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Background In adults, high-dose remifentanil during surgery has been reported to increase postoperative opioid consumption, but this has not been well documented in children. Multimodal analgesia is recommended in the perioperative period for adolescent idiopathic scoliosis (AIS), but no report has examined opioid consumption under epidural analgesia, which is one of the most common types of analgesia. Aims To investigate the association between intraoperative remifentanil dosage and postoperative opioid consumption in AIS in the setting of combined epidural analgesia for postoperative multimodal analgesia. Methods In this retrospective cohort study, patients aged 10-18 years who underwent surgery for scoliosis and epidural analgesia for postoperative pain between July 2012 and April 2019 were included. The primary endpoint was the association between intraoperative cumulative weight-adjusted remifentanil dosage and logarithmic transformation of cumulative weight-adjusted fentanyl consumption in the intensive care unit (ICU). Nonopioid analgesics were investigated as secondary endpoints. An epidural catheter was inserted by the surgeon intraoperatively, and a local anesthetic was administered at the end of the surgery. Multivariate linear regression analysis with adjustment for confounders was performed for all analyses. Results In total, 142 patients were included, and the median intraoperative remifentanil dosage for all patients was 0.27 (interquartile range, 0.24-0.34) µg/kg/min. No association was observed between cumulative weight-adjusted intraoperative dosage of remifentanil and fentanyl, even after adjusting for potential confounders (slope = -1.25; 95% confidence interval [CI], -4.35 to 1.85; P = 0.43). No association was observed between nonopioid analgesic use and intraoperative remifentanil dosage. Conclusion No association was noted between remifentanil dosage during surgery for AIS and postoperative opioid consumption with epidural analgesia. However, this study has limitations due to its retrospective design; thus, further prospective studies are warranted.

Introduction Rechargeable aqueous zinc-ion batteries (RAZIBs) have some inherent advantages such as intrinsic safety, low-cost and theoretically high energy density, making them a current topic of interest. The problem is, dendritic growth of zinc (Zn) metal during electrodeposition occurs whatever alkaline electrolyte or neutral electrolyte, which will break the separator and cause a short-circuit inside the battery. Unless a solution can be found to effectively limit the growth of dendrites, the real-world application of RAZIBs will be nowhere in sight. In this report, by using a glass fiber modified double network hydrogel consists of poly(2-acrylamido-2-methylpropanesulfonicacid)/polyacrylamide (PAMPS/PAM) as semi-solid-state electrolyte (coded as DNGF), we found the formation of Zn dendrites can be greatly alleviated. We attribute the elimination of Zn dendrites to a modified mechanical suppression effect. In addition, a Zn-MnO2 battery with high areal capacity (4.9 mAh cm-2) worked stably for 500 cycles with the help of DNGF. Experimental The obtained DNGF composite was prepared by the following steps: a piece of glass fiber contained PAMPS (PAMPS-GF) was soaked in a 3 mol L-1 acrylamide solution for 1 day, in order to thoroughly swell the PAMPS-GF skeleton with AM solution. 0.01 % N,N'-Methylenebisacrylamide (MBAA) was used as crosslinker. The AM-swollen PAMPS-GF was transferred to a glovebox and was polymerized by a 12 h UV irradiation. The high-capacity Zn-MnO2 battery was assembled by placing a Zn metal foil, a DNGF separator that was swollen by 2M ZnSO4 electrolyte (additive 0.2 M MnSO4) and an MnO2 cathode that consists of α-MnO2 nanowire and carbon black in a Swagelok cell. The cut-off voltage was set as 0.8 V - 1.8 V. Results and discussion The structure of DNGF is depicted in Figure 1a, the second network PAM entangled with the first-network PAMPS while the glass fiber is dispersed in the structure. The DNGF can sustain a stress of 6.9 MPa at a strain of 80%, which is 10 times higher than the PAM gel (Figure 1b). As shown in Figure 2, when DNGF is used as separator in a Zn-Zn symmetric cell, the electrodeposition of Zn crystal becomes uniform and flat. Here, we attribute the suppression of Zn dendrites to a modified mechanical suppression effect. Unlike the case in lithium-ion batteries, in which a stiff polymer separator can effectively prevent the uncontrollable growth of dendrites, the growth of Zn dendrites generally cannot be suppressed by using a polymer separator due to the shear modulus of conventional polymer cannot meet the demanded value (1.8 times higher than the anode metal).[1] The use of DNGF does not stop the upward growth of Zn crystal through the normal mechanical suppression effect, but it delays the growth of Zn dendrites and forces the deposited Zn crystals flat and uniform. As shown in Figure 3, when DNGF was used in a high-capacity Zn-MnO2 battery to protect the cell from short-circuit, the cell worked stably for 500 cycles. The success in the DNGF protected Zn-MnO2 batteries gives us an important information: even within real-world application requirements (e.g. electrode capacity > 4 mAh cm-2), using polymer with excellent mechanical properties as a separator still can suppress the growth of zinc dendrites via the modified mechanical suppression effect. [1] X. Zhang, A. Wang, X. Liu and J. Luo, Acc. Chem. Res., 2019, 52, 3223-3232 Figure 1

Graphene-covering is a promising approach for achieving an acid-stable, non-noble-metal-catalysed hydrogen evolution reaction (HER). Optimization of the number of graphene-covering layers and the density of defects generated by chemical doping is crucial for achieving a balance between corrosion resistance and catalytic activity. Here, we investigate the influence of charge transfer and proton penetration through the graphene layers on the HER mechanisms of the non-noble metals Ni and Cu in an acidic electrolyte. We find that increasing the number of graphene-covering layers significantly alters the HER performances of Ni and Cu. The proton penetration explored through electrochemical experiments and simulations reveals that the HER activity of the graphene-covered catalysts is governed by the degree of proton penetration, as determined by the number of graphene-covering layers., Graphene-covering technology provides a promising approach for achieving a non-noble-metal-catalyst with corrosion protection and catalytic activity under acidic media. Here, the authors unveil that the electrochemical hydrogen evolution mechanism is governed by the proton penetration phenomenon.

In this work, high-value-added N-doped hierarchical porous carbon (NHPC) for oxygen reduction reaction (ORR) electrocatalysis was prepared using biomass cellulose as the raw material. The pyrolysis of cellulose is accelerated by a redox combustion reaction of magnesium nitrate–carbohydrates (urea and cellulose) as absorbed in cellulose fibers, which endows doping with nitrogen, exfoliates the cellulose to highly porous particles, and creates numerous pores simultaneously. After being further carbonized at high temperature and washed with acid, NHPCs were produced that have hierarchical porous structure and large specific surface area. These features are beneficial to the ORR. The influence of four preparation parameters, including species of magnesium salt, carbonization temperature, urea amount, and magnesium salt amount, on the porous characteristics and ORR performance is comprehensively investigated.

The wide application of organic phase change materials for thermal energy storage and management is limited by their low thermal conductivity and poor shape stability. In this work, anisotropic thermally conductive and shape-stabilized phase change composites (PCCs) were successfully prepared with vertically aligned carbon fibers as supporting scaffolds. The aligned and hollow carbon fiber scaffolds with different densities were facilely fabricated by the direct carbonization of rolled cotton sheets with aligned and hollow cellulose fibers. PCCs were obtained by vacuum impregnation of paraffin wax. Because of the interconnected hollow carbon fiber frameworks with vertically aligned fibers and high porosity, PCCs present enhanced anisotropic thermal conductivity and good shape stability against leakage. The thermal conductivity in the axial direction along the fibers is higher than that in the lateral direction, since the aligned fiber scaffolds act as the thermal conduction pathway. The thermal conductivity of a PCC with a carbon ratio of 8.8 wt% is 0.77 W K-1 m(-1) (>3 times that of pure paraffin) in the axial direction, while the value in the lateral direction is 0.58 W K-1 m(-1). This work provides a novel strategy for designing anisotropic thermally conductive and shape-stabilized PCCs with potential applications in advanced thermal management and storage.

In this study, platelet-type carbon nanofibers prepared by the liquid phase carbonization of polymers in the pores of a porous anodic alumina template were used to prepare the Co3O4/carbon electrocatalysts. For comparison, Co3O4 nanoparticles were also deposited on multiwall carbon nanotubes (MWCNTs). Both the nitrogen-free platelet-type carbon nanofibers (pCNFs) and the nitrogen-containing analogue (N-pCNFs) exhibited better dispersion and higher amount of deposited Co3O4 nanoparticles compared to the MWCNTs. In addition, many individual Co3O4 nanoparticles were deposited separately on pCNF and N-pCNF, whereas aggregated deposition was commonplace on MWCNTs. The results indicated that the side wall of the pCNFs, which consisted of carbon edge planes, was the preferential nucleation site of Co3O4 nanoparticles rather than the basal planes of carbon that predominated the surface of the MWCNTs. The oxygen reduction reaction (ORR) activity of the Co3O4/pCNF composite in 0.1 mol dm−3 KOH solution was better than that of Co3O4/MWCNTs. The N-pCNF further enhanced the ORR activity of the Co3O4/pCNFs even though the dispersion and supported amount of Co3O4 nanoparticles were negligibly affected by the presence of the nitrogen species. Synergistic interactions of the Co3O4 nanoparticles with N-doped CNFs contributed to the increased ORR activity.

The utilization of a Li metal anode is necessary in the development of next generation high energy density Li batteries, which is still hindered by problems of dendrite growth, volume change and electrolyte depletion. To overcome these difficulties, the employment of 3D porous current collectors has been demonstrated to be an effective strategy. However, the widely used porous metallic current collectors, such as commercial Cu foam, are always too heavy to meet the demand for high energy density. In this work, we develop a low-weight, flexible, hierarchically porous and textile-structured Cu current collector via a smart cotton T-shirt template method. By employing a variant of Schweizer's reagent as the Cu source, the T-shirt moulded Cu framework can inherit the textile morphology. The hierarchically porous structure and high surface area can lower the local current density, and the unique 3D structure can confine the growth of Li crystals, all of which can endow the novel textile-structured Cu with superior performance as a current collector for Li metal anodes. Furthermore, this strategy provides a convenient route for designing template-structured frameworks, which is useful not only for the development of a current collector, but also for the preparation of numerous structure-oriented materials.

Herein, high-valence-state Mn(V) oxide, barium manganate(V) (Ba3(MnO4)2), is examined as an anode electrocatalyst of a H+-conducting solid oxide steam electrolysis cell (H-SOEC). Ba3(MnO4)2 comprises C3v-symmetric MnO43− oxo-anions with three long Mn–O bonds and one short Mn–O bond at room temperature. Ba3(MnO4)2 caused a conductivity jump by one order of magnitude at approximately 600 °C owing to the antiferromagnetic/paramagnetic phase transition, accompanied by a shape change of the tetrahedral MnO43− anions from C3v to Td symmetry, as confirmed by the electrical conductivity measurements and the extended X-ray absorption fine structure at an elevated temperature. Hence, the Ba3(MnO4)2 base anode of the H-SOEC exhibited improved performance, with anode polarization resistances being lower than those of Sm0.5Sr0.5CoO3, a well-known H-SOEC anode material. Impedance analysis in terms of oxygen and water partial pressure revealed that the superior performance of the Ba3(MnO4)2 base anode can be attributed to the extended reaction area. Since abundant unoccupied 3d states of the high-valence-state Mn5+ cations are favorable for charge transfer interactions with water electron donors, thereby facilitating water adsorption, the oxygen evolution reaction could occur directly over the electrode surface, and thus the reaction sites were not limited to the gas–electrode–electrolyte triple phase boundary.

This study was performed to investigate the association between the esophagectomy surgical Apgar score (eSAS) and 30-day morbidity after esophagectomy. We retrospectively identified patients who underwent esophagectomy in our facilities database from January 2011 through December 2015. We calculated the eSAS and modified eSAS, which was adjusted for the blood loss volume, according to our patients' data. After estimating the cut-off point of the eSAS using a receiver operating curve, the morbidity rates between the 2 groups were compared using Fisher's exact test. In addition, logistic regression analysis was performed to adjust the results by factors associated with morbidity. In total, 246 patients were included. Of these patients, 144 presented with major morbidity. The optimal cut-off value of the eSAS was 4 points. A total of 145 patients had an eSAS of4 points, and 89 of them developed morbidity. A total of 101 patients had an eSAS of ≥4 points, and 55 of them developed morbidity. Fisher's exact test showed that an eSAS of4 points was not significantly associated with morbidity after esophagectomy (P = 0.29). The association was improved after modification for the blood loss volume (P = 0.004). Multivariable analysis revealed that the modified eSAS and age were significantly associated with morbidity (odds ratio, 0.47 and 1.04, respectively). The validity of the eSAS to predict morbidity after esophagectomy could be low, and the modified blood loss volume may improve the predictive effect.

Semaphorin 3A (SEMA3A) is a well-known axon guidance molecule in the nervous system. It is also known as a tumor suppressor in various cancers. In the present study, we examined the relationships between SEMA3A and clinicopathologic features and neoangiogenesis and its prognostic significance for oropharyngeal cancer (OPC) patients. Thirty-two OPC patients who underwent biopsy and 17 normal patients who underwent tonsillectomy were analyzed for SEMA3A expression by immunohistochemical analysis. We also analyzed 22 OPC specimens for CD34 expression as a marker of neoangiogenesis. SEMA3A was significantly downregulated in OPC compared with normal tonsil tissues (p = 0.005). SEMA3A expression was negatively correlated with CD34 expression, which suggested that a higher microvascular density corresponded to a lower expression of SEMA3A (r = -0.466, p = 0.033). Moreover, the higher SEMA3A expression cohort showed better survival than the lower SEMA3A expression cohort regardless of human papillomavirus (HPV) status (p = 0.035). These results suggest that SEMA3A expression is a prognostic marker for survival and is associated with antiangiogenesis in OPC.

IntroductionSexual dysfunction is a common complication in men with type 2 diabetes and is often refractory to treatment. This study investigated the long-term influence of the phosphodiesterase 5 inhibitor (PDE5I) tadalafil on the level of sex hormones and sexual function in male Otsuka Long-Evans Tokushima Fatty (OLETF) rats as an animal model of spontaneous type 2 diabetes.Research design and methodsWe treated 36-week-old male OLETF and non-diabetic Long-Evans Tokushima Otsuka (LETO) rats with oral tadalafil (100 µg/kg/day) for 12 weeks; sham groups received vehicle for 12 weeks. Before and after tadalafil treatment, serum levels of total and free testosterone, estradiol, luteinizing hormone (LH), follicle-stimulating hormone and proinflammatory cytokines were compared among four treatment groups. Copulatory function was examined by matching each rat to an estrous female. After completion of the experiment, total fat mass in the abdomen was measured.ResultsTestosterone levels were significantly lower in OLETF versus LETO rats at 36 weeks. After 12 weeks of tadalafil treatment, levels of testosterone were significantly increased both in OLETF-tadalafil and LETO-tadalafil groups versus vehicle groups. Tadalafil decreased estradiol levels both in OLETF and LETO rats. Furthermore, tadalafil increased serum LH levels with a reduction of proinflammatory cytokines. Total fat mass was significantly lower in the OLETF-tadalafil group versus the OLETF-vehicle group. A significant suppression of copulatory behavior, that is, elongation of intromission latency was found in OLETF rats. However, tadalafil treatment for 12 weeks shortened the intromission latency.ConclusionOur results indicate that tadalafil treatment might improve copulatory disorder in the type 2 diabetic model via improvement of an imbalance in sex hormones and an increase in LH levels.

Porous carbon has attracted great interest because of its distinctive structure and superior properties for designing electrochemical energy storage devices. In this work, we report a novel and facile method to fabricate nitrogen-doped porous carbon (NPC) with designed hierarchical multi-porous structure. The NPC is prepared using a facile and scalable MgO template method as-mediated by a magnesium nitrate-glycine solution combustion synthesis (SCS), in which the preparation conditions of calcination temperature and glycine-nitrate ratio are carefully studied. The NPC shows a high specific surface area up to 1958 m(2) g(-1) and contains hierarchical multi-pores of interconnected macro-, meso-and micro-pores. When applied as ORR electrocatalyst, the NPC-n2-1000 sample shows the highest activity, good durability and high tolerance against methanol, which is among the best reported carbon-base catalysts. The NPC samples also shows great potential as the active electrode material for supercapacitors. NPC-n2-900 sample exhibits a high specific capacitance of 232 F g(-1) at 1 A g(-1) in 6 M KOH electrolyte, a superior rate capability (205 F g(-1) at 10 A g(-1)) and a good cycling performance. The present work demonstrates that the combination of glycine-nitrate SCS and template introduction in one-step can turn the carbohydrate fuel to advanced porous carbon with prospective applications in high-performance energy storage devices.

Electrocatalytic activity for the four-electron-transfer oxygen reduction reaction (ORR) was examined with perovskite-type La0.7Sr0.3Mn1–xNixO3—δ (x = 0–0.5) compounds in concentrated KOH. Electrochemical measurements by means of a rotating ring–disk electrode technique revealed that 10% substitution of Mn by Ni atoms significantly improved ORR activity whereas further Ni substitution significantly decreased the catalytic performance. Moreover, La0.7Sr0.3Mn0.9Ni0.1O3—δ could achieve the ideal reaction electron number (∼4) without the aid of carbon additives, whereas compounds with x > 0.1 achieved a number less than 4 in the absence of carbon cocatalysts, attributed to lowered reaction rates related to two-electron reduction from oxygen to peroxide. Combined with the results of X-ray photoelectron spectroscopy, the pronounced catalytic activity of La0.7Sr0.3Mn0.9Ni0.1O3—δ could be correlated with the population of Mn3+ states with (eg)1 configuration.

Objective Preoperative oral rehydration solutions (ORS) are frequently used in clinical practice in Japan, although their effect remains to be explained. The purpose of this study was to investigate the clinical outcomes associated with ORS usage. Design Systematic review and meta-analysis. Setting Surgical departments at each hospital. Participants A total of 546 patients with American Society of Anesthesiologists physical status classification I or II (non-pregnant adults only) reported in six articles. Interventions Patients in the included studies had originally been randomly allocated to the ORS or control group. Measurements Incidence of aspiration and vomiting during induction of anesthesia, gastric fluid volume (absolute volume), gastric pH, stroke volume variation (SVV) during induction of anesthesia. Risk difference (RD) or mean difference (MD) with 95% confidence interval (CI) were calculated using a random effects model. Main results There was no aspiration or vomiting in either group [3 studies, 428 patients, RD 0 (95% CI −0.01 to 0.01), I2 = 0%]. ORS administration caused no significant difference in gastric volume [4 studies, 486 participants, MD −1.12 ml (95% CI −5.61 to 3.36), I2 = 62%] or gastric pH [4 studies, 486 participants, MD −0.03. (95% CI −0.37 to 0.31), I2 = 0%] compared with the control group. In contrast, ORS resulted in a significant reduction in SVV during the anesthesia induction period [3 studies, 118 participants, MD −3.02 (95% CI −5.44 to −0.59), I2 = 65%]. Conclusions Our systematic review indicates that oral rehydration therapy does not increase the risk of aspiration or vomiting. In contrast, it may help stabilize circulatory dynamics during anesthesia induction.

The development of green and clean synthetic techniques to produce carbon materials for energy storage and conversion applications has motivated researchers to use sustainable biomass. In this study, hierarchical porous carbon (HPC) with very high specific surface area and controlled porosity is synthesized by a novel and facile method, which employs an exothermic pyrolysis process of starch–magnesium nitrate raw materials with subsequent high temperature thermal treatment and acid washing. The biomass starch acts as both a reductant and carbon source, while magnesium nitrate is an oxidant and provides MgO template as pore creator. The vigorous exothermic pyrolysis of starch–magnesium nitrate mixture introduces MgO@C precursor with a highly 3D porous network containing meso- and macropores. After MgO template is removed, plenty of micro- and mesopores are further created. Experimental parameters including calcination temperature, starch–nitrate ratio, and magnesium salt species are comprehensively evaluat...

The oxygen reduction reaction (ORR) catalytic activity was systematically studied on the BaLnMn2O5 series (Ln = Y, Gd, Nd, and La) with a layered double-perovskite-type structure in an alkaline aqueous solution. The onset ORR potential and the number of electrons involved in ORR were found to be strongly Ln-dependent: both values were significantly higher for larger Ln = La and Nd than for smaller Ln = Gd and Y, despite similarities in their chemical compositions and crystal structures. The enhanced ORR activity of the Ln = La and Nd compounds is likely attributed to their stronger affinity to oxygen species, consistent with the greater oxygen storage capability of these compounds, as revealed by the water dissolution reaction at elevated temperatures.

The growth of a uniform barrier-type anodic film on aluminum is usually terminated by electric breakdown, which is controlled by the resistance of electrolyte or anion concentration. In this study, highly resistive porous layers have been introduced by anodizing aluminum in sulfuric acid electrolyte followed by boiling water treatment to examine their influence on the electric breakdown potential. The pores of the porous alumina film are sealed by forming hydrated alumina (pseudo-boehmite) after the boiling water treatment. The breakdown potential increases to over 1500 V for the pore-sealed aluminum specimens on anodizing in sodium tungstate electrolyte. The electrochemical impedance spectroscopy measurements revealed an increased resistance of the porous layer after the pore-sealing treatment. GDOES depth profile analysis disclosed that the sealed porous layer impedes the incorporation of tungsten species into the barrier layer. The introduction of a highly resistive layer that also suppresses the anion incorporation on aluminum is effective in increasing the breakdown potential of anodic films.

This paper reports a survey of power generation characteristics of anode-supported thin film fuel cells with Zr-rich BaZrxCe0.8−xY0.2O3−δ (x = 0.4, 0.6, 0.7, and 0.8) proton-conducting electrolytes, which were fabricated by single step co-firing with Zn(NO3)2 additives at a relatively low temperature (1400 °C). The grain sizes significantly increased to several μm for x = 0.4 and 0.6, whereas the grain sizes remained in the sub-μm ranges for x = 0.7 and 0.8, which resulted in large gaps of the fuel cell performances at x over and below 0.6. The cells for x = 0.4 and 0.6 exhibited efficient power generation, yielding peak powers of 279 and 336 mW cm−2 at 600 °C, respectively, which were higher than those of the corresponding cells previously reported. However, the performances abruptly deteriorated with the increasing x to more than 0.7 because the electrolyte films were highly resistive due to the coarse-grained microstructures. Impedance spectroscopy for the dense sintered BaZrxCe0.8−xY0.2O3−δ discs confirmed that the total proton conductivity of BaZr0.6Ce0.2Y0.2O3−δ was higher than that of BaZr0.4Ce0.4Y0.2O3−δ at temperatures above 500 °C despite relatively small grain sizes. In addition, BaZr0.6Ce0.2Y0.2O3−δ cells could gain a stable current throughout a continuous run for a few days under CO2-containing fuel supply, which was due to high fraction of thermodynamically stable BaZrO3 matrices. It was demonstrated that BaZr0.6Ce0.2Y0.2O3−δ is a promising electrolyte for proton-conducting ceramic fuel cells with excellent proton conductivity and CO2 tolerance at intermediate temperatures.

Hydrogen permeability based on mixed hydride ion electron conduction was demonstrated for hafnium nitride HfNx (film thickness of 100–500 nm, x = 0.8 and 1.0) nanocrystalline membranes. Nanocrystalline films with a (100) orientation and crystallite sizes of a few tens of nanometers were prepared on porous alumina supports by radio frequency (RF) reactive sputtering. Combined spectroscopic, permeability, and microbalance analysis suggests that the nanocrystalline matrices were readily hydrogenated by the formation of Hf–H terminal groups on the internal grain surfaces at ambient temperature and thus efficient hydrogen permeation took place due to an enhanced diffusion of hydridic defects through the grain boundaries; this was further aided by the Hf–H bond exchange process. Hence, membranes with an average crystallite size of 11 nm yielded a hydrogen flux of 6 × 10−7 mol cm−2 s−1 at 25 °C at an applied hydrogen partial pressure of 50 kPa; this value is higher than those exhibited by the current state-of-the-art Pd membranes. These findings establish a new concept for Pd alternatives based on the pronounced hydric conductivity of transition metal nitride nanomaterials.

Anodizing involves a high-voltage electrochemical conversion process that forms barrier-type oxide layers or self-organized nanoporous/nanotubular structures. So far, Al2O3-like nanopores and TiO2-like nanotubes could be successfully synthesized on many metals and alloys. The proposed models of anodic oxide nanotubes growth, however, sacrifice from lack of evidence of the transition from nanopores to nanotubes. The present study demonstrates a missing piece of this anodizing puzzle, which is responsible for the formation of nanotubes in fluoride-containing organic electrolytes. For this purpose, we choose an anodic oxide formed on iron, as a model case, because both nanotubes and nanopores can be formed and slow kinetics of transition between those two forms allows us to observe, ex situ, a fluoride-rich-layer upon nanopores/nanotubes transition. The compositional fingerprints of this transition shed a light on the general mechanism of nanotubes growth in fluoride-containing electrolytes.

The production of pure hydrogen for use in energy applications and related industries often relies on the permeation of hydrogen through palladium-based membranes. However, the scarcity of Pd reserves necessitates the development of affordable alternatives with high hydrogen permeability. Here we report room-temperature hydrogen permeability of titanium nitrides (widely used as tough and inert coating materials) enabled by mixed hydride ion–electron conductivity. Combined spectroscopic, permeability and microgravimetric measurements reveal that nanocrystalline TiN x membranes feature enhanced grain-boundary diffusion of hydride anions associated with interfacial Ti cations on nanograins. Since the corresponding activation energies are very low (

The oxygen storage capability and related defect structure of tetrahedral orthochromite(V) compound YCr1–xPxO4 (x = 0, 0.3, 0.5, and 0.7) were investigated by employing thermal gravimetry and in situ X-ray spectroscopy for reversible oxygen store/release driven by heating–cooling cycles in the temperature range from 50 to 600 °C. YCr1–xPxO4 started releasing oxygen as heated from 50 °C under ambient atmosphere, with reduction of CrV to CrIV, while the reduced YCr1–xPxO4−δ phase was significantly reoxidized via absorbing oxygen by cooling to 50 °C under ambient atmosphere, recovering the original stoichiometric phase. Operando X-ray adsorption spectroscopy and first-principles calculations demonstrate that nonstoichiometric YCr1–xPxO4−δ phases were stabilized by forming linking polyhedral CrIV2O76– via corner sharing between oxygen-deficient CrIVO32– and adjacent CrIVO44–. YCr1–xPxO4 was found to have an extremely low reduction enthalpy of about 20 kJ mol–1 probably due to the relatively high reduction pot...

Here, we report remarkable oxygen evolution reaction (OER) catalytic activity of brownmillerite (BM)-type Ca2 FeCoO5 . The OER activity of this oxide is comparable to or beyond those of the state-of-the-art perovskite (PV)-catalyst Ba0.5 Sr0.5 Co0.8 Fe0.2 O3-δ (BSCF) and a precious-metal catalyst RuO2 , emphasizing the importance of the characteristic BM structure with multiple coordination environments of transition metal (TM) species. Also, Ca2 FeCoO5 is clearly advantageous in terms of expense/laboriousness of the material synthesis. These facts make this oxide a promising OER catalyst used in many energy conversion technologies such as metal-air secondary batteries and hydrogen production from electrochemical/photocatalytic water splitting.

Hydrogen membrane fuel cells, HMFC, were fabricated by RF sputtering deposition of BaZr0.1Ce0.7Y0.2O3-d thin films on Pd solid anode. The HMFC can give OCV of 1.0 V and peak power density of 0.8 W cm-2 at 600°C by using H2 fuels. The direct NH3 fueled HMFC reveals OCV of 0.92 V and peak power density of 0.58 W cm-2 at 600°C. These performances are superior to the champion data of direc ammmnonia PCFC.

Iron oxide has been considered as one of the most promising anode materials due to its high theoretical capacity, low cost and environmental friendliness. However, few simple and effective method is explored for preparing iron oxides with high electrochemical performance via alleviating the volume change and agglomeration of active particles. In this work, FeOx/carbon/graphene composites are fabricated by a facile solution combustion synthesis within several minutes in one step. Characterization demonstrates that FeOx nanoparticles are well-dispersed in the graphene matrix. The presence of graphene effectively alleviates the agglomeration of FeOx nanoparticles, and accommodates the volume changes during the cycling process, thereby resulting in the excellent electrochemical performance. FeOx/carbon/graphene (31.4 wt.% graphene) delivers a higher discharge capacity of 824 mAh g−1 after 100 cycles at 0.4 A g−1, in comparison to the value of 301 mAh g−1 for the composite without graphene. This easily prepared FeOx/carbon/graphene composite with excellent electrochemical performance can be considered as one promising anode material used for lithium-ion batteries.

Heat treatment of Zr-24 at% Ti alloy with barrier-type dielectric anodic oxide films was conducted at 473 K in air to examine the thermal stability of the dielectric oxide films for possible electrolytic capacitor application. The anodic oxide film was formed by anodizing of the alloy at 50 V for 30 min in 0.1 mol dm(-3) ammonium pentaborate electrolyte. The anodic oxide film of 125 nm thickness was crystalline, containing both monoclinic and tetragonal ZrO2 phase. It was found that marked thickening of the oxide film with generation of cracks occurred during heat treatment at 473 K. Thus, the dielectric loss was largely increased along with the capacitance increase. In contrast, the anodic oxide film formed on the oxygen-incorporated alloy remained uniform, and no significant increase in dielectric loss was observed even after the heat treatment. The capacitance of the anodic film became as high as 4.8 mF m(-2), which was nearly twice that on Ta. The high capacitance was associated with the preferential formation of tetragonal ZrO2 phase in the anodic oxide film on the oxygen-incorporated alloy. Findings indicated that the oxygen-incorporated Zr-Ti alloy is a promising novel material for capacitor application.

INTRODUCTION AND OBJECTIVE:To investigate the relationship between urgency and the components of Metabolic syndrome (MetS), including obesity, hyperglycemia, hypertension, and dyslipidemia, in a re...

Nocturia (waking from sleep at night to void) is a common cause of sleep disruption associated with increased comorbidity and impaired quality of life. However, its impact on mortality remains unclear. We performed a systematic review and meta-analysis to evaluate the association of nocturia with mortality as a prognostic factor and a causal risk factor.We searched PubMed®, Scopus®, CINAHL® (Cumulative Index of Nursing and Allied Health Literature) and major conference abstracts up to December 31, 2018. Random effects meta-analyses were done to address the adjusted RR of mortality in people with nocturia. Meta-regression was performed to explore potential determinants of heterogeneity, including the risk of bias. We applied the GRADE (Grades of Recommendation, Assessment, Development and Evaluation) framework to rate the quality of evidence for nocturia as a prognostic risk factor for mortality and separately as a cause of mortality.Of the 5,230 identified reports 11 observational studies proved eligible for inclusion. To assess nocturia 10 studies used symptom questionnaires and 1 used frequency-volume charts. Nocturia was defined as 2 or more episodes per night in 6 studies (55%) and as 3 or more episodes per night in 5 (45%). Pooled estimates demonstrated a RR of 1.27 (95% CI 1.16-1.40, INocturia is probably associated with an approximately 1.3-fold increased risk of death.

Xeroderma pigmentosum (XP) is a rare autosomal recessive disease caused by a defect in deoxyribonucleic acid repair. Along with cutaneous symptoms, neurological symptoms are important clinical features of XP. However, information on neurogenic bladder occurrence among XP cases is rare. Herein, we describe a case of neurogenic bladder in a patient with XP type A (XPA). In this case, low bladder compliance, impaired bladder emptying, and urethral sphincter discoordination were significant cystometric findings, and frequent febrile urinary tract infection was a clinical problem. XPA patients often cannot express their symptoms because of cognitive dysfunction. Close follow-up and assessments are necessary. Keywords: Xeroderma pigmentosum, Neurogenic bladder

Purpose The Japanese Intensive care PAtient Database (JIPAD) was established to construct a high-quality Japanese intensive care unit (ICU) database. Materials and methods A data collection structure for consecutive ICU admissions in adults (≥16 years) and children (≤15 years) has been established in Japan since 2014. We herein report a current summary of the data in JIPAD for admissions between April 2015 and March 2017. Results There were 21,617 ICU admissions from 21 ICUs (217 beds) including 8416 (38.9%) for postoperative or procedural monitoring, defined as adult admissions following elective surgery or for procedures and discharged alive within 24 h, 11,755 (54.4%) critically ill adults other than monitoring, and 1446 (6.7%) children. The standardized mortality ratios (SMRs) based on the Acute Physiology and Chronic Health Evaluation (APACHE) III-j, APACHE II, and Simplified Acute Physiology Score II scores in adults ranged from 0.387 to 0.534, whereas the SMR based on the Paediatric Index of Mortality 2 in children was 0.867. Conclusion The data revealed that the SMRs based on general severity scores in adults were low because of high proportions of elective and monitoring admission. The development of a new mortality prediction model for Japanese ICU patients is needed.

INTRODUCTION AND OBJECTIVES:Surgical therapy is an important therapeutic strategy for benign prostatic hyperplasia (BPH). However, the degree of improvement in postoperative clinical parameters can...

INTRODUCTION AND OBJECTIVES:Recent reports indicate that there may be a physiological link between hypogonadism and metabolic syndrome (MetS) (J Androl 2009, 30: 370). In fact, hyperinsulinemia and...

Anodizing of metals and alloys has attracted increased attention for the formation of nanostructured oxide films with self-ordered morphologies. The anodizing researches have been conducted mainly on valve metals, including aluminum, magnesium, titanium, zirconium, niobium and tantalum, because of ready formation of thick anodic films on these metals. Recent findings of organic electrolytes containing fluoride have expanded the anodizing studies to non-valve metals; nanoporous and nanotubular anodic films are now available even on iron and stainless steel 1-3. The nanoporous and nanotubular α-Fe2O3 films have been formed by anodizing of iron and subsequent heat treatments, and such oxide films are of interest for photoelectrochemical water splitting 4. Further functional oxide films will be formed by anodizing of iron alloys. In the present study, we examined the formation of nanoporous anodic films on an Fe-Ni alloy. The oxygen evolution properties of the anodic oxide films were also examined. An Fe-Ni invar alloy plate containing 41 mass% nickel was used in this study. For comparison, a high purity (99.99%) iron plate was also used. The specimens were anodized at 40 V in ethylene glycol electrolyte containing 0.1 mol dm-3 NH4F and 0.5 mol dm-3 H2O at 293 K. For anodizing of iron, the H2O concentration was increased to 1.5 mol dm-3 because the detachment of an oxide film formed at the H2O concentration of 0.5 mol dm-3 proceeded during heat treatment. After anodizing, heat treatment of the specimens was conducted in an argon atmosphere at temperatures between 673 K and 873 K to remove fluoride species in the anodic films and increase the crystallinity of the oxide films. During anodizing of the Fe-Ni alloy at 40 V the current density exceeded 200 A m-2, which was approximately 4 times that of iron in the same electrolyte. Because of the high current density, the film growth rate on the Fe-Ni alloy was as high as 0.3 μm min-1 and a 3-μm-thick anodic film was formed by anodizing only for 10 min. The anodic film exhibited a cylindrical nanoporous morphology, which was similar to that formed on iron. However, the pore size and the interpore distance for the Fe-Ni alloy were smaller than those on iron. The as-anodized specimens contained fluoride species in the anodic films, as confirmed by glow discharge optical emission spectroscopy depth profile analysis. The heat treatment of the anodized alloy in argon atmosphere at 873 K removed fluoride species and a crystalline spinel phase was developed. When anodized iron specimens were heat-treated in the argon atmosphere at 673 and 773 K, α-Fe2O3 phase was also detected by XRD as well as the Fe3O4 phase. The a-Fe2O3phase disappeared at 873 K. The oxygen evolution reaction (OER) was examined in 0.1 mol dm-3 KOH solution by anodic polarization measurements. For the iron specimens, the OER activity increased with an increase in the heat treatment temperature from 773 K to 873 K. The presence of α-Fe2O3heat-treated at 773 K may be associated with the lower OER activity. The alloy specimen heat-treated at 873 K showed further enhanced activity, confirming the beneficial effect of nickel incorporation into the anodic oxide for enhancing the OER activity. References 1. H. Habazaki, Y. Konno, Y. Aoki, P. Skeldon and G. E. Thompson, J. Phys. Chem. C, 114, 18853 (2010). 2. Y. Konno, E. Tsuji, P. Skeldon, G. E. Thompson and H. Habazaki, J. Solid State Electrochem., 1 (2012). 3. K. Kure, Y. Konno, E. Tsuji, P. Skeldon, G. E. Thompson and H. Habazaki, Electrochem. Commun., 21, 1 (2012). 4. S. K. Mohapatra, S. E. John, S. Banerjee and M. Misra, Chem. Mater., 21, 3048 (2009).

Spark anodizing of Ti6Al4V alloy has been performed in alkaline electrolytes containing aluminate to form wear-resistant coatings. Coatings obtained under potentiostatic conditions exhibit a better wear resistance, with a wear rate approx. 10 times lower than galvanostatic coatings, due to the formation of coatings with low porosity since potentiostatic mode controls the size of the micro-discharges. The coatings consist mainly of γ - Al 2 O 3 , whilst Al 2 TiO 5 is present in minor proportions. For some coatings, the formation of Al 6 KO 9.5 is observed due to the incorporation of potassium into the coating. EDS analysis shows that aluminum is the main constituent of the coatings, being mainly incorporated from the anodizing solution and homogeneously distributed into the coating. A decrease in pore density between 15 and 30% and roughness reduction of 10 to 60% was obtained with KOH and Na 2 WO 4 additions, improving the coating wear resistance in pin-on-disc wear tests, especially by Na 2 WO 4 addition.

Fuel cell performances at intermediate temperature 600°C were examined for the hydrogen membrane fuel cell (HMFC) designed by rf sputter deposition of a BaCe0.8Y0.2O3-δ thin film electrolyte (1 μm thickness) on a Pd1-xAgx (x = 0, 0.2 and 0.4) solid anode. The maximum power density reached to 1.2 W cm−2 at 600°C with the Pd0.8Ag0.2 anodes, and this value was much higher than the champion data of the recent anode-supported proton-conducting ceramic fuel cells (PCFCs). By electrochemical impedance analysis, it was demonstrated that the hydrogen permeability was crucial to the anode polarization losses of the HMFC because the charge transfer resistances and concentration overpotentials at BaCe0.8Y0.2O3-δ/Pd oxide-metal interfaces are simultaneously improved with the alloys having higher hydrogen permeability.

Highly corrosion-resistant, ∼65-nm-thick, layer-by-layer aluminosilicate coatings have been prepared by multiple spin casting on Type 430 stainless steel. These coatings have been characterized by field emission scanning electron microscopy, transmission electron microscopy, conductive atomic force microscopy, and micro-electrochemical measurements using a microcapillary cell. The coatings annealed at 400 °C are non-uniform and contain fine iron oxide nodules, which are formed in high densities on the {111} grain surface of the steel. The iron oxide nodules arise from the outward diffusion of the oxidized iron from the substrate through the coating. The coatings annealed at 400 °C are more insulating compared with those before annealing; however, the nodule sites are less insulating owing to the development of more conductive iron oxide channels in the coatings. A microcapillary cell study reveals that the coated specimens prepared from diluted precursor solutions by a layer-by-layer process exhibit higher pitting potential in 3.5 wt% NaCl solution compared with those prepared through a single-layer process. Moreover, the coated specimen obtained from the layer-by-layer process exhibits similarly high pitting potential even at the flaw sites in the coating; in contrast, the pitting potential in the flaw-containing regions of the coated specimen obtained from a single-layer process shifts towards the less noble direction. The layer-by-layer coating is also effective in suppressing the corrosion of the scratched region of the coated specimens, owing possibly to the excellent adhesion between the coating and the substrate.

Copper is an important practical metal with a high thermal conductivity that is widely used as a heat exchanger material. However, a liquid film often forms on the Cu surface through water vapor condensation, causing a large resistance to heat transfer. To address this issue, a superhydrophobic Cu metal nanowire surface is developed herein via Cu anodizing in a KOH electrolyte to form Cu(OH)2 nanowires, followed by hydrogen reduction at an elevated temperature and the application of a wet organic coating. The hydrogen treatment reduces the hydroxide to the metal while maintaining the nanowire morphology. The superhydrophobic Cu metal nanowire surface exhibits effective removal of water droplets formed through water vapor condensation. Furthermore, the metal nanowire surface exhibits highly improved heat transfer compared with the Cu(OH)2 nanowire surface. Therefore, the combined process of anodizing and hydrogen reduction is a simple approach that forms an effective superhydrophobic Cu surface with high thermal conductivity.

Anodizing of iron (100), (110) and (111) single crystals in mono-ethylene-glycol electrolyte containing 1.5 mol dm−3 water and 0.1 mol dm−3 ammonium fluoride leads to formation of anodic iron nanopores/nanotubes where the nanopores are essentially composed of oxide nanotubes separated by iron fluoride matrix. It was found that electrochemical thermodynamics for nanoporous/nanotubular film formation apparently depends on the index number of facet on which the anodic film is formed. The film formation on (100) facet is associated with extended gas evolution upon anodizing and consequently corresponds to a shift of current-time curve towards higher current density values comparing with those formed on higher index number facets. The nanotubes formed on (100) facet have a general chemical formula of Fe2O3.FeF2, whereas those formed on higher index number are composed of Fe3O4.FeF2. The anodic films formed on Fe (110) and Fe (111) are essentially amorphous whereas the one formed on (100) facet shows high degree of crystallinity. The results are discussed in view of anisotropic properties of iron.

Zinc-air secondary battery (ZAB) is a promising candidate for the development of new generation of energy conversion systems due to its relatively high theoretical energy density of 1370 Wh kg-1. The decrease of overpotential for oxygen-reduction-reaction (ORR) and oxygen-evolution-reaction (OER) in air electrode, together with providing of high durability, are essential for commercialization of zinc air battery. As precious-metal-free electrocatalysts, transition metal oxide nanoparticles supported on nanocarbon materials are promising for highly active ORR/OER catalysts. The carbon has an important role to provide enough electrical conductivity, but the carbon degradation at high OER potential is a key issue for practical application. Very recently, we reported that platelet-type carbon nanofibers (pCNFs) with high graphitization degree are very resistive in the OER environments in the highly concentrated alkaline media [1]. Surprisingly, carbon edge plane at the sidewall of the carbon nanofibers is exposed to electrolyte, but negligible oxidative dissolution occurs at the OER condition for 1 month. Thus, pCNFs have high potential as the durable carbon material for the air electrode of ZAB. In the present study, novel hybrid electrocatalyst consisting of pCNFs and spinel-type oxide nanoparticles are prepared by a solvothermal method as a durable and active ORR/OER electrocatalyst. The commercially available pCNFs (Sigma-Aldrich) were used in this study. Commercial carbon black (Denka black, DB) were also used for comparison. Each carbon support was treated in concentrated HNO3 aqueous solution at 110℃ for the surface activation. MnCo2O4 nanoparticles (MCO) were loaded on each carbon support by means of solvothermal synthesis; an ethanol solution containing manganese acetate and cobalt acetate was heated at 150℃ for 3 h. The electrochemical measurements were carried out with the carbon counter electrode and Hg/HgO/KOH aq. reference electrode in 4 and 8 mol dm-3 KOH aqueous solution, for the electrocatalytic activity evaluation and for the durability tests, respectively. HRTEM image of the MCO/pCNF hybrid (Fig. 1) reveals the uniform distribution of MCO nanoparticles, which are 5 nm in diameter on average, on the looped carbon planes of the pCNFs. It is likely that the MCO is strongly coupled with pCNF. The Mn/Co ratio obtained by TEM-EDS analysis of MCO nanoparticles loaded on pCNFs was 1/2 in agreement with the target composition. The electrochemical measurements demonstrated markedly high activity of MCO/carbon hybrid towards ORR with the onset potential as high as 0.90 V vs RHE. High catalytic performance probably results from the good interface formation between MCO and carbon due to the solvothermal synthesis. The durability test using gas-diffusion electrodes was carried out under repeated galvanostatic ORR/OER polarization at ±20 mA cm-2 for 1 h. Although the MCO/DB electrode shows the overpotential increase after 30 cycles, the overpotential for MCO/pCNF is stable even after 80 cycles. References [1] Y. Sato, D. Kowalski, Y. Aoki and H. Habazaki, Appl. Cat. A, 597 (2020) 117555. Acknowledgment This work is based on results obtained from a project, "Research and Development Initiative for Scientific Innovation of New Generation Batteries (RISING2)", JPNP16001, commissioned by the New Energy and Industrial Technology Development Organization (NEDO), Japan. Figure 1 HRTEM image of MCO/pCNF hybrid. Figure 1

Hydration treatment of aluminum is often used for corrosion protection of aluminum alloys and for the formation of dielectric alumina layer in aluminum electrolytic capacitors. Hydrated alumina layer is usually formed by immersing aluminum with and without a porous anodic alumina layer in hot water. The hydrated alumina layer plays an important role in enhancing the corrosion resistance and forming crystalline γ’-alumina in subsequent barrier-type anodic film growth by anodizing. However, the properties of the hydrated layer are not yet well understood. In this study, we examined the influence of anion incorporation properties into the barrier-type anodic alumina films through the hydrated alumina layer, which was formed in hot water. High purity (99.99%) aluminum plate was used in this study. After electropolishing in a HClO4–ethanol mixed solution below 283 K, a hydrated alumina layer was formed by immersing the electropolished aluminum in hot water (95ºC) for 10 min. The resultant hydrated layer consists of two layers, comprising a flake-like outer porous layer and a relatively dense inner layer. The thickness of the hydrated layer was ~430 nm. Then the aluminum with the hydrated layer was anodized in boric acid and tungstate electrolytes to grow the barrier-type anodic films. When the boric acid electrolyte was used, boron species were incorporated into the outer part of the barrier-type anodic films through the hydrated alumina layer. In contrast, no incorporation of tungsten species into the barrier-type anodic film through the hydrated layer occurred in the tungstate electrolyte. Phosphate anions are known to be incorporated into the 70% of the film thickness in the anodic amorphous alumina film, but in the present study, phosphate anions were not incorporated into the barrier-type anodic films through the hydrated layer. It is likely from the GDOES elemental depth profile analysis suggests that the inner hydrated layer becomes a barrier for the incorporation of tungsten and phosphorus species. Thus, apparently, the inner hydrated alumina layer has cation-selective permeation properties so that anion incorporation is limited. In boric acid electrolyte, the acid dissociation is limited, and non-charged boric acid species can be penetrated through the hydrated layer.

Protonic ceramic fuel cells (PCFCs) have been drawing considerable attentions because of their potential for high-power operating at intermediate temperature (IT), 400–600°C, which is a salient issue for their practical implementation. BaZr0.1Ce0.7Y0.2O3, popular proton-conducting ceramic electrolyte material, has notably high conductivity of 9 × 10−3 S cm−1 at 500°C [1], but vast majority of power outputs in current PCFC literature still lag far behind 1.0 W cm−2 at the IT regime. In general, PCFCs have structure of porous anode support composed proton-conducting ceramic electrolyte and metallic Ni. Meanwhile, a hydrogen membrane fuel cell (HMFC), which consist of a dense hydrogen-permeable metal anode and kindred electrolyte material, has achieved extraordinary performances of 1.4 W cm−2 at 600°C [2]. This is higher than any others ever reported to the best of our knowledge. However, what give rise to such high performance is obscure. Here, we simulated effect of oxide-ion blocking at anode/electrolyte on defect profile in HMFC and compared them with those of PCFCs to elucidate origins of the high performance. The one-dimensional concentration profiles of three charged defect carriers: oxygen vacancy, proton, and oxygen hole at steady state were computed based on Nernst–Planck–Poisson model with defect thermodynamics of BaZr0.8Y0.2O3 [3]. In PCFC, membrane is equilibrated with O2, H2, and H2O gases. In HMFC, however, boundary conditions at the anodic surface are unknown since the surface is sealed by dense metal anode. We made an assumption that a flux of oxygen vacancy is kept at 0 inside the electrolyte membrane of HMFC [4]. Simulations confirm that oxide-ion blocking at an electrolyte/anode interface greatly modifies the defects’ distribution across the membrane. Positively charged oxygen vacancies are depressed near electrolyte/anode interface owing to the oxide-ion blocking, and thus, protonic defects are alternatively accumulated near the regions for the charge neutrality preservation, which results in the enhancement of local proton conductivity (Attached image). Accordingly, the superior performance of HMFC to PCFC is attributable the proton pumping by utilizing the oxygen chemical potentials. References [1] C. Zuo et al., Ba(Zr0.1Ce0.7Y0.2)O3 as an electrolyte for low-temperature solid-oxide fuel cells, Adv. Mater. 2006, 18, 3318. [2] N. Ito et al., New intermediate temperature fuel cell with ultra-thin proton conductor electrolyte, J. Power Sources 2005, 152, 200. [3] H. Zhu et al., Defect incorporation and transport within dense BaZr0.8Y0.2O3− d proton-conducting membrane, J. Electrochem. Soc. 2018, 165, F581. [4] S. Jeong et al., Proton Pumping Boosts Energy Conversion in Hydrogen-Permeable Metal-Supported Protonic Fuel Cells, ACS Appl. Energy Mater. 2020, 3, 1222 Figure 1