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Increasing the intrinsic conductivity of LiFePO4 can improve its electrochemical performance. Solving this problem can be achieved by P-site doping of LiFePO4 powder. Here, B-Mg co-doped LiFePO4 is successfully synthesized by solvothermal methods. The physical and electrochemical properties of all samples are systematically characterized with various characterization methods. In particular, proper B ion doping is determined to be beneficial to electronic conductivity, which induces the rearrangement of the PO43+ electron cloud. Also, doping with Mg can balance the problems of oxygen vacancies caused by doping B, thereby smoothing the transmission path of lithium ions, resulting in enhanced electrochemical performance. Moreover, XRD and SEM results illustrated that co-doping B and Mg do not change the LiFePO4 structure but promote the formation of a uniform and small particle. Compared with other samples, LiFeMg0.02P0.98B0.02O4 demonstrates superior electrochemical performance, which showed a specific discharge capacity of 147.4 mAh g−1 at 1 C and a corresponding capacity retention rate of 98.6% after 100 cycles. Even at 10 C, the discharge capacity still maintains 114.9 mAh g−1. The results of this work indicate that enhancing electronic conductivity and balancing oxygen vacancy are attributed to high electrochemical performance.

In this study, a nitrogen-doped 3D porous starch-derived carbon/SnO2/carbon (PSC/SnO2/C) composite is synthesized with porous starch as a carbon source by biological enzymatic hydrolysis. Compared with the traditional complex acid-base reagent method, the biological enzymatic method is more environmentally friendly and economical, and it can also naturally introduce nitrogen sources and dope the carbon layer. Many mesoporous nanostructures provide enough buffer space and promote the ions' and electrons’ transmission rate. The formation of the Sn–O–C bond between SnO2 and carbon ensures the stability of the structure. As a result, the PSC/SnO2/C composite exhibits a high initial discharge capacity (1802 mAhg−1 at 0.2 A g−1 for LIBs and 549 mAh g−1 at 0.1 A g−1 for SIBs) and good cycle stability (701 mAh g−1 at 0.2 A g−1 after 100 cycles for LIBs and 271 mAh g−1 at 0.1 A g−1 after 100 cycles for SIBs). This synthesis method can prepare other energy storage systems such as fuel cells, supercapacitors, and metal ion batteries.

Hydrochar a carbon-rich material resulting from hydrothermal carbonization of biomass, has received substantial attention because of its potential application in various areas such as carbon sequestration, bioenergy production and environmental amelioration. A series of hydrochars were prepared by metal chloride-assisted hydrothermal carbonization of rice husk and characterized by elemental analysis, zeta potential, X-ray diffraction, Brunauer–Emmett–Teller measurements, Fourier transform infrared spectroscopy, thermogravimetric analysis, X-ray photoelectron spectroscopy and scanning electron microscopy. The results reveal that the prepared hydrochars have carbon contents ranging from 45.01 to 58.71%, BET specific areas between 13.23 and 45.97 m2/g, and rich O-containing functional groups on the surfaces. The metal chlorides added in the feedwater could improve the degree of carbonization and show significant effects on the physical, chemical and adsorption properties of the hydrochars. The adsorption of the selected organics on the hydrochars is a spontaneous and physisorption-dominated process. The hydrochars possess larger adsorption capacities for 2-naphthol than for berberine hydrochloride and Congo red, and the modeling maximum adsorption capacities of 2-naphthol are in the range of 170.1–2680 mg/g. The adsorption equilibrium could be accomplished in 10, 40 and 30 min for 2-naphthol, berberine hydrochloride and Congo red, respectively. These results suggest metal chloride-assisted hydrothermal carbonization a promising method for converting biomass waste into effective adsorbents for wastewater treatment.

Ribulose-1,5-bisphosphate carboxylase/oxygenase (Rubisco), the key CO2-fixing enzyme in photosynthesis, is notorious for its low carboxylation. We report a highly active and assembly-competent Form II Rubisco from the endosymbiont of a deep-sea tubeworm Riftia pachyptila (RPE Rubisco), which shows a 50.5% higher carboxylation efficiency than that of a high functioning Rubisco from Synechococcus sp. PCC7002 (7002 Rubisco). It is a simpler hexamer with three pairs of large subunit homodimers around a central threefold symmetry axis. Compared with 7002 Rubisco, it showed a 3.6-fold higher carbon capture efficiency in vivo using a designed CO2 capture model. The simple structure, high carboxylation efficiency, easy heterologous soluble expression/assembly make RPE Rubisco a ready-to-deploy enzyme for CO2 capture that does not require complex co-expression of chaperones. The chemosynthetic CO2 fixation machinery of chemolithoautotrophs, CO2-fixing endosymbionts, may be more efficient than previously realized with great potential for next-generation microbial CO2 sequestration platforms.

Tryptophan 2,3-dioxygnease 2 (TDO2) is specific for metabolizing tryptophan to kynurenine (KYN), which plays a critical role in mediating immune escape of cancer. Although accumulating evidence demonstrates that TDO2 overexpression is implicated in the development and progression of multiple cancers, its tumor-promoting role in esophageal squamous cell carcinoma (ESCC) remains unclear. Here, we observed that TDO2 was overexpressed in ESCC tissues and correlated significantly with lymph node metastasis, advanced clinical stage, and unfavorable prognosis. Functional experiments showed that TDO2 promoted tumor cell proliferation, migration, and colony formation, which could be prevented by inhibition of TDO2 and aryl hydrocarbon receptor (AHR). Further experimentation demonstrated that TDO2 could promote the tumor growth of KYSE150 tumor-bearing model, tumor burden of C57BL/6 mice with ESCC induced by 4-NQO, enhance the expression of phosphorylated AKT, with subsequent phosphorylation of GSK3β, and polarization of M2 macrophages by upregulating interleukin-8 (IL-8) to accelerate tumor progression in the tumor microenvironment (TME). Collectively, our results discovered that TDO2 could upregulate IL-8 through AKT/GSK3β to direct the polarization of M2 macrophages in ESCC, and suggested that TDO2 could represent as an attractive therapeutic target and prognostic marker to ESCC., Graphical abstract TDO2 expressed in ESCC cells participates in the regulation of the immune response and constitutes potential target for immunotherapy.Image 1

β-Alanine (3-aminopropionic acid) is the only naturally occurring β-amino acid and an important precursor for the synthesis of a variety of nitrogen-containing chemicals. Fermentative production of β-alanine from renewable feedstocks such as glucose has attracted significant interest in recent years. Methanol has become an emerging and promising renewable feedstock for biomanufacturing as an alternative to glucose. In this work, we demonstrated the feasibility of β-alanine production from methanol using Pichia pastoris (Komagataella phaffii) as a methylotrophic cell factory. L-Aspartate-α-decarboxylases (ADCs) from different sources were screened and expressed in P. pastoris, followed by the optimization of aspartate decarboxylation by increasing the ADC copy number and C4 precursor supply via the overexpression of aspartate dehydrogenase. The production potential of the best strain was further evaluated in a 1-L fermenter, and a β-alanine titer of 5.6 g/L was obtained. To our best knowledge, this is the highest metabolite production titer ever reached in P. pastoris using methanol as the substrate. Graphic abstract

The nanopore approach holds the possibility for achieving single-molecule protein sequencing. However, ongoing challenges still remain in the biological nanopore technology, which aims to identify 20 natural amino acids by reading the ionic current difference with the traditional current-sensing model. In this paper, taking aerolysin nanopores as an example, we calculate and compare the current blockage of each of 20 natural amino acids, which are all far from producing a detectable current blockage difference. Then, we propose a modified solution conductivity of σ' in the traditional volume exclusion model for nanopore sensing of a peptide. The σ' value describes the comprehensive result of ion mobility inside a nanopore, which is related to but not limited to nanopore-peptide interactions, and the positions, orientations, and conformations of peptides inside the nanopore. The nanopore experiments of a short peptide (VQIVYK) in wild type and mutant nanopores further demonstrate that the traditional volume exclusion model is not enough to fully explain the current blockage contribution and that many other factors such as enhanced nanopore-peptide interactions could contribute to a dominant part of the current change. This modified sensing model provides insights into the further development of nanopore protein sequencing methods.

Objective: To systematically characterize the impurity profile in Daptomycin raw material by 2 Dimensional LC/MSn. Method: The target impurity was separated by first Dimensional HPLC and enriched by a 500μl loop, then desalted using the on-line second Dimensional HPLC and analyzed by MS detector in positive mode. Their structures were characterized based on the degradation mechanism and mass fragmentation regularity of the cyclic lipopeptide, as well as the molecular thermodynamic calculation. Results: A total of 12 impurities were characterized in the raw material, including 6 degradation products; 8 impurities are reported for the first time. The mass fragmentation regularities of 2 β-isomers of Asp residue were summarized. Conclusion: The structures of impurities in Daptomycin raw material, especially for β-isomer impurities, could be rapidly identified by on-line 2 Dimensional LC/MSn method together with the molecular thermodynamic calculation.

Endogenously eliminating the hematoma is a favorable strategy in addressing intracerebral hemorrhage (ICH). This study sought to determine the role of retinoid X receptor-α (RXR-α) in the context of hematoma absorption after ICH. Our results showed that pharmacologically activating RXR-α with bexarotene significantly accelerated hematoma clearance and alleviated neurological dysfunction after ICH. RXR-α was expressed in microglia/macrophages, neurons, and astrocytes. Mechanistically, bexarotene promoted the nuclear translocation of RXR-α and PPAR-γ, as well as reducing neuroinflammation by modulating microglia/macrophage reprograming from the M1 into the M2 phenotype. Furthermore, all the beneficial effects of RXR-α in ICH were reversed by the PPAR-γ inhibitor GW9662. In conclusion, the pharmacological activation of RXR-α confers robust neuroprotection against ICH by accelerating hematoma clearance and repolarizing microglia/macrophages towards the M2 phenotype through PPAR-γ-related mechanisms. Our data support the notion that RXR-α might be a promising therapeutic target for ICH.

Background and Objectives Obesity is the accumulation of adipose tissue caused by excess energy in the body, accompanied by long-term chronic low-grade inflammation of adipose tissue. More than 50% of interstitial cells in adipose tissue are macrophages, which produce cytokines closely related to insulin resistance. Macrophage biology is driven by two polarization phenotypes, M1 (proinflammatory) and M2 (anti-inflammatory). This study aimed to investigate the effect of gastric hormone des-acyl ghrelin (DAG) on the polarization phenotype of macrophages and elucidate the role of macrophages in adipose tissue inflammation and insulin sensitivity and its molecular mechanism. Methods Mice were subcutaneously administrated with DAG in osmotic minipumps. The mice were fed a normal diet or a high-fat diet (HFD). Different macrophage markers were detected by real-time revere transcription polymerase chain reaction. Results Exogenous administration of DAG significantly inhibited the increase of adipocyte volume caused by HFD and reduced the number of rosette-like structures in adipose tissue. HFD in the control group significantly increased M1 macrophage markers, tumor necrosis factor α (TNFα), and inducible NO synthase (iNOS). However, these increases were reduced or even reversed after DAG administration in vitro. The M2 markers, macrophage galactose type C-type Lectin-1 (MGL1), arginase 1 (Arg1), and macrophage mannose receptor 1 (MRC1) were decreased by HFD, and the downward trend was inhibited or reversed after DAG administration. Although Arg1 was elevated after HFD, the fold increase after DAG administration in vitro was much greater than that in the control group. Conclusion DAG inhibits adipose tissue inflammation caused by HFD, reduces infiltration of macrophages in adipose tissue, and promotes polarization of macrophages to M2, thus alleviating obesity and improving insulin sensitivity.

LiFePO4 has been widely considered as a promising cathode material for lithium ion batteries because of its nontoxicity, high specific capacity, good safety characteristics and low cost. However, the actual fabrication of LiFePO4 typically uses LiH2PO4, NH4H2PO4 or H3PO4 as phosphorus sources, possibly leading to the corrosion of the experimental facilities and release of toxic gas during the synthesis process. Hence, we use phytic acid (PhyA) as a new eco-friendly and sustainable phosphorus source to synthesize LiFePO4. Results show that the reaction time and temperature have significant effects on the morphology. LiFePO4 prepared at 180 °C for 4 h (LFP-4) shows unique hierarchical structure and exhibits best electrochemical performance over a wide test temperature (25–55 °C). Through time-dependent experiments to explore the reaction mechanism of LiFePO4, it is found that an intermediate Fe3(PO4)2 is produced that acts as the substrate for the subsequent preparation of LiFePO4. After carbon coating, LFP/C-4 (after carbon coating, LFP-4 labeled as LFP/C-4) shows an outstanding initial discharge capacity (156.9 mAh g−1, 1C at 25 °C) and high temperature behavior (147.1 and 126.8 mAh g−1 at 1C and 2C under 55 °C). This result is highly important for the controllable synthesis and improvement of electrochemical characteristics of LiFePO4 cathode material.

In the present study, the objective was to evaluate the effects of barley kernel size, grind level, and extract solvent on the antioxidant activities associated with total phenolic content and phenolic acid compositions. Three barley varieties (Kindred, Azure, and Tradition), were used and the results showed that with the exception of superoxide anion radical scavenging activity, thin kernel size fraction (2.0 mm) showed much higher antioxidant activities and total phenolic content than those in the 2.4 mm and 2.8 mm fractions when averaged across barley cultivar, grind level, and extract solvent. A similar trend was found for individual phenolic acid compositions among kernel sizes. Simple correlation analysis revealed that total phenolic content showed strong correlation with DPPH· scavenging activity, ABTS + scavenging activity, and reducing power. Generally, fine grind and 80% acetone extract showed averaged highest values in antioxidant activities, total phenolic content, and individual phenolic acid compositions. Stepwise linear regression showed that extract solvent was the most important factor for DPPH· scavenging activity, ABTS + scavenging activity, reducing power, and iron chelating activity. The sum of syringic acid and caffeic acid exhibited a dominant role in explaining the major variation in antioxidant activities except for superoxide anion radical scavenging activity.

Photorespiration consumes fixed carbon and energy generated from photosynthesis to recycle glycolate and dissipate excess energy. The aim of this study was to investigate whether we can use the energy that is otherwise consumed by photorespiration to improve the production of chemicals which requires energy input. To this end, we designed and introduced an isoprene synthetic pathway, which requires ATP and NADPH input, into the cyanobacterium Synechocystis sp. 6803. We then deleted the glcD1 and glcD2 genes which encode glycolate dehydrogenase to impair photorespiration in isoprene-producing strain of Synechocystis. Production of isoprene in glcD1/glcD2 disrupted strain doubled, and stoichiometric analysis indicated that the energy saved from the impaired photorespiration was redirected to increase production of isoprene. Thus, we demonstrate we can use the energy consumed by photorespiration of cyanobacteria to increase the energy-dependent production of chemicals from CO2.

Glyoxylate is an important chemical and is also an intermediate involved in metabolic pathways of living microorganisms. However, it cannot be rapidly utilized by many microbes. We observed a very long lag phase (up to 120 h) when E. coli is growing in a mineral medium supplemented with 50 mM glyoxylate. To better understand this strange growth pattern on glyoxylate and accelerate glyoxylate utilization, a random genomic library of E. coli was transformed into E. coli BW25113, and mutants that showed significantly shortened lag phase on glyoxylate were obtained. Interestingly, mutations in BtsT/BtsS, a two component system that is involved in pyruvate transport, were found to be a common feature in all mutants retrieved. We further demonstrated, through reverse engineering, that the mutations in BtsT/BtsS can indeed increase glyoxylate uptake. Growth experiments with different concentration of glyoxylate also showed the higher the concentration of glyoxylate, the shorter the lag phase. These new findings thus increased our understanding on microbial utilization of glyoxylate.

Background An efficient supply of reducing equivalent is essential for chemicals production by engineered microbes. In phototrophic microbes, the NADPH generated from photosynthesis is the dominant form of reducing equivalent. However, most dehydrogenases prefer to utilize NADH as a cofactor. Thus, sufficient NADH supply is crucial to produce dehydrogenase-derived chemicals in cyanobacteria. Photosynthetic electron is the sole energy source and excess electrons are wasted in the light reactions of photosynthesis. Results Here we propose a novel strategy to direct the electrons to generate more ATP from light reactions to provide sufficient NADH for lactate production. To this end, we introduced an electron transport protein-encoding gene omcS into cyanobacterium Synechococcus elongatus UTEX 2973 and demonstrated that the introduced OmcS directs excess electrons from plastoquinone (PQ) to photosystem I (PSI) to stimulate cyclic electron transfer (CET). As a result, an approximately 30% increased intracellular ATP, 60% increased intracellular NADH concentrations and up to 60% increased biomass production with fourfold increased d-lactate production were achieved. Comparative transcriptome analysis showed upregulation of proteins involved in linear electron transfer (LET), CET, and downregulation of proteins involved in respiratory electron transfer (RET), giving hints to understand the increased levels of ATP and NADH. Conclusions This strategy provides a novel orthologous way to improve photosynthesis via enhancing CET and supply sufficient NADH for the photosynthetic production of chemicals.

Fortuneicyclidins A (1) and B (2), a pair of epimeric pyrrolizidine alkaloids containing an unprecedented 7-azatetracyclo[5.4.3.0.02,8]tridecane core, were isolated from the seeds of Cephalotaxus fortunei, along with two biogenetically relative known analogues, 3 and 4. The structures were determined by multiple spectral techniques and chemical derivatization methods. Compound 1 showed inhibitory activity against α-glucosidase.

Nano-Si/MWCNTs composite was a representative solution to improve Si-based anode material’s rate performance in lithium-ion batteries (LIBs). However, the problems of easy agglomeration of silicon nanoparticles and carbon nanotubes hindered Si/MWCNT’s further development. In this study, we combine silicon nanoparticles with MWCNTs cleverly by utilizing freeze-drying method to solve the problems and enhance silicon-based material’s rate performance. Compared with Si-MWCNTs composite treated by electric blast-drying method, the rate performance of Si-MWCNTs treated by freeze-drying is significantly improved, especially at different current densities. When Si-MWCNTs are encapsulated in FPC (flour-derived porous carbon, FPC), the as-obtained Si-MWCNTs-PVPC-FPC-SC-1 (sucrose-derived carbon, SC) prepared by freeze-drying method delivers a reversible capacity of 1347.5 mAh g−1 at 0.1 A g−1 after cycling at 5 A g−1 and a reversible capacity of 501 mAh g−1 at 1 A g−1 after 500 cycles. Our study demonstrates that the freeze-drying method can solve the problems of easy agglomeration of silicon nanoparticles and MWCNTs as well as improve Si-based anode’s rate performance for LIBs. The synthetic route presented in this paper is low-cost and easy to scale up for silicon-carbon (Si/C) composites with high rate performance and long cycle life.

Biological carbon fixation has recently attracted global interest. Since reduction of CO2 is thermodynamically challenging, the aim of this review is to analyze the thermodynamic characteristics of ten natural, hybrid and synthetic carbon fixation pathways (CFPs), hoping to gain deeper insights into the biological carbon fixation. The changes of Gibbs free energy of each reaction involved in the ten CFPs were calculated and thoroughly analyzed. Six natural CFPs could be classified into energy-intensive and energy-saving categories. In general, CFPs in aerobic microorganisms are thermodynamically more feasible than those in anaerobic ones. Interestingly, the thermodynamically unfeasible step was not always consistent with the biological rate-limiting step, which was usually determined by the low activity of the enzyme. Moreover, the essentiality of combining the availability of intracellular ATP and reducing equivalents for carbon fixation was investigated from a thermodynamic perspective. Among all the CFPs analyzed, synthetic CFPs have smaller thermodynamic barriers and require less ATP input. Based on these comparative analyses, suggestions for designing and constructing more efficient CFPs were proposed.

Novel yellow to blackish green Ni-doped aluminium titanate (Al2TiO5) ceramic pigments were synthesized by solid-state reaction method at 1400 ?C. Effects of nickel doping content on phase composition, microstructure, optical properties and stability were studied. The results show that the higher content of Al2TiO5 phase and the reduction of the lattice distortion of aluminium titanate could be attributed to the entry of nickel ions into aluminium titanate lattice resulting in the formation of solid solution. Ni-doped aluminium titanate ceramic pigments show exceptional glaze colouring and are expected to be promising high-temperature pigments.

An atom- and step-economic multi-component cobalt-catalyzed synthesis of amidines has been reported by using amines, isocyanides, and diazo compounds as carbene sources. This protocol provides a synthetically simple, highly efficient strategy for the straightforward synthesis of functionalized amidines with a range of substrates.

Decorating a high-efficiency oxygen evolution reaction (OER) electrocatalyst as a cocatalyst on an α-Fe2O3 photoanode is known to be one of the most efficient methods to improve the photoelectrochemical (PEC) water oxidation activity. In our work, different from traditional methods of transition metal sulfide cocatalyst synthesis, an NiFeSx–decorated Ti-Fe2O3 photoanode is synthesized through a simple one-step electrodeposition method, which benefits the interface between Ti-Fe2O3 and NiFeSx. With the help of this excellent OER electrocatalyst, the photocurrent density of the NiFeSx–Ti-Fe2O3 photoanode rises to 3 mA cm−2 at 1.23 V vs. RHE, which is 2.5 times greater than the photocurrent of Ti-Fe2O3. Moreover, the onset potential of NiFeSx–Ti-Fe2O3 shifts negatively by 170 mV compared with that of pure Ti-Fe2O3. Furthermore, surface photovoltage spectroscopy (SPV) and transient photovoltage (TPV) techniques and photoelectrochemical impedance spectroscopy (PEIS) were used to analyze the true effects of NiFeSx as an efficient cocatalyst for enhancing the PEC performance of the NiFeSx–Ti-Fe2O3 photoanode. This work provides a simple method for loading a low-cost and efficient cocatalyst to modify a Ti-Fe2O3 photoanode for the PEC water oxidation reaction.

Targeted proteomics has advantages over earlier conventional technologies for protein detection. We developed and validated an LC/MRM-MS-based targeted proteomic method combined with immunoaffinity precipitation for the enrichment and detection of low abundance chemerin isoforms in human biofluids. After tryptic digestion, each chemerin isoform was characterized by isoform-specific peptides, and the absolute quantification was achieved by using stable isotope-labeled peptides as internal standards. In serum, follicular fluid and synovial fluid, a total of 6 chemerin isoforms were identified and quantified, among which a novel natural isoform 153Q was discovered for the first time. The relative content of the six chemerin isoforms in human serum was 157S ≫ 156F ≫ 158K > 154F ≥ 155A > 153Q in the ratio of 25:17:5:2.5:2.2:1, respectively. The absolute contents were in the range of 88–3.5 ng/mL. This distribution remained consistent among the 3 biofluids analyzed. Total chemerin were found to be increased in both polycystic ovary syndrome (serum and follicular fluid) and rheumatoid arthritis (serum) patients. However, chemerin isoform analysis revealed that only 156F & 157S were increased in the former, while 155A, 156F & 157S were increased in the latter. This demonstrates the potential of this method in detailed characterization of changes in chemerin isoforms that may be of clinical relevance.

Background To investigate the odonto-immunomodulatory properties of dental pulp stem cell-derived small extracellular vesicles (DPSCs-sEV), which promote odontogenesis by switching macrophages toward the pro-healing M2 phenotype. Methods MicroRNA sequencing was carried out for microRNA profiling of DPSCs-sEV. Automated Western blot, qPCR, ELISA, and flow cytometry were performed to identify the functions of microRNA-enriched DPSCs-sEV in macrophages. A luciferase reporter gene assay was carried out to confirm exosomal miR-125a-3p’s direct target gene. DPSCs-sEV-stimulated macrophage-conditioned media were used to promote odontogenesis in DPSCs and explore the mechanism of immune response in DPSCs-SEV-stimulated odontogenesis. DPSCs-sEV were injected into the exposed pulp tissue of rat incisor to investigate the odonto-immunomodulatory properties of DPSCs-sEV in vivo. Results DPSCs-sEV switched macrophages to the pro-healing M2 phenotype by inhibiting TLR and NFκΒ signaling. MicroRNA sequencing found 81 microRNAs significantly altered in DPSCS-sEV, with miR-125a-3p showing a 12-fold upregulation. Exosomal miR-125a-3p switched macrophages toward the M2 phenotype via inhibiting NFκΒ and TLR signaling via direct IKBKB targeting. Interestingly, DPSCs-sEV and the encapsulated miR-125a-3p enhanced BMP2 release in macrophages, promoting odontogenesis in DPSCs through BMP2 pathway activation. The rat study confirmed that DPSCs-sEV could be used as ideal biomimetic tools to enhance odontogenesis by switching macrophages toward pro-healing M2 cells. Conclusions We firstly defined the odonto-immunomodulatory properties of microRNA-enriched DPSCs-sEV, which could be used as ideal biomimetic tools to enhance odontogenesis by switching macrophages toward the pro-healing M2 phenotype.

A highly sensitive and label-free fluorescence carcinoembryonic antigen (CEA) biosensor was developed via the target-triggered enzymatic recycling amplification reaction. To design this strategy, aggregation induced emission fluorogen (AIEgen) TPE-M was chosen as a signal reporter to enhance the detection efficiency, and L-cysteine (L-Cys) was utilized as a reactant to control over the fluorescence intensity due to its distinct capability of reacting with TPE-M and hemin/G-quadruplex. CEA triggered the in-situ generation of abundant hemin/G-quadruplex through polymerase/nicking enzyme-assisted recycling amplification, and the generated hemin/G-quadruplex could catalyze destruction of L-Cys. With L-Cys consuming, a significant decrease in fluorescence intensity was observed, demonstrating that the fluorescence intensity was indirectly relied on the CEA amount. As a consequence, a facile, precise and sensitive strategy for CEA assay was readily realized. Furthermore, the detection limit was 0.033 fmol/L (S/N = 3). The developed AIEgen-based biosensor provided a new method for the sensitive and reliable detection of CEA in biological liquids, thus displaying a significant promise for the CEA-related disease diagnosis.

The Shitoukengde Cu-Ni deposit is located in the eastern part of the East Kunlun Orogenic Belt (EKOB). The overall complex underwent emplacement into the surrounding rock, including the gneiss and marble. The ore-bodies exist in complex I, which is composed of peridotite, pyroxenite, and gabbro. The petrogeochemical characteristics of the rocks show that the m/f values range from 1.93 to 5.97, and the Fe3+/ΣFe ratios of the spinel are < 0.3, indicating that the Shitoukengde complexes have the potential to form a Cu-Ni ore deposit. Based on the evidence of marble and gneiss xenoliths, there are higher CaO and Al2O3 contents in the peridotite and pyroxene, there are Nb and Ta depletions, in the Shitoukengde; these results indicate that the ore-forming parental magma has been obviously contaminated by crustal material during the evolution process and that the materials responsible for the contamination mainly originated from the middle-upper crust. The mafic-ultramafic complex, which is closed to marble, has higher CaO and Al2O3 contents; higher (87Sr/86Sr)i values and lower Ni contents; thus, it is reasonable to infer that the Shitoukengde mafic-ultramafic rocks assimilated some marble, and the contamination of marble without sulfide suppresses the sulfide saturation. The pyroxenite with better mineralization is mainly orthopyroxene, and the increase in the sulfur isotope values in the pyroxenite and peridotite is accompanied by an increase in the Ni content; these results suggest that the SiO2 and S of biotite-plagioclase gneisses, especially the S addition, were important for the Shitoukengde intrusion to reach sulfide saturation. The whole-rock Ni content in the peridotite shows a positive relationship with the FeO content of spinel, indicating that the crystallization of spinel has little effect on sulfide saturation. The capable of crystallizing olivine with Fo content as high as 89.3 mol% and olivine Fo value exhibits a positive relationship with the olivine NiO content, indicating that olivine fractional crystallization did not play a significant role in sulfide saturation. The δ34SV-CDT value of the giant Xiarihamu deposit is much higher than that of Shitoukengde. The degree of crustal S contamination is probably responsible for the difference in the scale and ore grade of the Cu-Ni sulfide deposits in the East Kunlun area. The above indicators could guide the exploration and evaluation of similar deposits in the EKOB.

The simultaneous occurrence of multiple heterogeneous DNA phosphorylation statuses, which include 5' end phosphorylation, 5' end dephosphorylation, 3' end phosphorylation, and 3' end dephosphorylation, is crucial for regulating numerous cellular processes. Although there are many methods for detecting a single type of DNA phosphorylation, the direct and simultaneous identification of DNA phosphorylation/dephosphorylation on the 5' and/or 3' ends remains a challenge, let alone the unveiling of the heterogeneous catalysis processes of related phosphatases and kinases. Taking advantage of the charge-sensitive aerolysin nanopore interface, herein, an orientation-dependent sensing strategy is developed to enhance phosphorylation-site-dependent interaction with the nanopore sensing interface, enabling the direct and simultaneous electric identification of four heterogeneous phosphorylation statuses of a single DNA. By using this strategy, we can directly evaluate the heterogeneous dephosphorylation process of alkaline phosphatase (ALP) at the single-molecule level. Our results demonstrate that the ALP in fetal bovine serum preferentially catalyzes the 3' phosphate rather than both ends. The quantification of endogenous ALP activity in fetal bovine serum could reach the submilli-IU/L level. Our aerolysin measurements provide a direct look at the heterogeneous phosphorylation status of DNA, allowing the unveiling of the dynamic single-molecule functions of kinase and phosphatase.

Via using a mixed-ligand method, two novel coordination polymers based on Cu(II) ions as nodes {[Cu(Py2TTz)0.5(2,6-ndc)]·(DMF)·(C2H5OH)}n (1, Py2TTz = 2,5‐Bis(4‐pyridyl)thiazolo[5,4‐d]thiazole, 2,6-H2ndc = 2,6-naphthalenedicarboxylic acid) and [Cu2(2,6-ndc)2(4-bpdb)·(H2O)3·2DMF]n (2, 4-bpdb = 1,4-bis(4-pyridyl)-2,3-diaza-1,3-butadiene) were prepared under the solvothermal conditions. In addition, complexes 1 and 2 could be applied as a photocatalysts under ultraviolet light, the degradation property of methylene blue is relatively high. In the research of biological function, the protective activity of compound 1 and compound 2 was assessed. First of all, the accumulation of reactive oxygen species (ROS) in thyroid cancer cells was detected by ROS detection kit. Then, Annexin V-FITC/PI method was used to detect the percentage for thyroid cancer cells apoptosis after treated by compound.

Fatty acid oxidation (FAO) dysfunction is one of the important mechanisms of renal fibrosis. Sirtuin 3 (Sirt3) has been confirmed to alleviate acute kidney injury (AKI) by improving mitochondrial function and participate in the regulation of FAO in other disease models. However, it is not clear whether Sirt3 is involved in regulating FAO to improve the prognosis of AKI induced by cisplatin. Here, using a murine model of cisplatin‐induced AKI, we revealed that there were significantly FAO dysfunction and extensive lipid deposition in the mice with AKI. Metabolomics analysis suggested reprogrammed energy metabolism and decreased ATP production. In addition, fatty acid deposition can increase reactive oxygen species (ROS) production and induce apoptosis. Our data suggested that Sirt3 deletion aggravated FAO dysfunction, resulting in increased apoptosis of kidney tissues and aggravated renal injury. The activation of Sirt3 by honokiol could improve FAO and renal function and reduced fatty acid deposition in wide‐type mice, but not Sirt3‐defective mice. We concluded that Sirt3 may regulate FAO by deacetylating liver kinase B1 and activating AMP‐activated protein kinase. Also, the activation of Sirt3 by honokiol increased ATP production as well as reduced ROS and lipid peroxidation through improving mitochondrial function. Collectively, these results provide new evidence that Sirt3 is protective against AKI. Enhancing Sirt3 to improve FAO may be a potential strategy to prevent kidney injury in the future.

Highly conductive cathode material with enhanced Na+ diffusion kinetics is of great importance in the exploration of sodium ion batteries. In this work, Na0.91MnO2 porous microcube which is coated with highly conductive polypyrrole (PPy) is obtained. The high Na content in the layered sodium manganate oxide brings about wider interlayer distance resulting in high capacity and electrochemical kinetics. The higher sodium content of Na0.91MO2 makes capacity increase up to 50 mAh g-1 compared with Na0.7MnO2.05. Furthermore, the well-designed combination between porous structure and conductive PPy coating exhibits fast ion/electron transfer inside the electrode and high cycling stability. The PPy coated Na0.91MnO2 delivers a high initial capacity of 208 mAh g-1, encouraging capacity retention and rate capability. Based on the porous Na0.91MnO2@PPy cathode, the sodium ion full cells with puffed millet porous carbon anode show remarkably stable cycling and high-rate performances.

The gem-difluoroalkanes widely exist in pharmaceuticals, agrochemicals and materials. Reported herein is a facile synthesis of tosyloxylated gem-difluoroalkanes via an oxidative fluorination of readily available vinyl sulfonates. An intriguing [2,3]-sulfonyloxy migration is involved as a key step. The OTs group in the product enables a divergent and modular synthesis of a wide variety of functionalized gem-difluoroalkanes via reliable SN2 reactions. Notable features of this protocol include mild reaction conditions, high efficiency and remarkably good functional-group tolerance.

Aggregation-induced emission luminogens (AIEgens) with a large electron donor and acceptor (D-A) conjugated system have been widely used in the development of organic light emitting diodes (OLEDs), chemosensors, and bioimaging materials due to their excellent properties such as high quantum yields, long emission wavelengths, controllable luminescence lifetimes, and nonlinear optics (NLO) properties. However, most of the AIE materials have been derived from limited classic AIE cores such as tetraphenylethene (TPE) and tetraphenylpyrazine (TPP), and thus, tedious syntheses or later modifications toward those AIEgens have always been unavoidable. In this report, a type of atypical AIEgens (designated as ASIQs) composed of large conjugated structures with a natural electron D-A system is disclosed, which shows large Stokes shifts, high photostabilities, excellent cell permeabilities, low biotoxicities, and good two-photon excited capacities, making them suitable for applications of one-photon/two-photon targeted imaging in live cells. In short, this work offers a type of atypical AIEgens which will possibly become an ideal platform leading to more structurally diverse and functionally excellent AIE-based luminescent materials.

Multidrug resistance (MDR) efflux pumps are involved in bacterial intrinsic resistance to multiple antimicrobials. Expression of MDR efflux pumps can be either constitutive or transiently induced by various environmental signals, which are typically perceived by bacterial two-component systems (TCSs) and relayed to the bacterial nucleoid, where gene expression is modulated for niche adaptation. Here, we demonstrate that RstA/RstB, a TCS previously shown to control acid-induced and biofilm-related genes in Escherichia coli, confers resistance to multiple antibiotics in Pseudomonas fluorescens by directly regulating the MDR efflux pumps EmhABC and MexCD-OprJ. Moreover, we show that phosphorylation of the conserved Asp52 residue in RstA greatly enhances RstA-DNA interaction, and regulation of the multidrug resistance by RstA/RstB is dependent on the phosphorylation of the RstA Asp52 residue by RstB. Proteome analysis reveals RstA/RstB also positively regulates the efflux pump MexEF-OprN and enzymes involved in anaerobic nitrate respiration and pyoverdine biosynthesis. Our results suggest that, by coupling the expression of multiple efflux pumps and anaerobic nitrate respiration, RstA/RstB could play a role in defense against nitrosative stress caused by anaerobic nitrate respiration. IMPORTANCE Microenvironmental hypoxia typically increases bacterial multidrug resistance by elevating expression of multidrug efflux pumps, but the precise mechanism is currently not well understood. Here, we showed that the two-component system RstA/RstB not only positively regulated expression of several efflux pumps involved in multidrug resistance, but also promoted expression of enzymes involved in anaerobic nitrate respiration and pyoverdine biosynthesis. These results suggested that, by upregulating expression of efflux pumps and pyoverdine biosynthesis-related enzymes, RstA/RstB could play a role in promoting bacterial tolerance to hypoxia by providing protection against nitrosative stress.

Diabetes and cognitive dysfunction are highly prevalent disorders, while the underlying mechanism is still elusive. The effects of Gastrodin on central nervous system have been emphasized recently. In this study, we aim to explore the potential mechanism leading to cognitive dysfunction in diabetes and the therapeutic effect of Gastrodin. Diabetes was induced by a single injection of streptozotocin. RNA sequencing technique was used to identify the potential factors involved. Western blot and immunofluorescence were applied to detect the protein expression. Our results have shown that spatial learning was impaired and hippocampal pyramidal neurons were damaged in diabetic rats, which could be ameliorated by Gastrodin intervention. Transcriptional analysis identified differential expression genes, which were confirmed by qPCR and western blot. Furthermore, p21 activated kinase 2 (PAK2) was selected and its inhibitor could promote the survival of primary hippocampal neurons. It suggested that PAK2 pathway may be involved in cognitive dysfunction in diabetes and a therapeutic target for Gastrodin intervention.