Evolutionary Algorithm Directed Synthesis of Mixed Anion Compounds LaF2 X (X=Br, I) and LaFI2.

Mixed-anion compounds have attracted growing attentions, but their synthesis is challenging, making a rational search desirable. Here, we explored LaF3 -LaX3 (X=Cl, Br, I) system using ab initio structure searches based on evolutionary algorithms, and predicted LaF2 X and LaFX2 (X=Br, I), which are respectively isostructural with LaHBr2 and YH2 I, consisting of layered La-F blocks with single and double ordered honeycomb lattices, separated by van der Waals gaps. We successfully synthesized these compounds: LaF2 Br and LaFI2 crystallize in the predicted structure, while LaF2 I is similar to the predicted one but with different layer stacking. LaF2 I exhibits fluoride ion conductivity comparable to that of non-doped LaF3 , and has the potential to show better ionic conductivity upon appropriate doping, given the theoretically lower diffusion energy barrier and the presence of soft iodine anions. This study shows the structure prediction using evolutionary algorithms will accelerate the discovery of mixed-anion compounds in future, in particular those with an ordered anion arrangement.

Influence of Strong Ionic Interaction on the Kinetics of Graphite Intercalation Compound Formation.

Graphite intercalation compounds (GICs) of anions have attracted much attention as a positive electrode for use in dual-ion batteries. In this study, GICs of bis(trifluoromethanesulfonyl)amide (TFSA) anions were electrochemically synthesized in ionic liquids with lithium or magnesium salts to investigate the kinetics of GICs formation. By varying the concentrations of LiTFSA or Mg(TFSA)2 , the activation energy of interfacial anion transfer resistance was discovered to be correlated with the viscosity of the ionic liquid electrolytes. Such a change in activation energy is unique to ionic liquids and not seen in common molecular solvent electrolytes. In addition, ionic liquids with nearly identical viscosities exhibited similar resistances and activation energies. The relationship between the viscosity of ionic liquids and the kinetic parameters of interfacial anion transfer found in this study provides important insights for the construction of dual-ion batteries that aim for both high capacity and high rate capability.

Fluoride Ion-Selective Electrode for Organic Solutions.

Fluoride ions are used in battery electrolytes in fluoride shuttle batteries. Since organic solvents are used in battery electrolytes, there is a growing demand to develop appropriate methods for quantifying fluoride ion concentration in organic solvents. In this study, a fluoride ion-selective electrode (ISE) for organic solutions is proposed as an electrode of the second kind. A Ag|AgF electrode was made via the anodization of a silver wire in propylene carbonate (PC) containing dissolved fluoride ions. The resultant electrode exhibits a stable linear response of the open circuit potential to the logarithm of the fluoride ion concentration in PC solutions over a range of 10-4-10-2 mol dm-3. The lower and upper limits of the linear response were interpreted in terms of the solubility and the formation of a silver fluoride complex. The use of this electrode of the second kind is suitable for the analysis of fluoride ions in organic solutions and is a promising concept for the development of ISEs for the detection of ions in organic solutions under highly restrictive conditions.

Stabilizing the Nanosurface of LiNiO2 Electrodes by Varying the Electrolyte Concentration: Correlation with Initial Electrochemical Behaviors for Use in Aqueous Li-Ion Batteries.

This study attempted to stabilize the nanosurface of LiNiO2 (LNO) electrodes by varying the electrolyte concentration, significantly influencing its initial electrochemical behaviors for use in aqueous lithium-ion batteries. The charge/discharge capacities, reversibility, and cyclability of LNO were improved during initial cycles with an increase in the concentration of lithium bis(trifluoromethanesulfonyl)imide (LiTFSI). As determined by the galvanostatic intermittent titration technique, the superior diffusivity of Li+ ions in the LNO electrode is also obtained in the concentrated electrolyte. Nanoscale observation of the LNO surface revealed that its morphology is maintained relatively well in the concentrated electrolyte while it is destroyed in dilute electrolytes after the initial electrochemical cycles. These results are considered to be attributable to the variation of the interface condition in the electrical double layer with an increase in the electrolyte concentration, thus stabilizing the nanosurface of LNO by suppressing the dissolution of Ni ions from the surface. Additionally, in situ X-ray diffraction analysis demonstrated that LNO shows more stable phase transitions and volume changes as the electrolyte concentration increases, indicating that its structural changes in bulk can be directly related to the state of the nanosurface, which has a positive impact on the initial electrochemical behaviors in this system.

Sodium/Lithium-Ion Transfer Reaction at the Interface between Low-Crystallized Carbon Nanosphere Electrodes and Organic Electrolytes.

Carbon nanosphere (CNS) electrodes are the candidate of sodium-ion battery (SIB) negative electrodes with small internal resistances due to their small particle sizes. Electrochemical properties of low-crystallized CNS electrodes in dilute and concentrated sodium bis(trifluoromethanesulfonyl) amide/ethylene carbonate + dimethyl carbonate (NaTFSA/EC + DMC) were first investigated. From the cyclic voltammograms, both lithium ion and sodium ion can reversibly insert into/from CNSs in all of the electrolytes used here. The cycling stability of CNSs in concentrated electrolytes was better than that in dilute electrolytes for the SIB system. The interfacial charge-transfer resistances at the interface between CNSs and organic electrolytes were evaluated using electrochemical impedance spectroscopy. In the Nyquist plots, the semicircles at the middle-frequency region were assigned to the parallel circuits of charge-transfer resistances and capacitances. The interfacial sodium-ion transfer resistances in concentrated organic electrolytes were much smaller than those in dilute electrolytes, and the rate capability of CNS electrodes in sodium salt-concentrated electrolytes might be better than in dilute electrolytes, suggesting that CNSs with concentrated electrolytes are the candidate of SIB negative electrode materials with high rate capability. The calculated activation energies of interfacial sodium-ion transfer were dependent on electrolyte compositions and similar to those of interfacial lithium-ion transfer.

Electrochemical Lithiation/Delithiation of ZnO in 3D-Structured Electrodes: Elucidating the Mechanism and the Solid Electrolyte Interphase Formation.

Conversion/alloy active materials, such as ZnO, are one of the most promising candidates to replace graphite anodes in lithium-ion batteries. Besides a high specific capacity (qZnO = 987 mAh g-1), ZnO offers a high lithium-ion diffusion and fast reaction kinetics, leading to a high-rate capability, which is required for the intended fast charging of battery electric vehicles. However, lithium-ion storage in ZnO is accompanied by the formation of lithium-rich solid electrolyte interphase (SEI) layers, immense volume expansion, and a large voltage hysteresis. Nonetheless, ZnO is appealing as an anode material for lithium-ion batteries and is investigated intensively. Surprisingly, the conclusions reported on the reaction mechanism are contradictory and the formation and composition of the SEI are addressed in only a few works. In this work, we investigate lithiation, delithiation, and SEI formation with ZnO in ether-based electrolytes for the first time reported in the literature. The combination of operando and ex situ experiments (cyclic voltammetry, X-ray photoelectron spectroscopy, X-ray diffraction, coupled gas chromatography and mass spectrometry, differential electrochemical mass spectrometry, and scanning electron microscopy) clarifies the misunderstanding of the reaction mechanism. We evidence that the conversion and alloy reaction take place simultaneously inside the bulk of the electrode. Furthermore, we show that a two-layered SEI is formed on the surface. The SEI is decomposed reversibly upon cycling. In the end, we address the issue of the volume expansion and associated capacity fading by incorporating ZnO into a mesoporous carbon network. This approach reduces the capacity fading and yields cells with a specific capacity of above 500 mAh g-1 after 150 cycles.

Kimura's disease with recurrent bilateral lacrimal gland involvement in a male Japanese child successfully treated with cyclosporine A.

BACKGROUND: Kimura's disease (KD) is a rare chronic inflammatory disease of unknown etiology. Clinically, KD is characterized by nodular subcutaneous masses, that are typically localized to the neck and head. Involvement of the lacrimal glands and limbs is uncommon and seldom reported. CASE PRESENTATION: We report a case of a 4-year-old Japanese boy presenting with bilateral upper eyelid swelling with nodular subcutaneous lesions and peripheral eosinophilia. Based on clinical, histopathological, and laboratory findings, the patient was diagnosed with KD. An itchy subcutaneous mass on the left arm developed at the age of 14 years. Treatment with steroids was effective. However, as the steroids were tapered after the patient developed side effects, the masses relapsed within a few months. Treatment with cyclosporine A was then initiated, which led to an improvement of clinical features and serial levels of cytokines. CONCLUSIONS: We report a rare case of KD with a peculiar clinical presentation. The patient responded well to treatment with cyclosporine A.

Michaelis-Menten equation considering flow velocity reveals how microbial fuel cell fluid design affects electricity recovery from sewage wastewater.

Hydrodynamics has received considerable attention for application in improving microbial fuel cell (MFC) performance. In this study, a method is proposed to calculate the effect of fluid flow on MFC current production from sewage wastewater. First, the effect of flow velocity in an up-flow channel was evaluated, where an air-core MFC was polarized with external resistance (Rext). When tested at a flow velocity ranging from 0 to 20 cm s-1, the MFC with the higher flow velocity produced more current. In sewage wastewater with a chemical oxygen demand (COD) of 76 mg L-1, the MFC polarized with 3 Ω of Rext, and a flow velocity of 20 cm s-1 had 5.4 times more current than the MFC operating in a no-flow environment. This magnitude decreased with higher Rext and COD values. The Michaelis-Menten equation, modified herein by integrating COD and flow velocity, demonstrated the production of current by MFC operating under different conditions of flow. Calculation of current by MFC in a virtual fluid suggested that the flow surrounding the MFC varied with the configuration and affected the current production.

Pathophysiological clinical features of an infant with hypertension secondary to multicystic dysplastic kidney: a case report.

BACKGROUND: The association of hypertension with congenital renal hypoplasia has been established. We report a case of an infant who underwent nephrectomy for hypertension. CASE PRESENTATION: Magnetic resonance imaging for the mother revealed fetal renal masses, and fetal multicystic dysplastic kidney was suspected. Following birth, the baby developed hypertension. Numerous investigations revealed that the left kidney was non-functional, and she was initiated on benazepril hydrochloride. However, because the drug response was poor, the left kidney was removed at the age of 7 months. Examination of the renal specimen revealed abrupt transition from normal to atrophic cortex with lobar atrophy and cysts. Tubular atrophy, marked abnormal blood vessels with wall thickening, gathered immature glomeruli, and parenchymal destruction were observed. Renin was partially localized in the proximal tubules and the parietal epithelium of the Bowman's capsule in the immature glomeruli. We speculated that an abnormal vascular structure and irregular renin localizations may be the cause of hypertension. Serum renin and aldosterone levels gradually reduced post-surgery, reaching normal levels on the 90th postoperative day. A long follow-up is needed due to the possibility of the child developing hypertension in the future. CONCLUSION: This is a case of an infant with MCDK, which discusses the clinicopathological features based on the pathophysiological analysis, including renin evaluation.

Nephrotic syndrome relapse in a boy with COVID-19.

Clinical data on coronavirus disease-19 (COVID-19) in children during the management of nephrotic syndrome (NS) is lacking. Patients on prednisolone are compromised hosts at the risk of severe infections. Some infections may induce NS relapse. We describe the clinical course of a child with NS and COVID-19. A 3-year-old boy was admitted with clinical and laboratory findings indicative of NS. Induction therapy with prednisolone (2 mg/kg/day) induced complete remission. While tapering the dose, he was infected with severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2). He developed a high fever and periorbital edema. Urinalysis revealed proteinuria (protein-creatinine ratio: 6.3 g/gCr). He was transferred to our hospital for the concurrent management of COVID-19 and NS relapse. As proteinuria worsened, the prednisolone dose was increased to 2 mg/kg/day. Proteinuria gradually improved, and remission was noted a week after initiating full-dose steroid treatment. The fever subsided after 2 days without treatment for COVID-19. Anti-SARS-CoV-2 antibody including IgG levels decreased in the early convalescent phase. To the best of our knowledge, this is the first reported case with the recurrence of NS triggered by the SARS-CoV-2 infection in Asia. SARS-CoV-2 infection may induce NS relapse. Daily administration of full-dose of prednisolone may be effective for managing the recurrence of NS associated with SARS-CoV-2 infection.

The potentially therapeutic role of tonsillectomy in the alleviation of several renal diseases apart from IgA nephropathy.

Tonsils are located mainly at the gateway of the respiratory tract, and are reportedly one of the secondary lymphatic organs of the immune system. The development of several diseases including IgA nephropathy (IgAN) is associated with inflammatory stimulation and an aberrant immune response of the tonsils. Several studies have reported an improvement in and/or an increase in the stability of the clinicopathological findings of patients with IgAN post tonsillectomy. However, the efficacy in and precise mechanism of the alleviation of symptoms of other renal diseases by tonsillectomy remain unknown. We hypothesize that tonsillectomy may play a potentially therapeutic role in renal diseases apart from IgAN, which are thought to be caused by an impaired regulation of the immune system.

Mechanism of the Loss of Capacity of LiNiO2 Electrodes for Use in Aqueous Li-Ion Batteries: Unveiling a Fundamental Cause of Deterioration in an Aqueous Electrolyte through In Situ Raman Observation.

This study investigated the fundamental mechanisms of the loss of capacity of LiNiO2 (LNO) electrodes for Li+ insertion/deinsertion with a special focus on the origin of this deterioration in an aqueous system. In situ Raman spectra revealed that the intercalation of H+ ions formed a NiOOHx film at the surface of LNO during the initial electrochemical cycles; this NiOOHx film was also confirmed by X-ray photoelectron spectroscopy and transmission electron microscopy analysis. The formation of an electrochemically inactive spinel-like phase (Ni3O4) at the subsurface was triggered by the absence of Li in the NiOOHx film at the surface. These structural changes of LNO, accelerated by the intercalation of H+ ions, were considered to be the fundamental cause of the greater loss of capacity in the aqueous system.

Reproducible and stable cycling performance data on secondary zinc oxygen batteries.

Electrically rechargeable zinc oxygen batteries are promising energy storage devices. They appeal due to the abundance of zinc metal and their high energy density. Research on zinc oxygen batteries is currently focusing on the development of electrode materials. Since the progress is rapid and no state-of-the-art is agreed upon yet, it is difficult to benchmark their performance. This circumstance also complicates the use of the generated electrochemical data for model-based research - simulating the processes in the battery requires reliable performance data and material properties from experimental investigations. Herein we describe reproducible data on the cycling performance and durability of zinc oxygen batteries. We utilize anodes and gas diffusion electrodes (with the bifunctional catalysts Sr2CoO3Cl, Ru-Sn oxide, and Fe0.1Ni0.9Co2O4 with activated carbon) with low degradation during cycling, and present voltage data of current-dependent discharge and charge. All in all, we stimulate to reuse the data for parameter fitting in model-based work, and also to evaluate novel battery materials by preventing or minimizing side reactions with the testing protocol and setup utilized.

Charge-Transfer Kinetics of the Solid-Electrolyte Interphase on Li4 Ti5 O12 Thin-Film Electrodes.

Invited for this month's cover are the groups of Shih-kang Lin at the National Cheng Kung University and Takeshi Abe at Kyoto University. The image shows how interfacial chemistry design can play a role in unlocking higher-energy-density and fast-charging Li4 Ti5 O12 -based lithium-ion batteries for electric vehicle applications. The Full Paper itself is available at 10.1002/cssc.202001086.

Charge-Transfer Kinetics of The Solid-Electrolyte Interphase on Li4 Ti5 O12 Thin-Film Electrodes.

Charge-transfer kinetics between electrodes and electrolytes critically determines the performance of lithium-ion batteries (LIBs). Lithium titanate defect spinel (Li4 Ti5 O12 , LTO) is a safe and durable anode material, but its relatively low energy density limits the range of applications. Utilizing the low potential region of LTO is a straightforward strategy for increasing energy density. However, the electrochemical characteristics of LTO at low potentials and the properties of the solid-electrolyte interphase (SEI) on LTO are not well understood. Here, we investigate the charge-transfer kinetics of the SEI formed between model LTO thin-film electrodes and organic electrolytes with distinct solvation ability using AC impedance spectroscopy whereas their stability was assessed by cyclic voltammetry of ferrocene. With the SEI film on LTO, the Li+ desolvation was rate-determining step but with larger activation energies, which showed a strong dependence on the solvation ability of electrolyte. The activation energies of desolvation for the fluoroethylene carbonate+dimethyl carbonate- and ethylene carbonate+diethyl carbonate-based systems increased from 35 and 55 to 44 and 67 kJ mol-1 , respectively, and that for the propylene carbonate-based system did not noticeably change at around 67 kJ mol-1 . In addition, the SEI passivation of LTO was much slower than that of graphite, and the rate also strongly depended on the solvation ability of the electrolyte. Understanding the surface properties of LTO at low potentials opens the door for high-energy-density LTO-based LIBs.

A fluorescence method to visualize the nuclear boundary by the lipophilic dye DiI.

Here, we describe a procedure to fluorescently contrast the nuclear boundary using the lipophilic carbocyanine dye DiI in cultured human cells. Our procedure is simple and is applicable to detect nuclear boundary defects, which may be relevant to studies on nuclear envelope dynamics, micronuclei formation and cancer biology. ABBREVIATIONS: DiI: 1,1'-dioctadecyl-3,3,3',3'-tetramethylindocarbocyanine perchlorate; DiO: 3,3'-dioctadecyloxacarbocyanine perchlorate; NE: nuclear envelope; RanBP2: Ran-binding protein 2/Nucleoporin 358.

Early tonsillectomy for severe immunoglobulin A nephropathy significantly reduces proteinuria.

BACKGROUND: Early multiple-drug therapy for severe childhood immunoglobulin A (IgA) nephropathy prevents the progression of nephritis and improves the long-term prognosis. Recent studies have focused on the relationship between the pathophysiology of IgA nephropathy and tonsillar focal infection, and the efficacy of tonsillectomy with methylprednisolone pulse therapy in children has been demonstrated. However, no study has reported on the relationship between the period from diagnosis to tonsillectomy and the long-term prognosis of IgA nephropathy. METHODS: To clarify the long-term effects of an early tonsillectomy, 40 patients who were diagnosed with severe IgA nephropathy in childhood and underwent a tonsillectomy were divided into two groups based on the period from diagnosis to undergoing tonsillectomy: Group A, less than 3 years; and Group B, more than 3 years. The primary endpoint of this study was the change in the amount of proteinuria. Renal prognosis was evaluated 10 years after the diagnosis. RESULTS: This study enrolled 40 patients diagnosed with severe IgA nephropathy in childhood who underwent tonsillectomy after multiple-drug therapy with/without methylprednisolone pulse therapy at Kindai University Hospital; eight patients were excluded based on the exclusion criteria. Group A consisted of 18 patients and Group B, 14 patients. Proteinuria and hematuria levels were significantly reduced in the early surgery group (P < 0.01). No significant differences were found in serum creatinine, uric acid, and IgA/C3 ratio. CONCLUSIONS: High proteinuria levels worsen the renal prognosis in IgA nephropathy. Tonsillectomy in less than 3 years combined with multiple-drug therapy after the initial diagnosis could improve long-term prognosis.

Membranoproliferative glomerulonephritis related to a streptococcal infection in a girl with IgA deficiency: a case report.

BACKGROUND: IgA deficiency associated with glomerulonephritis is rare. In particular, there is no prior report regarding the association between IgA deficiency and membranoproliferative glomerulonephritis (MPGN) in children. Herein, we describe the case of a 5-year-old girl with selective IgA deficiency and MPGN. CASE PRESENTATION: The patient presented with persisting urinary abnormality and hypocomplementemia following a group A treptococcal infection. Renal biopsy revealed the presence of diffuse mesangial hypercellularity, endocapillary proliferation, and focal thickening of the walls of the glomerular capillaries using light microscopy, with IgG and moderate C3 deposits observed using immunofluorescence. Electron microscopy images revealed nodular deposits in the subendothelial areas, with hump-shaped subepithelial deposits. The pathological diagnosis was confirmed as MPGN. Treatment using oral prednisolone (PSL), mizoribine (MZR), and angiotensin-converting enzyme inhibitors reduced the proteinuria. The PSL dose was gradually tapered, with the low dose of PSL and MZR continued for 4 years. Histological findings were improved on repeated renal biopsy, and PSL and MZR administration was discontinued. CONCLUSIONS: We report a rare case of MPGN related to a streptococcal infection in a child. The clinical presentation included selective IgAD, with several pathological findings and a clinical course typical of glomerulopathy. The patient was successfully treated using multidrug therapy.