In catalytic asymmetric reactions, the formation of chiral molecules generally relies on a direct chirality transfer (point or axial chirality) from a chiral catalyst to products in the ...stereo-determining step. Herein, we disclose a transient-axial-chirality transfer strategy to achieve asymmetric reaction. This method relies on transferring point chirality from the catalyst to a dirhodium carbene intermediate with axial chirality, namely a transient-axial-chirality since this species is an intermediate of the reaction. The transient chirality is then transferred to the final product by C(sp
)-H functionalization reaction with exceptionally high enantioselectivity. We also generalize this strategy for the asymmetric cascade reaction involving dual carbene/alkyne metathesis (CAM), a transition-metal-catalyzed method to access chiral 9-aryl fluorene frameworks in high yields with up to 99% ee. Detailed DFT calculations shed light on the mode of the transient-axial-chirality transfer and the detailed mechanism of the CAM reaction.
An unprecedented gold-catalyzed bicyclization reaction of diaryl alkynes has been developed for the synthesis of indoles in good to high yields. Mechanistically, this alkyne bifunctionalization ...transformation was terminated by a stepwise formal X–H insertion reaction to furnish the corresponding polycyclic-frameworks with structural diversity, and the key intermediate 3H-indole was isolated and characterized for the first time. In addition, further transformation of these generated tetracyclic-indoles with PCC as the oxidant provided straightforward access to the spirooxindoles in high yields.
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IJS, KILJ, NUK, PNG, UL, UM
In recent years, a few asparaginyl endopeptidases (AEPs) from certain higher plants have been identified as efficient peptide ligases with wide applications in protein labeling and cyclic peptide ...synthesis. Recently, we developed a NanoLuc Binary Technology (NanoBiT)-based peptide ligase activity assay to identify more AEP-type peptide ligases. Herein, we screened 61 bamboo species from 16 genera using this assay and detected AEP-type peptide ligase activity in the crude extract of all tested bamboo leaves. From a popular bamboo species, Bambusa multiplex, we identified a full-length AEP-type peptide ligase candidate (BmAEP1) via transcriptomic sequencing. After its zymogen was overexpressed in Escherichia coli and self-activated in vitro, BmAEP1 displayed high peptide ligase activity, but with considerable hydrolytic activity. After site-directed mutagenesis of its ligase activity determinants, the mutant zymogen of G238VBmAEP1 was normally overexpressed in E. coli, but failed to activate itself. To resolve this problem, we developed a novel protease-assisted activation approach in which trypsin was used to cleave the mutant zymogen and was then conveniently removed via ion-exchange chromatography. After the noncovalently bound cap domain was dissociated from the catalytic core domain under acidic conditions, the recombinant G238VBmAEP1 displayed high peptide ligase activity with much lower hydrolytic activity and could efficiently catalyze inter-molecular protein ligation and intramolecular peptide cyclization. Thus, the engineered bamboo-derived peptide ligase represents a novel tool for protein labeling and cyclic peptide synthesis.
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BFBNIB, FZAB, GIS, IJS, KILJ, NLZOH, NUK, OILJ, SAZU, SBCE, SBMB, UL, UM, UPUK
Breakthroughs in micro/nanostructural optimization have led to significant improvements in the thermoelectric performance of CoSb
3
-based skutterudites these years. With regard to the severe service ...condition and the practically defective structure of skutterudites, a comprehensive understanding of the mechanical reliability is needed. The present work carries out molecular dynamics simulations to study the mechanical response and structural failure of single-crystalline bulk CoSb
3
with nanoscale defect holes subjected to uniaxial tension along 100 crystallographic direction at room temperature. To focus on the variation of mechanical failure with the hole size, each simulation model contains only one cylindrical cavity of circular cross section. For different models, the hole diameter changes, but the hole ratio remains constant and small. The variation of tensile stress with strain is obtained from models of different hole diameters. It is possible to make a mathematical fitting from the decrease in ultimate strength with the diameter increase. Critical hole diameter can be predicted from the fitting function, beyond which the hole diameter does not play a role in the structure’s load capacity. The cause of strength degradation, stress concentration at the hole edge, is analyzed as well. The crack happens at different locations on the hole edge for each hole diameter model based on local atomic configuration and interactions. The uniaxial tension is also performed along 110 and 210 directions, respectively, and the results show remarkable orientation discrepancy. Our simulation results are compared with those of the classical theory of elasticity, which helps understand the variation of mechanical responses when the scale comes down to nanometer for CoSb
3
.
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DOBA, EMUNI, FIS, FZAB, GEOZS, GIS, IJS, IMTLJ, IZUM, KILJ, KISLJ, MFDPS, NLZOH, NUK, OILJ, PILJ, PNG, SAZU, SBCE, SBJE, SBMB, SBNM, SIK, UILJ, UKNU, UL, UM, UPUK, VKSCE, ZAGLJ
The heat shock transcription factor (Hsf) is a crucial regulator of plant stress resistance, playing a key role in plant stress response, growth, and development regulation. In this study, we ...utilized bioinformatics tools to screen 25 VbHsf members, which were named VbHsf1-VbHsf25. We used bioinformatics methods to analyze the sequence structure, physicochemical properties, conserved motifs, phylogenetic evolution, chromosome localization, promoter cis-acting elements, collinearity, and gene expression of Hsf heat shock transcription factor family members under low-temperature stress. The results revealed that the majority of the Hsf genes contained motif1, motif2, and motif3, signifying that these three motifs were highly conserved in the Hsf protein sequence of Verbena bonariensis. Although there were some variations in motif deletion among the members, the domain remained highly conserved. The theoretical isoelectric point ranged from 4.17 to 9.71, with 21 members being unstable proteins and the remainder being stable proteins. Subcellular localization predictions indicated that all members were located in the nucleus. Phylogenetic analysis of the Hsf gene family in V. bonariensis and Arabidopsis thaliana revealed that the Hsf gene family of V. bonariensis could be categorized into three groups, with group A comprising 17 members and group C having at least two members. Among the 25 Hsf members, there were 1-3 exons located on seven chromosome fragments, which were unevenly distributed. Collinearity analysis demonstrated the presence of seven pairs of homologous genes in the VbHsf gene family. The Ka/Ks ratios were less than one, indicating that the VbHsf gene underwent purification selection pressure. Additionally, nine genes in V. bonariensis were found to have collinearity with A. thaliana. Promoter analysis revealed that the promoters of all VbHsf genes contained various types of cis-acting elements related to hormones and stress. Based on RNA-seq data, qRT-PCR analysis of six highly expressed genes was performed, and it was found that VbHsf5, VbHsf14, VbHsf17, VbHsf18, VbHsf20 and VbHsf21 genes were highly expressed at 12 h of low-temperature treatment, and the expression decreased after 24 h, among which VbHsf14 was up-regulated at 12 h of low-temperature by 70-fold. Our study may help reveal the important roles of Hsf in plant development and show insight for the further molecular breeding of V. bonariensis.
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DOBA, IZUM, KILJ, NUK, PILJ, PNG, SAZU, SIK, UILJ, UKNU, UL, UM, UPUK
Differential diagnosis between inflammatory mass and malignant glioma is of great significance to patients, which is the basis for developing accurate individualized treatment. Due to the lack of ...non-invasive imaging characterization methods in the clinical application, the current diagnosis grading of glioma mainly depended on the pathological biopsy, which is complicated and risky. This study aims to develop a non-invasive imaging differential diagnosis method of glioma based on the reduction activated strategy of intracellular aggregation of sensitive superparamagnetic Fe3O4 nanoparticles (SIONPs). In vitro and in vivo magnetic resonance imaging results indicated that SIONPs could specifically increase the T2 relaxation rate and enhance MR imaging in tumor with redox microenvironment by the response-aggregation in the tumorous site. In vivo experiments also demonstrate that the substantial improvement of T2-weighted imaging contrast could be used to differentiate inflammatory mass and malignant glioma. The reduction-active MR imaging contrast agent offers a new paradigm for designing “smart” MR imaging probes of differential diagnosis of the tumor.
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GEOZS, IJS, IMTLJ, KILJ, KISLJ, NLZOH, NUK, OILJ, PNG, SAZU, SBCE, SBJE, UILJ, UL, UM, UPCLJ, UPUK, ZAGLJ, ZRSKP
In this study, we performed an association analysis of metabolomics and transcriptomics to reveal the anthocyanin biosynthesis mechanism in a new purple-leaf tea cultivar Zikui (Camellia sinensis cv. ...Zikui) (ZK). Three glycosylated anthocyanins were identified, including petunidin 3-O-glucoside, cyanidin 3-O-galactoside, and cyanidin 3-O-glucoside, and their contents were the highest in ZK leaves at 15 days. This is the first report on petunidin 3-O-glucoside in purple-leaf tea. Integrated analysis of the transcriptome and metabolome identified eleven dependent transcription factors, among which CsMYB90 had strong correlations with petunidin 3-O-glucoside, cyanidin 3-O-galactoside, and cyanidin 3-O-glucoside (PCC > 0.8). Furthermore, we also identified key correlated structural genes, including two positively correlated F3’H (flavonoid-3′-hydroxylase) genes, two positively correlated ANS (anthocyanin synthase) genes, and three negatively correlated PPO (polyphenol oxidase) genes. Overexpression of CsMYB90 in tobacco resulted in dark-purple transgenic calluses. These results showed that the increased accumulation of three anthocyanins in ZK may promote purple-leaf coloration because of changes in the expression levels of genes, including CsMYB90, F3’Hs, ANSs, and PPOs. These findings reveal new insight into the molecular mechanism of anthocyanin biosynthesis in purple-leaf tea plants and provide a series of candidate genes for the breeding of anthocyanin-rich cultivars.
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IZUM, KILJ, NUK, PILJ, PNG, SAZU, UL, UM, UPUK
Abstract
The monitoring of cage longitudinal vibration can directly indicate the operational status of mine hoists. However, it is always challenging to collect the sensor signals of moving cages ...with high dynamic characteristics in real time from complex working environments using traditional monitoring methods. In this study, a more practical hybrid signal fusion approach is proposed to realize estimation of cage longitudinal vibration from a low sampling rate acceleration acquisition signal and a low cost encoder signal for state estimation. A nonlinear differentiator is applied to extract encoder differential signals and expand observation variables. An unscented Kalman observer based on nonlinear mine hoist model is designed to estimate the unknown state. To overcome the influence of the uncertain parameters, an improved differential evolution (DE) algorithm combining parameter adaptive method, reverse learning competition scheme and multiple parallel populations strategy is proposed to find unknown parameters of the observation model and autotune the parameters of the algorithms by using low sampling rate acceleration. Sensor data of the simulated experiment platform were collected and processed by the
x
PC system to validate the effectiveness of the proposed strategy. The experimental results showed that the improved DE (IDE) algorithm had a faster mean time for parameter tuning and the smallest fitness value compared to the standard DE, the particle swarm optimization algorithm and the genetic algorithm. Moreover, the longitudinal vibration estimation system, after parameter tuning by the IDE optimization algorithm, could achieve the purpose of signal estimation, with a smaller estimation error and a better estimation effect.
The aim of this study was to investigate the relationship between maternal body mass index and all congenital heart defects (CHDs) combined and 11 individual defects. PubMed, ELSEVIER ScienceDirect, ...and Springer Link (up to February 2013) were searched, and the reference list of retrieved articles was reviewed. Three authors independently extracted the data. The systematic review included 24 studies, 14 of which were included in a metaanalysis. Statistical software was used to perform all statistical analyses. Fixed-effects or random-effects model was used to pool the results of individual study (expressed as odds ratios ORs with 95% confidence intervals CIs). A dose-response effect was observed between overweight, moderate obesity, and severe obesity and a pregnancy with any CHD (the pooled ORs: OR, 1.08 95% CI, 1.02–1.15; OR, 1.15 95% CI, 1.11–1.20; and OR, 1.39 95% CI, 1.31–1.47, respectively) as well as some individual defects such as hypoplastic left heart syndrome, pulmonary valve stenosis, and outflow tract defects. When we excluded mothers with diabetes mellitus, the pooled ORs for all CHDs combined were 1.12 (95% CI, 1.04–1.20) and 1.38 (95% CI, 1.20–1.59) for moderately obese and severely obese, respectively. The highest increased risk was severely obese mothers for tetralogy of Fallot (OR, 1.94; 95% CI, 1.49–2.51). Being underweight did not increase the risk of any of the aforementioned CHDs but did increase the risk of aortic valve stenosis (OR, 1.47; 95% CI, 1.01–2.15). The results of our study showed that increasing maternal body mass index was associated with an increasing risk of CHDs; severe obesity was an even greater risk factor for the development of CHDs.
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GEOZS, IJS, IMTLJ, KILJ, KISLJ, NUK, OILJ, PNG, SAZU, SBCE, SBJE, UL, UM, UPCLJ, UPUK
Bamboos, regarded as therapeutic agents in ethnomedicine, have been used to inhibit inflammation and enhance natural immunity for a long time in Asia, and there are many bamboo associated fungi with ...medical and edible value. In the present study, a total of 350 fungal strains were isolated from the uncommon moso bamboo (Phyllostachys edulis) seeds for the first time. The molecular diversity of these endophytic fungi was investigated and bioactive compound producers were screened for the first time. All the fungal endophytes were categorized into 69 morphotypes according to culturable characteristics and their internal transcriber spacer (ITS) regions were analyzed by BLAST search with the NCBI database. The fungal isolates showed high diversity and were divided in Ascomycota (98.0%) and Basidiomycota (2.0%), including at least 19 genera in nine orders. Four particular genera were considered to be newly recorded bambusicolous fungi, including Leptosphaerulina, Simplicillium, Sebacina and an unknown genus in Basidiomycetes. Furthermore, inhibitory effects against clinical pathogens and phytopathogens were screened preliminarily and strains B09 (Cladosporium sp.), B34 (Curvularia sp.), B35 (undefined genus 1), B38 (Penicillium sp.) and zzz816 (Shiraia sp.) displayed broad-spectrum activity against clinical bacteria and yeasts by the agar diffusion method. The crude extracts of isolates B09, B34, B35, B38 and zzz816 under submerged fermentation, also demonstrated various levels of bioactivities against bambusicolous pathogenic fungi. This study is the first report on the antimicrobial activity of endophytic fungi associated with moso bamboo seeds, and the results show that they could be exploited as a potential source of bioactive compounds and plant defense activators. In addition, it is the first time that strains of Shiraia sp. have been isolated and cultured from moso bamboo seeds, and one of them (zzz816) could produce hypocrellin A at high yield, which is significantly different from the other strains published.
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DOBA, IZUM, KILJ, NUK, PILJ, PNG, SAZU, SIK, UILJ, UKNU, UL, UM, UPUK
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