Functional ionic liquids for enhancement of Li-ion transfer: the effect of cation structure on the charge-discharge performance of the Li4Ti5O12 electrode.

As the development of high energy-density Li-ion batteries moves ahead, ensuring safety of the batteries has become increasingly important. Among the unique physicochemical properties of ionic liquids, thermal stability can be one of the answers to the challenge. The use of ionic liquids, however, causes critical issues concerning the kinetics of Li-ion transfer at the electrode-electrolyte interface. In the present study, ionic liquids consisting of 1-((2-methoxyethoxy)methyl)-1-methylpiperidinium (PP1MEM) or 1-hexyl-1-methylpiperidinium (PP16) and bis(trifluoromethanesulfonyl)amide (TFSA) were applied to an electrolyte for Li-ion batteries, and we investigated the effect of cation structure on interfacial Li-ion transfer using Li4Ti5O12 as a model electrode by means of Raman spectroscopy and electrochemical impedance spectroscopy. It was found that the ether functional group in the PP1MEM cation has the meaningful function; the cation structure reduces the electrostatic interaction between the Li ion and TFSA anions in an ionic liquid electrolyte. The solvation number of the TFSA anion per Li ion consequently became smaller than that in PP16-TFSA, and the lower solvation number in PP1MEM-TFSA allowed the facile Li-ion diffusion in the electrolyte bulk rather than the interfacial Li-ion transfer and significantly improved the rate performance. The results offer the prospect of utilization of PP1MEM-TFSA as an electrolyte solvent. The knowledge obtained from this study contributes to the development of next-generation Li-ion batteries having both high energy density and high safety.

Synthesis and Structure-Activity Relationships of 2-Aminoacetamide Derivatives as Peroxisome Proliferator-Activated Receptor α/γ Dual Agonists.

We describe the design, syntheses, and structure-activity relationships of novel zwitterionic compounds as nonthiazolidinedion-based peroxisome proliferator-activated receptor (PPAR) α/γ dual agonists. In our previous report, we obtained compound 1 showing potent PPARα/γ dual agonistic activities, together with a sufficient glucose-lowering effect in db/db mice. However, this compound possessed an issue, i.e., the 1,3,4-oxadiazole ring was not stable in acidic conditions. Thus, we carried out further optimization to improve the stability while maintaining the other favorable profile features including potent PPARα/γ dual agonistic activity. We addressed the issue by changing the oxadiazole ring to a bioisostere amide group. These amide derivatives were stable in acidic conditions and decreased plasma glucose and plasma triglyceride levels significantly without marked weight gain.

Coating of Chlorophylls a and b Enhanced Photoelectrochemical Capacitor Reaction of TiO2/MnO2 Composite Electrode.

We prepared composite electrodes using TiO2 coated with chlorophylls a and b as photoelectric conversion material and MnO2 as energy storage material and investigated their photoelectrochemical capacitor properties. The coating with the combination of chlorophylls a and b improved the photoelectric conversion function of TiO2, compared with the coating with each alone. Na+ adsorption on MnO2 was enhanced with increasing the chlorophyll coating amount. The reason is that more chlorophylls a and b absorb visible light in different wavelengths to promote an easier photoexcited electron transfer to MnO2, just as they improve the efficiency of photosynthesis reactions in nature.

Synthesis and structure-activity relationships of novel zwitterionic compounds as peroxisome proliferator activated receptor α/γ dual agonists with improved physicochemical properties.

We describe herein the design, syntheses and structure-activity relationships (SAR) of novel zwitterionic compounds as non-thiazolidinedion (TZD) based peroxisome proliferator activated receptor (PPAR) α/γ dual agonists. In the previous report, we obtained compound 1 showing potent PPARα/γ dual agonistic activities, together with a great glucose lowering effect in the db/db mice. However, this compound possessed fatal issues such as potent cytochrome P450 (CYP)3A4 direct inhibitory activity. Thus, we carried out the medicinal optimization to improve these while maintaining the potent PPAR agonistic activity. As a result, the issues were addressed by changing the furan ring to a low lipophilic 1,3,4-oxadiazole ring. Additionally, these oxadiazole derivatives exhibited a significant decrease in plasma glucose and plasma triglyceride levels without marked weight gain.

Design, synthesis and evaluation of novel zwitterionic compounds as PPARα/γ dual agonists (1).

We describe here the design, syntheses and structure-activity relationships (SAR) of novel zwitterionic compounds as non-thiazolidinedion (TZD) based peroxisome proliferator activated receptor (PPAR) α/γ dual agonists. We commenced the medicinal research with compound 1 originated by Eli Lilly, which was reported to possess PPAR α/γ dual agonist activity. We incorporated an amine linker and optimized it on the nitrogen of the linker, thereby envisioning the enhancement of the PPAR α/γ dual agonist activity together with altering the physicochemical properties. As a result, we could generate compounds showing the PPAR α/γ dual activity, especially among which compound 22e had a franylmethyl group on the linker and 2,6-dimethyl phenyl ring at the carboxylic acid head group furnishing a highly potent dual agonist activity, together with a great glucose lowering effect. Moreover, it remedied the lipid profile, that is, triglyceride without body weight gain in the db/db mice model.

Discovery of novel tricyclic compounds as squalene synthase inhibitors.

In the present article, we have reported the design, synthesis, and identification of highly potent benzhydrol derivatives as squalene synthase inhibitors (compound 1). Unfortunately, the in vivo efficacies of the compounds were not enough for acquiring the clinical candidate. We continued our investigation to obtain a more in vivo efficacious template than the benzhydrol template. In our effort, we focused on a benzoxazepine ring and designed a new tricyclic scaffold by the incorporation of heterocycle into it. Prepared pyrrolobenzoxazepine derivatives showed further efficient in vitro and in vivo activities.

A simulation of allocation of participants engaging in group activities at community salons: Accessibility and self-stigma.

Community salons are places where older adults receive preventive healthcare and enjoy recreational activities. In Japan, some older adults are reluctant to attend group activity programs at community salons because they do not want to be seen by their neighbors as being elderly who need support from others, even though those activities are meant to prevent functional decline. The phenomenon can be conceptualized as self-stigma of community salon participation, which is a factor explaining why older adults hesitate to participate and some opt for activities at facilities farther away. This paper proposes an allocation problem (considering both accessibility and self-stigma within a Japanese context), demonstrating that participants go to facilities that are farther away, not just those that are closest. The allocation problem is expected to provide local public health agencies with a normative model to assess participants' current allocation (compared with the solutions) and to simulate how best to facilitate older adults' participation or intergroup contact (between those with and without self-stigma). Solutions to the allocation problem are analyzed regarding activity participation, intergroup contact, and distance from participants' home to allocated facilities. Results from the simulation in a virtual city environment show that there could be a segregation of activity groups between people with and without self-stigma. From a comparison among solutions from different geographical settings of residents and facilities, people without self-stigma are less likely to sacrifice their accessibility to allocated facilities in the case of uneven distribution. On the other hand, a larger number of participants with self-stigma is expected, especially in the case of concentrated residential location. The findings suggest that policymakers should consider both the geographical distribution of residents and facilities, the impact of self-stigma, and intergroup contact when they discuss how the policies for older adults' social participation can best result in greater social benefits.

Impact of Low Temperatures on the Lithiation and Delithiation Properties of Si-Based Electrodes in Ionic Liquid Electrolytes.

Lithium-ion batteries are used in various extreme environments, such as cold regions and outer space; thus, improvements in energy density, safety, and cycle life in these environments are urgently required. We investigated changes in the charge and discharge properties of Si-based electrodes in ionic liquid electrolytes with decreasing temperature and the cycle life at low temperature. The reversible capacity at low temperature was determined by the properties of the surface film on the electrodes and/or the ionic conductivity of the electrolytes. The electrode coated with a surface film formed at a low temperature exhibited insufficient capacity. In contrast, a Si-only electrode precoated with the surface film at room temperature exhibited a cycle life at low temperatures in ionic liquid electrolytes longer than that in conventional organic liquid electrolytes. Doping phosphorus into Si led to improved cycling performance, and its impact was more noticeable at lower temperatures.

Improvement of the Anode Properties of Lithium-Ion Batteries for SiO x with a Third Element.

Silicon oxide (SiO x ) has been placed into practical use as an anode active material for next-generation Li-ion batteries because it has a higher theoretical capacity than graphite anodes. However, the synthesis method is typically vapor deposition, which is expensive, and the poor electron conductivity of SiO x restricts high performance. In this study, we prepared M/SiO x active materials consisting of SiO x and a third element (M = Al, B, Sn) using a low-cost mechanical milling (MM) method and investigated their electrode properties as Li-ion battery anodes. Also, the authors added a third element to improve the conductivity of the SiO2 matrix. Al, B, and Sn were selected as elements that do not form a compound with Si, exist as a simple substance, and can be dispersed in SiO2. As a result, we confirmed that SiO x has a nanostructure of nanocrystalline Si dispersed in an amorphous-like SiO2 matrix and that the third element M exists not in the nanocrystalline Si but in the SiO2 matrix. The electron conductivity of SiO x was improved by the addition of B and Sn. However, it was not improved by the addition of Al. This is because Al2O3 was formed in the insulator due to the oxidization of Al. The charge-discharge cycle tests revealed that the cycle life was improved from 170 cycles to 330 or 360 cycles with the addition of B or Sn, respectively. The improvement in electron conductivity is assumed to make it possible for SiO2 to react with Li ions more uniformly and form a structure that can avoid the concentration of stress due to the volume changes of Si, thereby suppressing the electrode disintegration.

Discovery of a new 2-aminobenzhydrol template for highly potent squalene synthase inhibitors.

To obtain small and efficient squalene synthase inhibitors, a flexible 2-aminobenzhydrol open form structure was designed and showed potent inhibitory activity comparable to 4,1-benzoxazepin compounds. Further chemical modification led to the discovery of a novel template with a strong squalene synthase inhibitory activity, and its basic structure-activity relationship was revealed. The X-ray crystallographic data of compound 12 bound to the active site of squalene synthase provided an important insight into the binding mode of this alternative template that formed 11-membered ring conformations with an intramolecular hydrogen bond.

Discovery of atrop fixed alkoxy-aminobenzhydrol derivatives: novel, highly potent and orally efficacious squalene synthase inhibitors.

We have recently reported the discovery of the new benzhydrol template, which has a highly potent inhibitory activity for squalene synthase, as typified by compound 1 (SSI IC(50)=0.85 nM). However, it was composed of a pair of easy rotatable atropisomers. In the effort to fix the isomerization, a highly potent alkoxy-aminobenzhydrol scaffold was developed. Some of these acquired compounds demonstrating strong cholesterol synthesis inhibitory activities in a rat hepatic cell. Moreover, two of the series compounds exhibited specific plasma lipid-lowering effects in in vivo animal models.

Anode Properties of Cr x V1-x Si2/Si Composite Electrodes for Lithium-Ion Batteries.

We have reported the effects of substituting a transition metal in silicide on the electrochemical performance of the silicide/Si composite anode for lithium-ion batteries (LIBs); the Cr0.5V0.5Si2/Si electrode exhibited much better cyclability compared with CrSi2/Si and VSi2/Si electrodes. Herein, we investigated the electrochemical performance of a Cr x V1-x Si2/Si slurry electrode for its application in LIBs, and the results obtained were compared to those of a gas deposition (GD) electrode, which was comprised of only active materials. The slurry electrode exhibited a superior cycling life as with the GD electrode. After charge-discharge cycles, the expansion of the electrode thickness of CrSi2/Si and Cr0.5V0.5Si2/Si was smaller than that of VSi2/Si, and VSi2 was significantly pulverized compared with the other silicides. It is considered that VSi2 deformed easily by the stress from Si expansion and pulverized because the hardness of VSi2 was the smallest among the silicides used in this study. These results reveal that Cr0.5V0.5Si2/Si has great potential as an anode material for next-generation LIBs and hardness is an important property for compositing silicide with Si.

Regeneration of Nicotinamide Adenine Dinucleotide Phosphate by a Chlorophyll a-Coated TiO2 Film Electrode.

A TiO2 electrode was coated with chlorophyll a to regenerate nicotinamide adenine dinucleotide phosphate (NADPH), which can enhance the photovoltages of the electrodes for photoelectrochemical capacitors. The photovoltage of an uncoated TiO2 electrode was high during the first cycle but then steadily reduced owing to the oxidization of NADPH in the electrolyte during the photo-charge-discharge cycling. By contrast, a chlorophyll a-coated TiO2 electrode maintained high photovoltages for 100 cycles. Residual NADPH concentrations after 100 cycles increased from 73% to 90% because of the coating, demonstrating that NADPH was regenerated by photoexcited chlorophyll a similar to a photosynthetic reaction in nature.

Lithiation/Delithiation Properties of Lithium Silicide Electrodes in Ionic-Liquid Electrolytes.

We investigated the impact of electrolyte difference on lithiation and delithiation properties of a Li1.00Si electrode to improve the Coulombic efficiency (CE) of Si-based electrodes. The results of X-ray diffraction, Raman spectroscopy, and soft X-ray emission spectroscopy demonstrated that a portion of the Li in Li1.00Si desorbed by simply immersing the electrode in an ionic-liquid electrolyte, that is, the phase transition of Li1.00Si to Si occurred. In contrast, this phenomenon was not confirmed in an organic-liquid electrolyte. Instead, the desorbed Li was consumed for the formation of a surface film; thus, the Li in Li1.00Si did not elute into the electrolyte. The addition of vinylene carbonate (VC) to the ionic-liquid electrolyte suppressed the phase transition of Li1.00Si to Si. Although the Li1.00Si electrode showed a low initial CE and poor cycling performance in a VC-free electrolyte, the electrode exhibited a high CE and a remarkable cycle life in the VC-added electrolyte. It was considered that no desorption of the mechanically added Li in Li1.00Si contributed to the superior cycle life; thus, the characteristic ductility, malleability, and high electrical conductivity of lithium silicide should improve the electrochemical performance.

How Does Urban Farming Benefit Participants' Health? A Case Study of Allotments and Experience Farms in Tokyo.

In Japan, the world's most rapidly aging country, urban farming is attracting attention as an infrastructure for health activities. In Tokyo, urban residents generally participate in two types of farming programs: allotments and experience farms. The availability of regular interaction among participants distinguishes these two programs. We quantitatively examined the difference in changes in self-reported health status between participants in these two types of urban farming. We obtained retrospective cross-sectional data from questionnaire surveys of 783 urban farming participants and 1254 nonparticipants and analyzed the data using ordinal logistic regressions. As a result, compared with nonparticipants, participants in both types of urban farming reported significantly improved self-rated health (SRH) and mental health (MH). After controlling for changes in their physical activity (PA), although participants in allotments did not report significant improvement in SRH and MH, those in experience farms did, suggesting that their health improvement was not only caused by an increase in PA but also by social interaction among participants. From the perspective of health promotion, public support is needed not only for the municipality's allotments but also for the experience farms operated by the farmers themselves.

Three-Year Longitudinal Association Between Built Environmental Factors and Decline in Older Adults' Step Count: Gaining insights for Age-Friendly Urban Planning and Design.

This study examined the longitudinal association between the change in the step count of older adults and the neighborhood-built environment (BE) in Yokohama, Japan. We analyzed pedometer data in March 2016 and March 2019 that were acquired from 21,557 older adults aged 65-79 years at baseline, who lived in 758 neighborhoods in Yokohama City and participated in the Yokohama Walking Point Program (YWPP). Six BE variables were computed, for each of which neighborhoods were classified into quartiles. Using multilevel regression analysis, we examined the association between the BE variables, baseline step count, and change in step count. Higher population density, lower intersection density, and the second shortest quartile of the average distance to the nearest railway station were associated with a higher baseline step count. A lower intersection density and shorter average distance to the nearest railway station were associated with a smaller decline. The lowest quartile of population density was inversely associated with step-count decline. In conclusion, the neighborhood BEs were not only associated with their step count at baseline, but also widened the disparity of the step count over the three years. These findings would contribute to creating age-friendly cities where older adults can maintain and promote their health.

Reaction Behavior of a Silicide Electrode with Lithium in an Ionic-Liquid Electrolyte.

Silicides are attractive novel active materials for use in the negative-electrodes of next-generation lithium-ion batteries that use certain ionic-liquid electrolytes; however, the reaction mechanism of the above combination is yet to be clarified. Possible reactions at the silicide electrode are as follows: deposition and dissolution of Li metal on the electrode, lithiation and delithiation of Si, which would result from the phase separation of the silicide, and alloying and dealloying of the silicide with Li. Herein, we examined these possibilities using various analysis methods. The results revealed that the lithiation and delithiation of silicide occurred.

Indium-Doped Rutile Titanium Oxide with Reduced Particle Length and Its Sodium Storage Properties.

We hydrothermally synthesized In-doped rutile TiO2 particles in an anionic surfactant solution and investigated the influences of In doping and the particle morphology on the Na+ storage properties. The solid solubility limit was found to be 0.8 atom % in In-doped TiO2. In the case where no surfactant was used, the best anode performance was obtained for 0.8 atom % In-doped TiO2 electrode by the benefits of three doping effects: (i) expanded diffusion-path size, (ii) improved electronic conductivity, and (iii) reduced electron charge density in the path. Further enhancement in the performance was achieved for the In-doped TiO2 with a reduced particle length by the synthesis in the surfactant solution. This electrode exhibited a better cycle stability and maintained a high discharge capacity of 240 mA h g-1 for 200 cycles. The reason is probably that Na+ can be inserted in the inner part of TiO2 particles because of its reduced particle length.

Silicon-Based Anodes with Long Cycle Life for Lithium-Ion Batteries Achieved by Significant Suppression of Their Volume Expansion in Ionic-Liquid Electrolyte.

Elemental Si has a high theoretical capacity and has attracted attention as an anode material for high energy density lithium-ion batteries. Rapid capacity fading is the main problem with Si-based electrodes; this is mainly because of a massive volume change in Si during lithiation-delithiation. Here, we report that combining an ionic-liquid electrolyte with a charge capacity limit of 1000 mA h g-1 significantly suppresses Si volume expansion, improving the cycle life. Phosphorus-doping of Si also enhances the suppression and increases the Li+ diffusion coefficient. In contrast, the Si layer expands significantly in an organic electrolyte even with the charge capacity limit and even in an ionic-liquid electrolyte without the limit. We demonstrated that the homogeneously distributed Si lithiation-delithiation, phase-transition control from the Si to Li-rich Li-Si alloy phases, formation of a surface film with structural and/or mechanical stability, and faster Li+ diffusion contribute to suppressing Si volume expansion.

Optical transmittance of indium tin oxide nanoparticles prepared by laser-induced fragmentation in water.

Laser-induced fragmentation of indium tin oxide nanoparticles was performed in water by laser irradiation with various laser energies. Fragmentation of the nanoparticles proceeded with increased laser energy. The fragmented nanoparticles showed high transmittance in the visible region and lower transmittance in the ultraviolet and infrared regions. The optical band gap of the fragmented nanoparticles increased with decreasing average particle size. The increase of the band gap was possibly caused by the Burstein-Moss effect due to the increasing concentration of carriers generated by the surface defects of the oxygen vacancies on smaller nanoparticles.