The organic–inorganic halide CH3NH3PbI3 (MAPbI3) has been the most commonly used light absorber layer of perovskite solar cells (PSCs); however, solution‐processed MAPbI3 films usually suffer from ...random crystal orientation and high trap density, resulting in inferior power conversion efficiency (PCE) with open circuit voltage (Voc) being typically below 1.2 V for PSC devices. Herein, for the first time an imidazole sulfonate zwitterion, 4‐(1H‐imidazol‐3‐ium‐3‐yl)butane‐1‐sulfonate (IMS), is applied as a bifunctional additive in regular‐structure planar heterojunction PSC devices to regulate the crystal orientation, yielding highly ordered MAPbI3 film and passivating the trap states of the film. Such a dual effect of IMS is fulfilled via coordination interactions between the sulfonate moiety of IMS with the Pb2+ ion and the electrostatic interaction between the imidazole of IMS with the I– ion of MAPbI3. As a result, under a optimized IMS doping ratio of 0.5 wt%, the PSC device exhibits a significant increase in PCE from 18.77% to 20.84%, with suppressed current–voltage hysteresis and promoted ambient stability. Moreover, a high Voc of 1.208 V is achieved under a higher IMS doping ratio of 1.2 wt%, which is the highest Voc for regular‐structure MAPbI3 planar PSC devices based on TiO2 electron transport layer.
A bifunctional zwitterion additive affords efficiency enhancement of perovskite solar cells: an imidazole sulfonate zwitterion is doped into a CH3NH3PbI3 precursor solution as a bifunctional additive, enabling regulation of crystalline grain orientation and passivation of trap states. As a result, a significant efficiency enhancement and a high open circuit voltage (Voc) of 1.208 V are achieved.
α‐Allenol is a versatile synthon in organic synthesis. The catalytic asymmetric synthesis of α‐allenols from readily available starting materials remains a prominent challenge, especially when ...simultaneous control over axial and central chirality is required. Herein, we describe the Cr‐catalyzed enantioconvergent allenylation of aldehydes with racemic propargyl halides to rapidly access a wide range of chiral α‐allenols with adjacent axial and central chiralities. This method features excellent regio‐, diastereo‐ and enantioselectivity control with broad substrate scope, and provides facile access to all four stereoisomers when allied with a Mitsunobu reaction. Preliminary mechanistic studies support radical‐based reaction pathways. The synthetic utility is demonstrated by the application in late‐stage functionalization and the formal total synthesis of (+)‐varitriol.
A Cr‐catalyzed enantioconvergent allenylation reaction of aldehydes with racemic propargyl halides has been developed. This robust method employs simple and readily accessible materials, exhibits exceptional functional group tolerance and broad substrate scope, and provides facile access to a wide range of valuable optically enriched α‐allenols with two or three continuous chiral centers, including both central and axial chirality.
Transition‐metal dichalcogenides (TMDs) have attracted considerable attention in recent years because of their unique properties and promising applications in electrochemical energy storage and ...conversion. However, the limited number of active sites as well as blocked ion and mass transport severely impair their electrochemical performance. The construction of three‐dimensional (3D) architectures from TMD nanomaterials has been proven to be an effective strategy to solve the aforementioned problems as a result of their large specific surface areas and short ion and mass transport distances. This Review summarizes the commonly used routes to build 3D TMD architectures and highlights their applications in electrochemical energy storage and conversion, including batteries, supercapacitors, and electrocatalytic hydrogen evolution. The challenges and outlook in this research area are also discussed.
Electrochemistry in 3D: Three‐dimensional transition‐metal dichalcogenide architectures have shown great promise for electrochemical energy storage and conversion. This Review summarizes the commonly used strategies for the construction of such architectures, as well as their application in rechargeable batteries, supercapacitors, and electrocatalytic hydrogen evolution.
Although great progress has been achieved in the study of graphene, the small current ON/OFF ratio in graphene-based field-effect transistors (FETs) limits its application in the fields of ...conventional transistors or logic circuits for low-power electronic switching. Recently, layered transition metal dichalcogenide (TMD) materials, especially MoS2, have attracted increasing attention. In contrast to its bulk material with an indirect band gap, a single-layer (1L) MoS2 nanosheet is a semiconductor with a direct band gap of ∼1.8 eV, which makes it a promising candidate for optoelectronic applications due to the enhancement of photoluminescence and high current ON/OFF ratio. Compared with TMD nanosheets prepared by chemical vapor deposition and liquid exfoliation, mechanically exfoliated ones possess pristine, clean, and high-quality structures, which are suitable for the fundamental study and potential applications based on their intrinsic thickness-dependent properties. In this Account, we summarize our recent research on the preparation, characterization, and applications of 1L and multilayer MoS2 and WSe2 nanosheets produced by mechanical exfoliation. During the preparation of nanosheets, we proposed a simple optical identification method to distinguish 1L and multilayer MoS2 and WSe2 nanosheets on a Si substrate coated with 90 and 300 nm SiO2. In addition, we used Raman spectroscopy to characterize mechanically exfoliated 1L and multilayer WSe2 nanosheets. For the first time, a new Raman peak at 308 cm–1 was observed in the spectra of WSe2 nanosheets except for the 1L WSe2 nanosheet. Importantly, we found that the 1L WSe2 nanosheet is very sensitive to the laser power during characterization. The high power laser-induced local oxidation of WSe2 nanosheets and single crystals was monitored by Raman spectroscopy and atomic force microscopy (AFM). Hexagonal and monoclinic structured WO3 thin films were obtained from the local oxidization of single- to triple-layer (1L-3L) and quadruple- to quintuple-layer (4L-5L) WSe2 nanosheets, respectively. Then, we present Raman characterization of shear and breathing modes of 1L and multilayer MoS2 and WSe2 nanosheets in the low frequency range (<50 cm–1), which can be used to accurately identify the layer number of nanosheets. Magnetic force microscopy was used to characterize 1L and multilayer MoS2 nanosheets, and thickness-dependent magnetic response was found. In the last part, we briefly introduce the applications of 1L and multilayer MoS2 nanosheets in the fields of gas sensors and phototransistors.
Purpose To use meta-analysis techniques to evaluate the efficacy and safety of platelet-rich plasma (PRP) injections for the treatment knee of osteoarthritis (OA). Methods We performed a systematic ...literature search in PubMed, Embase, Scopus, and the Cochrane database through April 2016 to identify Level I randomized controlled trials that evaluated the clinical efficacy of PRP versus control treatments for knee OA. The primary outcomes were Western Ontario and McMaster Universities Osteoarthritis Index (WOMAC) pain and function scores. The primary outcomes were compared with their minimum clinically important differences (MCID)—defined as the smallest difference perceived as important by the average patient. Results We included 10 randomized controlled trials with a total of 1069 patients. Our analysis showed that at 6 months postinjection, PRP and hyaluronic acid (HA) had similar effects with respect to pain relief (WOMAC pain score) and functional improvement (WOMAC function score, WOMAC total score, International Knee Documentation Committee score, Lequesne score). At 12 months postinjection, however, PRP was associated with significantly better pain relief (WOMAC pain score, mean difference −2.83, 95% confidence interval CI −4.26 to −1.39, P = .0001) and functional improvement (WOMAC function score, mean difference −12.53, 95% CI −14.58 to −10.47, P < .00001; WOMAC total score, International Knee Documentation Committee score, Lequesne score, standardized mean difference 1.05, 95% CI 0.21-1.89, P = .01) than HA, and the effect sizes of WOMAC pain and function scores at 12 months exceeded the MCID (−0.79 for WOMAC pain and −2.85 for WOMAC function score). Compared with saline, PRP was more effective for pain relief (WOMAC pain score) and functional improvement (WOMAC function score) at 6 months and 12 months postinjection, and the effect sizes of WOMAC pain and function scores at 6 months and 12 months exceeded the MCID. We also found that PRP did not increase the risk of adverse events compared with HA and saline. Conclusions Current evidence indicates that, compared with HA and saline, intra-articular PRP injection may have more benefit in pain relief and functional improvement in patients with symptomatic knee OA at 1 year postinjection. Level of Evidence Level I, meta-analysis of Level I studies.
The first small follicles to appear in the mammalian ovaries are primordial follicles. The initial pool of primordial follicles serves as the source of developing follicles and oocytes for the entire ...reproductive lifespan of the animal. Although the selective activation of primordial follicles is critical for female fertility, its underlying mechanisms have remained poorly understood.
A search of PubMed was conducted to identify peer-reviewed literature pertinent to the study of mammalian primordial follicle activation, especially recent reports of the role of primordial follicle granulosa cells (pfGCs) in regulating this process.
In recent years, molecular mechanisms that regulate the activation of primordial follicles have been elucidated, mostly through the use of genetically modified mouse models. Several molecules and pathways operating in both the somatic pfGCs and oocytes, such as the phosphatidylinositol 3 kinase (PI3K) and the mechanistic target of rapamycin complex 1 (mTORC1) pathways, have been shown to be important for primordial follicle activation. More importantly, recent studies have provided an updated view of how exactly signaling pathways in pfGCs and in oocytes, such as the KIT ligand (KL) and KIT, coordinate in adult ovaries so that the activation of primordial follicles is achieved.
In this review, we have provided an updated picture of how mammalian primordial follicles are activated. The functional roles of pfGCs in governing the activation of primordial follicles in adulthood are highlighted. The in-depth understanding of the cellular and molecular mechanisms of primordial follicle activation will hopefully lead to more treatments of female infertility, and the current progress indicates that the use of existing primordial follicles as a source for obtaining fertilizable oocytes as a new treatment for female infertility is just around the corner.
Background and Aims
Hepatic ischemia‐reperfusion (I/R) injury, which mainly involves inflammatory responses and apoptosis, is a common cause of organ dysfunction in liver transplantation (LT). As a ...critical mediator of inflammation and apoptosis in various cell types, the role of tripartite motif‐containing (TRIM) 27 in hepatic I/R injury remains worthy of study.
Approach and Results
This study systemically evaluated the putative role of TRIM27/transforming growth factor β–activated kinase 1 (TAK1)/JNK (c‐Jun N‐terminal kinase)/p38 signaling in hepatic I/R injury. TRIM27 expression was significantly down‐regulated in liver tissue from LT patients, mice subjected to hepatic I/R surgery, and hepatocytes challenged by hypoxia/reoxygenation (H/R) treatment. Subsequently, using global Trim27 knockout mice (Trim27‐KO mice) and hepatocyte‐specific Trim27 transgenic mice (Trim27‐HTG mice), TRIM27 functions to ameliorate liver damage, reduce the inflammatory response, and prevent cell apoptosis. In parallel in vitro studies, activating TRIM27 also prevented H/R‐induced hepatocyte inflammation and apoptosis. Mechanistically, TRIM27 constitutively interacted with the critical components, TAK1 and TAK1 binding protein 2/3 (TAB2/3), and promoted the degradation of TAB2/3, leading to inactivation of TAK1 and the subsequent suppression of downstream JNK/p38 signaling.
Conclusions
TRIM27 is a key regulator of hepatic I/R injury by mediating the degradation of TAB2/3 and suppression of downstream TAK1‐JNK/p38 signaling. TRIM27 may be a promising approach to protect the liver against I/R‐mediated hepatocellular damage in transplant recipients.
Guest editors Manish Chhowalla, Zhongfan Liu and Hua Zhang introduce the Two-dimensional Transition Metal Dichalcogenide (TMD) Nanosheets issue of
Chemical Society Reviews
This paper focuses on the problem of global finite-time stabilization for a class of uncertain nonlinear systems with event-triggered inputs. The existing event-based design methods can only ...partially compensate for the effects of the event-triggered errors and cannot completely counteract them to achieve finite-time control. For this reason, a new method about event triggering mechanism and event-triggered controller codesign is presented based on the idea of backstepping design and the sign function technique. It is proved that the event-triggered control system is the Zeno-free and the newly proposed control strategy ensures the global finite-time stability of the closed-loop systems via Lyapunov analyses and finite-time stability theory, which improves the existing results of only boundedness or asymptotic stability. Finally, two examples are performed to demonstrate the validity of the proposed strategy.
Microbial abundance and community composition in marine sediments have been widely explored. However, high‐resolution vertical changes of benthic microbial diversity and co‐occurrence patterns are ...poorly described. The ecological contributions of abundant and rare species in sediments also remain largely unknown. Here, by analysing microbial populations at 14 depth layers of 10 subseafloor sediment cores (water depth 1,250–3,530 m) obtained in the South China Sea, we provided the vertical profiles of microbial β‐diversity and co‐occurrence influenced by subcommunities of different abundance. These 134 sediment samples were clustered into four groups according to sediment depth (1–2, 6–10, 30–90 and 190–790 cm) with obvious shifts in microbial community compositions. The vertical succession of microorganisms was consistent with redox zonation and influenced by terrestrial inputs. Partitioning of vertical β‐diversity showed extremely high species replacement between deep layers and the surface layer, indicating selection‐induced loss of rare species and dispersal of dormant cells and spores. By contrast, for horizontal β‐diversity, richness of rare species became increasingly significant in deep sediments. Accompanying this β‐diversity profile were clear changes in the association pattern, with microorganisms being less connected in deeper sediment layers, probably reflecting reduced syntrophic interactions. Rare species accounted for an indispensable proportion in the co‐occurrence network, and tended to form complex “small worlds.” The rare subcommunity also responded differently to various environmental factors compared with the abundant subcommunity. Our findings expand current knowledge on vertical changes of marine benthic microbial diversity and their association patterns, emphasizing the potential roles of rare species.
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