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     

Association and physical gelation of ABA triblock copolymer in selective solvent

Association behavior and physical gelation mechanism of ABA triblock copolymer dissolved in B-selective solvent have been studied systematically from dilute to moderately concentrated solutions. Static and dynamic light scattering and nuclear magnetic resonance measurements for dilute solutions of poly(methyl methacrylate)-block-poly(tert-butyl acrylate)-block-poly(methyl methacrylate) (PMMA-PtBuA-PMMA) in 1-butanol (PtBuA selective solvent) indicated that PMMA-PtBuA-PMMA chains are molecularly dissolved above 50 °C. With decreasing temperature, the triblock copolymers form associated micelles consisting PMMA associated core and PtBuA shell. Linear dynamic viscoelastic measurements for solutions with moderate concentration (3.9-12.0 wt%) revealed that the system was viscous sol state at 60 °C. Drastic increase of shear storage modulus (G′) occurred with decreasing temperature, and at 25 °C, G′ showed rubbery plateau with weak frequency dependency, means the formation of elastic physical gel. The consistency between the temperature for micelle formation and that at the increase in G′ indicates that the physical gelation is owing to the network formation as the result of the association of PMMA chains and the bridging PtBuA chains connecting the PMMA cores. Master curves for the dynamic moduli were derived by time-temperature superposition along the frequency axis. Just above sol-gel transition concentration (C_gel), the master curves suggest the existence of fairy amount of aggregate that is not incorporated in the macroscopic network. With the increase in polymer concentration, the master curves become to reveal Maxwell-type viscoelasticity with narrow relaxation time distribution, suggesting the formation of transient network with easily generation and destruction of crosslinks. Concentration dependency of the plateau modulus is stronger than the theoretically expected, means the macroscopic transient network grows with polymer concentration by increasing the fraction of elastically effective bridging PtBuA chain above C_gel.     

CeO2–ZrO2 Solid Solution Catalyst for Selective Synthesis of Dimethyl Carbonate from Methanol and Carbon Dioxide

CeO₂–ZrO₂ solid solution catalysts are very effective for the selective synthesis of dimethyl carbonate from methanol and CO₂. The activity was much dependent on the calcination temperature. The higher the calcination temperature, the higher the activity of the catalyst for DMC formation, though the BET surface area is lower on the catalyst calcined at higher temperature.     

EXPERIMENTAL STUDIES ON A NOVEL CHEMICAL HEAT PUMP DRYER USING A GAS-SOLID REACTION

The authors have been studying Chemical Heat Pumps (CHP) from the viewpoints of energy saving and environmental impact. The CHP can store thermal energy in the form of chemical energy by an endothermic reaction, and release it at various temperature levels during heat demand periods by exo/endothermic reactions. The authors have proposed in an earlier study a novel chemical heat pump (CHP) system for environmentally-friendly effective utilization of thermal energy in drying as a chemical heat pump dryer (CHPD). In this exploratory study, we test the effectiveness of operating the proposed CHPDs experimentally. Basic experiments on the CHPDs such as hot dry air production for convective drying are performed on lab-scale CHPD apparatuses using gas-solid reactions in calcium oxide/calcium hydroxide reactant beds. The proposed CHPDs are found to produce hot air by CHP operation for drying. The temperature levels of the produced hot air and the reaction rates/conversions are as good as in the case of hot water supply system using basically same CHP operation. The cold heat for air dehumidification is also found to be generated/recovered by the same CHPD system. The generated heat amounts can be increased by changing the operating conditions although the heat recovery must be enhanced for practical application of CHPDs.     

Novel fatty acid esters of (7E, 12E, 18R, 20Z)-variabilin from the marine sponge Ircinia felix

The methanolic extract of the marine sponge Ircinia felix has yielded nine novel fatty acid esters, (7E, 12E, 18R, 20Z)-variabilin (5Z, 9Z)-22-methyltricosadienoate, (7E, 12E, 18R, 20Z)-variabilin (5Z, 9Z)-tetracosadienoate, (7E, 12E, 18R, 20Z)-variabilin hexadecanoate, (7E, 12E, 18R, 20Z)-variabilin 10-methylhexadecanoate, (7E, 12E, 18R, 20Z)-variabilin 15-methylhexadecanoate, (7E, 12E, 18R, 20Z)-variabilin 14-methylhexadecanoate, (7E, 12E, 18R, 20Z)-variabilin 9-octadecenoate, (7E, 12E, 18R, 20Z)-variabilin octadecanoate, and (7E, 12E, 18R, 20Z)-variabilin 2,11-dimethyloctadecanoate, along with the recently described (7E, 12E, 18R, 20Z)-variabilin 11-methyloctadecanoate. The characterization of the new fatty acids (5Z, 9Z)-22-methyltricosadienoic and 2,11-dimethyloctadecanoic acids is also described. The chemical structures were determined by extensive spectroscopic, chromatographic, and chemical analyses.     

Increased hepatic β-oxidation of docosahexaenoic acid, elongation of eicosapentaenoic acid, and acylation of lysophosphatidate in rats fed a docosahexaenoic acid-enriched diet

Rats were fed a diet supplemented with corn oil (n-3 deficient), soy oil, or a mixture containing 8% 22∶6n-3 ethyl ester for 6 wk. The hepatic capacities for the β-oxidation and synthesis of 22∶6n-3, in addition to the acylation of lysophosphatidate, were tested in vitro. In rats that were fed a 22∶6n-3-enriched diet, both the β-oxidation of 22∶6n-3 and elongation of 20∶5n-3 were enhanced compared to those in rats fed the other diets. Acylation of lysophosphatidate was also enhanced in rats fed a 22∶6n-3-enriched diet, while the rate of dephosphorylation of phosphatidate was not changed. The amount of 22∶6n-3 in the liver was much less than that consumed in a docosahexaenoic acid-enriched diet. These results suggest that a significant amount of dietary 22∶6n-3 was degraded via β-oxidation, and that a portion of the retroconverted 20∶5n-3 was recycled for the synthesis of 22∶6n-3. The recycling of 20∶5n-3 might contribute to the low level of 22∶6n-3 in rats fed an n-3-deficient diet.     

Deterioration of diacylglycerol‐ and triacylglycerol‐rich oils during frying of potatoes

The stabilities of a commercial diacylglycerol‐rich oil (DAG) and a salad oil (TAG) that had been prepared from a mixture of rapeseed and soybean oils were compared while frying potatoes at 180 °C for 3 h. The representative chemical and physical characteristics of the oils were assessed before and after frying, together with the amount of volatile aldehydes in the exhaust of frying. Among the deterioration indications, the carbonyl value, polymer content, and residual polyunsaturated fatty acid content were similar and not significantly different between the TAG and DAG. On the other hand, the characteristics relating to free fatty acids, i.e. the acid value and emission of chemiluminescence at 100 °C, were greater and the smoke and flash points were lower in the DAG than in the TAG. An irritating odor was generated from the DAG after 1 h of frying and got stronger as frying continued. These results suggested that DAG more easily forms free fatty acids under frying conditions than TAG.     

Cerebral Hyperperfusion after Revascularization Inhibits Development of Cerebral Ischemic Lesions Due to Artery-to-Artery Emboli during Carotid Exposure in Endarterectomy for Patients with Preoperative Cerebral Hemodynamic Insufficiency: Revisiting the “Impaired Clearance of Emboli” Concept

The purpose of the present study was to determine whether cerebral hyperperfusion after revascularization inhibits development of cerebral ischemic lesions due to artery-to-artery emboli during exposure of the carotid arteries in carotid endarterectomy (CEA). In patients undergoing CEA for internal carotid artery stenosis (≥70%), cerebral blood flow (CBF) was measured using single-photon emission computed tomography (SPECT) before and immediately after CEA. Microembolic signals (MES) were identified using transcranial Doppler during carotid exposure. Diffusion-weighted magnetic resonance imaging (DWI) was performed within 24 h after surgery. Of 32 patients with a combination of reduced cerebrovascular reactivity to acetazolamide on preoperative brain perfusion SPECT and MES during carotid exposure, 14 (44%) showed cerebral hyperperfusion (defined as postoperative CBF increase ≥100% compared with preoperative values), and 16 (50%) developed DWI-characterized postoperative cerebral ischemic lesions. Postoperative cerebral hyperperfusion was significantly associated with the absence of DWI-characterized postoperative cerebral ischemic lesions (95% confidence interval, 0.001–0.179; p = 0.0009). These data suggest that cerebral hyperperfusion after revascularization inhibits development of cerebral ischemic lesions due to artery-to-artery emboli during carotid exposure in CEA, supporting the “impaired clearance of emboli” concept. Blood pressure elevation following carotid declamping would be effective when embolism not accompanied by cerebral hyperperfusion occurs during CEA.     

Correlations of Hepatic Hemodynamics,Liver Function,and Fibrosis Markers in Nonalcoholic Fatty Liver Disease: Comparison with Chronic Hepatitis Related to Hepatitis C Virus

The progression of chronic liver disease differs by etiology. The aim of this study was to elucidate the difference in disease progression between chronic hepatitis C (CHC) and nonalcoholic fatty liver disease (NAFLD) by means of fibrosis markers, liver function, and hepatic tissue blood flow (TBF). Xenon computed tomography (Xe-CT) was performed in 139 patients with NAFLD and 152 patients with CHC (including liver cirrhosis (LC)). The cutoff values for fibrosis markers were compared between NAFLD and CHC, and correlations between hepatic TBF and liver function tests were examined at each fibrosis stage. The cutoff values for detection of the advanced fibrosis stage were lower in NAFLD than in CHC. Although portal venous TBF (PVTBF) correlated with liver function tests, PVTBF in initial LC caused by nonalcoholic steatohepatitis (NASH-LC) was significantly lower than that in hepatitis C virus (C-LC) (p = 0.014). Conversely, the liver function tests in NASH-LC were higher than those in C-LC (p < 0.05). It is important to recognize the difference between NAFLD and CHC. We concluded that changes in hepatic blood flow occurred during the earliest stage of hepatic fibrosis in patients with NAFLD; therefore, patients with NAFLD need to be followed carefully.     

Discovery of a Novel Scaffold as an Indoleamine 2,3‐Dioxygenase 1 (IDO1) Inhibitor Based on the Pyrrolopiperazinone Alkaloid,Longamide B

Indoleamine 2,3‐dioxygenase 1 (IDO1) has emerged as a key target for cancer therapy, as IDO1 plays a critical role in the capacity of tumor cells to evade the immune system. The pyrrolopiperazinone alkaloid longamide B and its derivatives were identified as novel IDO1 inhibitors based on docking studies and small library synthesis. The thioamide derivative showed higher IDO1 inhibitory activity than longamide B, and displayed an activity similar to that of a representative IDO1 inhibitor, 1‐methyl‐tryptophan. These results suggest that the pyrrolopiperazinone scaffold of longamide B could be used in the development of IDO1 inhibitors.