Studies on sublimation of disperse dye out of dyed polymers. I. Rate of sublimation and amorphous transition points of poly(ethylene terephthalate)

Four samples of poly(ethylene terephthalate) film of various crystallinities and orientation were dyed with p-nitroaniline and disperse dyes. When these films were heated under a 2–3 × 10^?3 mm Hg vacuum at a specified temperature T, the dye sublimed out of the dyed specimen. The amount (M_t/M_∞) of sublimed dye is in linear proportion to the square root of the sublimation time, t^½, where M_t and M_∞ are the amounts of dye sublimed for times t and t = ∞. The diffusion coefficient D, calculated from the slope of the above plot, is independent of the dye concentration of the film. When log D is plotted against 1/T°K over the temperature range 320–520°K, the relation is composed of two to four intersecting lines with the slope decreasing with elevation of temperature and with the breaks at about 89°–98°, 122°–135°, 155° and 175°–176°C. These breaks are the amorphous transitions: the first is the glass transition temperature T_g, the second and the fourth are the amorphous transitions corresponding to the crystalline transition points, i.e., the cold crystallization temperature and the smectic–triclinic transition temperature. With some exceptions, these amorphous transitions are found also by dilatometry and electrical conductivity measurements. The apparent activation energy for diffusion decreases from about 100 kcal/mole for the glass state to 22–24 kcal/mole for the region above 180°C. The activation energy for each region changes slightly with the size of dye molecule and the crystallinity and orientation of the film.     

Antitumor activity of synthetic alkylphospholipids with or without PAF activity

1-O-Octadecyl-2-O-methyl-sn-glycero-3-phosphocholine (ET-18-OMe) has been reported to possess definite antitumor activity in vivo. Twenty-two alkyl lysophospholipid analogs were chemically synthesized, and their antitumor activity against mouse experimental tumors (Sarcoma 180, MM46, P388) was examined. Among them, 1-O-octadecyl-2-O-acetoacetyl-rac-glycerol-3-phosphocholine was found to show antitumor activity similar to ET-18-OMe with less acute toxicity. Intravenous injection of the ET-18-OMe withsn-3 configuration retarded the subcutaneous growth of Sarcoma 180 cells effectively, while the growth inhibition by thesn-1 isomer was much less effective. This stereospecificity was similar to that observed in their activities as platelet-activating factor (PAF) agonists. The acetoacetyl compound, another PAF agonist, showed similar stereospecific antitumor action in vivo. These findings suggest that some alkyl lysophospholipids may activate host cells to a cytostatic stage against tumor cells in vivo through binding to a PAF receptor. Our preliminary results indicated that the responsible cells under these conditions might be primarily immature macrophages present in the bone marrow. No appreciable or even adverse stereospecificity was observed in the different sets of experiments where the activity of ET-18-OMe against MM46 tumor cells in vivo or the direct cytotoxicity against human promyelocytic leukemia HL-60 cells in vitro was examined. Under, some conditions, the antitumor activity of ET-18-OMe in vivo may be revealed through direct cytotoxicity and/or modulation of the host defense system by “nonspecific” mechanisms. Some alkylphospholipids without PAF activity may also show antitumor activity through similar, “nonspecific” mechanisms.     

Carbon molecular sieve membranes derived from trimethylsilyl substituted poly(phenylene oxide) for gas separation

Carbon molecular sieve membranes for gas separation prepared using poly(phenylene oxide) (PPO) as precursor have been examined. The PPO precursor was modified by introducing a trimethylsilyl (TMS) substituent and its effect on the gas transport property of the resulting carbon membrane was examined. TMS-substituted PPO (TMSPPO) was prepared in a high yield by a simple one-step reaction, and its carbon membrane was successfully fabricated. The modification improved the gas permeability of the resulting membrane which also exhibited excellent O₂/N₂ and CO₂/CH₄ separation performance comparable to those of polyimide-derived carbon membranes. From the analysis of the microstructure of the TMSPPO carbon membranes, it is believed that the TMS groups improve gas diffusivity by increasing the micropore volume.     

Guinea pig bone marrow cells treated with platelet-activating factor generate factor(s) which affects their DNA synthesis and microbicidal activity

We have previously reported that platelet-activating factor (PAF) induces proliferation and microbicidal activity of guinea pig bone marrow cells. In the present study, we have found that the conditioned medium of PAF- or nonmetabolizable PAF agonist-treated guinea pig bone marrow cells augmented DNA synthesis and induced microbicial activity of bone marrow cells. A PAF specific antagonist, CV-6209, inhibited generation of the active conditioned medium by PAF. Addition of the PAF antagonist only partially suppressed the augmentative effect of the active conditioned medium on DNA synthesis; this is consistent with the fact that, because of the rapid breakdown, no appreciable amount of PAF remained in the conditioned medium of PAF-treated cells. Although mouse bone marrow cells did not respond to PAF unlike guinea pig cells, their DNA synthesis was significantly enhanced by the conditioned medium of PAF-treated guinea pig bone marrow cells. Thus, some newly generated factor(s) distinct from the originally inoculated PAF seemed to modulate the bioactions of PAF on bone marrow cells. An appreciable amount of PAF was produced by calcium ionophore-treated guinea pig bone marrow cells. These findings indicate that PAF synthesized in guinea pig bone marrow cells induces generation in the cells of some factor(s) which affects proliferation or microbicidal activity. Presented at The Third International Conference on Platelet-Activating Factor and Structurally Related Ether Lipids, Tokyo, Japan, May 1989.     

Toughening of cycloaliphatic epoxy resins by poly(ethylene phthalate) and related copolyesters

Poly(ethylene phthalate) (PEP) and poly(ethylene phthalate–co‐ethylene terephthalate) were used to improve the brittleness of the cycloaliphatic epoxy resin 3,4‐epoxycyclohexylmethyl 3,4‐epoxycyclohexane carboxylate (Celoxide 2021?), cured with methyl hexahydrophthalic anhydride. The aromatic polyesters used were soluble in the epoxy resin without solvents and effective as modifiers for toughening the cured epoxy resin. For example, the inclusion of 20 wt % PEP (MW, 7400) led to a 130% increase in the fracture toughness (K_IC) of the cured resin with no loss of mechanical and thermal properties. The toughening mechanism is discussed in terms of the morphological and dynamic viscoelastic behaviors of the modified epoxy resin system. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 388–399, 2002; DOI 10.1002/app.10363     

Free energy perturbation study on a Trp-binding mutant (Ser88 ->Cys) of the trp-repressor

The Ser⁸⁸Cys mutant of the trp-repressor showed a lower affinityfor the corepressor than the wild-type repressor [G = 1.7 ±0.3 kcal/mol, Chou and Matthews (1989) J. Biol. Chem., 264,18314–18319].A molecular dynamics/free energy cycle perturbation study wasperformed to understand the origin of the decreased affinity.A value (G = 1.58 ± 0.28 kcal/mol) comparable with theexperimental value was obtained by the simulation. Free energycomponent analysis revealed that destabilization of the vander Waals interaction between Ser⁸⁸ and Trp¹⁰⁹ (corepressor)mainly contributed to the decreased affinity of the mutant.The rotational transition of the hydroxyl (sulfhydryl) groupof Ser⁸⁸ (Cys⁸⁸) during the simulations affected the contributionsof Arg⁸⁴ and water to the free energy change in the aporepressorand those of Arg⁸⁴ and Trp ¹⁰⁹ to that in the holorepressor.However, the contributions from different residues compensatedeach other, and the total free energy changes were almost invariablein the various simulations.     

Shear-rate dependence of first normal stress difference of poly(isoprene-b-styrene) in solution near the order-disorder transition temperature

Viscoelastic properties of poly(isoprene-b-styrene) in dioctylphthalate under steady shear flow were measured near the order—disorder transition temperature. In ordered states, first normal stress difference N₁ is proportional to shear rate at low region, but becomes proportional to at the high region, similar to the N₁ behaviour of polymer blends undergoing shear-induced homogenization. Because the existence of microdomains was confirmed at the high region by the flow birefringence method, it is concluded that the above N₁ behaviour is not caused by shear-induced homogenization, but is probably caused by the shear-induced alignment of the microdomain structure.     

Phase evolution and <110>-orientation mechanism in RTGG-processed BaTiO3 ceramics with electrical properties

The <110>-oriented BaTiO₃ ceramics were fabricated using BaCO₃ matrix and H_1.08Ti_1.73O₄.nH₂O (HTO) template particles, and the mechanism of BaTiO₃ phase formation was investigated. The dielectric, ferroelectric, and piezoelectric properties were also investigated. The transformation of the HTO phase into the TiO₂ bronze or TiO₂ (B) phase was observed at 600°C, where the BaTiO₃ nucleation was accompanied by the formation of a Ba₂TiO₄ phase. The TiO₂ phase reacted with the Ba₂TiO₄ phase at 800°C to give a BaTiO₃ phase, whereas its reaction with the BaTiO₃ resulted in the formation of BaTi₂O₅ phase that got decomposed into BaTiO₃ and Ba₆Ti₁₇O₄₀ phase at sintering temperature ≥1300°C. Sintering with samples’ embedding in BaTiO₃ powders prevented the formation of the Ba₆Ti₁₇O₄₀ secondary phase. The crystallographic orientation along the <110> direction (F₁₁₀) was developed by the epitaxial grain growth mechanism. In addition to the contribution of the grain-size increment for enhancing the F₁₁₀, the preservation of the platelike structure was also found to have a significant impact. The ceramics prepared by the embedded sintering (grain size ≈12.4 µm and F₁₁₀ = 83%) exhibited the room-temperature dielectric constant of 1708 and piezoelectric strain constant of 445 pm/V, which are higher than those of the BaTiO₃ ceramics with randomly oriented grains.     

Measurement of self-diffusion coefficients in Li ionic conductors by using the short-lived radiotracer of 8Li

For the effective use of short-lived radioactive beams, soon to be available at the Tokai Radioactive Ion Accelerator Complex, the authors have developed a radiotracer method for diffusion studies in solids. The experimental test was performed by the measurement of the diffusion coefficients of Li in a sample of the compound βLiAl using an α-emitting radiotracer of ⁸Li (T_1/2=0.84 s). It was found that the time-dependent yields of the α particles from the diffusing ⁸Li that was initially implanted in the sample could be used as a measure of the diffusivity of the tracer in a nondestructive way. The method was applied to measure the self-diffusion coefficients of Li in βLiGa, and for investigating how the Li diffusion in the Li ionic conductors is affected by the concentration of atomic defects (i.e., the existence of the atomic vacancies of Li and the defects in Ga sites that are replaced by Li).     

Dynamic hybridization of MILES and RANS for predicting airfoil stall

Hybridization comprised of an algebraic turbulence model based on the Reynolds average Navier-Stokes (RANS) equations with a monotonically integrated large eddy simulation (MILES) is proposed to simulate transient fluid motion during separation and vortex shedding at high Reynolds numbers. The proposed hybridization utilizes the Baldwin-Lomax model with the Degani-Schiff modification as the RANS model in the near-wall region and a MILES far from the wall. Although the hybridization is assumed to be a MILES with wall modeling, the transition line between the RANS and the MILES modes is determined by the turbulent intensity that is dominated by the large eddies in the grid-scale. This hybrid model is applied to the flows past three different types of airfoils (NACA63₃-018, NACA63₁-012 and NACA64A-006) near stall, at a chord Reynolds number of Re = 5.8 × 10⁶. These airfoils are classified as trailing-edge-stall, leading-edge-stall and thin-airfoil-stall airfoils, respectively. The computed results are compared with wind tunnel experiments. The hybrid model successfully demonstrates accurate stall angle and surface pressure distribution predictions near the stall for each type of airfoil. The airfoil simulation results confirmed that the hybrid model provides a better prediction than the RANS model for unsteady turbulent flows with separation and vortex shedding simulations.