Dielectric properties above the glass transition for a series of epoxide prepolymers

Dielectric properties above the glass transition have been investigated for a series of bisphenol-A type epoxide prepolymers (388 ≤ M?_w ≤ 2640). Dielectric measurements were performed over a frequency range of 50 Hz–1 MHz using a vertical parallel plate cell which was constructed in the laboratory. The dielectric α-relaxation for each prepolymer fits the empirical model of the Havriliak–Negami equation. The temperature dependence of the dielectric relaxation time τ is described by the Williams–Landel–Ferry (WLF) equation as well as that of the direct current conductivity σ, which can be measured using the same cell. The relationship between τ and σ, σ^· τ^m = const, is derived from experimental results. The exponent m, which depends on the molecular weight of the prepolymer, is considered to correspond to the ratio of the segmental mobility to ionic mobility. The dielectric loss ε″ can be used as an indicator of the direct current conduction in the temperatures where the ionic component in ε″ becomes much larger than the dipole one.     

Maturation of the posterolateral spinal fusion and its effect on load-sharing of spinal instrumentation. An in vivo sheep model

We investigated the temporal relationship among the biomechanical, radiographic, and histological properties of a posterolateral spinal fusion mass to elucidate the changes in load-sharing of the spinal instrumentation and that of the fusion mass throughout the healing process. Destabilization of the posterior spinal column and transpedicular screw fixation at the segments between the third and fourth and the fifth and sixth lumbar vertebrae was performed in twenty-four sheep. A posterolateral spinal arthrodesis with use of autologous corticocancellous bone graft was done randomly at one of the two segments; the other segment (without bone graft) served as the instrumented control. Six animals each were killed at four, eight, twelve, and sixteen weeks postoperatively. Biomechanical testing showed that the posterolateral fusion mass had increased mechanical stiffness after the fourth week. The strain on the hardware, measured with use of rods instrumented with strain-gauges, decreased significantly (p < 0.01) beginning at eight weeks. Radiographically, three independent observations of each of the six animals at each time-period showed that, although all of the fusion masses were considered solid unions at sixteen weeks, bridging of trabecular bone was noted during only ten of eighteen observations at twelve weeks, three of eighteen observations at eight weeks, and none of eighteen observations at four weeks. Computerized tomography and histomorphometric analyses demonstrated that mineralization in the fusion mass increased in a linear fashion even after eight weeks. Histologically, the fusion mass consisted predominantly of woven bone at eight weeks; thereafter, it was gradually trabeculated. CLINICAL RELEVANCE: We found a great discrepancy between biomechanical stability and histological maturation of the posterolateral fusion mass. The biomechanical properties of a stable spinal fusion preceded the radiographic appearance of a solid fusion by at least eight weeks, suggesting that immature woven bone provided substantial stiffness to the fusion mass. The spinal instrumentation was subjected predominantly to bending stress rather than to axial stress, and the load-sharing of the spinal instrumentation decreased concurrently with the development of the spinal fusion.     

Residual amounts of chlorophylls and pheophytins in refined edible oils

The quantities of chlorophyll (CHL) A and B, and pheophytin (PHY) A and B in 10 kinds of refined edible oils were estimated by the fluorometric method. The results revealed that CHL and PHY were present in commercial edible oils. PHY A showed the highest content at ca. 67% in total pigments. Compositional ratios of CHL and PHY were similar in different kinds of plant oils. Through the analysis of rapessed oils at every refining step, we determined that PHY is not formed during oil refining. In the autoxidation of soybean oils to which various amounts of CHL mixtures had been added, the peroxide value of tested oils increased in proportion to the total chlorophyll content. In addition, the compositional changes of the 4 components during autoxidation were investigated.     

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.     

Antioxidant effects of chlorophyll and pheophytin on the autoxidation of oils in the dark. I. Comparison of the inhibitory effects

The effects of chlorophyll and pheophytin on the autoxidation of oils in the dark were investigated by oven tests. The results indicated that both chlorophyll and pheophytin show antioxidant activity when methyl linoleate is used as substrate. Furthermore, chlorophyll retarded the oxidative deterioration of triglycerides in rapeseed and soybean oils at 30 C. Among the four chlorophyll derivatives (chlorophylls a and b and pheophytins a and b), chlorophyll a showed the strongest antioxidant activity. The antioxidant effects of chlorophyll and pheophytin depended on the storage temperature and the kinds of oil used as substrate.     

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.     

High-strength–high-modulus polyimide fibers II. Spinning and properties of fibers

The polyimides based on 3,3′,4,4′-biphenyltetracarboxylic dianhydride (BPDA) described in Part I of this series were dissolved in p-chlorophenol and spun into fibers using a coagulating bath of ethanol. The fibers as spun had in general low tenacities and low moduli, but a heat treatment at 300–500°C under tension produced a remarkable increase in strength and modulus, and fibers with a tensile strength of 26 g/den (3.1 GPa) and an initial modulus higher than 1,000 g/den (120 GPa) could be obtained. Thus, the annealed fibers of polyimides are comparable to aramid fibers in mechanical properties. To heating in air and in the saturated steam, the polyimide fibers showed higher resistance than the aramid fibers. The polyimide fibers surpassed the aramid fibers in resistance to acid treatment and ultraviolet (UV) irradiation, but were inferior in resistance to alkali treatment. The annealed fibers of polyimides displayed distinct X-ray diffraction patterns. The chain repeat distance of 20.5 Å determined on the fibers of polyimide prepared from BPDA and o-tolidine, and 20.6 Å determined on the fibers of polyimide derived from BPDA and 3,4′-diaminodiphenyl ether are reasonable when the dimensions of monomeric units and the shapes of the molecular chains are considered. The X-ray reflections of both polyimide fibers were indexed satisfactorily on the basis of postulated unit cells.     

Autoxidation of ethyl eicosapentaenoate and docosahexaenoate

The extent of oxidation of ethyl esters of eicosapentaenoic (EPA) and docosahexaenoic acids (DHA) was compared quantitatively with that of ethyl linoleate (Lo) and ethyl linolenate (Ln) by oxygen uptake and formation of conjugated diene, hydroperoxide and secondary oxidation products. EPA and DHA esters were oxidized rapidly even at 5 C in the dark after an induction period of 3–4 days, while the induction periods of Ln and Lo esters were 20 days and more than 60 days, respectively. Oxygen uptake of EPA and DHA esters after the induction period was 5.2 and 8.5 times faster than that of ethyl Ln, respectively. Hydroperoxides of EPA and DHA esters are much less stable than those of ethyl Lo. The peroxide value is not necessarily a good indication of oxidation in these polyenoic acids because a considerable amount of secondary products is formed at the early stage of oxidation. Polymers were found to be major secondary products in these polyenoic esters.     

Antioxidant effects of chlorophyll and pheophytin on the autoxidation of oils in the dark. II. The mechanism of antioxidative action of chlorophyll

To understand the mechanism of the antioxidant effect of chlorophyll on the autoxidation of oils in the dark, antioxidant activities of several derivatives of chlorophyll were compared. Antioxidant activities were observed in chlorophyll derivatives such as protopor-phyrin methyl ester and its magnesium chelated compound. Porphyrin seems to be an essential chemical structure for the antioxidant activity of chlorophyll. Chlorophyll did not decompose the hydroperoxides, but reduced free radicals such as 1,1-diphenyl-2-picrylhydrazyl. Electron spin resonance spectrum of the π-cation radical was recorded during the oxidation of chlorophyll in methyl linoleate solution. These observations suggest that chlorophyll may act as a hydrogen donor to break the chain reaction.