Highly Durable Spin Filter Switching Based on Self-Assembled Chiral Molecular Motor

Chiral molecules have recently received renewed interest as highly efficient sources of spin-selective charge emission known as chiral-induced spin selectivity (CISS), which potentially offers a fascinating utilization of organic chiral materials in novel solid-state spintronic devices. However, a practical use of CISS remains far from completion, and rather fundamental obstacles such as (i) external controllability of spin, (ii) function durability, and (iii) improvement of spin-polarization efficiency have not been surmounted to date. In this study, these issues are addressed by developing a self-assembled monolayer (SAM) of overcrowded alkene (OCA)-based molecular motor. With this system, it is successfully demonstrated that the direction of spin polarization can be externally and repeatedly manipulated in an extremely stable manner by switching the molecular chirality, which is achieved by a formation of the covalent bonds between the molecules and electrode. In addition, it is found that a higher stereo-ordering architecture of the SAM of OCAs tailored by mixing them with simple alkanethiols considerably enhances the efficiency of spin polarization per a single OCA molecule. All these findings provide the creditable feasibility study for strongly boosting development of CISS-based spintronic devices that can simultaneously fulfill the controllability, durability, and high spin-polarization efficiency.     

Synthesis and antiulcer activity of N-2-(2-hydroxy-2-phenyl)ethyl-N"-(methanesulfonyl)guanidine analogue of ranitidine. Development of a new antiulcer agent T-593

A series of the aryl-substituted N'-2-(2-hydroxy-2-phenyl)ethyl derivatives of N"-methanesulfonyl-N-2-((5-dimethylaminomethyl or 5-methylaminomethyl) furfurylthio)ethylguanidine have been synthesized as potential antisecretory and mucosal protective antiulcer agents. The synthetic routes involves, at the last stage, the reaction of 2-hydroxy-2-phenylethylamines with N-2-(furfurylthio)-ethyl-N'-methanesulfonyl-S-methylisothiourea or its O-phenylisourea counterpart. The primary screening test to assess the inhibitory activity of the synthetic compounds on histamine-induced gastric acid secretion was carried out in anesthetized rats by the lumen-perfusion technique of Ghosh and Schild and also by the pylorus-ligated preparation method. The best profile of histamine H2-antagonist activity was much better than that of the prototype ranitidine, and obtained with N'-(2-(2-hydroxy-2-(4-hydroxyphenyl)) ethyl-N"-methanesulfonyl-N-2-(5-(methylaminomethyl)furfurylthio)et hylguanidine (12f), which was also characterized by enhancing the gastric mucosal blood flow in rabbits as observed by the thermoelectric method. This compound 12f, designated as T-593, significantly inhibited the formation of the indomethacin-induced gastric lesions in rats; 3.5-fold more potent than ranitidine, but 4-fold less active than famotidine. On the other hand, T-593 and famotidine displayed comparable activities in healing the acetic acid-induced gastric ulcer with and without the dosing of indomethacin. Additional notable features of T-593, as determined in rats, are that its protective effect on the hemorrhagic shock-induced lesion under the prior dosing of histamine is ca. 10- and 2-fold greater than ranitidine and famotidine, respectively, and that a decrease in the gastric mucosal blood flow caused by a partial blood-withdrawal is more strongly recovered with T-593 than with famotidine. These experimental results suggest that the antiulcer efficacy of T-593 can be explained by its dual activities: antisecretion of gastric acid and, more importantly, protection of gastric mucous membrane.     

Jamming layered membrane gripper mechanism for grasping differently shaped-objects without excessive pushing force for search and rescue missions

A gripper comprising a jamming membrane was developed with the capability of grasping collapsible, soft, and fragile objects without applying heavy pressure. In disaster sites, it is necessary for robots to grab various types of objects, such as fragile objects. Deformable grippers that contain bags filled with powder cannot handle collapsible or soft objects without excessive pressure. Changing powder density relatively by changing inner volume is one approach to overcome this problem. By expanding the concept and simplifying the variable inner volume of the gripping mechanism, we developed a jamming membrane comprising the following three layers: outer layer and inner layer made of rubber and a powder layer in between the outer and inner rubber layer. This jamming membrane allows collapsible, soft, or fragile objects to be held securely without applying too much pressure. We designed and developed a prototype of the jamming membrane gripper. Our experiments confirmed the validity of the proposed jamming membrane mechanism.     

Stable and Metastable Phase Relationships in the System ZrO2–ErO1.5

Stable and metastable phase relationships in the system ZrO₂–ErO_1.5 were investigated using homogeneous samples prepared by rapid quenching of melts and by arc melting. The rapidly quenched samples were annealed in air for 48 h at 1690°C or for 8 months at 1315°C. Two tetragonal phases ( t - and t '-phases) were observed after quenching samples heated at 1690°C to a room temperature, whereas one t -phase and cubic ( c -) phase were found in those treated at 1315°C. Since the t '-phase is obtained through a diffusionless transformation during cooling from a high-temperature c -phase, t - and c -phases can coexist at high temperature. The t - and c -phases field spans from 4 to 10 mol% ErO_1.5 at 1690°C and from 3 to 15 mol% ErO_1.5 at 1315°C. The equilibrium temperature T ^t-m ₀ between the t - and monoclinic ( m -) phases estimated from A_s and M_s temperatures decreased with increasing ErO_1.5 contents.     

Effects of operating potential and temperature on degradation of electrocatalyst layer for PEFCs

The objective of this research work is to clarify essential factors related to degradation of PEFC electrodes. The degradation of Pt catalysts and the carbon support after a daily start and stop (DSS) operation was evaluated separately by measuring the electrochemical active area (S_Pt) and the double layer charging current (I_DL) with cyclic voltammetry without and with CO adsorption on Pt catalyst surfaces, respectively. Corrosion of the carbon support was accelerated mainly by raising the operating potential to 0.90 V, which was observed by increase in I_DL. The high-temperature operation at 90 °C or high-potential operation at 0.90 V resulted in a dramatic decrease in S_Pt. In contrast, it was found that the apparent cell performance was not so degraded probably because the decrease in S_Pt was cancelled by an increase in the proton conductance in the swollen ionomer. The agglomeration of Pt catalyst particles and their migration in the electrolyte membrane were also analyzed by TEM observation after the DSS operations.     

Structural Investigation of a Rapidly Quenched 20Li4SiO4·80Li2WO4 Glass

A 20Li₄SiO₄·80Li₂WO₄ glass was prepared by the rapid quenching technique, and its structure was investigated by X-ray diffraction (XRD) and Raman scattering. The coordination number of the oxygen atoms around a tungsten atom, N_O/W, was determined to be 4.8 by XRD and 4.6 by Raman scattering. The deviation of N_O/W from 4 resulted from the coexistence of condensed structural units, such as WO₆, Si₂O⁶⁻₇ ions containing bridging oxygens, WO²⁻₄ ions, and SiO⁴⁻₄ ions.     

Synthesis and conformational studies of polymers and copolymers of O,O′-dimethyl-l-β-3,4-dihydroxyphenyl-α-alanine with γ-benzyl-l-glutamate

Eight different copolymers of $\text{O,O′-}\text{dimethyl-}\text{l}\text{-β-3,4-}\text{dihydroxyphenyl}\text{-α-}\text{alanine}$ ($\text{O,O′-}\text{dimethyl-}\text{l}\text{-}\text{Dopa}$) and γ-benzyl-l-glutamate with degrees of polymerization of 320-80 have been synthesized by the N-carboxyanhydride method. From the results obtained by a study of the optical rotatory dispersion and circular dichroism for the copolymer series, the conformation of $\text{poly}\text{(O,O′-}\text{dimethyl-}\text{l}\text{-Dopa}\text{)}$ is a right-handed helix in helicogenic solvents such as chloroform, dioxane or 2-chloroethanol. Copolymers containing less than 50 mol % glutamate show a circular dichroism peak at 285 nm suggesting stacking of aromatic groups in the side chain. $\text{Poly}\text{(O,O′-}\text{dimethyl-}\text{l}\text{-Dopa}\text{)}$ is in the random coil structure in trifluoroacetic acid or hexafluoroacetone. The results were compared with those of $\text{poly}\text{(O,O′-}\text{dicarbobenzoxy-}\text{l}\text{-Dopa}\text{)}$ and poly(l-Dopa).     

Synthesis of nitropyridine‐based π‐conjugated polymers and their chemical properties

π‐Conjugated poly(3‐nitropyridine‐2,5‐diyl) ( PPy‐3‐NO₂ ), poly(3,3′‐dinitro‐2,2′‐bipyridine‐5,5′‐diyl) ( PBpy‐3,3′‐diNO₂ ), and a poly(arylene ethynylene) type polymer consisting of a 3,3′‐dinitro‐2,2′‐bipyridine unit ( PAE‐1 ) were synthesized by Cu‐promoted Ullmann coupling reaction and Pd‐catalyzed coupling reaction. PPy‐3‐NO₂ and PAE‐1 were soluble in organic solvents such as DMSO, DMF, and chloroform, and gel permeation chromatography analysis showed a number average molecular weight (M_n) of 9,300 and 12,300, respectively. PPy‐3‐NO₂ gave intrinsic viscosity, [η], of 0.53 dL g^?1 in DMF. PBpy‐3,3′‐diNO₂ had somewhat lower solubility. The polymers exhibited a UV–vis peak at about 430 nm. PPy‐NO₂ received electrochemical reduction at ?1.5 V versus Ag⁺/Ag in acetonitrile, and gave an electrochemical redox cycle in a range from 0 to ?1.1 V versus Ag⁺/Ag in an aqueous solution. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 1763–1767, 2006     

Studies on syntheses and permeabilities of special polymer membranes: 30. Ultrafiltration and dialysis characteristics of cellulose nitrate-poly(vinyl pyrrolidone) polymer blend membranes

The ultrafiltration and dialysis characteristics of the semipermeable polymer blend membranes obtained from cellulose nitrate, poly(vinyl pyrrolidone), and N,N-dimethyl formamide were investigated under various conditions. The water content fraction and the ultrafiltration rate were dependent on the poly(vinyl pyrrolidone) content in the membranes, and the strengths were governed by the cellulose nitrate content in the polymer blend. If the pore radius in the membranes, calculated according to the Hagen-Poiseuilli equation for capillary model, was identical, the water content in each membrane was not identical. It was found that urea molecules broke very weak hydrogen bonds of the bound water in the membrane, but sodium chloride did not, also, the diffusion of urea through the membrane was more rapid than that of sodium chloride. The ratio of the membrane diffusion coefficient to the ultrafiltration rate was explained qualitatively by the capillary model, however, when the bound water in the water content fraction was considered, this ratio showed better agreement with the model.