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Low-cost, stable, and highly active electrocatalysts for oxygen reduction reaction (ORR), especially for pH-universal ORR, are vital for developing numerous renewable energy devices. Herein, a hierarchical N, S-codoped porous carbon-based catalyst (ZFP-800) coupled with abundant FeS/ZnS heterojunctions was facilely prepared via direct pyrolysis of a Ferrocene-crosslinked pyrrole hydrogel composited with zeolitic imidazolate framework-8 (ZIF-8) templates. Compared with the heterojunction-free catalytic activity, the ZFP-800 catalytic activity was significantly higher in pH-universal ranges. Moreover, the ZFP-800 exhibited competitive ORR performance to commercial Pt/C (20%) in various electrolytes, in terms of onset (Eonset), half-wave potentials (E1/2), limiting current density (JL), durability, and methanol immunity. For instance, it exhibited super ORR catalytic activity on Eonset and E1/2, and exceeded that of the benchmark Pt/C in both the alkaline and neutral media. Furthermore, the application of ZFP-800 as a cathode catalyst in a home-made Zn–air battery demonstrated its operation capability in ambient conditions with a competitive performance on the specific energy density (828 mA·h·gZn–1), maximum discharge power density (205.6 mW·cm−2), rate performance, and the long-term stability (188 h at 5 mA·cm−2). This study can facilitate the development of advanced heterojunction-based materials for renewable energy applications.

Carbon/silicon carbide (C/SiC) composites are usually regarded as thermal protective system materials and widely applied in hypersonic vehicles or ramjet. However, poor thermal conductivity of C/SiC composites, leading to severe heat concentration and thermal stress during the high-speed operation of hypersonic vehicle, limits their broad-range of practical applications. Modification with high thermal conductive fillers is an optional method; however, controllable dispersion and orientation of the fillers to construct continuous and ordered heat conductive channel has been proven to be a challenging task. Herein, based on high thermal conductivity fibers, a three-dimensional micro-pipeline preform was developed for the preparation of structure–function integrated C/SiC composites. The technical feasibility of the method, the characteristics of microstructures, and the thermal conductivity and bending strength of the as-obtained composites were systematically studied. Results revealed that the thermal conductivities of as-obtained composites reached 150.2 and 46.7 W m−1 K−1 for in-plane and out-of-plane direction, respectively. The bending strength obtained herein is 264.4 MPa, which is lower than that of polyacrylonitrile C/SiC composites. However, the fine control over the component and microstructure or densification could provide a higher value in the future research. In sum, the proposed method provides a convenient and feasible approach to prepare high thermal conductive C/SiC composites.

Objectives Danzhi Jiangtang capsule (DJC) is widely used for preventing and treating diabetic cardiomyopathy (DCM). However, the underlying mechanisms of the anti-inflammatory and antiapoptotic activities are unclear. Methods In the in vivo diabetic cardiomyopathy rat model, cardiac function was measured through echocardiography, histological changes in the myocardium were visualized using HE staining, and cardiomyocyte apoptosis was detected using TUNEL. The serum levels of anti-inflammatory cytokines were detected using ELISA. Finally, TLR4, MyD88, and NF-κB mRNA expressions were analyzed using RT-qPCR. In the in vitro experiments, the apoptosis rate of the H9c2 cells was detected using FCM; moreover, TLR4, MyD88 and NF-κB mRNA expressions were measured using RT-qPCR and related protein levels were investigated using Western blotting. Results In vivo, DJC effectively improved cardiac function, alleviated the pathological changes, and reduced the apoptosis rate. Moreover, DJC reduced TNF-α, IL-1β, and IL-6 activities, with significant inhibition of the TLR4, MyD88 and NF-κB p65 mRNA expression. Moreover, in vitro, DJC effectively inhibited high-glucose-induced H9c2 apoptosis-an effect similar to that for TAK242. Finally, both the DJC and TAK242 considerably reduced TLR4, MyD88, NF-κB, Bax, and caspase-3 protein expression but increased that of BCL-2. Conclusions DJC prevented the overactivation of the TLR4/MyD88/NF-κB signaling pathway and regulate cardiomyocyte apoptosis against DCM.

Full-length (pro)renin receptor (fPRR), a research hotspot of the renin-angiotensin system (RAS), plays a serious role in kidney injury. However, the relationship between fPRR and advanced oxidation protein product (AOPP) remains largely unexplored. This study was aimed at exploring the effect of fPRR, especially its 28 kDa soluble form called soluble PRR (sPRR), in AOPP-induced oxidative stress in HK-2 cells, a renal proximal tubular epithelial cell line. Incubation of HK-2 cells with 100 μg/ml AOPP resulted in significant upregulation of fPRR expression and caused an approximately fourfold increase in medium sPRR secretion. However, unmodified albumin did not demonstrate the same effects under the same concentration. Treatment of HK-2 cells with the site-1 protease (S1P) inhibitor PF429242 (40 μM) or S1P siRNA significantly inhibited AOPP-induced sPRR generation. fPRR decoy inhibitor PRO20 and PF429242 treatment for 24 h remarkably attenuated the AOPP-induced upregulation of RAS components. Furthermore, PF429242 significantly reduced the AOPP-stimulated expression of NADPH oxidase 4 (Nox4) and H2O2 expression. The use of a small recombinant protein, named sPRR-His, reversed these alterations. In conclusion, these results provided the first demonstration of AOPP-promoted activation of sPRR. Increased renal proximal tubule Nox4-derived H2O2 contributed to the aggravation of oxidative stress. Targeting S1P-derived sPRR is a promising intervention strategy for chronic kidney disease.

Efficient removal of pollutant formaldehyde (HCHO) at room temperature using transition-metal oxides remains a huge challenge to date. Manganese oxide can oxidize formaldehyde, however, how to control the valence states of manganese is the key to further improve the removal efficiency. We have successfully prepared porous manganese oxide nanowires (MnOx NWs) with large surface area and multiple valence states of manganese using simple electrospinning followed by thermal calcination and potassium permanganate solution post-treatment (C/S process). The contents of trivalent and tetravalent manganese increased significantly after C/S process. Moreover, the composition of silver oxide coated silver nanowires (Ag@Ag2O NWs) is realized by assistance with oxygen plasma, which further enhanced high valence manganese. The formaldehyde removal efficiency by Ag@Ag2O–MnOx composite nanowires can reach 93.7%. The high-efficient catalytic activity is confirmed to attribute to the higher surface area of composite nanowires, the high-valence manganese and the silver oxide for oxidation of formaldehyde.

Aluminum (Al) is an environmental neurotoxin to which humans are extensively exposed; however, the molecular mechanism of aluminum toxicity is unclear. Several studies have indicated that exposure to aluminum can cause abnormal phosphorylation of the tau protein. The purpose of this study was to investigate respectively the special molecular mechanism of abnormal regulation on synthesis and degradation of the tau protein induced by AlCl3 in cells of different species. The results of tau protein showed that the sites of abnormal tau phosphorylation induced by AlCl3 are Thr231, Ser262, and Ser396 in N2a cells. Meanwhile, the expressions of Thr181, Thr231, and Ser262 increased abnormally in SH-SY5Y cells. The result of the study showed that PP2A expression was high in N2a cells, while GSK-3β and PP2A in SH-SY5Y cells were involved in the synthesis process of abnormal tau phosphorylation induced by AlCl3. In N2a cells, the ubiquitin-proteasome pathway (UPP) mainly regulated tau phosphorylation at Ser262 and Ser396. Meanwhile, in SH-SY5Y cells, the UPP mainly regulated tau phosphorylation at Thr231 and Ser396. In summary, the UPP is involved in the degradation of Tau that is abnormally phosphorylated induced by AlCl3, but this process is site-specific and differs in cells of different species.

The effects of low-dose radiation (LDR, ≤0.1 Gy) on living organisms have been the hot areas of radiation biology but do not reach a definitive conclusion yet. So far, few studies have adequately accounted for the male reproductive system responses to LDR, particularly the regulation of testosterone content. Hence, this study was designed to evaluate the effects of LDR on Leydig cells and testicular tissue, especially the ability to synthesize testosterone. We found that less than 0.2-Gy 60 Co gamma rays did not cause significant changes in the hemogram index and the body weight; also, pathological examination did not find obvious structural alterations in testis, epididymis, and other radiation-sensitive organs. Consistently, the results from in vitro showed that only more than 0.5-Gy gamma rays could induce remarkable DNA damage, cycle arrest, and apoptosis. Notably, LDR disturbed the contents of testosterone in mice serums and culture supernatants of TM3 cells and dose dependently increased the expression of 3β-HSD. After cotreatment with trilostane (Tril), the inhibitor of 3β-HSD, increased testosterone could be partially reversed. Besides, DNA damage repair-related enzymes, including DNMT1, DNMT3B, and Sirt1, were increased in irradiated TM3 cells, accompanying by evident demethylation in the gene body of 3β-HSD. In conclusion, our results strongly suggest that LDR could induce obvious perturbation in the synthesis of testosterone without causing organic damage, during which DNA demethylation modification of 3β-HSD might play a crucial role and would be a potential target to prevent LDR-induced male reproductive damage.

Although numerous adsorbent materials have been reported for radioactive iodine capture, demands for the development of new absorbents that are economically viable and featured with reliable synthetic protocols still exist. Herein, in this paper, a coordination-driven self-assembly strategy towards adsorbents for sequential confinement of iodine molecules is reported. It should be noticed that these adsorbents are versatile heterometallic frameworks constructed from aluminum molecular rings of varying size, flexible copper ions and conjugated carboxylate ligands. Additionally, these materials can quickly remove iodine from cyclohexane solutions with a high removal rate (98.8%) and considerable loading capacity (555.06 mg/g). Heterometallic frameworks provided distinct pore sizes and binding sites toward iodine molecules and realize crystallographic visualization concerning sequential confinement of iodine molecules. This work not only sets up a bridge between molecular rings and infinite porous networks but also reveals molecular details for the underlying host-guest binding interactions at crystallographic resolution.

The secretory ducts of Ferula ferulaeoides (Steud.) Korov. are the main tissue of synthesis, secretion, and accumulation of resin. The formation of secretory ducts is closely related to the harvest and quality of resin, but the lumen formation mode and corresponding mechanism have not been thoroughly studied. This study of F. ferulaeoides investigated the microstructure and ultrastructure of the secretory ducts from a developmental point of view. Stem samples were analyzed by light microscopy, transmission electron microscopy, and fluorescence microscopy. The data results showed (1) the walls of secretory cells were intact during the development of secretory ducts in F. ferulaeoides; (2) the plastids and endoplasmic reticulum of secretory cells participated in the synthesis of resin; (3) pectinase was involved in the degradation of the middle lamella; and (4) no features of programmed cell death during the formation of secretory ducts. The results suggested that the formation of F. ferulaeoides' secretory ducts was schizogenous, and pectinase was involved in its formation. These data may be beneficial to further explore the formation of secretory duct in other species of Ferula L. and the formation mechanism of schizogenous secretory structures.

Chiglitazar (Carfloglitazar) is a novel non-thiazolidinedione (TZD) structured peroxisome proliferator-activated receptor (PPAR) pan-agonist that has shown promising effects on glycemic control and lipid regulation in patients with type 2 diabetes in previous clinical studies. This randomized phase 3 trial aimed to compare the efficacy and safety of chiglitazar with placebo in patients with type 2 diabetes with insufficient glycemic control by strict diet and exercise alone. Eligible patients were randomly assigned to receive chiglitazar 32 mg (n = 167), chiglitazar 48 mg (n = 166), or placebo (n = 202) once daily. The primary endpoint was the change in glycosylated hemoglobin A1c (HbA1c) at week 24 with superiority of chiglitazar over placebo. The results showed that both chiglitazar 32 and 48 mg resulted in significant and clinically meaningful reductions in HbA1c, and placebo-adjusted estimated treatment differences at week 24 for chiglitazar 32 and 48 mg were −0.87% (95% confidential interval (CI): −1.10 to −0.65; P

We investigated the hydrolysis of TiIV along with naturally abundant AlIII ions and reported the formation of a stable and semiconducting nanocluster. Interestingly, this compound exhibits an unusual odd-membered ring structure and also represents the largest Al-containing polyoxotitanium cluster (PTC) observed thus far. The presence of a shell of organic ligands as well as the incorporation of hetero-AlIII ions endowed the nanocluster with high air, thermal, and pH stabilities. The present compound exhibited a record photocatalytic hydrogen evolution of 402.88 μmol g−1 h−1 among PTC materials. This work not only paves the way towards stable PTC materials but also provides new insights into the design of novel photocatalysts.

Biopolymers have been extensively studied as biomaterials for clinical applications due to the specific advantages, such as ample natural abundance, outstanding biocompatibility and biodegradability, and non-inflammatory and enormous functional groups. Protein-based biomaterials have been used in many biotechnology and biomedicine applications. This article briefly introduces the structure and extraction of filament proteins, keratin, and then focuses on the recent researches on the application of keratin in drug delivery systems. At the same time, it briefly introduces the application of keratin in tissue engineering. Finally, the problems existing in the application of keratin in the above aspects are summarized.

Background:Sample preparation is one of the most challenging phases in pharmaceutical analysis, especially in biological matrices, affecting the whole analytical methodology.Objective:In this study, a new Ca(II)/Cu(II)/alginate/CuO Nanoparticles Hydrogel Fiber (CCACHF) was synthesized through a simple, green procedure and applied for fiber micro solid-phase extraction (FMSPE) of diazepam (DIZ) and oxazepam (OXZ) as model drugs prior to high-performance liquid chromatography-UV detection (HPLC-UV).Methods:Composition and morphology of the prepared fiber were characterized and the effect of main parameters on the fiber fabrication and extraction efficiency have been studied and optimized.Results:In optimal conditions, calibration curves were linear, ranging between 0.1–500 μg L−1with regression coefficients of 0.9938 and 0.9968. Limit of Detection (LOD) (S/N=3) and Limit of Quantification (LOQ) (S/N=10) of the technique for DIZ and OXZ were 0.03 to 0.1 μg L−1. Within-day and between-day Relative Standard Deviations (RSDs) for DIZ and OXZ were 6.0–12.5% and 3.3–9.4%, respectively.Conclusion:The fabricated adsorbent has been substantially employed to the extraction of selected benzo-diazepines (BZDs) from human serum real specimens and the obtained recoveries were also satisfactory (82.1-109.7%).

Summary Starch is the most abundant storage carbohydrate in maize kernels and provides calories for humans and other animals as well as raw materials for various industrial applications. Decoding the genetic basis of natural variation in kernel starch content is needed to manipulate starch quantity and quality via molecular breeding to meet future needs. Here, we identified 50 unique single quantitative trait loci (QTLs) for starch content with 18 novel QTLs via single linkage mapping, joint linkage mapping and a genome‐wide association study in a multi‐parent population containing six recombinant inbred line populations. Only five QTLs explained over 10% of phenotypic variation in single populations. In addition to a few large‐effect and many small‐effect additive QTLs, limited pairs of epistatic QTLs also contributed to the genetic basis of the variation in kernel starch content. A regional association study identified five non‐starch‐pathway genes that were the causal candidate genes underlying the identified QTLs for starch content. The pathway‐driven analysis identified ZmTPS9, which encodes a trehalose‐6‐phosphate synthase in the trehalose pathway, as the causal gene for the QTL qSTA4−2, which was detected by all three statistical analyses. Knockout of ZmTPS9 increased kernel starch content and, in turn, kernel weight in maize, suggesting potential applications for ZmTPS9 in maize starch and yield improvement. These findings extend our knowledge about the genetic basis of starch content in maize kernels and provide valuable information for maize genetic improvement of starch quantity and quality.

A two-dimensional (2-D) multi-component and multi-phase cellular automaton (CA) model coupled with the Calphad method and finite difference method (FDM) is proposed to simulate the gas pore formation and microstructures in solidification process of hypoeutectic Al-Si-Mg alloys. In this model, the pore growth, and dendritic and eutectic solidification are simulated using a CA technique. To achieve the equilibrium among multiple phases during ternary Al-based alloy solidification, the phase transition thermodynamics and kinetics are evaluated by adopting the Calphad method. The diffusion equations of hydrogen and two solutes are solved by FDM. The developed CA-FDM coupled model can be used for simulating the evolution of gas microporosity and microstructures, involving dendrites and irregular binary and ternary eutectics, of ternary hypoeutectic Al-Si-Mg alloys. It has the capability of reproducing the interactions between the hydrogen microporosity formation and the growth of dendrites and eutectics, the competitive growth among the growing gas pores of different sizes, together with the time-evolving concentration fields of hydrogen and solutes. The simulated morphology of gas pore and microstructure has a good agreement with the experimental observation. The influences of the initial hydrogen concentration and cooling rate on the microporosity formation are investigated. It is found that the main portion of porosity formation occurs in the eutectic solidification stage through analyzing the profiles of porosity percentage and solid fraction varying with solidification time. The varying features of simulated porosity percentage, the maximum and average pores radii indicate that increasing initial hydrogen concentration promotes the formation of higher final porosity percentage and larger pores, while the size of gas pores will significantly reduce with increasing cooling rate, leading to a lower final porosity percentage.

T helper cells are crucial for psoriasis pathogenesis. Communication between T cells and psoriatic keratinocytes (KCs) helps drive the Th1 and Th17 response, but the underlying mechanism is not well-understood. Small extracellular vesicles (sEVs) are emerging mediators of intercellular communication. Here, we investigated the role of KC-derived sEVs in the Th1 and Th17 response in psoriasis. We isolated and characterized sEVs from KCs under normal (untreated) and psoriatic (cytokine-treated) conditions. sEVs under both conditions exhibited a cup-shaped morphology and expressed markers CD63 and CD81. sEVs from cytokine-treated KCs can be taken up by CD4+T cells, leading to the induction of Th1 and Th17 polarization. Small RNA sequencing revealed that miR-381-3p was significantly increased in sEVs from cytokine-treated KCs and in CD4+T cells from patients with psoriasis. Moreover, sEVs-containing miR-381-3p was responsible for sEVs-induced Th1 and Th17 polarization. We further found that the miR-381-3p targeted to the 3′ untranslated region of E3 ubiquitin-ligase UBR5 and stabilized RORγt protein expression. It also targeted to the 3′ untranslated region of FOXO1, associated with activated T-bet and RORγt transcription. Taken together, we propose that psoriatic KCs transfer miR-381-3p to CD4+T cells through sEVs, inducing Th1 and Th17 polarization and promoting psoriasis development. Our findings motivate future studies of KC-derived sEVs or their specific cargoes as therapeutic candidates for psoriasis.

In recent years, studies have shown that cyfluthrin is harmful to the reproductive system. Lycium barbarum polysaccharide may be a protective agent. To investigate the effect of cyfluthrin (Cy) on testosterone B (inhibin B, INHB) in male rats and the intervention of Lycium barbarum polysaccharide (LBP). Compared with the control group, the mRNA and protein expression levels of INH α and INH βB in the testis tissue decreased, and the difference was statistically significant (P

Aconitine (AC) is well-known as the main toxic ingredient and active compound of Aconitum species, of which several aconites are essential herbal medicines of Traditional Chinese Medicine (TCM) and widely applied to treat diverse diseases for their excellent anti-inflammatory, analgesic, and cardiotonic effects. However, the cardiotoxicity and neurotoxicity of AC attracted a lot of attention and made it a favorite botanic poison in history. Nowadays, the narrow therapeutic window of AC limits the clinical application of AC-containing herbal medicines; overdosing on AC always induces ventricular tachyarrhythmia and heart arrest, both of which are potentially lethal. But the underlying cardiotoxic mechanisms remained chaos. Recently, beyond its cardiotoxic effects, emerging evidence shows that low doses of AC or its metabolites could generate cardioprotective effects and are necessary to aconite's clinical efficacy. Consistent with TCM's theory that even toxic substances are powerful medicines, AC thus could not be simply identified as a toxicant or a drug. To prevent cardiotoxicity while digging the unique value of AC in cardiac pharmacology, there exists a huge urge to better know the characteristic of AC being a cardiotoxic agent or a potential heart drug. Here, this article reviews the advances of AC metabolism and focuses on the latest mechanistic findings of cardiac efficacy and toxicity of this aconite alkaloid or its metabolites. We also discuss how to prevent AC-related cardiotoxicity, as well as the issues before the development of AC-based medicines that should be solved, to provide new insight into the paradoxical nature of this ancient poison.

Two monomeric complexes, [NiL2·3H2O] (1) and [Nd2L3(NO3)3] (2), with a tridentate ONO-donor Schiff base ligand HL (HL = 2-hydroxybenzaldehyde-4-aminoantipyrine) have been synthesized. Single-crystal X-ray diffraction analysis indicates that the asymmetric unit of 1 contains one Ni(II) and two L− ligands, while 2 consists of two Nd(III) ions, three L− ligands, and three NO3− ions. Complexes 1 and 2 are both 0-D discrete monomers, and there are intermolecular π–π interactions in 1 and intramolecular π–π interactions in 2. The discrete [NiL2·3H2O] monomers are further connected through π–π interactions, resulting in a 3-D supramolecular structure. Powder XRD and TG-DSC were performed for 1 and 2. Antimicrobial experiments show that 1 displays significant antibacterial effect against Bacillary dysentery and Escherichia coli in comparison with that of Schiff base ligand.

The hydrolysis of earth-abundant AlIII has implications in mineral mimicry, geochemistry and environmental chemistry. Third-order nonlinear optical (NLO) materials are important in modern chemistry due to their extensive optical applications. The assembly of AlIII ions with π-conjugated carboxylate ligands is carried out and the hydrolysis and NLO properties of the resultant material are studied. A series of Al32 -oxo clusters with hydrotalcite-like cores and π-conjugated shells are isolated. X-ray diffraction revealed boundary hydrolysis occurs at the equatorially unsaturated coordination sites of AlIII ions. Charge distribution analysis and DFT calculations support the proposed boundary substitution. The Al32 -oxo clusters possess a significant reverse saturable absorption (RSA) response with a minimal normalized transmittance up to 29 %, indicating they are suitable candidates for optical limiting (OL) materials. This work elucidates the hydrolysis of AlIII and provides insight into layered materials that also have strong boundary activity at the edges or corners.

The effective capture and storage of radioiodine are of worldwide interest for sustainable nuclear energy. However, the direct observation of ambiguous binding sites that accommodate iodine is extremely rare. We presented herein a crystallographic visualization of the binding of iodine within mesoporous cages assembled from aluminum molecular rings. These nanocages are formed through π-π interactions between adjacent aluminum molecular rings. Compared with the general nanotubes arrangement, the supramolecular nanocage isomer exhibits better iodine adsorption behavior. The robust molecular nanocages demonstrate a high iodine vapor saturation uptake capacity of 50.3 wt % at 80 °C. Furthermore, the resulting adsorbent can be recycled. Single-crystal X-ray diffraction reveals binding sites of molecular I2 within the pores of the phenyl-based linkers stabilized by the strong I···π interactions. These compounds represent an excellent model to deduce the trapping mechanism of guest molecules interacting with the host. In addition, this work develops a promising cluster-based aluminum material as iodine adsorbents.

A β-diketonate mononuclear dysprosium complex, with the formula [Dy(dpq)(BTFA)3] (1), has been prepared via self-assembly between 3-benzoyl-1,1,1-trifluoroacetone (BTFA) and dipyrido [3,2-d:2′,3′-f]quinoxaline (dpq) ligands. The crystallographic data reveal that the central Dy(III) ion is eight-coordinated by six oxygen atoms from three BTFA ligands and two N atoms from auxiliary dpq ligands, forming an approximately square-antiprismatic (SAP) coordination geometry with a D4d axial symmetry. Magnetic measurements point out that complex 1 exhibits single-molecule magnet (SMM) behaviours with an anisotropy barrier of 45.65 K under a zero direct-current (dc) field. With an applied dc field of 1200 Oe, the quantum tunnelling of the magnetization (QTM) is suppressed in 1 with an enhanced effective barrier of 178.42 K. A diamagnetic Y(III) analogue [Y(dpq)(BTFA)3] (2) and diluted species [Dy0.06Y0.94(BTFA)3(dpq)] (1@Y) were constructed to further perform the dilution experiment. The results unveil that the SMM behaviour observed in 1 is of molecular origin and is related to the single-ion magnetic behaviour of Dy(III) itself, even though the elimination of the dipolar and intermolecular interactions can modestly slow down the magnetic relaxation rate. The relaxation mechanisms and magneto-structure relationship are rationally discussed by ab initio calculations as well.

Two novel complexes were constructed by adsorption of two typical organic molecules, including one electron-donating molecule (TTF = tetrathiafulvalene) and one electron-withdrawing molecule (TCNQ = tetracyanoquinodimethane), on the surface of black phosphorus quantum dots (BPQDs). There exist considerable charge transfer and strong non-covalent interaction between organic molecules and BPQDs. The results of density functional theory (DFT) calculations show that the static first and second hyperpolarizabilities can be significantly enhanced by introducing TTF/TCNQ groups on BPQDs. Apart from static nonlinearity, hyper-Rayleigh scattering (HRS) first hyperpolarizability shows a remarkable value at a dispersion frequency of 1907 nm. Besides, the frequency-dependent first hyperpolarizability increases significantly while going from the gas to solvent phase. BPQDs–TTF presents a strong dipolar character, whereas BPQDs–TCNQ presents a relatively larger octupolar behavior. Compared with BPQDs–TTF, BPQDs–TCNQ exhibits better stability and larger first hyperpolarizability. This work highlights the superiority of combining TCNQ and BPQDs to construct high-performance nonlinear optical (NLO) molecules.

Homoleptic tris(6,6′-dimethyl-2,2′-bipyridine) rare earth metal complexes M(κ2-dmbp)3 (M = Y, Tb, Dy, Ho, Er; dmbp = 6,6′-dimethyl-2,2′-bipyridine) were synthesized by in situ reduction of 3 equiv. of dmbp with excess KC8 in the presence of 1 equiv. of rare earth metal trihalides. All compounds were characterized by X-ray crystallography, UV-Vis-NIR spectroscopy, infrared (IR) spectroscopy, elemental analysis, and magnetic measurements. While the structural parameters and spectroscopic data confirmed the existence of the trivalent rare earth metal cation and three dmbp radical anions, the electron paramagnetic resonance (EPR) spectrum and the measured magnetic moment of Y(κ2-dmbp)3 indicated that two parallel dmbp radical anions were antiferromagnetically coupled. For paramagnetic rare earth metal ions, room temperature magnetic susceptibility values indicated a weak ferromagnetic interaction between the metal ion and the remaining dmbp radical. Density functional theory (DFT) calculations were performed on Y(κ2-dmbp)3 to gain insight into the electronic structures of these homoleptic metal complexes. The computational results were consistent with the structural, spectroscopic, and magnetic data for a S = 1/2 ground state and spin densities mostly residing on one dmbp radical anion, while the spins on the other two parallel dmbp radical anions being antiferromagnetically coupled.

Presented herein is the synthesis, structure, and optical properties of the aluminum(III)–zinc(II) heterometallic compound AlOC-57. This compound was found to form a large unit cell (approximately sixteen thousand atoms) and a three-shell nano-plate structure. Based on the Z-scan patterns, the third-order nonlinear optical response of the heterometallic nano-plate was mainly attributed to its nonlinear absorption (reverse saturable absorption).

HighlightsContact angles of spray droplets were positively correlated with their surface tension.Wettability of rape leaves was generally poor for most pesticides.Surface structure and free energy determine the hydrophobicity of rape leaves.The size of the spray droplets had no significant influence on rape leaf wettability.Abstract. In order to improve the deposition and adherence of spray droplets on leaf surfaces, the wettability of rapeseed leaves was investigated. We explored the effect of different pesticides and test surfaces on droplet contact angles, and analyzed the effects of leaf surface properties, droplet sizes and the addition of organosilicone adjuvant on wettability. The results indicated that contact angles of different liquids were positively correlated with their surface tension for rapeseed leaves. The wettability of rapeseed leaves was generally poor using different pesticides, but was highest for a fungicide mixture of difenoconazole and propiconazole. The hydrophobicity of rapeseed leaves is largely determined by the complex microstructure and the low surface free energy of the leaves. The size of the spray droplets had no significant influence on the wettability. Moreover, the addition of an organosilicone adjuvant significantly reduced the surface tension of all spray droplets, with the best result for a 50% procymidone solution. In conclusion, the factors affecting rapeseed leaf surface wettability should be considered comprehensively before selecting the appropriate pesticide, so as to improve its utilization rates. Keywords: Contact angle, Leaf surface, Pesticide application, Spray droplet.

A range of titanium compounds containing the naturally occurring dyes quinizarin (QH2) and alizarin (AH2) was synthesized and structurally characterized in the solid state. Among these is the first examples of a discrete metallocyclic arrangement formed exclusively using quinizarin ligands and the first examples of lanthanide containing titanium compounds of the alizarin family of ligands.

Liquid metal (LM)-based elastomers have received growing interest for a wide range of applications spanning from soft robotics to flexible electronics. However, the fabrication of multifunctional LM-based elastomers, in particular, featuring recyclability and transience while simultaneously offering excellent mechanical performance and stability, remains a challenge. Herein, we report a strategy for the fabrication of durable and recyclable multifunctional LM elastomer composites, which consist of LM droplets as functional fillers and Diels–Alder (DA) bond crosslinked polyurethane (PU) networks as the polymer matrix. The composite shows good mechanical properties and can be spatially tuned from an electrical insulator to a conductor through a so-called “mechano-training” process. The mechano-trained composite exhibits extraordinarily stable electrical performance even after 10 000 stretching–releasing cycles at 100% tensile strain. The DA bond-crosslinked network endows the composite with good self-healing properties, high freedom in (re)programming of 3D shapes, and favorable transience. Moreover, spatially thermal and photothermal heating enables the repair/welding of broken circuits or programming of intricate shapes. Besides, the composite can be swiftly destructed by dissolution at an elevated temperature while the valuable LM can be retrieved at a yield of 89%. The multifunctionality, good mechanical and electrical performance, and in particular transience render this composite an environmentally friendly material for flexible transient electronics, actuators, and wearable devices.

Present herein is the first example of aluminium nanoring assembly by fatty acids. And the auxiliary alcohol sites can be modified either by monohydric alcohols (AlOC-33 to AlOC-35) or diols (AlOC-36 to AlOC-38). The monohydric alcohol modified ten-membered aluminium (Al10) rings are coplanar, while the diol modified ones possess a saddle-shaped configuration. Interestingly, the diol modified Al10 ring (AlOC-36) can convert into a coplanar ring (AlOC-33-B). AlOC-33-B possesses a similar molecular structure but a different supramolecular structure with AlOC-33. The structural transformation is confirmed to be a thermodynamically spontaneous process through density-functional theory (DFT) calculations.

A new porous 3D coordination polymer (CP), namely [Mn2(Htpim)2(odpa)]·8H2O (1, Htpim = 2,4,5-tri(4-pyridyl)-imidazole, odpa = 4,4′-oxydiphthalate), was successfully synthesized. Furthermore, comple...

In recent times, many scientists have given great attention to nutraceuticals (complementary medicine) as it widely used for promoting health status. In particular for the prevention and treatment of various neurological diseases or disorders without or less adverse effects. The current mini-review was intended to compile all popular (major) nutraceuticals against various neurodegenerative diseases (NDDs) including Parkinson’s disease (PD), Alzheimer’s disease (AD), Huntington’s disease (HD) with special reference to clinical trials. Preliminary reviews indicated that nutraceuticals like curcumin, resveratrol, Epigallocatechin-3-gallate (EGCG), Coenzyme Q10, ω-3 FA (DHA/EPA/ALA), showed better neuroprotective activity against various NDDs in human setting (clinical trial). Hence this contribution will focus only on those popular nutraceuticals with proposed brief mechanisms (antioxidant, anti-inflammatory, mitochondrial homeostasis, autophagy regulation, promote neurogenesis) and its recommendation. This mini-review would aid common people to choose better nutraceuticals to combat various NDDs along with standard neuroprotective agents and modified lifestyle pattern., Graphical abstract Image 1

Background: Paclitaxel plays a pivotal role in the chemotherapy of breast cancer, but resistance to this drug is an important obstacle in the treatment. It is reported that microRNA-152-3p (miR-152-3p) is involved in tamoxifen resistance in breast cancer, but whether it is involved in paclitaxel resistance in breast cancer remains unknown. Materials and methods: We examined the expression of miR-152-3p in breast cancer tissues and cells by qRT-PCR. After transfecting paclitaxel-resistant MCF-7/TAX cells with miR-152-3p mimics, we analyzed the function of miR-152-3p in these cells by MTT assay and flow cytometry. We screened the target gene, endothelial PAS domain-containing protein 1 (EPAS1), using bioinformatics analysis and verified it with the dual luciferase reporter gene experiment. The relationship between EPAS1 and miR-152-3p and their roles in paclitaxel resistance of breast cancer were further investigated using RNA interference and transfection techniques. Results: The expression of miR-152-3p in normal breast tissues and cells was markedly higher than that in breast cancer. Overexpression of miR-152-3p decreased the survival rate and increased the apoptosis rate and sensitivity of MCF-7/TAX cells to paclitaxel. We confirmed that EPAS1 is the target of miR-152-3p and is negatively regulated by this miRNA. Moreover, transfection with EPAS1 siRNA enhanced the susceptibility and apoptosis rate of MCF-7/TAX cells to paclitaxel. Co-transfection of miR-152-3p mimics and EPAS1 increased paclitaxel sensitivity and apoptosis induced by the drug. Conclusion: miR-152-3p inhibits the survival of MCF-7/TAX cells and promotes their apoptosis by targeting the expression of EPAS1, thereby, enhancing the sensitivity of these breast cancer cells to paclitaxel.

Phosphorus adsorption tests were carried out using poly-aluminum chloride sludge (PACS), which was collected from a water treatment plant in Nanjing. The amount of phosphorus adsorbed by PACS increased quickly within the first hour and reached equilibrium after about 48 h. The adsorption behavior of PACS for phosphorus is consistent with the Langmuir adsorption isotherm equation (R2 > 0.99) and parallel first-order kinetic equation (R2 > 0.98). With the increase of the PACS concentration, the adsorption capacity of PACS for phosphorus decreased, and the removal rate increased. The results of batch tests showed that the adsorption capacities of PACS for phosphorus ranged from 1.64 to 1.13 mg/g when the pH value varied from 4 to 10. However, the adsorption capacity of PACS was not evidently influenced by temperature. In comparison with the ion exchange resin, the adsorption capacity of PACS was barely inhibited by competitive ions, such as SO 4 2 − , NO 3 − , and Cl−. The PACS surface after adsorption became smooth, and the vibration peaks of Al–O and Al–OH shifted. Both HCl and NaOH have a strong desorption effect on PACS after adsorption saturation, and with higher concentrations of HCl and NaOH, the desorption effect was stronger. Results of column adsorption experiments showed that with lower phosphorus and hydraulic loads, the adsorption column took longer to reach saturation. This indicated that PACS could be used as an efficient material for removal of phosphorus from water. This study provides a new treatment method with PACS.

The new class of materials of metal cluster organic framework (MCOFs) derive from metal organic framework (MOFs) and metal oxo clusters (MOCs). In recent years, MCOFs has attracted considerable attention for their combination of metal oxo clusters and porous characteristics. We herein summarize the progress of lanthanide cluster organic framework (LnCOFs), and point out the induced aggregation and synergetic coordination strategy. This strategy is suitable for making MCOFs and MOCs.

Ag-Ti nanocomposite materials have drawn increasing research attention because of their superior catalytic properties. However, the preparation of a crystalline Ag-Ti material is an important challenge in synthetic chemistry. Herein, we report a family of atomically precise Ag-doped polyoxotitanium nanoclusters (PTCs) (PTC-253-PTC-256) with a size of 19.56 × 19.02 A. Each Ag-PTC is made up of a tiny Ag2 kernel and a double-decker Ti12 nanowheel as well as an organic protective shell. Hence, they can be regarded as Ag2@Ti12@(L)14(OMe)n unique triple core-shell structures. Notably, the peripheral organic shell can be modified with different benzoate derivatives. With precise atomic information, these compounds can be used as ideal molecular models of Ag-Ti nanocomposite materials for studying the growth or reaction mechanism via theoretical calculations. Meanwhile, a PTC-255-modified electrode presents efficient electrocatalytic CO2 reduction activity with a Faradaic efficiency (FE) of 29.4%. This work demonstrates that Ag-doped crystalline PTC materials are promising candidates for application to the electrocatalytic CO2 reduction reaction (CO2RR).

Securidaca inappendiculata is a xanthone rich medicinal plant that has been used in the treatment of inflammation and autoimmune diseases like rheumatoid arthritis (RA) for centuries; however, the material base and mechanism of action responsible for its anti‐arthritis effect still remains elusive. The objective of this study is to evaluate the therapeutic effects of xanthone‐enriched extract of the plant against collagen‐induced arthritis (CIA) in rats and explore the underlying mechanisms. The xanthone‐deprived fraction (XDF) and xanthone‐rich fraction (XRF) were obtained by using a resin adsorption coupled with acid‐base treatment method, and their chemical composition difference was characterized by UPLC‐MS/MS analysis. Effects of the two on CIA were analyzed using radiographic, histological, and immunohistochemical analyses. The results indicated that XRF alleviated joint structures destructions with the higher efficacy than XDF, and decreased levels of TNF‐α, IL‐6, and anti‐cyclic citrullinated peptide antibody in CIA rats significantly. Furthermore, XRF inhibited nicotinamide phosphoribosyl transferase (NAMPT) mediated fat biosynthesis and utilization indicated by clinical evidences and metabonomics analysis, which thereby disrupted energy‐metabolism feedback. In addition, Toll‐like Receptor 4 and High Mobility Group Protein 1 expressions were downregulated in XRF‐treated CIA rats. Collective evidences suggest NAMPT could be an ideal target for RA treatments and reveal a novel antirheumatic mechanism of S. inappendiculata by regulating NAMPT controlled fat metabolism.

Quantum information processing based on magnetic ions has potential for applications as the ions can be modified in their electronic properties and assembled by a variety of chemical methods. For these systems to achieve individual spin addressability and high energy efficiency, we exploited the electric field as a tool to manipulate the quantum behaviours of the rare-earth ion which has strong spin-orbit coupling. A Ce:YAG single crystal was employed with considerations to the dynamics and the symmetry requirements. The Stark effect of the Ce3+ ion was observed and measured. When demonstrated as a quantum phase gate, the electric field manipulation exhibited high efficiency which allowed up to 57 π/2 operations before decoherence with optimized field direction. It was also utilized to carry out quantum bang-bang control, as a method of dynamic decoupling, and the refined Deutsch-Jozsa algorithm. Our experiments highlighted rare-earth ions as potentially applicable qubits because they offer enhanced spin-electric coupling which enables high-efficiency quantum manipulation., We utilized the strong spin-orbit coupling in a Ce:YAG single crystal to demonstrate efficient coherent manipulation with the electric field on this electron spin qubit.