Simultaneous Monitoring of Crystalline Active Materials and Resistance Evolution in Lithium-Sulfur Batteries.

Operando X-ray diffraction (XRD) is a valuable tool for studying secondary battery materials as it allows for the direct correlation of electrochemical behavior with structural changes of crystalline active materials. This is especially true for the lithium-sulfur chemistry, in which energy storage capability depends on the complex growth and dissolution kinetics of lithium sulfide (Li2S) and sulfur (S8) during discharge and charge, respectively. In this work, we present a novel development of this method through combining operando XRD with simultaneous and continuous resistance measurement using an intermittent current interruption (ICI) method. We show that a coefficient of diffusion resistance, which reflects the transport properties in the sulfur/carbon composite electrode, can be determined from analysis of each current interruption. Its relationship to the established Warburg impedance model is validated theoretically and experimentally. We also demonstrate for an optimized electrode formulation and cell construction that the diffusion resistance increases sharply at the discharge end point, which is consistent with the blocking of pores in the carbon host matrix. The combination of XRD with ICI allows for a direct correlation of structural changes with not only electrochemical properties but also energy loss processes at a nonequilibrium state and, therefore, is a valuable technique for the study of a wide range of energy storage chemistries.

The molecular genetics of cellular senescence in the context of organismal aging.

Cellular senescence is a physiological state generally defined as a stable arrest of proliferation by preventing the cells from cycling. Unlike terminally differentiated cells, that also do not show proliferative activity, cellular senescence is stress induced and blocks the proliferation of cells with theoretical ability to divide (such as progenitor, stem or cancer cells) due to the activity of specific signaling pathways. The number of senescent cells increases during the ontogenesis of an organism. Senescent cells are not only associated with aging, but also significantly influence this process - a fact that is becoming increasingly well documented.

Operando EQCM-D with Simultaneous in Situ EIS: New Insights into Interphase Formation in Li Ion Batteries.

An operando electrochemical quartz crystal microbalance with dissipation monitoring (EQCM-D) with simultaneous in situ electrochemical impedance spectroscopy (EIS) has been developed and applied to study the solid electrolyte interphase (SEI) formation on copper current collectors in Li ion batteries. The findings are backed by EIS simulations and complementary analytical techniques, such as online electrochemical mass spectrometry (OEMS) and X-ray photoelectron spectroscopy (XPS). The evolution of mass and the mechanical properties of the SEI are directly correlated to the electrode impedance. Electrolyte reduction at the anode carbon active material initiates dissolution, diffusion, and deposition of reaction side products throughout the cell and increases electrolyte viscosity and the ohmic cell resistance as a result. On Cu the reduction of CuO x and HF occurs at >1.5 V and forms an initial LiF-rich interphase while electrolyte solvent reduction at <0.8 V vs Li+/Li adds a second, less rigid layer on top. Both the shear storage modulus and viscosity of the SEI generally increase upon cycling but-along with the SEI Li+ diffusion coefficient-also respond reversibly to electrode potential, likely as a result of Li+/EC interfacial concentration changes. Combined EIS-EQCM-D provides unique prospects for further studies of the highly dynamic structure-function relationships of electrode interphases in Li ion batteries.

A non-academic perspective on the future of lithium-based batteries.

In the field of lithium-based batteries, there is often a substantial divide between academic research and industrial market needs. This is in part driven by a lack of peer-reviewed publications from industry. Here we present a non-academic view on applied research in lithium-based batteries to sharpen the focus and help bridge the gap between academic and industrial research. We focus our discussion on key metrics and challenges to be considered when developing new technologies in this industry. We also explore the need to consider various performance aspects in unison when developing a new material/technology. Moreover, we also investigate the suitability of supply chains, sustainability of materials and the impact on system-level cost as factors that need to be accounted for when working on new technologies. With these considerations in mind, we then assess the latest developments in the lithium-based battery industry, providing our views on the challenges and prospects of various technologies.

Rapid determination of solid-state diffusion coefficients in Li-based batteries via intermittent current interruption method.

The galvanostatic intermittent titration technique (GITT) is considered the go-to method for determining the Li+ diffusion coefficients in insertion electrode materials. However, GITT-based methods are either time-consuming, prone to analysis pitfalls or require sophisticated interpretation models. Here, we propose the intermittent current interruption (ICI) method as a reliable, accurate and faster alternative to GITT-based methods. Using Fick's laws, we prove that the ICI method renders the same information as the GITT within a certain duration of time since the current interruption. Via experimental measurements, we also demonstrate that the results from ICI and GITT methods match where the assumption of semi-infinite diffusion applies. Moreover, the benefit of the non-disruptive ICI method to operando materials characterization is exhibited by correlating the continuously monitored diffusion coefficient of Li+ in a LiNi0.8Mn0.1Co0.1O2-based electrode to its structural changes captured by operando X-ray diffraction measurements.

Biomarkers and Strain Echocardiography for the Detection of Subclinical Cardiotoxicity in Breast Cancer Patients Receiving Anthracyclines.

The optimal surveillance and management strategies for breast cancer patients receiving anthracycline therapy are limited by our incomplete understanding of the role of biomarkers heralding the onset of cardiotoxicity. The purpose of this study was to determine whether there is a temporal correlation between cardiac biomarkers and subclinical left ventricular dysfunction in breast cancer patients receiving anthracycline chemotherapy. Thirty-one females between 46 and 55 years old with breast cancer treated with anthracycline chemotherapy were prospectively enrolled. Cardiac biomarkers were correlated with echocardiography with speckle tracking at baseline, post-anthracycline therapy, and 6 months post-anthracycline chemotherapy. Subclinical cardiotoxicity was defined as ≥ 10% reduction in global longitudinal strain (GLS). There was a relative reduction in left ventricular ejection fraction (LVEF) ≥ 10% in 5/30 (17%) and 7/27 (26%) patients post-anthracycline therapy and 6 months post-anthracycline therapy, respectively. Subclinical cardiotoxicity was noted in 8/30 (27%) and 10/26 (38%) patients post-anthracycline and 6 months post-anthracycline therapy, respectively. Baseline N-terminal pro B-type natriuretic peptide (NT-proBNP) was the strongest predictor of LVEF (ρ = -0.45; p = 0.019), with post-therapy NT-proBNP values illustrating similar predictive value (ρ = -0.40; p = 0.038). Interim changes in suppression of tumorigenicity 2 (ST2) and galectin-3 correlated with a 6-month change in LVEF (ρ = -0.48; p = 0.012 and ρ = -0.45; p = 0.018, for ST2 and galectin-3, respectively). Changes in galectin-3 from baseline to mid-therapy paralleled changes in GLS. NT-proBNP, ST2, and galectin-3 correlate with reduced LVEF among breast cancer patients receiving anthracycline therapy. Additional trials focusing on a cardiac biomarker approach may provide guidance in the early diagnosis and management of anthracycline-induced cardiotoxicity.

Towards reliable three-electrode cells for lithium-sulfur batteries.

Three-electrode measurements are valuable to the understanding of the electrochemical processes in a battery system. However, their application in lithium-sulfur chemistry is difficult due to the complexity of the system and thus rarely reported. Here, we present a simple three-electrode cell format with relatively good life time and minimum interference with the cell operation.

On the Durability of Protective Titania Coatings on High-Voltage Spinel Cathodes.

TiO2 -coating of LiNi0.5-x Mn1.5+x O4 (LNMO) by atomic layer deposition (ALD) has been studied as a strategy to stabilize the cathode/electrolyte interface and mitigate transition metal (TM) ion dissolution. The TiO2 coatings were found to be uniform, with thicknesses estimated to 0.2, 0.3, and 0.6 nm for the LNMO powders exposed to 5, 10, and 20 ALD cycles, respectively. While electrochemical characterization in half-cells revealed little to no improvement in the capacity retention neither at 20 nor at 50 °C, improved capacity retention and coulombic efficiencies were demonstrated for the TiO2 -coated LNMO in LNMO||graphite full-cells at 20 °C. This improvement in cycling stability could partly be attributed to thinner cathode electrolyte interphase on the TiO2 -coated samples. Additionally, energy-dispersive X-ray spectroscopy revealed a thinner solid electrolyte interphase on the graphite electrode cycled against TiO2 -coated LNMO, indicating retardation of TM dissolution by the TiO2 -coating.

Investigation of Water-Soluble Binders for LiNi0.5 Mn1.5 O4 -Based Full Cells.

Two water-soluble binders of carboxymethyl cellulose (CMC) and sodium alginate (SA) have been studied in comparison with N-methylpyrrolidone-soluble poly(vinylidene difluoride-co-hexafluoropropylene) (PVdF-HFP) to understand their effect on the electrochemical performance of a high-voltage lithium nickel manganese oxide (LNMO) cathode. The electrochemical performance has been investigated in full cells using a Li4 Ti5 O12 (LTO) anode. At room temperature, LNMO cathodes prepared with aqueous binders provided a similar electrochemical performance as those prepared with PVdF-HFP. However, at 55 °C, the full cells containing LNMO with the aqueous binders showed higher cycling stability. The results are supported by intermittent current interruption resistance measurements, wherein the electrodes with SA showed lower resistance. The surface layer formed on the electrodes after cycling has been characterized by X-ray photoelectron spectroscopy. The amount of transition metal dissolutions was comparable for all three cells. However, the amount of hydrogen fluoride (HF) content in the electrolyte cycled at 55 °C is lower in the cell with the SA binder. These results suggest that use of water-soluble binders could provide a practical and more sustainable alternative to PVdF-based binders for the fabrication of LNMO electrodes.

Nociceptin/orphanin FQ opioid receptor (NOP) selective ligand MCOPPB links anxiolytic and senolytic effects.

Accumulation of senescent cells may drive age-associated alterations and pathologies. Senolytics are promising therapeutics that can preferentially eliminate senescent cells. Here, we performed a high-throughput automatized screening (HTS) of the commercial LOPAC®Pfizer library on aphidicolin-induced senescent human fibroblasts, to identify novel senolytics. We discovered the nociceptin receptor FQ opioid receptor (NOP) selective ligand 1-[1-(1-methylcyclooctyl)-4-piperidinyl]-2-[(3R)-3-piperidinyl]-1H-benzimidazole (MCOPPB, a compound previously studied as potential anxiolytic) as the best scoring hit. The ability of MCOPPB to eliminate senescent cells in in vitro models was further tested in mice and in C. elegans. MCOPPB reduced the senescence cell burden in peripheral tissues but not in the central nervous system. Mice and worms exposed to MCOPPB also exhibited locomotion and lipid storage changes. Mechanistically, MCOPPB treatment activated transcriptional networks involved in the immune responses to external stressors, implicating Toll-like receptors (TLRs). Our study uncovers MCOPPB as a NOP ligand that, apart from anxiolytic effects, also shows tissue-specific senolytic effects.

Poly(Ethylene Glycol-block-2-Ethyl-2-Oxazoline) as Cathode Binder in Lithium-Sulfur Batteries.

Functional binders constitute a strategy to overcome several challenges that lithium-sulfur (Li-S) batteries are facing due to soluble reaction intermediates in the positive electrode. Poly (ethylene oxide) (PEO) and poly (vinylpyrrolidone) (PVP) are in this context a previously well-explored binder mixture. Their ether and amide groups possess affinity to the dissolved sulfur species, which enhances the sulfur utilization and mitigates the parasitic redox shuttle. However, the immiscibility of PEO and PVP is a concern for electrode stability. Copolymers comprising ether and amide groups are thus promising candidates to improve the stability the system. Here, a series of poly (ethylene glycol-block-2-ethyl-2-oxazoline) with various block lengths is synthesized and explored as binders in S/C composite electrodes in Li-S cells. While the electrochemical analyses show that although the sulfur utilization and capacity retention of the tested electrodes are similar, the integrity of the as-cast electrodes can play a key role for power capability.

Limitations of Ultrathin Al2O3 Coatings on LNMO Cathodes.

This study demonstrates the application of Al2O3 coatings for the high-voltage cathode material LiNi0.5-x Mn1.5+x O4-δ (LNMO) by atomic layer deposition. The ultrathin and uniform coatings (0.6-1.7 nm) were deposited on LNMO particles and characterized by scanning transmission electron microscopy, inductively coupled plasma mass spectrometry, and X-ray photoelectron spectroscopy. Galvanostatic charge discharge cycling in half cells revealed, in contrast to many published studies, that even coatings of a thickness of 1 nm were detrimental to the cycling performance of LNMO. The complete coverage of the LNMO particles by the Al2O3 coating can form a Li-ion diffusion barrier, which leads to high overpotentials and reduced reversible capacity. Several reports on Al2O3-coated LNMO using alternative coating methods, which would lead to a less homogeneous coating, revealed the superior electrochemical properties of the Al2O3-coated LNMO, suggesting that complete coverage of the particles might in fact be a disadvantage. We show that transition metal ion dissolution during prolonged cycling at 50 °C is not hindered by the coating, resulting in Ni and Mn deposits on the Li counter electrode. The Al2O3-coated LNMO particles showed severe signs of pitting dissolution, which may be attributed to HF attack caused by side reactions between the electrolyte and the Al2O3 coating, which can lead to additional HF formation. The pitting dissolution was most severe for the thickest coating (1.7 nm). The uniform coating coverage may lead to non-uniform conduction paths for Li, where the active sites are more susceptible to HF attack. Few benefits of applications of very thin, uniform, and amorphous Al2O3 coatings could thus be verified, and the coating is not offering long-term protection from HF attack.

Prospective Experience of Pulmonary Embolism Management and Outcomes.

OBJECTIVE: We sought to evaluate the impact of pulmonary embolism (PE) response teams (PERTs) on all consecutive patients with PE. BACKGROUND: Multidisciplinary PERTs have been promoted for the management and treatment of (PE); however, the impact of PERTs on clinical outcomes has not been prospectively evaluated. METHODS: We prospectively studied 220 patients with computed tomography (CT)-confirmed PE between January, 2019 and August, 2019. Baseline characteristics, as well as medical, interventional, and operational care, were captured. The total population was divided into 2 groups, ie, those with PERT activation and those without PERT activation. PERT activation was left at the discretion of the primary team. Our primary outcome was 90-day composite endpoint (rate of readmission, major bleeds, and mortality). Using 2:1 propensity-matched and multivariable-adjusted Cox proportional hazard analyses, we examined the impact of PERT activation on primary outcome, treatment approach, and length of stay. RESULTS: Of the total 220 patients, PERT was activated in 47 (21.4%). The PERT cohort, as compared with the non-PERT cohort, was more likely to present with dyspnea, syncope, lower systolic blood pressure, higher heart rate, higher respiratory rate, lower oxygen saturation, higher troponin levels, and higher right ventricular to left ventricular ratio. PERT activation was associated with increased use of advanced therapies (36.2% vs 1.2%; P<.001) and catheter-directed inventions (25.5% vs 0.6%; P<.001). In multivariable-adjusted analysis of propensity-matched cohorts, PERT activation was associated with lower 90-day outcomes (hazard ratio, 0.40; 95% confidence interval, 0.21-0.75; P<.01). CONCLUSION: At our institution, PERT had a clinically significant impact on therapeutic strategies and 90-day outcomes in patients with PE.

Beneficial Effect of Heat-induced Antigen Retrieval in Immunocytochemical Detection of Intracellular Antigens in Alcohol-fixed Cell Samples.

Immunohistochemistry and immunocytochemistry (ICC) play an irreplaceable role in research and diagnostics. It is well known that antigen retrieval (AR) can, as a technique, have beneficial outcomes on immunohistochemistry results when using formalin-fixed, paraffin-embedded tissue samples. The main purpose of AR is to break protein crosslinks which are formed during formalin fixation. Although AR was originally designed for formalin-fixed, paraffin-embedded samples, the usefulness of AR in ICC has been described in previous studies. Cytologic samples are often fixed in alcohol-based fixatives which does not lead to the formation of crosslinks. Therefore, alcohol-fixed samples can be successfully immunostained without AR. We investigated the effect of heat-induced antigen retrieval (HIAR) on alcohol-fixed HEK293 cell line samples and patient cytologic samples from thyroid gland obtained by fine needle aspiration technique. We compared indirect 2-step ICC staining results performed according to the protocol with or without HIAR in citrate buffer pH 6 for several antibodies. Utilizing HIAR against intracellular antigens has beneficial effects. Therefore, more diluted antibodies can be used for satisfactory results. However, surface antigens were probably damaged by HIAR treatment. We demonstrated evident changes in cell surface topography after HIAR treatment by atomic force microscopy. Staining specificity of patient samples improves and background staining is reduced, allowing higher dilutions of primary antibody. Improving staining specificity is necessary for accurate diagnostics. Although we have shown the beneficial effect of HIAR for immunostaining intracellular antigens, proper staining protocol should be tested on appropriate controls for individual antibodies.

Coronary Embolism: A Systematic Review.

BACKGROUND: Coronary embolism is a rare and potentially fatal phenomenon that occurs primarily in patients with valvular heart disease and atrial fibrillation. There is a lack of consensus regarding the diagnosis, treatment, and management of coronary embolism, leaving management at the discretion of the treating physician. Through this review, we aim to establish a better understanding of coronary embolism, and to identify treatment options - invasive and non-invasive - that may be used to manage coronary embolism. METHODS AND RESULTS: Our systematic review included 147 documented cases of coronary embolism from case reports and case series. The average age of our population was 54.2 ±â€¯17.6 years. The most common causes of coronary embolism included infective endocarditis (22.4%), atrial fibrillation (17.0%), and prosthetic heart valve thrombosis (16.3%). Initial presentation was indistinguishable from an acute coronary syndrome (ACS) due to coronary atherosclerosis, and the diagnosis required a high level of suspicion and evaluation with angiography. Treatment strategies included, but were not limited to, thrombectomy, thrombolysis, balloon angioplasty and stent placement. Myocardial dysfunction on echocardiography was observed in over 80% of patients following coronary embolism. "Good outcomes" were reported in 68.7% of case reports and case series, with a mortality rate of 12.9%. CONCLUSION: Coronary embolism is an under-recognized etiology of myocardial infarction with the potential for significant morbidity and mortality. To improve outcomes, physicians should strive for early diagnosis and intervention based on the underlying etiology. Thrombectomy may be considered with the goal of rapid restoration of coronary flow.

Impaired ribosome biogenesis: mechanisms and relevance to cancer and aging.

The biosynthesis of ribosomes is a complex process that requires the coordinated action of many factors and a huge energy investment from the cell. Ribosomes are essential for protein production, and thus for cellular survival, growth and proliferation. Ribosome biogenesis is initiated in the nucleolus and includes: the synthesis and processing of ribosomal RNAs, assembly of ribosomal proteins, transport to the cytoplasm and association of ribosomal subunits. The disruption of ribosome biogenesis at various steps, with either increased or decreased expression of different ribosomal components, can promote cell cycle arrest, senescence or apoptosis. Additionally, interference with ribosomal biogenesis is often associated with cancer, aging and age-related degenerative diseases. Here, we review current knowledge on impaired ribosome biogenesis, discuss the main factors involved in stress responses under such circumstances and focus on examples with clinical relevance.

Anuric Acute Kidney Injury Due to Infection-related Glomerulonephritis Secondary to Foot Osteomyelitis.

We report the case of a 76-year-old male who developed anuric acute kidney injury from infection-related glomerulonephritis (IRGN) secondary to foot osteomyelitis, confirmed via renal biopsy. The patient initially presented with wound dehiscence of the left foot following transmetatarsal amputation and Lisfranc operation in the setting of osteomyelitis. Hospitalization was complicated by worsening acute kidney injury requiring the initiation of hemodialysis. Despite successful surgical correction and the removal of the infectious source, the patient was unable to regain significant renal function and remained hemodialysis dependent. This case highlights a rarely seen complication of osteomyelitis and underscores the value of prompt and aggressive management of osteomyelitis in patients with infection-related glomerulonephritis.

Primary Small Bowel Adenocarcinoma Presenting with Duodenal Stricture and Hepatic and Gastroduodenal Artery Encasement: A Case Report.

Primary small bowel adenocarcinoma is rare, with an estimated U.S. annual incidence of 3.9 cases per million persons, and is often associated with a poor prognosis. We report a case of a 68-year-old male diagnosed with primary duodenal adenocarcinoma with hepatic artery and gastroduodenal artery encasement. The patient initially presented with persistent nausea and vomiting unresponsive to ondansetron and metoclopramide, and initial computed tomography (CT) of abdomen and pelvis revealed significant stomach distension concerning for gastric outlet obstruction. Esophagogastroduodenoscopy (EGD) revealed significant duodenal stricture, with results of triple phase CT of pancreas significant for tissue encasing the common hepatic artery and the origin of the gastroduodenal artery. Pathology results verified the presence of a moderately differentiated adenocarcinoma involving the small bowel. Due to artery encasement by the tumor, the patient was deemed to be a poor surgical candidate, and instead received a duodenal stent for symptomatic relief with initiation of a chemotherapy regimen consisting of folinic acid, oxaliplatin, and fluorouracil (FOLFOX) as an outpatient. This case highlights the presentation and diagnostic workup of a rare cancer.

ε-Caprolactone-based solid polymer electrolytes for lithium-ion batteries: synthesis, electrochemical characterization and mechanical stabilization by block copolymerization.

In this work, three types of polymers based on ε-caprolactone have been synthesized: poly(ε-caprolactone), polystyrene-poly(ε-caprolactone), and polystyrene-poly(ε-caprolactone-r-trimethylene carbonate) (SCT), where the polystyrene block was introduced to improve the electrochemical and mechanical performance of the material. Solid polymer electrolytes (SPEs) were produced by blending the polymers with 10-40 wt% lithium bis(trifluoromethane)sulfonimide (LiTFSI). Battery devices were thereafter constructed to evaluate the cycling performance. The best performing battery half-cell utilized an SPE consisting of SCT and 17 wt% LiTFSI as both binder and electrolyte; a Li|SPE|LiFePO4 cell that cycled at 40 °C gave a discharge capacity of about 140 mA h g-1 at C/5 for 100 cycles, which was superior to the other investigated electrolytes. Dynamic mechanical analysis (DMA) showed that the storage modulus E' was about 5 MPa for this electrolyte.