Synthesis and Characterization of Silica-Tantala Microporous Membranes for Gas Separations Fabricated Using Chemical Vapor Deposition.

Composite membranes consisting of microporous tantalum-doped silica layers supported on mesoporous alumina substrates were fabricated using chemical vapor deposition (CVD) in both thermal decomposition and counter-flow oxidative deposition modes. Tetraethyl orthosilicate (TEOS) was used as the silica precursor and tantalum (V) ethoxide (TaEO) as the tantalum source. Amounts of TaEO from 0 mol% to 40 mol% were used in the CVD gas mixture and high H2 permeances above 10-7 mol m-2 s-1 Pa-1 were obtained for all conditions. Close examination was made of the H2/CH4 and O2/CH4 selectivities due to the potential use of these membranes in methane reforming or partial oxidation of methane applications. Increasing deposition temperature correlated with increasing H2/CH4 selectivity at the expense of O2/CH4 selectivity, suggesting a need to optimize membrane synthesis for a specific selectivity. Measured at 400 °C, the highest H2/CH4 selectivity of 530 resulted from thermal CVD at 650 °C, whereas the highest O2/CH4 selectivity of 6 resulted from thermal CVD at 600 °C. The analysis of the membranes attempted by elemental analysis, X-ray photoelectron spectroscopy, and X-ray absorption near-edge spectroscopy revealed that Ta was undetectable because of instrumental limitations. However, the physical properties of the membranes indicated that the Ta must have been present at least at dopant levels. It was found that the pore size of the resultant membranes increased from 0.35 nm for pure Si to 0.37 nm for a membrane prepared with 40 mol% Ta. Similarly, an increase in Ta in the feed resulted in an increase in O2/CH4 selectivity at the expense of H2/CH4 selectivity. Additionally, it resulted in a decrease in hydrothermal stability, with the membranes prepared with higher Ta suffering greater permeance and selectivity declines during 96 h of exposure to 16 mol% H2O in Ar at 650 °C.

Penetration of MeV electrons into the mesosphere accompanying pulsating aurorae.

Pulsating aurorae (PsA) are caused by the intermittent precipitations of magnetospheric electrons (energies of a few keV to a few tens of keV) through wave-particle interactions, thereby depositing most of their energy at altitudes ~ 100 km. However, the maximum energy of precipitated electrons and its impacts on the atmosphere are unknown. Herein, we report unique observations by the European Incoherent Scatter (EISCAT) radar showing electron precipitations ranging from a few hundred keV to a few MeV during a PsA associated with a weak geomagnetic storm. Simultaneously, the Arase spacecraft has observed intense whistler-mode chorus waves at the conjugate location along magnetic field lines. A computer simulation based on the EISCAT observations shows immediate catalytic ozone depletion at the mesospheric altitudes. Since PsA occurs frequently, often in daily basis, and extends its impact over large MLT areas, we anticipate that the PsA possesses a significant forcing to the mesospheric ozone chemistry in high latitudes through high energy electron precipitations. Therefore, the generation of PsA results in the depletion of mesospheric ozone through high-energy electron precipitations caused by whistler-mode chorus waves, which are similar to the well-known effect due to solar energetic protons triggered by solar flares.

Factorial validation analysis of the Baby and Children's Eating Behavior Questionnaires in Samoa.

Survey instruments for assessing eating behaviors in infancy and early childhood have yet to be validated among Pacific Islanders, among whom the prevalence of pediatric obesity is steadily increasing. This study aimed to evaluate Baby Eating Behavior Questionnaire (BEBQ) and Children's Eating Behavior Questionnaire (CEBQ) factor structures against data collected from mother-infant dyads in Samoa. The BEBQ was administered across two time points: approximately 2 months (mean = 2.37 [SD = 0.34]; N = 105) and 4 months postpartum (mean = 4.22 [SD = 0.44]; N = 117). The CEBQ was administered at approximately 21 months postpartum (mean = 21.45 [SD = 1.72]; N = 113). Both the original four-factor BEBQ and seven-factor CEBQ models failed to replicate in confirmatory factor analyses. BEBQ data from 2 and 4 months demonstrated acceptable fit to a nine-item, two factor model, generated by elimination of factors with low internal reliability. A series of exploratory factor analyses on CEBQ data from 21 months postpartum ultimately revealed 16-item, three-factor structure. There was little correlation between BEBQ and CEBQ scores, suggesting either that infant feeding behaviors before and after weaning are not strongly associated, or that the BEBQ and CEBQ function better in cross-sectional, rather than longitudinal analyses. Newly derived CEBQ factors raise concerns regarding whether original CEBQ items and factors were sufficiently theoretically distinct. Study results suggest that demographic and cultural differences may impact both BEBQ and CEBQ factor structure. Further qualitative research is necessary to address these issues.

Safety profile of vonoprazan compared with proton pump inhibitors: insight from a pharmacovigilance study.

Proton pump inhibitors (PPIs) are used to treat acid-related disorders such as peptic ulcer and gastroesophageal reflux disease. Recently, vonoprazan, a novel potassium-competitive acid blocker (P-CAB), has been introduced as more effective treatment option. The purpose of this study was to clarify the adverse events associated with vonoprazan compared to PPIs using a spontaneous reporting system database. We performed a retrospective pharmacovigilance disproportionality analysis using the Japanese Adverse Drug Event Report (JADER) database. Adverse event reports submitted to the Pharmaceuticals and Medical Devices Agency between 2004 and 2017 were analyzed, and the reporting odds ratio (ROR) and 95% confidence interval (CI) for each adverse event were calculated. The database comprised 11,433 reports associated with PPIs, and 636 reports with vonoprazan. Hepatic and skin disorders were commonly detected in both PPIs and vonoprazan. There was a significant association of interstitial lung disease with PPIs as a class (ROR: 1.61, 95%CI: 1.47-1.77), but not with vonoprazan. Vonoprazan was strongly associated with haemorrhagic enterocolitis (ROR, 86.5; 95%CI, 59.7125). Among the PPIs, the signal score of microscopic colitis was noteworthy in the case of lansoprazole (ROR, 405; 95%CI, 348-472). It is suggested that there is a diversity in the strength of the association between PPIs and vonoprazan with adverse events. Our results may provide useful information for the treatment of acid-related disorders, but further research with more data is needed to finally clarify this.

The Direct Partial Oxidation of Methane to Dimethyl Ether over Pt/Y2 O3 Catalysts Using an NO/O2 Shuttle.

Using a mixture of NO + O2 as the oxidant enabled the direct selective oxidation of methane to dimethyl ether (DME) over Pt/Y2 O3 . The reaction was carried out in a fixed bed reactor at 0.1 MPa over a temperature range of 275-375 °C. During the activity tests, the only carbon-containing products were DME and CO2 . The DME productivity (µmol gcat -1 h-1 ) was comparable to oxygenate productivities reported in the literature for strong oxidants (N2 O, H2 O2 , O3 ). The NO + O2 mixture formed NO2 , which acted as the oxygen atom carrier for the ultimate oxidant O2 . During the methane partial oxidation reaction, NO and NO2 were not reduced to N2 . In situ FTIR showed the formation of surface nitrate species, which are considered to be key intermediate species for the selective oxidation.

Evaluation of adverse events associated with filgrastim originator and biosimilar using a spontaneous reporting system database.

Biosimilar products of filgrastim have become available for improved sustainability of cancer care; however, the real-world safety profile remains unknown. The purpose of this study was to clarify the adverse events associated with filgrastim originator and its biosimilar using the Japanese Adverse Drug Event Report (JADER) database. Adverse event reports submitted to the Pharmaceuticals and Medical Devices Agency between 2014-2018 were extracted. We calculated the reporting odds ratio and 95% confidence interval for each adverse event. We obtained 584 reports of adverse events associated with filgrastim originator and 102 reports with its biosimilar. Signals were detected for bone marrow failure and febrile neutropenia with both filgrastim originator and its biosimilar; whereas those for drug resistance and hypoxia only involved filgrastim originator, and those for interstitial lung disease only involved its biosimilar. The safety profiles of filgrastim originator and its biosimilar were partly different. Further studies are needed to confirm these findings.

Synthesis of Silica Membranes by Chemical Vapor Deposition Using a Dimethyldimethoxysilane Precursor.

Silica-based membranes prepared by chemical vapor deposition of tetraethylorthosilicate (TEOS) on γ-alumina overlayers are known to be effective for hydrogen separation and are attractive for membrane reactor applications for hydrogen-producing reactions. In this study, the synthesis of the membranes was improved by simplifying the deposition of the intermediate γ-alumina layers and by using the precursor, dimethyldimethoxysilane (DMDMOS). In the placement of the γ-alumina layers, earlier work in our laboratory employed four to five dipping-calcining cycles of boehmite sol precursors to produce high H2 selectivities, but this took considerable time. In the present study, only two cycles were needed, even for a macro-porous support, through the use of finer boehmite precursor particle sizes. Using the simplified fabrication process, silica-alumina composite membranes with H2 permeance > 10-7 mol m-2 s-1 Pa-1 and H2/N2 selectivity >100 were successfully synthesized. In addition, the use of the silica precursor, DMDMOS, further improved the H2 permeance without compromising the H2/N2 selectivity. Pure DMDMOS membranes proved to be unstable against hydrothermal conditions, but the addition of aluminum tri-sec-butoxide (ATSB) improved the stability just like for conventional TEOS membranes.

Human lung microvascular endothelial cells as potential alternatives to human umbilical vein endothelial cells in bio-3D-printed trachea-like structures.

BACKGROUND: We have been trying to produce scaffold-free structures for airway regeneration using a bio-3D-printer with spheroids, to avoid scaffold-associated risks such as infection. Previous studies have shown that human umbilical vein endothelial cells (HUVECs) play an important role in such structures, but HUVECs cannot be isolated from adult humans. The aim of this study was to identify alternatives to HUVECs for use in scaffold-free structures. METHODS: Three types of structure were compared, made of chondrocytes and mesenchymal stem cells with HUVECs, human lung microvascular endothelial cells (HMVEC-Ls), and induced pluripotent stem cell (iPSC)-derived endothelial cells. RESULTS: No significant difference in tensile strength was observed between the three groups. Histologically, some small capillary-like tube formations comprising CD31-positive cells were observed in all groups. The number and diameters of such formations were significantly lower in the iPSC-derived endothelial cell group than in other groups. Glycosaminoglycan content was significantly lower in the iPSC-derived endothelial cell group than in the HUVEC group, while no significant difference was observed between the HUVEC and HMVEC-L groups. CONCLUSIONS: HMVEC-Ls can replace HUVECs as a cell source for scaffold-free trachea-like structures. However, some limitations were associated with iPSC-derived endothelial cells.

Multiple time-scale beats in aurora: precise orchestration via magnetospheric chorus waves.

The brightness of aurorae in Earth's polar region often beats with periods ranging from sub-second to a few tens of a second. Past observations showed that the beat of the aurora is composed of a superposition of two independent periodicities that co-exist hierarchically. However, the origin of such multiple time-scale beats in aurora remains poorly understood due to a lack of measurements with sufficiently high temporal resolution. By coordinating experiments using ultrafast auroral imagers deployed in the Arctic with the newly-launched magnetospheric satellite Arase, we succeeded in identifying an excellent agreement between the beats in aurorae and intensity modulations of natural electromagnetic waves in space called "chorus". In particular, sub-second scintillations of aurorae are precisely controlled by fine-scale chirping rhythms in chorus. The observation of this striking correlation demonstrates that resonant interaction between energetic electrons and chorus waves in magnetospheres orchestrates the complex behavior of aurora on Earth and other magnetized planets.

Gas Separation Silica Membranes Prepared by Chemical Vapor Deposition of Methyl-Substituted Silanes.

The effect on the gas permeance properties and structural morphology of the presence of methyl functional groups in a silica membrane was studied. Membranes were synthesized via chemical vapor deposition (CVD) at 650 °C and atmospheric pressure using three silicon compounds with differing numbers of methyl- and methoxy-functional groups: tetramethyl orthosilicate (TMOS), methyltrimethoxysilane (MTMOS), and dimethyldimethoxysilane (DMDMOS). The residence time of the silica precursors in the CVD process was adjusted for each precursor and optimized in terms of gas permeance and ideal gas selectivity criteria. Final H2 permeances at 600 °C for the TMOS-, MTMOS-, and DMDMOS-derived membranes were respectively 1.7 × 10-7, 2.4 × 10-7, and 4.4 × 10-8 mol∙m-2∙s-1∙Pa-1 and H2/N2 selectivities were 990, 740, and 410. The presence of methyl groups in the membranes fabricated with the MTMOS and DMDMOS precursors was confirmed via Fourier-transform infrared (FTIR) spectroscopy. From FTIR analysis, an increasing methyl signal in the silica structure was correlated with both an improvement in the hydrothermal stability and an increase in the apparent activation energy for hydrogen permeation. In addition, the permeation mechanism for several gas species (He, H2, Ne, CO2, N2, and CH4) was determined by fitting the gas permeance temperature dependence to one of three models: solid state, gas-translational, or surface diffusion.

Mechanochemical Decomposition of Crystalline Cellulose in the Presence of Protonated Layered Niobium Molybdate Solid Acid Catalyst.

Direct depolymerization of crystalline cellulose into water-soluble sugars by solvent-free ball milling was examined in the presence of a strongly acidic layered metal oxide, HNbMoO6 , resulting in full conversion with 72 % yield of water-soluble sugars. Measurements by 13 C cross-polarization magic angle spinning NMR spectroscopy and X-ray diffraction revealed that amorphization of cellulose occurred rapidly within 10 min. Scanning electron microscopy equipped with an energy dispersive X-ray indicated that the substrate and the catalyst were well mixed during milling. The time course of the product distribution showed that most of the resultant water-soluble sugars were produced not by successive degradation of oligosaccharides but by direct depolymerization of cellulose chains. The products included glucose, mannose, and cello-oligomers, as well as anhydrosugars. Addition of small amounts of polar solvents increased the sugar yield, whereas further addition of water decreased the selectivity to anhydrosugars. Calculations of the mechanical energy required for the ball-milling process showed that 0.02 % was utilized for the chemical transformation under the conditions examined in this study.

Efficient Epimerization of Aldoses Using Layered Niobium Molybdates.

Both non-acidic LiNbMoO6 and strongly acidic HNbMoO6 efficiently catalyze the epimerization of sugars including glucose, mannose, xylose, and arabinose in water. The reactions over these oxides reached almost equilibrium within a few hours where yields of corresponding epimers from glucose, xylose, and arabinose were 24-29%. The layered mixed oxides functioned as heterogeneous catalysts and could be reused without loss of activity, whereas bulk molybdenum oxide MoO3 was completely dissolved during the reaction. A (13)C substitution experiment showed that the reaction proceeds through a 1,2-rearrangement mechanism. The surface Mo octahedra were responsible for the activity. The layered HNbMoO6 could also afford mannose from cellobiose through hydrolysis and successive epimerization.

Intercalation-controlled cyclodehydration of sorbitol in water over layered-niobium-molybdate solid acid.

Layered niobium molybdate (HNbMoO6 ) was used in the aqueous-phase dehydration of sorbitol and was found to exhibit remarkable selectivity toward its monomolecular-dehydrated intermediate 1,4-sorbitan. This was attributed to the selective intercalation of sorbitol within the interlayers with strong Brønsted acid sites.

The influence of recycling non-condensable gases in the fractional catalytic pyrolysis of biomass.

In this study, the effect of recycling the non-condensable gases (NCG) in the catalytic pyrolysis of hybrid poplar using FCC catalyst was investigated. A 50mm bench scale fluidized bed reactor at 475°C with a weight hourly space velocity (WHSV) of 2h(-1) and a gas recycling capability was used for the studies. Model fluidizing gas mixtures of CO/N(2), CO(2)/N(2), CO/CO(2)/N(2) and H(2)/N(2) were used to determine their independent effects. Recycling of the NCG in the process was found to potentially increase the liquid yield and decrease char/coke yield. The model fluidizing gases increased the liquid yield and the CO(2)/N(2) fluidizing gas had the lowest char/coke yield. The (13)C-NMR analysis showed that recycling of NCG increases the aromatic fractions and decreases the methoxy, carboxylic and sugar fractions. Recycling of NCG increased the higher heating value and the pH of the bio-oil as well as decreased the viscosity and density.

Operando QEXAFS studies of Ni2P during thiophene hydrodesulfurization: direct observation of Ni-S bond formation under reaction conditions.

Structural changes in Ni(2)P/MCM-41 were followed by quick extended X-ray absorption fine structure (QEXAFS) and were directly related to changes in X-ray absorption near-edge structure (XANES) which had been used earlier for the study of the active catalyst phase. An equation is proposed to correct the transient QEXAFS spectra up to second-order in time to remove spectral distortions induced by structural changes occurring during measurements. A good correlation between the corrected QEXAFS and the XANES spectral changes was found, giving support to the conclusions derived from the XANES in the previous work, namely that the formation of a Ni-S bond in a surface NiPS phase is involved in the active site for the hydrodesulfurization reaction.

Scanning tunneling microscopy and photoemission electron microscopy studies on single crystal Ni2P surfaces.

The surface structures of nickel phosphide (Ni2P) single crystals were studied by scanning tunneling microscopy (STM) and photoemission electron microscopy (PEEM). Atomically resolved 1 x 1 images of the Ni2P(0001) and (1010) surfaces are successfully obtained with STM, whose respective dimensions of (0.59 nm x 0.59 nm) and (0.34 nm x 0.59 nm) match the unit cell lengths. The Ni2P(0001) surface has two possible terminations in which the Ni:P ratios are 3:1 (Ni3P termination) or 3:2 (Ni3P2 termination). In the Ni3P terminated surface the Ni atoms have a square pyramidal structure, and in the Ni3P2 terminated surface the Ni atoms have a tetrahedral structure. Only the P is visible in the STM for Ni2P(0001) and this is explained as being due to the greater extension of the phosphorus p orbitals than the Ni d orbitals at the surface. The surface domain sizes of the Ni3P and Ni3P2 termination structures of Ni2P(0001) are determined to be 500 microm by means of PEEM using a Hg-Xe lamp through a low-pass UV-filter. Evidence is found for dissociative adsorbed hydrogen on the Ni3P termination surface of Ni2P(0001), but not on the Ni3P2 surface, indicating that the square pyramidal sites on the Ni3P surface have high reactivity.

Can immune-enhancing nutrients reduce postoperative complications in patients undergoing esophageal surgery?

Postoperative infection of esophageal neoplasm surgery is the major cause of prolonged postoperative hospitalization, as well as morbidity. The clinical benefits of administering immune-enhancing nutrients (IEN) to critically ill patients and those undergoing elective surgery were clarified. However, the benefits of preoperative administration of IEN for patients with esophageal cancer remain unclear. The present study was designed to clarify the clinical efficacy of administration of IEN prior to esophageal surgery. A total of 123 patients undergoing esophagectomy in single institute were retrospectively investigated. All patients received postoperative enteral nutrition by use of ordinal nutrients. Preoperative IEN were also given to 84 patients (IEN group), while the other 39 received an ordinary diet (control). Postoperative courses and laboratory data were compared between the two groups. The incidences of infectious complications in the IEN and control groups were 18% and 38%, respectively (P < 0.05). Pneumonia developed in 5 (6%) IEN and 7 (18%) control patients (P < 0.05). Postoperative hospitalization was shorter in the IEN group (P < 0.01). Prealbumin levels, retinal binding protein levels and the lymphocyte count were significantly higher in the IEN group on postoperative day 3. These results suggest that preoperative administration of IEN in patients undergoing esophagectomy reduces infectious complications, mainly pneumonia, and shortens postoperative hospitalization.

Propane reacts with O2 and H2 on gold supported TS-1 to form oxygenates with high selectivity.

Gold nanoparticles supported on a microporous titanosilicate (TS-1) were found to be highly selective (95%) towards the formation of acetone and isopropanol from propane, O(2), and H(2) at moderate temperatures (443 K).

Celiac lymph nodes: distant or regional for thoracic esophageal carcinoma?

Involvement of celiac nodes is defined as distant metastasis in the TNM classification for thoracic esophageal carcinoma. Some textbooks, however, describe dissection of these nodes as a standard technique. The present study was, therefore, undertaken to clarify which celiac nodes are regional for thoracic esophageal carcinoma and whether or not celiac node dissection would provide a survival benefit. Eight hundred and five patients who underwent R0 resection (no residual tumor) with systematic lymphadenectomy including the celiac axis area for thoracic esophageal carcinoma were retrospectively investigated. The frequency of metastasis and the therapeutic value of dissecting celiac nodes were compared to those associated with the left gastric artery area. The frequencies of left gastric and celiac nodal involvement were 15.4% and 9.6%, respectively, for thoracic esophageal carcinoma. As for tumor location, the incidences of metastasis around left gastric artery and celiac axis from the upper, middle and lower portion were 6.7% and 1.0%; 12.3% and 7.7%; and 25.7% and 17.4%, respectively. The 5-year survivals of patients with celiac but not left gastric metastasis were 36.3% and 41.8% for the middle and lower portions, respectively, while the corresponding values with left gastric involvement but no celiac metastasis were 24.1% and 27.9%. These differences were not significant. The frequency of celiac node involvement was not low. And, their dissection has equivalent therapeutic value to that of left gastric nodes. Revision of the TNM classification to account for celiac node involvement in thoracic esophageal carcinoma, especially of the middle and lower portions, is needed.

Design of a high-temperature and high-pressure liquid flow cell for x-ray absorption fine structure measurements under catalytic reaction conditions.

The design and performance of a new high-pressure and high-temperature cell for measurement of x-ray absorption fine structure (XAFS) spectra of solid catalysts working in a flowing liquid are presented. The cell has flat, high-purity sintered cubic boron nitride (c-BN) windows which can tolerate high temperature (900 K) and high pressure (10 MPa). The c-BN is a new material which has the highest tensile strength, second only to diamond, and is also chemically and thermally stable. The use of the cell is demonstrated for measurements of PtPdAl(2)O(3) and Ni(2)PSiO(2) hydrodesulfurization catalysts at reaction conditions. A technique called delta chi (Deltachi), involving determining the difference between XAFS spectra of the sample at reaction conditions and the bare sample, is introduced.