Two-phase system model to predict hydrophobic organic compound partition to heterogeneous soil dissolved organic matter across China.

Soil dissolved organic matter (SDOM) is an important part of the DOM pool in terrestrial systems, influencing the transport and fate of many pollutants. In this study, SDOMs from different regions across China were compared by a series of spectroscopic methods, including UV‒vis spectroscopy, fluorescence spectroscopy, and Fourier transform infrared (FTIR) spectroscopy, and the hydrophobicity was quantified by partition coefficients of SDOM in the aqueous two-phase system (KATPS). The molecular weight, aromaticity, and hydrophobicity of SDOM from different regions exhibited strong heterogeneity, KATPS combined with UV‒vis and fluorescence indices can be readily used for differentiating heterogeneous SDOM, and SDOMs were compositionally and structurally different from DOMs in aquatic systems based on spectral characterization. Importantly, the two-phase system (TPS) model has only been validated by DOMs in freshwater systems, and good organic carbon‒water partition coefficient (KOC) predictive power (RMSE = 0.11) could be provided by the TPS model when applied to heterogeneous SDOM without calibration, showing its broad applicability. Our results demonstrate the applicability of the TPS model for predicting the sorption behavior of terrestrial DOM, broadening the application scope of the TPS model and indicating its potential as a routine model for the risk assessment of hydrophobic organic compounds (HOCs) in organic contaminated sites.

Hypo-attenuating Berry Sign as a Novel Imaging Marker of Ruptured Aneurysm in Patients with Subarachnoid Hemorrhage; a Diagnostic Accuracy Study.

Introduction: Aneurysmal subarachnoid hemorrhage (SAH) constitutes a life-threatening condition, and identifying the ruptured aneurysm is essential for further therapy. This study aimed to evaluate the diagnostic accuracy of hypo-attenuating berry sign (HBS) observed on computed tomography (CT) scan in distinguishing ruptured aneurysms. Methods: In this diagnostic accuracy study, patients who had SAH and underwent non-enhanced brain CT scan were recruited. The HBS was defined as a hypo-attenuating area with an identifiable border in the blood-filled hyper-dense subarachnoid space. The screening performance characteristics of HBS in identifying ruptured aneurysms were calculated considering the digital subtraction angiography (DSA) as the gold standard. Results: A total of 129 aneurysms in 131 patients were analyzed. The overall sensitivity and specificity of HBS in the diagnosis of aneurysms were determined to be 78.7% (95%CI: 73.1% - 83.4%) and 70.7% (95%CI: 54.3% - 83.4%), respectively. Notably, the sensitivity increased to 90.9% (95%CI: 84.3% - 95.0%) for aneurysms larger than 5mm. The level of inter-observer agreement for assessing the presence of HBS was found to be substantial (kappa=0.734). The diagnostic accuracy of HBS in individuals exhibited enhanced specificity, sensitivity, and reliability when evaluating patients with a solitary aneurysm or assessing ruptured aneurysms. The multivariate logistic regression analysis revealed a statistically significant relationship between aneurysm size and the presence of HBS (odds ratios of 1.667 (95%CI: 1.238 - 2.244; p < 0.001) and 1.696 (95%CI: 1.231 - 2.335; p = 0.001) for reader 1 and reader 2, respectively). Conclusions: The HBS can serve as a simple and easy-to-use indicator for identifying a ruptured aneurysm and estimating its size in SAH patients.  .

LRP1 induces anti-PD-1 resistance by modulating the DLL4-NOTCH2-CCL2 axis and redirecting M2-like macrophage polarisation in bladder cancer.

The tumour microenvironment (TME) drives bladder cancer (BLCA) progression. Targeting the TME has emerged as a promising strategy for BLCA treatment in recent years. Furthermore, checkpoint blockade therapies are only beneficial for a minority of patients with BLCA, and drug resistance is a barrier to achieving significant clinical effects of anti-programmed cell death protein-1 (PD-1)/programmed death protein ligand-1 (PD-L1) therapy. In this study, higher low-density lipoprotein receptor-related protein 1 (LRP1) levels were related to a poorer prognosis for patients with various cancers, including those with higher grades and later stages of BLCA. Enrichment analysis demonstrated that LRP1 plays a role in the epithelial-mesenchymal transition (EMT), NOTCH signalling pathway, and ubiquitination. LRP1 knockdown in BLCA cells delayed BLCA progression both in vivo and in vitro. Furthermore, LRP1 knockdown suppressed EMT, reduced DLL4-NOTCH2 signalling activity, and downregulated M2-like macrophage polarisation. Patients with BLCA and higher LRP1 levels responded weakly to anti-PD-1 therapy in the IMvigor210 cohort. Moreover, LRP1 knockdown enhanced the therapeutic effects of anti-PD-1 in mice. Taken together, our findings suggest that LRP1 is a potential target for improving the efficacy of anti-PD-1/PD-L1 therapy by preventing EMT and M2-like macrophage polarisation by blocking the DLL4-NOTCH2 axis.

Detection of Dolichoectasia and Atherosclerosis by Automated MRA Tortuosity Metrics in a Population-Based Study.

BACKGROUND: Intracranial vessel tortuosity is a key component of dolichoectasia and has been associated with atherosclerosis and adverse neurologic outcomes. However, the evaluation of tortuosity is mainly a descriptive assessment. PURPOSE: To compare the performance of three automated tortuosity metrics (angle metric [AM], distance metric [DM], and distance-to-axis metric [DTA]) for detection of dolichoectasia and presence of segment-specific plaques. STUDY TYPE: Observational, cross-sectional metric assessment. POPULATION: 1899 adults from the general population; mean age = 76 years, female = 59%, and black = 29%. FIELD STRENGTH/SEQUENCE: 3-T, three-dimensional (3D) time-of-flight MRA and 3D vessel wall MRI. ASSESSMENT: Tortuosity metrics and mean luminal area were quantified for designated segments of the internal carotid artery, middle cerebral artery, anterior cerebral artery, posterior cerebral artery, vertebral artery, and entire length of basilar artery (BA). Qualitative interpretations of BA dolichoectasia were assessed based on Smoker's visual criteria. STATISTICAL TESTS: Descriptive statistics (2-sample t-tests, Pearson chi-square tests) for group comparisons. Receiver operating characteristics area under the curve (AUC) for detection of BA dolichoectasia or segment-specific plaque. Model inputs included 1) tortuosity metrics, 2) mean luminal area, and 3) demographics (age, race, and sex). RESULTS: Qualitative dolichoectasia was identified in 336 (18%) participants, and atherosclerotic plaques were detected in 192 (10%) participants. AM-, DM-, and DTA-calculated tortuosity were good individual discriminators of basilar dolichoectasia (AUCs: 0.76, 0.74, and 0.75, respectively), with model performance improving with the mean lumen area: (AUCs: 0.88, 0.87, and 0.87, respectively). Combined characteristics (tortuosity and mean luminal area) identified plaques with better performance in the anterior (AUCs ranging from 0.66 to 0.78) than posterior (AUCs ranging from 0.54 to 0.65) circulation, with all models improving by the addition of demographics (AUCs ranging from 0.62 to 0.84). DATA CONCLUSION: Quantitative vessel tortuosity metrics yield good diagnostic accuracy for the detection of dolichoectasia. LEVEL OF EVIDENCE: 1 TECHNICAL EFFICACY STAGE: 2.

Critical Contribution of Imbalanced Charge Loss to Performance Deterioration of Si-Based Lithium-Ion Cells during Calendar Aging.

Increasing the energy density of lithium-ion batteries, and thereby reducing costs, is a major target for industry and academic research. One of the best opportunities is to replace the traditional graphite anode with a high-capacity anode material, such as silicon. However, Si-based lithium-ion batteries have been widely reported to suffer from a limited calendar life for automobile applications. Heretofore, there lacks a fundamental understanding of calendar aging for rationally developing mitigation strategies. Both open-circuit voltage and voltage-hold aging protocols were utilized to characterize the aging behavior of Si-based cells. Particularly, a high-precision leakage current measurement was applied to quantitatively measure the rate of parasitic reactions at the electrode/electrolyte interface. The rate of parasitic reactions at the Si anode was found 5 times and 15 times faster than those of LiNi0.8Mn0.1Co0.1O2 and LiFePO4 cathodes, respectively. The imbalanced charge loss from parasitic reactions plays a critical role in exacerbating performance deterioration. In addition, a linear relationship between capacity loss and charge consumption from parasitic reactions provides fundamental support to assess calendar life through voltage-hold tests. These new findings imply that longer calendar life can be achieved by suppressing parasitic reactions at the Si anode to balance charge consumption during calendar aging.

Effect of low molecular weight organic acids on the lead and chromium release from widely-used lead chromate pigments under sunlight irradiation.

Lead chromate pigments are commonly used yellow inorganic pigments. They can pose environmental risks as they contain toxic heavy metals lead and chromium. Low molecular weight organic acids (LMWOAs), as widespread dissolved organic matter (DOM), affect the lead and chromium release from the pigment in water. In this work, the role of LMWOAs in the photodissolution of commercial lead chromate pigment was investigated. The pigment underwent significant photodissolution under simulated sunlight exposure with LMWOAs, and subsequently released Cr(III) and Pb(II). The photodissolution process is caused by the reduction of Cr(VI) by photogenerated electrons of the lead chromate pigment. The LMWOAs promoted photodissolution of the pigment by improving the electron-hole separation. The formation of Cr(III)-contained compounds leads to a slower release of chromium than lead. The photodissolution kinetics increase with decreasing pH and increasing LMWOAs concentration. The photodissolution of lead chromate pigment was basically positively related to the total number of hydroxyl and carboxyl groups in LMWOAs. The LMWOAs with stronger affinity to lead chromate pigment, lower adiabatic ionization potential (AIP) and higher energy of the highest occupied molecular orbital (EHOMO) are favorable to Cr(VI) reduction by photogenerated electrons and pigment photodissolution. 2.39% of chromium and 10.34% of lead released from the lead chromate pigment in natural conditions during a 6-h sunlight exposure. This study revealed the photodissolution mechanism of lead chromate pigment mediated by LMWOAs with different molecular structures, which helps understand the environmental photochemical behavior of the pigment. The present results emphasize the important role of DOM in the heavy metals release from commercial inorganic pigments.

Mitochondria-ER contact mediated by MFN2-SERCA2 interaction supports CD8+ T cell metabolic fitness and function in tumors.

Metabolic fitness of T cells is essential for their vitality, which is largely dependent on the behavior of the mitochondria. The nature of mitochondrial behavior in tumor-infiltrating T cells remains poorly understood. In this study, we show that mitofusin-2 (MFN2) expression is positively correlated with the prognosis of multiple cancers. Genetic ablation of Mfn2 in CD8+ T cells dampens mitochondrial metabolism and function and promotes tumor progression. In tumor-infiltrating CD8+ T cells, MFN2 enhances mitochondria-endoplasmic reticulum (ER) contact by interacting with ER-embedded Ca2+-ATPase SERCA2, facilitating the mitochondrial Ca2+ influx required for efficient mitochondrial metabolism. MFN2 stimulates the ER Ca2+ retrieval activity of SERCA2, thereby preventing excessive mitochondrial Ca2+ accumulation and apoptosis. Elevating mitochondria-ER contact by increasing MFN2 in CD8+ T cells improves the efficacy of cancer immunotherapy. Thus, we reveal a tethering-and-buffering mechanism of organelle cross-talk that regulates the metabolic fitness of tumor-infiltrating CD8+ T cells and highlights the therapeutic potential of enhancing MFN2 expression to optimize T cell function.

Fatty acids metabolism affects the therapeutic effect of anti-PD-1/PD-L1 in tumor immune microenvironment in clear cell renal cell carcinoma.

BACKGROUND: Clear cell renal cell carcinoma (ccRCC) is a highly invasive and metastatic subtype of kidney malignancy and is correlated with metabolic reprogramming for adaptation to the tumor microenvironment comprising infiltrated immune cells and immunomodulatory molecules. The role of immune cells in the tumor microenvironment (TME) and their association with abnormal fatty acids metabolism in ccRCC remains poorly understood. METHOD: RNA-seq and clinical data of KIRC from The Cancer Genome Atlas (TCGA) and E-MTAB-1980 from the ArrayExpress dataset. The Nivolumab group and Everolimus group of the CheckMate 025 study, the Atezolizumab arm of IMmotion150 and the Atezolizumab plus Bevacizumab group of IMmotion151 cohort were obtained for subsequent analysis. After differential expression genes identification, the signature was constructed through univariate Cox proportional hazard regression and simultaneously the least absolute shrinkage and selection operator (Lasso) analysis and the predictive performance of our signature was assessed by using receiver operating characteristic (ROC), Kaplan-Meier (KM) survival analysis, nomogram, drug sensitivity analysis, immunotherapeutic effect analysis and enrichment analysis. Immunohistochemistry (IHC), qPCR and western blot were performed to measure related mRNA or protein expression. Biological features were evaluated by wound healing, cell migration and invasion assays and colony formation test and analyzed using coculture assay and flow cytometry. RESULTS: Twenty fatty acids metabolism-related mRNA signatures were constructed in TCGA and possessed a strong predictive performance demonstrated through time-dependent ROC and KM survival analysis. Notably, the high-risk group exhibited an impaired response to anti-PD-1/PD-L1 (Programmed death-1 receptor/Programmed death-1 receptor-ligand) therapy compared to the low-risk group. The overall levels of the immune score were higher in the high-risk group. Additionally, drug sensitivity analysis observed that the model could effectively predict efficacy and sensitivity to chemotherapy. Enrichment analysis revealed that the IL6-JAK-STAT3 signaling pathway was a major pathway. IL4I1 could promote ccRCC cells' malignant features through JAK1/STAT3 signaling pathway and M2-like macrophage polarization. CONCLUSION: The study elucidates that targeting fatty acids metabolism can affect the therapeutic effect of PD-1/PD-L1 in TME and related signal pathways. The model can effectively predict the response to several treatment options, underscoring its potential clinical utility.

Molecular-Weight-Dependent Infiltration and Adsorption of Polymers into Nanochannels.

The mesoporous silica shell coating hydrogenolysis nano-catalysts alters the molecular weight distributions of cleaved polymer chains compared to catalysts without a shell. The shell, composed of radially aligned narrow cylindrical nanopores, reduces the formation of low-valued gaseous products and increases the median molecular weight of the product, thus enhancing the value of the products for polymer upcycling. To understand the role of the mesoporous shell, we have studied the spatial distribution of polystyrene chains, used as a model polymer, in the nanochannels in both the melt phase and solution phase. In the melt, we observed from small-angle X-ray scattering experiments that the infiltration rate of the polymer into the nanochannels is inversely proportional to the molecular weight, which is consistent with theory. In theta solution experiments using UV-vis spectroscopy, we found that the shell significantly enhances polymer adsorption compared to nanoparticles without pores. In addition, the degree of polymer adsorption is not a monotonic function of molecular weight but initially increases with the molecular weight before eventually decreasing. The molecular weight for the peak adsorption increases with the pore diameter. This adsorption behavior is rationalized as resulting from a balance between the mixing entropy gain by surface adsorption and the conformational entropy penalty incurred by chains confined in the nanochannels. The spatial distribution of polymer chains in the nanochannels is visualized by energy-dispersive X-ray spectroscopy (EDX), and inverse Abel-transformed data reveals a less uniform polymer distribution along the primary pore axis for longer chains.

Overexpression of TREM1 is Associated with the Immune-Suppressive Microenvironment and Unfavorable Prognosis in Pan-Cancer.

Background: Triggering receptors expressed by myeloid cells-1 (TREM1) is a receptor belonging to the immunoglobulin superfamily and plays an important role in pro-inflammation in acute and chronic inflammatory disorders. However, the understanding of the immunomodulatory roles of TREM1 in the tumor microenvironment remains incomplete. Methods: The expression patterns of TREM1 mRNA in tumors and adjacent normal tissues were compared by analyzing data obtained from the Genotype-Tissue Expression and The Cancer Genome Atlas datasets. Survival analysis was performed to determine the prognostic value of TREM1. Functional enrichment analysis was applied to decipher the discrepancy in biological processes between high- and low-TREM1 groups across various cancers. The correlation between TREM1 and immune cell infiltration determined by using multiple algorithms was evaluated with the Pearson method. Four independent immunotherapy cohorts were adopted to validate the role of TREM1 as a biomarker. Results: TREM1 was elevated in most cancers as verified with clinical samples. Overexpression of TREM1 was linked with undesirable prognosis in patients. Further analysis revealed that TREM1 was positively correlated with immune response, pro-tumor pathways, and myeloid cell infiltration, while being negatively correlated with CD8+ T cell (including infiltration level and biological processes). Concordantly, tumors with high TREM1 levels were more resistant to immunotherapy. Through connective map analysis, therapeutically potential compounds like tozasertib and TPCA-1 were identified, which can be used synergistically with immunotherapy to improve the poor prognosis of patients with high TREM1 levels. Conclusion: Through a systematic and comprehensive pan-cancer analysis, we demonstrated that overexpression of TREM1 in tumors correlated closely with unfavorable outcome, infiltration of immune-suppressive cells, and immune regulation, which highlights its potential use as a tumor prognostic biomarker and a novel target for immunotherapy.

EHBP1L1 Drives Immune Evasion in Renal Cell Carcinoma through Binding and Stabilizing JAK1.

High lymphocyte infiltration and immunosuppression characterize the tumor microenvironment (TME) in renal cell carcinoma (RCC). There is an urgent need to elucidate how tumor cells escape the immune attack and to develop novel therapeutic targets to enhance the efficacy of immune checkpoint blockade (ICB) in RCC. Overactivated IFN-γ-induced JAK/STAT signaling involves in such TME, but the underlying mechanisms remain elusive. Here, EH domain-binding protein 1-like protein 1 (EHBP1L1) is identified as a crucial mediator of IFN-γ/JAK1/STAT1/PD-L1 signaling in RCC. EHBP1L1 is highly expressed in RCC, and high EHBP1L1 expression levels are correlated with poor prognosis and resistance to ICB. EHBP1L1 depletion significantly inhibits tumor growth, which is attributed to enhanced CD8+ T cell-mediated antitumor immunity. Mechanistically, EHBP1L1 interacts with and stabilizes JAK1. By competing with SOCS1, EHBP1L1 protects JAK1 from proteasomal degradation, which leads to elevated JAK1 protein levels and JAK1/STAT1/PD-L1 signaling activity, thereby forming an immunosuppressive TME. Furthermore, the combination of EHBP1L1 inhibition and ICB reprograms the immunosuppressive TME and prevents tumor immune evasion, thus significantly reinforcing the therapeutic efficacy of ICB in RCC patient-derived xenograft (PDX) models. These findings reveal the vital role of EHBP1L1 in immune evasion in RCC, which may be a potential complement for ICB therapy.

Operando study of mechanical integrity of high-volume expansion Li-ion battery anode materials coated by Al2O3.

Group IV elements and their oxides, such as Si, Ge, Sn and SiO have much higher theoretical capacity than commercial graphite anode. However, these materials undergo large volume change during cycling, resulting in severe structural degradation and capacity fading. Al2O3coating is considered an approach to improve the mechanical stability of high-capacity anode materials. To understand the effect of Al2O3coating directly, we monitored the morphology change of coated/uncoated Sn particles during cycling using operando focused ion beam-scanning electron microscopy. The results indicate that the Al2O3coating provides local protection and reduces crack formation at the early stage of volume expansion. The 3 nm Al2O3coating layer provides better protection than the 10 and 30 nm coating layer. Nevertheless, the Al2O3coating is unable to prevent the pulverization at the later stage of cycling because of large volume expansion.

Crosstalk of necroptosis and pyroptosis defines tumor microenvironment characterization and predicts prognosis in clear cell renal carcinoma.

Pyroptosis and necroptosis are two recently identified forms of immunogenic cell death in the tumor microenvironment (TME), indicating a crucial involvement in tumor metastasis. However, the characteristics of necroptosis and pyroptosis that define tumor microenvironment and prognosis in ccRCC patients remain unknown. We systematically investigated the transcriptional variation and expression patterns of Necroptosis and Pyroptosis related genes (NPRGs). After screening the necroptosis-pyroptosis clusters, the potential functional annotation for clusters was explored by GSVA enrichment analysis. The Necroptosis-Pyroptosis Genes (NPG) scores were used for the prognosis model construction and validation. Then, the correlations of NPG score with clinical features, cancer stem cell (CSC) index, tumor mutation burden (TMB), TME, and Immune Checkpoint Genes (ICGs) were also individually explored to evaluate the prognosis predictive values in ccRCC. Microarray screenings identified 27 upregulated and 1 downregulated NPRGs. Ten overall survival associated NPRGs were filtered to construct the NPG prognostic model indicating a better prognostic signature for ccRCC patients with lower NPG scores (P< 0.001), which was verified using the external cohort. Univariate and multivariate analyses along with Kaplan-Meier survival analysis demonstrated that NPG score prognostic model could be applied as an independent prognostic factor, and AUC values of nomogram from 1- to 5- year overall survival with good agreement in calibration plots suggested that the proposed prognostic signature possessed good predictive capabilities in ccRCC. A high-/sNPG score is proven to be connected with tumor growth and immune-related biological processes, according to enriched GO, KEGG, and GSEA analyses. Comparing patients with a high-NPG score to those with a low-NPG score revealed significant differences in clinical characteristics, growth and recurrence of malignancies (CSC index), TME cell infiltration, and immunotherapeutic response (P< 0.005), potentially making the NPG score multifunctional in the clinical therapeutic setting. Furthermore, AIM2, CASP4, GSDMB, NOD2, and RBCK1 were also found to be highly expressed in ccRCC cell lines and tumor tissues, and GASP4 and GSDMB promote ccRCC cells' proliferation, migration, and invasion. This study firstly suggests that targeting the NPG score feature for TME characterization may lend novel insights into its clinical applications in the prognostic prediction of ccRCC.

Anti-tumour necrosis factor-alpha agent therapy, compared with conventional therapy, reduces the relapse of uveitis in patients with behçet's disease: A systematic review of controlled trials.

Purpose: Anti-tumour necrosis factor-alpha (TNF-α) agents are often used for Behçet's disease (BD) in clinical practice, but they have not been validated by a high level of evidence. We systematically reviewed published controlled trials to investigate the efficacy and safety of anti-TNF-α therapy and summarize the efficacy of anti-TNF-α therapy relative to the available therapeutic options. Methods: A systematic database search was conducted (PubMed, Embase and Cochrane) using specific search terms. All controlled studies of anti-TNF-α treatment of BD patients prior to December 2021 were included. Single-arm studies were excluded. The decision of whether to incorporate data into the meta-analysis or summarize the data by qualitative synthesis was based on the results of the literature screening. Results: Of 4389 screened studies, 13 (total 778 patients) were included in accordance with our retrieval strategy, comprising 1 randomized controlled trial, 1 prospective study, 10 retrospective studies, and 1 multicentre open-label study. Ten studies (76.9%) involved Behçet's uveitis (BU), 1 involved intestinal BD, and the other studies had undefined subtypes. Subgroup reviews were conducted according to the control drug. Four studies involving 167 participants reported relapse rates. Meta-analysis of three of these studies demonstrated that, compared with traditional immunosuppressant (TIS) therapy, anti-TNF-α therapy reduced the relapse rates in patients with BU. In targeted drug comparison studies, the efficacy appeared to be similar between the anti-TNF-α agent and interferon in BU patients. The rates of adverse events were comparable between a variety of different therapeutic controls. Serious adverse events were not observed in 53.8% (7/13) of the studies. Conclusions: Compared with TIS therapy, anti-TNF-a therapy reduces the relapse of uveitis in patients with BD. However, the evidence regarding anti-TNF-α therapy is very limited for the full spectrum of BD subtypes, which calls for caution.

Synchrotron X-ray-induced Synthesis of Copper Hydroxide Nitrate Nanoplates on Cu Thin Films in an Ambient Atmosphere.

Synchrotron X-rays are widely used for material characterizations. However, they can also ionize atoms and molecules to damage and manipulate probed materials. We report here an X-ray-induced growth of copper hydroxide nitrate, Cu2(OH)3NO3, on copper thin films in the ambient atmosphere without solvents and thermal treatment. In situ synchrotron X-ray diffraction measurements showed that the time-dependent growth process of theCu2(OH)3NO3 is accompanied by the consumption of Cu metal and can be described by a sigmoidal model. The growth rate was reduced after the initial fast growth period. Scanning electron microscopy (SEM) images show that the isolated islands of Cu2(OH)3NO3 nanoplates formed in the beginning, which grew together with new nanoplates formed under continued X-ray irradiation. The result demonstrated that high-flux synchrotron X-rays may provide an unconventional approach to synthesizing and manipulating materials, which will inspire future investigation both experimentally and theoretically.

Native lattice strain induced structural earthquake in sodium layered oxide cathodes.

High-voltage operation is essential for the energy and power densities of battery cathode materials, but its stabilization remains a universal challenge. To date, the degradation origin has been mostly attributed to cycling-initiated structural deformation while the effect of native crystallographic defects induced during the sophisticated synthesis process has been significantly overlooked. Here, using in situ synchrotron X-ray probes and advanced transmission electron microscopy to probe the solid-state synthesis and charge/discharge process of sodium layered oxide cathodes, we reveal that quenching-induced native lattice strain plays an overwhelming role in the catastrophic capacity degradation of sodium layered cathodes, which runs counter to conventional perception-phase transition and cathode interfacial reactions. We observe that the spontaneous relaxation of native lattice strain is responsible for the structural earthquake (e.g., dislocation, stacking faults and fragmentation) of sodium layered cathodes during cycling, which is unexpectedly not regulated by the voltage window but is strongly coupled with charge/discharge temperature and rate. Our findings resolve the controversial understanding on the degradation origin of cathode materials and highlight the importance of eliminating intrinsic crystallographic defects to guarantee superior cycling stability at high voltages.

Multiscale Understanding of Surface Structural Effects on High-Temperature Operational Resiliency of Layered Oxide Cathodes.

The worldwide energy demand in electric vehicles and the increasing global temperature have called for development of high-energy and long-life lithium-ion batteries (LIBs) with improved high-temperature operational resiliency. However, current attention has been mostly focused on cycling aging at elevated temperature, leaving considerable gaps of knowledge in the failure mechanism, and practical control of abusive calendar aging and thermal runaway that are highly related to the eventual operational lifetime and safety performance of LIBs. Herein, using a combination of various in situ synchrotron X-ray and electron microscopy techniques, a multiscale understanding of surface structure effects involved in regulating the high-temperature operational tolerance of polycrystalline Ni-rich layered cathodes is reported. The results collectively show that an ultraconformal poly(3,4-ethylenedioxythiophene) coating can effectively prevent a LiNi0.8 Co0.1 Mn0.1 O2 cathode from undergoing undesired phase transformation and transition metal dissolution on the surface, atomic displacement, and dislocations within primary particles, intergranular cracking along the grain boundaries within secondary particles, and intensive bulk oxygen release during high state-of-charge and high-temperature aging. The present work highlights the essential role of surface structure controls in overcoming the multiscale degradation pathways of high-energy battery materials at extreme temperature.

In-Situ Characterization of Dynamic Morphological and Phase Changes of Selenium-doped Germanium Using a Single Particle Cell and Synchrotron Transmission X-ray Microscopy.

The dynamic information of lithium-ion battery active materials obtained from coin cell-based in-situ characterizations might not represent the properties of the active material itself because many other factors in the cell could have impacts on the cell performance. To address this problem, a single particle cell was developed to perform the in-situ characterization without the interference of inactive materials in the battery electrode as well as the X-ray-induced damage. In this study, the dynamic morphological and phase changes of selenium-doped germanium (Ge0.9 Se0.1 ) at the single particle level were investigated via synchrotron-based in-situ transmission X-ray microscopy. The results demonstrate the good reversibility of Ge0.9 Se0.1 at high cycling rate that helps understand its good cycling performance and rate capability. This in-situ and operando technique based on a single particle battery cell provides an approach to understanding the dynamic electrochemical processes of battery materials during charging and discharging at the particle level.

Sorption fractionation of bacterial extracellular polymeric substances (EPS) on mineral surfaces and associated effects on phenanthrene sorption to EPS-mineral complexes.

Microbial extracellular polymeric substances (EPS) represent an important source of labile component in natural organic matter (NOM) pool. However, the sorption behavior of EPS to mineral surfaces and associated effects on sorption of hydrophobic organic contaminants (HOCs) are not well understood. Here, we systematically investigated the fractionation of EPS extracted from two different microbial sources (Gram-positive B. subtilis and Gram-negative E. coli) during sorption to montmorillonite, kaolinite, and goethite using collective characterization methods (SEM, electrophoretic mobility, FTIR, 1H NMR, UV-vis, fluorescence, and size exclusion chromatography). The peptide-like substances and acidic components with high aromaticity in B. subtilis EPS were more preferentially sorbed than those fractions in E. coli EPS by the three minerals, especially by goethite. Additionally, goethite sorbed more negatively charged and lower molecular weight fractions compared to montmorillonite. The presorption of EPS (1.68-3.79% organic carbon) on the three minerals increased the sorption distribution coefficient (Kd) of phenanthrene (a model apolar HOC) by 2.83-5.29 times, depending on the EPS-mineral complex. All the six examined EPS-mineral complexes exhibited approximately one order of magnitude larger organic carbon (OC)-normalized sorption coefficient (KOC) than the two pristine EPS, indicating that the sorptive interactions were pronouncedly facilitated by the sorbed EPS on mineral surfaces. Thus, the type and surface property of minerals as well as the biological source of EPS are key determinants of sorption fractionation of EPS on minerals and in turn affect sorption affinity of apolar HOCs to EPS-mineral complexes.

Crack-Free Silicon Monoxide as Anodes for Lithium-Ion Batteries.

The volume expansion of Si and SiO particles was investigated using a single-particle battery assembled with a focused ion beam and scanning electron microscopy (FIB-SEM) system. Single Si and SiO particles were galvanostatically charged and discharged as in real batteries. Microstructural changes of the particles were monitored in situ using FIB-SEM from two different angles. The results revealed that the volume expansion of micrometer size particle SiO was not only much smaller than that of Si, but it also kept its original shape with no sign of cracks. This isotropic mechanical property of a SiO particle can be attributed to its microstructure: nanosized Si domains mixed with SiO2 domains. The nanosized Si domains can mitigate the anisotropic swelling caused by the orientation-dependent lithium-ion insertion; the surrounding SiO2 domains can act as a buffer to further constrain the localized anisotropic swelling.