Molecular simulation of hydrogen adsorption in organic zeolite

The adsorption of molecular hydrogen on model zeolites has been simulated employing Grand Canonical Monte Carlo (GCMC) procedure. The effects of cation type, available volume, surface area, temperature, pressure and pre-adsorbed organics such as benzene on the hydrogen uptake are analyzed. The hydrogen adsorption can be affected mainly by the available volume and surface area per g-zeolite at the same temperature and pressure. Increase of temperature results in the decrease of sorption intensity and capacity. The adsorption capacity correlates well with the pressure with high linearity at room temperature. Adsorption is lowered by the pre-adsorbed benzene molecule. The orientation and the number of benzene molecule in zeolite affect the adsorption capacity. The organic zeolite with larger available volume shows larger adsorption capacity.     

Prooxidant effects of inorganic chromium compounds in the autoxidation of methyl linoleate

The prooxidant property of inorganic chromium compounds was determined in methyl linoleate free from natural antioxidants and metals. Prooxidant properties of inorganic chromium compounds appeared in order of sodium chromate > chromium (VI)-oxide > chromium chloride > potassium chromate > chromium (III)-oxide > potassium dichomate. In comparison with the control, additions of chromium compounds induced different amounts of autoxidation products derived from methyl linoleate, such as small amounts of hydroperoxides and conjugated dienes and large amounts of hydroxy groups,α,β,γ,δ-unsaturated carbonyls, isolatedtrans double bonds, polymers, and free radicals. From these analytical data, the catalysis of chromium compounds in the autoxidation of methyl linoleate seemed to be based on their abilities of abstracting a hydrogen from methyl linoleate and decomposing hydroperoxides derived from the autoxidation of methyl linoleate.     

Bis-(monoacylglyceryl) phosphate and acyl phosphatidylglycerol isolated from human livers of lipidosis induced by 4,4′-diethylaminoethoxyhexesterol

Bis-(monoacylglyceryl) phosphate and acyl phosphatidylglycerol were isolated from the liver of two patients with lipidosis induced by 4,4′-diethylaminoethoxyhexesterol. Identification was based upon the results of alkaline hydrolysis, acetolysis, IR spectrometry, and upon the determination of molar ratio of phosphorus-glycerol-ester. The contents of the bis-(monoacylglyceryl) phosphate were 10 and 16% total phospholipid phosphorus in them. The bis-(monoacylglyceryl) phosphate contained mainly docosahexaenoic (42%), oleic (29%), and linoleic acid (14%) and had the hemolytic activity of ca. one-eighth lysolecithin from egg yolk. Acidic lipids from the liver also were found to contain a lipid which is less polar than bis-(monoacylglyceryl) phosphate. The results of lipid analysis showed that the lipid possessed the structure of an acyl phosphatidylglycerol, and its content was ca. 2% total phospholipid phosphorus. Accumulation of 4,4′-diethylaminoethoxyhexesterol and its derivatives was found in clinical cases by thin layer chromatography and IR spectrometry. This fact suggested that human liver has an ability to metabolize the drug.     

Synthesis and physicochemical characterization of amphiphilic block copolymer self‐aggregates formed by poly(ethylene glycol)‐block‐poly(ϵ‐caprolactone)

Diblock copolymers with different poly(ε‐caprolactone) (PCL) block lengths were synthesized by ring‐opening polymerization of ε‐caprolactone in the presence of monomethoxy poly(ethylene glycol) (mPEG‐OH, MW 2000) as initiator. The self‐aggregation behaviors and microscopic characteristics of the diblock copolymer self‐aggregates, prepared by the diafiltration method, were investigated by using ¹H NMR, dynamic light scattering (DLS), and fluorescence spectroscopy. The PEG–PCL block copolymers formed the self‐aggregate in an aqueous environment by intra‐ and/or intermolecular association between hydrophobic PCL chains. The critical aggregation concentrations of the block copolymer self‐aggregate became lower with increasing hydrophobic PCL block length. On the other hand, reverse trends of mean hydrodynamic diameters were measured by DLS owing to the increasing bulkiness of the hydrophobic chains and hydrophobic interaction between the PCL microdomains. The partition equilibrium constants (K_v) of pyrene, measured by fluorescence spectroscopy, revealed that the inner core hydrophobicity of the nanoparticles increased with increasing PCL chain length. The aggregation number of PCL chain per one hydrophobic microdomain, investigated by the fluorescence quenching method using cetylpyridinium chloride as a quencher, revealed that 4–20 block copolymer chains were needed to form a hydrophobic microdomain, depending on PCL block length. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 99: 3520–3527, 2006     

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.     

Pervaporation study of water and tert‐butanol mixtures

The permeation behavior of water/tert‐butanol mixture through Sulzer Pervap2510 hydrophilic poly(vinyl alcohol) membranes was investigated and the effects of feed composition and temperature on separation efficiency of the membranes were studied. The pervaporation experiments were carried out with feed water content varying from 0 to 20 wt % according to the existing industrial needs and with the feed temperature from 60 to 100°C. Over this range, both water flux and separation factor increased with increasing water content and feed temperature. These phenomena may be attributed to (1) the strong interaction between water and the membrane, (2) the decoupling effect of the permeants and the membrane at elevated temperatures, and (3) the steric hindrance effect of branch chain alcohol. The permeability ratio (the ideal separation factor) of water to tert‐butanol across the membrane was calculated and found to follow the same relationship with increasing temperature and water content. Both flux and separation factor obtained from the Pervap2510 membrane in this study were much higher than previous reported values, possible causes for which were analyzed. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 91: 4082–4090, 2004     

Radiation-induced oxidative degradation of isotactic polypropylene

Gas evolution, oxygen consumption, and change of mechanical properties were studied for the γ-ray irradiation of isotactic polypropylene from ⁶⁰Co under various conditions, such as vacuum, air, and oxygen at room temperature. For irradiation under vacuum, G(H₂) = 2.9 and G (CH₄) = 0.09; the G values for other gases were very small. In the presence of oxygen, G(H₂) was the same, and the G values for other hydrocarbons were two times those under vacuum. The G values of oxidative products and oxygen consumption were G(CO₂) = 2.5, G(CO) = 1.1, and G(O₂) = 50 at oxygen pressure of 500 torr and were dependent on oxygen pressure. With irradiation under vacuum at 2–3 Mrad, mechanical properties scarcely changes immediately after irradiation but degrade gradually with storage time in air at room temperature.     

气体作冷却润滑剂的绿色切削试验

为实现绿色切削,研究了无污染、无危害的冷却润滑技术.采用氮气、氧气、二氧化碳气、氩气及过热水蒸气作冷却润滑剂,进行了单因素切削试验.试验结果表明,这些气体冷却润滑剂可以减小切削变形、切削力,降低切削温度,改善加工表面形貌.根据试验结果和冷却润滑作用机理分析可知,气体在切削中具有一定的冷却润滑作用,同时具有来源广泛、无毒害和污染、不用回收处理等绿色特点,故气体具备绿色切削的潜力.     

SAPMAC法蓝宝石单晶的生长、检测与超声震动加工

分析SAPMAC法生长大尺寸蓝宝石晶体的工艺技术,并对制备的晶体质量进行了检测与分析.研究结果表明:采用SAPMAC法生长的蓝宝石晶体结构完整,FHWM值很小,只有11arcsec;缺陷密度在102/cm2水平,纯度高于99.995%,常温下晶体在3～5μm波段红外透过率高于85%;用超声振动加工技术对大尺寸蓝宝石单晶进行加工,设计了专用金刚石磨削复合刀具,提高了加工效率.     

Control of molecular weight distribution of isotactic polypropylene obtained by a MgCl2-supported TiCl4 catalyst

It is of great importance in propene polymerization to control molecular weight and molecular weight distribution as well as isotacticity. Propene polymerization was carried out with an isospecific MgCl₂/TiCl₄-Cp₂TiMe₂ catalyst in the presence of various kinds of external Lewis bases. It was found that the molecular weight distribution of the isotactic polymer could be controlled while retaining high activity, high isospecificity and high molecular weight only by changing the kind and/or amount of the Lewis bases. © 1997 Elsevier Science Ltd.