Search

Lithium-rich oxides have been considered as one of the most promising cathode materials for lithium-ion batteries due to the competitively high specific capacity contributed by both anionic and cationic redox reactions. Recent years have witnessed the successful achievements of lithium-rich oxides with layered structure due to their high capacity. More recently, another new class of lithium-rich oxides with disordered-rocksalt structure has been demonstrated to possess high capacity and high energy density with moderate structural changes during cycling. A comprehensive comparison and greater fundamental understanding of these two classes of lithium-rich oxides have not been achieved, however, which has greatly hindered the further application of these lithium-rich materials. Herein, an overview of the lithium-rich oxide cathode materials, including the conventional layered and the emerging disordered structure, is provided. Their structural characteristics, mechanisms of anionic redox reactions, and lithium diffusion pathways are systematically summarized. The key challenges to practical application and related strategies to enhance the electrochemical performance of the lithium-rich oxide cathodes are also discussed. At the end, the possible directions for the future development of the lithium-rich oxide cathodes are outlined.

Bauxite reaction residue (BRR) produced from the poly-aluminum chloride (PAC) coagulant industry is a solid acidic waste that is harmful to environment. A low temperature synthesis route to convert the waste into water glass was reported. Silica dissolution process was systematically studied, including the thermodynamic analysis and the influence of calcium and aluminum on the leaching of amorphous silica. Simulation studies have shown that calcium and aluminum combine with silicon to form hydrated calcium silicate, silica–alumina gel, and zeolite, respectively, thereby hindering the leaching of silica. Maximizing the removal of calcium, aluminum, and chlorine can effectively improve the leaching of silicon in the subsequent process, and corresponding element removal rates are 42.81%, 44.15%, and 96.94%, respectively. The removed material is not randomly discarded and is reused to prepare PAC. The silica extraction rate reached 81.45% under optimal conditions (NaOH; 3 mol L−1, L S−1; 5/1, 75°C, 2 h), and sodium silicate modulus (nSiO2:nNa2O) is 1.11. The results indicated that a large amount of silica was existed in amorphous form. Precipitated silica was obtained by acidifying sodium silicate solution at optimal pH 7.0. Moreover, sodium silicate (1.11) further synthesizes sodium silicate (modulus 3.27) by adding precipitated silica at 75°C.

Macrobrachium nipponense, as one of the large-yield farmed shrimp, is facing germplasm degradation. Genetic improvement through hybridization is one of the effective methods to solve this problem. In this study, using a three-line hybrid strategy, two-hybrid F1 populations were obtained using three local populations of M. nipponense as parents for crossbreeding. Five populations were then cultured for 3 months. Growth rate performance was measured by the hepatosomatic index, weight gain, body length growth rate and special growth rate. Biochemical components were also assessed. The results showed that the survival rate and growth performance of the hybrid progeny were better than those of the parents. The levels of triglycerides, total cholesterol, glycogen and lactic acid of the hybrid population were higher than those of the parents. This was consistent with variation in the activity of four digestive enzymes. Compared with the results of the fatty acid and amino acid analysis, it was found that the contents of polyunsaturated fatty acids such as eicosapentaenoic acid, docosapentaenoic acid and docosahexaenoic acid and eight essential amino acids in the hybrid populations were significantly higher than those of their parents, and the contents of flavor amino acids were higher. The expression level of molting genes related to the growth of the parent populations was lower than that of the hybrids. These results show that crossbreeding is effective for the genetic improvement of M. nipponense germplasm. Hybrids showed advantages in growth and nutrition and multigenerational breeding will be required to form a stable germplasm.

Many biotherapeutics such as monoclonal antibodies (mAb) and Fc-domain fusion proteins contain heterogeneous glycan contents at one or multiple glycosylation site(s). Site-specific glycan profile characterization is critical for monitoring the quality of these molecules during different stages of drug development. Hydrophilic interaction chromatography (HILIC) as an orthogonal separation method to reversed-phase liquid chromatography (RPLC) can achieve better glycopeptide identification due to the effective separation between individual glycoforms as well as the separation of glycopeptides from high-abundance non-glycosylated peptides, which can be further improved by modifying the mobile phases with ion-pairing agents (IP-HILIC). However, an online IP-HILIC coupled to mass spectrometry (MS) detection may suffer from the suppression of mass spectrometry signal during electrospray ionization due to the trifluoroacetic acid (TFA), commonly used as an ion-pairing agent. Here, we reported an optimized experimental condition for IP-HILIC-MS where glycine is added in the TFA-containing mobile phases to enhance the MS detection sensitivity for glycopeptides up to ~ 50-fold by eliminating the ion-suppression effect of an ion-pairing agent while still retaining excellent separation capacity. We demonstrated that with enhanced detection sensitivity, IP-HILIC-MS can confidently identify an increased number of site-specific N-linked glycans for IgG1, and IgG4 mAbs as well as an Fc-domain fusion protein (containing five N-glycosylation sites) through MS/MS-based search in the data-dependent acquisition mode, meanwhile, achieve comparable quantitative results compared with the traditional methods. We also demonstrated that IP-HILIC-MS can be used to identify low-level O-glycosylation and non-consensus N-glycosylation on mAbs without any enrichment prior to LC-MS analysis. Graphical abstract.

Herein, we report an enantioselective dehydrative γ-arylation of α-indolyl propargylic alcohols with phenols via organocatalysis, which provides efficient access to chiral tetrasubstituted allenes and naphthopyrans in high yields with excellent regio- and enantioselectivities under mild conditions. This method features the use of cheaply available naphthols/phenols as the C-H aryl source and liberating water as the sole byproduct. Control experiments suggest that the excellent enantioselectivity and remote regioselectivity stem from dual hydrogen-bonding interaction with the chiral phosphoric acid catalyst.

High temperature stress is an inevitable environmental factor in certain geographical regions. To study the effect of day and night high temperature stress on male reproduction, the heat-sensitive cotton line H05 was subjected to high temperature stress. High day/normal night (HN) and normal day/high night (NH) temperature treatments were compared with normal day/normal night (NN) temperature as a control. At the anther dehiscence stage, significant differences were observed, with a reduction in flower size and filament length, and sterility in pollen, seen in NH more than in HN. A total of 36 806 differentially expressed genes were screened, which were mainly associated with fatty acid and jasmonic acid (JA) metabolic pathways. Fatty acid and JA contents were reduced more in NH than HN. Under NH, ACYL-COA OXIDASE 2 (ACO2), a JA biosynthesis gene, was down-regulated. Interestingly, aco2 CRISPR-Cas9 mutants showed male sterility under the NN condition. The exogenous application of methyl jasmonate to early-stage buds of mutants rescued the sterile pollen and indehiscent anther phenotypes at the late stage. These data show that high temperature at night may affect fatty acid and JA metabolism in anthers by suppressing GhACO2 and generate male sterility more strongly than high day temperature.

Single-atom catalysts (SACs) have attracted widespread interest for many catalytic applications because of their distinguishing properties. However, general and scalable synthesis of efficient SACs remains significantly challenging, which limits their applications. Here we report an efficient and universal approach to fabricating a series of high-content metal atoms anchored into hollow nitrogen-doped graphene frameworks (M-N-Grs; M represents Fe, Co, Ni, Cu, etc.) at gram-scale. The highly compatible doped ZnO templates, acting as the dispersants of targeted metal heteroatoms, can react with the incoming gaseous organic ligands to form doped metal–organic framework thin shells, whose composition determines the heteroatom species and contents in M-N-Grs. We achieved over 1.2 atom % (5.85 wt %) metal loading content, superior oxygen reduction activity over commercial Pt/C catalyst, and a very high diffusion-limiting current (6.82 mA cm–2). Both experimental analyses and theoretical calculations reveal the oxygen reduction activity sequence of M-N-Grs. Additionally, the superior performance in Fe-N-Gr is mainly attributed to its unique electron structure, rich exposed active sites, and robust hollow framework. This synthesis strategy will stimulate the rapid development of SACs for diverse energy-related fields., An efficient and universal approach to fabricating a series of high-content metal atoms anchored into hollow nitrogen-doped graphene frameworks is developed via a nicely designed process.

The constant increase in global energy demand and stricter environmental standards are calling for advanced energy storage technologies that can store electricity from intermittent renewable sources such as wind, solar, and tidal power, to allow the broader implementation of the renewables. The grid-oriented sodium-ion batteries, potassium ion batteries and multivalent ion batteries are cheaper and more sustainable alternatives to Li-ion, although they are still in the early stages of development. Additional optimisation of these battery systems is required, to improve the energy and power density, and to solve the safety issues caused by dendrites growth in anodes. Electrolyte, one of the most critical components in these batteries, could significantly influence the electrochemical performances and operations of batteries. In this review, the definitions and influences of three critical components (salts, solvents, and additives) in electrolytes are discussed. The significant advantages, challenges, recent progress and future optimisation directions of various electrolytes for monovalent and multivalent ions batteries (i.e. organic, ionic liquid and aqueous liquid electrolytes, polymer and inorganic solid electrolytes) are summarised to guide the practical application for grid-oriented batteries.

Understanding molecular mechanisms governing interactions of glycosaminoglycans (such as heparin) with proteins remains challenging due to their enormous structural heterogeneity. Commonly accepted approaches seek to reduce the structural complexity by searching for “binding epitopes” within the limited subsets of short heparin oligomers produced either enzymatically or synthetically. A top-down approach presented in this work seeks to preserve the chemical diversity displayed by heparin by allowing the longer and structurally diverse chains to interact with the client protein. Enzymatic lysis of the protein-bound heparin chains followed by the product analysis using size exclusion chromatography with on-line mass spectrometry detection (SEC/MS) reveals the oligomers that are protected from lysis due to their tight association with the protein, and enables their characterization (both the oligomer length, and the number of incorporated sulfate and acetylate groups). When applied to a paradigmatic heparin/antithrombin system, the new method generates a series of oligomers with surprisingly distinct sulfation levels. The extent of sulfation of the minimal-length binder (hexamer) is relatively modest yet persistent, consistent with the notion of six sulfate groups being both essential and sufficient for antithrombin binding. However, the masses of longer surviving chains indicate complete sulfation of disaccharides beyond the hexasaccharide core. Molecular dynamics simulations confirm the existence of favorable electrostatic interactions between the high charge-density saccharide residues flanking the “canonical” antithrombin-binding hexasaccharide and the positive patch on the surface of the overall negatively charged protein. Furthermore, electrostatics may rescue the heparin/protein interaction in the absence of the canonical binding element.

The integration of two transition metals with carbon materials provides a great potential to boost the catalytic and electrochemical properties of supercapacitor. However, a scalable fabrication of such composite materials remains a challenge. Here, ternary composites of NiS–NiCo2O4@C nanosheets were derived from nickel and cobalt oleate using Na2SO4 as both hard template and sulfur source. The NiS–NiCo2O4@C composites were then tested as catalysts toward rapid reduction of 4-nitrophenol (4-NP) and as electrode materials for supercapacitors. It was found that the catalytic and electrochemical properties of the composites were tuned by adjusting the ratios of Co to Ni and annealing temperature. The optimized composite showed the highest reduction rate constant for 4-NP reduction (1.78 min−1). In addition, this composite has also shown high specific capacitance of 1411 F g−1 at 1 A g−1and 99.5% capacity retention after 2000 continuous charge-discharge cycles at a current density of 3 A g−1, which is much higher than their respective monometallic Co and Ni composites. Furthermore, the ASC device (CN14//AC) achieved a high energy density of 37.2 W h kg−1 at a power density of 799.9 W kg−1, and a good cycling performance of retention(89%) after 5000 cycles.

Efficient catalysis of the methanol oxidation reaction (MOR) greatly determines the widespread implementation of direct methanol fuel cells. Exploring a suitable support for noble metal catalysts with regard to decreasing the mass loading and optimizing the MOR activity remains a key challenge. Herein, we achieve an over 60% activity enhancement of a palladium (Pd) catalyst by introducing a two-dimensional Ti3C2Tx MXene as the support compared to a commercial Pd/C catalyst. Not only are more catalytically active Pd sites exposed on the Pd/MXene catalyst while maintaining a low mass loading, but the introduction of the MXene support also significantly alters the surface electronic structure of Pd. Specifically, spectroscopy and density functional theory (DFT) computations indicate that sufficiently electronegative terminations of the Ti3C2Tx MXene surface can induce strong metal-support interactions (SMSI) with the Pd catalyst, leading to optimal methanol adsorption. This MXene-supported Pd catalyst exhibits a much higher MOR current density (12.4 mA cm-2) than that of commercial Pd/C (7.6 mA cm-2). Our work largely optimizes the intrinsic activity of a Pd catalyst by the utilization of MXene surface terminations, and the crucial SMSI effects revealed herein open a rational avenue to the design of more efficient noble metal catalysts for MOR.

The enhancer of zeste homolog 2 (EZH2) is a methylated modification enzyme of Histone H3-Lys 27. The high expression of EZH2 in cells is closely related to the progression, invasion, and metastasis of neoplasm. Therefore, this target is gradually becoming one of the research hot spots of tumor pathogenesis, and the inhibitors of the EZH2 enzyme are expected to become new antitumor drugs. This study used a series of virtual screening technologies to calculate the affinity between the compounds obtained from the ZINC15 database and the target protein EZH2, the stability of the ligand–receptor complex. This experiment also predicted the toxicity and absorption, distribution, metabolism, and excretion (ADME) properties of the candidate drugs in order to obtain compounds with excellent pharmacological properties. Finally, the ligand–receptor complex under in vivo situation was estimated by molecular dynamics simulation to observe whether the complex could exist steadily in the body. The experimental results showed that the two natural compounds ZINC000004217536 and ZINC000003938642 could bind tightly to EZH2, and the ligand–receptor complex could exist stably in vivo. Moreover, these two compounds were calculated to be nontoxic. They also had a high degree of intestinal absorption and high bioavailability. In vitro experiments confirmed that drug ZINC000003938642 could inhibit the proliferation and migration of osteosarcoma, which could serve as potential lead compounds. Therefore, the discovery of these two natural products had broad prospects in the development of EZH2 inhibitors, providing new clues for the treatment or adjuvant treatment of tumors.

As a key regulator of many biological processes, glycosylation is an essential post-translational modification (PTM) in the living system. Over 50% of human proteins are known to be glycosylated. Alterations in glycoproteins are directly linked to many diseases, making it crucial to understand system-wide glycosylation changes. The majority of known glycoproteins are from plasma membrane; however, glycosylation is a dynamic process that occurs throughout multiple subcellular organelles and involves sets of enzymes, chaperones, transporters, and sugar donor molecules. Many glycoproteins are expressed not only in plasma membranes but also in subcellular organelles. Here, we developed a mass-spectrometry-based quantitative workflow for the system-wide N-glycoproteomic analysis of membrane and cytosolic proteins extracted using a MEM-PER kit. The kit facilitates the extraction and solubilization of both membrane and cytosolic proteins in a simple, efficient, and reproducible manner. We analyzed the K562 cell line and mouse liver tissue to evaluate this approach. A total of 934 glycosites, 5154 glycopeptides, and 536 glycoproteins from the K562 cell line and a total of 1449 glycosites, 7549 glycopeptides, and 660 glycoproteins from mouse liver tissue were identified. This simple and reproducible approach provides a unique way to understand system-wide glycosylation in biological processes and enables the identification and quantitation of glycan profiles at glycosylation sites in proteins.

A large number of inhibitory receptors recruit SHP1 and/or SHP2, tandem-SH2-containing phosphatases through phosphotyrosine-based motifs immunoreceptor tyrosine-based inhibitory motif (ITIM) and immunoreceptor tyrosine-based switch motif (ITSM). Despite the similarity, these receptors exhibit differential effector binding specificities, as exemplified by the immune checkpoint receptors PD-1 and BTLA, which preferentially recruit SHP2 and SHP1, respectively. The molecular basis by which structurally similar receptors discriminate SHP1 and SHP2 is unclear. Here, we provide evidence that human PD-1 and BTLA optimally bind to SHP1 and SHP2 via a bivalent, parallel mode that involves both SH2 domains of SHP1 or SHP2. PD-1 mainly uses its ITSM to prefer SHP2 over SHP1 via their C-terminal SH2 domains (cSH2): swapping SHP1-cSH2 with SHP2-cSH2 enabled PD-1:SHP1 association in T cells. In contrast, BTLA primarily utilizes its ITIM to prefer SHP1 over SHP2 via their N-terminal SH2 domains (nSH2). The ITIM of PD-1, however, appeared to be de-emphasized due to a glycine at pY+1 position. Substitution of this glycine with alanine, a residue conserved in BTLA and several SHP1-recruiting receptors, was sufficient to induce PD-1:SHP1 interaction in T cells. Finally, structural simulation and mutagenesis screening showed that SHP1 recruitment activity exhibits a bell-shaped dependence on the molecular volume of the pY+1 residue of ITIM. Collectively, we provide a molecular interpretation of the SHP1/SHP2-binding specificities of PD-1 and BTLA, with implications for the mechanisms of a large family of therapeutically relevant receptors.

Exhibiting high specific energy and low cost, lithium-sulfur batteries are considered promising candidates for the next-generation battery. However, its wide applications are limited by the insulating nature of the sulfur, dissolution of polysulfide species, and large volume change of the sulfur cathode. In this work, a conductive binder, crosslinked polyfluorene (C-PF) is synthesized and employed in Li-S batteries to enhance the overall electrochemical performance from the following three aspects: 1) possessing high electronic conductivity, C-PF facilitates lowered areal resistance for the sulfur electrode and leads to an improved rate capability; 2) owing to the cross-linked polymer structure, favorable mechanical properties of the electrode can be achieved, hence the well-preserved electrode integrity; 3) forming strong binding with various polysulfide species, C-PF manages to trap them from diffusing to the Li anode, which greatly improves the cycling stability of Li-S cells. Through designing a multifunctional binder to comprehensively enhance the Li-S cathode, this proposed approach could be broadly applied to fully harness the energy from S redox in addition to cathode material modifications.

A novel method for synthesizing poly-silicate aluminum sulfate coagulant (PSAS) using a silica-alumina sol was reported. Herein, two modalities (nSiO2/nNa2O: 1.11 and 3.27) of self-made water glasses were used as the silica source for synthesizing the sol precursor. Then, the PSAS1.11 and PSAS3.27 with different basicity were obtained by controlling the Al molar ratio of precursor to aluminum sulfate. The results showed that the PSAS1.11 coagulant prepared with low modulus water glass (LMWS, 1.11) has low turbidity and good stability. Using low modulus water glass, the effect of the Al molar ratio of precursor to aluminum sulfate on the basicity and stability of PSAS1.11 with Al/Si of 20 and the effect of the molar ratio of aluminum to silicon on the basicity and stability of PSAS1.11 were studied, respectively. Based on XRD and Fourier infrared (FTIR) characterization of the sol precursor and PSAS1.11, the synthesis mechanism of PSAS by the silica-alumina sol method was discussed. Al species distribution of PSAS1.11 was determined using the Al-Ferron timed spectrophotometric method. Moreover, the performance of PSAS1.11 coagulant was examined, regarding its efficiency towards color removal of Congo red. The results showed that PSAS1.11 coagulant with Al/Si of 20 and Al molar ratio of 1/12 exhibits excellent performance, and the color removal rate reached 98.6% at an initial pH of 11 and coagulant dosage of 40 mg L−1 (Al mg L−1). Finally, the PSAS coagulant mechanism was discussed in detail through infrared characterization, 27Al NMR, Raman, morphology and mapping of the flocs.

Desaturase is one of the key enzymes in the unsaturated fatty acid synthesis pathway. Δ9 desaturase catalyzes the synthesis of oleic acid from stearic acid by introducing double bonds in the 9th and 10th carbon chains, thereby increasing the content of MUFAs in the body. In order to explore the main function of the Δ9 desaturase gene under low temperature stress, RACE-PCR technology was used in this study to clone the full-length sequence of the CqFAD9-like from the hepatopancreas of red claw crayfish, Cherax quadricarinatus. The full length of the sequence is 1236 bp, and the open reading frame is 1041 bp, encoding 346 amino acid residues. The 5 ‘UTR is 116 bp, the 3′ UTR is 79 bp, and the 3 ‘UTR contains a PloyA tail. The predicted theoretical isoelectric point and molecular weight are 8.68 and 40.28 kDa, respectively. Homology analysis showed that the sequence had the highest similarity with FAD9 from crustaceans. The results of real-time PCR showed that the expression level of this gene was highest in the hepatopancreas, which was significantly higher than other tissues, followed by the ovaries, brain ganglion and stomach. At the same time, the expression of the CqFAD9-like in hepatopancreas of crayfish cultured at 25, 20, 15 and 9 °C for four weeks was detected. The results showed that expression of the FAD9 gene increased gradually with decreasing temperature, indicating that metabolic desaturation might play a regulatory role during cold stress.

REGEN-COV is a cocktail of two human IgG1 monoclonal antibodies (REGN10933 + REGN10987) that targets severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2) spike protein and has shown great promise to reduce the SARS-CoV-2 viral load in COVID-19 patients enrolled in clinical studies. A liquid chromatography-multiple reaction monitoring-mass spectrometry (LC-MRM-MS)-based method, combined with trypsin and rAspN dual enzymatic digestion, was developed for the determination of total REGN10933 and total REGN10987 concentrations in several hundreds of pharmacokinetic (PK) serum samples from COVID-19 patients participating in phase I, II, and III clinical studies. The performance characteristics of this bioanalytical assay were evaluated with respect to linearity, accuracy, precision, selectivity, specificity, and analyte stability before and after enzymatic digestion. The developed LC-MRM-MS assay has a dynamic range from 10 to 2000 μg/mL antibody drug in the human serum matrix, which was able to cover the serum drug concentration from day 0 to day 28 after drug administration in two-dose groups for the clinical PK study of REGEN-COV. The concentrations of REGEN-COV in the two-dose groups measured by the LC-MRM-MS assay were comparable to the concentrations measured by a fully validated electrochemiluminescence (ECL) immunoassay.

Numerous inhibitory immunoreceptors operate by recruiting phosphatase effectors Shp1 and Shp2 through conserved motifs ITIM and ITSM. Despite the similarity, these receptors exhibit distinct effector binding specificities, as exemplified by PD-1 and BTLA, which preferentially recruit Shp2 and Shp1 respectively. The molecular basis of Shp1/Shp2 discrimination is unclear. Here, we provide evidence that optimal PD-1 and BTLA binding to both Shp1 and Shp2 occurs via a bivalent, parallel mode that involves both SH2 domains of Shp1/Shp2. Moreover, PD-1 mainly uses its ITSM to discriminate Shp2 from Shp1 via their C-terminal SH2 domains. Supportive of this model, swapping the Shp1-cSH2 with Shp2-cSH2 enabled PD-1:Shp1 association in T cells. In contrast, BTLA primarily utilizes its ITIM to discriminate Shp1 from Shp2 via their N-terminal SH2 domains. Substitution of glycine at pY+1 position of the PD-1-ITIM with alanine, a residue conserved in several Shp1-recruiting receptors, was sufficient to induce PD-1:Shp1 interaction in T cells. Finally, mutagenesis screening shows that Shp1 recruitment exhibits a bell-shaped dependence on the side chain volume of the pY+1 residue of ITIM. Collectively, we provide a molecular interpretation of the Shp1/Shp2-binding specificities of PD-1 and BTLA, with general implications for the mechanism of effector discrimination by inhibitory receptors.

An enantioselective chemical synthesis of arene cis-dihydrodiols has been realized from 2-pyrones through sequential ytterbium-catalyzed asymmetric inverse-electron-demand Diels-Alder (IEDDA) reaction of 2-pyrones and retro-Diels-Alder extrusion of CO2 . By using this strategy, a series of substituted arene cis-dihydrodiols can be obtained efficiently with high enantioselectivity (>99 % ee in many cases). Based on this strategy, efficient and concise asymmetric total syntheses of (+)-MK7607 and 1-epi-(+)-MK7607 were accomplished.

Gaseous elemental mercury removal by activated carbon impregnated with SO2 was studied under simulated flue gas conditions. Brunauer–Emmett–Teller (BET) measurements and X-ray photoelectron spectro...

A highly regioselective and enantioselective C7-Friedel-Crafts alkylation of 4-aminoindoles with trifluoromethyl ketones promoted by a spirocyclic phosphoric acid was developed. This strategy was applicable to various substituted trifluoromethyl ketones and 4-aminoindole derivatives, affording the corresponding C7-functionalized indole derivatives, bearing a pharmaceutically interesting trifluoromethylated tertiary alcohol scaffold, in 21%-98% yields with up to >99% enantiomeric excess (ee).

Nonmetal elements strictly govern the electrochemical performance of molybdenum compounds. Yet, the exact role played by nonmetals during electrocatalysis remains largely obscure. With intermetallic MoSi2 comprising silicene subunits, we present an unprecedented hydrogen evolution reaction (HER) behavior in aqueous alkaline solution. Under continuous operation, the HER activity of MoSi2 shows a more than one order of magnitude improvement in current density from 1.1 to 21.5 mA cm−2 at 0.4 V overpotential. Meanwhile, this activation behavior is highly reversible, such that voltage withdrawal leads to catalyst inactivation but another operation causes reactivation. Thus, the system shows dynamics strikingly analogous to the legendary Sisyphus labor, which drops and recovers in a stepwise manner repeatedly, but never succeeds in reaching the top of the mountain. Isomorphic WSi2 behaves almost the same as MoSi2, whereas other metal silicides with silicyne subunits, including CrSi2 and TaSi2, do not exhibit any anomalous behavior. A thin amorphous shell of MoSi2 is observed after reaction, within which the Si remains partially oxidized while the oxidation state of Mo is basically unchanged. First-principles calculations further reveal that the adsorption of hydroxide ions on silicene subunit edges and the subsequent Si vacancy formation in MoSi2 jointly lead to the anomalous HER kinetics of the adjacent Mo active centers. This work demonstrates that the role of nonmetal varies dramatically with the electronic and crystallographic structures of silicides and that silicene structural subunit may serve as a promoter for boosting HER in alkaline media.

Silicon oxides (SiOx) represent an attractive high-capacity lithium-ion battery (LIB) anode material. However, the huge volume variation of SiOx causes rapid capacity fading and unstable solid electrolyte interface, seriously limiting the practical application. To address the inherent defects of SiOx, herein, we designed a yolk@shell structured SiOx/C anode with semi-graphitic carbon coatings on the exterior and interior surfaces (SiOx/C-CVD) through sol-gel process, selective etching, and chemical vapor deposition. The unique composite nanostructure endows the SiOx/C-CVD high electrical conductivity and excellent structural stability. The as-prepared SiOx/C-CVD composite demonstrates a high reversible capacity (1165 mA h g-1 at 100 mA g-1) as well as outstanding durability (972 mA h g-1 after 500 cycles at 500 mA g-1). Furthermore, the full cells of SiOx/C-CVD//LiCoO2 are also assembled, delivering a high energy density of ~428 W h kg-1 with a stable cycling behavior. The carbon coated yolk@shell design might be applied to optimize the lithium storage performances of other high-capacity anode materials suffering from poor electrical conductivity and large volume variations.

We evaluated the effects of dietary vitamin E on growth, immunity and regulation of the hepatopancreas in male oriental river prawn, Macrobrachium nipponense. Shrimps were fed 0, 40, 80, 160, 320 or 640 mg vitamin E/kg for 60 days. The 80 mg/kg group had the highest weight gain rate, specific growth rate and lowest feed conversion rate while there were no significant differences in survival rate and hepatosomatic index. The highest crude fat and lowest crude protein content were observed in the 160 mg/kg group. In the hepatopancreas, lysozyme, acid phosphatase and alkaline phosphatase activities were highest in the 160 mg/kg group, while superoxide dismutase, catalase and glutathione peroxidase activities decreased with increasing vitamin E levels. Malondialdehyde content initially decreased then increased with vitamin E levels, whereas the reverse was seen with total antioxidant capacity. Linoleic acid, DPA, DHA, total n‐3 polyunsaturated fatty acid and total polyunsaturated fatty acid first increased then decreased, while EPA and total saturated fatty acid rose with vitamin E levels. Total n‐6 polyunsaturated fatty acid content declined while there were no significant differences in linolenic and total monounsaturated fatty acid content. Following a toxicity test with Aeromonas hydrophila, hepatopancreas ultrastructure revealed that appropriate vitamin E levels promote an increase in mitochondria, endoplasmic reticulum and Golgi bodies, but excess vitamin E can damage cell structure. These results provide evidence that 80–160 mg/kg dietary vitamin E has a positive impact on growth, immunity and regulation of the hepatopancreas in male shrimp.

The safety, durability and power density of lithium-ion batteries (LIBs) are currently inadequate to satisfy the continuously growing demand of the emerging battery markets. Rapid progress has been made from material engineering to system design, combining experimental results and simulations to enhance LIB performance. Limited by spatial and temporal resolution, state-of-the-art advanced characterization techniques fail to fully reveal the complex multi-scale degradation mechanism in LIBs. Strengthening interaction and iteration between characterization and modeling improves the understanding of reaction mechanisms as well as design and management of LIBs. Herein, a seed cyber hierarchy and interactional network framework is demonstrated to evaluate the overall lifecycle of LIBs. The typical examples of bridging the characterization techniques and modeling are discussed. The critical parameters extracted from multi-scale characterization can serve as digital inputs for modeling. Furthermore, advanced computational techniques including cloud computing, big data, machine learning, and artificial intelligence can also promote the comprehensive understanding and precise control of the whole battery lifecycle. Digital twins techniques will be introduced enabling the real-time monitoring and control of LIBs, autonomous computer-assisted characterizations and intelligent manufacturing. It is anticipated that this work will provide a roadmap for further intensive research on developing high-performance LIBs and intelligent battery management.

Trifluoroacetic acid (TFA) is a commonly used mobile phase additive in liquid chromatography-mass spectrometry (LC-MS)-based biopharmaceutical characterization to enhance reversed-phase chromatographic performance of peptide separation; however, it leads to significant mass spectrometry signal suppression during electrospray ionization. Previous studies have shown that introducing large amounts of carboxylic acids or ammonium hydroxide to LC eluents postcolumn can improve MS sensitivity. In this study, we discovered glycine as a simple additive for TFA mobile phases, which mitigates ion suppression through a similar mechanism but in a more effective way than weak acid or weak base and boosts mass spectrometry responses (signal-to-noise ratio) of peptides by more than 1 order of magnitude on average after directly adding a small amount (e.g., 2 mM) into TFA mobile phases without compromising the chromatographic performance of peptide separation. Other small molecule additives in TFA mobile phases, such as amino acids containing extended side chains with different chemical properties and glycine-based variants, were also evaluated. The results demonstrated that glycine offered the best response boosting on peptides. The discovery of this glycine additive in TFA mobile phases provides a simple and conventional approach to achieve greater mass spectrometry detection sensitivity than TFA mobile phases for LC-MS-based characterization of biopharmaceuticals.

Identifying structural elements within heparin (as well as other glycosaminoglycan) chains that enable their interaction with a specific client protein remains a challenging task due to the high degree of both intra- and inter-chain heterogeneity exhibited by this polysaccharide. The new experimental approach explored in this work is based on the assumption that the heparin chain segments bound to the protein surface will be less prone to collision-induced dissociation (CID) in the gas phase compared to the chain regions that are not involved in binding. Facile removal of the unbound chain segments from the protein/heparin complex should allow the length and the number of sulfate groups within the protein-binding segment of the heparin chain to be determined by measuring the mass of the truncated heparin chain that remains bound to the protein. Conformational integrity of the heparin-binding interface on the protein surface in the course of CID is ensured by monitoring the evolution of collisional cross-section (CCS) of the protein/heparin complexes as a function of collisional energy. A dramatic increase in CCS signals the occurrence of large-scale conformational changes within the protein and identifies the energy threshold, beyond which relevant information on the protein-binding segments of heparin chains is unlikely to be obtained. Testing this approach using a 1 : 1 complex formed by a recombinant form of an acidic fibroblast growth factor (FGF-1) and a synthetic pentasaccharide GlcNS,6S-GlcA-GlcNS,3S,6S-IdoA2S-GlcNS,6S-Me as a model system indicated that a tri-saccharide fragment is the minimal-length FGF-binding segment. Extension of this approach to a decameric heparin chain (dp10) allowed meaningful binding data to be obtained for a 1 : 1 protein/dp10 complex, while the ions representing the higher stoichiometry complex (2 : 1) underwent dissociation via asymmetric charge partitioning without generating truncated heparin chains that remain bound to the protein.

Lipids play an important role in protecting poikilotherms from cold stress, but relatively little is known about the regulation of lipid metabolism under cold stress, especially in crustaceans. In the present study, red-clawed crayfish Cherax quadricarinatus was employed as a model organism. Animals were divided into four temperature groups (25, 20, 15 and 9 °C) and treated for 4 weeks, with the 25 °C group serving as a control. The total lipid content in the hepatopancreas as well as the triglyceride, cholesterol and free fatty acid levels in the hemolymph were determined. Lipids stored in the hepatopancreas and hemolymph decreased with decreasing temperature, with changes in the 9 °C group most pronounced, indicating that lipids are the main energy source for crayfish at low temperatures. Furthermore, enzyme activity of lipase, fatty acid synthase, acetyl-CoA carboxylase, and lipoprotein esterase, and gene expression analysis of fatty acid synthase gene, acetyl-CoA carboxylase gene and carnitine palmitoyltransferase gene showed that the digestion, synthesis and oxidation of lipids in the hepatopancreas were inhibited under low temperature stress, but expression of sphingolipid delta-4 desaturase (DEGS) was increased, indicating an increase in the demand for highly unsaturated fatty acids at low temperatures. Analysis of the expression of genes related to the AMP-activated protein kinase (AMPK) signalling pathway revealed that the adiponectin receptor gene was rapidly upregulated at low temperatures, which may in turn activate the expression of the downstream AMPKα gene, thereby inhibiting lipid anabolism.

The rational design of flexible electrodes is essential for achieving high performance in flexible and wearable energy-storage devices, which are highly desired with fast-growing demands for flexible electronics. Owing to the one-dimensional structure, nanowires with continuous electron conduction, ion diffusion channels, and good mechanical properties are particularly favorable for obtaining flexible freestanding electrodes that can realize high energy/power density, while retaining long-term cycling stability under various mechanical deformations. This Minireview focuses on recent advances in the design, fabrication, and application of nanowire-based flexible freestanding electrodes with diverse compositions, while highlighting the rational design of nanowire-based materials for high-performance flexible electrodes. Existing challenges and future opportunities towards a deeper fundamental understanding and practical applications are also presented.

The mesoporous of ultra-thin CoxNi(1-x)/C nano-sheets (NSs) have been synthesized by a molten-salt calcination approach. The nanocrystalline, composition, morphology and structure of the hybrid nano-sheets are confirmed with phenetic analysis of XRD, EDS, XPS, TEM and SEM. The as-synthesized of CoxNi(1-x)/C NSs were obtained under varied temperature and ratio of Ni and Co, and the ultra-thin carbon species with thickness of 10–30 nm were fabricated from a novel and economical carbon source (potassium fulvic acid, P-FA). The Co0.5Ni0.5/C-600 NSs that was obtained from calcination temperature 600 °C and molar ratio of Co:Ni = 1:1 showed the best catalytic activity though the reduction of 4-nitrophenol (4-NP) as a common benchmark reaction. Furthermore, the homologous apparent rate constant kapp of the Co0.5Ni0.5/C-600 nanocatalyst is 1.3949 min−1 for reduction of 4-NP in presence of NaBH4, and all rate constant for CoxNi(1-x)/C NSs were calculated with Pseudo-first rate equation. The excellent catalytic activity of the nanocatalyst was attributed to the larger specific surface area with 202.8 m2/g, excellent electrical conductivity of carbon material and synergistic effect of cobalt and nickel bimetal. We believe that our method can provide useful assistance for the synthesis of humic acid-based materials, and those may be applied to other domains.

SUMMARY The PD-1 pathway, consisting of the co-inhibitory receptor PD-1 on T cells and its ligand (PD-L1) on antigen-presenting cells (APCs), is a major mechanism of tumor immune evasion. PD-1 and PD-L1 blockade antibodies have produced remarkable clinical activities against a subset of cancers. Binding between T cell-intrinsic PD-1 and APC-intrinsic PD-L1 triggers inhibitory signaling to attenuate the T cell response. Here, we report that PD-1 is co-expressed with PD-L1 on tumor cells and tumor-infiltrating APCs. Using reconstitution and cell culture assays, we demonstrate that the co-expressed PD-1 binds to PD-L1 in cis. Such interaction inhibits the ability of PD-L1 to bind T cell-intrinsic PD-1 in trans and, in turn, represses canonical PD-L1/PD-1 inhibitory signaling. Selective blockade of tumor-intrinsic PD-1 frees up tumor-intrinsic PD-L1 to inhibit T cell signaling and cytotoxicity. Our study uncovers another dimension of PD-1 regulation, with important therapeutic implications., In Brief Zhao et al. show that the T cell inhibitory receptor PD-1 expressed on tumor cells and tumor-infiltrating APCs neutralizes its ligand, PD-L1, in cis to inhibit canonical PD-1 signaling. Selective blockade of tumor-intrinsic PD-1 frees up tumor PD-L1 for T cell suppression.

We evaluated the effects of dietary vitamin E on the reproductive performance and antioxidant capacity of Macrobrachium nipponense female shrimp. Prawns were fed 0, 40, 80, 160, 320 or 640 mg vitamin E/kg diet for 60 days. The 80 mg/kg group had the highest weight gain and lowest feed conversion rates. And the highest spawning rates were observed in the 80 mg/kg group with no significant differences among the groups. The highest activities of lysozyme, acid phosphatase and alkaline phosphatase in hepatopancreas were obtained in the 160 mg/kg group. The activities of superoxide dismutase, catalase and glutathione peroxidase showed a decreasing trend in the hepatopancreas. The lowest content of malondialdehyde was obtained with 80 and 160 mg/kg vitamin E. Histological results showed that the number of restzellen cells in hepatopancreas and a number of follicular cells in ovaries increased with 160 mg/kg vitamin E. However, 640 mg/kg vitamin E resulted in damaged hepatopancreas tubules and oocytes. The highest vitellogenin and vitellogenin receptor gene expressions were observed with 160 mg/kg vitamin E. These results provide evidence that dietary vitamin E with 80 and 160 mg/kg plays a positive impact on reproductive performance and antioxidant capacity of female shrimp.

Pseudocapacitive charge storage has been regarded as a promising mechanism to achieve both high specific energy and power energy storage devices. Some pseudocapacitive anode materials show great high-rate performance, however, it remains a significant challenge to develop the cathode ones. Herein, for the first time, we report a layered iron vanadate (Fe5V15O39(OH)9⋅9H2O, named as kazakhstanite) nanosheets (FeVO NSs) with featuring ultrathin layer thickness (

TiO2-MoO3 nanocomposites have been hydrothermally fabricated at 180 °C using (NH4)6Mo7O24 ⋅ 4H2O and TiCl4 as the Mo and Ti source, respectively. The TiO2 and MoO3 nanocrystalline can be confirmed in the products with the X-ray diffraction (XRD). Transmission electron microscopy (TEM) clear showed that the size of MoO 3 becomes smaller with the increase of the Ti-doping amount. The MoO3 was embraced by anatase TiO2 nanoparticles with an average size of 10 nm. The TiO2-MoO3 nanocomposites showed good adsorption activity for Rhodamine B (RhB) is approximately 290 mg g−1, Methylene blue (MB) and the Cr(VI) of heavy metal ion are 180 mg g−1 and 59 mg g−1, respectively.

The effect of cold acclimation on growth performance, non-specific immune responses, and expression level of HSP21 and CSP gene were studied in red claw crayfish (Cherax quadricarinatus) using a 4-week stress trial. We set a four-temperature gradient, with water temperatures of 25, 20, 15, and 9 °C, respectively. With the gradual decrease of temperature, the survival rate, feeding rate, and hepatopancreas index (HIS) of the red claw crayfish showed a decreasing trend. Decreased total hemocyte count (THC) and hemocyanin concentration were observed when water temperature decreased. The activities of superoxide dismutase (SOD) and total antioxidant capacity (T-AOC) in the hepatopancreas and hemolymph all gradually declined with decreasing temperatures and then significantly lowered at 9 °C compared with those at 25 °C. The activity of glutathione peroxidase (GPx) in these two tissues showed in the opposite trend, indicating that they may have different regulation mechanisms. A gradual increase of malondialdehyde (MDA) concentration was detected in the hepatopancreas and hemolymph when the temperature decreased. Low temperature stress also affected the expression of heat shock proteins 21(HSP21) and cold shock domain protein (CSP). These results indicate that cold acclimation may induce oxidative stress on the crayfish and then cause oxidative damage and hemocyte apoptosis, as well as immunosuppression in Cherax quadricarinatus, which may finally affect the growth and survival of Cherax quadricarinatus.

Cladocerans have been widely used as bioassay organisms to evaluate the impact of toxic substances. In this study, the activities of selected immunological enzymes and MDA level were investigated to characterizeDaphnia similoides’ immune response to ammonia stress. The activity of ACP and CAT showed no significant change during the test. The activity of AKP was significantly increased in the 0.19 and 0.38 mg/l NH3-N exposure groups after 6 h. After 24 h, a significant depression occurred in the high concentrations. After 24 h, significant decreases in SOD activity were observed at the concentrations of 0.38, 0.57 and 0.76 mg/l NH3-N. After 24 h, a significant change in MDA was also observed in 0.57 and 0.76 mg/l. These results suggest that changes in whole-body immune parameters ofDaphnia similoidesare effective to predict sub-lethal ammonia toxicity and useful as an early warning tool in monitoring studies of natural environments.

The fluoride anion (F−) sensing abilities of 1-hydroxyl-3,4,9,10-tetra (n-butoxyloxycarbonyl) perylene (probe 1) and 1-hydroxyl-mono-five-membered S-heterocyclic annulated tetra (n-butoxyloxycarbonyl) perylene (probe 2) were studied through visual detection experiments, UV-Vis, fluorescence, and 1H NMR titrations. The probes were sensitive and selective for distinguishing F− from other anions (Cl−, Br−, I−, SO4−, PF6−, H2PO4−, BF4−, ClO4−, OH−, CH3COO−, and HPO42−) through a change of UV-Vis and fluorescence spectra. The absorption and fluorescence emission properties of the probes arise from the intermolecular proton transfer (IPT) process between a hydrogen atom on the phenolic O position of probe and the F− anion. The sensing mechanism was supported by theoretical investigation. Moreover, probe-based test strips can conveniently detect F− without any additional equipment, and they can be used as fluorescent probes for monitoring F− in living cells.

Al2O3/carbon (Al2O3/C) composites obtained from the alkaline wastewater of oil refinery and acid wastewater of aluminum anodizing factory have been studied with the principle of “using waste to treat waste”. The process includes these steps: (1) acid-alkali neutralization, (2) evaporation, (3) calcination, (4) washing and drying. The Al2O3/C composites prepared by calcinating the precursors under Ar atmosphere are used as high-capacity adsorbents for removal of Pb(II) and Cd(II) from aqueous solutions. For Pb(II), the adsorptive behavior satisfies the Langmuir assumptions and the maximum adsorption capacity reaches to 709.2 mg g−1. For Cd (II), the adsorptive behavior satisfies the Freundlich assumptions and the equilibrium adsorption capacity is up to 1299.4 mg g−1. For single adsorption of Pb(II) and Cd(II), the adsorption kinetics follows Pseudo-second-order model well. This route shows a possible way of reducing emissions to the environment, recovering resource as a valuable material, and providing a novel strategy for wastewater treatment.

A type of switchable tertiary amine Gemini surfactant, N,N′-di(N,N-dimethyl propylamine)-N,N′-didodecyl ethylenediamine, was synthesized by two substitution reactions with 3-chloro-1-(N,N-dimethyl) propylamine, bromododecane and ethylene diamine as main raw materials. The structure of the product was characterized by FTIR and 1H-NMR. We also investigated the surface tension when CO2 was bubbled in different concentrations of surfactant solution and the influence of different CO2 volumes on surface tension under a constant surfactant concentration. Finally the surface tension curve and the related parameters were acquired by surface tension measurements. The experimental results showed that the structure of the synthesized compounds were in conformity with the expected structure of the surfactant, and displayed a better surface activity after bubbling CO2. The critical micelle concentration (CMC) surface tension at CMC (γ cmc) pC20 (negative logarithm of the surfactant’s molar concentration C20, required to reduce the surface tension by 20 mN/m) surface excess (Γ max) at air/solution interface and the minimum area per surfactant molecule at the air/solution interface (A min) were determined. Results indicate that the target product had good surface activity after bubbling CO2.

The simulation of bubbling fluidized beds (BFB) residence time distribution (RTD) based on the structure-based drag model are conducted for the single and binary gas-solid phases systems, a comparison of computed results with experimental data proves that our model is applicable to both systems with better accuracy. The revised drag coefficient (Hd) increases with decreasing the gas velocity or increasing the particle diameter. The increase of the feed rate could improve the solids flow pattern to be close to the plug flow, while increasing gas velocity or bed height would lead to a wider RTD. The particles in the binary mixture are in more diffusion-oriented movement so as to have less MRT (mean residence time) than that of the single system. The coarse particles with longer MRT are simulated to accumulate into the bed bottom with a slower vertical velocity.