Reaction of poly(vinyl alcohol) with superoxide anion

Reaction of pol(vinyl alcohol) (PVA) with superoxide anion was carried out in a dimethyl sulfoxide solution at 40°C under nitrogen and changes in the yield of recovered polymer, molecular weight, and chemical structure were examined. Appreciable decreases in the yield of recovered polymer and molecular weight were observed during the reaction, which indicated that a main chain scission of the polymer had occurred. Residual acetyl groups identified by the absorption peaks at ca. 1720 and 1250 cm^?1 in infrared (IR) spectra were removed rapidly and β-diketone groups identified by the peaks at ca. 1640 and 1560 cm^?1 in IR spectra and at ca. 255 nm in ultraviolet (UV) spectra were formed during the reaction. Formation of carboxylate groups was also assumed. The reaction mechanism was discussed on the basis of the results obtained.     

High static pressure alters spin trapping rates in solution. Dependence on the structure of nitrone spin traps

Using a competitive spin trapping method, relative spin trapping rates were quantified for various short-lived radicals (methyl, ethyl, and phenyl radicals). High static pressure was applied to the competitive spin-trapping system by employing high-pressure electron spin resonance (ESR) equipment. Under high pressure (490 bar), spin trapping rate constants for alkyl and phenyl radicals increased by 10 to 40%, and the increase was dependent on the structure of nitrone spin traps. A maximum increase was obtained when tert-butyl(4-pyridinylmethylene)amine N-oxide (4-POBN) was used as a spin trap. Activation volumes (DeltaDeltaV(double dagger)) for the two spin trapping reactions were calculated to be -17-(-9) cm(3) mol(-1) for the 4-POBN system.     

Redox-responsive supramolecular polymeric networks having double-threaded inclusion complexes

Stimuli-responsive hydrogels have attracted attention as soft actuators that act similarly to muscles. In this work, hydrogel actuators controlled by host–guest interactions have been developed. The introduction of a 1:1 inclusion complex into a hydrogel is a popular design for achieving a change in cross-linking density. To realize faster and larger deformation properties, the introduction of a 1:2 inclusion complex is effective because the alteration in cross-linking density in a hydrogel with 1:2 complexes is larger than that in a hydrogel with 1:1 complexes. A redox-responsive hydrogel actuator cross-linked with 1:2 inclusion complexes is designed, where γ-cyclodextrin (γCD) and viologens modified with an alkyl chain derivative (VC11) were employed as the host and guest units, respectively. γCD includes two VC11 molecules in its cavity. The obtained γCD–VC11 hydrogel cross-linked with the 1:2 complex showed faster and larger deformation behaviour than the αCD–VC11 and the βCD–VC11 hydrogels cross-linked with a 1:1 complex. The deformation ratio and response speed of the γCD–VC11 hydrogel, which forms a supramolecular cross-linking structure by stimuli, are 3 and 11 times larger, respectively, than those of our previous hydrogel consisting of a βCD/ferrocene 1:1 inclusion complex.

A hydrogel actuator with a 1:2 host–guest complex controlled by redox stimuli has been developed to realize faster and larger deformation.     

M-Mode Color Doppler Ultrasonic Imaging of Vertical Tongue Movement During Articulatory Movement

To observe and estimate the movement of the tongue, ultrasonic investigation is the most harmless real-time monitoring procedure for analyzing articulatory movements. Color Doppler ultrasonic imaging is special in that it can only sample a moving target, and it can indicate the velocity and direction of the target by color and brightness in real time. This study assessed and demonstrated the validity of M-mode color Doppler ultrasonic imaging to observe the movements of the tongue during syllable repetition tasks performed by normal subjects and dysarthric patients, those affected by amyotrophic lateral sclerosis, cerebellar ataxia, Parkinsonism, and polymyopathy. When the transducer was set below the jaw, upward movement was indicated by a blue signal and downward movement was indicated by a red one on the screen of the ultrasound machine. We also measured the velocity of the tongue by contrast scale classified by 15 degrees. Thus, we could observe vertical tongue movement by a color-coded pattern after quantitative analysis. The Doppler signal patterns of normal subjects were verified by simultaneous video x-ray fluorography recordings. The findings for dysarthric patients corresponded well with previously reported features analyzed by other methods. Therefore, color Doppler ultrasonic imaging of the tongue is a useful procedure to researchers for clinical speech and voice studies.     

Physiological Studies of Retrusive Movements of the Human Tongue

SUMMARY: This study identified that physiologically the superior pharyngeal constrictor muscle at the level of the base of the tongue contributes to retrusive movement of the tongue with constriction of the mid-pharyngeal cavity and possesses unique properties in terms of motor speech control along with the genioglossus muscle. From a kinematic study involving trans-nasal fiberscopy and lateral X-ray fluorography, retrusive movement of the tongue was highly correlated with constrictive movement of the mid-pharyngeal cavity. An electromyographic study revealed that the superior pharyngeal constrictor muscle at the level of the base of the tongue contributes to retrusive movement of the tongue and that the genioglossus muscle contributes to protrusive movement. We also noted that this relationship between the activities of these two muscles were in response to postural changes during vowel productions without changes in the acoustic features. These findings suggest that these two muscles act not only antagonistically to produce retrusive and protrusive movement of the tongue, but also they complement each other to conserve the shape of the vocal tract for speech production. The functional relationship between these two muscles could contribute the consecutive movement of human speech production under various conditions and might be useful when applying rehabilitation approaches for the patients with neurological speech and swallowing disorders.     

A novel method for the direct derivatization of straight-chain aliphatic carboxylates after trapping on anion-exchange resin

A novel procedure for the characterization of traces of lipophilic straight-chain aliphatic carboxylate ions in aqueous samples is described. The carboxylates are adsorbed on an Amberlyst A26 [Cl^-] resin column. The resin is then dried and suspended in methyl iodide at room temperature. A gas Chromatographic analysis of the methyl iodide solution allows the determination of the carboxylates as their methyl esters. Full characterization of each carboxylate with an overall recovery over 84% from 1 ppm aqueous sample solutions is attained.     

Stereoselective tris-glycosylation to introduce beta-(1-->3)-branches into gentiotetraose for the concise synthesis of phytoalexin-elicitor heptaglucoside

Dodecyl thioglycosides (3, 4, 5) were prepared by conventional transformation of d-glucose and used as new glycosyl donors for a short-step synthesis of phytoalexin elicitor heptaglucoside. A gentio-tetraoside derivative (6) having three hydroxyl groups was synthesized by NIS-TfOH promoted glycosylate in more than 90% yield followed by selective removal of temporary protective groups. Undesired formation of alpha-glycosides at the introduction of beta-(1-->3)-branches into gentio-oligosaccharides was found to be suppressed by use of a thiophilic reagent system, BSP (1-benzenesulfinyl piperidine)-Tf2O, giving the heptaglucoside in only four glycosylation steps.     

Detection of modified tyrosines as an inflammation marker in a photo-aged skin model

Reactive nitrogen species, produced during the process of inflammation induced by various factors including UV radiation, modify amino acids in crucial proteins. It is assumed that skin tissue is more likely to be modified, as it is located at the outer layer of a body that is exposed to UV radiation on a daily basis. To investigate the influence of the modified tyrosine on UV-exposed skin, we detected the nitrotyrosine or halogenated tyrosine and dityrosine in photo-aged model mice. The back skin of mice was exposed to a dose of 10 J cm(-2) day(-1) every day for 15 weeks. Samples exhibiting typical symptoms of photo aging were provided to the immunofluorescence study. The quantification of modified proteins was accomplished through a chemical analytical method known as HPLC-tandem mass spectrometry. Analysis of the irradiated skin samples showed that all modified tyrosine except nitrotyrosine demonstrated statistically significant increases. The molecular weights of major modified proteins, confirmed as 25-50 kDa, were measured using Western blot analysis with an anti-nitrotyrosine antibody. Furthermore, the immunofluorescence study verified that the localization of myeloperoxidase conformed to that of nitrotyrosine. This result suggests that the modified tyrosine was produced during the process of inflammation by UV irradiation. In this study, we used a low dose of UV irradiation to which we are exposed in daily life. Our results suggest that UV exposure in daily life may induce the production of modified tyrosines and skin aging.