Co-compartmentalization of Enzymes and Cofactors within Pickering Emulsion Droplets for Continuous-Flow Catalysis.

Co-immobilization of enzymes and cofactors in a manner suitable for use in continuous flow catalysis remains a great challenge because of the difficulty in ensuring the free accessibility of immobilized enzymes and cofactors. Herein, we present a continuous flow catalysis system based on co-compartmentalization of enzymes and cofactors within Pickering emulsion droplets, enabling regeneration of cofactors within the droplets. As exemplified by enzyme-catalyzed ketone enantioselective reduction and enantioselective transamination, our systems exhibit long-term stability (300-400 h), outstanding total turnover number (TTN, 59204 mol mol-1 ) and several-fold enhancement in the enzyme catalytic efficiency (CEe ) in comparison to conventional biphasic reactions. As well as giving insight into the co-compartmentalization effects, our system will provide the opportunity to significantly advance continuous-flow biocatalysis towards the level of practical applications.

A Facile Strategy to Construct Silver-Modified, ZnO-Incorporated and Carbon-Coated Silicon/Porous-Carbon Nanofibers with Enhanced Lithium Storage.

For Si anode materials used for lithium ion batteries (LIBs), developing an effective solution to overcome their drawbacks of large volume change and poor electronic conductivity is highly desirable. Here, the composites of ZnO-incorporated and carbon-coated silicon/porous-carbon nanofibers (ZnO-Si@C-PCNFs) are designed and synthesized via a traditional electrospinning method. The prepared ZnO-Si@C-PCNFs can obviously overcome these two drawbacks and provide excellent LIB performance with excellent rate capability and stable long cycling life of 1000 cycles with reversible capacity of 1050 mA h g-1 at 800 mA g-1 . Meanwhile, anodes of ZnO-Si@C-PCNFs attached with Ag particles display enhanced LIB performance, maintaining an average capacity of 920 mA h g-1 at a large current of 1800 mA g-1 even for 1000 cycles with negligible capacity loss and excellent reversibility. In addition, the assembling method with important practical significance for a simple pouch full cell is designed and used to evaluate the active materials. The Ag/ZnO-Si@C-PCNFs are prelithiated and assembled in full cells using LiNi0.5 Co0.2 Mn0.3 O2 (NCM523) as cathodes, exhibiting higher energy density (230 W h kg-1 ) of 18% than that of 195 W h kg-1 for commercial graphite//NCM523 full pouch cells. Importantly, the comprehensive mechanisms of enhanced electrochemical kinetics originating from ZnO-incorporation and Ag-attachment are revealed in detail.

Fluorescent Biomass-Based Platform for Detection of ClO- in Cells and Water-Soluble Systems.

The generation and presence of excessive hypochlorous acid derivative ionic form (ClO-) could cause various diseases, such as arteriosclerosis, DNA damage, and cardiovascular illness. It is a critical need to develop a highly sensitive sensor for reliable detection of ClO- in cells and water-soluble systems. In this work, a hydroxyl group has been introduced into the compound 2-amino-3-(((E)-4-(2-(2-(2-hydroxyethoxy)ethyl)-1,3-dioxo-2,3-dihydro-1H-benzo[de]isoquinolin-6-yl)benzylidene)amino)maleonitrile (NDC) to increase its solubility in water, at the same time, the hydrazone unit was designed as a specific recognition group for the "off-on" fluorescence probe of ClO-. The probe NDC presents high selectivity, sensitivity, anti-interference, and low detection limit (67 nM) for ClO-. The recognition mechanism that ClO- breaks the C=N bond and forms the fluorescent compound 4-(2-(2-(2-hydroxyethoxy)ethyl)-1,3-dioxo-2,3-dihydro-1H-benzo[de]isoquinolin-6-yl)benzaldehyde (ND-3) has been confirmed by time-of-flight mass spectrometry. The probe NDC presents a good performance in the actual test of water samples and can be designed as the test papers for the quick and convenient detection of ClO- range from 0 to 1 µM. Moreover, the practical application was demonstrated by the successful imaging of endogenous and exogenous ClO- in HeLa cells. Our fluorescent biomass-based platform opens vast possibilities for repeatability, sensitivity, and selectivity detection of ClO- in cells and water-soluble systems.

Drying Acoustically Levitated Droplets as Signal-Amplifying Platforms for Ultrasensitive and Multimode Laser Sensing.

Ultrasensitive sensing to trace atomic and molecular analytes has gained interest for its intimate relation to industrial sectors and human lives. One of the keys to ultrasensitive sensing for many analytical techniques lies in enriching trace analytes onto well-designed substrates. However, the coffee ring effect, nonuniform distribution of analytes onto substrates, in the droplet drying process hinders the ultrasensitive and stable sensing onto the substrates. Here, we propose a substrate-free strategy to suppress the coffee ring effect, enrich analytes, and self-assemble a signal-amplifying (SA) platform for multimode laser sensing. The strategy involves acoustically levitating and drying a droplet, mixed with analytes and core-shell Au@SiO2 nanoparticles, to self-assemble an SA platform. The SA platform with a plasmonic nanostructure can dramatically enrich analytes, enabling enormous spectroscopic signal amplification. Specifically, the SA platform can promote atomic detection (cadmium and chromium) to the 10-3 mg/L level by nanoparticle-enhanced laser-induced breakdown spectroscopy and can promote molecule detection (rhodamine 6G) to the 10-11 mol/L level by surface-enhanced Raman scattering. All in all, the SA platform, self-assembled by acoustic levitation, can intrinsically suppress the coffee ring effect and enrich trace analytes, enabling ultrasensitive multimode laser sensing.

Insertable, Scabbarded, and Nanoetched Silver Needle Sensor for Hazardous Element Depth Profiling by Laser-Induced Breakdown Spectroscopy.

Sensing of hazardous metals is urgent in many areas (e.g., water pollution and meat products) as heavy metals threaten people's health. Laser-induced breakdown spectroscopy (LIBS), as a rapid, in situ, and multielemental analytical technique, has been widely utilized in rapid hazardous heavy metal sensing. However, loose and water-containing samples (e.g., meat, plant, and soil) are hard to analyze by LIBS directly, and heavy metal depth profiling for bulk samples remains suspenseful. Here, inspired by the Needle, the sword of Arya Stark in Game of Thrones, we propose an insertable, scabbarded, and nanoetched silver (NE-Ag) needle sensor for rapid hazardous element sensing and depth profiling. The NE-Ag needle sensor features a micro-nanostructure surface for inserting into the bulk sample and absorbing hazardous analytes. For accurate elemental depth profiling, we design a stainless-steel scabbard to wrap and protect the NE-Ag needle from pollution (unexpected contaminant absorption) during the needle insertion and extraction process. The results for cadmium (Cd) show that the relative standard deviation equals to 6.7% and the limit of detection reaches 0.8 mg/L (ppm). Furthermore, the correlations (Pearson correlation coefficient) for Cd and chromium (Cr) depth profiling results are no less than 0.96. Furthermore, the total testing time could be less than 1 h. All in all, the insertable and scabbarded NE-Ag needle senor has high potential in rapid hazardous heavy metal depth profiling in different industries.

Multi-heterostructured SnO2/SnSx embedded in carbon framework for high-performance sodium-ion storage.

Heterostructure materials, as newborn electrode materials for rechargeable batteries, are attracting increasing attention due to their robust architectures and superior electrochemical performances. It is widely believed that the inner electric field induced at the interface can improve the electric conductivity and ion diffusion kinetics, thus enhancing the long-term stability and high-rate performance of the batteries. Although much progress is made on heterostructure construction, the performance of the batteries is still far from satisfying the commercial applications. In this work, a new type of SnO2/SnSx (x = 1, 1.5) heterostructure embedded in carbon framework (C@SnO2/SnSx) is constructed via a facile sulfidation process. Compared to a single heterojunction, the multi-heterojunctions generated at SnO2/SnSx interface can induce an intensified built-in electric field, which promotes charge transportation and reaction kinetics of the electrode for Na-ions storage. Upon the sodiation process, the induced intensified electric field drives Na ions from Sn2S3 or SnO2 to SnS, while an inverse transportation of Na ions are accelerated upon the desodation process. As a result, C@SnO2/SnSx exhibits an outstanding reversible capacity of 510 mA h g-1 after 300 cycles at 200 mA g-1.

Stable and ultrasensitive analysis of organic pollutants and heavy metals by dried droplet method with superhydrophobic-induced enrichment.

Herein, a dried droplet method (DDM) with superhydrophobic-induced enrichment is reported for stable and ultrasensitive analysis of organic pollutants and heavy metals. A superhydrophobic (SHB) substrate was prepared as an analytical detection platform for the DDM. This SHB substrate was synthesized by sequentially coating polydimethylsiloxane (PDMS) and titanium dioxide nanoparticles (TiO2 NPs) onto glass substrate surface. In the droplet drying process, the SHB substrate was demonstrated to suppress the coffee ring effect (CRE) and enriched analyte concentration. Combining with Raman spectroscopy for analysis of methylene blue (MB), and with laser-induced breakdown spectroscopy (LIBS) for analysis of chromium (Cr), the results indicated high stability and ultra-sensitivity for organic pollutants and heavy metals detection. Overall, the DDM with superhydrophobic-induced enrichment has big potential in applications requiring stable and ultrasensitive analysis.

Synthesis and in-vitro anti-hepatitis-B virus activity of 6H-[1]benzothiopyrano[4,3-b] quinolin-10-ols.

A series of 9-methoxy-6H-[1]benzothiopyrano[4,3-b]quinolin-10-ols with a Mannich side chain were synthesized and evaluated for their anti-Hepatitis B virus (HBV) activity in HepG2.2.15 cells. Some compounds showed significant anti-HBV activity with IC(50) values less than 41 microM. Among them, compound 9b was the most effective anti-HBV agent (IC(50) = 1.7 microM, SI = 60.3).

Bottom-up synthesis of iron and nitrogen dual-doped porous carbon nanosheets for efficient oxygen reduction.

Iron and nitrogen co-doped porous carbon nanosheets (Fe,N-PCNs) with a small thickness, smooth surface and high specific surface area are fabricated by a facile bottom-up approach as highly efficient noble metal-free catalysts for the oxygen reduction reaction (ORR). The Fe,N-PCN catalyst exhibits a positive half-wave potential (E1/2) (0.87 V vs. RHE), a similar four-electron pathway in 0.1 M KOH medium, and an excellent long-term stability.

Two-Dimensional Cobalt Phosphate Hydroxide Nanosheets: A New Type of High-Performance Electrocatalysts with Intrinsic CoO6 Lattice Distortion for Water Oxidation.

Despite the recent advances in electrochemical water splitting, developing cost-effective and highly efficient electrocatalysts for oxygen evolution reaction (OER) still remains a substantial challenge. Herein, two-dimensional cobalt phosphate hydroxides (Co5(PO4)2(OH)4) nanosheets, a unique stacking-disordered phosphate-based inorganic material, are successfully prepared via a facile and scalable method for the first time to serve as a superior and robust electrocatalyst for water oxidation. On the basis of the detailed characterization (e.g., X-ray absorption near-edge structure and X-ray photoelectron spectroscopy), the obtained nanosheets consist of special zigzag CoO6 octahedral chains along with intrinsic lattice distortion and excellent hydrophilicity, in which these factors contribute to the highly efficient performance of prepared electrocatalysts for OER. Specifically, Co5(PO4)2(OH)4 deposited on glassy carbon electrode (loading amount ≈0.553 mg cm-2) can exhibit an unprecedented overpotential of 254 mV to drive a current density of 10 mA cm-2 with a small Tafel slope of 57 mV dec-1 in alkaline electrolytes, which outperforms the ones of CO3(PO4)2 (370 mV) and Co(OH)2 (360 mV) as well as other advanced catalysts. Evidently, this work has opened a new pathway to the rational design of promising metal phosphate hydroxides toward the efficient electrochemical energy conversion.