Energy-Efficient Electrosynthesis of High Value-Added Active Chlorine Coupled with H2 Generation from Direct Seawater Electrolysis through Decoupling Electrolytes.

Direct saline (seawater) electrolysis is a well-recognized system to generate active chlorine species for the chloride-mediated electrosynthesis, environmental remediation and sterilization over the past few decades. However, the large energy consumption originated from the high cell voltage of traditional direct saline electrolysis system, greatly restricts its practical application. Here, we report an acid-saline hybrid electrolysis system for energy-saving co-electrosynthesis of active chlorine and H2. We demonstrate that this system just requires a low cell voltage of 1.59 V to attain 10 mA cm-2 with a large energy consumption decrease of 27.7 % compared to direct saline electrolysis system (2.20 V). We further demonstrate that such acid-saline hybrid electrolysis system could be extended to realize energy-saving and sustainable seawater electrolysis. The acidified seawater in this system can absolutely avoid the formation of Ca/Mg-based sediments that always form in the seawater electrolysis system. We also prove that this system in the half-flow mode can realize real-time preparation of active chlorine used for sterilization and pea sprout production.

Deep Learning Enhanced Electrochemiluminescence Microscopy.

Limited by the efficiency of electrochemiluminescence, tens of seconds of exposure time are typically required to get a high-quality image. Image enhancement of short exposure time images to obtain a well-defined electrochemiluminescence image can meet the needs of high-throughput or dynamic imaging. Here, we propose deep enhanced ECL microscopy (DEECL), a general strategy that utilizes artificial neural networks to reconstruct electrochemiluminescence images with millisecond exposure times to have similar quality as high-quality electrochemiluminescence images with second-long exposure time. Electrochemiluminescence imaging of fixed cells demonstrates that DEECL allows improvement of the imaging efficiency by 1 to 2 orders than usual. This approach is further used for a data-intensive analysis application, cell classification, achieving an accuracy of 85% with ECL data at an exposure time of 50 ms. We anticipate that the computationally enhanced electrochemiluminescence microscopy will enable fast and information-rich imaging and prove useful for understanding dynamic chemical and biological processes.

Nature-Derived Hollow Micron-Tubular Signal Tracers Conquering the Size Limitations for Multimodal Immunochromatographic Detection of Antibiotics.

Developing signal tracers (STAs) with large size, multifunctionality, and high retention bioaffinity is believed to be a potential solution for achieving high-performance immunochromatographic assays (ICAs). However, the size limitations of STAs on strips are always a challenge because of the serious steric hindrance. Here, based on metal-quinone coordination and further metal etching, hollow micron-tubular STAs formed by natural alizarin and Fe3+ ions (named ALIFe) are produced to break through size limitations, provide more active sites, and achieve three-mode ICAs (ALIFe STAs-ICAs). Thanks to the special tubular morphology, ALIFe can successfully pass through the strip and provide an ideal signal intensity within 7 min at low mAb and probe dosages to achieve stable ICA analysis. Importantly, ALIFe shows excellent antibody enrichment and bioaffinity retention capability. With a proof-of-concept for streptomycin, the ALIFe STAs-ICAs showed the limit of detection (LOD) at 0.39 ng mL-1 for colorimetric mode, 0.32 ng mL-1 for catalytic mode, and 0.016 ng mL-1 for photothermal mode with total recoveries ranging from 80.46 to 121.59% in mike and honey samples. We anticipate that our study will help expand the ideas for the design of high-performance STAs with large size and broaden the practical application of ICA.

KLF13 overexpression protects sepsis-induced myocardial injury and LPS-induced inflammation and apoptosis.

Sepsis remains a worldwide public health problem. This study aims to explore the role and mechanism of transcriptional factors (TFs) in sepsis-induced myocardial injury. Firstly, TF KLF13 was selected to explore its role in sepsis-induced myocardial injury. The caecal ligation and puncture (CLP) -induced sepsis mouse model was established and the septic mice were examined using standard histopathological methods. KLF13 expression was detected in the septic mouse heart and was also seen in a lipoploysaccharide (LPS) -induced cellular inflammation model. To explore this further both pro-apoptotic cleaved-caspase3/caspase3 and Bax levels and anti-apoptotic Bcl2 levels were examined, also in both models, In addition inflammatory cytokine (IL-1ß, TNF-α, IL-8 and MCP-1) production and IκB-α protein level and p65 phosphorylation were examined in both septic mice and LPS-induced cells. Thus three parameters - cardiomyocyte apoptosis, inflammatory response and NF-κB pathway activation were evaluated under similar conditions. The septic mice showed significant oedema, disordered myofilament arrangement and degradation and necrosis to varying degrees in the myocardial cells. KLF13 was downregulated in both the septic mouse heart and the LPS-induced cellular inflammation model. Furthermore, both models showed abnormally increased cardiomyocyte apoptosis (increased cleaved-caspase3/caspase and Bax protein levels and decreased Bcl2 level), elevated inflammation (increased production of inflammatory cytokines) and the activated NF-κB pathway (increased p65 phosphorylation and decreased IκB-α protein level). KLF13 overexpression notably ameliorated sepsis-induced myocardial injury in vivo and in vitro. KLF13 overexpression protected against sepsis-induced myocardial injury and LPS-induced cellular inflammation and apoptosis via inhibiting the inflammatory pathways (especially NF-κB signalling) and cardiomyocyte apoptosis.

[Droplet freeze-thawing system based on solid surface vitrification and laser rewarming].

Ultra-rapid cooling and rewarming rate is a critical technical approach to achieve ice-free cells during the freezing and melting process. A set of ultra-rapid solid surface freeze-thaw visualization system was developed based on a sapphire flim, and experiments on droplet freeze-thaw were carried out under different cryoprotectant components, volumes and laser energies. The results showed that the cooling rate of 1 µL mixed cryoprotectant [1.5 mol/L propylene glycol (PG) + 1.5 mol/L ethylene glycol (EG) + 0.5 mol/L trehalose (TRE)] could be 9.2×10 3 °C/min. The volume range of 1-8 µL droplets could be vitrified. After comparing the proportions of multiple cryoprotectants, the combination of equal proportion mixed permeability protectant and trehalose had the best vitrification freezing effect and more uniform crystallization characteristics. During the rewarming operation, the heating curve of glassy droplets containing gold nanoparticles was measured for the first time under the action of 400-1 200 W laser power, and the rewarming rate was up to the order of 10 6 °C/min. According to the droplet images of different power rewarming processes, the laser power range for ice-free rewarming with micron-level resolution was clarified to be 1 400-1 600 W. The work of this paper simultaneously realizes the ultra-high-speed temperature ramp-up, transient visual observation and temperature measurement of droplets, providing technical means for judging the ice free droplets during the freeze-thaw process. It is conducive to promoting the development of ultra-rapid freeze-thaw technology for biological cells and tissues.

Quantitative Single-Molecule Electrochemiluminescence Bioassay.

A single-molecule electrochemiluminescence bioassay is developed here which allows imaging and direct quantification of single biomolecules. Imaging single biomolecules is realized by localizing the electrochemiluminescence events of the labeled molecules. Such an imaging system allows mapping the spatial distribution of biomolecules with electrochemiluminescence and contains quantitative single-molecule insights. We further quantify biomolecules by spatiotemporally merging the repeated reactions at one molecule site and then counting the clustered molecules. The proposed single-molecule electrochemiluminescence bioassay is used to detect carcinoembryonic antigen, showing a limit of detection of 67 attomole concentration which is 10 000 times better than conventional electrochemiluminescence bioassays. This spatial resolution and sensitivity enable single-molecule electrochemiluminescence bioassay a new toolbox for both specific bioimaging and ultrasensitive quantitative analysis.

Etching-Assisted Route to Heterophase Au Nanowires with Multiple Types of Active Surface Sites for Silane Oxidation.

The construction of multiple types of active sites on the surface of a metallic catalyst can markedly enhance its catalytic activity toward specific reactions. Here, we show that heterophase gold nanowires (Au NWs) with multiple types of active surface sites can be synthesized using an etching-assisted process, yielding the highest reported turnover frequency (TOF) for Au catalysts toward the silane oxidation reaction by far. We use synchrotron powder X-ray diffraction (PXRD) and aberration-corrected (scanning) transmission electron microscopy (TEM) to show that the Au NWs contain heterophase structures, planar defects, and surface steps. Moreover, the contribution to the catalytic performance from each type of active sites was clarified. Surface steps on the Au NW catalysts, which were identified using aberration-corrected (scanning) TEM, were shown to play the most important role in enhancing the catalytic performance. By using synchrotron PXRD, it was shown that a small ratio of metastable phases within Au NWs can enhance catalytic activity by a factor of 1.35, providing a further route to improve catalytic activity. Of the three types of surface active sites, surface terminations of planar defects such as twin boundaries (TB) and stacking faults (SF) are less active than metastable phases and surface steps for Au catalysts toward the silane oxidation reaction. Such an etching-assisted synthesis of heterophase Au NWs promises to open new possibilities for catalysis, plasmonic, optics, and electrical applications.

Loss of Par1b/MARK2 primes microglia during brain development and enhances their sensitivity to injury.

BACKGROUND: Microglia, the resident immune cells of the brain, exhibit various morphologies that correlate with their functions under physiological and pathological conditions. In conditions such as aging and stress, microglia priming occurs, which leads to altered morphology and lower threshold for activation upon further insult. However, the molecular mechanisms that lead to microglia priming are unclear. METHODS: To understand the role of Par1b/MARK2 in microglia, we first expressed shRNA targeting luciferase or Par1b/MARK2 in primary microglial cells and imaged the cells using fluorescent microscopy to analyze for morphological changes. A phagocytosis assay was then used to assess functional changes. We then moved in vivo and used a Par1b/MARK2 knockout mouse model to assess for changes in microglia density, morphology, and phagocytosis using immunohistochemistry, confocal imaging, and 3D image reconstruction. Next, we used two-photon in vivo imaging in live Par1b/MARK2 deficient mice to examine microglia dynamics. In addition, a controlled-cortical impact injury was performed on wild-type and Par1b/MARK2-deficient mice and microglial response was determined by confocal imaging. Finally, to help rule out non-cell autonomous effects, we analyzed apoptosis by confocal imaging, cytokine levels by multiplex ELISA, and blood-brain barrier permeability using Evans Blue assay. RESULTS: Here, we show that loss of the cell polarity protein Par1b/MARK2 facilitates the activation of primary microglia in culture. We next found that microglia in Par1b/MARK2 deficient mice show increased density and a hypertrophic morphology. These morphological changes are accompanied with alterations in microglia functional responses including increased phagocytosis of neuronal particles early in development and decreased surveillance of the brain parenchyma, all reminiscent of a primed phenotype. Consistent with this, we found that microglia in Par1b/MARK2 deficient mice have a significantly lower threshold for activation upon injury. CONCLUSIONS: Together, our studies show that loss of Par1b/MARK2 switches microglia from a surveillant to a primed state during development, resulting in an increased neuroinflammatory response to insults.

NH2-MIL-53(Al) Metal-Organic Framework as the Smart Platform for Simultaneous High-Performance Detection and Removal of Hg2.

The worsening pollution due to mercury species makes it inevitable to explore prospective versatile materials, which not only can detect mercury ions (Hg2+) with high sensitivity but also possesses efficient capture and removal ability. In this study, a series of classic organic ligand-based luminescence MOFs materials with high oxidation state central metals (Al3+, Zr4+, Cr3+, Fe3+, and Ti4+) were synthesized and were screened to achieve simultaneously Hg2+ detection and removal through the strong coordination of amino groups or nitrogen centers with Hg2+ and the intrinsic fluorescence intensity of MOFs regulated by the ligand-to-metal charge transfer (LMCT) effect. Among these checked materials, NH2-MIL-53(Al) exhibited the excellent ability for Hg2+ detection with wide response interval (1-17.3 µM), low detection limit (0.15 µM), good selectivity, wide pH adaptation (4.0-10.0), and strong anti-interference ability. Meanwhile, the resultant NH2-MIL-53(Al) possessed an efficient removal capability toward Hg2+, accompanied by a fast uptake kinetics (within 60 min) and large loading capacity (153.85 mg g-1). Furthermore, NH2-MIL-53(Al) also displayed satisfactory stability before and after Hg2+ treatment because of the formation of strong coordination bonds between high oxidation state aluminum (Al3+) and organic carboxylate ligands. Notably, the prepared NH2-MIL-53(Al) had no significant loss of adsorption performance even after being reused four times. All of these superior properties render the smart NH2-MIL-53(Al) nanohexahedron a great potential for simultaneous Hg2+ detection and removal from water.

Portable Colorimetric Detection of Mercury(II) Based on a Non-Noble Metal Nanozyme with Tunable Activity.

The nanozyme-based strategy is currently one of the frontiers in the detection of toxic heavy metal ions. However, the utilization of noble metal free nanozymes to construct an economically and environmentally sustainable methodology remains largely unknown. Here, chitosan-functionalized molybdenum(IV) selenide nanosheets (CS-MoSe2 NS), greenly synthesized by an ionic liquid-assisted grinding method, were exploited for the colorimetric sensing of mercury ions (Hg2+). The sensing principle was based on the activating effect of Hg2+ on CS-MoSe2 NS nanozyme activities, triggered by the in situ reduction of chitosan-captured Hg2+ ions on a MoSe2 NS surface. Using 3,3',5,5'-tetramethylbenzidine (TMB) as a colorimetric indicator, the concentrations of activator-like Hg2+ ions could be quantitatively and selectively monitored, reaching a limit of detection of 3.5 nM with the ultraviolet-visible spectrophotometer. In addition, the integration system of CS-MoSe2 NS with a smartphone achieved a portable detection limit as low as 8.4 nM Hg2+ within 15 min and showed high specificity and anti-interfering ability over other ions and great practicability in real water and serum samples. The eco-friendly properties of such sensing system were also confirmed. This work emphasizes the rational portable assembly of biocompatible nanozymes like CS-MoSe2 NS for the field detection of Hg2+ in food, biological, and environmental samples.

Two-Dimensional Zeolitic Imidazolate Framework-L-Derived Iron-Cobalt Oxide Nanoparticle-Composed Nanosheet Array for Water Oxidation.

Rational design of various functional nanomaterials using MOFs as a template provides an effective strategy to synthesize electrocatalysts for water splitting. In this work, we reported that an iron-cobalt oxide with 2D well-aligned nanoflakes assembling on carbon cloth (Fe-Co3O4 NS/CC), fabricated by an anion-exchange reaction followed by an annealing process, could serve as a high-performance oxygen-evolving catalyst. Specifically, the zeolitic imidazolate framework-L-Co nanosheet array (ZIF-L-Co NS/CC) was synthesized through a facile ambient liquid-phase deposition reaction, and then reacted with [Fe(CN)6]3- ions as precursors during the anion-exchange reaction at room temperature. Finally, the Fe-Co3O4 NS/CC was obtained via annealing treatment. On account of the compositional and structural superiority, this 3D monolithic anode exhibited outstanding electrocatalytic performance with a low overpotential of 290 mV to obtain a geometrical current density of 10 mA cm-2 and good durability for water oxidation in base.

Surface Engineering of a Nickel Oxide-Nickel Hybrid Nanoarray as a Versatile Catalyst for Both Superior Water and Urea Oxidation.

Developing efficient and low-cost oxygen evolution reaction (OER) electrodes is a pressing but still challenging task for energy conversion technologies such as water electrolysis, regenerative fuel cells, and rechargeable metal-air batteries. Hence, this study reports that a nickel oxide-nickel hybrid nanoarray on nickel foam (NiO-Ni/NF) could act as a versatile anode for superior water and urea oxidation. Impressively, this anode could attain high current densities of 50 and 100 mA cm-2 at extremely low overpotentials of 292 and 323 mV for OER, respectively. Besides, this electrode also shows excellent activity for urea oxidation with the need for just 0.28 and 0.36 V (vs SCE) to attain 10 and 100 mA cm-2 in 1.0 M KOH with 0.33 M urea, respectively. The enhanced oxidation performance should be due to the synergistic effect of NiO and Ni, improved conductivity, and enlarged active surface area.

Conductive Leaflike Cobalt Metal-Organic Framework Nanoarray on Carbon Cloth as a Flexible and Versatile Anode toward Both Electrocatalytic Glucose and Water Oxidation.

Transition metal-organic frameworks (MOFs), on account of their unique inherent properties of large pore volume, high specific surface area, tunable pores, and good catalytic activity, have been highly regarded as superior catalysts recently for water electrolysis, supercapacitors, batteries, sensors, and so on. Herein, we report on a cobalt MOF phase with 3D well-aligned nanosheets array architecture on carbon cloth (Co-MOF NS/CC), fabricated by a facile ambient liquid-phase deposition, could serve as a self-standing Janus catalytic electrode toward both glucose and water oxidation. It shows good glucose-sensing performance with low determination limit and large detection range. Also, it exhibits high water-oxidation efficiency with low overpotential and good durability. This work demonstrates the potential of utilizing transition-metal based well-aligned MOF nanoarrays for electrocatalytic oxidation.

Development of a paper-based microfluidic analytical device by a more facile hydrophobic substrate generation strategy.

Microfluidic paper-based analytical devices (µPADs) have a significant potential in developing portable and disposable point-of-care testing (POCT). Herein, a facile, rapid, cost-effective and environment friendly strategy for µPADs fabrication is proposed. Specifically, the substrate paper was hydrophobized by coating with trimethoxysilane (TOS), and then the selected area was hydrophilized by treating with surfactant. The whole fabrication process was implemented within 7 min, with no need for complex pre-treatment, high-temperature and special equipment. As a proof-of-concept application, the as-prepared µPAD was applied to determination of the glucose content in human serum samples. The results agreed well with those obtained by a glucometer. We believe that the µPADs fabrication method proposed here could provide a facile, rapid and low-cost reference for other related studies.

Layered vanadium(IV) disulfide nanosheets as a peroxidase-like nanozyme for colorimetric detection of glucose.

The authors have discovered that vanadium disulfide (VS2) nanosheets, synthesized by a hydrothermal method, exert stable peroxidase-like activity. The catalytic activity, with H2O2 as a cosubstrate, follows Michaelis-Menten kinetics and varies with temperature, pH value and H2O2 concentration. Two-dimensional VS2 sheets acting as peroxidase (POx) mimics can replace horseradish peroxidase due to their availability, robustness, and reusability. The POx-like activity of VS2 sheets was exploited to design a colorimetric glucose assay by using 3,3',5,5'-tetramethylbenzidine as a substrate and by working at an analytical wavelength of 652 nm. The assay covers the 5 to 250 µM glucose concentration range with a 1.5 µM detection limit. It was applied to the analysis of glucose in fruit juice. In our perception, the peroxidase-like nanozyme out of the family of transition metal dichalcogenides presented here has a wide scope in that it may stimulate promising biocatalytic applications in biotechnology and analytical chemistry. Graphical abstract Layered VS2 nanosheets were prepared via hydrothermal synthesis and are shown to exert superior peroxidase-mimicking activity. Using these POx nano-mimics, a sensitive colorimetric assay for glucose was developed and applied to fruit juice analysis. This work unlocks the access of VS2 to biocatalysis and bioassays.

Cobalt phosphide nanowall arrays supported on carbon cloth: an efficient monolithic non-noble-metal hydrogen evolution catalyst.

Hydrogen has been considered as an ideal energy carrier for replacing fossil fuels to mitigate global energy crises. Hydrolysis of sodium borohydride (NaBH4) is simple and effective for hydrogen production but needs active and durable catalysts to accelerate the kinetics. In this paper, we demonstrate that cobalt phosphide nanowall arrays supported on carbon cloth (CoP NAs/CC) efficiently catalyze the hydrolytic dehydrogenation of NaBH4 with an activation energy of 42.1 kJ mol-1 in alkaline media. These monolithic CoP NAs/CC show a maximum hydrogen generation rate of [Formula: see text] and are robust with superior durability and reusability. They are also excellent in activity and durability for electrochemical hydrogen evolution in 1.0 M KOH, with the need of an overpotential of only 80 mV to drive 10 mA cm-2. They offer us a promising low-cost hydrogen-generating catalyst for applications.

Cobalt phosphide nanowires: an efficient electrocatalyst for enzymeless hydrogen peroxide detection.

In this letter, we demonstrate for the first time that cobalt phosphide nanowires (CoP NWs) exhibit remarkable catalytic activity toward electrochemical detection of hydrogen peroxide (H2O2). As an enzymeless H2O2 sensor, such CoP NWs show a fast amperometric response within 5 s and a low detection limit of 0.48 µM. In addition, this nonenzymatic sensor displays good selectivity, long-term stability and excellent reproducibility.

The inhibitory effect of selenium nanoparticles on protein glycation in vitro.

Selenium nanoparticles (Se NPs) possess well-known excellent biological activities and low toxicity, and have been employed for numerous applications except as inhibitors to protein glycation. Herein, the present study is carried out to investigate the inhibitory effect of Se NPs on protein glycation in a bovine serum albumin (BSA)/glucose system. By measuring the amount of glucose covalently bound onto BSA, the formation of fructosamine and fluorescent products, it is found that Se NPs can hinder the development of protein glycation in a dose-dependent but time-independent manner under the selected reaction conditions (55 °C, 40 h). And after comparing the increase of inhibitory rate in different stages, it is observed that Se NPs show the greatest inhibitory effect in the early stage, then in the advanced stage, but no effect in the intermediate stage. Fourier transform infrared spectroscopy characterization of Se NPs collected after glycation and determination of ·OH influence and glyoxal formation show that the mechanism for the inhibitory efficacy of Se NPs is related to their strong competitive activity against available amino groups in proteins, their great scavenging activity on reactive oxygen species and their inhibitory effect on α-dicarbonyl compounds' formation. In addition, it is proved that Se NPs protect proteins from structural modifications in the system and they do not exhibit significant cytotoxicity towards BV-2 and BRL-3A cells at low concentrations (10 and 50 µg mL(-1)). Consequently, Se NPs may be suitable for further in vivo studies as novel anti-glycation agents.

A G-quadruplex DNAzyme-based colorimetric method for facile detection of Alicyclobacillus acidoterrestris.

The rapid and sensitive detection of Alicyclobacillus acidoterrestris (AA) has become very important due to the frequent occurrence of fruit juice spoilage by AA. In the present study, using guaiacol, both as the metabolic product of AA related to its concentration and as a green colorimetric substrate of G-quadruplex DNAzyme, a novel G-quadruplex DNAzyme-based colorimetric method for a rapid detection of AA has been developed for the first time. Under optimal conditions, AA has been successfully detected in the concentration range of 10(2)-10(5) cfu mL(-1) with a detection limit of 85 cfu mL(-1). The recoveries ranging from 71.8% to 115.7% with relative standard deviation from 1.2% to 6.6% in spiked apple and orange juice samples were obtained. Results demonstrate that the sensitivity and precision of the developed method is comparable with most other analytical methods and is prominently rapid than them. We believe that the work provides a novel and effective approach and is beneficial for monitoring and reducing the risk of AA contaminations during the process of fruit juice production.