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Background Liver fibrosis develops from various chronic liver diseases, and there is currently a lack of specific treatment strategies. Yiqi Rougan decoction (YQRG) is a traditional Chinese medicine that has shown durative effects in the treatment of liver fibrosis; however, the mechanism associated with YQRG-related improvements in liver fibrosis remains to be experimentally determined. This study evaluated the therapeutic effect of YQRG on carbon tetrachloride (CCl4)-induced liver fibrosis in rats and its molecular mechanism. Methods We used low-, medium-, and high-dose YQRG to treat CCl4-induced liver fibrosis in rats, followed by assessment of liver injury and fibrosis according to liver appearance, body weight, liver mass index, histopathologic examination, and serum testing. Additionally, we performed transcriptome analysis using RNA-sequencing (RNA-seq) technology, including cluster, Gene Ontology (GO), and pathway analyses, to identify differentially expressed genes (DEGs), and protein and gene expression were detected by immunofluorescence (IFC), western blot and real-time quantitative PCR. Results The results showed that YQRG effectively alleviated CCl4-induced liver injury and fibrosis in rats, including observations of improved liver function, decreased activity of hepatic stellate cells (HSCs), and decreased extracellular matrix (ECM) deposition. Moreover, we identified downregulated and upregulated DEGs in the model group relative to the control and YQRG-treated groups, with GO analysis revealing their enrichment in biological processes, such as endoplasmic reticulum stress (ERS), apoptosis, and autophagy. Furthermore, pathway analysis showed that YQRG treatment downregulated the mitogen-activated protein kinase (MAPK) and phosphoinositide 3-kinase/Akt (PI3K/AKT) signalling pathways and upregulated other signalling pathways, including those related to peroxisome proliferator-activated receptors(PPAR) and AMP-activated protein kinase(AMPK), with these findings subsequently verified experimentally. Conclusion These findings showed that YQRG improved CCl4-induced liver fibrosis through multiple mechanisms and pathways, offering critical insight into the YQRG-related therapeutic mechanism and promoting further research into its potential application.

A double acid corrosion and subsequent hydrothermal treatment were used to fabricate a micro–nano-structured Ti substrates (Ti–M–N). Afterward, the mesoporous polydopamine (MPDA) nanoparticles as photothermal agent were prepared and immobilized on the surface of Ti–M–N samples, in order to obtain Ti–M–N-MPDA sample. Unique micro–nanostructure properties and the photothermal effect of the modified Ti implant caused physical stress on the bacteria and the bacterial membrane damage, and eventually led to bacteria death. More importantly, based on excellent bioactivity and cytocompatibility of mussel-inspired materials, MPDA promoted adhesion, proliferation and osteogenic differentiation of mesenchymal stem cells in vitro. Furthermore, animal experiments in vivo further confirmed that the modified Ti implants could enhance osseointegration. 使用双酸腐蚀和随后的水热处理来制造微纳米结构的 Ti 衬底 (Ti-M-N)。 随后, 制备了作为光热剂的介孔聚多巴胺 (MPDA) 纳米颗粒并将其固定在 Ti-M-N 样品的表面, 以获得 Ti-M-N-MPDA 样品。 独特的微纳米结构特性和改性钛植入物的光热效应对细菌造成物理压力和细菌膜损伤, 最终导致细菌死亡。 更重要的是, 基于贻贝材料优异的生物活性和细胞相容性, MPDA在体外促进间充质干细胞的粘附、增殖和成骨分化。 此外, 体内动物实验进一步证实, 改性钛植入物可以增强骨整合

Forrestiacids A (1) and B (2) are a novel class of [4+2] type pentaterpenoids derived from a rearranged lanostane moiety (dienophile) and an abietane unit (diene). These unprecedented molecules were isolated using guidance by molecular ion networking (MoIN) from Pseudotsuga forrestii, an endangered member of the Asian Douglas Fir Family. The intermolecular hetero-Diels-Alder adducts feature an unusual bicyclo[2.2.2]octene ring system. Their structures were elucidated by spectroscopic analysis, GIAO NMR calculations and DP4+ probability analyses, electronic circular dichroism calculations, and X-ray diffraction analysis. This unique addition to the pentaterpene family represents the largest and the most complex molecule successfully assigned using computational approaches to predict accurately chemical shift values. Compounds 1 and 2 exhibited potent inhibitory activities (IC50 s

Interlayer coupling as a unique feature for two-dimensional (2D) materials may influence their thickness-dependent physical properties, especially the bandgap due to quantum confinement effect. Widely-studied 2D materials usually possess strong interlayer coupling such as most of transition metal dichalcogenides (TMDs), PtS2 and so on. However, 2D materials with weak interlayer coupling are rarely referred that mainly focus on ReS2, as well as its counterpart ReSe2. Here we report a new member of weak interlayer coupling 2D materials, germanium disulfide (GeS2). The interlayer interaction in GeS2 is investigated from theory to experiment. By density functional theory calculations, we find that this extraordinarily weak interlayer coupling in GeS2 originates from the weak hybridization of interlayer S atoms. Thickness-dependent Raman spectra of GeS2 flakes exhibit that the Raman peaks remain unchanged when increasing the thickness; and a small first-order temperature coefficient of −0.00857 cm−1·K−1 is obtained from the temperature-dependent Raman spectra. These experimental results further confirm the weak interlayer coupling in GeS2.

The electrochemical carbon dioxide reduction (ECR) into high-value-added chemicals is a promising approach to alleviate the energy crisis and greenhouse effect. However, the lack of efficient, highly selective, and durable electrocatalysts limits the further application of ECR. Herein, a molecular linking strategy is developed to anchor the monodispersed Bi nanoparticles on a carbon matrix, enabling the durable and efficient CO2 reduction into formate. Systematic characterizations and experimental measurements reveal that tetra-aminophenyl porphyrin (TAPP) can act as an effective molecular linker to secure Bi nanoparticles on porous carbon matrix (Bi NPs/TAPP-PC) via its strong interaction with both the support and nanoparticles, resolving the issues of their peel-off and agglomeration during ECR. Benefiting from the linkage of TAPP molecules, Bi NPs/TAPP-PC exhibits significantly improved ECR performance with a Faradaic efficiency of 92.1% and partial current density of 55.8 mA cm–2 as well as a long-term durability of over 20 h, compared with Bi NPs/PC without TAPP. This strategy using a molecular linker to enhance the activity and durability of the host catalyst provides new insights for developing applicable catalysts for diverse electrocatalytic applications.

To elucidate the response of oxidative metabolism, triggered by elevated ammonium (NH4+) concentrations, on root growth of wheat seedlings, Yumai 49 (NH4+-tolerant) and Lumai 15 (NH4+-sensitive) cultivars were supplied with either 5.0 mmol L−1 NH4+-N (EAC) or 5.0 mmol L−1 NO3–-N (CON) under hydroponic conditions. Root growth in both cultivars was significantly reduced under EAC, and the negative effect was greater in Lumai 15. EAC enhanced the activities of monodehydroascorbate reductase and dehydroascorbate reductase in the roots of both cultivars, while it decreased ascorbic acid (ASA) content and GDP-mannose pyrophosphorylase (GMPase) activity at the 12th day after treatment in Lumai 15 by 62.0 and 71.4%; and in Yumai 49 by 38.8 and 62.2%, respectively, indicating that the regeneration of ASA was increased, but the biosynthesis of ASA was reduced under EAC treatment. Moreover, EAC increased DHA/ASA, reactive oxygen species (ROS), and malondialdehyde contents, as well as antioxidant enzyme activities in the roots of both cultivars. Relatively greater increases in ROS and soluble sugar, and lower antioxidant enzyme activities in Lumai 15 indicate severe disruption of oxidative metabolism when compared to Yumai 49. Results reveal that the reduction of ASA biosynthesis via decreased GMPase activity under the EAC condition probably acts as a trigger for accumulated ROS and imbalanced redox status, resulting in root growth inhibition during wheat seedling growth stage. Yumai 49, being an NH4+ -tolerant cultivar, had the stronger capacity to protect itself from oxidative stress, which allowed it to retain a lower DHA to ASA ratio by maintaining a better redox homeostasis than could be maintained in the NH4+ -sensitive cultivar Lumai 15.

Objective: Aminomethylphenol molecules have wider applications in pharmaceuticals, agrochemicals, plant protection and promising functional materials. The development of an efficient and practical method to prepare this class of compound is highly desirable from both environmental and economical points of view. Materials and Methods: In order to establish an effective synthetic method for preparing aminomethylphenol derivatives, the Petasis borono-Mannich reaction of salicylaldehyde, phenylboronic acid and 1,2,3,4- tetrahydroisoquinoline was selected as a model reaction. A variety of reaction conditions are investigated, including solvent and temperature. The generality and limitation of the established method were also evaluated. Results and Discussion: It was found that model reaction can be carried out in cyclopentyl methyl ether at 80 °C under catalyst-free conditions. This protocol, with broad substrate applicability, the reaction of various arylboronic acid, secondary amine and salicylaldehyde proceeded smoothly under optimal reaction conditions to afford various aminomethylphenol derivatives in high yields. A practical, scalable, and high-yielding synthesis of aminomethylphenol derivatives was successfully accomplished. Conclusion: A catalyst-free practical method for the synthesis of minomethylphenol derivatives based on Petasis borono–Mannich (PBM) reaction of various arylboronic acid, secondary amine and salicylaldehyde in cyclopentyl methyl ether has been developed. The salient features of this protocol are avoidance of any additive/catalyst and toxic organic solvents, use of cyclopentyl methyl ether as the reaction medium, clean reaction profiles, easy operation, and high to excellent yield.

Germanium monoselenide (GeSe) is an emerging promising photovoltaic absorber material due to its attractive optoelectronic properties as well as non-toxic and earth-abundant constitutes. However, all previously reported GeSe solar cells rely on a superstrate configuration coupled with a CdS buffer layer, and suffer from unsatisfactory performance. Here we demonstrate that this low efficiency arises from the inevitable high-temperature treatment of p-n junction in superstrate configuration. This results in the diffusion of Cd atoms from CdS layer into GeSe film that introduces detrimental deep trap states inside the bandgap of GeSe (∼0.34 eV below conduction band minimum). We adopt therefore a substrate configuration that enables the deposition of CdS atop pre-deposited polycrystalline GeSe film at room temperature, avoiding the Cd diffusion. By optimizing the annealing temperature of complete devices via a high-throughput screening method, the resulting substrate solar cells annealed at 150°C achieve an efficiency of 3.1%, two times that of the best previously reported superstrate GeSe results.

Zinc–air batteries (ZABs) are among the most promising electrochemical energy storage devices which feature high energy density, decent rechargeability, low cost, and eco-friendliness. However, the...

As low-cost electrocatalysts for oxygen reduction reaction applied to fuel cells and metal-air batteries, atomic-dispersed transition metal-nitrogen-carbon materials are emerging, but the genuine mechanism thereof is still arguable. Herein, by rational design and synthesis of dual-metal atomically dispersed Fe,Mn/N-C catalyst as model object, we unravel that the O2 reduction preferentially takes place on FeIII in the FeN4 /C system with intermediate spin state which possesses one eg electron (t2g4eg1) readily penetrating the antibonding π-orbital of oxygen. Both magnetic measurements and theoretical calculation reveal that the adjacent atomically dispersed Mn-N moieties can effectively activate the FeIII sites by both spin-state transition and electronic modulation, rendering the excellent ORR performances of Fe,Mn/N-C in both alkaline and acidic media (halfwave positionals are 0.928 V in 0.1 M KOH, and 0.804 V in 0.1 M HClO4), and good durability, which outperforms and has almost the same activity of commercial Pt/C, respectively. In addition, it presents a superior power density of 160.8 mW cm−2 and long-term durability in reversible zinc–air batteries. The work brings new insight into the oxygen reduction reaction process on the metal-nitrogen-carbon active sites, undoubtedly leading the exploration towards high effective low-cost non-precious catalysts., The working mechanism of several low-cost electrocatalyst materials is still arguable. Here the authors show a model Fe,Mn/N-C catalyst where the oxygen reduction preferentially takes place on Fe(III) sites with the intermediate spin state (t2g4 eg1) caused by the adjacent Mn-N moieties.

Flowering time, a key transition point from vegetative to reproductive growth, is regulated by an intrinsic complex of endogenous and exogenous signals including nutrient status. For hundreds of years, nitrogen has been well known to modulate flowering time, but the molecular genetic basis on how plants adapt to ever-changing nitrogen availability remains not fully explored. Here we explore how Arabidopsis natural variation in flowering time responds to nitrate fluctuation. Upon nitrate availability change, we detect accession- and photoperiod-specific flowering responses, which also feature a accession-specific dependency on growth traits. The flowering time variation correlates well with the expression of floral integrators, SOC1 and FT, in an accession-specific manner. We find that gene expression variation of key hub genes in the photoperiod-circadian-clock (GI), aging (SPLs) and autonomous (FLC) pathways associates with the expression change of these integrators, hence flowering time variation. Our results thus shed light on the molecular genetic mechanisms on regulation of accession- and photoperiod-specific flowering time variation in response to nitrate availability.

This work presents a simple effective strategy to synthesize N-doped and shell-controlled carbon nanocages through a package baking approach. A green approach to synthesize core-shell ZIF-8@PTZ nanoparticles involves zinc contained ZIF-8 core wrapped by a N-enriched polytriazine (PTZ). Synthesized core-shell ZIF-8@PTZ nanoparticles are calcinated to further sublime zinc through PTZ shell and washed by HCl, leaving a porous carbon structure. At the meantime, hollow cavities were introduced into N-doped carbon polyhedrons via the sacrifice of ZIF-8 template (noted as ZIF-8@C/N-x). The electrochemical performance of the ZIF-8@C/N-x as supercapacitor electrode has demonstrated high energy density and specific capacitance, as well as a long-term cycleability showing 92% capacitance retention after 10,000 cycles. There is a systematic correlation between micro-/meso-porosity of ZIF-8@C/N-x and their electrochemical performances.

A novel anaerobic maifanite-immobilized sludge reactor (AMSR) was employed to investigate the feasibility and performance of continuous hydrogen production for the treatment of pharmaceutical intermediate wastewater (PIW) at different organic loading rates (OLR) (from 12 to 96 g COD L−1 d−1) according to changes in the hydraulic retention time (HRT). A reactor without maifanite was also employed as a control. The results indicate that maifanite accelerates granular sludge formation and the AMSR presents more efficient and stable performance than the control in terms of the hydrogen production rate. In the AMSR, the highest hydrogen production rate of 11.2 ± 0.4 mmol L−1 h−1 was achieved at an optimum OLR of 72 g COD L−1 d−1. The main metabolic route for hydrogen production was ethanol-type fermentation, which was reflected in the relative abundance of E. harbinense, which was dominant for all of the OLRs. The maximum energy conversion efficiency in the dual production of hydrogen and ethanol was determined to be 24.5 kJ L−1 h−1 at an OLR of 72 g COD L−1 d−1.

Here, three different materials were prepared containing high-conductivity multi-walled carbon nanotubes (MWCNTs), a high power density of mesoporous ordered silica SBA-15 (due to the high specific surface area), and nanoporous walls to improve the energy and power densities of energy storage devices. Thus, a hybrid composite of SBA-15 and MWCNTs was fabricated. The new composite of SBA-15/CNTs was decorated with a tri-metal organic framework, NiCoCu-BTC (1,3,5-benzenetricarboxylic acid, H3BTC), via a simple, low-cost, and one-step solvothermal method. The structural features of the prepared nanomaterial play a key role in increasing the number of active sites and accelerating ion/electron transfer. Also, the trimetallic organic framework (due to its different oxidation states) provides richer redox reactions than monometallic and bimetallic ones to produce a high energy density material. This nanocomposite was used as an efficient electrode material in the fabrication of high-performance supercapacitors. The prepared nanocomposite demonstrated excellent electrochemical performance with a high specific capacity of 868 C g−1 (2067 F g−1) at a current density of 1.0 A g−1, good rate capability (563 C g−1 at 10 A g−1), and high cycling durability. The excellent electrochemical performance of SC@NCC-BTC suggests that this composite is a promising candidate for energy storage applications.

Winter haze events are frequent occurrences in central China, however, their characteristics and formational mechanisms in the region are still poorly understood. In this study, we conducted continuous observations of PM2.5 during a haze event (from January 13 to 24, 2018) in Huanggang in central China to identify the characteristics of water-soluble inorganic ions (WSIIs) associated with PM2.5. The observation period was divided into the pre-haze episode (Pre-HE, January 13 to 14), haze episode (HE, January 15 to 21) and post-haze episode (Post-HE, January 22 to 24). The daily average PM2.5 mass concentration during the Pre-HE, HE and Post-HE was 51.7, 134.9 and 92.2 μg m−3, respectively. The WSIIs accounted for 57.3% of the total PM2.5 content throughout the entire observation period and were predominantly composed of nitrate, sulfate, and ammonium. During the HE, the major ions predominantly occurred in the form of (NH4)2SO4, NH4NO3, NH4Cl, and HCl. Moreover, the sulfur oxidation ratios and nitrogen oxidation ratios were relatively high, inferring the high contribution of secondary transformation. During the HE, homogeneous and heterogeneous reactions played an important role in the formation of nitrate and sulfate in PM2.5, respectively. The results of the principal component analysis-multiple linear regression suggest that the major sources of WSIIs were secondary inorganic aerosols, combustion and dust. The results of the backward trajectory analysis and the potential source contribution function model infer the strong influence of both local and regional air masses on haze formation and dissipation in Huanggang.

Tin halide perovskites are rising as promising materials for lead-free perovskite solar cells (PSCs). However, the crystallization rate of tin halide perovskites is much faster than the lead-based analogs, leading to more rampant trap states and lower efficiency. Here, we disclose a key finding to modulate the crystallization kinetics of FASnI3 through a non-classical nucleation mechanism based on pre-nucleation clusters (PNCs). By introducing piperazine dihydriodide to tune the colloidal chemistry of the FASnI3 perovskite precursor solution, stable clusters could be readily formed in the solution before nucleation. These pre-nucleation clusters act as intermediate phase and thus can reduce the energy barrier for the perovskite nucleation, resulting in a high-quality perovskite film with lower defect density. This PNCs-based method has led to a conspicuous photovoltaic performance improvement for FASnI3 -based PSCs, delivering an impressive efficiency of 11.39 % plus improved stability.

Among the various types of heterogeneous catalysts, supported metal nanocatalysts (SMNCs) have attracted widespread interest in chemistry and materials science, due to their advantageous features, such as high efficiency, stability, and reusability for catalytic reactions. However, to obtain well-defined SMNCs and inhibit nanoparticle aggregation, traditional approaches generally involve numerous organic reagents, complex steps, and specialized equipment, thus hindering the practical and large-scale synthesis of SMNCs. In this review, we summarize green and sustainable synthetic methodologies for the assembly of SMNCs, including low temperature pyrolysis and solid-state, surfactant- and reductant-free, and ionic liquid assisted syntheses. The conventional application of SMNCs for electrochemical hydrogen evolution and the corresponding achievements are subsequently discussed. Finally, future perspectives toward the sustainable production of SMNCs are presented.

Astrocytes have multiple functions in the brain, including affecting blood vessel (BV) homeostasis and function. However, the underlying mechanisms remain elusive. Here, we provide evidence that astrocytic neogenin (NEO1), a member of deleted in colorectal cancer (DCC) family netrin receptors, is involved in blood vessel homeostasis and function. Mice with Neo1 depletion in astrocytes exhibited clustered astrocyte distribution and increased BVs in their cortices. These BVs were leaky, with reduced blood flow, disrupted vascular basement membranes (vBMs), decreased pericytes, impaired endothelial cell (EC) barrier, and elevated tip EC proliferation. Increased proliferation was also detected in cultured ECs exposed to the conditioned medium (CM) of NEO1-depleted astrocytes. Further screening for angiogenetic factors in the CM identified netrin-1 (NTN1), whose expression was decreased in NEO1-depleted cortical astrocytes. Adding NTN1 into the CM of NEO1-depleted astrocytes attenuated EC proliferation. Expressing NTN1 in NEO1 mutant cortical astrocytes ameliorated phenotypes in blood-brain barrier (BBB), EC, and astrocyte distribution. NTN1 depletion in astrocytes resulted in BV/BBB deficits in the cortex similar to those in Neo1 mutant mice. In aggregate, these results uncovered an unrecognized pathway, astrocytic NEO1 to NTN1, not only regulating astrocyte distribution, but also promoting cortical BV homeostasis and function.

Strong metal-support interaction (SMSI), commonly happening between metal and metal oxide support, has drawn significant attention in heterogeneous catalysis due to its capability of enhancing the activity and stability of catalysts. Herein, the strong interaction between metal oxide and carbon supports is discovered to significantly boost the performance for electrocatalytic CO2 reduction reaction (CO2RR). A molecular engineering strategy is designed to develop undoped, N-doped, S-doped, and N,S-codoped porous carbon supports with similar physical properties (denoted as C, NC, SC, and NSC, respectively). These supports can host high-density SnO2 nanoparticles (over 60 wt. %) in a small size of ∼3.5 nm and good distribution, providing an excellent platform to understand the strong metal oxide-support interaction (SMOSI) and their influence on electrocatalytic performance. Systematic experimental and theoretical investigations discover the SMOSI between SnO2 nanoparticles and carbon supports in an order of SnO2/NSC > SnO2/NC > SnO2/SC > SnO2/C. Such SMOSI enables the effective electron transfer from carbon support to SnO2 nanoparticles, strengthening the adsorption of key reaction intermediate of CO2- and thus promoting CO2RR. With the strongest SMOSI, SnO2/NSC exhibits significantly enhanced selectivity and activity for CO2 reduction to HCOOH with a high faradaic efficiency of 94.4% and an extraordinary partial current density of 56.0 mA·cm-2 in an H-cell, outperforming the majority of Sn-based catalysts. Notably, SMOSI can simultaneously secure the active sites and thus remarkably enhance their catalytic durability, making it a promising strategy for exploring efficient and stable catalysts for diverse applications.

The outer wall of pollen and spores, namely the exine, is composed of sporopollenin, which is highly resistant to chemical reagents and enzymes. In this study, we demonstrated that phenylpropanoid pathway derivatives are essential components of sporopollenin in seed plants. Spectral analyses showed that the autofluorescence of Lilium and Arabidopsis sporopollenin is similar to that of lignin. Thioacidolysis and NMR analyses of pollen from Lilium and Cryptomeria further revealed that the sporopollenin of seed plants contains phenylpropanoid derivatives, including p-hydroxybenzoate (p-BA), p-coumarate (p-CA), ferulate (FA), and lignin guaiacyl (G) units. The phenylpropanoid pathway is expressed in the tapetum in Arabidopsis, consistent with the fact that the sporopollenin precursor originates from the tapetum. Further germination and comet assays showed that this pathway plays an important role in protection of pollen against UV radiation. In the pteridophyte plant species Ophioglossum vulgatum and Lycopodium clavata, phenylpropanoid derivatives including p-BA and p-CA were also detected, but G units were not. Taken together, our results indicate that phenylpropanoid derivatives are essential for sporopollenin synthesis in vascular plants. In addition, sporopollenin autofluorescence spectra of bryophytes, such as Physcomitrella and Haplocladium, exhibit distinct characteristics compared with those of vascular plants, indicating the diversity of sporopollenin among land plants.

The development of advanced transition metal/nitrogen/carbon-based (M/N/C) catalysts with high activity and extended durability for oxygen reduction reaction (ORR) is critical for platinum-group-metal (PGM) free fuel cells but still remains great challenging. In this review, we summarize the recent progress in two typical M/N/C catalysts (atomically dispersed metal-nitrogen-carbon (M-N-C) catalysts and carbon-supported metal nanoparticles with N-doped carbon shells (M@NC)) with an emphasis on their potential applications in fuel cells. Starting with understanding the active sites in these two types of catalysts, the representative innovative strategies for enhancing their intrinsic activity and increasing the density of these sites are systematically introduced. The synergistic effects of M-N-C and M@NC are subsequently discussed for those M/N/C catalysts combining both of them. To translate the material-level catalyst performance into high-performance devices, we also include the recent progress in engineering the porous structure and durability of M/N/C catalysts towards efficient performance in fuel cell devices. From the viewpoint of industrial applications, the scale-up cost-effective synthesis of M/N/C catalysts has been lastly briefed. With this knowledge, the challenges and perspectives in designing advanced M/N/C catalysts for potential PGM-free fuel cells are proposed.

Type I edge-localized modes (ELMs) in the Experimental Advanced Superconducting Tokamak (EAST) were completely suppressed via boron powder injection into the X-point region of an upper-single null configuration over a wide range of operating conditions (2.8

Two mixed-metal zirconium iodates were prepared and studied as a case of chemical cosubstitution. The structure of Ag2 Zr(IO3 )6 (P21 /c) features 0D [Zr(IO3 )6 ]2- anion group and 1D [Ag(IO3 )2 ]- anionic chain, with the [Zr(IO3 )6 ]2- anion groups interconnected by Ag+ ions into 3D network; LaZr(IO3 )5 F2 (P21 /n) features 0D [Zr(IO3 )5 F2 ]3- anion group and 2D [La(IO3 )5 ]2- anionic layer, with the [Zr(IO3 )5 F2 ]3- groups interlinked by La3+ ions into 3D structure. Notably, LaZr(IO3 )5 F2 is the first zirconium iodate fluoride reported. Wide optical band gaps of 3.77 and 4.13 eV are given for Ag2 Zr(IO3 )6 and LaZr(IO3 )5 F2 , respectively. Theoretical calculations confirmed that the weak d-d transition of Zr4+ in the band structure leads to a moderate band gap of Ag2 Zr(IO3 )6 , and the introduction of F- into the zirconium iodate compound results in a large band gap of LaZr(IO3 )5 F2 . Both of the compounds are birefringent materials with birefringences of 0.064 @1064 nm and 0.082 @1064 nm, respectively.

A phytochemical investigation of the MeOH extract of the leaves and twigs of Amentotaxus argotaenia, a relict vulnerable coniferous species endemic to China, led to the isolation and characterization of 35 diterpenoids/norditerpenoids. Twenty of these are new, including 11 ent-kaurane-type (amentotaxins C-M, 1-11, respectively), three icetexane-type [= 9(10→20)abeo-abietane-type (amentotaxins N-P, 12-14, respectively)], four ent-labdane-type (amentotaxins Q-T, 15-18, respectively), and two isopimarane-type [amentotaxins U (19) and V (20)] compounds. Their structures were elucidated on the basis of spectroscopic data, single-crystal X-ray diffraction, the modified Mosher's method, and electronic circular dichroism data analyses. Compounds 1-9 are rare 18-nor-ent-kaurane-type diterpenoids featuring a 4β,19-epoxy ring. All the isolates were evaluated for their cytotoxic effects against a small panel of cultured human cancer cell lines (HeLa, A-549, MDA-MB-231, SKOV3, Huh-7, and HCT-116), and some of them exhibited cytotoxicities with IC50 values ranging from 1.5 to 10.0 μM.

Data on direct-acting antiviral agent (DAA) treatment for mixed genotype hepatitis C virus (HCV) infection are scant. This study examined the effectiveness of glecaprevir/pibrentasvir (GLE/PIB) and ledipasvir/sofosbuvir (LDV/SOF) for mixed HCV genotype infection in a real-world setting in Taiwan. We analysed the data from all patients with mixed HCV genotype infections treated with GLE/PIB or LDV/SOF from 2017 to 2019 in three Chang Gung Memorial Hospitals in Taiwan. The primary treatment outcome was sustained virologic response 12 weeks after treatment cessation (SVR12). Adverse events (AEs) were also evaluated. A total of 5190 HCV patients received DAA treatment during this time period. Among them, 116 patients (2.2%) had mixed infections of any 2 or 3 genotypes of 1a, 1b, 2, 3 and 6. Fifty-four patients received GLE/PIB and 62 received LDV/SOF. SVR12 rates for LDV/SOF vs GLE/PIB therapy were 96.6% (56/58) vs 100% (51/51) by the per-protocol analysis and 90.3% (56/62) vs 94.4% (51/54) by the evaluable population analysis. Two patients with 1b + 6 and 1b + 2 genotype infections in the LDV/SOF group had relapse. Evaluating the GLE/PIB vs LDV/SOF groups for the most common AEs revealed pruritus (16.7% vs 4.8%), abdominal discomfort (5.6% vs 8%) and fatigue (5.6% vs 4.8%). One patient with AE-related treatment discontinuation presented with liver decompensation after 4-week GLE/PIB therapy. DAA-related significant laboratory abnormalities occurred in two patients with >3× elevated bilirubin level in the GLE/PIB group. GLE/PIB and LDV/SOF are well tolerated and achieve high SVR12 rates for patients with mixed HCV genotype infection.

To enhance the electrochemical performance of lithium–air/oxygen batteries, it is extremely important to design and synthesize cathodes with porous structures and bifunctional catalytic activity. W...

A preliminary phytochemical investigation of the stems of the endangered plant Ulmus elongata led to the isolation of a new coumarin derivative (named ulmuselactone A, 1) and eight known compounds (2-9). The new structure was elucidated by detailed analysis of comprehensive spectroscopic methods, and its absolute configuration was established by comparing experimental and calculated electronic circular dichroism (ECD) spectra. The isolated compounds were evaluated for their antibacterial activities.

Nitrogen-doped carbon materials (N-Cmat ) are emerging as low-cost metal-free electrocatalysts for the electrochemical CO2 reduction reaction (CO2 RR), although the activities are still unsatisfactory and the genuine active site is still under debate. We demonstrate that the CO2 RR to CO preferentially takes place on pyridinic N rather than pyrrolic N using phthalocyanine (Pc) and porphyrin with well-defined N-Cmat configurations as molecular model catalysts. Systematic experiments and theoretic calculations further reveal that the CO2 RR performance on pyridinic N can be significantly boosted by electronic modulation from in-situ-generated metallic Co nanoparticles. By introducing Co nanoparticles, Co@Pc/C can achieve a Faradaic efficiency of 84 % and CO current density of 28 mA cm-2 at -0.9 V, which are 18 and 47 times higher than Pc/C without Co, respectively. These findings provide new insights into the CO2 RR on N-Cmat , which may guide the exploration of cost-effective electrocatalysts for efficient CO2 reduction.

Phosphate concentration above 10 mM reduces the production of many secondary metabolites; however, the phenomenon is not mechanistically understood yet. Specifically, the problem of phosphorus limitation in antibiotic production remains unresolved. This study investigates the phosphorus inhibition effect on spinosad production and alleviates it by calcium and phosphate supplementation to fermentation media. Furthermore, we examined the mechanism of fatty acids induced increase in polyketides production. NaH2PO4 was found to be the most effective phosphate. Under the optimal phosphate condition, the maximal spinosad production reached 520 mg/L, showing a 1.65-fold increase over the control treatment. In the NaH2PO4-CaCO3 system, the de novo fatty acid biosynthesis was significantly downregulated while spinosad biosynthesis and β-oxidation were upregulated. The coordination of de novo fatty acid biosynthesis and β-oxidation promoted intracellular acetyl-CoA concentration. The results demonstrate that NaH2PO4-CaCO3 combined addition is a simple and effective strategy to alleviate phosphorus inhibition effect through the regulation of fatty acid metabolism and accumulation of immediate precursors. This information improves our understanding of phosphates' influence on the large-scale production of polyketides.

The pressing need for SARS-CoV-2 controls has led to a reassessment of strategies to identify and develop natural product inhibitors of zoonotic, highly virulent, and rapidly emerging viruses. This review article addresses how contemporary approaches involving computational chemistry, natural product (NP) and protein databases, and mass spectrometry (MS) derived target-ligand interaction analysis can be utilized to expedite the interrogation of NP structures while minimizing the time and expense of extraction, purification, and screening in BioSafety Laboratories (BSL)3 laboratories. The unparalleled structural diversity and complexity of NPs is an extraordinary resource for the discovery and development of broad-spectrum inhibitors of viral genera, including Betacoronavirus, which contains MERS, SARS, SARS-CoV-2, and the common cold. There are two key technological advances that have created unique opportunities for the identification of NP prototypes with greater efficiency: (1) the application of structural databases for NPs and target proteins and (2) the application of modern MS techniques to assess protein-ligand interactions directly from NP extracts. These approaches, developed over years, now allow for the identification and isolation of unique antiviral ligands without the immediate need for BSL3 facilities. Overall, the goal is to improve the success rate of NP-based screening by focusing resources on source materials with a higher likelihood of success, while simultaneously providing opportunities for the discovery of novel ligands to selectively target proteins involved in viral infection.

RFWD2, an E3 ubiquitin ligase, is overexpressed in numerous human cancers, including leukemia, lung cancer, breast cancer, renal cell carcinoma, and colorectal cancer. The roles of RFWD2 in cancer are related to the targeting of its substrates for ubiquitination and degradation. This study aimed to investigate the role of TRIB2 in relation to the regulation of protein degradation through RFWD2. inBio Discover™ results demonstrated that TRIB2 can perform its functions by interacting with RFWD2 or other factors. TRIB2 can interact with and regulate RFWD2, which further attends the proteasome-mediated degradation of the RFWD2 substrate p-IκB-α. TRIB2 colocalizes with RFWD2-related IκB-α to form a ternary complex and further affects the IκB-α degradation by regulating its phosphorylation. Specific domain analysis showed that TRIB2 may bind to RFWD2 via its C-terminus, whereas it binds to IκB via its pseudokinase domain. TRIB2 acts as an oncogene and promotes cancer cell proliferation and migration, whereas RFWD2 knockdown reversed the role of TRIB2 in promoting cancer cell growth and colony formation in vitro and in vivo. In summary, this study reveals that TRIB2 promotes the progression of cancer by affecting the proteasome-mediated degradation of proteins through the interaction with RFWD2.

Understanding the relationship between the electronic state of active sites and N2 reduction reaction (NRR) performance is essential to explore efficient electrocatalysts. Herein, atomically dispersed Fe and Mo sites are designed and achieved in the form of well‐defined FeN4 and MoN4 coordination in polyphthalocyanine (PPc) organic framework to investigate the influence of the spin state of FeN4 on NRR behavior. The neighboring MoN4 can regulate the spin state of Fe center in FeN4 from high‐spin (d xy 2 dyz 1 dxz 1 dz2 1 dx2−y2 1) to medium‐spin (dxy 2 dyz 2 dxz 1 dz2 1), where the empty d orbitals and separate d electron favor the overlap of Fe 3d with the N 2p orbitals, more effectively activating N≡N triple bond. Theoretical modeling suggests that the NRR preferably takes place on FeN4 instead of MoN4, and the transition of Fe spin state significantly lowers the energy barrier of the potential determining step, which is conducive to the first hydrogenation of N2. As a result, FeMoPPc with medium‐spin FeN4 exhibits 2.0 and 9.0 times higher Faradaic efficiency and 2.0 and 17.2 times higher NH3 yields for NRR than FePPc with high‐spin FeN4 and MoPPc with MoN4, respectively. These new insights may open up opportunities for exploiting efficient NRR electrocatalysts by atomically regulating the spin state of metal centers., The atomically dispersed Mo–N moieties induce charge accumulation and spin‐state transition of single atom Fe sites, and the eg orbital occupies one electron, which is more conducive to the Fe 3d orbitals overlap with the N 2p orbitals promoting the N2 reduction reaction performance.

The electrochemical nitrogen reduction reaction (NRR) as an energy-efficient approach for ammonia synthesis is hampered by the low ammonia yield and ambiguous reaction mechanism. Herein, phosphorus-doped carbon nanotube (P-CNTs) is developed as an efficient metal-free electrocatalyst for NRR with a remarkable NH3 yield of 24.4 μg·h−1·mg−1cat. and partial current density of 0.61 mA·cm−2. Such superior activity is found to be from P doping and highly conjugated CNTs substrate. Experimental and theoretical investigations discover that the electron-deficient phosphorus sites with Lewis acidity should be genuine active sites and NRR on P-CNTs follows the distal pathway. These findings provide insightful understanding on NRR processes on P-CNTs, opening up opportunities for the rational design of highly-active cost-effective metal-free catalysts for electrochemical ammonia synthesis.

A novel mixed-anion NLO crystal, namely, Bi4O(I3O10)(IO3)3(SeO4), containing a brand-new “pinwheel-like” I3O105− polyiodate anion group was constructed from the trimeric condensation of IO43− monomers. Bi4O(I3O10)(IO3)3(SeO4) exhibits a complex 3D topological structure and gives a moderate second harmonic generation (SHG) signal about 1.1 times that of KH2PO4 (KDP).

Thin-film solar cells made from non-toxic and earth-abundant materials are needed to substitute the current best-developed absorbers such as cadmium telluride (CdTe) and copper indium gallium selenide (CIGS) due to the toxicity of Cd and scarcity of In and Te. In this aspect, germanium monoselenide (GeSe) satisfies the aforementioned criteria and has recently emerged as a potential replacement. Moreover, GeSe possesses a suitable bandgap of 1.14 eV (optimal for single junction solar cells), high absorption coefficient (>105 cm−1) at a wavelength close to the absorption onset, high hole mobility (128.6 cm2 V−1 s−1), and simple binary composition with fixed orthorhombic phase at room temperature. This review introduces the properties of GeSe with special emphasis on the material, optical and electrical properties, and then summarizes the recent progress of GeSe-based solar cells. Finally, we give guidance on optimizing GeSe thin-film solar cells to their full performance potential, and provide a brief outlook for the further development of GeSe thin-film solar cells.

Fourteen previously undescribed naturally occurring C-23 carboxylated triterpenoids, stewartiacids A–N (1–14), were isolated and characterized from the twigs and leaves of the ornamental and medicinal plant Stewartia sinensis (Chinese Stewartia), a ‘vulnerable’ species endemic to China. The new structures were elucidated on the basis of spectroscopic data, single crystal X-ray diffraction, and electronic circular dichroism (ECD) analyses. Stewartiacids A (1) and B (2) are isoursenol derivatives. Stewartiacid C (3) is a 12-oxo-γ-amyrin analogue. Both isoursenol and γ-amyrin derivatives are quite rare in nature. Stewartiacids D (4) and E (5) are 13,27-cycloursane-type compounds. Stewartiacids K (11) and L (12) are ursane-type triterpene and phenylpropanol adducts built through a 1,4-dioxane ring, which are also seldom reported in the literature. The rest are common C-23 carboxylated ursane-type (6–10) and oleanane-type (13, 14) pentacyclic triterpenoids. Stewartiacids G (7), K (11), and L (12) showed moderate inhibitory effects against ATP-citrate lyase (ACL), with IC50 values of 12.5, 2.8, and 10.6 μM, respectively. Stewartiacid K (11) also exhibited moderate inhibition (IC50: 16.8 μM) of NF-κB.

The development of efficient and cost-effective electrocatalysts is essential for the electrochemical reduction of N2 to produce NH3 under ambient conditions. Herein, various well-dispersed Mo-based nanoparticles are selectively synthesized to reveal the influences of the compositions and hetero-interfaces on the performance for the N2 reduction reaction (NRR). Systematic experiments discovered that compared with single-component Mo2C or Mo nanoparticles, the heterostructured binary MoC/Mo2C and ternary Mo/MoC/Mo2C nanoparticles exhibit significantly enhanced NRR performance by creating abundant hetero-interfaces. Moreover, theoretical calculations reveal that the integration of metallic Mo with MoC/Mo2C appreciably reduces the energy demand for NH3 desorption, contributing to the enhanced NRR process. As a result, a remarkable NH3 yield rate of up to 20.4 μg h−1 mg−1 and a FE up to 18.9% can be achieved. These findings suggest that engineering crystalline phases and hetero-interfaces represents a new avenue for advancing the electrocatalytic performance of a NRR catalyst.

Fe-doped Co3O4 polycrystalline nanosheets vertically grown on carbon cloth were developed as self-standing efficient bifunctional electrocatalysts for oxygen reduction and evolution, enabling high-performance Zn–air batteries with a power density of 268.6 mW cm−2 and superior cycling stability.

Although the significance of charge diffusion has been recognized in many high-performance energy devices, it has received very less attention in the design of electrocatalysts for the oxygen evolution reaction (OER), which is particularly crucial for highly active but less conductive OER electrocatalysts, such as two-dimensional metal hydroxides (MHs) with anisotropic conductivity. Herein, we report the elaborate design of a series of CoFe hydroxide nanosheets on graphene (CFH@G) composites to demonstrate the importance of charge diffusion regulation in improving the OER activity of MHs. It was discovered that the few-layer-thick CFH nanosheets lying on the graphene substrate provided an effective in-plane charge diffusion pathway, while keeping the substrate surface entirely covered by the laid nanosheets is necessary for providing sufficient active sites. The overly thick or stacked nanosheets are not favourable for charge diffusion, especially at large current outputs. By regulating the charge diffusion properties, the best-performing CFH@G-based material can deliver a steady OER current density of 2000 mA cm−2 at a cost of only 1.507 V under near-industrial conditions (6 M KOH and 60 °C). A practical water electrolyzer also demonstrated an impressive current output of 400 mA cm−2 at 1.694 V as well as a steady solar-to-hydrogen efficiency of 17.41%. These findings provide new insights into the role of charge diffusion in water oxidation and may open up an avenue for developing low-cost, stable and efficient electrocatalysts for practical water electrolysis and diverse energy devices.

As a representative in-plane anisotropic two-dimensional (2D) material, germanium monoselenide (GeSe) has attracted considerable attention recently due to its various in-plane anisotropic material properties originating from the low symmetry of a puckered honeycomb structure. Although there have been plenty of reports on the in-plane anisotropic vibrational, electrical and optical properties of GeSe, the strain effect on those appealing anisotropies is still under exploration. Here we report a systematic first-principles computational investigation of strain-engineering of the anisotropic electronic properties of GeSe monolayers. We found that the anisotropic ratio of the effective mass and mobility of charge carriers (electrons and holes) of GeSe along two principle axes can be controlled by using simple strain conditions. Notably, the preferred conducting direction of GeSe can be even rotated by 90° under an appropriate uniaxial strain (>5%). Such effective strain modulation of the electronic anisotropy of GeSe monolayers provides them abundant opportunities for future mechanical-electronic devices.

Alkaline hydrogen evolution reaction (HER), consisting of Volmer and Heyrovsky/Tafel steps, requires extra energy for water dissociation, leading to more sluggish kinetics than acidic HER. Despite the advances in electrocatalysts, how to combine active sites to synergistically promote both steps and understand the underlying mechanism remain largely unexplored. Here, Density Functional Theory (DFT) calculations predict that NiO accelerates the Volmer step while metallic Ni facilitates the Heyrovsky/Tafel step. A facile strategy is thus developed to control Ni/NiO heterosurfaces in uniform and well-dispersed Ni-based nanocrystals, targeting both reaction steps synergistically. By systematically modulating the surface composition, we find that steering the elementary steps through tuning the Ni/NiO ratio can significantly enhance alkaline HER activity, and Ni/NiO nanocrystals with a Ni/NiO ratio of 23.7% deliver the best activity, outperforming other state-of-the-art analogues. The results suggest that integrating bicomponent active sites for elementary steps is effective for promoting alkaline HER, but they have to be balanced.

Fe-N-C materials with Fe-Nx coordination sites are promising to replace the state-of-the-art Pt-based electrocatalysts for oxygen reduction reaction (ORR) due to high activity and low cost although there is still debate on its activity origin. Herein, we develop a strategy to investigate the role of iron species in Fe-N-C nanohybrids for catalysing ORR by delicately tuning the iron chemical state. By engineering peripheral substituents of iron porphyrin precursors, two Fe-N-C nanohybrids with metallic or oxidized iron species inside are achieved while holding the similar catalyst structure. Systematic experiments and theoretical analysis discover that metallic iron species promote the electrocatalytic activity of Fe-Nx sites for ORR, while oxidative ones inhibit O2 adsorption on Fe-Nx sites, decreasing their ORR activity. This finding sheds light on unravelling the activity origin in Fe-N-C electrocatalysts for ORR towards their applications in energy devices.

Electrocatalytic N2 reduction to NH3 is an attractive method for artificial N2 fixation at ambient conditions. Herein, we demonstrate that Fe-NC materials could be efficient for electrochemical N2 ...

Both nitrogen (N) and nitric oxide (NO) postpone plant flowering. However, we still don't know whether N and NO trigger the same signaling pathways leading to flowering delay. Our previous study found that ferredoxin NADP+ oxidoreductase (FNR1) and the blue-light receptor cryptochrome 1 (CRY1) are involved in nitrogen-regulated flowering-time control. However, NO-induced late-flowering does not require FNR1 or CRY1. Sucrose supply counteracts the flowering delay induced by NO. However high-N-induced late-flowering could not be reversed by 5% sucrose supplementation. The high nitrogen condition decreased the amplitudes of all transcripts of the circadian clock. While NO increased the amplitudes of circadian transcripts of CRY1, LHY (LATE ELONGATED HYPOCOTYL), CCA1 (CIRCADIAN CLOCK ASSOCIATED 1) and TOC1 (TIMING OF CAB EXPRESSION 1), but decreased the amplitudes of circadian transcripts of CO (CONSTANS) and GI (GIGANTEA). 5% sucrose supplementation reversed the declines in amplitudes of circadian transcripts of CO and GI after the NO treatment. NO induced S-nitrosation modification on oscillators CO and GI, but not on the other oscillators of the circadian clock. Sucrose supply interestingly reduced S-nitrosation levels of GI and CO proteins. Thus N and NO rely on overlapping but distinct signaling pathways on plant flowering.

In-plane anisotropic two-dimensional (2D) materials, especially black phosphorus and ReS2, have attracted significant interest recently as they can provide one more dimension to manipulate their ph...

Organic–inorganic hybrid perovskite single crystals have attracted much attention due to their superior optoelectronic properties. Herein, we report a facile vapor-solution sequential route to prepare single-crystalline nanosheets of hybrid lead triiodide perovskite. It is found that this two-step deposition is able to fabricate sizeable high-quality single-crystalline nanosheets with no need of delicate control of crystallization conditions such as concentration or temperature for normal single crystal growth. The resulting perovskite nanosheets show good reproducibility and single crystallinity with bright and uniform photoluminescence. Our study provides a promising strategy for scalable fabrication of perovskite single crystals with great potential in optoelectronic applications.