Alumina - Stabilized SEI and CEI in Potassium Metal Batteries.

Aluminum oxide (Al2O3) nanopowder is spin-coated onto both sides of commercial polypropene separator to create artificial solid-electrolyte interphase (SEI) and artificial cathode electrolyte interface (CEI) in potassium metal batteries (KMBs). This significantly enhances the stability, including of KMBs with Prussian Blue (PB) cathodes. For example, symmetric cells are stable after 1,000 cycles at 0.5 mA/cm2 - 0.5 mAh/cm2 and 3.0 mA/cm2 - 0.5 mAh/cm2. Alumina modified separators promote electrolyte wetting and increase ionic conductivity (0.59 vs. 0.2 mS/cm) and transference number (0.81 vs. 0.23). Cryo-stage focused ion beam (cryo-FIB) analysis of cycled modified anode demonstrates dense and planar electrodeposits, versus unmodified baseline consisting of metal filaments (dendrites) interspersed with pores and SEI. Alumina-modified CEI also suppresses elemental Fe crossover and reduces cathode cracking. Mesoscale modeling of metal - SEI interactions captures crucial role of intrinsic heterogeneities, illustrating how artificial SEI affects reaction current distribution, conductivity and morphological stability.

Cellular response of keratinocytes to the entry and accumulation of nanoplastic particles.

Plastic accumulation in the environment is rapidly increasing, and nanoplastics (NP), byproducts of environmental weathering of bulk plastic waste, pose a significant public health risk. Particles may enter the human body through many possible routes such as ingestion, inhalation, and skin absorption. However, studies on NP penetration and accumulation in human skin are limited. Loss or reduction of the keratinized skin barrier may enhance the skin penetration of NPs. The present study investigated the entry of NPs into a human skin system modeling skin with compromised barrier functions and cellular responses to the intracellular accumulations of NPs. Two in vitro models were employed to simulate human skin lacking keratinized barriers. The first model was an ex vivo human skin culture with the keratinized dermal layer (stratum corneum) removed. The second model was a 3D keratinocyte/dermal fibroblast cell co-culture model with stratified keratinocytes on the top and a monolayer of skin fibroblast cells co-cultured at the bottom. The penetration and accumulation of the NPs in different cell types were observed using fluorescent microscopy, confocal microscopy, and cryogenic electron microscopy (cryo-EM). The cellular responses of keratinocytes and dermal fibroblast cells to stress induced by NPs stress were measured. The genetic regulatory pathway of keratinocytes to the intracellular NPs was identified using transcript analyses and KEGG pathway analysis. The cellular uptake of NPs by skin cells was confirmed by imaging analyses. Transepidermal transport and penetration of NPs through the skin epidermis were observed. According to the gene expression and pathway analyses, an IL-17 signaling pathway was identified as the trigger for cellular responses to internal NP accumulation in the keratinocytes. The transepidermal NPs were also found in co-cultured dermal fibroblast cells and resulted in a large-scale transition from fibroblast cells to myofibroblast cells with enhanced production of α-smooth muscle actin and pro-Collagen Ia. The upregulation of inflammatory factors and cell activation may result in skin inflammation and ultimately trigger immune responses.

Identifying biochemical constituents involved in the mycosynthesis of zinc oxide nanoparticles.

Filamentous fungi are known to secrete biochemicals that drive the synthesis of nanoparticles (NPs) that vary in composition, size, and shape; a process deemed mycosynthesis. Following the introduction of precursor salts directly to the fungal mycelia or their exudates, mycosynthesis proceeds at ambient temperature and pressure, and near neutral pH, presenting significant energy and cost savings over traditional chemical or physical approaches. The mycosynthesis of zinc oxide (ZnO) NPs by various fungi exhibited a species dependent morphological preference for the resulting NPs, suggesting that key differences in the biochemical makeup of their individual exudates may regulate the controlled nucleation and growth of these different morphologies. Metabolomics and proteomics of the various fungal exudates suggest that metal chelators, such as hexamethylenetetramine, present in high concentrations in exudates of Aspergillus versicolor are critical for the production dense, well-formed, spheroid nanoparticles. The results also corroborate that the proteinaceous material in the production of ZnO NPs serves as a surface modifier, or protein corona, preventing excessive coagulation of the NPs. Collectively, these findings suggest that NP morphology is regulated by the small molecule metabolites, and not proteins, present in fungal exudates, establishing a deeper understanding of the factors and mechanism underlying mycosynthesis of NPs.

Real-Time Observation of Nanoscale Kink Band Mediated Plasticity in Ion-Irradiated Graphite: An In Situ TEM Study.

Graphite IG-110 is a synthetic polycrystalline material used as a neutron moderator in reactors. Graphite is inherently brittle and is known to exhibit a further increase in brittleness due to radiation damage at room temperature. To understand the irradiation effects on pre-existing defects and their overall influence on external load, micropillar compression tests were performed using in situ nanoindentation in the Transmission Electron Microscopy (TEM) for both pristine and ion-irradiated samples. While pristine specimens showed brittle and subsequent catastrophic failure, the 2.8 MeV Au2+ ion (fluence of 4.378 × 1014 cm-2) irradiated specimens sustained extensive plasticity at room temperature without failure. In situ TEM characterization showed nucleation of nanoscale kink band structures at numerous sites, where the localized plasticity appeared to close the defects and cracks while allowing large average strain. We propose that compressive mechanical stress due to dimensional change during ion irradiation transforms buckled basal layers in graphite into kink bands. The externally applied load during the micropillar tests proliferates the nucleation and motion of kink bands to accommodate the large plastic strain. The inherent non-uniformity of graphite microstructure promotes such strain localization, making kink bands the predominant mechanism behind unprecedented toughness in an otherwise brittle material.

A Rare Case of Gemella haemolysans Endocarditis: A Challenging Diagnosis.

Gemella haemolysans bacterium is an opportunistic pathogen that can cause localized or systemic infections. Here we describe a rare case of infective endocarditis secondary to Gemella haemolysans infection. In our case, although the bacteremia was cleared with antibiotics, the mitral valve vegetations continued to enlarge and the course was complicated by septic brain emboli.

Microdissection of the supraoptic nucleus and posterior pituitary gland from fresh unfixed tissue.

The rat supraoptic nucleus (SON) contains magnocellular neurons that project long axons that terminate in the posterior pituitary gland. To perform molecular characterization of these regions, such as transcriptome and methylome profiling, it is necessary to obtain large quantities of high-quality RNA and DNA. Prior methods to isolate molecular material from these small regions required fixing or freezing and laser microdissection of whole tissue, which can compromise recovery and integrity. We have established a straight-forward method of dissecting out the SON and posterior pituitary gland from fresh, unfixed tissue that allows for the isolation of RNA or DNA without compromising nucleic acid integrity. Furthermore, this method can be used as a framework for the microdissection of any region of the brain to isolate any sensitive material. In this manuscript, we describe step-by-step instructions from the macro scale dissection, to brain sectioning, and finally the microdissection of the appropriate tissue.•Transcardial perfusion without fixative prevents the shortcomings of nucleic acid cross-linking.•A fast method and the maintenance of tissue in ice-cold HBSS during dissection and sectioning prevents nucleic acid degradation.•A vibratome is used for the sectioning of fresh brain tissue without freezing or gelatin embedding (i.e. cryostat or microtome).

Transcriptome and methylome of the supraoptic nucleus provides insights into the age-dependent loss of neuronal plasticity.

The age-dependent loss of neuronal plasticity is a well-known phenomenon that is poorly understood. The loss of this capacity for axonal regeneration is emphasized following traumatic brain injury, which is a major cause of disability and death among adults in the US. We have previously shown the intrinsic capacity of magnocellular neurons within the supraoptic nucleus to undergo axonal regeneration following unilateral axotomization in an age-dependent manner. The aim of this research was to determine the age-dependent molecular mechanisms that may underlie this phenomenon. As such, we characterized the transcriptome and DNA methylome of the supraoptic nucleus in uninjured 35-day old rats and 125-day old rats. Our data indicates the downregulation of a large number of axonogenesis related transcripts in 125-day old rats compared to 35-day old rats. Specifically, several semaphorin and ephrin genes were downregulated, as well as growth factors including FGF's, insulin-like growth factors (IGFs), and brain-derived neurotrophic factor (BDNF). Differential methylation analysis indicates enrichment of biological processes involved in axonogenesis and axon guidance. Conversely, we observed a robust and specific upregulation of MHCI related transcripts. This may involve the activator protein 1 (AP-1) transcription factor complex as motif analysis of differentially methylated regions indicate enrichment of AP-1 binding sites in hypomethylated regions. Together, our data suggests a loss of pro-regenerative capabilities with age which would prevent axonal growth and appropriate innervation following injury.

Future of Mesoporous Silica Nanoparticles in Nanomedicine: Protocol for Reproducible Synthesis, Characterization, Lipid Coating, and Loading of Therapeutics (Chemotherapeutic, Proteins, siRNA and mRNA).

Owing to their uniform and tunable particle size, pore size, and shape, along with their modular surface chemistry and biocompatibility, mesoporous silica nanoparticles (MSNs) have found extensive applications as nanocarriers to deliver therapeutic, diagnostic and combined "theranostic" cargos to cells and tissues. Although thoroughly investigated, MSN have garnered FDA approval for only one MSN system via oral administration. One possible reason is that there is no recognized, reproducible, and widely adopted MSN synthetic protocol, meaning not all MSNs are created equal in the laboratory nor in the eyes of the FDA. This manuscript provides the sol-gel and MSN research communities a reproducible, fully characterized synthetic protocol to synthesize MSNs and corresponding lipid-coated MSN delivery vehicles with predetermined particle size, pore size, and drug loading and release characteristics. By carefully articulating the step-by-step synthetic procedures and highlighting critical points and troubleshooting, augmented with videos and schematics, this Article will help researchers entering this rapidly expanding field to yield reliable results.

Influence of Potassium Metal-Support Interactions on Dendrite Growth.

Combined synchrotron X-ray nanotomography imaging, cryogenic electron microscopy (cryo-EM) and modeling elucidate how potassium (K) metal-support energetics influence electrodeposit microstructure. Three model supports are employed: O-functionalized carbon cloth (potassiophilic, fully-wetted), non-functionalized cloth and Cu foil (potassiophobic, nonwetted). Nanotomography and focused ion beam (cryo-FIB) cross-sections yield complementary three-dimensional (3D) maps of cycled electrodeposits. Electrodeposit on potassiophobic support is a triphasic sponge, with fibrous dendrites covered by solid electrolyte interphase (SEI) and interspersed with nanopores (sub-10 nm to 100 nm scale). Lage cracks and voids are also a key feature. On potassiophilic support, the deposit is dense and pore-free, with uniform surface and SEI morphology. Mesoscale modeling captures the critical role of substrate-metal interaction on K metal film nucleation and growth, as well as the associated stress state.

The onset of rare earth metallosis begins with renal gadolinium-rich nanoparticles from magnetic resonance imaging contrast agent exposure.

The leitmotifs of magnetic resonance imaging (MRI) contrast agent-induced complications range from acute kidney injury, symptoms associated with gadolinium exposure (SAGE)/gadolinium deposition disease, potentially fatal gadolinium encephalopathy, and irreversible systemic fibrosis. Gadolinium is the active ingredient of these contrast agents, a non-physiologic lanthanide metal. The mechanisms of MRI contrast agent-induced diseases are unknown. Mice were treated with a MRI contrast agent. Human kidney tissues from contrast-naïve and MRI contrast agent-treated patients were obtained and analyzed. Kidneys (human and mouse) were assessed with transmission electron microscopy and scanning transmission electron microscopy with X-ray energy-dispersive spectroscopy. MRI contrast agent treatment resulted in unilamellar vesicles and mitochondriopathy in renal epithelium. Electron-dense intracellular precipitates and the outer rim of lipid droplets were rich in gadolinium and phosphorus. We conclude that MRI contrast agents are not physiologically inert. The long-term safety of these synthetic metal-ligand complexes, especially with repeated use, should be studied further.

Mycosynthesis of Zinc Oxide Nanoparticles Exhibits Fungal Species Dependent Morphological Preference.

Filamentous fungi can synthesize a variety of nanoparticles (NPs), a process referred to as mycosynthesis that requires little energy input, do not require the use of harsh chemicals, occurs at near neutral pH, and do not produce toxic byproducts. While NP synthesis involves reactions between metal ions and exudates produced by the fungi, the chemical and biochemical parameters underlying this process remain poorly understood. Here, the role of fungal species and precursor salt on the mycosynthesis of zinc oxide (ZnO) NPs is investigated. This data demonstrates that all five fungal species tested are able to produce ZnO structures that can be morphologically classified into i) well-defined NPs, ii) coalesced/dissolving NPs, and iii) micron-sized square plates. Further, species-dependent preferences for these morphologies are observed, suggesting potential differences in the profile or concentration of the biochemical constituents in their individual exudates. This data also demonstrates that mycosynthesis of ZnO NPs is independent of the anion species, with nitrate, sulfate, and chloride showing no effect on NP production. These results enhance the understanding of factors controlling the mycosynthesis of ceramic NPs, supporting future studies that can enable control over the physical and chemical properties of NPs formed through this "green" synthesis method.

Stable Anode-Free All-Solid-State Lithium Battery through Tuned Metal Wetting on the Copper Current Collector.

A stable anode-free all-solid-state battery (AF-ASSB) with sulfide-based solid-electrolyte (SE) (argyrodite Li6 PS5 Cl) is achieved by tuning wetting of lithium metal on "empty" copper current-collector. Lithiophilic 1 µm Li2 Te is synthesized by exposing the collector to tellurium vapor, followed by in situ Li activation during the first charge. The Li2 Te significantly reduces the electrodeposition/electrodissolution overpotentials and improves Coulombic efficiency (CE). During continuous electrodeposition experiments using half-cells (1 mA cm-2 ), the accumulated thickness of electrodeposited Li on Li2 Te-Cu is more than 70 µm, which is the thickness of the Li foil counter-electrode. Full AF-ASSB with NMC811 cathode delivers an initial CE of 83% at 0.2C, with a cycling CE above 99%. Cryogenic focused ion beam (Cryo-FIB) sectioning demonstrates uniform electrodeposited metal microstructure, with no signs of voids or dendrites at the collector-SE interface. Electrodissolution is uniform and complete, with Li2 Te remaining structurally stable and adherent. By contrast, an unmodified Cu current-collector promotes inhomogeneous Li electrodeposition/electrodissolution, electrochemically inactive "dead metal," dendrites that extend into SE, and thick non-uniform solid electrolyte interphase (SEI) interspersed with pores. Density functional theory (DFT) and mesoscale calculations provide complementary insight regarding nucleation-growth behavior. Unlike conventional liquid-electrolyte metal batteries, the role of current collector/support lithiophilicity has not been explored for emerging AF-ASSBs.

Comparing a Novel Hand-Held Device for Chest Tube Insertion to the Traditional Open Tube Thoracostomy for Simple Pneumothorax in a Porcine Model.

BACKGROUND: Tube thoracostomy is the most effective treatment for pneumothorax, and on the battlefield, is lifesaving. In combat, far-forward adoption of open thoracostomy has not been successful. Therefore, the ability to safely and reliably perform chest tube insertion in the far-forward combat theatre would be of significant value. The Reactor is a hand-held device for tube thoracostomy that has been validated for tension pneumothorax compared to needle decompression. Here we investigate whether the Reactor has potential for simple pneumothorax compared to open thoracostomy. Treatment of pneumothorax before tension physiology ensues is critical. METHODS: Simple pneumothoraces were created in 5 in-vivo swine models and confirmed with x-ray. Interventions were randomized to open technique (OT, n = 25) and Reactor (RT, n = 25). Post-procedure radiography was used to confirm tube placement and pneumothorax resolution. Video Assisted Thoracoscopic Surgery (VATS) was used to evaluate for iatrogenic injuries. 50 chest tubes were placed, with 25 per group. RESULTS: There were no statistical differences between the groups for insertion time, pneumothorax resolution, or estimated blood loss (p = .91 and .83). Injury rates between groups varied, with 28% (n = 7) in the Reactor group and 8% (n = 2) the control group (p = .06). The most common injury was violation of visceral pleura (10%, n = 5, both groups) and violation of the mediastinum (8%, n = 4, both groups). CONCLUSION: The Reactor device was equal compared to open thoracostomy for insertion time, pneumothorax resolution, and injury rates. The device required smaller incisions compared to tube thoracostomy and may be useful adjunct in simple pneumothorax management.

Effect of manganese substitution of ferrite nanoparticles on particle grain structure.

To investigate the influence of manganese substitution on the saturation magnetization of manganese ferrite nanoparticles, samples with various compositions (Mn x Fe3-x O4, x = 0, 0.25, 0.5, 0.75, and 1) were synthesized and characterized. The saturation magnetization of such materials was both calculated using density functional theory and measured via vibrating sample magnetometry. A discrepancy was found; the computational data demonstrated a positive correlation between manganese content and saturation magnetization, while the experimental data exhibited an inverse correlation. X-ray diffraction (XRD) and magnetometry results indicated that the crystallite diameter and the magnetic diameter decrease when adding more manganese, which could explain the loss of magnetization of the particles. For 20 nm nanoparticles, with increasing manganese substitution level, the crystallite size decreases from 10.9 nm to 6.3 nm and the magnetic diameter decreases from 15.1 nm to 3.5 nm. Further high resolution transmission electron microscopy (HRTEM) analysis confirmed the manganese substitution induced defects in the crystal lattice, which encourages us to find ways of eliminating crystalline defects to make more reliable ferrite nanoparticles.

The choroid plexus and its role in the pathogenesis of neurological infections.

The choroid plexus is situated at an anatomically and functionally important interface within the ventricles of the brain, forming the blood-cerebrospinal fluid barrier that separates the periphery from the central nervous system. In contrast to the blood-brain barrier, the choroid plexus and its epithelial barrier have received considerably less attention. As the main producer of cerebrospinal fluid, the secretory functions of the epithelial cells aid in the maintenance of CNS homeostasis and are capable of relaying inflammatory signals to the brain. The choroid plexus acts as an immunological niche where several types of peripheral immune cells can be found within the stroma including dendritic cells, macrophages, and T cells. Including the epithelia cells, these cells perform immunosurveillance, detecting pathogens and changes in the cytokine milieu. As such, their activation leads to the release of homing molecules to induce chemotaxis of circulating immune cells, driving an immune response at the choroid plexus. Research into the barrier properties have shown how inflammation can alter the structural junctions and promote increased bidirectional transmigration of cells and pathogens. The goal of this review is to highlight our foundational knowledge of the choroid plexus and discuss how recent research has shifted our understanding towards viewing the choroid plexus as a highly dynamic and important contributor to the pathogenesis of neurological infections. With the emergence of several high-profile diseases, including ZIKA and SARS-CoV-2, this review provides a pertinent update on the cellular response of the choroid plexus to these diseases. Historically, pharmacological interventions of CNS disorders have proven difficult to develop, however, a greater focus on the role of the choroid plexus in driving these disorders would provide for novel targets and routes for therapeutics.

Cryo-FIB for TEM investigation of soft matter and beam sensitive energy materials.

Primarily driven by structural biology, the rapid advances in cryogenic electron microscopy techniques are now being adopted and applied by materials scientists. Samples that inherently have electron transparency can be rapidly frozen (vitrified) in amorphous ice and imaged directly on a cryogenic transmission electron microscopy (cryo-TEM), however this is not the case for many important materials systems, which can consist of layered structures, embedded architectures, or be contained within a device. Cryogenic focused ion beam (cryo-FIB) lift-out procedures have recently been developed to extract intact regions and interfaces of interest, that can then be thinned to electron transparency and transferred to the cryo-TEM for characterization. Several detailed studies have been reported demonstrating the cryo-FIB lift-out procedure, however due to its relative infancy in materials science improvements are still required to ensure the technique becomes more accessible and routinely successful. Here, we review recent results on the preparation of cryo-TEM lamellae using cryo-FIB and show that the technique is broadly applicable to a range of soft matter and beam sensitive energy materials. We then present a tutorial that can guide the materials scientist through the cryo-FIB lift-out process, highlighting recent methodological advances that address the most common failure points of the technique, such as needle attachment, lift-out and transfer, and final thinning.

Cesium Lead Halide Perovskite Nanocrystals Assembled in Metal-Organic Frameworks for Stable Blue Light Emitting Diodes.

All inorganic cesium lead trihalide nanocrystals are promising light emitters for bright light emitting diodes (LEDs). Here, CsPb(BrCl)1.5 nanocrystals in metal-organic frameworks (MOF) thin films are demonstrated to achieve bright and stable blue LEDs. The lead metal nodes in the MOF thin film react with Cs-halide salts, resulting in 10-20 nm nanocrystals. This is revealed by X-ray scattering and transmission electron microscopy. Employing the CsPbX3 -MOF thin films as emission layers, bright deep blue and sky-blue LEDs are demonstrated that emit at 452 and 476 nm respectively. The maximum external quantum efficiencies of these devices are 0.72% for deep blue LEDs and 5.6% for sky blue LEDs. More importantly, the device can maintain 50% of its original electroluminescence (T50 ) for 2.23 h when driving at 4.2 V. Detailed optical spectroscopy and time-of-flight secondary ion mass spectroscopy suggest that the ion migration can be suppressed that maintains the emission brightness and spectra. The study provides a new route for fabricating stable blue light emitting diodes with all-inorganic perovskite nanocrystals.

Review of Multifunctional Separators: Stabilizing the Cathode and the Anode for Alkali (Li, Na, and K) Metal-Sulfur and Selenium Batteries.

Alkali metal batteries based on lithium, sodium, and potassium anodes and sulfur-based cathodes are regarded as key for next-generation energy storage due to their high theoretical energy and potential cost effectiveness. However, metal-sulfur batteries remain challenged by several factors, including polysulfides' (PSs) dissolution, sluggish sulfur redox kinetics at the cathode, and metallic dendrite growth at the anode. Functional separators and interlayers are an innovative approach to remedying these drawbacks. Here we critically review the state-of-the-art in separators/interlayers for cathode and anode protection, covering the Li-S and the emerging Na-S and K-S systems. The approaches for improving electrochemical performance may be categorized as one or a combination of the following: Immobilization of polysulfides (cathode); catalyzing sulfur redox kinetics (cathode); introduction of protective layers to serve as an artificial solid electrolyte interphase (SEI) (anode); and combined improvement in electrolyte wetting and homogenization of ion flux (anode and cathode). It is demonstrated that while the advances in Li-S are relatively mature, less progress has been made with Na-S and K-S due to the more challenging redox chemistry at the cathode and increased electrochemical instability at the anode. Throughout these sections there is a complementary discussion of functional separators for emerging alkali metal systems based on metal-selenium and the metal-selenium sulfide. The focus then shifts to interlayers and artificial SEI/cathode electrolyte interphase (CEI) layers employed to stabilize solid-state electrolytes (SSEs) in metal-sulfur solid-state batteries (SSBs). The discussion of SSEs focuses on inorganic electrolytes based on Li- and Na-based oxides and sulfides but also touches on some hybrid systems with an inorganic matrix and a minority polymer phase. The review then moves to practical considerations for functional separators, including scaleup issues and Li-S technoeconomics. The review concludes with an outlook section, where we discuss emerging mechanics, spectroscopy, and advanced electron microscopy (e.g. cryo-transmission electron microscopy (cryo-TEM) and cryo-focused ion beam (cryo-FIB))-based approaches for analysis of functional separator structure-battery electrochemical performance interrelations. Throughout the review we identify the outstanding open scientific and technological questions while providing recommendations for future research topics.