Cathode-Electrolyte Interphase in a LiTFSI/Tetraglyme Electrolyte Promoting the Cyclability of V2_{2}O5_{5}

[Image: see text] V(2)O(5), one of the earliest intercalation-type cathode materials investigated as a Li(+) host, is characterized by an extremely high theoretical capacity (441 mAh g(–1)). However, the fast capacity fading upon cycling in conventional carbonate-based electrolytes is an unresolved issue. Herein, we show that using a LiTFSI/tetraglyme (1:1 in mole ratio) electrolyte yields a highly enhanced cycling ability of V(2)O(5) (from 20% capacity retention to 80% after 100 cycles at 50 mA g(–1) within 1.5–4.0 V vs Li(+)/Li). The improved performance mostly originates from the V(2)O(5) electrode itself, since refreshing the electrolyte and the lithium electrode of the cycled cells does not help in restoring the V(2)O(5) electrode capacity. Electrochemical impedance spectroscopy (EIS), post-mortem scanning electron microscopy (SEM), energy-dispersive X-ray (EDX) spectroscopy, and X-ray photoelectron spectroscopy (XPS) have been employed to investigate the origin of the improved electrochemical behavior. The results demonstrate that the enhanced cyclability is a consequence of a thinner but more stable cathode–electrolyte interphase (CEI) layer formed in LiTFSI/tetraglyme with respect to the one occurring in 1 M LiPF(6) in EC/DMC (1:1 in weight ratio, LP30). These results show that the cyclability of V(2)O(5) can be effectively improved by simple electrolyte engineering. At the same time, the uncovered mechanism further reveals the vital role of the CEI on the cyclability of V(2)O(5), which can be helpful for the performance optimization of vanadium-oxide-based batteries

Metal–Organic Framework Derived Copper Chalcogenides-Carbon Composites as High-Rate and Stable Storage Materials for Na Ions

Transition metal chalcogenides have been regarded as promising storage materials for sodium ions owing to their high theoretical capacity. Herein, copper-based metal–organic frameworks (Cu-BTC) are reported as precursors to fabrica copper chalcogenides-carbon composites, namely Cu$_{1.8}$S@C and Cu$_{2-x}$Se@C. The materials exhibit excellent electrochemical performance with high specific capacities (504 mAh g$^{-1}$ for Cu$_{1.8}$S@C and 317 mAh g$^{-1}$ for Cu$_{2-x}$Se@C at 0.1 A g$^{-1}$) and long-term cycling stability when used as anode materials in cells employing carbon-coated Na$_{3}$V$_{2}$(PO$_{4}$)$_{3}$ (NVP/C) positive electrodes. The Cu$_{2-x}$Se@C||NVP/C cell delivers a specific capacity of 73 mAh g$^{-1}$ at 1.2 A g$^{-1}$ (based on cathode mass) and excellent cycling stability (capacity retention of 85% after 500 cycles at 0.12 A g$^{-1}$) with Coulombic efficiency of ≈99.9%. Moreover, the Cu$_{2-x}$Se@C composite performs well as positive electrode storage material in a sodium-metal cell, offering a high reversible capacity of 216 mAh (per gram of Cu$_{2-x}$Se@C) after 1800 cycles at 2 A g$^{-1}$ and enabling high specific energy and power

Osterix and RUNX2 are Transcriptional Regulators of Sclerostin in Human Bone

Sclerostin, encoded by the SOST gene, works as an inhibitor of the Wnt pathway and therefore is an important regulator of bone homeostasis. Due to its potent action as an inhibitor of bone formation, blocking sclerostin activity is the purpose of recently developed antiosteoporotic treatments. Two bone-specific transcription factors, RUNX2 and OSX, have been shown to interact and co-ordinately regulate the expression of bone-specific genes. Although it has been recently shown that sclerostin is targeted by OSX in mice, there is currently no information of whether this is also the case in human cells. We have identified SP-protein family and AML1 consensus binding sequences at the human SOST promoter and have shown that OSX, together with RUNX2, binds to a specific region close to the transcription start site. Furthermore, we show that OSX and RUNX2 activate SOST expression in a co-ordinated manner in vitro and that SOST expression levels show a significant positive correlation with OSX/ RUNX2 expression levels in human bone. We also confirmed previous results showing an association of several SOST/RUNX2 polymorphisms with bone mineral density

Hypercalcemia in patients with rheumatoid arthritis: a retrospective study

Objetivo: Investigar la prevalencia de hipercalcemia en pacientes con artritis reumatoide (AR) y analizar las características clínicas y las causas de la hipercalcemia. Material y métodos: Estudio retrospectivo de revisión basado en casos que incluyó 500 pacientes con AR. Se identificaron los pacientes con niveles de calcio aumentados en al menos dos ocasiones. Resultados: La hipercalcemia estuvo presente en 24 de los 500 pacientes con AR (4,8%). La edad osciló entre 50 y 80 años, con una media de 68±10 años. La duración media de la enfermedad fue de 10±7 años. De los pacientes con hipercalcemia, 22 eran mujeres postmenopáusicas (92%) y solo dos eran hombres (8%). El hiperparatiroidismo se encontró en 9 pacientes de la serie; solo un paciente tenía una hipercalcemia maligna debido a un mieloma múltiple, y un caso fue consecuencia de una intoxicación por vitamina D. En un paciente la hipercalcemia parecía relacionada con el síndrome calcio-alcalino. En el resto de pacientes, la hipercalcemia fue idiopática (8/24) o el estudio fue incompleto (4/24). No se encontró una relación evidente entre la actividad de la enfermedad y la aparición de hipercalcemia. Conclusión: Al igual que sucede en la población general, el hiperparatiroidismo primario es la causa más común de hipercalcemia en pacientes con AR. En algunos pacientes no se identificaron otros trastornos causantes de hipercalcemia, lo que plantea la posibilidad de una relación causal entre la AR y la hipercalcemia.Objetive: To investigate the prevalence of hypercalcemia in patients with rheumatoid arthritis (RA) and analyze the clinical features and causes of hypercalcemia. Material and methods: Retrospective case?based review study that included 500 patients with RA. Patients with increased calcium levels on at least two occasions were identified. Results: Hypercalcemia was present in 24 of the 500 RA patients (4.8%). The age ranged between 50 and 80 years, with a mean of 68±10 years. The mean duration of the disease was 10±7 years. Of the patients with hypercalcemia, 22 were postmenopausal women (92%) and only two were men (8%). Hyperparathyroidism was found in 9 patients in the series; only one patient had malignant hypercalcemia due to multiple myeloma, and one case was a consequence of vitamin D intoxication. In one patient, hypercalcemia appeared to be related to calcium?alkali syndrome. In the remaining patients, hypercalcemia was idiopathic (8/24) or the study was incomplete (4/24). No obvious relationship was found between disease activity and the appearance of hypercalcemia. Conclusion: As in the general population, primary hyperparathyroidism is the most common cause of hypercalcemia in patients with RA. In some patients, no other disorders causing hypercalcemia were identified, raising the possibility of a causal relationship between RA and hypercalcemia

Calidad de vida en pacientes con fosfatasa alcalina persistentemente baja portadores o no de mutaciones del gen ALPL

Introducción: Los niveles bajos de fosfatasa alcalina (FAlc) en suero son el sello distintivo de la hipofosfatasia, un trastorno debido a variantes patogénicas del gen ALPL. Nuestro objetivo fue determinar la calidad de vida relacionada con la salud en adultos con fosfatasa alcalina baja y explorar las diferencias entre pacientes con y sin mutaciones en ALPL. Material y métodos: Estudiamos 35 pacientes adultos con FAlc persistentemente baja en los que se excluyeron causas adquiridas y se secuenció ALPL. Se compararon con 35 controles de igual edad. Se completaron tres cuestionarios sobre dolor (Brief Pain Inventory, BPI), discapacidad física (Health Assessment Questionnaire Disability Index, HAQ-DI) y calidad de vida relacionada con la salud (36-item Short-Form Health Survey, SF-36). Resultados: Las puntuaciones medias de intensidad e interferencia del dolor en el BPI fueron mayores en el grupo de pacientes (p=0,04 y 0,004, respectivamente). Todos los dominios del instrumento HAQ tendieron a puntuar peor en los pacientes, con diferencias significativas en la puntuación de "alcance" (p=0,037) y la puntuación media general (0,23 frente a 0,09; p=0,029). Los pacientes puntuaron peor que los controles en varias dimensiones del SF-36 (rol físico, p=0,039; dolor corporal p=0,046; rol emocional, p=0,025). Sin embargo, los pacientes con y sin variantes patogénicas puntuaron de manera similar en todas las pruebas, sin diferencias significativas entre los grupos. Conclusiones: Los pacientes con niveles persistentemente bajos de FAlc tienen puntuaciones significativamente peores en dolor corporal y otras dimensiones de calidad de vida relacionadas con la salud, sin diferencias entre pacientes con y sin variantes patogénicas en el gen ALPL. Esto es consistente con la hipótesis de que estos últimos presenten mutaciones en regiones reguladoras, habitualmente no secuenciadas, del gen ALPL

Screening pulmonary arteriovenous malformations in a large cohort of Spanish patients with hemorrhagic hereditary telangiectasia

39 p.-1 fig.-7 tab.Background and objectives Because of the serious nature of potential complications, screening for pulmonary arteriovenous malformations is required in patients with hereditary hemorrhagic telangiectasia. The aim of this study was to evaluate the utility of contrast echocardiography and compare the performance of two contrast agents: agitated saline and Gelofusine.Material and methods Two hundred and five patients screened for PAVMs using TTCE and computed tomography (CT) performed with an interval of less than 180 days. Contrast echocardiography studies were graded on a 4-point semiquantitative scale based on the amount of microbubbles seen in left heart chambers.Results Positive TTCE findings were seen in 137 (66.8%) patients, whereas CT confirmed PAVMs in 59 (43.1%). Two of 67 grade 1 patients; 18 of 42 grade 2; 17 of 22 grade 3 and all grade 4 had PAVMs on CT. Embolotherapy was feasible in 38.9% patients in grade 2 and 82.3% and 95.2% in grades 3–4. No patients in grade 1 were embolized. The mean cardiac cycle in which bubbles were first seen in the left heart in patients without and with PAVMs on CT was 6.1 and 3.9 (p < 0.0001). Compared to saline, Gelofusine produced an overall increase in grade.Conclusions No grade 1 patients had treatable PAVMs. There is a need for improvement in the selection of patients for CT in grade 2, where less than half have PAVMs on CT. The cardiac cycle may help to differentiate between patients with and without PAVMs. Gelofusine was not better than saline for PAVM screening.This study has been supported by grants from Instituto de Salud Carlos III (ISCIII; PI11/0246 to JAP), FEDER (to JAP), Ministerio de Economía y Competitividad of Spain (SAF2011-23475 to LMB and SAF2013-43421-R to CB), and Centro de Investigación Biomédica en Red de Enfermedades Raras (CIBERER; ISCIIICB06/ 07/0038 to CB).Peer reviewe

LiNi0.5Mn1.5O4 Thin Films Grown by Magnetron Sputtering under Inert Gas Flow Mixtures as High-Voltage Cathode Materials for Lithium-Ion Batteries

Delivering a commercial high-voltage spinel LiNi0.5Mn1.5O4 (LNMO) cathode electrode for Li-ion batteries would result in a significant step forward in terms of energy density. However, the structural ordering of the spinel and particle size have considerable effects on the cathode material's cyclability and rate capability, which are crucial challenges to address. Here, a novel mid-frequency alternating current dual magnetron sputtering method was presented, using different Ar-N-2 gas mixtures ratios for the process gas to prepare various LNMO thin films with highly controlled morphology and particle size; as determined from X-ray diffraction, Raman spectroscopy and electron microscopy. It resulted in enhanced cycling and rate performance. This processing method delivered N-containing LNMO thin film electrodes with up to 15 % increased discharge capacity at 1 C (120 mAh g(-1)) with respect to standard LNMO (grown under only Ar gas flow) thin film electrodes, along with outstanding rate performance up to 10 C (99 mAh g(-1)) in the operating voltage window 3.5-4.85 V vs. Li+/Li. Besides, electrochemical impedance spectroscopy results showed that the intricate phase transitions present in standard LNMO electrodes were almost suppressed in N-containing LNMO thin films grown under different Ar-N-2 gas flow mixtures

Abnormal bone turnover in individuals with low serum alkaline phosphatase

The clinical spectrum of hypophosphatasia (HPP) is broad and variable within families. Along severe infantile forms, adult forms with mild manifestations may be incidentally discovered by the presence of low alkaline phosphatase (ALP) activity in serum. However, it is still unclear whether individuals with persistently low levels of ALP, in the absence of overt manifestations of HPP, have subclinical abnormalities of bone remodeling or bone mass. The aim of this study was to obtain a better understanding of the skeletal phenotype of adults with low ALP by analyzing bone mineral density (BMD), bone microarchitecture (trabecular bone score, TBS), and bone turnover markers (P1NP and ß-crosslaps). We studied 42 individuals with persistently low serum ALP. They showed lower levels of P1NP (31.4?±?13.7 versus 48.9?±?24.4 ng/ml; p?=?0.0002) and ß-crosslaps (0.21?±?0.17 versus 0.34?±?0.22 ng/ml, p?=?0.0015) than individuals in the control group. There were no significant differences in BMD, bone mineral content, or TBS. These data suggest that individuals with hypophosphatasemia have an overall reduction of bone turnover, even in the absence of overt manifestations of HPP or low BMD. We evaluated bone mineral density (BMD), bone microarchitecture, and bone turnover markers in patients with low serum levels of alkaline phosphatase. Our results show that these patients have low bone remodeling even in the absence of BMD abnormalities, thus supporting the recommendation of avoiding antiresorptives such as bisphosphonates in these subjects

Relationship of sclerostin and secreted frizzled protein polymorphisms with bone mineral density: an association study with replication in postmenopausal women

Objectives.- Secreted frizzled-related protein and sclerostin, encoded by FRZB and SOST genes, respectively, are extracellular Wnt inhibitors that tend to decrease bone formation. The purpose of this study was to explore the association of sets of polymorphisms capturing common variations of these genes with bone mineral density (BMD). Methods.- Twelve polymorphic loci of the FRZB gene and 7 of the SOST gene were genotyped in postmenopausal women from two Spanish regions (Cantabria, n=1043, and Valencia, n=342). The polymorphisms included tagging SNPs and SNPs with possible functional consequences assessed in silico. Results.-The rs4666865 polymorphism of the FRZB gene was associated with spine BMD in the Cantabria cohort in the single-locus (p=0.008) and the haplotypic analysis. However, the results were not replicated in the Valencia cohort. Several polymorphisms at the 5´region of the SOST gene, and particularly rs851056, were associated with BMD in women from both cohorts (p=0.002 in Cantabria and 0.005 in Valencia). When the results of both cohorts were combined, the mean BMD difference across rs851056 genotypes was 47 mg/cm2 or 0.31 standard deviations (p<0.001). No differences in FRZB and SOST expression was detected across genotypes. Conclusions.- Polymorphisms in the 5’ region of SOST gene are associated with BMD in postmenopausal women, and consequently contribute to explain in part the hereditary influence on bone mass