Visualization of Heterogeneity in Materials for Lithium Batteries Using Micro X-ray Diffraction

The ultimate goal of this thesis is to establish correlations between local investigated properties and macroscopic electrochemical performance that affect the performance of batteries and inform their future design toward overcoming existing frontiers in the technology. X-ray diffraction (XRD) is a powerful characterization technique which has been extensively applied in the study of crystalline materials in many different fields, including pharmaceutical industry, forensic science, mineralogy, microelectronics industry, corrosion analysis even in glass industry. This thesis focuses on the design and the development of protocols to implement methods of XRD using microbeams to study local electrochemical phenomena relevant to cathode materials and solid electrolytes for batteries based on shuttling Li ions to store charge. With the resulting maps, heterogeneity at several length scales, and their associated chemical and physical properties, can be visualized and assessed both qualitatively and quantitatively. The μXRD mapping methods demonstrated in Chapter 3, was applied to evaluate the electrochemical performance of a complete NCA cathode by visualizing how the local distribution of states of charge after cycling is affected by storing the electrode under different conditions. The domains of different delithiation states revealed by the μXRD maps were consistent with the structural analysis based on the bulk powder XRD. By showing the local phase distribution, insight was revealed into the effects on the macroscopic transport of lithium ions of the formation of insulating impurities on the surface of NCA cathode during storage. Taking advantage of an extremely powerful X-ray source, a synchrotron, at Argonne National Laboratory, operando μXRD was developed and performed to map secondary particles in Chapter 4. The diffraction patterns of each mapping position revealed compositional gradients within single secondary particles of NCA during galvanostatic cycling, based on the comparison of the position and shape of selected diffraction peaks to reference data. The μXRD diffraction patterns were also compared with a previous study with the same technique to reveal the effect of cycling rates on the electrochemical behavior of NCA secondary particles. In Chapter 5, a novel μXRD mapping method with Laue diffraction at a synchrotron was successfully developed and applied to create deviatoric strain maps of garnet-typed solid state electrolytes compositionally derived from LLZO. These deviatoric strain maps helped to visualize the variation in microstructure within the solid electrolytes, which helped rationalize differences in local stability of lithium electrodeposition during cycling

Palaeoproterozoic granitic magmatism in the northern segment of the Jiao-Liao-Ji Belt: implications for orogenesis along the Eastern Block of the North China Craton

<p>As the northern segment of the Jiao-Liao-Ji Belt (JLJB), the Palaeoproterozoic Liaoji Belt is a key region for deciphering the formation and evolution of the North China Craton (NCC). In this study, we present the geochronology, geochemical, and isotopic studies on the monzogranitic gneiss, which is one of the major lithotectonic elements of the Liaoji Belt. LA-ICP-MS zircon U–Pb dating reveals that the studied monzogranitic gneisses were formed in the period of 2213–2178 Ma. They are in tectonic contact with the Palaeoproterozoic volcano-sedimentary rocks in the field. The monzogranitic gneisses belong to the high-K calc-alkaline series, and are metaluminous to peraluminous. They have 10,000 Ga/Al ratios of 2.63–3.14 with an average of 2.90, and are thus classified as aluminous A-type granites. Their <i>ε</i>_Nd(<i>t</i>) values vary from −3.4 to +2.5, indicating heterogeneous source region. The monzogranitic gneisses are characterized by enrichment in LREE and LILE (e.g. Rb, Ba, Th, and K) and depletion in HREE and HFSE (such as Nb, Ta, and Ti), and are typical to magmatism in active continental margins formed in a subduction-related tectonic setting. Taking into account their A-type affinity and regional geological data, we suggest that the monzogranitic gneisses were most probably generated in a local extensional back-arc environment during subduction.</p

Table_1_Case report: Clinical and single-cell transcriptome sequencing analysis of a mixed gangliocytoma-adenoma presenting as acromegaly.xlsx

BackgroundMixed gangliocytoma-adenoma (MGA) is a rare tumor of pituitary gland. It’s difficult to distinguish it from pituitary adenoma by clinical manifestations, imaging features or serological testing. Thus, the histopathological examination is still the golden standard for diagnosis. Besides, studies on molecular level are still lacking.Case informationIn this case report, we described a 28-year-old male with MGA presenting as acromegaly, who suffered staging operation and post-operation gamma knife radiosurgery, but finally died of secondary hyperglycemic hyperosmolar collapse. A complete data including clinical, histopathological, ultrastructural and single-cell transcriptome level information were collected and analyzed.ConclusionThis case report detailed the only clinical and molecular report of MGA following operation and radiotherapy. Complete clinical data enhanced the understanding of the diagnosis and treatment of this disease. Besides, the single-cell transcriptome sequencing analysis further disclosed the intra-tumoral heterogeneity and provided support for subsequent basic research.</p

Image_1_Case report: Clinical and single-cell transcriptome sequencing analysis of a mixed gangliocytoma-adenoma presenting as acromegaly.tif

BackgroundMixed gangliocytoma-adenoma (MGA) is a rare tumor of pituitary gland. It’s difficult to distinguish it from pituitary adenoma by clinical manifestations, imaging features or serological testing. Thus, the histopathological examination is still the golden standard for diagnosis. Besides, studies on molecular level are still lacking.Case informationIn this case report, we described a 28-year-old male with MGA presenting as acromegaly, who suffered staging operation and post-operation gamma knife radiosurgery, but finally died of secondary hyperglycemic hyperosmolar collapse. A complete data including clinical, histopathological, ultrastructural and single-cell transcriptome level information were collected and analyzed.ConclusionThis case report detailed the only clinical and molecular report of MGA following operation and radiotherapy. Complete clinical data enhanced the understanding of the diagnosis and treatment of this disease. Besides, the single-cell transcriptome sequencing analysis further disclosed the intra-tumoral heterogeneity and provided support for subsequent basic research.</p

Tuning Wet Adhesion of Weak Polyelectrolyte Multilayers

Weak polyelectrolyte multilayers (PEMs) assembled by the layer-by-layer method are known to become tacky upon contact with water and behave as a viscoelastic fluid, but this wet adhesive property and how it can be modified by external stimuli has not yet been fully explored. We present here a study on the wet adhesive performance of PEMs consisting of branched poly­(ethylene imine) and poly­(acrylic acid) under controlled conditions (e.g., pH, type of salt, and ionic strength) using a 90° peel test. The multilayers demonstrate stick–slip behavior and fail cohesively in nearly all cases. The peel force is the highest at neutral pH, and it decreases in both acidic/basic environments because of inhibited polyelectrolyte mobility. The addition of salts with various metal ions generally reduces the peel force, and this effect tracks with the ionic strength. When transition metal ions are used, their ability to form coordination bonds increases the peel force, with two exceptions (Cu²⁺ and Zn²⁺). With a transition metal ion such as Fe³⁺, the peel force first increases as a function of the concentration and then eventually decreases. The peel force increases proportionally to the peel rate. The films are also characterized via zeta potential (when assembled onto colloidal particles) and shear rheometry. This work provides insight into both the wet adhesive properties of PEMs and the interactions between PEMs and metal ions

Tuning Wet Adhesion of Weak Polyelectrolyte Multilayers

Weak polyelectrolyte multilayers (PEMs) assembled by the layer-by-layer method are known to become tacky upon contact with water and behave as a viscoelastic fluid, but this wet adhesive property and how it can be modified by external stimuli has not yet been fully explored. We present here a study on the wet adhesive performance of PEMs consisting of branched poly­(ethylene imine) and poly­(acrylic acid) under controlled conditions (e.g., pH, type of salt, and ionic strength) using a 90° peel test. The multilayers demonstrate stick–slip behavior and fail cohesively in nearly all cases. The peel force is the highest at neutral pH, and it decreases in both acidic/basic environments because of inhibited polyelectrolyte mobility. The addition of salts with various metal ions generally reduces the peel force, and this effect tracks with the ionic strength. When transition metal ions are used, their ability to form coordination bonds increases the peel force, with two exceptions (Cu²⁺ and Zn²⁺). With a transition metal ion such as Fe³⁺, the peel force first increases as a function of the concentration and then eventually decreases. The peel force increases proportionally to the peel rate. The films are also characterized via zeta potential (when assembled onto colloidal particles) and shear rheometry. This work provides insight into both the wet adhesive properties of PEMs and the interactions between PEMs and metal ions

Tuning Wet Adhesion of Weak Polyelectrolyte Multilayers

Weak polyelectrolyte multilayers (PEMs) assembled by the layer-by-layer method are known to become tacky upon contact with water and behave as a viscoelastic fluid, but this wet adhesive property and how it can be modified by external stimuli has not yet been fully explored. We present here a study on the wet adhesive performance of PEMs consisting of branched poly­(ethylene imine) and poly­(acrylic acid) under controlled conditions (e.g., pH, type of salt, and ionic strength) using a 90° peel test. The multilayers demonstrate stick–slip behavior and fail cohesively in nearly all cases. The peel force is the highest at neutral pH, and it decreases in both acidic/basic environments because of inhibited polyelectrolyte mobility. The addition of salts with various metal ions generally reduces the peel force, and this effect tracks with the ionic strength. When transition metal ions are used, their ability to form coordination bonds increases the peel force, with two exceptions (Cu²⁺ and Zn²⁺). With a transition metal ion such as Fe³⁺, the peel force first increases as a function of the concentration and then eventually decreases. The peel force increases proportionally to the peel rate. The films are also characterized via zeta potential (when assembled onto colloidal particles) and shear rheometry. This work provides insight into both the wet adhesive properties of PEMs and the interactions between PEMs and metal ions

CuI-Catalyzed C–N Bond Formation and Cleavage for the Synthesis of Benzimidazo[1,2‑<i>a</i>]quinazoline Derivatives

A copper­(I)-catalyzed domino reaction of <i>N</i>-(2-benzimidazolyl)-2-aminobenzamide and 2-halogenated benzaldehyde has been studied. The procedure is based on a sequential CuI-catalyzed Ullmann reaction (C–N bond formation) and two bond cleavage reactions and provides an efficient strategy for the synthesis of benzimidazo­[1,2-<i>a</i>]­quinazolines catalyzed by CuI/l-proline

Image1_Case report: Endovascular intervention of internal carotid artery pseudoaneurysm secondary to nasopharyngeal carcinoma radiotherapy.tif

BackgroundInternal carotid artery pseudoaneurysm (PSA) is a serious complication after radiotherapy for nasopharyngeal carcinoma, and once it ruptures and bleeds, it will seriously affect the patient's survival and prognosis. However, because of its relatively low incidence, many medical institutions lack experience in managing this type of emergency.Case informationIn this case report, we described two cases suffered ruptured internal carotid artery PSA after radiotherapy for nasopharyngeal carcinoma, including their history, diagnosis, and treatment. Both cases underwent emergency endovascular interventions, one of which with long-term healing after embolization of the PSA, and the other one with re-bleeding after embolization and was eventually stopped by embolization of the parent artery. Ultimately, both cases received timely and effective treatment.ConclusionThis case report detailed the diagnosis and treatment course of internal carotid artery PSA after radiotherapy for nasopharyngeal carcinoma, which enhanced the understanding of this emergency, and provided valuable information and experience for the treatment strategy of similar PSA on the internal carotid artery.</p

Table3_A nine–consensus–prognostic –gene–based prognostic signature, recognizing the dichotomized subgroups of gastric cancer patients with different clinical outcomes and therapeutic strategies.XLSX

Background: The increasing prevalence and mortality of gastric cancer (GC) has promoted the urgent need for prognostic signatures to predict the long-term risk and search for therapeutic biomarkers.Methods and materials: A total of 921 GC patients from three GEO cohorts were enrolled in the current study. The GSE15459 and GSE62254 cohorts were used to select the top prognostic gene via the evaluation of the area under the receiver operating characteristic (ROC) curve (AUC) values. The GSE84437 cohort was used as the external validation cohort. Least absolute shrinkage and selector operation (LASSO) regression analysis was applied to reduce the feature dimension and construct the prognostic signature. Furthermore, a nomogram was constructed by integrating the independent prognostic analysis and validated by calibration plot, decision curve analysis and clinical impact curve. The molecular features and response to chemo-/immunotherapy among risk subgroups were evaluated by the “MOVICS” and “ESTAMATE” R packages and the SubMap algorithm. Lauren classification and ACRG molecular subtype were obtained to compare with the risk model.Results: Forty-four prognosis-associated genes were identified with a preset cutoff AUC value of 0.65 in both the GSE62254 and GSE15459 cohorts. With the 10-fold cross validation analysis of LASSO, nine genes were selected to construct the nine-consensus-prognostic-gene signature. The signature showed good prognostic value in the GSE62254 (p Conclusion: In summary, we constructed a robust nine-consensus-prognostic-gene signature for the prediction of GC prognosis, which can also predict the personalized treatment of GC patients.</p