Electroneutrality coupling of electron transfer at an electrode surface and ion transfer across the interface between thin-layer of 1-octyl-3-methylimidazolium bis(perfluoroalkylsulfonyl)imide covering the electrode surface and an outer electrolyte solution.

The electrode reaction of decamethylferrocene (DMFc) dissolved in a thin layer of a room-temperature molten salt (RTMS), 1-octyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (C8mimC1C1N) or 1-octyl-3-methylimidazolium bis(pentafluoroethylsulfonyl)imide (C8mimC2C2N), on a self-assembled monolayer-modified gold electrode is coupled with the ion transfer across the interface between the RTMS and the outer aqueous solution (W) to give a voltammogram whose shape resembles a voltammogram of a simple one-electron transfer process. The electroneutrality of the RTMS layer during the oxidation of DMFc to decamethylferricenium ion is maintained by the concomitant dissolution of C8mim+ ion from the RTMS phase to the W phase, and the reduction of decamethylferricenium ion to DMFc is accompanied by the transfer of either C1C1N- or C2C2N- from RTMS to W. The midpoint potential of the voltammogram varies with the concentration of the salt in the aqueous phase, C8mimCl or LiCnCnN (n = 1 or 2), in a Nernstian manner, showing that the phase-boundary potential between the RTMS and the W is controlled by the partition of these ions. Although the phase-boundary potential across the RTMS / W interface is Nernstian with respect to the ions common to both phases at the equilibrium, the polarization at the RTMS / W interface under current flow distorts the shape of the voltammograms, resulting in a wider peak separation in the voltammogram.     

Synthesis and properties of polydiene and polypentenamer having formyl or hydroxymethyl groups and their photosensitive derivatives

cis-1,4-Polybutadiene and polypentenamer having pendant functional groups such as formyl, aldoxime, hydroxymethyl, or cinnamoyloxymethyl groups have been prepared, and some of their properties were investigated in terms of structural effect on physical properties of these polymers. cis-1, 4-Polybutadiene and polypentenamer having a different content of formyl group were prepared by the hydroformylation reaction with rhodium catalyst under mild conditions. The pendant formyl group was reduced to a hydroxymethyl group by using various reducing agents such as sodium borohydride or sodium trimethoxyborohydride which were effective to avoid a crosslinking reaction among the formyl groups. Glass transition temperature of polypentenamer having hydroxymethyl groups increased with increasing the content of the hydroxymethyl groups in the polymer. Cinnamoyl group was introduced into the polypentenamer having hydroxymethyl groups by reacting with cinnamoyl chloride so as to prepare a photosensitive rubber. The relationships between the photosensitivity of the cinnamoylated polypentenamer and the mobility of polymer main chains have been elucidated. A linear relationship between the photodimerization rate constant and the difference between ultraviolet (UV) irradiation temperature and the glass transition temperature of the polymer was found. It has become apparent that the photosensitivity of cinnamoylated polypentenamer can be estimated by the glass transition temperature of the original polymer, UV irradiation temperature, activation energy of the dimerization, and γ, which is a coefficient of the relationship between the photosensitive group concentration and the glass transition temperature of the polymer.     

Cyclopolycondensations

Fully aromatic polyquinazolinediones of high molecular weight were prepared by the cyclopolycondensation reaction of 4,4′-diamino-3,3′-biphenyldicarboxylic acid with aromatic diisocyanates. The poly(phosphoric acid) solution polymerization techniques yielded tractable poly(urea acid), which was converted to polyquinazolinediones by thermal cyclodehydration at 300–400°C. under reduced pressure. The polyquinazolinediones thus obtained have excellent thermal stability both in nitrogen and in air. The poly(urea acid) is soluble in dimethyl sulfoxide, and films can be cast from the polymer solution of poly(urea acid) (η_inh = 0.8 to 1.8). The films are made tough by being heated in nitrogen or under reduced pressure at 300–400°C. The polymerization mechanism of the cyclopolycondensation reaction was studied, and it was established that the polymerization proceeded through the formation of tractable poly(urea acid), Structure (I), of high molecular weight, followed by cyclodehydration, yielding poly(1,2-dihydro-2-imino-4H-3,1-benzoxazin-4-one), Structure (II). On subsequently being heated this undergoes intramolecular rearrangement along the polymer chain, giving the thermodynamically stable polyquinazolinedione, Structure (III).     

Salt effects in the base-catalyzed polymerization of unsaturated amide compounds. II. Polymerization of p-vinylbenzamide and acrylamide

In the presence of a variety of inorganic salts, p-vinylbenzamide underwent vinyl-type polymerization by anionic initiators to form the polystyrene derivative, whereas in dimethyl sulfoxide as solvent the aromatic polyamide was always obtained through a proton-transfer mechanism regardless of the presence of the salts. In the presence of of the salts, acrylamide is generally polymerized to the polyamide through a proton transfer reaction.     

Salt effect in the base-catalyzed polymerization of unsaturated amide compounds. III. Nature of the polymerization system

Coordination complexes of lithium chloride with polar solvents and monomers were isolated, and their physical properties were studied. The parallel between stabilities of isolated complexes and coordination function in the polymerization system is discussed. The increase of the Q and e values of p-vinylbenzamide (VBA) supports the mechanism of vinyl-type polymerization of VBA in the presence of the salt. The specific solvent effect of dimethyl sulfoxide was determined by measurement of electrical conductivity of a model system.     

Discrete palladium clusters that consist of two mutually bisecting perpendicular planes

The construction of novel molecules with unprecedented alignments of the constituent elements has revolutionized the field of functional materials. The arrangement of two or more planar subunits in a mutually perpendicular fashion is a frequently encountered approach to produce novel functional materials. Previous examples of such materials can be categorized into two well-investigated families: spiro-conjugated and dumbbell-shaped structures, wherein the two planes are aligned orthogonally via a single atom or an axis, respectively. This article describes a third family: reaction of [Pd(CN^tBu)₂]₃ with Sn₃Me₈ or Ge₆Me₁₂ afforded a Pd₇Sn₄ cluster and a Pd₈Ge₆ cluster that consist of two mutually bisecting perpendicular planes. In the Pd₇Sn₄ cluster, the two equivalent Pd₅Sn₂ planes share three palladium atoms that include a dihedral angle of 85.6°.

The construction of Pd₇Sn₄ and Pd₈Ge₆ clusters that consist of two mutually bisecting perpendicular planes was accomplished by the reaction of [Pd(CN^tBu)₂]₃ with Me₃Sn–SnMe₂–SnMe₃ or Ge₆Me₁₂.     

Examination of Changes in 6-minute Walk Distance and Related Factors in Patients with Perioperative Peripheral Arterial Disease

Objective: This study aimed to clarify the effects of pre- and postoperative physical function on the 6-minute walking distance (6MWD) in patients with peripheral arterial disease (PAD). Method: Forty-two elderly patients with PAD who were hospitalized for revascularization and able to walk independently were included in the study. The 6MWD, ankle brachial index (ABI), weight-bearing index (WBI), gait, and intermittent claudication distance (ICD) were measured before and after the surgery, and skeletal muscle index was measured only before surgery. Analyses were performed by comparing the pre- and postoperative values of each factor using a paired t-test. In addition, multiple regression analysis was performed with 6MWD as the dependent variable before and after surgery. Results: Postoperatively, pain disappeared in 22 patients, and ABI, ICD, 6MWD, and stride length improved significantly. ICD and stride length were extracted as factors related to 6MWD before and after surgery, and ABI, WBI, and stride length were extracted as factors related to 6MWD after surgery. Conclusion: The improvement of intermittent claudication associated with revascularization suggests a stronger influence of functional aspects on postoperative 6MWD.     

Universal generation of higher-order multiringed Laguerre-Gaussian beams by using a spatial light modulator

Laguerre-Gaussian (LG) beams of various higher-order radial modes are generated by using a reflective phase-only liquid crystal on silicon (LCOS) spatial light modulator (SLM). Because of the LCOS SLM's phase-modulation characteristic of a wide spatial bandwidth, a phase modulation scheme effectively generates higher-order LG beams of up to the fifth-order radial mode. We also perform correlation analyses between the observed and the theoretical two-dimensional mode profiles to universally obtain correlation coefficients of more than 0.946, which suggest mode generations of high quality.