The oxidative coupling of methane (OCM) over a K2WO4/SiO2 catalyst was investigated using a CH4–O2 flow system. The addition of H2O to the reactant stream caused an increase in the CH4 conversion ...rate and C2 selectivity, consistent with the kinetics associated with the equilibrated OH radical generation, followed by H-abstraction from CH4 with OH radicals. The C2+ (a sum of C2 and higher hydrocarbons) yield reaches a maximum of 24.7% (C2H4 yield 17.0%) at a CH4 conversion of 47.1%, comparable to those over the previously reported Na2WO4/SiO2 catalyst. In situ near ambient pressure X-ray photoelectron spectroscopy uncovered K2O2 and KO2 species at and above 560 °C in the presence of gas-phase O2. These K2O2/KO2 species are considered to catalyze H2O activation for OH radical generation. By in situ high-temperature X-ray diffraction, K2WO4 maintained a crystalline phase in the bulk during the OCM reaction at 850 °C in contrast to the molten state of Na2WO4 previously reported. This indicates that the melting of the supported component and the covering of support are not essential to achieve a high C2 yield in supported alkali metal tungstate catalysts as long as inert support materials are used toward OCM.
We report a new molecular‐design principle for creating double‐gyroid nanostructured molecular assemblies based on atropisomerization. Ionic amphiphiles containing two imidazolium rings close to each ...other were designed and synthesized. NMR data revealed that the rotation of the imidazolium rings is restricted, with an activation energy as high as 63 kJ mol−1 in DMSO‐d6 solution (DFT prediction for a model compound in the vacuum: 90–100 kJ mol−1). Due to the restricted rotation, the amphiphiles feature “double” atropisomeric axes in their ionic segments and form three stable atropisomers: meso, R, and S. These isomers co‐organize into Ia3‾d
‐type bicontinuous cubic liquid‐crystalline mesophases through nanosegregation of the ionic and non‐ionic parts. Considering the intrinsic characteristic of Ia3‾d
‐type bicontinuous cubic structures that they are composed of intertwined right‐ and left‐handed single gyroids, we propose that the simultaneous presence of both R‐ and S‐atropisomers is an important contributor to the formation of double‐gyroid structures.
With both hands: A new molecular‐design principle for creating double‐gyroid nanostructured molecular assemblies based on atropisomerization is reported. Ionic amphiphiles with rotationally restricted imidazolium rings are used. Three stable atropisomers co‐organize into bicontinuous cubic liquid‐crystalline mesophases through nanosegregation of the ionic and non‐ionic parts.
The effect of aqueous environment on fast heavy-ion radiation damage of biomolecules was studied by comparative experiments using liquid- and gas-phase amino acid targets. Three types of amino acids ...with different chemical structures were used: glycine, proline, and hydroxyproline. Ion-induced reaction products were analyzed by time-of-flight secondary-ion mass spectrometry. The results showed that fragments from the amino acids resulting from the C-C
bond cleavage were the major products for both types of targets. For liquid-phase targets, specific products originating from chemical reactions in solutions were observed. Interestingly, multiple dissociated atomic fragments were negligible for the liquid-phase targets. We found that the ratio of multifragment to total fragment ion yields was approximately half of that for gas-phase targets. This finding agreed with the results of other studies on biomolecular cluster targets. It is concluded that the suppression of molecular multifragmentation is caused by the energy dispersion to numerous water molecules surrounding the biomolecular solutes.
Patients with Alzheimer's disease dementia (ADD) are thought to exhibit taste disorders; however, this has not been extensively studied. We investigated gustatory functions and factors affecting ...taste in patients with ADD or mild cognitive impairment (MCI) and in non-demented controls (NDCs) and evaluated associations between cognitive impairment and gustatory functions.
We recruited 29 patients with ADD, 43 with MCI, and 14 with NDCs. We obtained medical and medication history, measured salivary secretion volumes, and performed cognitive function tests, blood tests, whole-mouth gustatory tests, and dietary and gustatory questionnaires.
Patients with ADD showed significantly higher recognition threshold values than NDCs (p < 0.05). Many individuals did not recognize umami at the maximum concentration, and this happened more frequently in patients with ADD or MCI than in NDCs. Evaluation items other than cognitive function tests did not show significant differences among the groups, but many individuals had decreased salivation, low serum zinc levels, and were on multiple medications. We found a significant correlation between recognition threshold and age (r = 0.229, p < 0.05) and cognitive function test score (r = 0.268, p < 0.05).
Patients with ADD showed impairment of gustatory function. Gustatory impairment in patients with MCI could not be confirmed. However, many individuals with MCI did not recognize umami, either. Our results suggest that taste disorders in elderly people with cognitive decline occur independently of factors affecting taste such as salivation, zinc levels, or prescription drugs.
The study was registered in the UMIN Clinical Trials Registry on February 10, 2017, with reference number UMIN000026087.
Genetic and epidemiological evidence has suggested that genetic factors are important in schizophrenia, although its pathophysiology is poorly understood. This study used whole-exome sequencing to ...investigate potential novel schizophrenia-causing genes in a Japanese family containing several members affected by severe or treatment-resistant schizophrenia. A missense variant, chr12:132064747C>T (rs200626129, P2805L), in the E1A-binding protein P400 (EP400) gene completely segregated with schizophrenia in this family. Furthermore, numerous other EP400 mutations were identified in the targeted sequencing of a schizophrenia patient cohort. We also created two lines of Ep400 gene-edited mice, which had anxiety-like behaviours and reduced axon diameters. Our findings suggest that rs200626129 in EP400 is likely to cause schizophrenia in this Japanese family, and may lead to a better understanding and treatment of schizophrenia.
The optimal treatment strategy of multiple station N2 stage ⅢA non-small-cell lung cancer remains controversial. A 66-yearold man was diagnosed with lung adenocarcinoma, pathological multiple station ...N2 stage ⅢA. After three lines of chemotherapy were administered, partial response was obtained. Since 18F-fluorodeoxyglucose (18F-FDG) positron emission tomographycomputed tomography (PET-CT) showed reduced uptake in every lesion, salvage surgery was performed. In the resected lung, adenocarcinoma was detected, but no lymph node metastasis was seen. The down-staging by PET-CT well reflected the pathological findings and effectively worked in this case. More than eleven years after surgery, no recurrence has been confirmed. A combination of chemotherapy, PET-CT, and salvage surgery is one of the strategies that could bring patients with multiple station N2 stage ⅢA non-small cell lung cancer a long-term survival.
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