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  1. Numerous studies have linked a wide range of diseases including respiratory illnesses to harmful particulate matter (PM) emissions indoors and outdoors, such as incense PM and industrial PM. Because of their ability to penetrate the lower respiratory tract and the circulatory system, fine particles with diameters of 2.5 µm or less (PM2.5) are believed to be more hazardous than larger PMs. Despite the enormous number of studies focusing on the intracellular processes associated with PM2.5 exposure, there have been limited reports studying the biophysical properties of cell membranes, such as nanoscale morphological changes induced by PM2.5. Our study assesses the membrane topographical and structural effects of PM2.5 from incense PM2.5 exposure in real time on A549 lung carcinoma epithelial cells and SH-SY5Y neuroblastoma cells that had been fixed to preclude adaptive cell responses. The size distribution and mechanical properties of the PM2.5 sample were characterized with atomic force microscopy (AFM). Nanoscale morphological monitoring of the cell membranes utilizing scanning ion conductance microscopy (SICM) indicated statistically significant increasing membrane roughness at A549 cells at half an hour of exposure and visible damage at 4 h of exposure. In contrast, no significant increase in roughness was observed on SH-SY5Y cells after half an hour of PM2.5 exposure, although continued exposure to PM2.5 for up to 4 h affected an expansion of lesions already present before exposure commenced. These findings suggest that A549 cell membranes are more susceptible to structural damage by PM2.5 compared to SH-SY5Y cell membranes, corroborating more enhanced susceptibility of airway epithelial cells to exposure to PM2.5 than neuronal cells. SICM · Particulate matter · Membrane topography · Single-cell imaging 
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  2. Abstract

    A new concentrated ternary salt ether‐based electrolyte enables stable cycling of lithium metal battery (LMB) cells with high‐mass‐loading (13.8 mg cm−2, 2.5 mAh cm−2) NMC622 (LiNi0.6Co0.2Mn0.2O2) cathodes and 50 μm Li anodes. Termed “CETHER‐3,” this electrolyte is based on LiTFSI, LiDFOB, and LiBF4with 5 vol% fluorinated ethylene carbonate in 1,2‐dimethoxyethane. Commercial carbonate and state‐of‐the‐art binary salt ether electrolytes were also tested as baselines. With CETHER‐3, the electrochemical performance of the full‐cell battery is among the most favorably reported in terms of high‐voltage cycling stability. For example, LiNixMnyCo1–xyO2(NMC)‐Li metal cells retain 80% capacity at 430 cycles with a 4.4 V cut‐off and 83% capacity at 100 cycles with a 4.5 V cut‐off (charge at C/5, discharge at C/2). According to simulation by density functional theory and molecular dynamics, this favorable performance is an outcome of enhanced coordination between Li+and the solvent/salt molecules. Combining advanced microscopy (high‐resolution transmission electron microscopy, scanning electron microscopy) and surface science (X‐ray photoelectron spectroscopy, time‐of‐fight secondary ion mass spectroscopy, Fourier‐transform infrared spectroscopy, Raman spectroscopy), it is demonstrated that a thinner and more stable cathode electrolyte interphase (CEI) and solid electrolyte interphase (SEI) are formed. The CEI is rich in lithium sulfide (Li2SO3), while the SEI is rich in Li3N and LiF. During cycling, the CEI/SEI suppresses both the deleterious transformation of the cathode R‐3m layered near‐surface structure into disordered rock salt and the growth of lithium metal dendrites.

     
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  3. Abstract

    Despite the great promise of genetic code expansion technology to modulate structures and functions of proteins, external addition of ncAAs is required in most cases and it often limits the utility of genetic code expansion technology, especially to noncanonical amino acids (ncAAs) with poor membrane internalization. Here, we report the creation of autonomous cells, both prokaryotic and eukaryotic, with the ability to biosynthesize and genetically encode sulfotyrosine (sTyr), an important protein post-translational modification with low membrane permeability. These engineered cells can produce site-specifically sulfated proteins at a higher yield than cells fed exogenously with the highest level of sTyr reported in the literature. We use these autonomous cells to prepare highly potent thrombin inhibitors with site-specific sulfation. By enhancing ncAA incorporation efficiency, this added ability of cells to biosynthesize ncAAs and genetically incorporate them into proteins greatly extends the utility of genetic code expansion methods.

     
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    Prussian blue is an iron-cyanide-based pigment steadily becoming a widely used electrochemical sensor in detecting hydrogen peroxide at low concentration levels. Prussian blue nanoparticles (PBNPs) have been extensively studied using traditional ensemble methods, which only provide averaged information. Investigating PBNPs at a single entity level is paramount for correlating the electrochemical activities to particle structures and will shed light on the major factors governing the catalyst activity of these nanoparticles. Here we report on using plasmonic electrochemical microscopy (PEM) to study the electrochemistry of PBNPs at the individual nanoparticle level. First, two types of PBNPs were synthesized; type I synthesized with double precursors method and type II synthesized with polyvinylpyrrolidone (PVP) assisted single precursor method. Second, both PBNPs types were compared on their electrochemical reduction to form Prussian white, and the effect from the different particle structures was investigated. Type I PBNPs provided better PEM sensitivity and were used to study the catalytic reduction of hydrogen peroxide. Progressively decreasing plasmonic signals with respect to increasing hydrogen peroxide concentration were observed, demonstrating the capability of sensing hydrogen peroxide at a single nanoparticle level utilizing this optical imaging technique. 
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    Lithium metal–selenium (Li–Se) batteries offer high volumetric energy but are limited in their cycling life and fast charge characteristics. Here a facile approach is demonstrated to synthesize hierarchically porous hollow carbon spheres that host Se (Se@HHCS) and allow for state-of-the-art electrochemical performance in a standard carbonate electrolyte (1 M LiPF 6 in 1 : 1 EC : DEC). The Se@HHCS electrodes display among the most favorable fast charge and cycling behavior reported. For example, they deliver specific capacities of 442 and 357 mA h g −1 after 1500 and 2000 cycles at 5C and 10C, respectively. At 2C, Se@HHCS delivers 558 mA h g −1 after 500 cycles, with cycling coulombic efficiency of 99.9%. Post-mortem microstructural analysis indicates that the structures remain intact during extended cycling. Per GITT analysis, Se@HHCS possesses significantly higher diffusion coefficients in both lithiation and delithiation processes as compared to the baseline. The superior performance of Se@HHCS is directly linked to its macroscopic and nanoscale pore structure: the hollow carbon sphere morphology as well as the remnant open nanoporosity accommodates the 69% volume expansion of the Li to Li 2 Se transformation, with the nanopores also providing a complementary fast ion diffusion path. 
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    Sodium metal battery (SMB, NMB) anodes can become dendritic due to an electrochemically unstable native Na-based solid electrolyte interphase (SEI). Herein Li-ion activated tin sulfide graphene nanocomposite membrane (A-SnS–G) is employed as an artificial SEI layer, allowing cyclability of record-thin 100 μm Na metal foils. The thin Na metal is prepared by a self-designed metallurgical rolling protocol. A-SnS–G is initially placed onto the polypropylene (PP) separator but becomes in situ transferred onto the Na metal surface. Symmetric metal cells protected by A-SnS–G achieve low-overpotential extended high-rate cycling in a standard carbonate electrolyte (EC : DEC = 1 : 1, 5% FEC). Accumulated capacity of 1000 mA h cm −2 is obtained after 500 cycles at 4 mA cm −2 , with accumulated capacity-to-foil capacity (A/F) ratio of 90.9. This is among the most favorable cycle life, accumulated capacity, and anode utilization combinations reported. Protection by non-activated SnS–G membrane yields significantly worse cycling, albeit still superior to the baseline unprotected sodium. Post-mortem and dedicated light optical analysis indicate that metal swelling, dendrite growth and dead metal formation is extensive for the unprotected sample, but is suppressed with A-SnS–G. Per XPS, post-100 cycles near-surface structure of A-SnS–G is rich in metallic Sn alloys and inorganic carbonate salts. Even after 300 cycles, Li-based SEI components ROCO 2 -Li, Li 2 CO 3 and LiF are detected with A-SnS–G. As a proof of principle, an SMB with a high mass loading (6 mg cm −2 ) NVP cathode and a A-SnS–G protected anode delivered extended cyclability, achieving 74 mA h g −1 after 400 cycles at 0.4C. 
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