Synthesis of lithium oxy-thiophosphate solid electrolytes with Li10GeP2S12 structure by a liquid phase process using 2-propanol.

Lithium oxy-thiophosphates isostructural with Li10GeP2S12 (LGPS) were synthesized by a liquid-phase process using 2-propanol as the solvent and Li2S and P2S5 as the starting materials. The XRD and 31P NMR results indicate that the synthesized compound has a slightly shrieked LGPS-type crystal structure where sulfur in PS43- is partially replaced by oxygen. The sample synthesized from the nominal composition of Li2S : P2S5 = 2.5 : 1 and at the annealing temperature of 300 °C exhibited the ionic conductivity of 1.6 × 10-4 S cm-1 at 25 °C. The synthesized solid electrolyte was found to be electrochemically stable in the potential range of 0-5 V, and also relatively stable under air with low relative humidity.

Long-term Findings in Bullous Sarcoidosis: A Case Report and Literature Review.

Pulmonary sarcoidosis may occasionally present with large bullae, but the clinical implications of this finding remain unclear. We herein report the complete clinical course of a case of pulmonary bullous sarcoidosis. Chest computed tomography initially showed subpleural and peribronchovascular lung opacities, and bullae spontaneously developed in adjacent less-affected regions, probably via a retraction mechanism. Bullae progression was refractory to corticosteroid treatment and associated with deterioration of respiratory symptoms. The later phase involved repeated bacterial and fungal infections of the bullous lungs, eventually causing respiratory failure and mortality. Postmortem examinations revealed aggressive pulmonary Mycobacterium avium infection and diffuse alveolar damage.

Effects of π-conjugation on the solid-state photoresponsive coloring behavior of bipyridine-boronium complexes.

Solid-state photoinduced coloring of boronium complexes consisting of 9-borabicyclononane and 2,2'-bipyridine with π-conjugated substituents at the 4,4'- or 5,5'-positions was investigated. The substitution position affected the highest occupied molecular orbital distribution and determined the coloring capability. The 4,4'-substituted complexes exhibited coloration upon irradiation, whereas most of the 5,5'-substituted complexes did not.

The temporal relationship of thresholds between muscle activity and ventilation during bicycle ramp exercise in community dwelling elderly males.

[Purpose] To compare the appearance time of the ventilatory threshold point and the electromyographic threshold in the activity of the vastus lateralis, rectus femoris, biceps femoris long head and gastrocnemius lateral head muscles during ramp cycling exercise in elderly males. [Subjects and Methods] Eleven community dwelling elderly males participated in this study. Subjects performed exercise testing with an expiratory gas analyzer and surface electromyography to evaluate the tested muscle activities during ramp exercise. [Results] The electromyographic threshold for rectus femoris was not valid because the slope after electromyographic threshold was not significant as compared to that before electromyographic threshold. The slope of the regression line for vastus lateralis was significantly decreased after electromyographic threshold while biceps femoris and gastrocnemius were increased. The electromyographic threshold appearance times for vastus lateralis and gastrocnemius were significantly earlier than ventilatory threshold point. There were no difference in electromyographic threshold appearance times among three muscles. [Conclusion] These results suggest that the increase in the slope of the regression line after electromyographic threshold for vastus lateralis was decreased, possibly indicating to postpone muscular fatigue resulting from the activation of biceps femoris and gastrocnemius as biarticular antagonists. This recruitment pattern might be an elderly-specific strategy.

Helicobacter pylori infection is associated with a decreased risk of tooth loss in healthy Japanese men.

The association between Helicobacter pylori infection and tooth loss has been studied in Western countries; however, this relationship remains controversial. Although the prevalence of H. pylori infection is higher and atrophic gastritis is usually observed in patients with H. pylori infection in Japan unlike that in Western population, no study has examined the association between H. pylori infection and tooth loss. We examined 959 healthy adults who participated in a mass survey. We counted the number of residual teeth and measured both H. pylori stool antigen and serum anti-H. pylori antibodies. Serum pepsinogen levels were measured to determine the presence of atrophic gastritis. Multiple logistic regression analysis was performed after adjustments for age, body mass index (BMI), smoking and alcohol habits, and educational background. In men, H. pylori infection was a significantly reduced risk factor for loss of all the teeth even after adjustments for other factors (OR, 0.32; 95% CI, 0.12-0.81; P < 0.05). However, such an association was not found in women (0.91; 0.49-1.69). The calculated OR for the presence of atrophic gastritis among individuals with tooth loss was not significant in both men and women. H. pylori infection was associated with a decreased risk of tooth loss in healthy Japanese men.

Elongation of phenoxide C-O bonds due to formation of multifold hydrogen bonds: statistical, experimental, and theoretical studies.

Statistical studies using the Cambridge Structural Database have revealed that there are several elongated phenoxide C-O bonds. They are characterized by the formation of 3-fold (or occasionally 2-fold) hydrogen bonds to the phenoxide oxygen atoms, and their mean bond length extends up to 1.320 Å, which is quite different from the theoretically predicted carbon-oxygen bond length of C(6)H(5)O(-) (1.26 Å). Elongated phenoxide C-O bonds associated with the formation of 3-fold hydrogen bonds were also observed in the X-ray structures of proton-transfer complexes (2X-O(-))(TEAH(+))s derived from 5'-X-substituted 5,5''-dimethyl-1,1':3',1''-terphenyl-2,2',2''-triols (2X-OHs, where X = NO(2), CN, COOCH(3), Cl, F, H, and CH(3)) and triethylamine (TEA). By comparing the X-ray structures, C-O bond elongation was found to be only slightly affected by an electron-withdrawing substituent at the para position (X). This along with strong bathochromic shifts of N-H(···O(-)) and O-H(···O(-)) stretching vibrations in the IR spectra indicates that the elongated C-O bonds in (2X-O(-))(TEAH(+))s essentially have single-bond character. This is further confirmed by molecular orbital calculations on a model complex, showing that the negatively charged phenoxide oxygen atom is no longer conjugated to the central benzene ring, and the NICS values of the three benzene rings are virtually identical. However, C-O bond elongation in (2X-O(-))(TEAH(+))s was considerably influenced by a change in the hydrogen-bond geometry. This also suggests that hydrogen bonds significantly affect phenoxide C-O bond elongation.

Objectively measured age-related changes in the intensity distribution of daily physical activity in adults.

BACKGROUND: The purpose of the present investigation was to examine the relationship between age and the intensity of the daily physical activity in men and women, aged 18 to 69 years. METHODS: A total 507 volunteers continuously wore a pedometer with a uni-axial accelerometer (Lifecorder, Kenz, Japan) for 7 days, to determine the number of steps (steps/ day) as well as the time spent in physical activity (minutes/day) at light (below 3 METs), moderate (3 to 6 METs), and vigorous (above 6 METs) intensities, respectively. All procedures carried out in the present investigation were conducted from 1999 to 2000 in Japan. RESULTS: The time spent in moderate to vigorous intensity physical activity significantly decreased with aging (P < 0.01). In contrast, the middle- to older-aged individuals spent a longer time in light intensity physical activity in comparison with the younger individuals (P < 0.05). Furthermore, these age-associated differences of physical activity were also significant, even though the number of steps did not differ significantly. CONCLUSIONS: These results indicate that the intensity of daily physical activity decreases with increasing age regardless of the amount of daily physical activity.

Comparative studies on electronic spectra and redox behaviors of isomeric benzo[1,2-b:4,5-b']difurans and benzo[1,2-b:5,4-b']difurans.

Electronic absorption/emission spectra, absolute fluorescence quantum yields, and oxidation potentials of isomeric benzo[1,2-b:4,5-b']difurans (1a) and benzo[1,2-b:5,4-b']difurans (2a) along with their alpha,alpha'-di-n-butyl (1b and 2b) and bis(3,5-dihexyloxyphenyl) derivatives (1c and 2c) were studied. The longest wavelength absorption maxima were very close between 1a and 2a and between 1b and 2b; however, the maximum absorption of 1c was significantly red-shifted compared to that of 2c, due to cross-conjugation in the latter. Unlike related compounds, the fluorescence quantum yields of syn (1a-c) and anti (2a-c) isomers were virtually identical. On the other hand, the oxidation potentials of the syn isomers were significantly lower than those of the anti isomers. Molecular orbital calculations revealed that this is likely to be characteristic of benzodifurans, because HOMO energy levels of the [1,2-b:4,5-b'] and [1,2-b:5,4-b'] isomers were estimated to be virtually identical in the other benzodichalcogenophenes.

Supramolecular chirogenesis in weakly interacting hosts: role of the temperature, structural, and electronic factors in enhancement of chiroptical sensitivity.

A new supramolecular chirogenic system on the basis of tetrakis(nickel porphyrin) and various enantiopure solvents, which was specifically designed for investigation of the chirogenic phenomenon upon extremely weak interaction modes and marginal chiroptical responses, is reported. The temperature was found to be a key factor controlling the chirality transfer process in these assemblies.

Synthesis, structure, and properties of benzoquinone dimer and trimers bearing t-Bu substituents.

Highly soluble and stable quinone dimer and trimers were successfully yielded by introduction of t-Bu substituents. In X-ray structure analysis, the dimer quinone moiety was distorted into the boat shape, which was clarified by MO calculations. X-ray and UV/vis studies indicated that the covalently linked quinone moieties bear a large torsional angle. Nevertheless, the reduction potentials rose significantly with the order of monomer < dimer < trimer, indicating that the negative charge was efficiently delocalized within the radical anions.

Preparation and characterization of pi-stacking quinodimethane oligothiophenes. Predicting semiconductor behavior and bandwidths from crystal structures and molecular orbital calculations.

A series of new quinodimethane-substituted terthiophene and quaterthiophene oligomers has been investigated for comparison with a previously studied quinoid oligothiophene that has demonstrated high mobilities and ambipolar transport behavior in thin-film transistor devices. Each new quinoidal thiophene derivative shows a reversible one-electron oxidation between 0.85 and 1.32 V, a quasi-reversible one-electron second oxidation between 1.37 and 1.96 V, and a reversible two-electron reduction between -0.05 and -0.23 V. The solution UV-vis-NIR spectrum of each compound is dominated by an intense (epsilon congruent with 100 000 M(-1) cm(-1)) low energy pi-pi transition that has a lambda(max) ranging between 648 and 790 nm. All X-ray crystal structures exhibit very planar quinoidal backbones and short intermolecular pi-stacking distances (3.335-3.492 A). Structures exhibit a single pi-stacking distance with parallel cofacial stacking (sulfur atoms of equivalent rings pointed in the same direction) or with alternating distances and antiparallel cofacial stacking (sulfur atoms of equivalent rings pointed in the opposite direction). Examples of the layered and herringbone-packing motifs are observed for both the parallel and the antiparallel cofacial stacking. Analysis of the X-ray structures and molecular orbital calculations indicates that all of these compounds have one-dimensional electronic band structures as a result of the pi-stacking. For structures with a unique pi-stacking distance, a simple geometric overlap parameter calculated from the shape of the molecule and the slip from perfect registry in the pi-stack correlates well with the transfer integrals (t) calculated using molecular orbital theory. The calculated valence (633 meV) and conduction (834 meV) bandwidths for a quinoid quaterthiophene structure are similar to those calculated for the benchmark pentacene and indicate that both hole and electron mobilities could be significant.

Post-exercise hyperemia after ischemic and non-ischemic isometric handgrip exercise.

Post-exercise related time course of muscle oxygenation during recovery provides valuable information on peripheral vascular disease. The purpose of the present study was to examine post-exercise hyperemia (forearm blood flow; FBF, Doppler ultrasound) assessed by peak FBF, excess FBF and the time constant for FBF (FBF(Tc)) following isometric handgrip exercise (IHE). Post-exercise hyperemia was assessed in an ischemic and non-ischemic state at different exercise intensities and durations. Peak FBF and excess FBF were defined as the maximum FBF during recovery, and the total amount of FBF volume, respectively. FBF(Tc) represents the time to reach approximately 37% of the change in FBF between peak FBF and resting FBF (delta peak FBF). Ten subjects performed IHE at "10% and 30% maximum voluntary contraction (MVC)" for 2 min with or without arterial occlusion (AO), followed by 2 min of AO alone (Study I). In Study II, six subjects performed 30%MVC-IHE with AO for "100%, 66%, 33% and 10% of the exhausted exercise duration" (time to exhaustion). In Study I, although peak FBF and excess FBF were significantly higher in ischemic than non-ischemic IHE for both 10% and 30%MVC (p<0.05), FBF(Tc) was similar in the ischemic and non-ischemic conditions. The peak FBF, excess FBF and FBF(Tc) were all significantly higher at 30% than at 10%MVC (p<0.05). In Study II, the peak FBF and excess FBF increased linearly compared to the absolute and relative exercise durations for ischemic IHE. FBF(Tc) increased exponentially when compared to the absolute and relative exercise durations. These data suggest the ischemic exercise has a larger hyperemic response compared to the non-ischemic exercise. In conclusion, the peak FBF, excess FBF and FBF(Tc) seen during post-exercise hyperemia are closely correlated with exercise intensity and duration, not only in non-ischemic, but also in the ischemic exercise. In combination with the ischemic exercise, these parameters could potentially prove to be valuable indicators of peripheral vascular disease.

Muscle oxygen consumption at onset of exercise by near infrared spectroscopy in humans.

In this study, we tried to continuously measure muscle oxygen consumption (m-VO2) by near infrared spectroscopy (NIRS) without arterial occlusions. We used an intermittent isometric exercise at high intensity, which elicits a spontaneous occlusion of the blood flow to the muscle due to an increase in intramuscular pressure. Changes in muscle oxygenation and phosphocreatine (PCr) concentration were monitored in 5 subjects during an intermittent isometric exercise (5 sec. contraction/5 sec. relaxation) at 50% of maximum voluntary contraction for 3 minutes. The rate of deoxygenation was measured from the 2nd sec. to the 3rd sec. of each muscle contraction. The rate of deoxygenation at the onset of exercise followed an exponential time course with a time constant of 42.0 +/- 12.5 sec. (mean +/- SD). This value agreed with the time constant of the decrease in PCr (48.2 +/- 10.2 sec.). This result suggests that m-VO2 was successfully monitored with a time resolution of 10 sec. by NIRS during exercise without arterial occlusion.

Quinonoid oligothiophenes as electron-donor and electron-acceptor materials. A spectroelectrochemical and theoretical study.

Two quinonoid bis(dicyanomethylene) oligothiophenes, terthiophene and quaterthiophene analogues of TCNQ, have been investigated by spectroelectrochemical experiments and density functional theory calculations. Electrochemical data show that the molecules can be both reduced and oxidized at relatively low potentials, and that the quaterthiophene derivative forms four stable redox species, the dianion, neutral, cation radical, and dication. The neutral oligomers are characterized by a strong electronic absorption in the red or near-infrared region and can be viewed as structural and electronic analogues of aromatic oligothiophenes in the dication or bipolaron state. Upon reduction, dianions, not anion radicals, are formed which absorb in the visible region. The theoretical calculations show that the dianions have aromatic oligothiophene moieties with two anionic dicyanomethylene groups. The transition from a quinonoid to an aromatic structure is fully supported by UV-vis-near-IR and vibrational spectroscopic data. Oxidation, generating cation radicals and dications, occurs at rather low potentials similar to those reported for oligothiophenes. The electronic spectra of these cations are understood from the calculations, which suggest that the oxidized species are stabilized by the partial aromatization of the oligothiophene backbone. IR spectra of the species, especially the CN stretching frequencies, confirm the structural conclusions and allow comparison with TCNQ and the TCNQ dianion.

Validation of three alternative methods to measure total energy expenditure against the doubly labeled water method for older Japanese men.

In a previous study using young Japanese men as subjects, Ebine et al. found that accelerometer (AC) represents a promising technique for measuring free-living total energy expenditure (TEE) when compared to activity records (AR) and heart rate monitoring (HR). Thus, the present study was designed to validate the use of an AC and to determine whether or not the previous findings regarding the three alternative field methods (AC, AR, and HR) could be extended to older Japanese men (n = 24; mean +/- SD age 48 +/- 10 y, body mass index 23.1 +/- 2.7 kg/m2 and body fat 18.7 +/- 4.8%). TEE values obtained over a 3 d period by AR, HR, and AC (3dAC), and AC over a 14 d period (14dAC) were simultaneously validated against TEE measured by the doubly labeled water (DLW) method applied within a 14 d period. TEE values obtained by AR, HR, 3dAC, and 14dAC ranged from 1,750 to 3,447 kcal/d, 1,691 to 5,286 kcal/d, 1,716 to 2,765 kcal/d, and 1,700 to 2,855 kcal/d, respectively. Expenditures obtained by HR were similar to those obtained using the DLW method, with a mean difference of 57 +/- 603 kcal/d (2%), but those obtained using AR, 3dAC, and 14dAC differed substantially from the DLW method, with mean differences of -335 +/- 289 kcal/d (12%), -542 +/- 249kcal/d (-19%), and -566 +/- 223kcal/d (-20%), respectively. AR, HR, 3dAC, and 14dAC were significantly correlated with the DLW method, with r values of 0.76 (p < 0.0001), 0.67 (p < 0.001), 0.78 (p < 0.0001), and 0.83 (p < 0.0001), respectively. Intra-individual variation indicated by the coefficient of variation (CV) was significantly higher for HR (15 +/- 11%, p < 0.001) than for AR (7 +/- 4%), 3dAC (7 +/- 5%), and 14dAC (8 +/- 31%). The same findings were obtained using Bland and Altman plots at the population level. Interestingly, 3dAC and 14dAC were significantly correlated with r = 0.97 (p < 0.0001), with a lower mean difference of 24 kcal/d. These results suggest that, same as the previous study, AC is superior to HR in estimating TEE, and seems to be satisfactory for estimation at both group and individual levels, particularly for large-scale studies of older individuals when compared to the DLW method. However, some modifications of the AC method may be needed to compensate for the underestimation of TEE.