Uptake by macrophages of low-density lipoprotein damaged by nitrogen dioxide in air

In order to know whether nitrogen dioxide, an environmental and endogenous free radical toxin, can participate in the formation of atherosclerotic lesions, damage to low-density lipoprotein (LDL) by nitrogen dioxide and uptake of the damaged LDL by macrophages were investigated. A solution of LDL at pH 7.5 was exposed to an atmosphere of nitrogen dioxide (70 ppm) in air at 37°C for 5 or 10 h. Lipid oxidation was induced by the exposure as assessed by the formation of thiobarbituric acid reactive substances. Apolipoprotein B was covalently cross-linked via nondisulfide bonds. Fluorescence analysis showed that tryptophan residues were extensively decreased, and amino acid analysis indicated that the contents of histidine, lysine, and tyrosine residues were decreased by 30–40, 10–20, and 20–30%, respectively. Binding of LDL to thioglycolate-induced mouse peritoneal macrophages was markedly increased by the exposure as observed by the binding of mouse erythrocytes coated with LDL. The activity of LDL to convert macrophages into lipid-laden foam cells was also increased by the exposure. Modification of lysine residues of apo B with lipid oxidation products formed by the exposure may be responsible for the uptake by macrophages. The results suggest the possibility that exposure of LDLin vivo to nitrogen dioxide participates in the formation of atherosclerotic lesions.     

Influence of vitamin E and nitrogen dioxide on lipid peroxidation in rat lung and liver microsomes

Rat lung and liver microsomes were used to examine the effects of dietary vitamin E deficiency on membrane lipid peroxidation. Microsomes from vitamin-E-deficient rats displayed increased lipid peroxidation in comparison to microsomes from vitamin-E-supplemented controls. The extent of lipid peroxidation, as determined by measurement of thiobarbituric acid reacting materials, was enhanced by addition of reduced iron and ascorbate (or NADPH). Rats fed a vitamin-E-supplemented diet and exposed to 3 ppm NO₂ for 7 days did not exhibit increases in microsomal lipid peroxidation compared to air-breathing controls. However, increases were found in microsomes prepared from rats fed a vitamin-E-deficient diet and exposed to NO₂. Lung microsomes from vitamin-E-fed rats contained almost 10 times as much vitamin E as liver microsomes when expressed in terms of polyunsaturated fatty acid content. The extent of lipid peroxidation was, in turn, considerably less in lung than in liver microsomes. Lipid peroxidation in lung microsomes from vitamin-E-deficient rats was comparable to liver microsomes from vitamin-E-supplemented rats as was the content of vitamin E in these respective microsomal samples. A combination of vitamin E deficiency and NO₂ exposure resulted in the greatest increases in lung and liver microsomal lipid peroxidation with the largest relative increases occurring in lung microsomes. An inverse relationship was found between the extent of lipid peroxidation and vitamin E content. Most of the peroxidation in lung microsomes appeared to proceed nonenzymatically whereas peroxidation in liver was largely enzymatic. Vitamin E appears to be assimilated by the lung during oxidant inhalation, but with dietary vitamin E deprivation, the margin for protection in lung may be less than in liver.     

Epoxides as products of lipid autoxidation in rat lungs

The nature and content of lipid epoxides in rat lung were examined in air-breathing control rats and those exposed to nitrogen dioxide. Exposure to 6.5 ppm NO₂ for 24 hr resulted in significantly greater epoxide content in a number of lipid classes. It is proposed that lipid autoxidation in lung tissues may contribute to the levels of epoxide-containing lipids. Furthermore, the processes involved in epoxide formation may be predicted from autoxidation studies utilizing a system of unsaturated fatty acid monolayers on silica gel which serves as a model for biomembranes. The findings indicate that exposure to oxidizing gases can lead to an accumulation of lipid epoxides in both lung parenchymal tissue and on the alveolar surface.     

Harmful by-products in selective catalytic reduction of nitrogen oxides by olefins over alumina

The selective reduction of nitrogen dioxide and nitrogen monoxide by olefins (ethene, propene) has been studied over two different -aluminium oxides in the temperature range 473–873 K. Nitrogen dioxide was reduced more effectively than nitrogen monoxide with both, ethene and propene, as a reductant. At temperatures exceeding 700 K, ammonia was formed as a by-product over one type of alumina. Concentrations in the range 30–40 ppm were determined for propene in combination with both, NO and NO₂, while no ammonia was produced with ethene as a reductant. In addition, significant formation of hydrogen cyanide up to 70 ppm was observed with propene over both aluminium oxides starting from either NO or NO₂. In contrast, hydrogen cyanide formation remained below 10 ppm with ethene as a reductant. Nitrous oxide formation did not exceed 10 ppm for all investigations. The results show that for alumina catalysts ethene is a more suitable reductant than propene due to its lower tendency to form undesired by-products.     

Effect of vitamin E on pentane exhaled by rats treated with methyl ethyl ketone peroxide

One useful method to monitor in vivo lipid peroxidation is the measurement of volatile hydrocarbons, mainly pentane and ethane, that derive from unsaturated fatty acid hydroperoxides. Vitamin E, the biological antioxidant, inhibits lipid peroxidation and the production of pentane and ethane. The rates of pentane production by male Sprague-Dawley rats fed a diet that contained 10% vitamin E-stripped corn oil and 0, 1, 3, 5 or 10 IU dl-α-tocopherol acetate/kg were monitored over a 12-wk period. During the eleventh and twelfth weeks, the rats were injected intraperitoneally with 3.3 and 13 mg of methyl ethyl ketone peroxide (MEKP)/kg body wt, respectively. Pentane production was then measured at intervals over a 50-min period, and the total amount of pentane produced over this time interval was estimated. An asymptotic function was found to describe the relationship between exhaled pentane and the low levels of dietary vitamin E that were fed to the rats. As measured by pentane production, rats had a higher minimal vitamin E requirement after they were treated with the potent peroxidation initiator MEKP than they did prior to treatment. The level of pentane exhaled by rats injected with 13 mg MEKP/kg body wt was significantly correlated with kidney and spleen tocopherol levels.     

Volatile hydrocarbon and carbonyl products of lipid peroxidation: A comparison of pentane,ethane, hexanal,and acetone as in vivo indices

A study was undertaken to determine whether respiratory hexanal and acetone as well as pentane and ethane could be measured as potential indices of lipid peroxidation in vivo. The tests of induction of lipid peroxidation in rats included injection of iron-dextran and the vitamin E deficiency status. Injection of 460 mg of iron/100 g body wt over a 28-day period increased pentane and ethane production 4- and 6-fold, respectively. Hexanal production was increased 7-fold after injection of 60 mg of iron/100 g body wt, and then it fell back to the preinjection level in spite of continued injection of iron-dextran. Acetone production was lower in iron-injected rats than in controls, and it was ca. 10-fold higher in fasted vitamin E-deficient rats than in vitamin E-supplemented rats, being ca 48 and 5 nmol/100 g/min, respectively. It was observed that halomethane injection did not increase hexanal production, while acetone and pentane production were increased. Pentane and hexanal, but not acetone, were found to arise from decomposition of linoleic acid hydroperoxide in vitro. It was concluded that hydrocarbon gases are better indices of lipid peroxidation than hexanal, which is enzymatically metabolized, and acetone, the production of which is dominated by factors such as altered carbohydrate metabolism.     

The reaction of low levels of nitrogen dioxide with methyl linoleate in the presence and absence of oxygen

The reaction of methyl linoleate with low levels of nitrogen dioxide in a carrier gas, such as helium or air, at nitrogen dioxide concentrations ranging from 2 to 228 ppm was studied and the products formed were monitored. In both aerobic and anaerobic conditions, low concentrations of nitrogen dioxide reacted with methyl linoleate predominately to form allylic products. When a 1∶1 mixture of methyl palmitate/methyl linoleate was layered over an aqueous buffer and a nitrogen dioxide stream was passed from underneath, so that the stream passed through the aqueous layer before contacting the organic layer, allylic products again predominated. In the absence of air, the allylic products consisted of allylic nitro and nitrite derivatives of linoleate, whereas in the presence of air, allylic hydroperoxides were the principal products. The findings suggest that fatty acids with doubly allylic hydrogen atoms react preferentially by a hydrogen atom abstraction reaction rather than by the addition of nitrogen dioxide to a double bond.     

Effect of initial slight oxidation on stability of polyunsaturated fatty acid/protein mixtures under controlled atmospheres

A mixture of unsaturated fatty acids (FA), mainly linolenic acid, and bovine serum albumin (BSA) was incubated under several different atmospheres to study the effect of these atmospheres on the stability of FA to oxidation. Four experiments were carried out simultaneously, which consisted of the incubation of the FA/BSA mixture under air, nitrogen, air in the presence of 200 ppm of butylated hydroxytoluene, and air for 6 h and then under nitrogen. The four experiments were tested for lipid oxidation and color changes by measuring absorbances at 234 and 270 nm, formation of thiobarbituric acid-reactive substances, and color differences and yellowness index. The samples that were oxidized with air before storage under nitrogen were the most stable against lipid peroxidation and exhibited the smallest color changes. These results suggest that a slight and controlled lipid oxidation improved the oxidative stability of FA/BSA mixtures.     

Effect of initial slight oxidation on stability of polyunsaturated fatty acid/protein mixtures under controlled atmospheres

A mixture of unsaturated fatty acids (FA), mainly linolenic acid, and bovine serum albumin (BSA) was incubated under several different atmospheres to study the effect of these atmospheres on the stability of FA to oxidation. Four experiments were carried out simultaneously, which consisted of the incubation of the FA/BSA mixture under air, nitrogen, air in the presence of 200 ppm of butylated hydroxytoluene, and air for 6 h and then under nitrogen. The four experiments were tested for lipid oxidation and color changes by measuring absorbances at 234 and 270 nm, formation of thiobarbituric acid-reactive substances, and color differences and yellowness index. The samples that were oxidized with air before storage under nitrogen were the most stable against lipid peroxidation and exhibited the smallest color changes. These results suggest that a slight and controlled lipid oxidation improved the oxidative stability of FA/BSA mixtures.     

Accelerated test method for resistance of plastics to nitrogen dioxide

The discoloration produced by the exposure of plastics to a polluted atmosphere containing nitrogen oxides and other gases is well known. New formulations with increased resistance to such discoloration require reliable accelerated tests for characterization of additives and products. The new procedure is based on an exposure of plastics to an atmosphere with a controlled concentration of nitrogen dioxide and evaluation of subsequent discoloration by optical measurements.     

Kinetic separation of carbon dioxide from hydrocarbons using carbon molecular sieve

Experimental results are reported on a pressure swing adsorption (PSA) process using carbon molecular sieve (CMS) for the separation of a gas mixture containing carbon dioxide, hydrocarbons (methane, ethane, propane, etc.) and nitrogen. This PSA process has direct applications in carbon dioxide removal or purification from landfill gas, natural gas processing plants and tertiary oil recovery effluent streams. The CMS-based PSA process separates the carbon dioxide in a single stage by using the differences in component diffusivities. This approach, therefore, provides a significant advantage compared to conventional equilibrium adsorption processes which require one separation stage for removing components such as ethane and propane that are more strongly adsorbed than carbon dioxide and another separation stage for removing components such as methane and nitrogen that are less strongly adsorbed than carbon dioxide. The CMS-based PSA process operates between a feed pressure of 20 to 40 bars and a regeneration pressure of 1.5 bars at ambient temperature and produces a 98+% carbon dioxide product. The PSA process can be integrated with a liquid carbon dioxide plant to produce food grade product.     

气提法去除油田污水中二氧化碳气体的实验研究

采用氮气气提装置处理油田污水中溶解的CO2气体,考察了气液比、温度、pH及含油量对CO2去除效果的影响。结果表明,气提法去除油田污水中的CO2效果明显,在气液比为5∶1、温度为30℃、pH为5条件下,污水中的CO2去除率可达98%以上;升高温度、降低污水中的含油量有助于增强氮气气提对CO2的去除效果;处理后的污水CO2质量浓度降到2 mg/L,pH升高到7,碳钢的腐蚀速率降到0.02 mm/a以下。     

Reduction of nitrogen dioxide by propene over acidic mordenites: influence of acid site concentration, formation of by-products and mechanism

The reduction of nitrogen dioxide to nitrogen by propene was studied over a variety of acidic mordenite zeolites differing in their Si : Al ratio and thus, in their concentration of acid sites. The formation of by-products was monitored applying an ion–molecule reaction (IMR) mass spectrometer. It was found that at fixed conditions the yield of nitrogen increases with increasing concentration of acid sites, confirming that acid sites are the active catalytic centres in the reaction. Apart from nitrogen and nitric oxide, acrylonitrile and ammonia are formed as nitrogen containing gas-phase products in the reaction. In separate experiments, it was shown that acrylonitrile is hydrolysed by water over the acidic zeolites to yield ammonia and acrylic acid. When acrylonitrile is used as reducing agent for nitrogen dioxide, formation of nitrogen is strongly enhanced in the presence of water. Water also has a promoting effect on the formation of nitrogen in the reaction between nitrogen dioxide and propene. Acrylonitrile and its product of hydrolysis, ammonia, are considered to be intermediates of nitrogen dioxide reduction to nitrogen by propene over acidic zeolites.     

Comparative study of hydrophilic modification of polyacrylonitrile membranes by nitrogen and carbon dioxide RF plasma

Low temperature plasma treatment using radio frequency (RF) discharge of nitrogen and carbon dioxide gases was employed to enhance hydrophilicity of the polyacrylonitrile copolymer membrane surface. Influence of various plasma operating conditions, namely, power and exposure time on improvement of surface energy, permeability, and hydrophilicity of the membrane was investigated. Surface energy of RF nitrogen plasma‐treated membrane (70 W, 8 min) was enhanced by 70%. Surface etching due to plasma treatment was confirmed by weight loss of the treated membranes. About 78% increase in average pore size was obtained using RF carbon dioxide plasma treatment due to surface etching. Hydrophilicity of nitrogen plasma modified membrane was enhanced by 32% and it was maintained up to 100 days. The pore enlargement due to plasma etching is more effective compared to surface energy in enhancing permeability (70%) of RF carbon dioxide modified (70 W, 6 min) membrane throughout the aging period. The permeability of nitrogen RF plasma‐treated membrane is affected by surface energy and pore enlargement for initial 20 days of aging. After that, the permeability of treated PAN only depends on pore enlargement due to plasma etching. The nitrogen plasma modified surfaces appear to retain their functionality better than carbon dioxide plasma‐treated samples. Oxygen and nitrogen functional groups were identified to be responsible for surface hydrophilicity. POLYM. ENG. SCI., 59:2148–2158, 2019. © 2019 Society of Plastics Engineers     

The effect of conjugated linoleic acid on the antioxidant enzyme defense system in rat hepatocytes

Short-term effects of physiological concentrations of conjugated linoleic acid (CLA) on membrane integrity, metabolic function, cellular lipid composition, lipid peroxidation, and antioxidant enzymes were examined using rat hepatocyte suspension cultures. Incubation with CLA (5–20 ppm) for 3 h decreased the ability of hepatocyte plasma membranes to exclude trypan blue by approximately 25%, and caused leakage of cytosolic lactate dehydrogenase (LDH) into the medium. The significant decrease (P<0.02) in hepatocyte viability as measured by LDH leakage during cell incubation with 10 and 20 ppm CLA was not associated with significant changes in cellular ATP content. Protein synthesis in hepatocytes was elevated (P<0.05) in the presence of 5 and 10 ppm CLA, but at a higher concentration (20 ppm), protein synthesis was similar to that of control cells. Gluconeogenesis was maintained in cells incubated with lower concentrations of CLA (5 and 10 ppm) but was decreased (P<0.02) at the higher concentration. Incubation with 20 ppm CLA for 3 h did not affect the specific activity of 3-hydroxy-3-methylglutaryl coenzyme A reductase, the rate-limiting enzyme of cholesterol synthesis. Both cis-9,trans-11/trans-9,cis-11, and cis-10,trans-12/trans-10,cis-12 isomers of CLA were incorporated to a similar level into hepatocytes. Levels ranged from 3.9 to 4.1%, respectively, of total fatty acids in neutral lipids, and from 0.7 to 0.8%, respectively, of total fatty acids in phospholipids. Cellular lipid peroxidation remained unchanged in the presence of CLA (5–20 ppm), despite significant inhibition (P<0.05) of superoxide dismutase. Catalase activity was maintained near control levels in the presence of 5 and 10 ppm CLA but was significantly decreased in the presence of 20 ppm CLA. Glutathione peroxidase activity was significantly decreased in the presence of 10 ppm CLA. The apparent sensitivity of the antioxidant enzyme defense system of liver cells to CLA, coupled with the lack of effect of CLA on lipid peroxidation in cells, suggests that cytotoxic effects of CLA as described by LDH leakage and decreased gluconeogenesis were not mediated by a prooxidant action in hepatocytes.     

High-resolution FTIR analysis of coal gas

Coal gas samples collected from a laboratory scale gasifier have been analysed using high-resolution (0.125 cm^?1) Fourier transform infrared spectrometry (FTIR). The gas samples were introduced into an evacuated 8.76 m path-length gas cell and backfilled with nitrogen to 1 atm. Carbonyl sulphide and ammonia were quantified in samples with concentrations ranging from trace to 370 ppm, and non-detectable to 25 ppm, respectively. Other compounds identified in the coal gas samples include: methane, ethane, ethylene, ?C₃ hydrocarbons, acetylene, carbon monoxide, carbon dioxide, ethylene oxide, methane thiol, hydrogen cyanide, formaldehyde, cyanogen (?), ethane thiol (?), methanol, and nitric acid (?). Several compounds were sought but were not present in detectable quantities (less than ≈ 1 ppm). These include: nickel carbonyl, arsine, benzene, methyl chloride, methylamine, HCI, nitrogen oxides, and phosgene. Selected compounds, e.g. ammonia, were quantified by calibration with a standard gas. High resolution FTIR, a nearly universal detector, is especially useful for determining presence or absence of specific pollutants or interest which are not easily determined by routine gas chromatographie methods.     

Phase equilibria of binary clathrate hydrates of nitrogen+cyclopentane/cyclohexane/methyl cyclohexane and ethane+cyclopentane/cyclohexane/methyl cyclohexane

In this communication, we first report hydrate dissociation conditions for the nitrogen+cyclopentane, cyclohexane or methyl cyclohexane+water and ethane+cyclopentane, cyclohexane or methyl cyclohexane+water systems at various temperatures. The experimental data were generated using an isochoric pressure-search method. The hydrate dissociation data for the aforementioned systems along with the hydrate dissociation data for the methane, carbon dioxide or hydrogen sulfide+cyclopentane, cyclohexane or methyl cyclohexane+water systems collected from the literature are compared with the corresponding literature data in the absence of the aforementioned heavy hydrocarbons in order to study the hydrate promotion effects of cyclopentane, cyclohexane or methyl cyclohexane. It is shown that these effects on ethane simple hydrate are not considerable unlike the corresponding effects on nitrogen, methane, carbon dioxide and hydrogen sulfide simple hydrates.     

Oxidation of petroleum sulphides with nitrogen dioxide

• 1.1. Petroleum sulphides (obtained as concentrates from appropriate distillates) were oxidized with a mixture of air and nitrogen dioxide to sulphoxides, with yields of 75 to 80% for sulphoxide sulphur, but the process was complicated by secondary processes: the formation of up to 30% of nitrosulphoxides of variable structure; sulphones and carbonyl compounds were present as traces. The target product was separated from most impurities by an alkaline wash, followed by chromatography.
• 2.2. Oxidation of individual sulphides under the conditions adopted gave sulphoxides, which contained only traces of compounds with a nitro-group, easily removed by recrystallization or elution chromatography.

     

Determination of ethane and pentane in free oxygen radical-induced lipid peroxidation

It has been proposed that ethane and pentane reflect free oxygen radical-induced lipid peroxidation. However, methodological difficulties limit the use of these gases for assessment of free oxygen radical activity. In the present report we describe an improved method for the accurate analysis of picomole quantities (≥1 pmol) of ethane and pentane. They are first quantitatively trapped into an adsorbent and then heat-desorbed directly into a capillary column for gas chromatographic quantitation. During oxidation of linolenic (n−3) and linoleic (n−6) acid, ethane and pentane were formed, respectively. Nonstimulated granulocytes formed pentane. Upon addition of phorbol 13-myristate 12-acetate, the generation of pentane was increased by 540%. Addition of superoxide dismutase plus catalase inhibited lipid peroxidation in both a cell-free system and in isolated cells. The present method is useful in the evaluation of free oxygen radical induced damage.     

Effect of dietary vitamin E on expiration of pentane and ethane by the rat

An analytical method for the measurement of hydrocarbon gases in the breath of rats is described. The method was used to follow the expiration in rat breath of in vivo formed scission products of hydroperoxides. The major products are pentane from the linoleic acid family and ethane from the linolenic acid family. Rats were fed 0, 11 or 40 i.u. vitamin E acetate/kg diet for 7 wk starting at age 21 days. Data obtained by gas chromatographic analysis of breath samples were analyzed by the Mann-Whitney nonparametricU-test. This statistical analysis showed that pentane evolved by the group of rats not supplemented with vitamin E was significantly higher during the period 1–7 wk than that evolved by either of the two supplemented groups of rats. Ethane from the nonsupplemented group was significantly higher than that from the group supplemented with 40 i.u. vitamin E/kg of diet by 5 wk, and significantly higher than both supplemented groups by 6 wk. By 7 wk, pentane production was tenfold greater in the nonsupplemented group than in either supplemented group, and ethane was about twofold greater. There was no significant difference between the groups supplemented with 11 and 40 i.u. vitamin E/kg diet for either ethane or pentane. This new technique, which measures scission products from in vivo lipid peroxidation, promises to be useful for application to many experimental areas where lipid peroxidation is expected or known to occur.