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Background: Primary familial brain calcification (PFBC) is a monogenic disorder characterized by bilateral calcifications in the brain. The genetic basis remains unknown in over half of the PFBC patients, indicating the existence of additional novel causative genes. NAA60 was a recently reported novel causative gene for PFBC. Objective: The aim was to identify the probable novel causative gene in an autosomal recessive inherited PFBC family. Methods: We performed a comprehensive genetic study on a consanguineous Chinese family with 3 siblings diagnosed with PFBC. We evaluated the effect of the variant in a probable novel causative gene on the protein level using Western blot, immunofluorescence, and coimmunoprecipitation. Possible downstream pathogenic mechanisms were further explored in gene knockout (KO) cell lines and animal models. Results: We identified a PFBC co‐segregated homozygous variant of c.460_461del (p.D154Lfs*113) in NAA60. Functional assays showed that this variant disrupts NAA60 protein localization to Golgi and accelerated protein degradation. The mutant NAA60 protein alters its interaction with the PFBC‐related proteins PiT2 and XPR1, affecting intracellular phosphate homeostasis. Further mass spectrometry analysis in NAA60 KO cell lines revealed decreased expression of multiple brain calcification–associated proteins, including reduced folate carrier (RFC), a folate metabolism–related protein. Conclusions: Our study replicated the identification of NAA60 as a novel causative gene for autosomal recessive PFBC, demonstrating our causative variant leads to NAA60 loss of function. The NAA60 loss of function disrupts not only PFBC‐related proteins (eg, PiT2 and XPR1) but also a wide range of other brain calcification–associated membrane protein substrates (eg, RFC), and provided a novel probable pathogenic mechanism for PFBC. © 2024 International Parkinson and Movement Disorder Society. [ABSTRACT FROM AUTHOR]

Semihydrogenation is a crucial industrial process. Noble metals such as Pd have been extensively studied in semihydrogenation reactions, owing to their unique catalytic activity toward hydrogen activation. However, the overhydrogenation of alkenes to alkanes often happens due to the rather strong adsorption of alkenes on Pd active phases. Herein, we demonstrate that the incorporation of Pd active phases as single‐atom sites in perovskite lattices such as SrTiO3 can greatly alternate the electronic structure and coordination environment of Pd active phases to facilitate the desorption of alkenes rather than further hydrogenation. Furthermore, the incorporated Pd sites can be well stabilized without sintering by a strong host–guest interaction with SrTiO3 during the activation of H species in hydrogenation reactions. As a result, the Pd incorporated SrTiO3 (Pd‐SrTiO3) exhibits an excellent time‐independent selectivity (>99.9 %) and robust durability for the photocatalytic semihydrogenation of phenylacetylene to styrene. This strategy based on incorporation of active phases in perovskite lattices will have broad implications in the development of high‐performance photocatalysts for selective hydrogenation reactions. [ABSTRACT FROM AUTHOR]

Photocatalytic synthesis of H2O2 is an advantageous and ecologically sustainable alternative to the conventional anthraquinone process. However, achieving high conversion efficiency without sacrificial agents remains a challenge. In this study, two covalent organic frameworks (COF−O and COF−C) were prepared with identical skeletal structures but with their pore walls anchored to different alkyl chains. They were used to investigate the effect of the chemical microenvironment of pores on photocatalytic H2O2 production. Experimental results reveal a change of hydrophilicity in COF−O, leading to suppressed charge recombination, diminished charge transfer resistance, and accelerated interfacial electron transfer. An apparent quantum yield as high as 10.3 % (λ=420 nm) can be achieved with H2O and O2 through oxygen reduction reaction. This is among the highest ever reported for polymer photocatalysts. This study may provide a novel avenue for optimizing photocatalytic activity and selectivity in H2O2 generation. [ABSTRACT FROM AUTHOR]

Photocatalytic synthesis of H2O2 is an advantageous and ecologically sustainable alternative to the conventional anthraquinone process. However, achieving high conversion efficiency without sacrificial agents remains a challenge. In this study, two covalent organic frameworks (COF−O and COF−C) were prepared with identical skeletal structures but with their pore walls anchored to different alkyl chains. They were used to investigate the effect of the chemical microenvironment of pores on photocatalytic H2O2 production. Experimental results reveal a change of hydrophilicity in COF−O, leading to suppressed charge recombination, diminished charge transfer resistance, and accelerated interfacial electron transfer. An apparent quantum yield as high as 10.3 % (λ=420 nm) can be achieved with H2O and O2 through oxygen reduction reaction. This is among the highest ever reported for polymer photocatalysts. This study may provide a novel avenue for optimizing photocatalytic activity and selectivity in H2O2 generation. [ABSTRACT FROM AUTHOR]

The Poyang Lake region is home to large‐blackspot loaches (LBL), small‐blackspot loaches (SBL), and non‐blackspot loaches (NBL), Misgurnus anguillicaudatus. To investigate the impact of tyrosinase on spot development, the complementary DNAs (cDNA) of tyrosinase in M. anguillicaudatus (designated as Matyr) were cloned using the rapid amplification of cDNA ends (RACE)‐PCR method. The full‐length cDNA for Matyr was 2020 bp, and the open‐reading frame comprised 1617 bp, encoding a predicted protein with 538 amino acids. Phylogenetic studies revealed that MaTyr was first grouped with Tyr of Triplophysa tibetana and Leptobotia taeniops, and then Tyr of other cyprinid fish. The quantitative reverse‐transcription‐PCR results show that Matyr was highly expressed in the muscle, caudal fin, and dorsal skin. The Matyr gene's messenger RNA expression pattern steadily increased from the fertilized ovum period to the somitogenesis period, and from the muscle effect stage to 6 days after fertilization, it considerably increased (p < 0.01). The Matyr hybridization signals with similar location could be found in all developmental stages of three kinds of loaches using whole‐mount in situ hybridization (WISH) technology and were the strongest during the organ development period and melanin formation period. Dot hybridization signals in LBLs rapidly spread to the back of the body beginning at the period when the eyes first formed melanin, and their dimensions were larger than those of NBLs during the same time period. The body color of loaches could change reversibly with black/white background adaptation. The α‐msh, mitfa, and tyr are mainly expressed in loaches adapted with a black background. Tyr gene could be involved in the development of blackspots and body color polymorphism, and contribute to organ development in the loach. [ABSTRACT FROM AUTHOR]

Travel intentions are influenced by not only personal background but also external factors such as national disasters, infectious diseases, and government policy. While international flights and the travel market are sharply recovering from the effects of the COVID‐19 pandemic, travel risk will affect future travel demand. This study analyzed the relationship between potential risk of destination and travel avoidance intention using the stimulus‐organism‐response (SOR) model. The survey was conducted with 303 Chinese and 253 South Korean respondents living in countries adjacent to Japan. The results reveal that travel avoidance intentions may be influenced by emotional reactions to the complexity of the geopolitical environment or the diverse protection motivation perceptions of travelers. This study proposes that nationality has a moderate effect on tentative travel avoidance intention compared to gender. [ABSTRACT FROM AUTHOR]

Photocatalytic hydrogen production based on noble metal‐free systems is a promising technology for the conversion of solar energy into green hydrogen, it is pivotal and challenging to tailor‐make photocatalysts for achieving high photocatalytic efficiency. Herein, we reported a hollow double‐shell dyad through uniformly coating covalent organic frameworks (COFs) on the surface of hollow Co9S8. The double shell architecture enhances the scattering and refraction efficiency of incident light, shortens the transmission distance of the photogenerated charge carriers, and exposes more active sites for photocatalytic conversion. The hydrogen evolution rate is as high as 23.15 mmol g−1 h−1, which is significantly enhanced when compared with that of their physical mixture (0.30 mmol g−1 h−1) and Pt‐based counterpart (11.84 mmol g−1 h−1). This work provides a rational approach to the construction of noble‐metal‐free photocatalytic systems based on COFs to enhance hydrogen evolution performance. [ABSTRACT FROM AUTHOR]

We report a photochemical bismuth vanadate (BiVO4) sensing material, which possesses a large proportion of (110) and (011) facets combined with the additional (111) facets, for the selective detection of ultra‐low concentration hydrogen sulfide (H2S) driven by visible light. Specifically, the obtained octadecahedron BiVO4 (Octa‐BiVO4) performs a high response value (67) and short response time (47.4 s) to 100 ppm H2S with good stability for nearly 100 days, as well as undisturbedness by moist air. With the combination of experimental and theoretical calculation results, the adsorption and carrier transfer behaviors of H2S molecules on the Octa‐BiVO4 crystal surface are investigated. By adjusting the ratio of different crystal facets and controlling the facets with characteristic adsorption, we achieve improved anisotropic photoinduced carrier separation and high selectivity for a specific gas. Furthermore, this facial facet engineering can be extended to the synthesis of other sensing materials, offering huge opportunities for fundamental research and technological applications. [ABSTRACT FROM AUTHOR]

In situ photo‐deposition of both Pt and CoOx cocatalysts on the facets of poly (triazine imide) (PTI) crystals has been developed for photocatalytic overall water splitting. However, the undesired backward reaction (i.e. water formation) on the noble Pt surface is a spontaneously down‐hill process, which restricts their efficiency to run the overall water splitting reaction. Herein, we demonstrate that the efficiency for photocatalytic overall water splitting could be largely promoted by the decoration of Rh/Cr2O3 and CoOx as H2 and O2 evolution cocatalysts, respectively. Results reveal that the dual cocatalysts greatly extract charges from bulk to surface, while the Rh/Cr2O3 cocatalyst dramatically restrains the backward reaction, achieving an apparent quantum efficiency (AQE) of 20.2 % for the photocatalytic overall water splitting reaction. [ABSTRACT FROM AUTHOR]

Poly (triazine imide) (PTI/Li+Cl−), one of the crystalline versions of polymeric carbon nitrides, holds great promise for photocatalytic overall water splitting. In principle, the photocatalytic activity of PTI/Li+Cl− is closely related to the morphology, which could be reasonably tailored by the modulation of the polycondensation process. Herein, we demonstrate that the hexagonal prisms of PTI/Li+Cl− could be converted to hexagonal nanosheets by adjusting the binary eutectic salts from LiCl/KCl or NaCl/LiCl to ternary LiCl/KCl/NaCl. Results reveal that the extension of in‐plane conjugation is preferred, when the polymerisation was performed in the presence of ternary eutectic salts. The hexagonal nanosheets bears longer lifetimes of charge carriers than that of hexagonal prisms due to lower intensity of structure defects and shorter hopping distance of charge carriers along the stacking direction of triazine nanosheets. The optimized hexagonal nanosheets exhibits a record apparent quantum yield value of 25 % (λ=365 nm) for solar hydrogen production by one‐step excitation overall water splitting. [ABSTRACT FROM AUTHOR]

Diabetic retinopathy (DR) is the most prevalent type of retinal vasculopathy and the most widespread cause of preventable blindness in adults. Excessive increases in reactive oxygen species (ROS) and vascular endothelial growth factor are major initiators and drivers of DR progression, respectively. However, current DR treatment options remain limited, particularly for early DR. Nanotechnology‐mediated antioxidant strategies are gaining increasing popularity to treat ocular diseases. Quercetin has excellent ROS scavenging efficiency but poor stability and low bioavailability in physiological environments. In this study, ultrasmall Fe‐Quer nanozymes (NZs) formed by coupling quercetin with low‐toxic iron ions are reported that can mimic the activities of three important antioxidant enzymes, superoxide dismutase, catalase, and peroxidase, thereby exhibiting excellent water dispersion and efficient ROS scavenging ability. In vitro and in vivo assays validate the effects of Fe‐Quer NZs against inflammation, oxidative stress damage, microvascular leakage, and angiogenesis, particularly their vascular protective effect in early DR. Transcriptomic analysis further reveals a potential multitarget‐specific therapeutic mechanism of Fe‐Quer NZs against DR. These observations open avenues for Fe‐Quer NZs, composed of molecules of a natural product and metal ions with artificial NZ activity, as microvascular protective agents for DR and other ROS‐related diseases. [ABSTRACT FROM AUTHOR]

Earth's primordial atmosphere was rich in ammonia and methane. To understand the evolution of the atmosphere, these two gases were used to make photoredox‐active nitrogen‐doped carbon (NDC). Photocatalysts such as NDC might play an important role in the development of geological and atmospheric chemistry during the Archean era. This study describes the synthesis of NDC directly from NH3 and CH4 gases. The photocatalyst product can be used to selectively synthesize imines by photo‐oxidization of amines, producing H2O2 simultaneously in the photoreduction reaction. Our findings shed light on the chemical evolution of the Earth. [ABSTRACT FROM AUTHOR]

A new series of donor‐acceptor (D‐A)‐type semiconductive polymers were generated by the integration of electron‐deficient alkyl chain anchored triazole (TA) moieties and electron‐rich pyrene units into the polymer skeleton. The polymer series demonstrated satisfactory light‐harvesting ability and suitable band gaps. In the series, polymer P‐TAME benefits from a minimized exciton binding energy, strongest D‐A interaction, and favorable hydrophilicity, affording an outstanding photocatalytic H2 evolution rate of ca. 100 μmol h−1 (10 mg polymer, AQY420 nm=8.9 %) and H2O2 production rate of ca. 190 μmol h−1 (20 mg polymer) under visible‐light irradiation, which is superior to most currently reported polymers. All polymers in the series can mediate water oxidation reactions to evolve O2. Thus, these TA‐based polymers open up a new avenue toward tailor‐made efficient photocatalysts with broad photocatalytic activities. [ABSTRACT FROM AUTHOR]

Broadening the visible light absorption range and accelerating the separation and migration process of charge carriers are effective ways to improve photocatalytic quantum efficiencies. In this study, we show that poly heptazine imides with enhanced optical absorption and promoted charge carrier separation and migration could be obtained by means of a rational design of the band structures and crystallinity of polymeric carbon nitride. Copolymerization of urea with monomers such as 2‐aminothiophene‐3‐carbonitrile would first generate amorphous melon with enhanced optical absorption, while further ionothermal treatment of melon in eutectic salts would increase the polymerization degree and create condensed poly heptazine imides as final products. Accordingly, the optimized poly heptazine imide presents an apparent quantum yield of 12 % at 420 nm for photocatalytic hydrogen production. [ABSTRACT FROM AUTHOR]

Light‐driven fixation of CO2 in organics has emerged as an appealing alternative for the synthesis of value‐added fine chemicals. Challenges remain in the transformation of CO2 as well as product selectivity due to its thermodynamic stability and kinetic inertness. Here we develop a boron carbonitride (BCN) with the abundant terminal B/N defects around the mesoporous walls, which essentially enhances surface active sites as well as charge transfer kinetics, boosting the overall rate of CO2 adsorption and activation. In this protocol, anti‐Markovnikov hydrocarboxylation of alkenes with CO2 to an extended carbon chain is achieved with good functional group tolerance and specific regioselectivity under visible‐light irradiation. The mechanistic studies demonstrate the formation of CO2 radical anion intermediate on defective boron carbonitride, leading to the anti‐Markovnikov carboxylation. Gram‐scale reaction, late‐stage carboxylation of natural products and synthesis of anti‐diabetic GPR40 agonists reveal the utility of this method. This study sheds new insight on the design and application of metal‐free semiconductors for the conversion of CO2 in an atom‐economic and sustainable manner. [ABSTRACT FROM AUTHOR]

Conjugated polymers (CPs) represent a promising platform for photocatalytic CO2 fixation owing to their suitable band structures that meet the requirements of the reduction potential of CO2 to value‐added fuels. However, the photocatalytic performance of CPs is rather restrained by the low charge transfer efficiency. Herein, we rationally designed three CPs with a more delocalized electronic transmission channel and planar molecular structure, which are regarded to evidently reduce the exciton binding energy (Eb) and accelerate the internal charge transfer process. Besides, the assembly of suitable electron‐output "tentacles" and cocatalysts on the surface of CPs could effectively facilitate interfacial electron delivery. Accordingly, the optimal P‐2CN exhibits an apparent quantum yield of 4.6 % at 420 nm for photocatalytic CO2 to CO. Further adjusting the amounts of cyano groups and cocatalysts, the CO selectivity could be obtained in the range of 0–80.5 %. [ABSTRACT FROM AUTHOR]

Constructing low‐dimensional heterojunctions via hybridizing 0D, 1D, and 2D building blocks is an effective means to devise higher‐order architectures with excellent photocatalytic reaction activities. Developing a versatile topology optimization strategy paves the way for guiding the rational structural design of a wide range of heterostructures. Herein, taking the ZnO‐CdS hybrids with mixed topology structures (including 0D‐1D, 0D‐0D, and 1D‐1D composites) as a model system, the work unveils a ubiquitous, yet unrecognized, topology dependence of photocatalytic performances and the 0D‐1D topology combination coupled with an annealing treatment gives rise to an optimal photocatalytic redox activity, far exceeding those of 0D‐0D and 1D‐1D counterparts. The 0D‐1D topology integrates the structural merits of both constituent units, where the 1D unit acts as a rigid matrix to allow the uniform dispersity of 0D units for exposing abundant active sites, and a mobile 0D unit contributes to the interfacial reconstruction for forming charge‐migration‐expediated heterointerfaces via thermal‐induced grain rotations. Such thermal‐annealing‐coupled topology optimization methodology shows applicability for a large spectrum of low‐dimensional heterojunctions, offering a prototype for the precise structural design of low‐dimensional heterojunctions with enhanced catalytic performance. [ABSTRACT FROM AUTHOR]

Poly (triazine imide) photocatalysts prepared via molten salt methods emerge as promising polymer semiconductors with one‐step excitation capacity of overall water splitting. Unveiling the molecular conjugation, nucleation, and crystallization processes of PTI crystals is crucial for their controllable structure design. Herein, microscopy characterization was conducted at the PTI crystallization front from meso to nano scales. The heptazine‐based precursor was found to depolymerize to triazine monomers within molten salts and KCl cubes precipitate as the leading cores that guide the directional stacking of PTI molecular units to form aggregated crystals. Upon this discovery, PTI crystals with improved dispersibility and enhanced photocatalytic performance were obtained by tailoring the crystallization fronts. This study advances insights into the directional assembling of PTI monomers on salt templates, placing a theoretical foundation for the ordered condensation of polymer crystals. [ABSTRACT FROM AUTHOR]

Background: RNA‐binding protein Quaking‐5 (QKI‐5), a major isoform of QKIs, inhibits tumor progression in non‐small cell lung cancer (NSCLC). However, the underlying molecular mechanisms of QKI‐5 in the cell cycle of NSCLC are still largely unknown. Methods: MTT, flow cytometry, and colony formation assays were used to investigate cellular phenotypic changes. Mice xenograft model was used to evaluate the antitumor activities of QKI‐5. Co‐immunoprecipitation, RNA immunoprecipitation (RIP), and RIP sequencing were used to investigate protein–protein interaction and protein–mRNA interaction. Results: The QKI‐5 expression was downregulated in NSCLC tissues compared with that in paired normal adjacent lung tissues. Overexpression of QKI‐5 inhibited NSCLC cell proliferative and colony forming ability. In addition, QKI‐5 induced cell cycle arrest at G0/G1 phase through upregulating p21Waf1/Cip1 (p21) expression and downregulating cyclin D1, cyclin‐dependent kinase 4 (CDK4), and CDK6 expressions. Further analyses showed that QKI‐5 interacts with p21 protein and CDK4, CDK6 mRNAs, suggesting a critical function of QKI‐5 in cell cycle regulation. In agreement with in vitro study, the mouse xenograft models validated tumor suppressive functions of QKI‐5 in vivo through altering cell cycle G1‐phase‐associated proteins. Moreover, we demonstrated that QKI‐5 is a direct target of miR‐31. The QKI‐5 expression was anticorrelated with the miR‐31 expression in NSCLC patient samples. Conclusion: Our results suggest that the miR‐31/QKI‐5/p21‐CDK4–CDK6 axis might have critical functions in the progression of NSCLC, and targeting this axis could serve as a potential therapeutic strategy for NSCLC. [ABSTRACT FROM AUTHOR]

Conjugated polymers (CPs) have garnered increasing attention in the field of photocatalysis due to their stability and molecular tunability. Understanding the structure–property relationship in CPs and addressing appropriate molecular design strategies are pivotal to improving the photocatalytic performance of CPs. Herein, a new efficient cyano (CN) engineering approach was proposed to promote the photocatalytic performance of CPs, and three representative CP‐based photocatalysts with different CN contents were tailor‐made to investigate the relationship between CN functionalization and photocatalytic activity. A series of systematically experimental and theoretical studies reveal that CN functionalization contributes to strengthening the donor‐acceptor (D‐A) interaction, enhancing the light absorption ability, charge separation/transfer efficiency, and hydrophilicity of CPs, and also facilitating the output of separated photoinduced electrons from CPs to Pt cocatalyst. Thus, the dicyano‐functionalized polymer (P‐2CN) manifests an attractive photocatalytic performance in hydrogen production. This study provides a facile strategy to develop excellent CP‐based photocatalysts for solar fuel production. [ABSTRACT FROM AUTHOR]

Poly(heptazine imide) (PHI), one of the attractive allotropes of polymeric carbon nitride, has recently received extensive attention in photocatalysis due to its extended conjugation for fast separation and transfer of the charges. However, pristine PHI bears an intrinsic optical absorption band edge at 460 nm, which largely restrains the visible light utilization. Herein, the narrow‐bandgap PHI (N‐PHI) with an ordered‐distorted interface was fabricated from polycondensation of the mixture of NaSCN, cyanuric chloride, and LiCl. Results revealed that the enhanced optical absorption and the promoted separation and transfer of the charge carriers at the interface greatly improved the photocatalytic performance, which endowed N‐PHI with an apparent quantum yield of 20 % for hydrogen production at 450 nm. [ABSTRACT FROM AUTHOR]

The construction of heterojunctions is a promising manner to accelerate the separation and transfer of the charge carriers at the interface. Herein, a binary poly(heptazine‐triazine) imides (PHI/PTI) with semi‐coherent interfaces was fabricated via a facile two‐step salt‐melt synthetic process. The built‐in electric fields at the semi‐coherent interface endow prompt exciton splitting and charge carrier separation. Hence, the optimized PHI/PTI‐based copolymer presents a high apparent quantum yield (AQY=64 %) for visible‐light driven hydrogen production, by the aids of K2HPO4 as charge transfer mediator. This study provides physical insights for the rational promotion of the photocatalytic performance from the viewpoint of interfacial engineering of photocatalytic junctions on crystalline carbon nitride based semiconductors. [ABSTRACT FROM AUTHOR]

Photocatalytic overall water splitting (OWS) is an appealing strategy to convert solar energy and produce hydrogen fuel. NiTiO3 (NTO) is an earth‐abundant material, which is studied as a robust photocatalyst with broad absorptance of sunlight spectrum, ranging from ultraviolet to infrared regions. Herein, by a rational design of an NTO‐based photocatalytic system, the activity for photocatalytic OWS is realized under both ultraviolet and visible light illuminations, and H2 and O2 evolution is achieved within the stoichiometric ratio of 2:1. Specifically, Gallium is doped into the NTO crystal to activate the material for photocatalytic OWS by improving photoexcited charge migration. Meanwhile, Co and Pt species are screened out as the oxygen evolution and hydrogen evolution co‐catalysts, respectively. Theoretical stimulations, steady state experiments, and operando characterizations are acquired to investigate the OWS performance. This research paves the pathway to apply this small‐bandgap photocatalyst for OWS by maximizing the solar energy harvesting. [ABSTRACT FROM AUTHOR]

It has been established that Cutaneous T‐Cell lymphomas (CTCL) are caused by the monoclonal proliferation of T lymphocytes in the skin. This heterogeneous group of diseases represents a significant source of distress to patients since the diagnosis and treatment are often challenging. As one of the most abundant internal modifications in mRNA in higher eukaryotes, N6‐methyladenosine (m6A) is widely recognized to affect the development and progression of cancers. However, knowledge on the involvement of m6A in CTCL is still limited. In this work, we revealed the role of METTL3‐mediated m6A modification in CTCL progression. ELISA, western blot, and qRT‐PCR assays demonstrated that METTL3 was significantly downregulated in CTCL cells both in vivo and in vitro. CCK‐8, EdU, flow cytometry, and transwell assays showed that the decline in METTL3 levels was responsible for CTCL cell proliferation and migration. Furthermore, using small interfering RNAs against METTL3 and the RIP assay, we showed that CDKN2A was a key regulator during this process in vitro and in vivo, and insufficient methylation modification blocked the interaction between CDKN2A and m6A reader IGF2BP2, resulting in mRNA degradation. To the best of our knowledge, this is the first study to depict the role of m6A in CTCL development and provide potential bio‐targets for therapy. [ABSTRACT FROM AUTHOR]

A major challenge in the nitride‐based materials for photocatalytic oxidation reaction is their low stability under oxidizing and acidic environment. To solve these problems, highly crystallized hexagonal boron carbon nitride (BCN) with more homogeneous mixing of B, C, and N atoms is achieved by pyrolysis of precursor materials in the presence of NaOH as a crystallization promoter. The high crystallinity and chemical homogeneity features of the fabricated BCN reduce the structural defects and accelerate the interfacial charge transfer and separation, thus inhibiting the self‐oxidation and endowing it with a superior oxidation resistance. With these prominent advantages, the highly crystallized BCN exhibits markedly enhanced photocatalytic activity and long‐term anticorrosion stability under oxygen and self‐generated acidic condition, far beyond polycrystalline BCN. This work offers new insights into the catalyst design of crystalline BCN and demonstrates its great promise for solar energy applications. [ABSTRACT FROM AUTHOR]

Covalent triazine‐based frameworks (CTFs) are typically produced by the salt‐melt polycondensation of aromatic nitriles in the presence of ZnCl2. In this reaction, molten ZnCl2 salt acts as both a solvent and Lewis acid catalyst. However, when cyclotrimerization takes place at temperatures above 300 °C, undesired carbonization occurs. In this study, an ionothermal synthesis method for CTF‐based photocatalysts was developed using a ternary NaCl‐KCl‐ZnCl2 eutectic salt (ES) mixture with a melting point of approximately 200 °C. This temperature is lower than the melting point of pure ZnCl2 (318 °C), thus providing milder salt‐melt conditions. These conditions facilitated the polycondensation process, while avoiding carbonization of the polymeric backbone. The resulting CTF‐ES200 exhibited enhanced optical and electronic properties, and displayed remarkable photocatalytic performance in the hydrogen evolution reaction. [ABSTRACT FROM AUTHOR]

Polymeric carbon nitride (PCN) has attracted intensive interest as sustainable, metal‐free semiconductor for photoelectrochemical (PEC) water splitting. Charge transfer along the films acts as the main concern to restrict the performance due to the amorphous nature of polymer. Herein, gradient concentration of cobalt disulfide (CoS2) merged in PCN films was realized as CSCN photoanode by a one‐pot synthesis. Owing to the unique properties of CoS2, namely high conductivity, the charge transfer of the CSCN photoanode was promoted, and thus the performance for PEC water oxidation was improved. The optimal photoanode exhibited a photoanodic current of 200 μA cm−2 at 1.23 V versus reversible hydrogen electrode under air mass 1.5 global (AM 1.5G) illumination, which was approximately 4 times that of the pristine PCN photoanode. This work provides a new design of metal‐free photoanodes to improve the performance of water splitting. [ABSTRACT FROM AUTHOR]

Photocatalytic conversion of carbon dioxide (CO2) to valuable products is one of the promising approaches to mitigate climate change and provide chemical fuels. The structural design of photocatalysts has been therefore directed to enhancing the CO2 conversion efficiency and selectivity. Herein, we report that the metalated porous polycarbazoles, made by facile one‐pot oxidative polymerization and successive transition metal impregnation, can effectively convert CO2 into carbon monoxide (CO) with high selectivity under visible light irradiation. The high porosity of the porous polycarbazoles provides enhanced CO2 adsorption and the incorporated metals facilitate the CO2 activation. The type of metal ions influences the CO selectivity by altering surface reaction kinetics for CO2 reduction. Our approach proves that the photocatalytic CO2 reduction ability and selectivity of porous conjugated polymers can be improved by decorating functional metal species to modulate the adsorption and activation behavior of CO2 molecules. [ABSTRACT FROM AUTHOR]

Covalent organic frameworks (COFs) are regarded as new platforms for solar‐to‐chemical energy conversion due to their tailor‐made functions and pre‐designable structures. Their intrinsic reversibility and the high polarization of organic linkages inevitably result in poor chemical stability and weak optoelectronic properties. Herein, one N‐acylhydrazone‐linked COF (H‐COF) was converted into a stable and π‐conjugated oxadiazole‐linked COF via post‐oxidative cyclization. Both chemical stability and π‐electron delocalization throughout the reticular framework are significantly improved, leading to a high hydrogen evolution rate of 2615 μmol g−1 h−1 upon visible light irradiation, which is over four times higher than that of H‐COF. This work provides a facile protocol for the fabrication of π‐conjugated COFs and the modulation of photophysical properties for photocatalytic application. [ABSTRACT FROM AUTHOR]

Conventional polymerization for the synthesis of carbon nitride usually generates amorphous heptazine‐based melon with an abundance of undesired structural defects, which function as charge carrier recombination centers to decrease the photocatalytic efficiency. Herein, a fully condensed poly (triazine imide) crystal with extended π‐conjugation and deficient structure defects was obtained by conducting the polycondensation in a mild molten salt of LiCl/NaCl. The melting point of the binary LiCl/NaCl system is around 550 °C, which substantially restrain the depolymerization of triazine units and extend the π‐conjugation. The optimized polymeric carbon nitride crystal exhibits a high apparent quantum efficiency of 12 % (λ=365 nm) for hydrogen production by one‐step excitation overall water splitting, owing to the efficient exciton dissociation and the subsequent fast transfer of charge carriers. [ABSTRACT FROM AUTHOR]

The techniques for the production of the environment have received attention because of the increasing air pollution, which results in a negative impact on the living environment of mankind. Over the decades, burgeoning interest in polymeric carbon nitride (PCN) based photocatalysts for heterogeneous catalysis of air pollutants has been witnessed, which is improved by harvesting visible light, layered/defective structures, functional groups, suitable/adjustable band positions, and existing Lewis basic sites. PCN‐based photocatalytic air purification can reduce the negative impacts of the emission of air pollutants and convert the undesirable and harmful materials into value‐added or nontoxic, or low‐toxic chemicals. However, based on previous reports, the systematic summary and analysis of PCN‐based photocatalysts in the catalytic elimination of air pollutants have not been reported. The research progress of functional PCN‐based composite materials as photocatalysts for the removal of air pollutants is reviewed here. The working mechanisms of each enhancement modification are elucidated and discussed on structures (nanostructure, molecular structue, and composite) regarding their effects on light‐absorption/utilization, reactant adsorption, intermediate/product desorption, charge kinetics, and reactive oxygen species production. Perspectives related to further challenges and directions as well as design strategies of PCN‐based photocatalysts in the heterogeneous catalysis of air pollutants are also provided. [ABSTRACT FROM AUTHOR]

Herein, we explore a general Cu2−xS nanocube template‐assisted and reverse cation exchange‐mediated growth strategy for fabricating hollow multinary metal sulfide. Unlike the traditional cation exchange method controlled by the metal sulfide constant, the introduction of tri‐n‐butylphosphine (TBP) can reverse cation exchange to give a series of hollow metal sulfides. A variety of hollow multinary metal sulfide cubic nanostructures has been demonstrated while preserving anisotropic shapes to the as‐synthesized templates, including binary compounds (CdS, ZnS, Ag2S, PbS, SnS), ternary compound (CuInS2, ZnxCd1−xS), and quaternary compound (single‐atom platinum anchored ZnxCd1−xS; ZnxCd1−xS‐Pt1). Experimental and density functional theory (DFT) calculations show that the hollow metal sulfide semiconductors obtained could significantly improve the separation and migration of photogenerated electron‐hole pairs. Owing to the efficient charge transfer, the ZnxCd1−xS‐Pt1 exhibited outstanding photocatalytic performance of CO2 to CO, with the highest CO generation rate of 75.31 μmol h−1. [ABSTRACT FROM AUTHOR]

The use of polymeric carbon nitride (PCN) for photoredox catalysis is innovating and promoting toward sustainable energy economy. One of the drawbacks of this metal‐free photocatalyst is its insufficient charge separation and transfer. Herein, a metal‐free system was achieved by anchoring PCN on conductive carbon cloth (CCC). CCC in this system facilitated the charge separation and transport of the photoexcitation charges when PCN films were illuminated. Both photoelectrochemical water oxidation and photocatalytic overall water splitting were achieved, and the performances were improved two‐fold with respect to the powder PCN. [ABSTRACT FROM AUTHOR]

Cobalt phosphide (CoP) has been demonstrated as a cocatalyst for visible‐light‐sensitized CO2 reduction, but just with moderate selectivity, due to the competitive H2 generation reaction. Herein, the porous N‐doped carbon (NC) layer is in situ coated on the surface of CoP nanoparticles to fabricate the core‐shell CoP@NC composite cocatalyst. Benefiting from the outstanding electric conductivity and high surface area of the NC shell, the CoP@NC hybrid attains strengthened capabilities for charge separation/transfer and CO2 capture/activation. Besides, the direct contact of CoP with H2O is prevented by the porous NC shell with high hydrophobicity. Consequently, the photosensitized CO2‐to‐CO conversion efficiency and selectivity of CoP@NC hybrid are enhanced by 2.7 and 2.4 times, respectively, compared to bare CoP. [ABSTRACT FROM AUTHOR]

Charge generation and separation are regarded as the major constraints limiting the photocatalytic activity of polymeric photocatalysts. Herein, two new linear polyarylether‐based polymers (PAE–CPs) with distinct linking patterns between their donor and acceptor motifs were tailor‐made to investigate the influence of different linking patterns on the charge generation and separation process. Theoretical and experimental results revealed that compared to the traditional single‐stranded linker, the double‐stranded linking pattern strengthens donor–acceptor interactions in PAE–CPs and generates a coplanar structure, facilitating charge generation and separation, and enabling red‐shifted light absorption. With these prominent advantages, the PAE–CP interlinked with a double‐stranded linker exhibits markedly enhanced photocatalytic activity compared to that of its single‐strand‐linked analogue. Such findings can facilitate the rational design and modification of organic semiconductors for charge‐induced reactions. [ABSTRACT FROM AUTHOR]

Photocatalytic CO2 conversion is a promising method to yield carbon fuels, but it remains challenging to regulate catalytic materials for enhanced reaction efficiency and tunable product selectivity. This study concerns the development of a facile and efficient thermal post‐treatment method to improve the crystallinity and surface hydrophobicity of a cobalt phosphide (CoP) cocatalyst, which promotes the separation and transfer of photoexcited charge carriers, reinforces CO2 chemisorption, and weakens the H2O affinity. Compared with pristine CoP, the optimal CoP‐600 cocatalyst displays a 3.5‐fold enhancement in activity and a 2.3‐fold increase in selectivity for the reduction of CO2 to CO with a high rate of 68.1 μmol h−1. [ABSTRACT FROM AUTHOR]

Polymeric carbon nitride (PCN) is a promising class of materials for solar‐to‐chemical energy conversion. The increase of the photocatalytic activity of PCN is often achieved by the incorporation of heteroatoms, whose impact on the electronic structure of PCN remains poorly explored. This work reveals that the local electronic structure of PCN is strongly altered by doping with sulfur and iron using X‐ray absorption spectroscopy (XAS) and resonant inelastic X‐ray scattering (RIXS). From XAS at the carbon and nitrogen K‐edges, sulfur atoms are found to mostly affect carbon atoms, in contrast to iron doping mostly altering nitrogen sites. In RIXS at the nitrogen K‐edge, a vibrational progression, affected by iron doping, is evidenced, which is attributed to a vibronic coupling between excited electrons in nitrogen atoms and C–N stretching modes in PCN heterocycling rings. This work opens new perspectives for the characterization of vibronic coupling in polymeric photocatalysts. [ABSTRACT FROM AUTHOR]

The increased emission of CO2 has negative impacts on the environment. Among the strategies, photocatalytic reduction is promising to convert the CO2 into chemicals. In this report, CoOx nanoparticles were loaded in the channels of MIL‐101(Cr), a kind of metal‐organic frameworks (MOF), to construct a novel CoOx/MIL‐101(Cr) system to facilitate CO2 photoreduction. Under the optimal conditions, the CoOx/MIL‐101(Cr) showed a significantly enhanced performance for photocatalytic CO2 reduction compared with bare CoOx and MIL‐101(Cr). Our findings provide a pathway for a rational design of efficient MOF systems for the photocatalytic reduction of CO2. [ABSTRACT FROM AUTHOR]

Construction of local donor–acceptor architecture is one of the valid means for facilitating the intramolecular charge transfer in organic semiconductors. To further accelerate the interface charge transfer, a ternary acceptor–donor–acceptor (A1‐D‐A2) molecular junction is established via gradient nitrogen substituting into the polymer skeleton. Accordingly, the exciton splitting and interface charge transfer could be promptly liberated because of the strong attracting ability of the two different electron acceptors. Both DFT calculations and photoluminescence spectra elucidate the swift charge transfer at the donor‐acceptor interface. Consequently, the optimum polymer, N3‐CP, undergoes a remarkable photocatalytic property in terms of hydrogen production with AQY405 nm=26.6 % by the rational design of asymmetric molecular junctions on organic semiconductors. [ABSTRACT FROM AUTHOR]

The polarity of a semiconducting molecule affects its intrinsic photophysical properties, which can be tuned by varying the molecular geometry. Herein, we developed a D3h‐symmetric tricyanomesitylene as a new monomer which could be reticulated into a vinylene‐linked covalent organic framework (g‐C54N6‐COF) via Knoevenagel condensation with another D3h‐symmetric monomer 2,4,6‐tris(4′‐formyl‐biphenyl‐4‐yl)‐1,3,5‐triazine. Replacing tricyanomesitylene with a C2v‐symmetric 3,5‐dicyano‐2,4,6‐trimethylpyridine gave a less‐symmetric vinylene‐linked COF (g‐C52N6‐COF). The octupolar conjugated characters of g‐C54N6‐COF were reflected in its scarce solvatochromic effects either in ground or excited states, and endowed it with more promising semiconducting behavior as compared with g‐C52N6‐COF, such as enhanced light‐harvesting and excellent photo‐induced charge generation and separation. Along with the matched energy level, g‐C54N6‐COF enabled the two‐half reactions of photocatalytic water splitting with an average O2 evolution rate of 51.0 μmol h−1 g−1 and H2 evolution rate of 2518.9 μmol h−1 g−1. Such values are among the highest of state‐of‐the‐art COF photocatalysts. [ABSTRACT FROM AUTHOR]

It is a challenge to explore photocatalytic materials for sunlight‐driven water splitting owing to the limited choice of a single semiconductor with suitable band energy levels but with a minimized band gap for light harvesting. Here, we report a one‐photon excitation pathway by coupling polymeric carbon nitride (PCN) semiconductor with LaOCl to achieve overall water splitting. This artificial photosynthesis composite catalyzes the decomposition of H2O into H2 and O2, with evolution rates of 22.3 and 10.7 μmol h−1, respectively. The high photocatalytic performance of PCN/LaOCl can be ascribed to the simultaneously accomplished reduction and oxidation of water on LaOCl and PCN domains, respectively, as well as the fast charge separation and migration induced by the interfacial electric field related to LaOCl modification. This study provides new insights on the development of composite photocatalysts for pure water splitting based on polymer‐based materials via charge modulation. [ABSTRACT FROM AUTHOR]

The first examples of linear conjugated organic polymer photocatalysts that produce oxygen from water after loading with cobalt and in the presence of an electron scavenger are reported. The oxygen evolution rates, which are higher than for related organic materials, can be rationalized by a combination of the thermodynamic driving force for water oxidation, the light absorption of the polymer, and the aqueous dispersibility of the relatively hydrophilic polymer particles. We also used transient absorption spectroscopy to study the best performing system and we found that fast oxidative quenching of the exciton occurs (picoseconds) in the presence of an electron scavenger, minimizing recombination. [ABSTRACT FROM AUTHOR]

Polymeric carbon nitride modified with selected heteroatom dopants was prepared and used as a model photocatalyst to identify and understand the key mechanisms required for efficient photoproduction of H2O2 via selective oxygen reduction reaction (ORR). The photochemical production of H2O2 was achieved at a millimolar level per hour under visible‐light irradiation along with 100 % apparent quantum yield (in 360–450 nm region) and 96 % selectivity in an electrochemical system (0.1 V vs. RHE). Spectroscopic analysis in spatiotemporal resolution and theoretical calculations revealed that the synergistic association of alkali and sulfur dopants in the polymeric matrix promoted the interlayer charge separation and polarization of trapped electrons for preferable oxygen capture and reduction in ORR kinetics. This work highlights the key features that are responsible for controlling the photocatalytic activity and selectivity toward the two‐electron ORR, which should be the basis of further development of solar H2O2 production. [ABSTRACT FROM AUTHOR]

The visible‐light‐driven photocatalytic CO2 reduction is one appealing approach to simultaneously mitigate the energy crisis and environmental issues. It is highly desirable but challenging to selectively and efficiently convert CO2 into desirable products. Herein, a covalent organic framework hosting metalloporphyrin‐based carbon dots (M‐PCD@TD‐COF, M = Ni, Co, and Fe) is first presented, which serves as heterogeneous catalysts for CO2 photoreduction. M‐PCD@TD‐COF not only enriches available COF‐based catalytic materials, but also provides suitable environment for CO2 adsorption and activation on metalloporphyrin‐based carbon dots. The advantages of the host environment in COFs are highlighted by the satisfactory catalytic activity and remarkable selectivity of CO2‐to‐CO conversion over H2 generation up to 98%. The photocatalytic system is effective for both pure CO2 and the simulated flue gas. This work provides new protocols for the rational design of COF‐based heterogeneous catalysts for selective CO2 photoreduction. [ABSTRACT FROM AUTHOR]

Long non‐coding RNAs (lncRNAs) have been well demonstrated to emerge as crucial regulators in cancer progression, and they can function as regulatory network based on their interactions. Although the biological functions of FAM83H‐AS1 have been confirmed in various tumour progressions, the underlying molecular mechanisms of FAM83H‐AS1 in oesophageal squamous cell carcinoma (ESCC) remained poorly understood. To address this, we treated human oesophageal cancer cell line Eca109 cells with TGF‐β and found FAM83H‐AS1 was notably overexpressed. In the present study, FAM83H‐AS1 was observed to be significantly up‐regulated in ESCC tissues and was associated with TNM stage, pathological differentiation and lymph node metastasis. FAM83H‐AS1 reinforced oesophageal cancer cell proliferation, migration and invasion, and participated in epithelial‐to‐mesenchymal transition (EMT) process at mRNA and protein levels. In addition, a concordant regulation between FAM83H‐AS1 and its sense strand FAM83H was detected at the transcriptional and translational levels. Furthermore, FAM83H‐AS1 could act as competing endogenous RNA to affect the expression of Girdin by sponging miR‐10a‐5p verified by RIP and luciferase reporter assays. Consequently, the study provided a unique perspective of FAM83H‐AS1 in ESCC progression, which may be considered as potential biomarker and therapeutic target for ESCC therapy. [ABSTRACT FROM AUTHOR]

Photoelectrochemical water oxidation by polymeric carbon nitride (PCN) has recently received increasing scientific interest. Herein, phosphorus (P) is doped into PCN (p‐PCN) films through in situ polymerization. p‐PCN sheets are formed and vertically aligned on a conductive substrate, which is used as a photoanode. The optimal photocurrent density of the photoanode is ≈120 μA cm−2, which is more than two times that of the undoped one. The improved performance is accounted as the introduction of P in PCN. On the one hand, P doping increases the valence potential of PCN and improves the ability of water oxidation. On the other hand, charge transfer is improved by extra charges from P. [ABSTRACT FROM AUTHOR]

The development of metal‐free photocatalysts with high efficiency, stability, and broadband solar absorption is a major challenge to realize green and sustainable chemical development. Recently, metal‐free nanohybrids (BP/CN) composed of black phosphorus (BP) and polymeric carbon nitride (CN) are emerged as photocatalytic hybrids with broadband light‐harvesting capabilities and higher photocatalytic performance. Herein, the latest progress of BP/CN hybrids for multifarious photoredox reactions is summarized. The different heterojunction types of BP/CN hybrid photocatalysts, including type I, type II, and multicomponent heterojunctions, are illustrated. Furthermore, the relevant applications of BP/CN hybrid photocatalysts for photocatalytic water splitting, CO2 photoreduction, N2 fixation, H2O2 production, pollutant decomposition, and bacterial inactivation are discussed. An overview of the challenge in this area and the directions for the future is presented. [ABSTRACT FROM AUTHOR]