Aerosol-into-liquid capture and detection of atmospheric soluble metals across the gas-liquid interface using Janus-membrane electrodes.

The soluble fraction of atmospheric transition metals is particularly associated with health effects such as reactive oxygen species compared to total metals. However, direct measurements of the soluble fraction are restricted to sampling and detection units in sequence burdened with a compromise between time resolution and system bulkiness. Here, we propose the concept of aerosol-into-liquid capture and detection, which allowed one-step particle capture and detection via the Janus-membrane electrode at the gas-liquid interface, enabling active enrichment and enhanced mass transport of metal ions. The integrated aerodynamic/electrochemical system was capable of capturing airborne particles with a cutoff size down to 50 nm and detecting Pb(II) with a limit of detection of 95.7 ng. The proposed concept can pave the way for cost-effective and miniaturized systems, for the capture and detection of airborne soluble metals in air quality monitoring, especially for abrupt air pollution events with high airborne metal concentrations (e.g., wildfires and fireworks).

Strained Au skin on Mesoporous Intermetallic AuCu3 Nanocoral for Electrocatalytic Conversion of Nitrate to Ammonia across a Wide Concentration Range.

Electrochemical nitrate reduction reaction (NitRR) uses nitrate from wastewater, offering a hopeful solution for environmental issues and ammonia production. Yet, varying nitrate levels in real wastewater greatly affect NitRR, slowing down its multi-step process. Herein, a multi-strategy approach was explored through the design of ordered mesoporous intermetallic AuCu3 nanocorals with ultrathin Au skin (meso-i-AuCu3@ultra-Au) as an efficient and concentration-versatile catalyst for NitRR. The highly penetrated structure, coupled with the compressive stress exerted on the skin layer, not only facilitates rapid electron/mass transfer, but also effectively modulates the surface electronic structure, addressing the concentration-dependent challenges encountered in practical NitRR process. As expected, the novel catalyst demonstrates outstanding NitRR activities and Faradaic efficiencies exceeding 95% across a real and widespread concentration range (10-2000 mM). Notably, its performance at each concentration matched or exceeded that of the best-known catalyst designed for that concentration. Multiple operando spectroscopies unveiled the catalyst concurrently optimized the adsorption behavior of different intermediates (adsorbed *NOx and *H) while expediting the hydrogenation steps, leading to an efficient overall reduction process. Moreover, the catalyst also displays promising potential for use in ammonia production at industrial-relevant current densities and in conceptual zinc-nitrate batteries, serving trifunctional nitrate conversion, ammonia synthesis and power supply.

Grain-Boundary-Rich RuO2 Porous Nanosheet for Efficient and Stable Acidic Water Oxidation.

RuO2 has been considered as the most likely acidic oxygen evolution reaction (OER) catalyst to replace IrO2, but its performance, especially long-term stability under harsh acidic conditions, is still unacceptable. Here, we propose a grain boundary (GB) engineering strategy by fabricating the ultrathin porous RuO2 nanosheet with abundant of grain boundaries (GB-RuO2) as an efficient acid OER catalyst. The involvement of GB induces significant tensile stress and creates an unsaturated coordination environment, effectively optimizing the adsorption of intermediates and stabilizing active site structure during OER process. Notably, the GB-RuO2 not only exhibits a low overpotential (η10=187 mV) with an ultra-low Tafel slope (34.5 mV dec-1), but also steadily operates for over 550 h in 0.1 M HClO4. Quasi in situ/operando methods confirm that the improved stability is attributed to GB preventing Ru dissolution and greatly inhibiting the lattice oxygen oxidation mechanism (LOM). A proton exchange membrane water electrolysis (PEMWE) using the GB-RuO2 catalyst operates a low voltage of 1.669 V at 2 A cm-2 and operates stably for 100 h at 100 mA cm-2.

Amorphous Fe-Phytate Enables Fast Polysulfide Redox for High-Loading Lithium Sulfur Batteries.

Utilizing catalysts to accelerate polysulfides conversion are of paramount importance to eliminate the shuttling effect and improve the practical performance of lithium-sulfur (Li-S) batteries. The amorphism, attributes to the abundant unsaturated surface active sites, has recently been recognized as a contribution to increase the activity of catalysts. However, the investigation on amorphous catalysts has received limited interest in lithium-sulfur batteries due to lack of understanding of their composition structure activity. Herein, a amorphous Fe-Phytate structure is proposed to enhance polysulfide conversion and suppress polysulfide shuttling by modifying polypropylene separator (C-Fe-Phytate@PP). The polar Fe-Phytate with distorted VI coordination Fe active centers strongly intake polysulfide electron by forming FeS bond to accelerate the polysulfide conversion. The surface mediated polysulfides redox gives rise to a higher exchange current in comparison with carbon. Furthermore, Fe-Phytate owns robust adsorption to polysulfide and effectively reduce the shuttling effect. With the C-Fe-Phytate@PP separator, the Li-S batteries exhibit an outstanding rate capability of 690 mAh g-1 at 5 C and an ultrahigh areal capacity of 7.8 mAh cm-2 even at a high sulfur loading of 7.3 mg cm-2 . The work provides a novel separator for facilitating the actual applications of Li-S batteries.

Reconstruction of Solid Electrolyte Interphase with SrI2 Reactivates Dead Li for Durable Anode-Free Li-Metal Batteries.

Without excess Li, anode-free Li-metal batteries (AFLMBs) have been proposed as the most likely solution to realizing highly-safe and cost-effective Li-metal batteries. Nevertheless, short cyclic life puzzles conventional AFLMBs due to anodic dead Li accumulation with a local current concentration induced by irreversible electrolyte depletion, insufficient active Li reservoir and slow Li+ transfer at the solid electrolyte interphase (SEI). Herein, SrI2 is introduced into carbon paper (CP) current collector to effectively suppress dead Li through synergistic mechanisms including reversible I- /I3 - redox reaction to reactivate dead Li, dielectric SEI surface with SrF2 and LiF to prevent electrolyte decomposition and highly ionic conductive (3.488 mS cm-1 ) inner layer of SEI with abundant LiI to enable efficient Li+ transfer inside. With the SrI2 -modified current collector, the NCM532/CP cell delivers unprecedented cyclic performances with a capacity of 129.2 mAh g-1 after 200 cycles.

A Single-Layer Composite Separator with 3D-Reinforced Microstructure for Practical High-Temperature Lithium Ion Batteries.

Incorporation of ceramic materials into separators has been frequently applied in both research and industry to improve the overall high-temperature performances of lithium ion batteries. However, inorganic ceramic particles tend to form aggregation in separators and even fall off in the separator matrix due to the inferior combination between ceramic particles and polymer matrix, giving rise to a decrease in separator porosity and thus the degradation of battery performances. Herein, a single-layer core-shell architecture is designed to reinforce the polymer matrix through encircling Al2 O3 particles by poly(vinylidene fluoride) with strong inter-molecular interaction. The 3D-reinforced microstructure effectively improves pore distribution and thermal stability to resist the dimensional deformation at high temperatures, thus giving rise to a high Coulombic efficiency of 99.16% and 87.5% capacity retention after 500 cycles at 80 °C for LiFePO4 /Li batteries. In particular, the excellent performances of the proposed separator microstructure are confirmed with a thickness value of commercial separators. This work provides a promising strategy to fabricate a core-shell structural composite separator for stable lithium ion batteries at high temperatures.

Ten Thousand-Cycle Ultrafast Energy Storage of Wadsley-Roth Phase Fe-Nb Oxides with a Desolvation Promoting Interfacial Layer.

Developing advanced electrode materials with enhanced charge-transfer kinetics is the key to realizing fast energy storage technologies. Commonly used modification strategies, such as nanoengineering and carbon coating, are mainly focused on electron transfer and bulk Li+ diffusion. Nonetheless, the desolvation behavior, which is considered as the rate-limiting process for charge-storage, is rarely studied. Herein, we designed a nitridation layer on the surface of Wadsley-Roth phase FeNb11O29 (FNO-x@N) to act as a desolvation promoter. Theoretical calculations demonstrate that the adsorption and desolvation of solvated Li+ is efficiently improved at FNO-x@N/electrolyte interphase, leading to the reduced desolvation energy barrier. Moreover, the nitridation layer can also help to prevent solvent cointercalation during Li+ insertion, leading to advantageous shrinkage of block area and reduced volume change of lattice cell during cycling. Consequently, FNO-x@N exhibits a high-rate capacity of 129.7 mAh g-1 with negligible capacity decay for 10 000 cycles.

Biomimetic-Inspired One-Step Strategy for Improvement of Interfacial Interactions in Cellulose Nanofibers by Modification of the Surface of Nitramine Explosives.

Recently, a burgeoning category of biocompatible botanically derived nanomaterial cellulose nanofibers (CNFs) has captured tremendous attention on account of its entangled nanostructured network, natural abundance, and outstanding mechanical properties. Biomimetically inspired by the superior properties of CNFs, this paper examined them as the coating material to cover cyclotrimethylenetrinitramine (RDX), cyclotetramethylenetetranitramine (HMX), and hexanitrohexaazaisowurtzitane (CL-20) via a facile water suspension method and the ultrasonic technology. The core-shell structure and the composition of energetic crystal@CNF were examined through scanning electron microscopy, X-ray diffraction, Fourier transform infrared spectroscopy, Raman spectroscopy, and X-ray photoelectron spectroscopy analyses. The obtained outcomes demonstrated that the dispersibility of the CNF enhanced favorably upon covering the surface of explosive crystals; the interfacial contact ability between CNFs and energetic crystals was also manifested to be increased, which could be ascribed to the interfacial interaction of hydrogen bonds and the electrostatic force of self-assembly. In addition, the stable crystalloid construction of ß-HMX and ε-CL-20 has been preserved positively in the preparation process. In comparison with raw explosives, the thermal stability and sensitivity performances of the core-shell structure composites were outstanding. Accordingly, this work demonstrated the rewarding application of coating CNFs uniformly on the surface of energetic crystals, ulteriorly offering a potential fabrication strategy for the embellishment of high-explosive crystals.

CMAUP: a database of collective molecular activities of useful plants.

The beneficial effects of functionally useful plants (e.g. medicinal and food plants) arise from the multi-target activities of multiple ingredients of these plants. The knowledge of the collective molecular activities of these plants facilitates mechanistic studies and expanded applications. A number of databases provide information about the effects and targets of various plants and ingredients. More comprehensive information is needed for broader classes of plants and for the landscapes of individual plant's multiple targets, collective activities and regulated biological pathways, processes and diseases. We therefore developed a new database, Collective Molecular Activities of Useful Plants (CMAUP), to provide the collective landscapes of multiple targets (ChEMBL target classes) and activity levels (in 2D target-ingredient heatmap), and regulated gene ontologies (GO categories), biological pathways (KEGG categories) and diseases (ICD blocks) for 5645 plants (2567 medicinal, 170 food, 1567 edible, 3 agricultural and 119 garden plants) collected from or traditionally used in 153 countries and regions. These landscapes were derived from 47 645 plant ingredients active against 646 targets in 234 KEGG pathways associated with 2473 gene ontologies and 656 diseases. CMAUP (http://bidd2.nus.edu.sg/CMAUP/) is freely accessible and searchable by keywords, plant usage classes, species families, targets, KEGG pathways, gene ontologies, diseases (ICD code) and geographical locations.

Organosulfur Compounds Enable Uniform Lithium Plating and Long-Term Battery Cycling Stability.

Lithium metal represents an ultimate anode material of lithium batteries for its high energy density. However, its large negative redox potential and reactive nature can trigger electrolyte decomposition and dendrite formation, causing unstable cycling and short circuit of batteries. Herein, we engineer a resilient solid electrolyte interphase on the Li anode by compositing the battery separator with organosulfur compounds and inorganic salts from garlic. These compounds take part in battery reactions to suppress dendrite growth through reversible electrochemistry and attenuate ionic concentration gradient. When the Li anode and the separator are paired with the LiFePO4 cathode, one obtains a battery delivering long-term cycling stability of 3000 cycles, a rate capacity of 100 mAh g-1 at 10 C (2.5 mA cm-2), a Coulombic efficiency of 99.9%, and a low battery polarization. Additionally, with high-loading 20 mg cm-2 LiFePO4 cathodes, an areal capacity of 3.4 mAh cm-2 is achieved at 0.3 C (1 mA cm-2).

Rapid UV-radiation synthesis of polyacrylate cryogel oil-sorbents with adaptable structure and performance.

Macro-porous poly(lauryl acrylate) cryogel sheets as oil-sorbents were prepared through UV-radiation cryo-polymerizations in 1, 4-dioxane at low temperatures (-5, -2 and 0 °C) within 30 min. The influences of total monomer concentration, crosslinking monomer amount and polymerization temperature on the formation of cryogels were studied. The chemical structure and porous morphology were characterized through the techniques of Fourier transform infrared spectroscopy, thermal gravimetric analysis, contact angle measurement and scanning electron microscopy, confirming the features of high hydrophobicity, macro-porosity and good thermal stability. As well, the comparison between conventional gels prepared at room temperature and cryogels at lower temperatures was made, showing the higher rate of cryo-polymerization than conventional polymerization under the same UV-radiation condition. The swelling investigation was carried out with several organic solvents and oils. Enhanced performance of oil absorption was observed for those cryogels considering the absorption capacity and absorption rate. Variation of initiator amount and acrylate monomers could also modulate the absorption capacity. Those cryogel oil-sorbents exhibited wide adaptability, good reusability and high-temperature tolerance. Thus, this rapid and low-cost fabrication opens out a novel pathway to prepare efficient oil-sorbents used in waste water treatment.

NPASS: natural product activity and species source database for natural product research, discovery and tool development.

There has been renewed interests in the exploration of natural products (NPs) for drug discovery, and continuous investigations of the therapeutic claims and mechanisms of traditional and herbal medicines. In-silico methods have been employed for facilitating these studies. These studies and the optimization of in-silico algorithms for NP applications can be facilitated by the quantitative activity and species source data of the NPs. A number of databases collectively provide the structural and other information of ∼470 000 NPs, including qualitative activity information for many NPs, but only ∼4000 NPs are with the experimental activity values. There is a need for the activity and species source data of more NPs. We therefore developed a new database, NPASS (Natural Product Activity and Species Source) to complement other databases by providing the experimental activity values and species sources of 35 032 NPs from 25 041 species targeting 5863 targets (2946 proteins, 1352 microbial species and 1227 cell-lines). NPASS contains 446 552 quantitative activity records (e.g. IC50, Ki, EC50, GI50 or MIC mainly in units of nM) of 222 092 NP-target pairs and 288 002 NP-species pairs. NPASS, http://bidd2.nus.edu.sg/NPASS/, is freely accessible with its contents searchable by keywords, physicochemical property range, structural similarity, species and target search facilities.

Recent Development in Separators for High-Temperature Lithium-Ion Batteries.

Lithium-ion batteries (LIBs) are promising energy storage devices for integrating renewable resources and high power applications, owing to their high energy density, light weight, high flexibility, slow self-discharge rate, high rate charging capability, and long battery life. LIBs work efficiently at ambient temperatures, however, at high-temperatures, they cause serious issues due to the thermal fluctuation inside batteries during operation. The separator is a key component of batteries and is crucial for the sustainability of LIBs at high-temperatures. The high thermal stability with minimum thermal shrinkage and robust mechanical strength are the prime requirements along with high porosity, ionic conductivity, and electrolyte uptake for highly efficient high-temperature LIBs. This Review deals with the recent studies and developments in separator technologies for high-temperature LIBs with respect to their structural layered formation. The recent progress in monolayer and multilayer separators along with the developed preparation methodologies is discussed in detail. Future challenges and directions toward the advancement in separator technology are also discussed for achieving remarkable performance of separators in a high-temperature environment.

A Nanostructured Si/SiOC Composite Anode with Volume-Change-Buffering Microstructure for Lithium-Ion Batteries.

Si/SiOC composites are promising high-capacity anode materials for lithium-ion batteries since the SiOC matrix can effectively buffer the volumetric change of Si during cycling. However, a structure of Si nanoparticles (NPs) enwrapped by a continuous SiOC phase typically shows poor cyclic stability and low charge/discharge rate due to structure failure of bulk SiOC shells derived from carbon-rich organosilicon. To address this issue, in this work, an Si/SiOC nanocomposite with volume-change-buffering microstructure, in which Si NPs are uniformly dispersed in a matrix of SiOC nanospheres, has been synthesized. Our results show that the space between Si and SiOC NPs can accommodate the large volume change of Si during cycling and facilitate infiltration of the electrolyte. The nanostructured SiOC skeleton serves as both a mechanically robust buffer to alleviate the intrinsic expansion of Si and an effective electron conductor. The Si/SiOC NP composite displays significantly increased capacity and cyclic stability compared with pure SiOC, and delivers reversible capacities of around 800 mA h-1 g-1 at a current density of 100 mA g-1 (approximately 100 % capacity retention after 100 cycles) and around 600 mA h-1 g-1 at 500 mA g-1 (capacity retention about 80 % after 500 cycles).

High-Performance SERS Substrate Based on Hierarchical 3D Cu Nanocrystals with Efficient Morphology Control.

Cu nanocrystals of various shapes are synthesized via a universal, eco-friendly, and facile colloidal method on Al substrates using hexadecylamine (HDA) as a capping agent and glucose as a reductant. By tuning the concentration of the capping agent, hierarchical 3D Cu nanocrystals show pronounced surface-enhanced Raman scattering (SERS) through the concentrated hot spots at the sharp tips and gaps due to the unique 3D structure and the resulting plasmonic couplings. Intriguingly, 3D sword-shaped Cu crystals have the highest enhancement factor (EF) because of their relatively uniform size distribution and alignment. This work opens new pathways for efficiently realizing morphology control for Cu nanocrystals as highly efficient SERS platforms.

A Single-Step Hydrothermal Route to 3D Hierarchical Cu2 O/CuO/rGO Nanosheets as High-Performance Anode of Lithium-Ion Batteries.

As anodes of Li-ion batteries, copper oxides (CuO) have a high theoretical specific capacity (674 mA h g-1 ) but own poor cyclic stability owing to the large volume expansion and low conductivity in charges/discharges. Incorporating reduced graphene oxide (rGO) into CuO anodes with conventional methods fails to build robust interaction between rGO and CuO to efficiently improve the overall anode performance. Here, Cu2 O/CuO/reduced graphene oxides (Cu2 O/CuO/rGO) with a 3D hierarchical nanostructure are synthesized with a facile, single-step hydrothermal method. The Cu2 O/CuO/rGO anode exhibits remarkable cyclic and high-rate performances, and particularly the anode with 25 wt% rGO owns the best performance among all samples, delivering a record capacity of 550 mA h g-1 at 0.5 C after 100 cycles. The pronounced performances are attributed to the highly efficient charge transfer in CuO nanosheets encapsulated in rGO network and the mitigated volume expansion of the anode owing to its robust 3D hierarchical nanostructure.

HEROD: a human ethnic and regional specific omics database.

MOTIVATION: Genetic and gene expression variations within and between populations and across geographical regions have substantial effects on the biological phenotypes, diseases, and therapeutic response. The development of precision medicines can be facilitated by the OMICS studies of the patients of specific ethnicity and geographic region. However, there is an inadequate facility for broadly and conveniently accessing the ethnic and regional specific OMICS data. RESULTS: Here, we introduced a new free database, HEROD, a human ethnic and regional specific OMICS database. Its first version contains the gene expression data of 53 070 patients of 169 diseases in seven ethnic populations from 193 cities/regions in 49 nations curated from the Gene Expression Omnibus (GEO), the ArrayExpress Archive of Functional Genomics Data (ArrayExpress), the Cancer Genome Atlas (TCGA) and the International Cancer Genome Consortium (ICGC). Geographic region information of curated patients was mainly manually extracted from referenced publications of each original study. These data can be accessed and downloaded via keyword search, World map search, and menu-bar search of disease name, the international classification of disease code, geographical region, location of sample collection, ethnic population, gender, age, sample source organ, patient type (patient or healthy), sample type (disease or normal tissue) and assay type on the web interface. AVAILABILITY AND IMPLEMENTATION: The HEROD database is freely accessible at http://bidd2.nus.edu.sg/herod/index.php. The database and web interface are implemented in MySQL, PHP and HTML with all major browsers supported. CONTACT: phacyz@nus.edu.sg.

Coordination-dependent surface strain and rational construction of robust structures.

A surface relaxation model is established to study the elastic properties of nanoscale structures. This model predicts coordination-dependent strain at the surface and thickness-dependent stiffness of a material. Several atomic layers at the surface endure a significant strain gradient, which is dominated by the intrinsic properties of the material. The stiffness of low-dimensional materials is enhanced by surface relaxation effect. Surface effects on strong structures, including honeycomb structure and octet-truss structure with a high stiffness-to-weight ratio, are discussed. For these structures assembled with nanobeams, the Young's modulus decreases with decreasing size of the struts. The coupling between Young's modulus and relative density can be scaled down by engineering tensile strain on the struts.

Gold Nanoparticles Grafted with PLL-b-PNIPAM: Interplay on Thermal/pH Dual-Response and Optical Properties.

Narrowly distributed poly(l-lysine-b-N-isopropylacrylamide) (PLL-b-PNIPAM) was prepared through ring-opening polymerization of ε-benzyloxycarbonyl-l-lysine N-carboxy-α-amino anhydride and atom transfer radical polymerization of NIPAM, followed with the removal of ε-benzyloxycarbonyl group. Then gold nanoparticles (AuNPs) grafted with PLL-b-PNIPAM (PNIPAM-PLL-AuNPs) were obtained by the reduction of chloroauric acid with sodium citrate in the presence of PLL-b-PNIPAM. PNIPAM-PLL-AuNPs and its precursors were thoroughly characterized by proton magnetic resonance spectroscope, Fourier transform infrared spectroscope, UV-vis spectroscope, transmission electron microscopy, dynamic light scattering, thermogravimetric analysis, and circular dichroism. The obtained PNIPAM-PLL-AuNPs exhibited high colloid stability even at strong alkaline (pH = 12) and acidic (pH = 2) conditions. The thermal and pH dual-responsive behaviors of the grafting PLL-b-PNIPAM chains was observed to be affected by AuNPs, while not for the secondary structure of PLL chains. Correspondingly, the surface plasmon resonance (SPR) of AuNPs was found to be sensitive to both pH value and temperature. A blue shift in the SPR happened both with increasing pH value and increasing temperature. The stimuli-response was reversible in heating-cooling cycles. The gold nanoparticles with both pH and temperature response may have potential applications in biomedical areas and biosensors.

Size- and dimensionality-dependent optical, magnetic and magneto-optical properties of binary europium-based nanocrystals: EuX (X = O, S, Se, Te).

Europium chalcogenides (EuX, X = O, S, Se, Te), a class of prototypical Heisenberg magnetic semiconductors, exhibit intriguing properties in optics, magnetism, and magneto-optics at the nanoscale, and have broad application potential in optical/magnetic sensors, spintronics, optical isolators, etc. EuX nanocrystals (NCs) exhibit enhanced properties, such as high saturation magnetization, a strong magneto-optic effect (Faraday rotation), and high magneto resistance, which are all unanimously dependent on the NC's size, shape, and surface information. In this report, we give an overview of the fundamental properties of bulk EuX, and illustrate the quantum confinement effects on the optical, magnetic and magneto-optical properties of EuX nanostructures. We then focus on doping and self-assembly-two efficient methods that enhance magnetic properties by manipulating magnetic coupling in EuX nanostructures. In particular, we look towards future research on Eu(2+) NCs, which along with the overview provides an up-to-date platform for evaluating the fundamental properties and application potential of Eu-based semiconductors.