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Organic scintillators are praised for their abundant element reserves, facile preparation procedures, and rich structures. However, the weak X-ray attenuation ability and low exciton utilization efficiency result in unsatisfactory scintillation performance. Herein, a new family of highly efficient organic phosphonium halide salts with thermally activated delayed fluorescence (TADF) are designed by innovatively adopting quaternary phosphonium as the electron acceptor, while dimethylamine group and halide anions (I - ) serve as the electron donor. The prepared butyl(2-[2-(dimethylamino)phenyl]phenyl)diphenylphosphonium iodide (C4-I) exhibits bright blue emission and an ultra-high photoluminescence quantum yield (PLQY) of 100 %. Efficient charge transfer is realized through the unique n-π and anion-π stacking in solid-state C4-I. Photophysical studies of C4-I suggest that the incorporation of I accounts for high intersystem crossing rate (k ISC ) and reverse intersystem crossing rate (k RISC ), suppressing the intrinsic prompt fluorescence and enabling near-pure TADF emission at room temperature. Benefitting from the large Stokes shift, high PLQY, efficient exciton utilization, and remarkable X-ray attenuation ability endowed by I, C4-I delivers an outstanding light yield of 80721 photons/MeV and a low limit of detection (LoD) of 22.79 nGy ⋅ s -1 . This work would provide a rational design concept and open up an appealing road for developing efficient organic scintillators with tunable emission, strong X-ray attenuation ability, and excellent scintillator performance., (© 2024 Wiley-VCH GmbH.)

Organic-inorganic metal halide (OIMH) glass offers the advantages of large-scale production, high transparency, and minimal light scattering. However, undesired crystallization in OIMH glass can occur, leading to deteriorated transparency. Herein, a series of bisphosphonium organic cations were designed to construct Mn-based metal halide crystals with a photoluminescence quantum yield (PLQY) near unity, alongside the development of highly thermally stable OIMH glasses. Two strategies were employed to lower the melting point of OIMH: alkyl chain elongation and fluorine substitution. The (Hex-3,4-2F)MnBr 4 ·MeOH (Hex-3,4-2F = hexane-1,6-diylbis((3,4-difluorobenzyl)diphenylphosphonium)) crystal delivers a glass transition temperature of 100 °C and the highest T g / T m ratio (0.82) among OIMHs. The resulting OIMH glass exhibits a PLQY of 47.6%, achieves an impressive resolution of 25 lp mm -1 in X-ray imaging, and remains transparent even after being heated at 90 °C for six weeks. These bisphosphonium-based OIMH glasses present a feasible design for the practical application of OIMH glasses in radiation detection., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

Low-dimensional lead halide materials have proved to be intrinsically stable semiconductor materials. However, the development of one-dimensional (1D) perovskites or perovskitoids with both robust water stability and high optoelectronic performance still faces significant challenges. Here, we report a new class of 1D (TzBIPY)Pb 2 X 6 (X = Cl, Br, I) perovskitoids featuring a π-conjugated diamine cation (TzBIPY = 2,5-di(pyridin-4-yl)thiazolo[5,4-d]thiazole). The TzBIPY 2+ cation with delocalized electrons directly contributes to the electronic structure and hence reduces the band gap. Especially, the Br-based material exhibits enhanced carrier separation and transport capacity, benefiting from the improved electronic conjugation together with a type II intramolecular heterojunction between conjugated organic cations and Pb-X octahedra. The (TzBIPY)Pb 2 Br 6 photodetector exhibits an impressive photocurrent on/off ratio of 8.1 × 10 5 , which is much superior to the previous three-dimensional (3D) perovskite benchmark. Additionally, the π-conjugated cations serve as dense protective shields for vulnerable Pb-X inorganic lattice against being attacked by water, thus demonstrating exceptional stability even immersed in water for over 3000 h., (Copyright © 2024 Science China Press. Published by Elsevier B.V. All rights reserved.)

Lead-free halide perovskites as a new kind of potential candidate for photocatalytic organic synthesis have attracted much attention recently. The rational heterojunction construction is regarded as an efficient strategy to delicately regulate their catalytic performances. Herein, a semi-conductive covalent organic framework (COF) nanosheet, C 4 N, is employed as the functional component to construct Cs 2 AgBiCl 6 /C 4 N (CABC/C 4 N) heterojunction. It is found that the C 4 N nanosheets with rich surface functional groups can serve as heterogeneous nucleation sites to manipulate the growth of CABC nanocrystals and afford close contact between each other, therefore facilitate the transfer and spatial separation of photogenerated charge carriers, as verified by in situ X-ray photoelectronic spectroscopy and Kelvin probe force microscopy. Moreover, the oxygen affinity of C 4 N endows the heterojunctions with outstanding aerobic reactivity, thus improving the photocatalytic performance largely. The optimal CABC/C 4 N heterojunction delivers a thioanisole conversion efficiency of 100% after 6 h, which is 2.2 and 7.7-fold of that of CABC and C 4 N. This work provides a new ideal for the design and application of lead-free perovskite heterojunction photocatalysts for organic reactions., (© 2024 Wiley‐VCH GmbH.)

Fiber light-emitting diodes (Fi-LEDs), which can be used for wearable lighting and display devices, are one of the key components for fiber/textile electronics. However, there exist a number of impediments to overcome on device fabrication with fiber-like substrates, as well as on device encapsulations. Here, we uniformly grew all-inorganic perovskite quantum wire arrays by filling high-density alumina nanopores on the surface of Al fibers with a dip-coating process. With a two-step evaporation method to coat a surrounding transporting layer and semitransparent electrode, we successfully fabricated full-color Fi-LEDs with emission peaks at 625 nanometers (red), 512 nanometers (green), and 490 nanometers (sky-blue), respectively. Intriguingly, additional polydimethylsiloxane packaging helps instill the mechanical bendability, stretchability, and waterproof feature of Fi-LEDs. The plasticity of Al fiber also allows the one-dimensional architecture Fi-LED to be shaped and constructed for two-dimensional or even three-dimensional architectures, opening up a new vista for advanced lighting with unconventional formfactors.

Low-dimensional perovskites afford improved stability against moisture, heat, and ionic migration. However, the low dimensionality typically results in a wide bandgap and strong electron-phonon coupling, which is undesirable for optoelectronic applications. Herein, semiconducting A-site organic cation engineering by electron-acceptor bipyridine (bpy) cations (2,2'-bpy 2+ and 4,4'-bpy 2+ ) is employed to optimize band structure in low-dimensional perovskites. Benefiting from the merits of lower lowest unoccupied molecular orbital (LUMO) energy for 4,4'-bpy 2+ cation, the corresponding (4,4'-bpy)PbI 4 is endowed with a smaller bandgap (1.44 eV) than the (CH 3 NH 3 )PbI 3 (1.57 eV) benchmark. Encouragingly, an intramolecular type II band alignment formation between inorganic Pb-I octahedron anions and bpy 2+ cations favors photogenerated electron-hole pairs separation. In addition, a shortening distance between inorganic Pb-I octahedral chains in (4,4'-bpy)PbI 4 single crystal (SC) can effectively promote carrier transfer. As a result, a self-powered photodetector based on (4,4'-bpy)PbI 4 SC exhibits 131 folds higher on/off ratio (3807) than the counterpart of (2,2'-bpy) 2 Pb 3 I 10 SC (29). The presented result provides an effective strategy for exporting novel organic cation-based low-dimensional perovskite SC for high-performance optoelectronic devices., (© 2023 Wiley‐VCH GmbH.)

Vaccines against SARS-CoV-2 have been recommended across the world, yet no study has investigated whether COVID-19 vaccination influences short-term warfarin anti-coagulation levels. Patients on stable warfarin treatment who received anti-SARS-CoV-2 vaccination were prospectively enrolled and followed up for three months. INR values less than 10 days before vaccination (baseline), 3-5 days (short-term) and 6-14 days (medium-term) after vaccination were recorded as INR0, INR1, and INR2, respectively. The variations of INR values within individuals were compared, and the linear mixed effect model was used to evaluate the variations of INR values at different time points. Logistic regression analysis was performed to determine covariates related to INR variations after COVID-19 vaccination. Vaccination safety was also monitored. There was a significant difference in INR values between INR0 and INR1 (2.15 vs. 2.26, p = 0.003), yet no marked difference was found between INR0 and INR2. The linear mixed effect model also demonstrated that INR variation was significant in short-term but not in medium-term or long-term period after vaccination. Logistic regression analysis showed that no investigated covariates, including age, vaccine dose, genetic polymorphisms of VKORC1 and CYP2C9 etc., were associated with short-term INR variations. Two patients (2.11%) reported gingival hemorrhage in the short-term due to increased INR values. The overall safety of COVID-19 vaccines for patients on warfarin was satisfying. COVID-19 vaccines may significantly influence warfarin anticoagulation levels 3-5 days after vaccination. We recommend patients on warfarin to perform at least one INR monitoring within the first week after COVID-19 vaccination., (© 2024. The Author(s), under exclusive licence to Springer Science+Business Media, LLC, part of Springer Nature.)

Rational design and facile synthesis of efficient environmentally friendly all-inorganic lead-free halide perovskite catalysts are of great significance in photocatalytic CO 2 reduction. Aiming at photogenerated charge carrier separation and CO 2 reaction dynamics, in this paper, a CsCuCl 3 /Cu nanocrystals (NCs) heterojunction catalyst is designed and synthesized via a simple acid-etching solution process by using Cu 2 O as the sacrificed template. Due to the disproportionation reaction of Cu 2 O induced by concentrated hydrochloric acid, Cu NCs can be deposited onto the surface of CsCuCl 3 microcrystals directly and tightly. As revealed by photoelectrochemical analysis, in situ Fourier transform infrared spectra, etc., the Cu NCs contribute a lot to extracting photoelectrons of CsCuCl 3 to improve the charge separation efficiency, regulating the CO 2 adsorption and activation, and also stabilizing the reaction intermediates. Therefore, CsCuCl 3 /Cu heterojunction exhibits a total electron consumption rate of 58.77 µmol g -1 h -1 , which is 2.9-fold of that of single CsCuCl 3 . Moreover, high CH 4 selectivity of up to 92.7% is achieved, which is much higher than that of CsCuCl 3 (50.4%) and most lead-free halide perovskite-based catalysts. This work provides an ingenious but simple strategy to rationally design cocatalysts in situ decorated perovskite catalysts for manipulating both the catalytic activity and the product selectivity., (© 2023 Wiley-VCH GmbH.)

Metal halide perovskites have shown great promise as a potential candidate for next-generation solid state lighting and display technologies. However, a generic organic ligand-free and antisolvent-free solution method to fabricate highly efficient full-color perovskite light-emitting diodes has not been realized. Herein, by utilizing porous alumina membranes with ultra-small pore size as templates, we have successfully fabricated crystalline all-inorganic perovskite quantum wire arrays with ultrahigh density and excellent uniformity, using a generic organic ligand-free and anti-solvent-free solution method. The quantum confinement effect, in conjunction with the high light out-coupling efficiency, results in high photoluminescence quantum yield for blue, sky-blue, green and pure-red perovskite quantum wires arrays. Consequently, blue, sky-blue, green and pure-red LED devices with spectrally stable electroluminescence have been successfully fabricated, demonstrating external quantum efficiencies of 12.41%, 16.49%, 26.09% and 9.97%, respectively, after introducing a dual-functional small molecule, which serves as surface passivation and hole transporting layer, and a halide vacancy healing agent., (© 2023. The Author(s).)

In recent years, halide perovskites have shown great application potential in X-ray detection due to their superior optoelectronic properties and high X-ray attenuation coefficient. However, large-area perovskite fabrication for high performance X-ray detectors remains extremely challenging. Herein, ultrasound-assisted crystallization combined with the hot-pressing method is proposed to prepare large-area (10 cm × 10 cm) and high-quality quasi-monocrystalline thick film of a mixed-cation perovskite MA 0.42 FA 0.58 PbI 3 . The rapid ultrasound-assisted crystallization provides more homogeneous nucleation, which is essential to the fabrication of large-area and uniform perovskite microcrystalline film. Furthermore, the post hot-pressing treatment is implemented to fuse the crystal boundaries, rearrange the crystal grains, and eliminate the voids between crystals, resulting in a quasi-monocrystalline film. After the hot-pressing treatment, the carrier mobility and the carrier mobility-lifetime product increased about 13-fold (from 1.8 to 23.5 cm 2 s -1 V -1 ) and 18 times (from 8.4 × 10 -6 to 1.5 × 10 -4 cm 2 V -1 ), respectively. As a result, a high-performance MA 0.42 FA 0.58 PbI 3 quasi-monocrystalline X-ray detector is achieved with an impressively high sensitivity (1.16 × 10 6 µC Gy air -1 cm -2 ) and low detection limit (37.4 nGy air s -1 ), demonstrating the potential of the ultrasound-assisted crystallization and hot-pressing strategy from an industrial perspective., (© 2023 Wiley-VCH GmbH.)

Glass is a group of materials with appealing qualities, including simplicity in fabrication, durability, and high transparency, and they play a crucial role in the optics field. In this paper, a new organic-inorganic metal halide luminescent glass exhibiting >78 % transmittance at 506-800 nm range together with a high photoluminescence quantum yield (PLQY) of 28.5 % is reported through a low-temperature melt-quenching approach of pre-synthesized (HTPP) 2 MnBr 4 (HTPP=hexyltriphenylphosphonium) single crystal. Temperature-dependent X-ray diffraction, polarizing microscopy, and molecular dynamics simulations were combined to investigate the glass-crystal interconversion process, revealing the disordered nature of the glassy state. Benefiting from the transparent nature, (HTPP) 2 MnBr 4 glass yields an outstanding spatial resolution of 10 lp mm -1 for X-ray imaging. The superb optical properties and facility of large-scale fabrication distinguish the organic-inorganic metal halide glass as a highly promising class of materials for optical devices., (© 2022 Wiley-VCH GmbH.)

An S-doped CdO@In 2 O 3 nanofiber was successfully designed by in-situ electrospinning along and subsequent calcination treatment. Under artificial sunlight illumination, the S/CdO@In 2 O 3 -25 displayed a superior photocatalytic hydrogen evolution rate of 4564.58 μmol·g -1 ·h -1 , with approximately 22.0 and 1261.0-fold of those shown by the S/CdO and S/In 2 O 3 samples, respectively. The experimental and theoretical analyses illustrate that the unique one-dimensional (1D) nanofiber morphology and rich oxygen vacancies optimized the electronic structure of the nanofibers and adsorption/desorption behaviors of reaction intermediates, contributing to the realization of the remarkable solar-to-H 2 conversion efficiencies. Moreover, the staggered band structure and intimate contact heterointerfaces facilitate the formation of a type-II double charge-transfer pathway, promoting the spatial separation of photoexcited charge carriers. These results could inform the design of other advanced catalyst materials for photocatalytic reactions.

Current X-ray imaging scintillators are dominated by inorganic scintillators grown through a high-temperature process. Exploring new types of scintillators with mild growth conditions, high light yields, and eco-friendly chemical compositions is essential and challenging. Herein, the zero-dimensional large-area laminar organic-inorganic hybrid metal halide TEA 2 MnI 4 (TEA = tetraethylammonium) single crystal with dimensions of 50 mm × 60 mm × 0.82 mm is grown via a local-heating solvent evaporation method. Compared with its Cl- and Br-based counterparts, the incorporation of the iodine component enhances the X-ray attenuation ability and significantly accelerates the decay of the photoluminescence of TEA 2 MnI 4 . Interestingly, the prepared TEA 2 MnI 4 exhibits a high transmittance of >90% over the range of 515-765 nm and exhibits a high light yield of 26288 photons/MeV, which provides the prerequisite for high-resolution X-ray imaging. The TEA 2 MnI 4 single-crystal scintillator displays an astonishing spatial resolution exceeding 25 line pairs per millimeter, which provides a design concept for a Mn-I-based single crystal for high-performance scintillator applications.

In view of the toxicity of the Pb element, exploring eco-friendly Pb-free halide perovskites with excellent photoelectric properties is of great research and practical application significance. Herein, copper-based halide perovskite CsCuCl 3 and the corresponding Br - -substituted sample (CsCuCl 2 Br) are designed and explored as the catalysts for photocatalytic CO 2 reduction for the first time. A facile antisolvent recrystallization process with pre-prepared single crystals as the precursor is employed to controllably synthesize CsCuCl 3 and CsCuCl 2 Br microcrystals (MCs). The electronic structure and charge transfer property analysis by theoretical and experimental investigation reveal that CsCuCl 3 possesses a satisfying bandgap (1.92 eV) and conduction band minimum (CBM) to harvest the sunlight and drive the conversion of CO 2 to CH 4 and CO. The Br - substitution can not only narrow the bandgap but also facilitate the transportation of charge carriers. Thus, a total electron consumption rate of 44.71 μmol g -1 h -1 is achieved for CsCuCl 2 Br MCs, which is much better than that of same-sized CsPbBr 3 microcrystals or even better than many perovskite nanocrystal photocatalysts. This study suggests that Cu-based perovskites can serve as promising candidates for artificial photosynthesis or other photocatalytic applications, which may propose a new thought to construct lead-free, low-cost photocatalysts.

Though fluorescence-tag-based anti-counterfeiting technology has distinguished itself with cost-effective features and huge information loading capacity, the clonable decryption process of spatial-resolved anti-counterfeiting cannot meet the requirements for high-security-level anti-counterfeiting. Herein, we demonstrate a spatial-time-dual-resolved anti-counterfeiting system based on new organic-inorganic hybrid halides BAPPZn 2 (Cl y Br 1-y ) 8 (BAPP=1,4-bis(3-ammoniopropyl)piperazinium, y=0-1) with ultra-long room-temperature phosphorescence (RTP). Remarkably, the afterglow lifetime can be facilely tuned by regulating the halide-induced heavy-atom effect and can be identified by the naked eyes or with the help of a simple machine vision system. Therefore, the short-lived unicolor fluorescence and lasting-time-tunable RTP provide the prerequisites for unicolor-time-resolved anti-counterfeiting, which lowers the decryption-device requirements and further provides the design strategy of advanced portable anti-counterfeiting technology., (© 2022 Wiley-VCH GmbH.)

The quality of wide-band-gap (WBG) perovskite films plays an important role in tandem solar cells. Therefore, it is necessary to improve the performance of WBG perovskite films for the development of tandem solar cells. Here, we employ F-type pseudo-halogen additives (PF 6 - or BF 4 - ) into perovskite precursors. The perovskite films with F-type pseudo-halogen additives have a larger grain size and higher crystal quality with lower defect density. At the same time, the perovskite lattice increases due to substitution of F-type pseudo-halogen anions for I - /Br - , and the stress distortion in the film is released, which effectively suppresses the recombination of carriers, reduces the charge transfer loss, and inhibits the phase separation. Finally, the power conversion efficiency (PCE) of the inverted 1.67 eV perovskite devices is significantly improved to over 20% with an impressive fill factor of 84.02% and excellent device stability. In addition, the PCE of the four-terminal (4T) perovskite/silicon tandem solar cells reached 27.35% (PF 6 - ) and 27.11% (BF 4 - ), respectively. This provides important guidance for further improving WBG perovskite solar cell performance.

Due to the large distance or weak electronic conjugation between adjacent Bi-I octahedrons, the charge transport in the low-dimensional bismuth-based hybrid perovskites is impeded and thus hinders their future developments. In this work, A-site cation engineering by monoamine BZA (benzylamine) and diamine 3-AMP (3-(aminomethyl)pyridine) has been demonstrated as an efficient strategy to regulate the corresponding activation energy of ionic migration and carrier transport capacity. Given the higher polarity of 3-AMP than BZA, producing a more efficient dielectric screening effect, it gives rise to obtaining the small exciton binding energy (50 meV) and low defect states (3.53×10 9  cm -3 ). The reduced distance of adjacent Bi-I octahedrons by the bilateral anchoring of the 3-AMP 2+ diamine cation enhances both electronic conjugation and charge transport performance. Therefore, the photodetector for (3-AMP)BiI 5 SC shows a 243-fold increase in on/off ratio compared with the (BZA) 3 BiI 6 SC., (© 2022 Wiley-VCH GmbH.)

Color tunability of perovskite light-emitting diodes (PeLEDs) by mixed halide compositional engineering is one of the primary intriguing characteristics of PeLEDs. However, mixed halide PeLEDs are often susceptible to color red-shifting caused by halide ion segregation. In this work, strongly quantum-confined perovskite nanowires (QPNWs) made of CsPbBr 3 are grown in nanoporous anodic alumina templates using a closed space sublimation process. By tuning the pore size with atomic layer deposition, QPNWs with a diameter of 6.6 to 2.8 nm have been successfully obtained, with continuous tunable photoluminescence emission color from green (512 nm) to pure blue (467 nm). To better understand the photophysics of QPNWs, carrier dynamics and the benefit of alumina passivation are studied and discussed in detail. Eventually, PeLEDs using various diameters of CsPbBr 3 QPNWs are successfully fabricated with cyan color (492 nm) PeLEDs, achieving a record high 7.1% external quantum efficiency (EQE) for all CsPbBr 3 -based cyan color PeLEDs. Sky blue (481 nm) and pure blue (467 nm) PeLEDs have also been successfully demonstrated, respectively. The work here demonstrates a different approach to achieve quantum-confined one-dimensional perovskite structures and color-tunable PeLEDs, particularly blue PeLEDs.

Low-dimensional organic-inorganic metal halides have recently emerged as a class of promising luminescent materials. However, the intrinsic toxicity of lead would strongly hamper future application. Herein, we synthesized a new type of lead-free zero-dimensional (0D) antimony-based organic-inorganic metal halide single crystals, (PPZ) 2 SbCl 7 ·5H 2 O (PPZ = 1-phenylpiperazine), which features a broadband emission at 720 nm. Ultrafast transient absorption and temperature-dependent photoluminescence (PL) spectra are combined to investigate the PL mechanism, revealing that self-trapped exciton recombination was involved. Furthermore, it is interesting that (PPZ) 2 SbCl 7 ·5H 2 O material shows reversible PL emission transformation between red light (720 nm) and yellow light (590 nm) as water molecules are inserted or removed from the lattice. Such reversible emission transformation phenomenon renders the (PPZ) 2 SbCl 7 ·5H 2 O as a potential low-cost water sensing material.

Although single-source white emissive perovskite has emerged as a class of encouraging light-emitting material, the synthesis of lead-free halide perovskite materials with high luminous efficiency is still challenging. Here, we report a series of zero-dimensional indium-antimony (In/Sb) alloyed halide single crystals, BAPPIn 2-2 x Sb 2 x Cl 10 (BAPP = C 10 H 28 N 4 , x = 0 to 1), with tunable emission. In BAPPIn 1.996 Sb 0.004 Cl 10 , bright yellow emission with near 100% photoluminescence quantum yield (PLQY) is yielded when it was excited at 320 nm, which turns into bright white-light emission with a PLQY of 44.0% when excited at 365 nm. Combined spectroscopy and theoretical studies reveal that the BAPP 4+ -associated blue emission and inorganic polyhedron-afforded orange emission function as a perfect pair of complementary colors affording white light in BAPPIn 1.996 Sb 0.004 Cl 10 Moreover, the interesting afterglow behavior, together with excitation-dependent emission property, makes BAPPIn 2-2 x Sb 2 x Cl 10 as high-performance anti-counterfeiting/information storage materials., (Copyright © 2021 The Authors, some rights reserved; exclusive licensee American Association for the Advancement of Science. No claim to original U.S. Government Works. Distributed under a Creative Commons Attribution NonCommercial License 4.0 (CC BY-NC).)

Halide perovskite single-crystals have recently been widely highlighted to possess high light harvesting capability and superior charge transport behaviour, which further enable their attractive performance in photovoltaics. However, their application in photoelectrochemical cells has not yet been reported. Here, a methylammonium lead bromide MAPbBr 3 single-crystal thin film is reported as a photoanode with potential application in photoelectrochemical organic synthesis, 2,5-dimethoxy-2,5-dihydrofuran. Depositing an ultrathin Al 2 O 3 layer is found to effectively passivate perovskite surface defects. Thus, the nearly 5-fold increase in photoelectrochemical performance with the saturated current being increased from 1.2 to 5.5 mA cm -2 is mainly attributed to suppressed trap-assisted recombination for MAPbBr 3 single-crystal thin film/Al 2 O 3 . In addition, Ti 3+ -species-rich titanium deposition has been introduced not only as a protective film but also as a catalytic layer to further advance performance and stability. As an encouraging result, the photoelectrochemical performance and stability of MAPbBr 3 single-crystal thin film/Al 2 O 3 /Ti-based photoanode have been significantly improved for 6 h continuous dimethoxydihydrofuran evolution test with a high Faraday efficiency of 93%.

Akin to single-site homogeneous catalysis, a long sought-after goal is to achieve reaction site precision in heterogeneous catalysis for chemical control over patterns of activity, selectivity and stability. Herein, we report on metal phosphides as a class of material capable of realizing these attributes and unlock their potential in solar-driven CO 2 hydrogenation. Selected as an archetype, Ni 12 P 5 affords a structure based upon highly dispersed nickel nanoclusters integrated into a phosphorus lattice that harvest light intensely across the entire solar spectral range. Motivated by its panchromatic absorption and unique linearly bonded nickel-carbonyl-dominated reaction route, Ni 12 P 5 is found to be a photothermal catalyst for the reverse water gas shift reaction, offering a CO production rate of 960 ± 12 mmol g cat -1  h -1 , near 100% selectivity and long-term stability. Successful extension of this idea to Co 2 P analogs implies that metal phosphide materials are poised as a universal platform for high-rate and highly selective photothermal CO 2 catalysis.

NADPH oxidase 2 (NOX2) is a major subtype of NOX and is responsible for the generation of reactive oxygen species (ROS) in brain tissues. MicroRNAs (miRNAs/miRs) are important epigenetic regulators of NOX2. The present study aimed to identify the role of NOX2 miRNA‑targets in ischemic stroke (IS). A rat cerebral ischemia/reperfusion (CI/R) injury model and a SH‑SY5Y cell hypoxia/reoxygenation (H/R) model were used to simulate IS. Gene expression levels, ROS production and apoptosis in tissue or cells were determined, and bioinformatic analysis was conducted for target prediction of miRNA. In vitro experiments, including function‑gain and luciferase activity assays, were also performed to assess the roles of miRNAs. The results indicated that NOX2 was significantly increased in brain tissues subjected to I/R and in SH‑SY5Y cells subjected to H/R, while the expression of miR‑532‑3p (putative target of NOX2) was significantly decreased in brain tissues and plasma. Overexpression of miR‑532‑3p significantly suppressed NOX2 expression and ROS generation in SH‑SY5Y cells subjected to H/R, as well as reduced the relative luciferase activity of cells transfected with a reporter gene plasmid. Collectively, these data indicated that miR‑532‑3p may be a target of NOX2 and a biomarker for CI/R injury. Thus, the present study may provide a novel target for drug development and IS therapy.

Two three-dimensional symmetric tetraphenylbutadiene derivatives decorated with diphenylamine or triphenylamine fragments are first prepared for use as hole-transporting materials (HTMs) in perovskite solar cells (PSCs). The HTMs are acquired using straightforward synthetic methods and facile purification techniques. The thermal stability, photophysical properties, electrochemical behaviors, computational study, hole mobility, X-ray diffraction, hole transfer dynamics, hydrophobicity, surface morphology, and photovoltaic performances of the HTMs are discussed. The highest power conversion efficiency (PCE) of CJ-04 -based cell is 13.75%, which is increased to 20.06% when CJ-03 is used as HTM, superior to the PCE of the cell based on 2,2',7,7'-tetrakis( N , N -di- p -methoxyphenylamine)-9,9'-spirobifluorene (spiro-OMeTAD) (18.90%). The preparation cost of CJ-03 accounts for merely 23.1% of the price of commercial spiro-OMeTAD, while the concentration of CJ-03 solution used in the device fabrication (60.0 mg mL -1 ) is lower compared with that of the spiro-OMeTAD solution (72.3 mg mL -1 ). These results corroborate that the screw-like HTMs with a highly distorted configuration are facilely available and promising candidates for PSCs. More importantly, a practical solution is proposed to achieve moderate charge mobility and good film-formation ability of the HTMs simultaneously.

The first coordination disk-type nano-Saturn complexes, [Cu10(Mim)10]⊃C60 and [Cu10(Mim)10]⊃C70 (Mim = 2-methylimidazolate), were assembled under one-pot solvothermal conditions. The highest number of 30 C-Hπ interactions between the [Cu10(Mim)10] disk and the C60/C70 surfaces drives the formation of the nano-Saturns. The calculated interaction energy is much larger than that of most of the reported disk-type nano-Saturns. Different photoinduced charge/energy transfer mechanisms are present for both nano-Saturn systems to quench the intrinsic luminescence of the [Cu10(Mim)10] disk.

The power conversion efficiencies (PCEs) of perovskite solar cells (PSCs) are already higher than those of other thin-film photovoltaic technologies, but the high-efficiency cells are based on complicated device architectures with multiple layers of coating. A promising strategy to commercialize this emerging technology is to simplify the device structure while simultaneously maintaining high-efficiency. Charge transport layers (CTLs) are generally indispensable for achieving high-performance PSCs, but the high cost and possibility of instability hinder the mass production of efficient, stable PSCs in a cost-effective manner. The ambipolar carrier transfer characteristic of perovskite materials makes it possible to fabricate efficient PSCs even in the absence of electron and/or hole transport layers. Encouragingly, the reported PCEs of CTL-free PSCs are already over 20%. However, it is still a mystery about why and how CTL-free devices can work efficiently. Here, we summarize the recent strategies developed to improve the performance of CTL-free PSCs, aiming at strengthening the comprehensive understanding of the fundamental carrier dynamics, heterojunction merits and device physics behind these mysteriously simple yet efficient devices. This review sheds light on identifying the limiting and determining factors in achieving high-efficiency CTL-free devices, and proposes some empirical charge transport models (e.g. p-type doping of perovskites for HTL-free PSCs, n-type doping of perovskites for ETL-free PSCs, constructing efficient p-n heterojunctions and/or homojunctions at one side/interface or employing perovskite single crystal-based lateral geometry for both HTL and ETL-free PSCs, etc.) that are useful to further improve device performance. In addition, an insightful perspective for the future design and commercial development of large-scale, efficient and stable optoelectronic devices by employing carbon electrodes is provided.

Low-dimensional lead halide perovskite materials recently have drawn much attention owing to the intriguing broadband emissions; however, the toxicity of lead will hinder their future development. Now, a lead-free (C 4 H 14 N 2 ) 2 In 2 Br 10 single crystal with a unique zero-dimensional (0D) structure constituted by [InBr 6 ] 3- octahedral and [InBr 4 ] - tetrahedral units is described. The single crystal exhibits broadband photoluminescence (PL) that spans almost the whole visible spectrum with a lifetime of 3.2 μs. Computational and experimental studies unveil that an excited-state structural distortion in [InBr 6 ] 3- octahedral units enables the formation of intrinsic self-trapped excitons (STEs) and thus contributing the broad emission. Furthermore, femtosecond transient absorption (fs-TA) measurement reveals that the ultrafast STEs formation together with an efficient intersystem crossing has made a significant contribution to the long-lived and broad STE-based emission behavior., (© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Heterojunction engineering has played an indispensable role in the exploitation of innovative artificial materials with exceptional properties and has consequently triggered a new revolution in achieving high-performance optoelectronic devices. Herein, an intriguing halide perovskite (PVK) and metal dichalcogenide (MD) heterojunction, i.e., a lead-free Cs 2 SnI 6 perovskite nanocrystal/SnS 2 nanosheet hybrid, was fabricated in situ for the first time. Comprehensive investigations with experimental characterizations and theoretical calculations demonstrate that cosharing of the Sn atom enables intimate contact in the Cs 2 SnI 6 /SnS 2 hybrid together with a type II band alignment structure. Additionally, ultrafast carrier separation between SnS 2 and Cs 2 SnI 6 has been observed in the Cs 2 SnI 6 /SnS 2 hybrid by transient absorption measurements, which efficiently prolongs the lifetime of the photogenerated electrons in SnS 2 (from 1290 to 3080 ps). The resultant spatial charge separation in the Cs 2 SnI 6 /SnS 2 hybrid evidenced by Kelvin probe force microscopy (KPFM) significantly boosts the photocatalytic activity toward CO 2 reduction and the photoelectrochemical performance, with 5.4-fold and 10.6-fold enhancements compared with unadorned SnS 2 . This work provides a facile and effective method for the in situ preparation of PVK-MD heterojunctions, which may significantly stimulate the synthesis of various perovskite-based hybrid materials and their further optoelectronic applications.

Low-dimensional luminescent lead halide perovskites have attracted tremendous attention for their fascinating optoelectronic properties, while the toxicity of lead is still considered a drawback. Herein, we report a novel lead-free zero-dimensional (0D) indium-based perovskite (Cs 2 InBr 5 ⋅H 2 O) single crystal that is red-luminescent with a high photoluminescence quantum yield (PLQY) of 33 %. Experimental and computational studies reveal that the strong PL emission might originate from self-trapping excitons (STEs) that result from an excited-state structural deformation. More importantly, the in situ transformation between hydrated Cs 2 InBr 5 ⋅H 2 O and the dehydrated form is accompanied with a switchable dual emission, which enables it to act as a PL water-sensor in humidity detection or the detection of traces of water in organic solvents., (© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Ordered 1D metal oxide structure is desirable in thin film solar cells owing to its excellent charge collection capability. However, the electron transfer in 1D electron transporting layer (ETL)-based devices is still limited to a submicrometer-long pathway that is vertical to the substrate. Here, an innovative closely packed rutile TiO 2 nanowire (CRTNW) network parallel to the facet of fluorine-doped tin oxide (FTO) substrate is reported, which can serve as a 1D nanoscale electron transport pathway for efficient perovskite solar cells (PSCs). The PSC constructed using newly prepared CRTNW ETL achieves an impressive power conversion efficiency of 21.10%, which can be attributed to the facilitated electron extraction induced by the favorable junctions formed at FTO/ETL and ETL/perovskite interfaces and also the suppressed charge recombination originating from improved perovskite morphology with large grains, flat surface, and good surface coverage. The bifacial contact junctions engineering also enables large-area device fabrication. The PSC with 1 cm 2 aperture yields an efficiency of 19.50% under one sun illumination. This work highlights the significance of controlling the orientation and packing density of the ordered 1D oxide nanostructured thin films for highly efficient optoelectronic devices in a large-scale manner., (© 2019 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The development of an all-inorganic lead-free perovskite nanocrystal is of crucial importance to solve the instability and lead toxicity of organic-inorganic lead hybrid perovskites. Herein, single-layered Cs4CuSb2Cl12 nanocrystals (NCs) with a narrow band gap of 1.6 eV were prepared for the first time via an ultrasonic exfoliation technique. This powerful top-down method was further generalized to synthesize a class of lead-free perovskite (Cs3Bi2X9 and Cs3Sb2X9) NCs. The experimental and theoretical studies revealed that not only inter-layer van der Waals forces but also in-plane chemical bonds played a critical role in the exfoliation process. Specifically, smaller uniform-sized NCs were observed for Cs4CuSb2Cl12 (∼3 nm) as compared to those for Cs3Sb2Cl9 (∼20 nm) although both Cs4CuSb2Cl12 and Cs3Sb2Cl9 exhibited a similar exfoliation energy (∼0.310 J m-2). This can be ascribed to the weaker in-plane chemical bonds of Cu-Cl (2.808 Å) and Sb-Cl (2.924 Å) in Cs4CuSb2Cl12 than the uniform Cl-Sb bond (2.69 Å) in Cs3Sb2Cl9 that allow for an easier exfoliation process. In addition, exfoliation of the Cs4CuSb2Cl12 microcrystal into NCs results in an indirect-to-direct bandgap transition and a reduced electron effective mass, which provides a rapid and steady photoelectrochemical response, demonstrating that Cs4CuSb2Cl12 NCs are a promising candidate for optoelectronic applications.

The utilization of solar energy and the development of its related optoelectronic devices have become more important than ever. Solar cells or photoelectrochemical (PEC) cells that require the design of light harvesting assemblies for efficiently converting solar light into electricity or solar fuels are of particular interest. Semiconductor TiO 2 , serving as the photoelectrode for photovoltaic devices (e.g., dye- or quantum dot-sensitized solar cells (DSSCs/QDSSCs) or perovskite solar cells (PSCs)) and PEC cells, has aroused intense research interest owing to its inherent characteristics of wide band gap and promising optical and electrical properties. TiO 2 nanowires (TNWs) have been widely used in optoelectronic devices due to their unique 1D geometry and salient optical and electrical properties. However, the insufficient surface area resulting from the relatively large diameter of NWs and considerable free space between adjacent NWs restricts their optoelectronic performance. Hence, it is desirable to explore every feasible aspect of TNWs in terms of structural design and optical management, aiming to further improve the performance of optoelectronic devices. In this Account, we present a brief survey of strategies for designing branched or hyperbranched TNW-based photoelectrodes and their applications in solar cells and PEC cells. The general strategies (e.g., alkaline/acid hydrothermal method, lift-off transfer, and self-assembly approach) are discussed to address the challenges associated with fabricating TNWs on transparent conducting oxide (TCO) substrates. A series of strategies to fabricate judiciously designed 3D branched array architectures, including length tuning and sequential surface branched or hyperbranched modification, are proposed. The versatile implantation of the TNWs onto other backbones (nanosheets, nanotubes, hollow spheres, or multilayered electrodes) and substrates (fiber-shaped metal wire or mesh, flexible metal foil, or plastic sheet) is demonstrated to construct a new class of the TNW-embedded composite electrode materials with desired morphological characteristics and optoelectronic properties, for example, favorable energy level alignment for cascade charge transfer and rational homogeneous/heterogeneous interfacial engineering. The functionalities of TNW-based electrodes include enlarged surface area and superior light scattering for maximized light harvesting, as well as facilitated charge transport and suppressed charge recombination for enhanced charge collection, which are promising in optoelectronic fields such as solar cells, photocatalysis, and PEC cells. Beyond TNWs, one can also integrate other types of semiconductor (e.g., Fe 2 O 3 or WO 3 ) NWs into rationally designed structures for preparing novel photocatalytic materials with panchromatic absorption, efficient charge transfer, and excellent catalytic properties. Finally, an insightful perspective for rational design of advanced NW-based materials is provided.

Though coating CsPbBr 3 nanocrystal (NC) with an outer layer has been regarded as an effective strategy to address its instability issues, deep investigations into the electronic interaction between CsPbBr 3 NC and coating layer have yet to be conducted. In this study, the dynamics of hot carrier and charge carrier of CsPbBr 3 nanocrystal with various MO 2 (M = Si, Ti, Sn) coating layers have been comprehensively studied. Combined transient optical characterizations (time-resolved photoluminescence and ultrafast transient absorption) and photoelectrochemical measurements reveal that coating with insulating SiO 2 accelerates the hot carrier relaxation and enhances the radiative recombination by passivating surface traps, whereas efficient charge-carrier separation and extraction are observed after coating with SnO 2 and TiO 2 . The electron injection from CsPbBr 3 NC to SnO 2 (1.14 × 10 8 s -1 ) is 2-fold faster than to TiO 2 (5.4 × 10 7 s -1 ) owing to the lower conduction band edge and the higher electron mobility of SnO 2 . Particularly, the first time fabricated CsPbBr 3 NC/SnO 2 composite exhibits superior stability against UV light and moisture, as well as the best photocurrent response in this study. This work has implied that rational design of the coating layer for perovskite NC can not only improve the stability but also tailor the electronic and optoelectronic properties for various applications.

Lead halide perovskite nanocrystals (NCs) have demonstrated great potential as appealing candidates for advanced optoelectronic applications. However, the toxicity of lead and the intrinsic instability toward moisture hinder their mass production and commercialization. Herein, to solve such thorny problems, novel lead-free Cs 2 AgBiBr 6 double perovskite NCs fabricated via a simple hot-injection method are reported, which exhibit impressive stability in moisture, light, and temperature. Such materials are then applied into photocatalytic CO 2 reduction, achieving a total electron consumption of 105 µmol g -1 under AM 1.5G illumination for 6 h. This study offers a reliable avenue for Cs 2 AgBiBr 6 perovskite nanocrystals preparation, which holds a great potential in the further photochemical applications., (© 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Layer-by-layer assembly of the dirhodium complex [Rh 2 (O 2 CCH 3 ) 4 ] (Rh 2 ) with linear N , N '-bidentate ligands pyrazine (L S ) or 1,2-bis(4-pyridyl)ethene (L L ) on a gold substrate has developed two series of redox active molecular wires, (Rh 2 L S ) n @Au and (Rh 2 L L ) n @Au ( n = 1-6). By controlling the number of assembling cycles, the molecular wires in the two series vary systematically in length, as characterized by UV-vis spectroscopy, cyclic voltammetry and atomic force microscopy. The current-voltage characteristics recorded by conductive probe atomic force microscopy indicate a mechanistic transition for charge transport from voltage-driven to electrical field-driven in wires with n = 4, irrespective of the nature and length of the wires. Whilst weak length dependence of electrical resistance is observed for both series, (Rh 2 L L ) n @Au wires exhibit smaller distance attenuation factors ( β ) in both the tunneling ( β = 0.044 Å -1 ) and hopping ( β = 0.003 Å -1 ) regimes, although in (Rh 2 L S ) n @Au the electronic coupling between the adjacent Rh 2 centers is stronger. DFT calculations reveal that these wires have a π-conjugated molecular backbone established through π(Rh 2 )-π(L) orbital interactions, and (Rh 2 L L ) n @Au has a smaller energy gap between the filled π*(Rh 2 ) and the empty π*(L) orbitals. Thus, for (Rh 2 L L ) n @Au, electron hopping across the bridge is facilitated by the decreased metal to ligand charge transfer gap, while in (Rh 2 L S ) n @Au the hopping pathway is disfavored likely due to the increased Coulomb repulsion. On this basis, we propose that the super-exchange tunneling and the underlying incoherent hopping are the dominant charge transport mechanisms for shorter ( n ≤ 4) and longer ( n > 4) wires, respectively, and the Rh 2 L subunits in mixed-valence states alternately arranged along the wire serve as the hopping sites.

Patients with chronic heart failure (CHF) are often accompanied with varying degrees of renal diseases. The purpose of this study was to identify rs37369 polymorphism of AGXT2 specific to the renal function of CHF patients. A total of 1012 southern Chinese participants, including 487 CHF patients without history of renal diseases and 525 healthy volunteers, were recruited for this study. Polymerase chain reaction-restriction fragment length polymorphism (PCR-RFLP) was used to determine the genotypes of AGXT2 rs37369 polymorphism. Levels of blood urea nitrogen (BUN) and serum creatinine (SCr) were detected to indicate the renal function of the participants. BUN level was significantly higher in CHF patients without history of renal diseases compared with healthy volunteers (p=0.000). And the similar result was also obtained for SCr (p=0.000). Besides, our results indicated that the level of BUN correlated significantly with SCr in both the CHF patients without renal diseases (r=0.4533, p<0.0001) and volunteers (r=0.2489, p<0.0001). Furthermore, we found that the AGXT2 rs37369 polymorphism could significantly affect the level of BUN in CHF patients without history of renal diseases (p=0.036, AA+AG vs GG). Patients with rs37369 GG genotype showed a significantly reduced level of BUN compared to those with the AA genotype (p=0.024), and the significant difference was still observed in the smokers of CHF patients without renal diseases (p=0.023). In conclusion, we found that CHF might induce the impairment of kidney and cause deterioration of renal function. AGXT2 rs37369 polymorphism might affect the renal function of CHF patients free from renal diseases, especially in patients with cigarette smoking., (Copyright © 2017. Published by Elsevier B.V.)

What Is Known and Objective: Essential hypertension (EH) is a common disease exhibiting large individual difference in occurrence, development and treatment response. Genetic factors are implicated in the development and progression of EH. This study aimed to explore the association between NPR3 single nucleotide polymorphism rs2270915 (A/G, Asn521Asp) and the risk of EH in a Chinese Han population by a case-control study., Methods: The study was a single-centre, case-control trial, in which a total of 287 EH patients and 289 age- and sex-matched healthy controls were enrolled. The inclusion criteria were as follows: Han Chinese origin, male or female patients, systolic blood pressure (SBP) ≥140 mm Hg and/or diastolic blood pressure (DBP) ≥90 mm Hg. The healthy controls were subjects without histories of cardiovascular or cerebrovascular diseases. NPR3 rs2270915 polymorphism was genotyped by polymerase chain reaction-restriction fragment length polymorphism (PCR-RFLP). In addition, primary human umbilical vein endothelial cells (HUVECs) were isolated from 19 fresh human umbilical cords and cultured. Atrial natriuretic peptide (ANP) concentration in cell medium was determined by enzyme-linked immunosorbent assay (ELISA). NPR3 mRNA expression was determined by real-time semi-quantitative PCR., Results and Discussion: No significant difference in genotype distribution of NPR3 rs2270915 polymorphism was observed between cases and controls (P>.05). Patients carrying the rs2270915 G allele showed decreased SBP, and the difference was marginal. As compared with cells carrying the rs2270915 AA genotype, those with the AG genotype showed significantly lower NPR3 mRNA expression levels (P<.05) and lower medium ANP concentration (P<.001)., What Is New and Conclusion: This study suggested that NPR3 rs2270915 polymorphism was associated with decreased SBP level marginally in EH patients in a Chinese Han population, and the polymorphism may function through decreasing NPR3 mRNA expression and ANP level., (© 2017 John Wiley & Sons Ltd.)

Transition metal phosphides have recently been regarded as robust, inexpensive electrocatalysts for both the hydrogen evolution reaction (HER) and the oxygen evolution reaction (OER). Thus far, tremendous scientific efforts have been applied to improve the catalytic activity of the catalyst, whereas the scale-up fabrication of morphology-controlled catalysts while maintaining their desired performance remains a great challenge. Herein, we present a facile and scalable approach to fabricate the macroporous Ni 2 P/nickel foam electrode. The obtained electrocatalyst exhibits superior bifunctional catalytic activity and durability, as evidenced by a low overpotential of 205 and 300 mV required to achieve a high current density of 100 mA cm -2 for HER and OER, respectively. Such a spray-based strategy is believed to widely adapt for the preparation of electrodes with uniform macroporous structures over a large area (e.g., 100 cm 2 ), which provides a universal strategy for the mass fabrication of high performance water-splitting electrodes.

Nowadays, obtaining a thin and large-area perovskite single-crystal (SC) is still challenging. Herein, we report a novel strategy to prepare a laminar MAPbBr 3 SC with a controllable thickness of 16 μm and a size of 6 × 8 mm. Additionally, the SC solar cell achieves an intriguing efficiency of 7.11% with an impressive stability, maintaining 93% initial PCE after aging for 1000 h.

Halide perovskite quantum dots (QDs), primarily regarded as optoelectronic materials for LED and photovoltaic devices, have not been applied for photochemical conversion (e.g., water splitting or CO 2 reduction) applications because of their insufficient stability in the presence of moisture or polar solvents. Herein, we report the use of CsPbBr 3 QDs as novel photocatalysts to convert CO 2 into solar fuels in nonaqueous media. Under AM 1.5G simulated illumination, the CsPbBr 3 QDs steadily generated and injected electrons into CO 2 , catalyzing CO 2 reduction at a rate of 23.7 μmol/g h with a selectivity over 99.3%. Additionally, through the construction of a CsPbBr 3 QD/graphene oxide (CsPbBr 3 QD/GO) composite, the rate of electron consumption increased 25.5% because of improved electron extraction and transport. This study is anticipated to provide new opportunities to utilize halide perovskite QD materials in photocatalytic applications.

Organometal trihalide perovskites have been attracting intense attention due to their enthralling optoelectric characteristics. Thus far, most applications focus on polycrystalline perovskite, which however, is overshadowed by single crystal perovskite with superior properties such as low trap density, high mobility, and long carrier diffusion length. In spite of the inherent advantages and significant optoelectronic applications in solar cells and photodetectors, the fabrication of large-area laminar perovskite single crystals is challenging. In this report, an ingenious space-limited inverse temperature crystallization method is first demonstrated to the in situ synthesis of 120 cm 2 large-area CH 3 NH 3 PbBr 3 crystal film on fluorine-doped tin oxide (FTO) glass. Such CH 3 NH 3 PbBr 3 perovskite crystal film is successfully applied to narrowband photodetectors, which enables a broad linear response range of 10 -4 -10 2 mW cm -2 , 3 dB cutoff frequency (f 3 dB ) of ≈110 kHz, and high narrow response under low bias -1 V., (© 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Objective: To investigate whether microRNA (miRNA) miR-21 regulates dimethylarginine dimethylaminohydrolase 1 (DDAH1) expression through binding 3'-UTR region directly in human umbilical venous endothelial cells (HUVECs) and to explore whether DDAH1-V2/V3 transcripts can function as microRNA sponge, thereby modulating DDAH1-V1 expression., Methods: The DDAH1 3'-UTR containing miR-21 recognizing sequence was cloned into PmirGLO dual-luciferase miRNA target expression plasmid to construct PmirGLO-miR-21. The plasmid and miR-21 (at concentrations of 25, 50, 100 nM, respectively) or negative control (100 nM) were co-transfected into HUVECs, luciferase activity was detected at 24 h. HUVECs were incubated with 2 μg/ml Actinomycin D for the indicated time after miR-21 (25 nM) transfection, half-lives of DDAH1 mRNA were determined. HUVECs were transfected with PmirGLO-miR-21 alone or co-transfected with miR-21 for 24 h, DDAH1 transcripts mRNA, eNOS activity and DDAH1 protein expression were determined., Results: MiR-21 decreased luciferase activity of PmirGLO-miR-21 in a dose-dependent manner (P < 0.05 for 25 nM miR-21, P < 0.01 for 50 nM and 100 nM miR-21), and miR-21 inhibitor increased reporter activity of PmirGLO-miR-21 and mRNA expression of all three DDAH1 transcript variants significantly (P < 0.05, respectively). The degree of increase in endogenous DDAH1 mRNA expression by miR-21 inhibitor was more obvious for DDAH1-V3. Overexpression of miR-21 decreased mRNA expression and mRNA half-life time of all DDAH1 transcripts significantly (P < 0.05), and DDAH1-V2 displayed significantly decreased half-life time than DDAH1-V1 and -V3 with or without miR-21 transfection (P < 0.05, respectively). MiR-21 (100 nM) decreased DDAH1 protein expression and eNOS activity significantly (P < 0.05), which was reversed by PmirGLO-miR-21 transfection (P < 0.05). Transfection of PmirGLO-miR-21 alone increased intracellular miR-21 expression by approximately 5.6-fold, but only showed a trend of increase in DDAH1 protein expression., Conclusion: Our results confirmed DDAH1 3'-UTR as a target for miR-21, and endogenous miR-21 showed increased inhibitory effect on DDAH1-V3 transcript. DDAH1 3'-UTR, especially for DDAH1-V3, may function as miR-21 sponge to regulate DDAH1 protein expression. Modulation of miR-21-DDAH1 interaction may provide a new approach for tackling cardiovascular diseases., (Copyright © 2016 Elsevier Inc. All rights reserved.)

Cupric oxide (CuO), a narrow-bandgap semiconductor, has a band alignment that makes it an ideal photocathode for the renewable production of solar fuels. However, the photoelectrochemical performance of CuO is limited by its poor conductivity and short electron diffusion lengths. Herein, a three-dimensional (3D) architecture consisting of CuO nanosheets supported onto transparent conducting macroporous antimony-doped tin oxide (mpATO@CuONSs) is designed as an excellent photocathode for promoting the hydrogen evolution reaction (HER). Owing to the 3D structure affording superior light-harvesting characteristics, large contact areas with the electrolyte, and highly conductive pathways for separation and transport of charge carriers, the mpATO@CuONSs photocathode produces an impressively high photocurrent density of -4.6 mA cm -2 at 0 V versus the reversible hydrogen electrode (RHE), which is much higher than that of the CuONSs array onto planar FTO glass (-1.9 mA cm -2 )., (© 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Background and Aims: Alanine-glyoxylate aminotransferase 2 (AGXT2) polymorphisms have been extensively studied to be associated with many cardiovascular diseases, with the exception of chronic heart failure (CHF). The aim of this study was to determine whether the AGXT2 rs37369 (V140I) polymorphism is associated with risk for and prognosis of CHF in Chinese patients., Methods: 1000 CHF patients and 1200 healthy controls were recruited and polymerase chain reaction-restriction fragment length polymorphism analysis (PCR-RFLP) was used to determine the genotypes of rs37369 polymorphism. Tube formation assay and transwell migration assay were performed to assess the effects of asymmetric dimethylarginine (ADMA) and to explore the significance of rs37369 polymorphism in the pathogenesis of CHF. 140 CHF patients underwent a median follow-up of 38.7 months by telephone., Results: The rs37369 GG genotype was significantly over-represented in CHF patients compared to controls (18.9% vs 14.7%, p = 0.009) and was significantly associated with increased risk of CHF (p = 0.030), especially in patients with hypertension (p = 0.021). Besides, the rs37369 GG genotype marginally increased the risk for CHF in smokers. ADMA stimulated migration and inhibited tube formation of cultured human umbilical vein endothelial cells (HUVECs). Overexpression of AGXT2 with pcAGXT2-rs37369-A or G plasmid reversed ADMA-induced HUVECs migration and tube formation. AGXT2 rs37369-A showed increased ADMA degradation activity and marginally prolonged the lifetime of CHF patients., Conclusions: ADMA might accelerate the progression of CHF possibly by inhibiting angiogenesis and promoting migration of HUVECs. AGXT2 rs37369 polymorphism is associated with increased risk for CHF, which may due to distinct disparities of alleles in ADMA degradation., (Copyright © 2016 Elsevier Ireland Ltd. All rights reserved.)

Two new electron-rich molecules based on 3,4-phenylenedioxythiophene (PheDOT) were synthesized and successfully adopted as hole-transporting materials (HTMs) in perovskite solar cells (PSCs). X-ray diffraction, absorption spectra, photoluminescence spectra, electrochemical properties, thermal stabilities, hole mobilities, conductivities, and photovoltaic parameters of PSCs based on these two HTMs were compared with each other. By introducing methoxy substituents into the main skeleton, the energy levels of PheDOT-core HTM were tuned to match with the perovskite, and its hole mobility was also improved (1.33×10(-4)  cm(2)  V(-1)  s(-1) , being higher than that of spiro-OMeTAD, 2.34×10(-5)  cm(2)  V(-1)  s(-1)). The PSC based on MeO-PheDOT as HTM exhibits a short-circuit current density (Jsc) of 18.31 mA cm(-2) , an open-circuit potential (Voc ) of 0.914 V, and a fill factor (FF) of 0.636, yielding an encouraging power conversion efficiency (PCE) of 10.64 % under AM 1.5G illumination. These results give some insight into how the molecular structures of HTMs affect their performances and pave the way for developing high-efficiency and low-cost HTMs for PSCs., (© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Utilizing photoelectrochemical (PEC) cells to directly collecting solar energy into chemical fuels (e.g., H 2 via water splitting) is a promising way to tackle the energy challenge. α-Fe 2 O 3 has emerged as a desirable photoanode material in a PEC cell due to its wide spectrum absorption range, chemical stability, and earth abundant component. However, the short excited state lifetime, poor minority charge carrier mobility, and long light penetration depth hamper its application. Recently, the elegantly designed hierarchical macroporous composite nanomaterial has emerged as a strong candidate for photoelectrical applications. Here, a novel 3D antimony-doped SnO 2 (ATO) macroporous structure is demonstrated as a transparent conducting scaffold to load 1D hematite nanorod to form a composite material for efficient PEC water splitting. An enormous enhancement in PEC performance is found in the 3D electrode compared to the controlled planar one, due to the outstanding light harvesting and charge transport. A facile and simple TiCl 4 treatment further introduces the Ti doping into the hematite while simultaneously forming a passivation layer to eliminate adverse reactions. The results indicate that the structural design and nanoengineering are an effective strategy to boost the PEC performance in order to bring more potential devices into practical use.

The development of a novel nanoarray photoanode with a heterostructure on a transparent conducting oxide substrate provides a promising scheme to fabricate efficient energy conversion devices. Herein, we successfully synthesize the vertically aligned hierarchical TiO2 nanowire/ZnO nanorod or TiO2 nanowire/ZnO nanosheet hybrid arrays, which are proven to be excellent anode candidates for superior light utilization. Consequently, the quantum-dot-sensitized solar cells based on such hybrid arrays exhibit an impressive power conversion efficiency (PCE) under AM 1.5G one sun illumination with improved short-circuit current density (JSC) and fill factor compared to pristine TiO2 nanowire arrays. Combined with the chemical-bath-deposited Cu2S counter electrode, the eventual PCE can be further optimized to as high as 4.57% for CdS/CdSe co-sensitized quantum dot solar cells.

Three cone-calix[4]arene-based sensitizers (Calix-1-Calix-3) with multiple donor-π-acceptor (D-π-A) moieties are designed, synthesized, and applied in dye-sensitized solar cells (DSSCs). Their photophysical and electrochemical properties are characterized by measuring UV/Vis absorption and emission spectra, cyclic voltammetry, and density functional theory (DFT) calculations. Calix-3 has excellent thermo- and photostability, as illustrated by thermogravimetric analysis (TGA) and dye-aging tests, respectively. Importantly, a DSSC using the Calix-3 dye displays a conversion efficiency of 5.48 % in under standard AM 1.5 Global solar illumination conditions, much better than corresponding DSSCs that use the rod-shaped dye M-3 with a single D-π-A chain (3.56 %). The dyes offer advantages in terms of higher molar extinction coefficients, longer electron lifetimes, better stability, and stronger binding ability to TiO2 film. This is the first example of calixarene-based sensitizers for efficient dye-sensitized solar cells., (© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The high-performance of a well-aligned 1D nanostructured electrode relies largely on a smart and rational modification with other active nanomaterials. Herein, we present a facile solution-based route to fabricate a well-aligned metal oxide-based core-shell hybrid arrays on TCO substrate. Demonstrated samples included nanowire@nanoparticle (TNW@NP) or nanowire@nanosheet (TNW@NS) with a unique porous core/shell nanowire arrays architecture in the absence or presence of DETA during the solvothermal treatment process. The "alcoholysis" and "ripening" growth mechanism is proposed to explain the formation of honeycomb-like nanosheets shell on nanowires core. Based on careful control of experimental condition, a novel double layered TiO2 photoanode (DL-TNW@NS-YSHTSs) consisting of 16 μm thick TNW@NS under layer and 6 μm thick yolk-shell hierarchical TiO2 microspheres (YSHTSs) top layer can be obtained, exhibiting an impressive PCE over 10% at 100 mW cm(-2), which can be attributed to the well-organized photoanode composed of hierarchical core-shell arrays architecture and yolk-shell hollow spheres architecture with synergistic effects of high dye loading and superior light scattering for prominent light harvesting efficiency.