Esterification affects phytosterol oxidation

The effect of esterification with rapeseed oil fatty acids on the oxidation reactions of sitosterol, campesterol and sitostanol was investigated, as well as the interactions between phytosterol/stanol compounds and the saturated lipid matrix at 100 °C and 180 °C. Free and esterified phytosterols differed in their reactivity in terms of the formation and profile of secondary oxidation products. Phytosteryl esters were more reactive than free phytosterols during prolonged heating at 100 °C. In contrast, free phytosterols were slightly more reactive than phytosteryl esters at 180 °C. The oxidation reactions of phytostanol compounds were low under all conditions studied. Changes in the phytosterol compounds during heating were also studied via the losses in the original phytosterol contents. This study revealed that the formation of secondary oxides did not account for all the phytosterol losses; this indicates the presence of other oxidation products, especially at 180 °C, and during the heating of free sitosterol. Thus, in order to understand the overall deterioration of phytosterol and phytostanol compounds, both the secondary oxide formation and the sterol loss need to be studied. The deterioration of the saturated lipid matrix used in this study was rather low and was mainly associated with the heating temperature and time.     

Phytosterols in 17 Turkish hazelnut (Corylus avellana L.) cultivars

The phytosterol contents of the oils from 17 Turkish hazelnut cultivars were determined by gas chromatography with a flame ionization detector. The total phytosterol content varied from 1180.4 (Uzunmusa‐Ordu) to 2239.4 mg/kg (Cavcava), and the average was 1581.6 ± 265.1 mg/kg. One of the most significant commercial cultivars, Tombul, contained quite low total phytosterols (1297.7 mg/kg). Total and individual phytosterol contents of hazelnut cultivars were significantly different at p <0.01, except for phytostanol and campestanol. The main component was β‐sitosterol which ranged from 82.8 to 86.7% in all cultivars. This was followed by campesterol, Δ⁵‐avenasterol, sitostanol and stigmasterol. Interestingly, the same cultivars from different regions showed similar total phytosterol contents, and fall almost within the same range according to Duncan's test, which may indicate that the phytosterol content is highly related to the cultivar.     

Serum and aortic levels of phytosterols in rabbits fed sitosterol or sitostanol ester preparations

Campesterol is present in all the phytosterol-containing dietary hypocholesterolemic agents in current use. Campesterol is absorbed more efficiently than sitosterol, and the question of its possible atherogenicity has been raised. To test this possibility, rabbits were fed either a semipurified, cholesterol-free diet that has been shown to be atherogenic for this species or the same diet augmented with 0.5 g of phytosterol-rich diet preparations (spreads) containing either sitosterol or sitostanol. The diets contained 295 mg phytosterol per 100 g. After 60 d, serum cholesterol levels in the two phytosterol groups were 78±4 mg/dL (sitosterol) and 76±4 mg/dL (sitostanol), respectively. The serum cholesterol level of rabbits fed the control diet was 105±8 mg/dL. Serum campesterol (μg/mL) levels were higher than sitosterol or sitostanol levels in all groups. Aortic phytosterols were present in nanogram quantities compared to cholesterol, which was present in microgram quantities. The ratio of campesterol/sitosterol/sitostanol in the aortas was: control, 1.00∶0.43∶0.02; sitosterol, 1∶00∶0.32∶0.01; sitostanol, 1∶00∶0.34∶0.11. Aortic campesterol was present at 4% the concentration of aortic cholesterol, sitosterol at 1.4%, and sitostanol at 0.14%. Aortic lesions were not present in any of the animals.     

Lymphatic absorption of phytosterol oxides in rats

Two of the main classes of oxyphytosterols (7-keto and epoxides) were synthesized from sitosterol and campesterol and given to mesenteric duct-cannulated adult male rats. Lymph was collected during 24 h and was analyzed for oxysterols. The results showed that the lymphatic recovery of the phytosterol oxides was low: 4.7% of the given dose for epoxy derivatives and 1.5% for 7-keto compounds. The campesterol oxides presented a better absorption than the sitosterol oxides. During the process of absorption’ the epoxyphytostanols were also partly transformed in campestanetriol and stigmastanetriol.     

Oxidation of phytosterols in a test food system

The oxidative stability of phytosterols in canola, coconut, peanut, and soybean oils was examined under simulated frying conditions of 100, 150, and 180°C for 20 h. The degree of oxidative decomposition was assessed by the loss of phytosterols, accumulation of phytosterol oxides, and the change in fatty acid profiles. The phytosterol oxides produced in the oils were identified using mass spectroscopy. Oils with higher levels of polyunsaturated fatty acids showed greater amounts of sterol loss; however, the sterol loss was less complete than in the more saturated oils. A greater variety of sterol oxides was observed at the lower temperatures of 100 and 150°C compared to 180°C. This study demonstrates that under conditions similar to frying, there is a loss of phytosterols and polyunsaturated fatty acids. The accumulation of phytosterol oxides may be temperature-limited because of further break-down into products not measurable by typical gas chromatography-mass spectrometry techniques.     

Characterization of Al2O3-ZrO2 mixed oxide catalytic supports prepared by the sol-gel method

A series of Al₂O₃-ZrO₂ mixed oxides was prepared by the sol-gel method with variable amounts of ZrO₂ between pure alumina and pure zirconia. Textural, bulk and surface characterization of the samples was carried out by nitrogen physisorption (S_BET, porosity), surface acidity, zero point charge (ZPC), thermal analysis (DSC, TGA), X-ray diffraction (XRD) and FT-Raman spectroscopy. The textural results show that at low zirconia contents, higher surface areas than those of pure alumina are obtained, and that the mixed oxides samples show a bimodal pore size distribution different from that of a mechanical mixture of the pure oxides. Also, in the zirconia-rich samples, higher surface areas than for pure zirconia are stabilized. The ZPC results indicate the formation of a surface composition equivalent to the bulk composition of the two oxides. The acidity measurements show that, as the density of acid sites in the mixed oxides increases steadily with zirconia content, a sharp increase is observed between the zirconia-rich mixed oxides and the pure ZrO₂. It appears possible then to tune the acidity of the mixed oxide by changing its composition. The XRD and FT-Raman results show that the incorporation of alumina in the support stabilizes the metastable cubic and tetragonal zirconia phases, possibly by a matrix effect which constrains the size of the ZrO₂ particles below the critical size beyond which the crystallization and transformation process to a more stable zirconia phase occurs.     

Studies on phytosterol oxides. I: Effect of storage on the content in potato chips prepared in different vegetable oils

Potato chips fried in palm oil, sunflower oil, and high-oleic sunflower oil were studied for the content of different phytosterol oxides during 0 to 25 weeks of storage in the dark. Oxidation products of sitosterol (24α-ethyl-5-cholesten-3β-ol) and campesterol (24α-methyl-t-cholesten-3β-ol) were synthesized to help identify the phytosterol oxides. The oxides of phytosterols were analyzed by preparative thin-layer chromatography, solid-phase extraction, capillary column gas chromatography (GC), and GC-mass spectrometry. Epimers of 7-hydroxysitosterol and 7-hydroxycampesterol; 7-ketositosterol and 7-ketocampesterol; epimers of 5,6-epoxy-sitosterol and 5,6-epoxy-campesterol; 24α-ethylcholestane-3β,5,6β-triol (dihydroxysitosterol) and 24α-methylcholestane-3β,5,6β-triol (dihydroxycampesterol) were detected and quantitated in the samples of chips fried in different vegetable oils. Potato chips fried in palm oil had the lowest level of total sterol oxides, ranging from 5 to ca. 9 ppm in the lipids from time 0 to 25 wk of storage. The level of total sterol oxides in chip samples fried in sunflower oil ranged from 46 to 47 ppm, and the lipids in samples fried in high-oleic sunflower oil ranged from 35 to 58 ppm from 0 time to 25 wk of storage. During 25 wk of storage no considerable increase in sterol oxides was observed in the samples of chips fried in palm oil and sunflower oil. The chip samples fried in high-oleic sunflower oil had slightly higher levels of sterol oxides after 10 and 25 weeks of storage. In addition to the levels of individual sterol oxides, a new method for enrichment of phytosterol oxides from the unsaponifiables and full-scan mass spectra of various oxidation products of sitosterol and campesterol are reported in this paper. Part of the results were presented at the 86th Annual Meeting of the AOCS, May 7–11, 1995, San Antonio, TX.     

DRYING OF Y-Ba-Cu-O COMPLEX OXIDE SUSPENSION BY SUPERCRITICAL CARBON DIOXIDE

Fine and homogeneous powders of Y-Ba-Cu complex oxides are necessary to improve the quality of YBCO bulk high temperature superconductors. The powders which contain BaCO₃ must be sintered for producing YBCO super-conductors at temperature above 850 °C. Therefore, complex oxide is desired. In order to prepare fine complex oxides powders, suspension was synthesized by simultaneous hydrolization of 2-propanol solution of metal isopropoxides. However, the suspension was not dried by a hot air drying method, because aggregation occurs due to cohesion of particle along with evaporation. Also, the suspension could not be freeze-dried, because the freezing point of 2-propanol is -88.5°C. So, supercritical fluid drying method using supercritical carbon dioxide was applied. The results from these experiments suggest that this method is useful for drying of the suspension prepared by the alkoxide route.     

Studies on phytosterol oxides. II: Content in some vegetable oils and in French fries prepared in these oils

Hydrogenated rapeseed oil/palm oil blend, sunflower oil and high-oleic sunflower oil, and French fries fried in these oils were assessed for contents of sterol oxidation products. Different oxidation products of phytosterols (7α- and 7β-hydroxy-sito-and campesterol, 7-ketosito- and 7-ketocampesterol, 5α,6α-epoxy-sito- and campesterol, 5β,6β-epoxy-sito-and campesterol, dihydroxysitosterol and dihydroxycampesterol) were identified and quantiated by gas chromatography (GC) and GC-mass spectroscopy. Rapeseed oil/palm oil blend contained 41 ppm total sterol oxides before frying operations. After two days of frying, this level was increased to 60 ppm. Sunflower oil and high-oleic sunflower oil had 40 and 46 ppm sterol oxides, respectively, before frying operations. After two days of frying operations, these levels increased to 57 and 56 ppm, respectively. In addition to campesterol and sitosterol oxidation products, small amounts of 7α- and 7β-hydroxystigmasterol were detected in the oil samples. Total sterol oxides in the lipids of French fries fried at 200°C in rapeseed oil/palm oil blend, sunflower oil, and high-oleic sunflower oil were 32, 37, and 54 ppm, respectively. The levels of total oxidized sterols, calculated per g sample, ranged from 2.4 to 4.0 ppm. In addition to the content of phytosterol oxides, full scan mass spectra of several oxidation products of stigmasterol are reported for the first time. Part of these results were presented at the 86th Annual Meeting of the AOCS, May 7–11, 1995, San Antonio, TX.     

High-temperature electrochemical synthesis of oxide thin films and nanopowders of some metal oxides

An electrochemical method is proposed for preparing metal (aluminum, titanium, tantalum, zirconium) oxides with a high affinity to oxygen in a chloride-nitrate melt at temperatures above 830 K in an argon atmosphere. It is demonstrated that either dense metal oxide layers firmly bonded to the metal base can be produced or large amounts of nanosized oxides can be formed in the melt bulk depending on the anodic oxidation conditions (electrolyte composition, oxidation temperature).     

The characterization of the V species and the identification of the promoting effect of dopants in V/Ti/O catalysts for o-xylene oxidation

The present work deals with the study of the role of promoters in TiO₂-supported vanadium oxide, catalyst for the oxidation of o-xylene to phthalic anhydride. Two different series of catalysts were prepared, the first one consisting of undoped samples having different vanadium oxide content, and the second one of samples having 7 wt.% V₂O₅ and variable amounts of Sb and Cs as promoters. All the samples were characterized by means of Raman spectroscopy, X-ray diffraction and thermal-programmed reduction and oxidation, in order to define a method for the quantification of the different V species (i.e., isolated vanadium, dispersed polyvanadate and bulk vanadium oxide) that develop on TiO₂ support in the presence of promoters. It was found that polyvanadate and bulk vanadium oxide spontaneously release molecular oxygen at 600–650 °C, whereas the isolated V is not susceptible of self-reduction. The latter species is predominant in samples having low vanadium oxide loading (≤2 wt.% V₂O₅, with TiO₂ surface area 22.5 m²/g), and possesses the highest intrinsic activity in o-xylene conversion. The presence of Sb, a promoter of activity, increases the dispersion of the most active species and also hinders its segregation in the reaction environment. These promoting effects are more pronounced when both Cs and Sb are present.     

Propane ammoxidation on bulk, diluted and supported VSb oxides

VSb oxides diluted with Mg, Al and Zr displayed substantially higher selectivity for propane ammoxidation to acrylonitrile than their bulk and supported analogues. Diluted catalysts were found to consist of oxide compounds of antimony with diluent element, such as AlSbO₄ or MgSb₂O₆, and small amounts of individual oxides of antimony and diluent element. No VSbO₄ phase was detected in their body in contrast with bulk and supported catalysts. It appears that better isolation of vanadium and antimony entities in the structure of diluted oxides was responsible for their enhanced catalytic behavior. Tungsten loaded to the surface of diluted catalysts further improved their selectivity through tuning the surface acidity.     

DRYING OF Y-Ba-Cu-O COMPLEX OXIDE SUSPENSION BY SUPERCRITICAL CARBON DIOXIDE

Abstract

Fine and homogeneous powders of Y-Ba-Cu complex oxides are necessary to improve the quality of YBCO bulk high temperature superconductors. The powders which contain BaCO₃ must be sintered for producing YBCO super-conductors at temperature above 850 °C. Therefore, complex oxide is desired. In order to prepare fine complex oxides powders, suspension was synthesized by simultaneous hydrolization of 2-propanol solution of metal isopropoxides. However, the suspension was not dried by a hot air drying method, because aggregation occurs due to cohesion of particle along with evaporation. Also, the suspension could not be freeze-dried, because the freezing point of 2-propanol is ?88.5°C. So, supercritical fluid drying method using supercritical carbon dioxide was applied. The results from these experiments suggest that this method is useful for drying of the suspension prepared by the alkoxide route.     

Coordination polymers as precursors of simple and complex oxides

Coordination polymers (CPs) are assembled from metal ions and organic linker molecules. Here, we demonstrate that CPs can be used as precursors for simple and complex oxide synthesis. First, we investigated the conditions for linker solutions in which CP was obtained as precipitate only by mixing and stirring the solutions for each of the 28 metal–ion aqueous solutions. Evaluation of the crystalline phase of the samples obtained by firing the precipitates revealed that CPs could be used as precursors of simple oxides for 21 metal ions. Next, we conducted experiments to prepare precursors of 10 complex oxides with an A_nB_nO_m composition containing equimolar amounts of metal ions. Seven complex oxides were successfully synthesized. Three of them were complex oxides that could not be synthesized by the spray coprecipitation method. The present method has a comparable precursor preparation capability to the spray coprecipitation method. Because of the much shorter time for the precursor synthesis, the present method should be useful for parallel and automated experiments.     

Effect of palladium and nickel on the temperature programmed reduction of metal oxides and metal oxide layers

A new binary oxide support was suggested as being useful in many commercial reactions. Our study was focused on the reduction effect of metal oxide layer on alumina during reaction. Hence temperature programmed reduction of both bulk metal oxide and metal oxide layer on alumina was studied first and the effect of palladium and nickel on the reduction of the oxide support was also investigated. Vanadium oxide was mainly studied and niobium oxide, tantalum oxide, titanium oxide and zirconium oxide were also compared. Some metal oxides were reduced in a hydrogen stream at elevated temperature. In these cases both the bulk metal oxide and metal oxide layer were reduced. A tiny amount of palladium or nickel affected the reduction by decreasing the reduction temperature. The decrease of the reduction temperature was explained by means of increased adsorption of hydrogen on the transition metal and ability of the metal to spillover of the hydrogen to the oxides.     

LOW-LEAD,BRIGHT OPAQUE GLAZES AT CONES 08 TO 06*

This investigation covered several systematic fields of opaque fritted glazes for cones 08 to 06 (1733° to 1841°F.) in which lead oxide was replaced by barium, strontium, and zinc oxides. All glaze ingredients except the kaolin and the Ultrox zirconium opacifier were incorporated in the frits. Glazes of low-lead content as well as some lead-free compositions were obtained which possessed excellent gloss and opacity on wall tile of low and of medium tale content. Barium oxide was the best substitute for lead oxide from the standpoint of gloss, although moderate amounts of strontium and zinc oxides can be used to advantage. The whitest and most opaque glazes were obtained with the use of zinc oxide.     

Analysis of sterols from various food matrices

Two methods suitable for routine phytostanol/phytosterol analysis of various sterol‐enriched food matrices and phytostanyl/phytosteryl fatty acid ester ingredients are introduced. A method based on hot saponification of a sample with ethanolic potassium hydroxide in the presence of an internal standard (5β‐cholestan‐3α‐ol) is adequate for most matrices, such as spread, milk and yoghurt. Some matrices, like pasta, require acid hydrolysis in order to release matrix‐incorporated bound sterols or sterols from steryl glycosides before the saponification step. After saponification, the unsaponifiable material containing phytostanols and phytosterols is extracted into an organic solvent (e.g. heptane), followed by evaporation of the solvent to dryness. Sterols are separated as their trimethylsilyl ether derivatives with a gas‐liquid chromatograph (GC), on a column coated with 5% phenyl/95% dimethylpolysiloxane, and detected with a flame ionization detector. The GC conditions applied provide efficient separation of the most abundant phytostanols/phytosterols in 15 min, a wide linear range of stanols/sterols without the need of defining sterol response factors. The methods are repeatable and accurate, as shown with standard addition trials. These methods were applied to determine phytostanol/phytosterol contents of several sterol‐enriched functional food products, and the analyzed amounts were in good accordance with the information provided on the packaging labels.     

钴铈复合氧化物催化降解2,4,6-三氯酚

采用溶胶-凝胶法制备了一种疏松多孔的钴铈复合氧化物,该复合氧化物具有较大的比表面积和孔体积。并以废水中一定浓度的2,4,6-三氯酚作为模型化合物,研究自制的钴铈复合氧化物对水中的2,4,6-三氯酚的催化降解效果。研究结果表明,自制的钴铈复合氧化物所具有的氧化还原性能以及协同催化作用使其对废水中的2,4,6-三氯酚具有一定的催化降解活性。初始溶液的pH值对降解影响较大,酸性条件更有利于2,4,6-三氯酚的降解。100 mg自制的钴铈复合氧化物与10 mL 100 mg/L的2,4,6-三氯酚在25℃下恒温振荡30 h,2,4,6-三氯酚的降解率可达到86.3%,溶液中可被氧化的有机物含量下降了36.7%。     

Sterols and Stanols in Foods and Dietary Supplements Containing Added Phytosterols: A Collaborative Study

An international, multilaboratory collaborative study was carried out to evaluate the performance of Official Method Ce 12‐16 of the American Oil Chemists’ Society (AOCS) for the determination of plant sterols and stanols, collectively referred to as phytosterols, in foods and dietary supplements containing added phytosterols and in the phytosterol food additive concentrates used to prepare such products. AOCS Official Method Ce 12‐16 involves the extraction of free sterols/stanols and saponified steryl/stanol esters followed by the gas chromatographic separation and flame ionization detection of phytosterol trimethylsilyl ether derivatives. A total of 14 laboratories from six countries successfully completed the analysis of collaborative samples of foods (e.g., baked goods, beverages, margarines; n = 9), dietary supplements (n = 5), and phytosterol concentrates (n = 4). Study results for the contents of total phytosterols (weight/weight) were 0.19–8.4% for foods, 8.7–49% for dietary supplements, and 57–97% for concentrates. AOCS Official Method Ce 12‐16 showed acceptable performance for total and individual phytosterols, indicating that this method was suitable for the determination of added phytosterols in a wide variety of market products and concentrates. AOCS Official Method Ce 12‐16 is appropriate for the determination of the five major phytosterols (i.e., campesterol, stigmasterol, β‐sitosterol, campestanol, and sitostanol) that are the subject of the United States Food and Drug Administration's health claim for phytosterols and the reduced risk of coronary heart disease.     

Dietary sitostanol and campestanol: Accumulation in the blood of humans with sitosterolemia and xanthomatosis and in rat tissues

Dietary sitostanol has a hypocholesterolemic effect because it decreases the absorption of cholesterol. However, its effects on the sitostanol concentrations in the blood and tissues are relatively unknown, especially in patients with sitosterolemia and xanthomatosis. These patients hyperabsorb all sterols and fail to excrete ingested sitosterol and other plant sterols as normal people do. The goal of the present study was to examine the absorbability of dietary sitostanol in humans and animals and its potential long-term effect. Two patients with sitosterolemia were fed the margarine Benecol (McNeill Nutritionals, Ft. Washington, PA), which is enriched in sitostanol and campestanol, for 7–18 wk. Their plasma cholesterol levels decreased from 180 to 167 mg/dL and 153 to 113 mg/dL, respectively. Campesterol and sitosterol also decreased. However, their plasma sitostanol levels increased from 1.6 to 10.1 mg/dL and from 2.8 to 7.9 mg/dL, respectively. Plasma campestanol also increased. After Benecol withdrawal, the decline in plasma of both sitostanol and campestanol was very sluggish. In an animal study, two groups of rats were fed high-cholesterol diets with and without sitostanol for 4 wk. As expected, plasma and liver cholesterol levels decreased 18 and 53%, respectively. The sitostanol in plasma increased fourfold, and sitostanol increased threefold in skeletal muscle and twofold in heart muscle. Campestanol also increased significantly in both plasma and tissues. Our data indicate that dietary sitostanol and campestanol are absorbed by patients with sitosterolemia and xanthomatosis and also by rats. The absorbed plant stanols were deposited in rat tissues. Once absorbed by sitosterolemic patients, the prolonged retention of sitostanol and campestanol in plasma might increase their atherogenic potential.