A highly enantioselective synthesis of various chiral heterobicyclic molecules including spiroaminals and fused bicyclic acetals has been developed via a chiral copper catalyzed ...cyclopropanation‐rearrangement (CP‐RA) approach under mild reaction conditions. Remarkably, the asymmetric CP‐RA for exocyclic vinyl substrates without a pro‐stereogenic carbon at the β‐position has been realized for the first time and a broad substrate scope with excellent results (33 examples; 34–99 % yields; >95/5 dr and 91–99 % ee) has been achieved. An application of a successive enantioselective CP‐RA approach was also described, providing a concise access to complex chiral heteropolycycles.
An effective divergent synthesis of chiral spiroaminals and fused bicyclic acetals has been realized in up to 99 % yield with up to 99 % ee via an unusual enantioselective cyclopropanation‐rearrangement process.
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BFBNIB, FZAB, GIS, IJS, KILJ, NLZOH, NUK, OILJ, SAZU, SBCE, SBMB, UL, UM, UPUK
The Hengduan Mountains (HDM) biodiversity hotspot exhibits exceptional alpine plant diversity. Here, we investigate factors driving intraspecific divergence within a HDM alpine species Salix ...brachista (Cushion willow), a common component of subnival assemblages. We produce a high-quality genome assembly for this species and characterize its genetic diversity, population structure and pattern of evolution by resequencing individuals collected across its distribution. We detect population divergence that has been shaped by a landscape of isolated sky island-like habitats displaying strong environmental heterogeneity across elevational gradients, combined with population size fluctuations that have occurred since approximately the late Miocene. These factors are likely important drivers of intraspecific divergence within Cushion willow and possibly other alpine plants with a similar distribution. Since intraspecific divergence is often the first step toward speciation, the same factors can be important contributors to the high alpine species diversity in the HDM.
Aim: The Himalaya-Hengduan Mountain (HHM) biodiversity hotspot including the 'sky islands' of Southwest China harbour exceptional plant diversity and endemicity at subnival summits (most of them ...exceeding 4300 m a.s.l.). This study is the first using a comparative phylogeographical framework to gain insights into the temporal origin of this highly fragmented subnival flora, and the historical factors shaping its genetic architecture as exemplified by four perennial herbs. Location: Himalaya-Hengduan Mountains, China. Methods: Based on nuclear and/or chloroplast (cp) DNA sequences for each of the four studied species, we performed AMOVA and mismatch distributional analyses to assess molecular structure, diversity and demographic history in relation to current and last glacial distributions using ecological niche modelling (ENM). Time-calibrated phylogenetic reconstructions of cpDNA data were used to infer species-specific stem and crown ages. Results: Our time estimates suggest that these species originated during the Late Pliocene or early-to-mid Pleistocene, whereas their onset of diversification generally falls into the mid-Pleistocene. All four species exhibited island-like population genetic structures, with all of them showing signatures of recent population growth and/or spatial expansion based on cpDNA. By contrast, ENM indicated that species broad-scale distributions remained fairly stable over the last glacial/post-glacial cycle. Main conclusions: The temporal origin of the four subnival HHM species is likely associated with tectonic changes in the region, while their near-simultaneous onset of diversification during the 'Naynayxungla Glaciation' (0.72-0.50 Ma) could reflect initial population divergence through climate-induced habitat fragmentation. Despite a rather stable distributional history, geographical population isolation and localized range expansion/contractions likely resulted in significant genetic structure and differentiation over the last glacial/post-glacial cycle. Overall, the present results are strongly indicative of shared evolutionary histories and phylogeographical structures among subnival plants from the 'sky island system' of the HHM region.
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BFBNIB, FZAB, GIS, IJS, KILJ, NLZOH, NMLJ, NUK, OILJ, PNG, SAZU, SBCE, SBMB, UL, UM, UPUK
A thorough insight into the initiation, segmentation, propagation and interaction of multitrend basin‐bounding faults is crucial to restoring the growth history of the faults and clarifying the fault ...growth pattern and its influence on the structures developed along the margin due to the growth of the basin‐bounding faults, but systematic studies on the individual influence of the evolution of each fault segment on the present structure are lacking. Based on 3D seismic data, the timing and growth of multitrend basin‐bounding faults were analysed using T‐z plots and throw backstripping, allowing us to determine the individual effects that each fault segment evolution exerteds on the present‐day configuration of the northern margin of the Nanpu Sag. The basin‐bounding fault is composed of the Xinanzhuang and Baigezhuang faults, and the Xinanzhuang fault comprises three linked segments with varying orientations (i.e., NE–SW, E–W, and NNE–SSW). In comparison, the Baigezhuang fault comprises only two linked NW–SE‐oriented fault segments. The evolution process can be divided into three stages. (1) During the early synrift I stage, namely, the isolated fault stage, five isolated multitrend basin‐bounding segments were active. (2) During the late synrift I stage, namely, the hard‐linkage stage, the five segments propagated laterally and linked with each other, behaving as a single fault. Meanwhile, the NE‐trending No. 5 Fault bifurcated upward from the basin‐bounding fault to accommodate local stress, and the NW‐trending Gaobei Fault deviated from the basin‐bounding fault controlled by local stresses induced by differential activities of the multitrend fault segments under the same far‐field stress. (3) During the synrift II to postrift linkage development stage, the extension orientation changed from NW–SE‐ to N–S, and additional displacement accumulated along the basin‐bounding fault without further lateral propagation. Newly formed E–W‐trending faults developed orthogonal to the extension orientation and linked with preexisting NE‐ or NW‐trending faults, forming a complex fault zone. In addition, influenced by the geometry of the basin‐bounding fault, the Laoyemiao Anticline formed by gravitational collapse under the dual action of a rollover anticline and transverse anticline. Furthermore, the evolution of the basin‐bounding faults played an important role in controlling the source‐to‐sink system, and the transition zone was the main provenance channel formed by the segmented growth of the faults. This study provides new insight into multitrend large fault evolution, and their impact on basin development provides a comprehensive explanation of the later structures developed in polyphase rifts.
Related deformation of the hanging‐wall of XF1, XF2 and XF3 of the Nanpu Sag in three‐dimensional views (a–c) and the conceptual model (d–f). Branch lines are highlighted by bold lines.
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FZAB, GIS, IJS, KILJ, NLZOH, NUK, OILJ, SAZU, SBCE, SBMB, UL, UM, UPUK
A rotating packed bed (RPB) is recognized for its merits in chemical process intensification. In most studies of RPB mass transfer modeling, however, the effects of the end and cavity zones have not ...been taken into consideration, since it was very difficult to distinguish the end and bulk zones by hydrodynamics and mass transfer process. In this work, the radial thickness of the end zone was obtained by developing a probability method and imaging experiments to separate the end and bulk zones. A three‐zone model, including end, bulk, and cavity zones, of the overall gas‐side volumetric mass transfer coefficient (KGa)t was first established. Experiments of dissolved MEA chemisorption of CO2 were carried out to validate the proposed three‐zone mass transfer model. The results of the MEA‐CO2 absorption experiments showed that the experimentally obtained values of CO2 absorption efficiency were in agreement within ±20% with the model predictions.
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BFBNIB, FZAB, GIS, IJS, KILJ, NLZOH, NUK, OILJ, SAZU, SBCE, SBMB, UL, UM, UPUK
Long noncoding RNAs (lncRNAs) play roles in the development and progression of many cancers; however, the contributions of lncRNAs to human gallbladder cancer (GBC) remain largely unknown. In this ...study, we identify a group of differentially expressed lncRNAs in human GBC tissues, including prognosis-associated gallbladder cancer lncRNA (lncRNA-PAGBC), which we find to be an independent prognostic marker in GBC. Functional analysis indicates that lncRNA-PAGBC promotes tumour growth and metastasis of GBC cells. More importantly, as a competitive endogenous RNA (ceRNA), lncRNA-PAGBC competitively binds to the tumour suppressive microRNAs miR-133b and miR-511. This competitive role of lncRNA-PAGBC is required for its ability to promote tumour growth and metastasis and to activate the AKT/mTOR pathway. Moreover, lncRNA-PAGBC interacts with polyadenylate binding protein cytoplasmic 1 (PABPC1) and is stabilized by this interaction. This work provides novel insight on the molecular pathogenesis of GBC.
Synopsis
Long noncoding RNAs play roles in the development and progression of many cancers. In this study the lncRNA PAGBC is identified as promoting tumorigenesis in human gallbladder cancer by competitive binding to the tumour suppressive microRNAs miR-133b and miR-511.
LncRNA-PAGBC is up-regulated in GBC and increased levels associate with poor prognosis.
LncRNA-PAGBC promotes tumour growth and metastasis, and activates AKT/mTOR signaling by competitively binding to mirR-133b and mirR-511.
LncRNA-PAGBC interacts with and is stabilized by the polyadenylate binding protein PABPC1.
Graphical Abstract
Long noncoding RNAs play roles in the development and progression of many cancers. In this study the lncRNA PAGBC is identified as promoting tumorigenesis in human gallbladder cancer by competitive binding to the tumour suppressive microRNAs miR-133b and miR-511.
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FZAB, GIS, IJS, KILJ, NLZOH, NUK, OILJ, SAZU, SBCE, SBMB, UL, UM, UPUK
Systemic analyses using large‐scale genomic profiles have successfully identified cancer‐driving somatic copy number variations (SCNVs) loci. However, functions of vast focal SCNVs in “protein‐coding ...gene desert” regions are largely unknown. The integrative analysis of long noncoding RNA (lncRNA) expression profiles with SCNVs in hepatocellular carcinoma (HCC) led us to identify the recurrent deletion of lncRNA‐PRAL (p53 regulation‐associated lncRNA) on chromosome 17p13.1, whose genomic alterations were significantly associated with reduced survival of HCC patients. We found that lncRNA‐PRAL could inhibit HCC growth and induce apoptosis in vivo and in vitro through p53. Subsequent investigations indicated that the three stem‐loop motifs at the 5′ end of lncRNA‐PRAL facilitated the combination of HSP90 and p53 and thus competitively inhibited MDM2‐dependent p53 ubiquitination, resulting in enhanced p53 stability. Additionally, in vivo lncRNA‐PRAL delivery efficiently reduced intrinsic tumors, indicating its potential therapeutic application. Conclusions: lncRNA‐PRAL, one of the key cancer‐driving SCNVs, is a crucial stimulus for HCC growth and may serve as a potential target for antitumor therapy. (Hepatology 2016;63:850‐863)
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BFBNIB, FZAB, GIS, IJS, KILJ, NLZOH, NUK, OILJ, SAZU, SBCE, SBMB, UL, UM, UPUK
Here, the consecutive‐competitive reaction system about aspirin and sodium hydroxide was proposed as a unified chemical probe to characterize the homogenous and heterogeneous liquid–liquid mixing. ...The kinetics of the reaction system was clearly studied. Then the mixing efficiencies were assessed in a standard stirred tank with this chemical probe and the obtained segregation index (XS) could well characterize the mixing performance. Based on the incorporation model, the estimation formula of micromixing time was established as tm=13.956ν/ε0.5. The chemical probe could show the influence of stirring intensity, interphase resistance, and two‐phase ratio on the mixing efficiency sensitively when it was extended to heterogeneous mixing. Using this chemical probe, we found the mixing efficiencies of homogeneous and heterogeneous process tended to be the same at sufficiently high stirring intensity. The reason for this phenomenon was unveiled by investigating the dispersed phase size and calculating mass transfer time.
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BFBNIB, FZAB, GIS, IJS, KILJ, NLZOH, NUK, OILJ, SAZU, SBCE, SBMB, UL, UM, UPUK
A two-marker combination of plastid rbcL and matK has previously been recommended as the core plant barcode, to be supplemented with additional markers such as plastid trnH–psbA and nuclear ribosomal ...internal transcribed spacer (ITS). To assess the effectiveness and universality of these barcode markers in seed plants, we sampled 6,286 individuals representing 1,757 species in 141 genera of 75 families (42 orders) by using four different methods of data analysis. These analyses indicate that (i) the three plastid markers showed high levels of universality (87.1–92.7%), whereas ITS performed relatively well (79%) in angiosperms but not so well in gymnosperms; (ii) in taxonomic groups for which direct sequencing of the marker is possible, ITS showed the highest discriminatory power of the four markers, and a combination of ITS and any plastid DNA marker was able to discriminate 69.9–79.1% of species, compared with only 49.7% with rbcL + matK; and (iii) where multiple individuals of a single species were tested, ascriptions based on ITS and plastid DNA barcodes were incongruent in some samples for 45.2% of the sampled genera (for genera with more than one species sampled). This finding highlights the importance of both sampling multiple individuals and using markers with different modes of inheritance. In cases where it is difficult to amplify and directly sequence ITS in its entirety, just using ITS2 is a useful backup because it is easier to amplify and sequence this subset of the marker. We therefore propose that ITS/ITS2 should be incorporated into the core barcode for seed plants.
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BFBNIB, NMLJ, NUK, PNG, SAZU, UL, UM, UPUK
In this work, the kinetics study on the reaction between CO2 and tertiary amine catalyzed by zinc(II)‐1,4,8,11‐tetraazacyclotetradecane complexes (CM) and zinc(II)‐1,4,7,10‐tetraazacyclododecane ...complexes (CN) was carried out in a stopped‐flow device. The effects of the catalyst concentration, type of tertiary amines, and temperature on the reaction rate (ν) and catalytic activity (φ) were studied. It was found that the catalyst concentration, tertiary amine with higher pKa, and temperature had positive effects on ν. ν in N‐methyl diethanolamine solution with 10.0 mol m−3 CM and CN were 16.62 and 26.05 folds than the uncatalyzed ν at 298 K, respectively. φ increased with increasing catalyst concentration, decreasing temperature and tertiary amine's pKa. In addition, the kinetics behavior of tertiary amine‐CM/CN‐CO2 systems conformed to the Michaelis–Menten model. The activation energies in catalytic systems were 4%–15% lower than that in the non‐catalytic systems.
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