o-Azophenylboronic Acid-Based Colorimetric Sensors for d-Fructose: o-Azophenylboronic Acids with Inserted Protic Solvent Are the Key Species for a Large Color Change.

Many boronic acid-based chemosensors for saccharides have been developed; however, their detection mechanisms have seldom been studied. In this study, we synthesized 10 o-azophenylboronic acid derivatives (azoBs) and conducted a fundamental study on the reactivity and the sensing mechanism of azoBs, which undergoes a large color change, e.g., from red to yellow, upon a reaction with saccharides. Their pH-independent formation constants were determined by spectrophotometric titration and then converted to the conditional formation constant K' at pH 7.4. A linear free energy relationship was established between log K' and the pKa of azoB. 11B NMR measurements indicate that in aprotic solvents, azoB forms a trigonal planar structure, while in protic solvents, it forms a quasi-tetrahedral structure (azoB-ROH) with a protic solvent molecule (ROH) inserted between the boronic acid moiety and the azo group. In addition, UV-vis spectroscopic studies showed that the color change during the reaction between azoB and d-fructose in ROH was caused by the release of the ROH from azoB-ROH by d-fructose. Based on the findings in this study, we proposed a guideline for designing an azoB-based chemosensor that exhibits high reactivity toward saccharides and a sufficient color change to allow for the visual detection of saccharides.

On the Maximum Obtainable Purity and Resultant Maximum Useful Membrane Selectivity of a Membrane Separator.

Design considerations concerning the maximum purity of a membrane separator, and the resultant maximum effective selectivity of the membranes were explored by modeling a binary gas membrane separator (pressure-driven permeance) using a dimensionless form. Although the maximum purity has an analytical solution at the limit of zero recovery or stage cut, this solution over-predicts the obtained purity as the recovery is increased. Furthermore, at combinations of high recovery, low feed mole fraction, and low pressure ratio, the maximum purity becomes independent of selectivity above some critical selectivity. As a consequence of this purity limitation, a maximum selectivity is defined at which further increases in selectivity will result in less than a 1% change in the final purity. An equation is obtained that specifies the region in which a limiting purity is less than unity (indicating the existence of a limiting selectivity); operating at less than the limiting pressure ratio results in a purity limitation less than unity. This regime becomes larger and more significant as the inlet mole fraction decreases (e.g., inlet feed mole fraction of 10% and pressure ratio of 100 results in a maximum useful membrane selectivity of only 130 at 95% recovery). These results suggest that membrane research should focus on increasing permeance rather than selectivity for low-concentration separations. The results found herein can be used to set benchmarks for membrane development in various gas separation applications.

Cadmium exposure increases susceptibility to testicular autoimmunity in mice.

Cadmium, one of various environmental toxicants, is known to suppress systemic immunity and to injure the testicular capillary endothelia with resultant necrosis of testicular tissues in mice and rats treated with high doses. Recently, it also became evident that cadmium can affect the integrity of the blood-testis barrier (BTB), the endocrine function of Leydig cells, apoptosis of germ cells and systemic immunity, even on treatment with a low dose that does not induce spermatogenic disturbance. Experimental autoimmune orchitis (EAO), i.e., an organ-specific autoimmunity of the testis, can be induced by repeated immunization with testicular antigens, and its pathology is characterized by lymphocytic inflammation and spermatogenic disturbance. In the present study, we investigated the morphological and functional changes of testes in mice treated with a low dose of cadmium chloride (CdCl2 ) and also examined its toxicity as to susceptibility to EAO. The results showed that exposure to 3 mg CdCl2 kg(-1) body weight did not affect the spermatogenic state. However, the BTB at the tubuli recti and the rete testis, but not the seminiferous tubules, was slightly weakened, and intra-testicular mRNA expression of interleukin (IL)-6, tumor necrosis factor-α and IL-1ß was significantly increased by the CdCl2 treatment. Furthermore, immunization with testicular antigens after the CdCl2 exposure significantly augmented the EAO severity. Therefore, exposure to a low dose of CdCl2 induces no significant disturbance of spermatogenesis, however, it does change the immunological microcircumstances in the testis, resulting in increased susceptibility to testicular autoimmunity.

Carbonylation of propargyl carbamates with palladium(II) bisoxazoline catalysts: efficient synthesis of 5-methoxy-3(2H)-furanones.

Palladium and CO: Carbonylation of 1 with [Pd(tfa)2(±)-L1] (tfa = trifluoroacetate) affords the spirofuranone 2 with inversion of the stereochemistry at C17 in 96 % yield. C17-epi-1 also gave the same product 2 with retention of the stereochemistry at C17. Labelling studies show that (13)CO was incorporated into the C5' position of the furanone ring. The first asymmetric version of this new reaction was achieved.

Estimation of CO2 Separation Performances through CHA-Type Zeolite Membranes Using Molecular Simulation.

Chabazite (CHA)-type zeolite membranes are a potential material for CO2 separations because of their small pore aperture, large pore volume, and low aluminum content. In this study, the permeation and separation properties were evaluated using a molecular simulation technique with a focus on improving the CO2 separation performance. The adsorption isotherms of CO2 and CH4 on CHA-type zeolite with Si/Al = 18.2 were predicted by grand canonical Monte Carlo, and the diffusivities in zeolite micropores were simulated by molecular dynamics. The CO2 separation performance of the CHA-type zeolite membrane was estimated by a Maxwell-Stefan equation, accounting for mass transfer through the support tube. The results indicated that the permeances of CO2 and CH4 were influenced mainly by the porosity of the support, with the CO2 permeance reduced due to preferential adsorption with increasing pressure drop. In contrast, it was important for estimation of the CH4 permeance to predict the amounts of adsorbed CH4. Using molecular simulation and the Maxwell-Stefan equation is shown to be a useful technique for estimating the permeation properties of zeolite membranes, although some problems such as predicting accurate adsorption terms remain.

Evaluation of FAU-type Zeolite Membrane Stability in Transesterification Reaction Conditions.

The transesterification conversion of methyl ether can be enhanced by the removal of the byproduct methanol using methanol permselective faujasite (FAU-type) zeolite membranes. However, the authors previously observed that the methanol flux during the transesterification reaction was lower than the predicted flux. Therefore, this study investigated the stability of FAU-type zeolite membranes in the presence of organic components associated with the transesterification reaction of methyl hexanoate and 1-hexanol. The stability was defined in terms of changes in methanol permeance and zeolite structure. The effect of reaction components (methanol, 1-hexanol, methyl hexanoate, and hexyl hexanoate) on the FAU-type zeolite structure and the methanol permeation performance of the FAU-type zeolite membranes were evaluated to find the component causing the lower methanol flux. From these results, two esters were found to adsorb strongly on the FAU-type zeolite. The methanol flux of the FAU-type zeolite membrane was examined after vapor exposure of each of the four reaction chemicals at 373 K for 8 h. In the case of methyl hexanoate and hexyl hexanoate vapor exposure, the methanol flux was reduced by about 75% compared to the initial flux of 15 kg m-2 h-1. These results indicated methanol permeation performance was inhibited by the adsorption of esters.

A multi-lab test of the facial feedback hypothesis by the Many Smiles Collaboration.

Following theories of emotional embodiment, the facial feedback hypothesis suggests that individuals' subjective experiences of emotion are influenced by their facial expressions. However, evidence for this hypothesis has been mixed. We thus formed a global adversarial collaboration and carried out a preregistered, multicentre study designed to specify and test the conditions that should most reliably produce facial feedback effects. Data from n = 3,878 participants spanning 19 countries indicated that a facial mimicry and voluntary facial action task could both amplify and initiate feelings of happiness. However, evidence of facial feedback effects was less conclusive when facial feedback was manipulated unobtrusively via a pen-in-mouth task.

Development of Methanol Permselective FAU-Type Zeolite Membranes and Their Permeation and Separation Performances.

The separation of non-aqueous mixtures is important for chemical production, and zeolite membranes have great potential for energy-efficient separation. In this study, the influence of the framework structure and composition of zeolites on the permeation and separation performance of methanol through zeolite membranes were investigated to develop a methanol permselective zeolite membrane. As a result, the FAU-type zeolite membrane prepared using a solution with a composition of 10 SiO2:1 Al2O3:17 Na2O:1000 H2O showed the highest permeation flux of 86,600 µmol m-2 s-1 and a separation factor of 6020 for a 10 wt% methanol/methyl hexanoate mixture at 353 K. The membrane showed a molecular sieving effect, reducing the single permeation flux of alcohol with molecular size for single-component alcohols. Moreover, the permeation flux of methanol and the separation factor increased with an increase in the carbon number of the alcohols and methyl esters containing 10 wt% methanol. In this study, the permeation behavior of FAU-type zeolite membranes was also discussed based on permeation data. These results suggest that the FAU-type zeolite membrane has the potential to separate organic solvent mixtures, such as solvent recycling and membrane reactors.

Pervaporative Dehydration of Organic Solvents Using High-Silica CHA-Type Zeolite Membrane.

A high-silica chabazite (CHA) type zeolite membrane was prepared on the porous α-Al2O3 support tube by the secondary growth of seed particles. The dehydration performances of the membrane were determined using methanol, ethanol, 2-propanol, acetone, acetic acid, methyl ethyl ketone (MEK), tetrahydrofuran (THF), N,N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO), and N-methyl-2-pyrolidone (NMP) at 303-373 K. As a result, the dehydration performances of the membrane were categorized to following three types: (1) 2-propanol, acetone, THF, and MEK; (2) ethanol and acetic acid; and (3) methanol, DMF, and DMSO, and NMP. The adsorption isotherms of water, methanol, ethanol, and 2-propanol were determined to discuss the influences of the organic solvents on the permeation and separation performances of the membrane. For 2-propanol, acetone, MEK, and THF solutions, the high permeation fluxes and separation factors were obtained because of the preferential adsorption of water due to molecular sieving. In contrast, the permeation fluxes and separation factors were relatively low for methanol, DMF, and DMSO, and NMP solutions. The lower dehydration performance for the methanol solution was due to the adsorption of methanol. The permeation fluxes for ethanol and acetic acid solution were ca. 1 kg m-2 h-1. The significantly low flux was attributed to the similar molecular diameter to the micropore size of CHA-type zeolite.

Gas Permeation Properties of High-Silica CHA-Type Zeolite Membrane.

The polycrystalline CHA-type zeolite layer with Si/Al = 18 was formed on the porous α-Al2O3 tube in this study, and the gas permeation properties were determined using single-component H2, CO2, N2, CH4, n-C4H10, and SF6 at 303-473 K. The membrane showed permeation behavior, wherein the permeance reduced with the molecular size, attributed to the effect of molecular sieving. The separation performances were also determined using the equimolar mixtures of N2-SF6, CO2-N2, and CO2-CH4. As a result, the N2/SF6 and CO2/CH4 selectivities were as high as 710 and 240, respectively. However, the CO2/N2 selectivity was only 25. These results propose that the high-silica CHA-type zeolite membrane is suitable for the separation of CO2 from CH4 by the effect of molecular sieving.

Influence of Organic Solvent Species on Dehydration Behaviors of NaA-Type Zeolite Membrane.

In this study, an NaA-type zeolite membrane was prepared, and the dehydration performances of the membrane were determined by the pervaporation for several organic solvents to understand the lower dehydration performances of zeolite membranes for NMP solutions than those for alcohols. For a 90 wt% ethanol solution at 348 K, the permeation flux and separation factor of the membrane were 3.82 kg m-2 h-1 and 73,800, respectively. The high dehydration performances were also obtained for alcohols and low boiling solvents (acetonitrile, acetone, methyl ethyl ketone (MEK) and tetrahydrofuran (THF)). However, the permeation flux and separation factors decreased significantly for high boiling solvents, such as N,N-dimethylacetamide (DMA), N,N-dimethyl formamide (DMF), dimethyl sulfoxide (DMSO) and N-methyl-2-pyrrolidone (NMP). The influences of the water content and temperature on the dehydration performances for the NMP solutions were determined to understand the lower dehydration performances for those solvents. Those results suggest that the lower dehydration performances for the high boiling solvents were attributed to the lower vapor pressures of water and the higher permeances of those solvents. Furthermore, this study proposes that the permeation behaviors through zeolite membranes could be understood by the determination of the effect of temperature on the permeance of individual components.

Permeation Properties of Ions through Inorganic Silica-Based Membranes.

The development of inorganic membranes has mainly found applicability in liquid separation technologies. However, only a few reports cite the permeation and separation of liquids through inorganic nanofiltration membranes compared with the more popular microfiltration membranes. Herein, we prepared silica membranes using 3,3,3-trifluoropropyltrimethoxysilane (TFPrTMOS) to investigate its liquid permeance performance using four different ion solutions (i.e., NaCl, Na2SO4, MgCl2, and MgSO4). The TFPrTMOS-derived membranes were deposited above a temperature of 175 °C, where the deposition behavior of TFPrTMOS was dependent on the organic functional groups decomposition temperature. The highest membrane rejection was from NaCl at 91.0% when deposited at 200 °C. For anions, the SO42- rejections were the greatest. It was also possible to separate monovalent and divalent anions, as the negatively charged groups on the membrane surfaces retained pore sizes >1.48 nm. Ions were also easily separated by molecular sieving below a pore size of 0.50 nm. For the TFPrTMOS-derived membrane deposited at 175 °C, glucose showed 67% rejection, which was higher than that achieved through the propyltrimethoxysilane membrane. We infer that charge exclusion might be due to the dissociation of hydroxyl groups resulting from decomposition of organic groups. Pore size and organic functional group decomposition were found to be important for ion permeation.

Warning 'Don't spread' versus 'Don't be a spreader' to prevent the COVID-19 pandemic.

The coronavirus disease 2019 (COVID-19) outbreak is threatening not only health but also life worldwide. It is important to encourage citizens to voluntarily practise infection-prevention (IP) behaviours such as social distancing and self-restraint. Previous research on social cognition suggested that emphasizing self-identity is key to changing a person's behaviour. The present study investigated whether reminders that highlight self-identity would be effective in changing intention and behaviour related to the COVID-19 outbreak, and hypothesized that those who read reminders highlighting self-identity (Don't be a spreader) would change IP intention and behaviour better than those who read 'Don't spread' or no reminder. We conducted a two-wave survey of the same participants with a one-week interval, during which we assigned one of three reminder conditions to the participants: 'Don't spread' (spreading condition), 'Don't be a spreader' (spreader condition) and no reminder (control condition). Participants marked their responses to IP intentions and actual behaviours each week based on the Japanese Ministry of Health, Labour and Welfare guidelines. While the results did not show significant differences between the conditions, the post hoc analyses showed significant equivalence in either IP intentions or behavioural scores. We discussed the results from the perspective of the effect size, ceiling effects and ways of manipulation checks as future methods with more effective persuasive messaging. Following in-principle acceptance, the approved Stage 1 version of this manuscript was pre-registered on the OSF at https://doi.org/10.17605/OSF.IO/KZ5Y4. This pre-registration was performed prior to data collection and analysis.

Your Face and Moves Seem Happier When I Smile.

In this experiment, we replicated the effect of muscle engagement on perception such that the recognition of another's facial expressions was biased by the observer's facial muscular activity (Blaesi & Wilson, 2010). We extended this replication to show that such a modulatory effect is also observed for the recognition of dynamic bodily expressions. Via a multilab and within-subjects approach, we investigated the emotion recognition of point-light biological walkers, along with that of morphed face stimuli, while subjects were or were not holding a pen in their teeth. Under the "pen-in-the-teeth" condition, participants tended to lower their threshold of perception of happy expressions in facial stimuli compared to the "no-pen" condition, thus replicating the experiment by Blaesi and Wilson (2010). A similar effect was found for the biological motion stimuli such that participants lowered their threshold to perceive happy walkers in the pen-in-the-teeth condition compared to the no-pen condition. This pattern of results was also found in a second experiment in which the no-pen condition was replaced by a situation in which participants held a pen in their lips ("pen-in-lips" condition). These results suggested that facial muscular activity alters the recognition of not only facial expressions but also bodily expressions.

Presence of thrombin-activatable fibrinolysis inhibitor in Helicobacter pylori-associated gastroduodenal disease.

Thrombin-activatable fibrinolysis inhibitor (TAFI) plays a role in the regulation of coagulation and inflammation. In addition to inhibiting the fibrinolytic system, TAFI may also regulate the bradykinin and complement systems. We hypothesized that TAFI also plays a role in defense mechanisms of the gastric mucosa during Helicobacter pylori infection. This study comprised 65 patients with gastroduodenal disorders: 41 patients with H. pylori infection, 13 without, and 11 patients with cured H. pylori infection. The gastric intramucosal concentrations of TAFI were measured by enzyme immunoassay. The gastric levels of TAFI and plasminogen activator inhibitor-1 were significantly increased in patients with H. pylori compared to those without infection or cured H. pylori. The presence of TAFI was detected in gastric mucosal epithelial cells. The concentration of TAFI was correlated with the degree of gastric mucosal atrophy, inflammation, and disease activity. These results show that TAFI is present in the gastric mucosa and that it may play a role in the pathogenesis of H. pylori infection-associated gastroduodenal disorders.

Silica-Based RO Membranes for Separation of Acidic Solution.

The development of acid separation membranes is important. Silica-based reverse osmosis (RO) membranes for sulfuric acid (H2SO4) solution separation were developed by using a counter diffusion chemical vapor deposition (CVD) method. Diphenyldimethoxysilane (DPhDMOS) was used as a silica precursor. The deposited membrane showed the H2SO4 rejection of 81% with a total flux of 5.8 kg m-2 h-1 from the 10-3 mol L-1 of H2SO4. The γ-alumina substrate was damaged by the permeation of the H2SO4 solution. In order to improve acid stability, the silica substrates were developed. The acid stability was checked by the gas permeation tests after immersing in 1 mol L-1 of the H2SO4 solution for 24 h. The N2 permeance decreased by 11% with the acid treatment through the silica substrate, while the permeance decreased to 94% through the γ-alumina substrate. The flux and the rejection through the DPhDMOS-derived membrane on the silica substrate were stable in the 70 wt % H2SO4 solution.

The effect of occlusal contacts on adjacent tooth.

PURPOSE: The purpose of this study was to clarify the influence of changes of occlusal contacts on adjacent tooth displacement during articulation. MATERIALS AND METHODS: The amount and direction of displacement of the maxillary left first molar and adjacent teeth were measured using a displacement transducer, Type M-3. Seven subjects were included in this study. On the maxillary left first molar, 8 experimental occlusal contact points were established using platinum foil and these were divided into 2 groups, the buccal and lingual groups, which corresponded to the buccal and lingual cusps, respectively. RESULTS: During clenching, the buccal group showed differences in the direction of the tooth displacement paths among the 3 teeth (second premolar, first and second molar), but there was no difference in the lingual group and the direction of displacement of these 3 teeth was similar to the natural teeth. CONCLUSION: It is necessary to make at least one lingual occlusal contact point to obtain displacement of not only the abutment tooth but also the adjacent teeth.

Reactivity of a nitrosyl ligand on dinuclear ruthenium hydrotris(pyrazolyl)borato complexes toward a NO molecule.

A cationic mononitrosyl dinuclear ruthenium complex was prepared by removing one NO ligand of a dicationic dinitrosyl ruthenium complex using NaN3. Reduction and oxidation reactions of the mononitrosyl complex led to the isolation of a neutral nitrosyl-bridged complex and a dicationic mononitrosyl complex, respectively, as expected from the cyclic voltammogram. According to the electron count, their reactions with a second NO molecule resulted in an N-N coupling complex from the nitrosyl-bridged complex and the dicationic dinitrosyl complex from the dicationic mononitrosyl complex.

Involvement of Fas/Fas-L and Bax/Bcl-2 systems in germ cell death following immunization with syngeneic testicular germ cells in mice.

Experimental autoimmune orchitis (EAO) is characterized by T cell-dependent lymphocytic inflammation and seminiferous tubule damage, which can result in the death of germ cells. The aim of the present study is to investigate the roles of the Fas/Fas-L and Bax/Bcl-2 systems in the death of germ cells in mice with EAO that is induced by immunization with syngeneic testicular germ cells (TGC). The results using real-time reverse transcription-polymerase chain reaction and immunostaining show that many terminal deoxynucleotidyl transferase-mediated dUTP nick-end labeling staining germ cells were present in seminiferous tubules during the active inflammation stage, and these cells were persistently observed in the seminiferous epithelium until the postactive inflammation stage. Intratesticular mRNA expression levels of both Fas and Bax were increased during the active inflammation stage and were dramatically decreased during the post-active inflammation stage. In contrast, the intratesticular mRNA expression levels of both Fas-L and Bcl-2 did not show significant changes during the active inflammation stage but showed extreme increases during the post-active inflammation stage. Immunohistochemically, some Fas- and Bax-positive germ cells were detected during the active inflammation stage, but these were hardly found during the post-active inflammation stage. In contrast, some Fas-L- and Bcl-2-positive germ cells were found during the active inflammation stage, and many of these were also observed during the post-active inflammation stage. These results indicate that germ cell death during TGC-induced EAO is mediated by the Fas/Fas-L and Bax/Bcl-2 systems during the active inflammation stage but not during the post-active inflammation stage.