The design and synthesis of advanced semiconductors is crucial for the full utilization of solar energy. Herein, colloidal selective‐epitaxial hybrid of tripartite semiconducting sulfides ...CuInS2Cd(In)SMoS2 heteronanostructures (HNs) via lateral‐ and vertical‐epitaxial growths, followed by cation exchange reactions, are reported. The lateral‐epitaxial CuInS2 and Cd(In)S enable effective visible to near‐infrared (NIR) solar spectrum absorption, and the vertical‐epitaxial ultrathin MoS2 offer sufficient edge sulfur sites for the hydrogen evolution reaction (HER). Furthermore, the integrated structures exhibit unique epitaxial‐staggered type II band alignments for continuous charge separation. They achieve the H2 evolution rate up to 8 mmol h−1 g−1, which is ≈35 times higher than bare CdS and show no deactivation after long‐term cycling, representing one of the most efficient and robust noble‐metal‐free photocatalysts. This design principle and transformation protocol open a new way for creating all‐in‐one multifunctional catalysts in a predictable manner.
A wet‐chemical strategy for the selective‐epitaxial hybrid of unique tripartite semiconducting sulfide heteronanostructures CuInS2Cd(In)SMoS2 is reported. The stepwise integrated structures demonstrate superior solar‐to‐hydrogen conversion performance due to the enhanced capabilities for solar absorption and charge separation, together with sufficient catalytically active sites.
Our previous works have indicated that extracellular ATP is an important prometastasis factor. However, the molecular mechanism involved needs to be further studied. We demonstrated that ...extracellular ATP treatment could upregulate the expression of connective tissue growth factor (CTGF) in both triple‐negative breast cancer (TNBC) cells and endothelial cells (ECs). Extracellular ATP stimulated the migration of TNBC cells and ECs, and angiogenesis of ECs via the P2Y2––YAP‐CTGF axis. Furthermore, we demonstrated that adenosine triphosphate (ATP) stimulated TNBC cell adhesion to ECs and transmigration through the EC layer via CTGF by upregulation of integrin β1 on TNBC cells and VCAM‐1 on ECs. Both apyrase (ATP‐diphosphohydrolase) and CTGF shRNA treatments could inhibit the metastasis of inoculated tumors to lung and liver in a mouse model, and these treated tumors had fewer blood vessels. Collectively, our data indicated that extracellular ATP promotes tumor angiogenesis and the interactions between TNBC cells and ECs through upregulation of CTGF, thereby stimulating TNBC metastasis. The pleiotropic effects of ATP in angiogenesis and cell adhesion suggest that extracellular ATP or CTGF could be an effective target for TNBC therapy.
The proposed model for the ATP–CTGF axis in TNBC invasion and metastasis. ATP upregulates CTGF expression and secretion in TNBC cells and ECs. For TNBC cells, secreted CTGF enhanced their migration and integrin β1 expression. For EC cells, secreted CTGF enhanced their migration and angiogenesis, as well as VCAM‐1 expression. The upregulated integrin β1 and VCAM‐1 promoted TNBC cell adhesion to ECs and transmigration through the ECs layer.
Reported is a highly enantioselective copper‐catalyzed Markovnikov protoboration of unactivated terminal alkenes. A variety of simple and abundant feedstock α‐olefins bearing a diverse array of ...functional groups and heterocyclic substituents can be used as substrates, and the reaction proceeds under mild reaction conditions at ambient temperature to provide expedient access to enantioenriched alkylboronic esters in good regioselectivity and with excellent enantiocontrol. Critical to the success of the protocol was the development and application of a novel, sterically hindered N‐heterocyclic carbene, (R,R,R,R)‐ANIPE, as the ligand for copper.
By design: A highly enantioselective copper‐catalyzed Markovnikov protoboration of α‐olefins is described. This mild and general process effectively converts simple and abundant feedstock α‐olefins into a diverse array of chiral alkylboronic esters with excellent enantiocontrol. Key to the success of the protocol was the use of a newly developed, sterically hindered N‐heterocyclic carbene, (R,R,R,R)‐ANIPE, as the ligand.
1,8-Naphthalimide, as one of the classical dyes and fluorophores, has been widely used in analytical chemistry, materials chemistry, and biochemistry fields because of its excellent characteristic ...photostability, good structural flexibility, high fluorescence quantum yield, and large Stokes shift. This review mainly focuses on 1,8-naphthalimide and its derivatives in ion detection, molecular recognition, material applications, and bioimaging in the past five years. Simultaneously, we hope to develop more powerful fluorescent chemosensors for broad and exciting applications in the future.
Application of the classic fluorescent dye 1,8-naphthalimide.
The innate immune system, the first line of defense against pathogens, is activated by nucleic acids from microbial invaders that are recognized by nucleic acid‐sensing receptors. Recent evidence ...affirms the ability of these receptors to respond to nucleic acids released by damaged cancer cells. The innate immune system is also involved in cancer immunosurveillance, and could be modulated for devising effective antitumor therapies by targeting nucleic acid‐sensing pathways. A systematic, comprehensive analysis of dysregulation in nucleic acid‐sensing pathways in cancer is required to fully understand its role. Based on multidimensional data of The Cancer Genome Atlas pan‐cancer cohort, we revealed that upregulation of cytosolic DNA‐sensing genes like AIM2 and CGAS was common in tumor tissues. We used 15 genes in the nucleic acid‐sensing pathway to cluster all tumor patients into 2 subgroups and found that the subgroup with higher expression of nucleic acid‐sensing pathway genes was associated with poorer prognosis across cancer types. However, in homologous recombination deficient patients, the nucleic acid recognition activated subgroup was associated with better prognosis, which confirms the therapeutic effect of nucleic acid recognition. This study contributes to a better understanding of the functions and mechanisms of nucleic acid recognition in cancer, lays the foundation for new therapeutic strategies, and enlarges the scope of development of new drugs.
Overview of the analysis workflow.
Polymer self‐assembly in solution prior to film fabrication makes solution‐state structures critical for their solid‐state packing and optoelectronic properties. However, unraveling the ...solution‐state supramolecular structures is challenging, not to mention establishing a clear relationship between the solution‐state structure and the charge‐transport properties in field‐effect transistors. Here, for the first time, it is revealed that the thin‐film morphology of a conjugated polymer inherits the features of its solution‐state supramolecular structures. A “solution‐state supramolecular structure control” strategy is proposed to increase the electron mobility of a benzodifurandione‐based oligo(p‐phenylene vinylene) (BDOPV)‐based polymer. It is shown that the solution‐state structures of the BDOPV‐based conjugated polymer can be tuned such that it forms a 1D rod‐like structure in good solvent and a 2D lamellar structure in poor solvent. By tuning the solution‐state structure, films with high crystallinity and good interdomain connectivity are obtained. The electron mobility significantly increases from the original value of 1.8 to 3.2 cm2 V−1 s−1. This work demonstrates that “solution‐state supramolecular structure” control is critical for understanding and optimization of the thin‐film morphology and charge‐transport properties of conjugated polymers.
A supramolecular self‐assembly strategy is used to control the solution‐state structure of a conjugated polymer. It is revealed that the thin‐film morphology of the conjugated polymer inherits the features of their solution‐state supramolecular structures. Through “solution‐state supramolecular structure control”, the electron mobility of the polymer is boosted to 3.2 cm2 V−1 s−1, nearly doubling the original performance.
Peroxymonosulfate (PMS) is extensively used as an oxidant to develop the sulfate radical-based advanced oxidation processes in the decontamination of organic pollutants and various PMS activation ...methods have been explored. Visible-light-assisted PMS activation to construct a Fenton-like process has shown a great potential for pollution control. In our work, BiVO4 nanosheets were prepared using a hydrothermal process and used to activate PMS under visible light. A rapid degradation of ciprofloxacin (CIP) was achieved by dosing PMS (0.96 g/L), BiVO4 (0.32 g/L) under visible light with a reaction rate constant of 77.72-fold higher than that in the BiVO4/visible light process. The electron spin resonance and free radical quenching experiments indicate that reactive species of •O2−, h+, •OH and SO4•− all worked, where h+, •OH and SO4•− were found as the dominant contributors to the CIP degradation. The spectroscopic analyses further demonstrate that the photoinduced electrons were directly involved in the PMS activation process. The generated •O2− was partially utilized to activate PMS and more •OH was produced because of the chain reactions between SO4•− and H2O/OH−. In this process, PMS acted as an electron acceptor to transfer the photo-induced charges from the conduction band of BiVO4 and PMS was successfully activated to yield the high-powered oxidative species. From the degradation intermediates of CIP detected by a liquid-chromatography-mass spectrometer, the possible degradation pathways were proposed. The substantially decreased toxicity of CIP after the reaction was also observed. This work might provide new insights into the visible-light-assisted PMS activation mechanisms and is useful to construct environmentally-friendly catalytic processes for the efficient degradation of organic pollutants.
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•PMS was effectively activated by BiVO4 nanosheets for water purification under visible light.•Separation of electron/hole pairs and generation of oxidative species were enhanced.•Visible-light-assisted PMS activation Fenton-like mechanism was elucidated.•High mineralization and low biotoxicity validated the application potential of the system.
Conjugated polymers usually form crystallized and amorphous regions in the solid state simultaneously, making it difficult to accurately determine their precise microstructures. The lack of ...multiscale microstructures of conjugated polymers limits the fundamental understanding of the structure–property relationships in polymer‐based optoelectronic devices. Here, crystals of two typical conjugated polymers based on four‐fluorinated benzodifurandione‐based oligo(p‐phenylene vinylene) (F4BDOPV) and naphthalenediimide (NDI) motifs, respectively, are obtained by a controlled self‐assembly process. The strong diffractivity of the polymer crystals brings an opportunity to determine the crystal structures by combining X‐ray techniques and molecular simulations. The precise polymer packing structures are useful as initial models to evaluate the charge transport properties in the ordered and disordered phases. Compared to the spin‐coated thin films, the highly oriented polymer chains in crystals endow higher mobilities with a lower hopping energy barrier. Microwire crystal transistors of F4BDOPV‐ and NDI‐based polymers exhibit high electron mobilities of up to 5.58 and 2.56 cm2 V−1 s−1, respectively, which are among the highest values in polymer crystals. This work presents a simple method to obtain polymer crystals and their precise microstructures, promoting a deep understanding of molecular packing and charge transport for conjugated polymers.
Conjugated polymer microwire crystals are obtained from solvated aggregates. The precise crystal packing and electronic structure in the polymer microwires are evaluated for understanding of the charge transport properties. Polymer crystal transistors of F4BDOPV‐2T exhibit higher electron mobilities of up to 5.58 cm2 V−1 s−1 with a much lower hopping energy barrier compared with conventional thin‐film transistors.
Recently, two-dimensional (2D) layered organic–inorganic hybrid perovskites have attracted a huge amount of interest due to their unique layered structure, and potential optical properties. However, ...amongst researchers it has long been disputed as to whether it is suitable for use as a photovoltaic material or light-emitting device. Here, we present a detailed theoretical investigation to discuss the photovoltaic and optoelectronic properties of a novel synthetic 2D layered perovskite (PEA)2PbI4. Based on the calculated geometric and electronic structure, charge carrier mobilities of the 2D layered (PEA)2PbI4 are predicted theoretically. In addition, the linear dichroism and exciton binding energies are also calculated. We found that the carrier mobilities of the 2D layered (PEA)2PbI4 reach the same order of magnitude as those of the optoelectronic material MoS2, but smaller than those of the photovoltaic material MAPbI3 and Si crystal, whereas exciton binding energies (Eb) enlarge with the thinning layers, being obviously higher than MAPbI3 and Si crystal. Moreover, the system exhibits a strong linear dichroism, suggesting weak absorption along the c axis in the visible spectrum, which is detrimental to photovoltaics. Our work provides a theoretical basis to prove that ultrathin two-dimensional (2D) materials may be potential candidates for optoelectronic detection devices, rather than solar absorbers.