Phomactins K–M,three novel phomactin-type diterpenes from a marine-derived fungus

Three novel diterpenes, phomactins K–M (1–3), were isolated from the cultures of an unidentified marine-derived fungus. The structures of 1–3 were elucidated from spectroscopic data (NMR, MS, IR), and the absolute configurations of 1, 2, and the relative configuration of 3 were determined by X-ray diffraction analysis.     

9,9′‐spirobifluorene‐containing polycarbonates: Transparent polymers with high refractive index and low birefringence

Syntheses of 2,2′‐bisalcoholic group‐substituted 9,9′‐spirobifluorene monomers 2 were performed by the reaction of 2,2′‐dihydroxy‐9,9′‐spirobifluorene 2a with haloalcohols. Polycarbonates consisting of 9,9′‐spirobifluorene skeleton in the main chain (PC 4 ) were synthesized by the polycondensation of 2,2′‐bisalcoholic monomers 2 and triphosgene or diphenyl carbonate. PC 4 showed good thermal stability: the 5% weight loss temperature was over 330 °C under both nitrogen and air atmospheres. The glass transition temperature was in a range of 16–269 °C estimated by differential scanning calorimetry, depending on the flexibility of the alkylene or oxyethylene chains of 2 . PC 4 showed high solubility toward ordinary organic solvents such as CHCl₃, benzene, and THF, making possible the preparation of the flexible thin films. Very high refractive index in a range of 1.62–1.66 at 589 nm was observed although PC 4 consists only of C, H, and O atoms, whereas very low degree of birefringence was confirmed. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 3658–3667, 2010     

Effect of glycyrrhizinate on dissolution behavior and rectal absorption of amphotericin B in rabbits.

The effects of dipotassium glycyrrhizinate (GLYK) on the dissolution behavior and bioavailability of amphotericin B (AMB) were investigated. The mixtures of AMB and GLYK were prepared at different molar ratios by lyophilization. Lyophilization resulted in amorphous AMB either alone or in the mixture. Dissolution rates of AMB of the mixtures were markedly faster than that of lyophilized AMB alone, which was followed by a decrease of dissolution. The initially-enhanced dissolution rate was likely to be due to the improvement of surface wettability of drug particles with GLYK rather than the amorphous state of AMB. A phase solubility study of AMB with GLYK indicated that the increasing solubility was caused by micellar solubilization. The in vitro release rate of AMB from suppositories containing the lyophilized mixtures was significantly accelerated by increasing the amount of GLYK. The rectal absorption of AMB from suppositories containing either the drug alone, a physical mixture or a lyophilized mixture was studied using rabbits. The absorption of the mixture (AMB/GLYK = 1/9) was about 35 times greater in the area under the serum concentration-time curve (0-24 h) than that of lyophilized AMB alone. These results suggest that GLYK is useful for improving the dissolution property of AMB and the bioavailability of the drug incorporated in suppositories.     

Melt rheology of hyperbranched‐polystyrene synthesized with multisite macromonomer

Melt rheological behaviors of hyperbranched‐polystyrene (PS) copolymerized by dendric macromonomer technique are presented. The time–temperature superposition principle was applicable to the hyperbranched‐PS. The branched‐PS showed slightly lower zero‐shear viscosity in comparison with linear PS regardless of a presence of a number of branches expected from the dendric macromonomer technique. Although the influence of use of multimethacryloyl macromonomer in the polymerization process was marginal for linear viscoelastic regime, nonlinear shear and uniaxial elongational flows showed distinct differences between linear and branched‐PS. The strain dependence of the damping function became weak as increase of macromonomer content. The branched‐PS exhibited the growing elongational viscosity function comparing with linear PS. This prominent effect on the elongational flow behavior can be explained by the molecular architecture of the branched‐PS. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 2226–2237, 2009     

Thermal phase transition of RbMnFe(CN)6 observed by X-ray emission and absorption spectroscopy

The thermal phase transition of RbMnFe(CN)₆ has been observed by Mn and Fe 3p-1s X-ray emission spectroscopy (XES) and 1s X-ray absorption spectroscopy (XAS). The thermal variations of the spin states and the valences of Mn and Fe were determined to be Mn²⁺(S=5/2)-NC-Fe³⁺(S=1/2) for the high-temperature (HT) phase and Mn³⁺(S=2)-NC-Fe²⁺(S=0) for the low-temperature (LT) phase. These transitions are thus caused by charge transfer between Mn and Fe. The temperature dependences of Mn and Fe 3p-1s XES and 1s XAS were observed as the composition of the spectra of the HT and LT phases. The ratios of the HT component in each spectrum show good agreement with the thermal transition curves observed with magnetic susceptibility measurements.     

Rheological properties of poly(vinyl chloride)/plasticizer systems—relation between sol–gel transition and elongational viscosity

Poly(vinyl chloride) (PVC)/di-isononyl phthalate systems with PVC content of 45.5 (PVC8) and 70.4 wt% (PVC6) were prepared by a hot roller at 150 °C and press molded at 180 °C. The dynamic viscoelasticity and elongational viscosity of PVC8 and PVC6 were measured in the temperature range from 150 to 220 °C. We have found that the storage and loss shear moduli, G′ and G″, of PVC8 and PVC6 exhibited the power-law dependence on the angular frequency ω at 190 and 210 °C, respectively. Correspondingly, the tan δ values did not depend on ω. These temperatures indicate the critical gel temperature T _gel of each system. The critical relaxation exponent n obtained from these data was 0.75 irrespective of PVC content, which was in agreement with the n values reported previously for the low PVC concentration samples. These results suggest that the PVC gels of different plasticizer content have a similar fractal structure. Below T _gel, the gradual melting of the PVC crystallites takes place with elevating temperature, and above T _gel, a densely connected network throughout the whole system disappears. Correspondingly, the elongational viscosity behavior of PVC8 and PVC6 exhibited strong strain hardening below T _gel, although it did not show any strain hardening above T _gel. These changes in rheological behavior are attributed to the gradual melting of the PVC crystallites worked as the cross-linking domains in this physical gel, thereby inapplicability of the of time–temperature superposition for PVC/plasticizer systems.     

Two phase boundary layers in laminar film boiling

The laminar film boiling is analyzed by means of an integral procedure. The method treats the film boiling as a two phase boundary layer problem; thereby the effect of the interfacial shear on the heat transfer rate can be investigated. The problem is attacked by simultaneously solving the vapor and liquid boundary layer equations. An extensive comparison of the predicted results with the exact solutions substantiates the validity of the present integral procedure. Even the details of the velocity and temperature profiles turn out to be in close agreement with the exact solutions.     

Phase structure change and ER effect in liquid crystalline polymer/dimethylsiloxane blends

The mechanism of the electrorheological (ER) effect in two types of liquid crystalline polymer (LCP)/dimethylsiloxane (DMS) blends was investigated by rheological measurements and by structure observation under electric field and shear flow. The results show that the phase structures of these immiscible blends can be categorized into slipping (low viscosity) and non-slipping (high viscosity) states. In the non-slipping state, higher viscosity LCP domains connect the electrodes. In the slipping state, on the other hand, LCP domains do not connect the electrodes and the shear is mainly confined in the lower viscosity DMS domains. The ER effect (electrically induced viscosity increase) originates from the electrically induced slipping to non-slipping transition. In one of the blends, the ER effect occurs only at high shear rate, since this blend is in non-slipping state even under no field if the shear rate is low. Received: 29 April 1997 Accepted: 3 November 1997     

An integral treatment for non-Darcy free convection over a vertical flat plate and cone embedded in a fluid-saturated porous medium

An integral treatment was proposed for analysis of non-Darcy free convection over a vertical flat plate and cone within a fluid-saturated porous medium. A flexible one-parameter family of third order polynomials was employed to cope with vast changes in the velocity and temperature profiles encountered in the Darcy flow limit through to the Forchheimer flow limit. Zero curvature requirement for the temperature profile at the wall was exploited as an auxiliary relation to determine the shape parameter. Comparison of the approximate results with the exact solution reveals a high performance of the present integral procedure for heat transfer rat prediction.