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The potential of muirapiranga (Brosimun sp.) as a substitute material for violin bows was estimated in terms of vibrational properties, and the influence of extractives on the vibrational properties was examined. The loss tangent of muirapiranga was somewhat higher and the specific dynamic Young’s modulus was rather lower than the respective values for pernambuco, which is regarded as the best material for violin bows. Therefore, muirapiranga is a poorer bow material in terms of vibrational properties. Impregnation of crude extractives from muirapiranga decreased the loss tangent of other wood specimens. The main compounds of the extractives were identified as xanthyletin and luvangetin. Impregnations of isolated xanthyletin and commercially available methoxsalen, which was tested as an analogue of luvangetin, markedly decreased the loss tangent of other wood specimens. Methoxsalen and xanthyletin differ from conventional loss tangent-decreasing substances, namely protosappanin B and hematoxylin, in terms of water insolubility and the absence of hydroxyl groups. From the similarity in molecular characteristics of loss tangent-decreasing substances found so far, restriction of molecular motion due to an impregnated substance in the wood matrix is suggested as one loss tangent-decreasing mechanism. [ABSTRACT FROM AUTHOR]

Abstract  Spruce wood blocks were acetylated in the presence of potassium acetate (KAc) at 20, 40, 60, 80 and 120°C. At 20°C, the weight percent gain (WPG) due to the KAc-catalyzed acetylation reached 20% in 18 days, whereas that due to pyridine-catalyzed acetylation did not exceed 8%. The hygroscopicity and dimensional stability of the KAc-acetylated wood were the same as those of conventionally acetylated wood at the same WPG, irrespective of reaction temperature. These facts suggest that the KAc enables simplified acetylation of wood at room temperature. The activation energy (E a) of the KAc-acetylation in the lower temperature range (20–40°C, 121–131 kJ/mol) was comparable to that of the acetylation of wood meal (140–146 kJ/mol). It was speculated that diffusion became a minor factor at reduced reaction rates in the lower temperature range, thus requiring a greater E a. [ABSTRACT FROM AUTHOR]

Abstract  Ezomatsu wood blocks were impregnated with potassium acetate (KAc) and then exposed to acetic anhydride vapor at 25°C and 120°C. The KAc-impregnated wood was rapidly acetylated at 120°C, and only 6 min was needed to achieve 20% weight percent gain (WPG). The WPG increased with increasing catalyst loading (CL), but it turned to decrease above 20% CL probably because the diffusion of acetic anhydride vapor was hindered by excess KAc depositing in the cell lumina. Thus, careful control of CL is necessary in the vapor-phase acetylation. KAc was also effective in catalyzing the vapor-phase acetylation at 25°C: the KAc-impregnated wood attained 20% WPG within 7 days, whereas the WPG did not exceed 10% even after 1 month in the uncatalyzed system. Irrespective of treatment methods, the hygroscopicity of wood was reduced and its dimensional stability was improved with an increase of WPG. These results confirm that the use of KAc simplifies the acetylation process at room temperature with minimal loss of acetic anhydride. [ABSTRACT FROM AUTHOR]

Abstract  Ezomatsu wood blocks were acetylated in a mixture of acetic anhydride and acetic acid containing excess potassium acetate (KAc). The mixture method enabled rapid acetylation at 120°C: a 20% weight gain (weight percent gain; WPG) was achieved within 30 min while the WPG did not exceed 18% after 120 min of conventional uncatalyzed acetylation. At 40°C, however, a satisfactory WPG was not achieved with the mixture method because both the wood swelling and KAc concentration in the reagent solution were limited at that temperature. In addition, the antiswelling efficiency attained by the mixture method was irregularly low, probably because of nonuniform reaction involving shrinkage of the cell lumina. These results suggest that the mixture method is not advantageous for low-temperature acetylation, whereas it enables simple and rapid acetylation at high temperature. [ABSTRACT FROM AUTHOR]

Abstract  To analyze the effects of lignin on the destabilization of wood due to quenching, we examined the dielectric properties of untreated and delignified wood before and after quenching at 20°C from 50 Hz to 100 MHz. For untreated wood, the inflection points of log ε′ and log σ vs log f and the peak of log(tan δ) vs log f were attributed to interfacial polarization before quenching, and the location of the inflection point shifted to a higher frequency with increasing moisture content because of changes in the water cluster. After quenching, the inflection points of log ε′ and log σ and the peak of log(tan δ ) shifted to higher frequency; however, the values of log ε′, log σ recovered to those before quenching with the passage of time. For delignified wood, dielectric relaxation was observed at a higher frequency than for untreated wood irrespective of quenching. It was inferred that the mobility of water molecules was influenced by the cluster surroundings because of increased number of adsorption sites in hemicellulose. Moreover, after quenching, the recovery process did not change greatly over time; it was shown that the matrix structure was affected more by quenching with the loss of lignin. [ABSTRACT FROM AUTHOR]

Abstract  In order to investigate the effects of chemical components and matrix structure on the destabilization of quenched wood, we examined the physical and mechanical properties of steam-treated wood, hemicellulose-extracted wood, and delignified wood, which were treated at different levels. For steam-treated and hemicellulose-extracted wood,the relative relaxation modulus of the quenched sample was lower than that of the respective control sample. For delignified wood, the relative relaxation modulus fell with weight loss and reached a minimum value at a certain weight loss, and subsequently increased significantly. The hygroscopicity of all treated samples changed slightly by steaming, whereas increased with removing the component. More-over, the average volumetric swelling per 1% MC at 100% relative humidity (RH) was less than at 75% RH and 93% RH for component-removed wood. It was clear that a void structure existed. As a result, the destabilization evaluated by the fluidity (1 - E t/E 0) of steam-treated wood was influenced by the amount of adsorbed water. For component-removed wood, destabilization increased temporarily at lower weight loss because of nonuniform cohesive structure. At high weight loss, destabilization will decreased because capillary-condensed water gathered in the voids and obstructed the motion of adsorbed water. However, the destabilization of all treated wood changed less than that of chemically modified wood. [ABSTRACT FROM AUTHOR]

Abstract  In order to examine the contribution of wood components to the acetylation of wood, we acetylated wood meal that had been partially delignified. The results were analyzed in terms of the reaction kinetics. The first-order rate equation was successfully adjusted to the weight gain data. The rate constant for acetylation initially increased with progress of lignin elimination and then turned to decrease; the apparent activation energy showed the reverse tendency and ranged from about 90 to 130 kJ/mol. These results suggest that lignin elimination brings not only separation of lignin but also drastic change of the chemical and/or physical structure in the residual lignin, and this affects the reactivity of wood meal as a whole. The ultimate weight gain estimated by the regression of the rate equation showed a minimum when lignin was moderately eliminated, which was explained in terms of enhanced reactivity of lignin and lower accessibility for holocellulose than predicted. The equilibrium moisture content had a maximum when lignin was moderately eliminated. This tendency is the opposite of that observed for the ultimate weight gain, and suggests that the sites for acetylation do not always correspond to those for moisture adsorption. [ABSTRACT FROM AUTHOR]

Abstract  Wood specimens were prepared in a swollen state using solvent exchange (PS) treatment. The swollen wood specimens were acetylated using acetic anhydride by heating at 80–120C. At the beginning of heating, the weight percent gain (WPG) of PS-treated wood was greater than that of conventionally acetylated wood. This acceleration effect of the PS treatment was explained by the introduction of treating reagent into the wood polymers where the intermolecular hydrogen bonds were previously broken. On the other hand, the PS treatment had no influence on the final WPG and moisture sorption characteristics of acetylated wood. This indicated that the intrinsic reactivity of wood constituents was unaffected by the PS treatment. The acetylation of PS-treated wood produced greater bulking and slightly higher dimensional stability than that in the case of conventional acetylation at the same WPG. It was speculated that the expansion of cell lumina due to the PS treatment resulted in greater bulking on acetylation and lesser swelling of acetylated wood with moisture sorption. [ABSTRACT FROM AUTHOR]

Abstract  Participation of lignin in the reaction between vapor-phase formaldehyde and wood was examined by using gradually delignified wood meal. A fi rst-order rate equation was successfully applied to the weight gain data. From the estimated reaction parameters such as rate constant, k, and ultimate weight gain, a, the reactivity toward formaldehyde was discussed among wood components, and compared with that for acetylation. k decreased monotonously with progress of the elimination of lignin, suggesting that the reaction rate of lignin is dominant over that of whole wood, and the decrease in the ratio of lignin retarded the reaction of wood as a whole. On the other hand, a increased with decreasing lignin content. This may be attributable to the enhanced reactivity of the remaining lignin due to some structural changes and to the increase in the number of reactive sites in polysaccharides as a result of their exposure accompanying the elimination of lignin. The dependencies of k and a on the lignin content were not similar to the case for acetylation, probably because of the difference in the reaction phase. In vapor-phase formaldehyde treatment, the remaining lignin reacts as it is, whereas in liquid-phase acetylation it would undergo rearrangement or swelling of the structure in the reaction solution. [ABSTRACT FROM AUTHOR]

Using a murine model, topical application of glucocorticoid ([GC], 50 μg diflucortolone valerate in ethanol) on a sensitized site (flank skin) for 7 times before and 2 times after sensitization on alternate days, augmented expression of contact sensitivity reactions on the challenged site (ear skin). This augmentation was due to the systemic effect of percutaneously absorbed GC, because topical GC also augmented the skin reaction in mice that had been sensitized on a separate site from that of the GC application. In contrast, topical application of GC inhibited the contact sensitivity skin reaction when applied on the challenged sites. Intraperitoneal injection of the same dose of GC also failed to augment the skin reactions. Glucocorticoid augmented the contact sensitivity skin reactions and these persisted for 96 h after the control skin reactions subsided. Early phase (1–6 h) skin reactions were also induced or augmented when dinitrofluorobenzene or trinitrochlorobenzene but not oxazolone were used as the sensitizer; GC also augmented the non-specific reactions to croton oil or to suboptimal concentration of hapten in normal mice. The numbers of Langerhans cells (LC) were reduced in both the GC-application and challenged sites. Haptenated LC from GC-treated skin showed a rather weak sensitizing ability, which was not statistically significant. Transfer of lymph node cells and/or spleen cells or serum from GC-pre-treated mice failed to induce a contact sensitivity reaction in normal recipient mice. These results suggest that topical GC might augment cutaneous inflammation through a possible modulation of local cytokine production, regardless of the number of LC or the presence of sensitized lymphocytes.