfacial Trap States,Vertical Stratification,and Exciton Dissociation

Bulk heterojunction (BHJ) nonfullerene organic solar cells prepared from sequentially deposited donor and acceptor layers (sq‐BHJ) have recently been shown to be highly efficient, environmentally friendly, and compatible with large area and roll‐to‐roll fabrication. However, the related photophysics at donor‐acceptor interface and the vertical heterogeneity of donor‐acceptor distribution, critical for exciton dissociation and device performance, have been largely unexplored. Herein, steady‐state and time‐resolved optical and electrical techniques are employed to characterize the interfacial trap states. Correlating with the luminescent efficiency of interfacial states and its nonradiative recombination, interfacial trap states are characterized to be about 40% more populated in the sq‐BHJ devices than the as‐cast BHJ (c‐BHJ), which probably limits the device voltage output. Cross‐sectional energy‐dispersive X‐ray spectroscopy and ultraviolet photoemission spectroscopy depth profiling directly visualize the donor–acceptor vertical stratification with a precision of 1–2 nm. From the proposed “needle” model, the high exciton dissociation efficiency is rationalized. This study highlights the promise of sequential deposition to fabricate efficient solar cells, and points toward improving the voltage output and overall device performance via eliminating interfacial trap states.     

Highly tunable thiosulfonates as a novel class of cysteine protease inhibitors with anti-parasitic activity against Schistosoma mansoni

The development of a new class of cysteine protease inhibitors utilising the thiosulfonate moiety as an SH specific electrophile is described. This moiety has been introduced into suitable amino acid derived building blocks, which were incorporated into peptidic sequences leading to very potent i.e. sub micromolar inhibitors of the cysteine protease papain in the same range as the vinyl sulfone based inhibitor K11777. Therefore, their inhibitory effect on Schistosoma mansoni, a human blood parasite, that expresses several cysteine proteases, was evaluated. The homophenylalanine side chain containing compounds 27–30 and especially 36 showed promising activities compared with K11777 and warrant further investigations of these peptidic thiosulfonate inhibitors as new potential anti-parasitic compounds.     

几种氧代丙酸化合物在诱捕白纹伊蚊中的应用

为了从氧代丙酸化合物中筛选出对白纹伊蚊Aedes albopictus具有良好引诱效果的化合物,采用陷阱诱捕法分别测定了丙酮酸（α-氧代丙酸）、3-甲氧基-2-甲基-3-氧代丙酸、3-(苄氧基)-3-氧代丙酸和3-氨基-3-氧代丙酸4种氧代丙酸化合物及丙酸对白纹伊蚊成虫的诱捕效果。结果表明,在供试的5种化合物中,α-氧代丙酸、3-甲氧基-2-甲基-3-氧代丙酸和3-(苄氧基)-3-氧代丙酸3种氧代丙酸化合物及丙酸的诱捕效果显著,同剂量的各化合物对白纹伊蚊的诱蚊效果依次是3-甲氧基-2-甲基-3-氧代丙酸>3-(苄氧基)-3-氧代丙酸>α-氧代丙酸=丙酸。相同质量α-氧代丙酸∶3-(苄氧基)-3-氧代丙酸=1∶1至1∶2的配方比,具有协同增效作用,平均累计诱捕量均显著优于单组分α-氧代丙酸、3-(苄氧基)-3-氧代丙酸和对照纯水（P<0.05）。其中最优配方比是α-氧代丙酸∶3-(苄氧基)-3-氧代丙酸=1∶2,平均累计诱捕量比单组分α-氧代丙酸增加45.45%,比单组分3-(苄氧基)-3-氧代丙酸增加32.33%和比对照纯水增加73.11%（P<0.05）。现场诱蚊试验结果表明,根据相似相溶原理将液体的氧代丙酸（α-氧代丙酸、3-甲氧基-2-甲基-3-氧代丙酸）分别与固体的氧代丙酸（3-(苄氧基)-3-氧代丙酸）混配并结合陷阱诱捕器,能够显著提高对白纹伊蚊的持效性及诱捕数量（混合物60 d的累计诱蚊总数量是单组分的1.28~2.15倍）。研究结果为进一步开发适用于家居办公环境中使用的诱蚊剂提供了研究基础。     

A comparative spin trapping study of the interaction of hypobromous and hypochlorous acids with <Emphasis Type="Italic">tert</Emphasis>-butyl hydroperoxide

Hypochlorite (HOCl/OCl^?) and hypobromite (HOBr/OBr^?) are shown to react with tert-butyl hydroperoxide with close rate constants (10.8 and 8.9 M^?1 s^?1, respectively). Using a spin trap α-(4-pyridyl-1-oxide)-N-tert-butyl nitrone, both reactions are shown to proceed through decomposition of the hydroperoxide yielding butylperoxyl [˙OOC(CH₃)₃] and butoxyl [˙OC(CH₃)₃] radicals in a ratio depending on the hydroperoxide concentration. Thus, like hypochlorite, hypobromite can generate free radicals in reactions with organic hydroperoxides, which can be important for intensification of free-radical processes, e.g., lipid peroxidation at the chain branching stage.     

信息素在文物害虫防治中的应用与展望

文物害虫会对文物古建筑造成不可逆的破坏,因此害虫防治是文物保护的重要工作。随着博物馆引入有害生物综合防治（Integrated Pest Management,IPM）策略,博物馆的害虫防治也开始遵循“预防为主,防治结合”理念。昆虫体外信息素是IPM中重要的技术手段。该技术可对害虫进行监测与诱杀,有利于对害虫发生规律的研究与数量控制。且信息素具有用量少,不接触文物等优点。本文概述信息素的发展、种类与功能,整理了文物害虫信息素及其应用中的遇到的问题,并展望信息素的应用前景。     

Synthetic biology and metabolic engineering of actinomycetes for natural product discovery

Actinomycetes are one of the most valuable sources of natural products with industrial and medicinal importance. After more than half a century of exploitation, it has become increasingly challenging to find novel natural products with useful properties as the same known compounds are often repeatedly re-discovered when using traditional approaches. Modern genome mining approaches have led to the discovery of new biosynthetic gene clusters, thus indicating that actinomycetes still harbor a huge unexploited potential to produce novel natural products. In recent years, innovative synthetic biology and metabolic engineering tools have greatly accelerated the discovery of new natural products and the engineering of actinomycetes. In the first part of this review, we outline the successful application of metabolic engineering to optimize natural product production, focusing on the use of multi-omics data, genome-scale metabolic models, rational approaches to balance precursor pools, and the engineering of regulatory genes and regulatory elements. In the second part, we summarize the recent advances of synthetic biology for actinomycetal metabolic engineering including cluster assembly, cloning and expression, CRISPR/Cas9 technologies, and chassis strain development for natural product overproduction and discovery. Finally, we describe new advances in reprogramming biosynthetic pathways through polyketide synthase and non-ribosomal peptide synthetase engineering. These new developments are expected to revitalize discovery and development of new natural products with medicinal and other industrial applications.     

A cell culture platform for quantifying metabolic substrate oxidation in bicarbonate-buffered medium

Complex diseases such as cancer and diabetes are underpinned by changes in metabolism, specifically by which and how nutrients are catabolized. Substrate utilization can be directly examined by measuring a metabolic endpoint rather than an intermediate (such as a metabolite in the tricarboxylic acid cycle). For instance, oxidation of specific substrates can be measured in vitro by incubation of live cultures with substrates containing radiolabeled carbon and measuring radiolabeled carbon dioxide. To increase throughput, we previously developed a miniaturized platform to measure substrate oxidation of both adherent and suspension cells using multiwell plates rather than flasks. This enabled multiple conditions to be examined simultaneously, ideal for drug screens and mechanistic studies. However, like many metabolic assays, this was not compatible with bicarbonate-buffered media, which is susceptible to alkalinization upon exposure to gas containing little carbon dioxide such as air. While other buffers such as HEPES can overcome this problem, bicarbonate has additional biological roles as a metabolic substrate and in modulating hormone signaling. Here, we create a bicarbonate-buffered well-plate platform to measure substrate oxidation. This was achieved by introducing a sealed environment within each well that was equilibrated with carbon dioxide, enabling bicarbonate buffering. As proof of principle, we assessed metabolic flux in cultured adipocytes, demonstrating that bicarbonate-buffered medium increased lipogenesis, glucose oxidation, and sensitivity to insulin in comparison to HEPES-buffered medium. This convenient and high-throughput method facilitates the study and screening of metabolic activity under more physiological conditions to aid biomedical research.     

Status and distribution of jaguarundi in Texas and Northeastern México: Making the case for extirpation and initiation of recovery in the United States

The jaguarundi (Puma yagouaroundi) is a small felid with a historical range from central Argentina through southern Texas. Information on the current distribution of this reclusive species is needed to inform recovery strategies in the United States where its last record was in 1986 in Texas. From 2003 to 2021, we conducted camera‐trap surveys across southern Texas and northern Tamaulipas, México to survey for medium‐sized wild cats (i.e., ocelots [Leopardus pardalis], bobcats [Lynx rufus], and jaguarundi). After 350,366 trap nights at 685 camera sites, we did not detect jaguarundis at 16 properties or along 2 highways (1050 km²) in Texas. However, we recorded 126 jaguarundi photographic detections in 15,784 trap nights on 2 properties (125.3 km²) in the northern Sierra of Tamaulipas, Tamaulipas, México. On these properties, latency to detection was 72 trap nights, with a 0.05 probability of detection per day and 0.73 photographic event rate every 100 trap nights. Due to a lack of confirmed class I sightings (e.g., specimen, photograph) in the 18 years of this study, and no other class I observations since 1986 in the United States, we conclude that the jaguarundi is likely extirpated from the United States. Based on survey effort and results from México, we would have expected to detect jaguarundis over the course of the study if still extant in Texas. We recommend that state and federal agencies consider jaguarundis as extirpated from the United States and initiate recovery actions as mandated in the federal jaguarundi recovery plan. These recovery actions include identification of suitable habitat in Texas, identification of robust populations in México, and re‐introduction of the jaguarundi to Texas.     

Gene trap insertional mutagenesis in mice: New vectors and germ Line mutations in two novel genes

Insertional mutagenesis based on gene trap vectors that capture endogenous splice sites is a promising tool for functional genomics. Several groups have proposed large-scale gene trap screens, but questions remain as to the type of vectors and their design. We report a set of plasmid-encoded gene trap vectors and the disruption of two novel genes. Our results include a comparison of the relative gene trapping efficiencies of two different splice acceptor sequences in ES cells and an analysis of the structure of several gene trap insertions.