Impact of weighting agents and sucrose on gravitational separation of beverage emulsions

The influence of weighting agents and sucrose on gravitational separation in 1 wt % oil-in-water emulsions was studied by measuring changes in the intensity of backscattered light from the emulsions with height. Emulsions with different droplet densities were prepared by mixing weighting agents [brominated vegetable oil (BVO), ester gum (EG), damar gum (DG), or sucrose acetate isobutyrate (SAIB)] with soybean oil prior to homogenization. Sedimentation or creaming occurred when the droplet density was greater than or lower than the aqueous phase density, respectively. The weighting agent concentrations required to match the oil and aqueous phase densities were 25 wt % BVO, 55 wt % EG, 55 wt % DG, and 45 wt % SAIB. The efficiency of droplet reduction during homogenization also depended on weighting agent type (BVO > SAIB > DG, EG) due to differences in oil phase viscosity. The influence of sucrose (0-13 wt %) on the creaming stability of 1 wt % soybean oil-in-water emulsions was also examined. Sucrose increased the aqueous phase viscosity (retarding creaming) and increased the density contrast between droplets and aqueous phase (accelerating creaming). These two effects largely canceled one another so that the creaming stability was relatively insensitive to sucrose concentration.     

Elucidation of lignin structure through degradative methods: comparison of modified DFRC and thioacidolysis

Milled wood and milled wood lignin (MWL) samples were subjected to DFRC and thioacidolysis. Despite the fact that both methods selectively cleave aryl ether bonds, substantial differences in results were obtained. Lignin thioacidolysis gave total molar yields of degradation monomer products in the range of 3.5-7 mol % higher than DFRC. GPC analysis showed that the thioacidolysis-treated lignin was degraded to a lower average molecular weight than that treated by DFRC. Contrary to results reported for lignin model compounds, these results indicate that the DFRC method does not completely or efficiently degrade the lignin polymer. In fact, the DFRC-degraded lignin retained much of the characteristics of the original MWL. Elemental analysis revealed the presence of bromine in the DFRC-treated lignin, and two-dimensional (1)H-(13)C HMQC NMR spectroscopy showed the presence of beta-O-4 linkages in the DFRC-treated lignin. No beta-O-4 interunit linkages were detected in the thioacidolysis-treated lignin. These results are consistent with the lower monomer yields and the higher average molecular weight of the DFRC-treated lignin and indicate inefficiency in the chemistry of the method, probably due to steric constraints of the polymeric nature of lignin.     

Hapten syntheses and antibody generation for the development of a polybrominated flame retardant ELISA

Polybrominated diphenyl ethers (PBDEs) are a class of brominated flame retardants that are increasingly an environmental concern. Several antibodies were developed for the polybrominated diphenyl ether flame retardant BDE-47 (1), often found in the highest concentration in human milk, plasma, and adipose tissue. Four haptens with different bromine and linker substitution patterns were synthesized and utilized to generate five polyclonal antibodies from goats and two polyclonal antibodies from rabbits. Competition was assessed using four different coating antigens for all seven antibodies. The coating antigen showed marked effects on competition. When the same hapten was used for antibody and the coating antigen less competition was observed. The effect of BDE structure on competition was evaluated by using BDE-47 (1), BDE-99 (2), BDE-100 (3), BDE-153 (4), and BDE-183 (5). None of the compounds showed high competition with antibody I-KLH, presumably because steric hindrance prevented formation of an efficient binding site. As predicted from structural considerations, BDE-47 (1) competed well with the remaining antibodies, whereas BDE-100 (3) competed well with only II-KLH. The remaining congeners (BDE-99 (2), BDE-153 (4), and BDE-183 (5)) contain bromines that cannot be positioned in binding sites and thus cross-react poorly. The competition study demonstrated that a bromine substitution on the congener could occupy a position analogous to the linker's position.     

THE REMOVAL OF ORGANIC MATTER FROM SOIL EXTRACTS BY BROMINE OXIDATION

Brown-coloured extracts are frequently obtained when chemical dissolution techniques are applied to soils. The colour, arising from the presence of organic material, interferes in subsequent spectrophotometric determinations of extractable inorganic components. A bromine oxidation method for the complete removal of interfering organic matter has been devised. This involves the oxidation of the organic matter with alkaline bromine solution and the subsequent removal of excess bromine by acid and heat treatment. To test the effectiveness of the method extracts from chemical dissolution procedures, containing organic matter, were examined before and after bromine treatment by ultra-violet and infra-red adsorption and mass spectrometric techniques.     

Cytoprotective effect of hydroxytyrosyl alkyl ether derivatives after oral administration to rats in a model of glucose-oxygen deprivation in brain slices

This study was designed to determine whether the oral administration of hydroxytyrosol (HT) alkyl ether derivatives has a neuroprotective effect in rats. The animals were treated for 7 days with HT or ethyl, butyl, hexyl, octyl, and dodecyl HT ether. A method of in vitro hypoxia-reoxygenation in brain slices was used. Hexyl, octyl, and dodecyl HT derivatives reduced brain cell death (LDH efflux). Lipid peroxidation and nitrite concentrations were inhibited most by hexyl, octyl, and dodecyl derivatives. Concentrations of 3-nitrotyrosine were reduced by HT butyl, hexyl, octyl, and dodecyl ether derivatives. Interleukin-1β was significantly reduced in brain slices from rats treated with all HT ether derivatives. LDH efflux showed a linear correlation with brain concentrations of lipid peroxides, nitrites plus nitrates, and interleukin 1β. The reduction in oxidative and nitrosative stress and decreased production of pro-inflammatory interleukins may be the basis for the observed neuroprotective effects.     

Determination of p-hydroxybenzoic acid esters in cosmetics by liquid chromatography with ultraviolet and fluorescence detection

A simple, precise, and accurate liquid chromatographic method with both ultraviolet (UV) and fluorescence detection is described for the determination of methyl, ethyl, propyl, and butyl p-hydroxybenzoates (PHBA-esters) in cosmetics. sec-Butyl p-hydroxybenzoate is added to the sample as an internal standard. Then the PHBA-esters are extracted with ether, the ether is evaporated to dryness, and the residue is dissolved in 60% (v/v) acetonitrile. The acetonitrile solution is passed through a Sep-Pak C18 cartridge to remove co-extracted lipids. PHBA-esters are determined by reverse-phase liquid chromatography with UV detection at 254 nm and fluorescence detection at ex 280 nm, em 305 nm. The mobile phase is acetonitrile-water (35 + 65). The method was linear over the concentration range of 0.005-0.15 mg/mL. Mean recoveries of each PHBA-ester were 98.9-102.7% (coefficients of variation less than or equal to 2.0%).     

Tomato metabolism and porphyrin-catalyzed oxidation of pyriproxyfen

Investigation of the metabolism of [(14)C]pyriproxyfen [4-phenoxyphenyl (R,S)-2-(2-pyridyloxy)propyl ether] in tomato fruits (Lycopersicon esculentum Mill. cv. Ponterosa) was conducted by topical application of acetonitrile solution or emulsifiable concentration formulation three times at 35, 21, and 7 days before harvest. Most of the radioactivity remained on the fruit surface or in the plant tissues as intact pyriproxyfen with minor metabolites formed via hydroxylation at the 4'-position of the phenoxy ring or cleavage of ether linkages. The biomimic chemical oxidation model using iron porphyrin as a catalyst and hydrogen peroxide was found to well reproduce the primary metabolites detected in the metabolism study. The electrophilic reaction indices obtained by AM1 molecular orbital calculations supposing involvement of cytochrome P-450 were successfully applied to evaluate the potentially higher reactive sites in pyriproxyfen.     

Bromine in wheat grown on soil fumigated with methyl bromide

Abstract

Patches of discoloured ("scorched") plants developed on winter wheat growing in a field that had been fumigated with methyl bromide. Scorching was most marked round the methyl bromide injection sites and was associated with bromine uptake by the plants: the above‐ground parts of the scorched plants contained up to 0.61% bromine. In one scorched area, the first, second and third wheat crops after fumigation contained 0.42, 0.25 and 0.09% bromine respectively, so that three years was not sufficient to leach all the residual bromine from the soil.

The greater the organic content of a soil, the more bromine remained after fumigation with methyl bromide. Thus a soil containing 2.81% organic carbon contained 63 ppm bromine after fumigation in the laboratory, whereas an otherwise similar soil with 0.93 organic carbon contained only 25 ppm. The residual bromine from methyl bromide fumigation could be extracted with N potassium sulphate, whereas the native soil bromine could not.     

Effect of alkali and enzymatic pretreatments of Eucommia ulmoides leaves and barks on the extraction of gutta percha

This paper exploited a novel method of single solvent recycling plus enzymatic pretreatment. Petroleum ether (60-90 degrees C) was an ideal solvent to extract Eucommia gum at high temperature (approximately 80 degrees C) and to precipitate the gum (flocculent) as the temperature of the solution fell to below 40 degrees C. The gutta percha was almost completely precipitated from solution as the temperature cooled down to below 0 degree C. After filtration and recovery of the precipitated gum, the filtrate, petroleum ether, was applied to an activated carbon column to remove dissolved impurities and reused for next gutta percha extraction. Because impurities were kept in solution, the precipitated gutta percha was highly pure. In an experiment of enzyme hydrolyzing the plant cell wall, cuticle layers on the surfaces of leaves prevented cellulase from approaching to and hydrolyzing the cellulose of the cell wall. NaOH (1%) at 70 degrees C efficiently degraded the cuticle layer, which greatly improved the enzymatic hydrolysis of cellulose within eucommia leaves. Gutta percha that was extracted from the alkali- and cellulase-treated leaves had a degree of polymerization as high as in the leaves, and the yield increased from 2.5% of milled leaves up to over 3.2%. The tensile strength of obtained gutta percha increased from 0.02 MPa of milled Eucommia leaves to 60.5 MPa, the breakage extensibility ranged from about 0 to 24%, and the tearing strength ranged from 0.5 to 36 kN/m.     

Trihalomethanes Adsorption on Activated Carbon Fiber and Granular Activated Carbon

Isotherms and the effects on activated carbon fiber (ACF), compared with granular activated carbon (GAC), adsorption of trihalomethans (THMs) in water were studied. It was found that the isotherms for ACF or GAC were not agree to Langmuir equation well, but successfully correlated by Freundlich equation, and the coefficients of Freundlich isotherm were given and compared to isotherms reported in the literatures for THMs. ACF and GAC adsorbing THMs was exothermic, isotheric heats of adsorption were calculated and increased with increasing bromine substitution in CHCl₃. The adsorptive capacity of ACF was about two-fold greater than that of GAC, and increased with THMs more hydrophobic or bromine substitution. pH value and temperature had no significant effect on the adsorptive capacity of ACF. The adsorptive capacity of GAC was decreased with temperature slightly. The adsorptive capacities of ACF or GAC was increased with the THMs initial concentration rising. Fixed-bed reactor studies were measured, the amount of THMs adsorbed on ACF column at saturation was much greater than that of GAC at the same operating conditions, and the running time of ACF column was two-fold longer than that of GAC column. The mass transfer zones of ACF column were less than those of GAC column and decreased as the chlorine atoms in CHCl₃ substituted by bromine atoms, while the mass transfer zones of GAC column were quite uniform.     

甲醇微量元素溶液对凤仙花及小白菜生长的影响

对凤仙花或小白菜植株，喷淋０．１％～０．２５％甲醇溶液、微量元素溶液或两者混合溶液，植株的鲜重、干重比对照处理均表现增重效果。在小白菜的试验中，０．１％甲醇溶液处理的植株干重，在先后两次分析中，分别比对照增加１２．６％和１０．９％；而鲜重则分别增加１１．５％和１１％。在用０．２５％甲醇溶液处理凤仙花植株时，在２０ｄ内，可使植株干重增加，但继续施用时，可因药物的浓度或剂量过高，导致植株黄化，干重下降。     

Photodecomposition of an acaricide,fenazaquin, in aqueous alcoholic solution

Fenazaquin (I) is a new acaricide of the quinazoline class. The photodecomposition of I was studied in aqueous methanolic and 2-propanolic solution under UV light (30 h) and sunlight (70 h) separately. The photolytic half-lives in aqueous methanolic solution were found to be 17.1 h (UV) and 38.1 h (sunlight), whereas these were 12.9 h (UV) and 29.2 h (sunlight) for aqueous 2-propanolic solution; all followed a first-order reaction kinetics. Six photoproducts were obtained: beta-phenyl (p-tert-butyl) ethyl alcohol (II), 4-hydroxyquinazoline (III), p-tert-butyl vinyl benzene (IV), 2,4-dihydroxyquinazoline (V), phenyl (p-tert-butyl) acetic acid (VI), and 2-methyl-2-[4'-(2' '-hydroxyethyl)phenyl]propanoic acid (VII). Compounds VI and VII could be isolated only from aqueous 2-propanolic solution under sunlight irradiation. The major degradation products are formed as a result of cleavage of the ether bridge linking the quinazoline and phenyl ring systems of the molecule, oxidation of the tert-butyl substituent, and oxidation of the heterocyclic portion of the quinazoline ring. A probable mechanism of formation of the photoproducts is also suggested.     

A review of bromine determination in foods.

Organic compounds containing bromine, including methyl bromide, ethylene dibromide, and 1,2-dibromo-3-chloropropane, have been used extensively for the fumigation of foods, or soils in which foods grow, making it necessary to determine residues of bromine and bromine-containing organic compounds. A large number of methods for the determination of bromine in foods, as organic, inorganic, and combined total bromide, have been developed. In methods for organic bromide, the bromine is converted to the inorganic form for measurement by titration, photometry, or other means. In recent years, instrumental methods have been developed in which the total bromine in the sample is determined, regardless of the state in which it exists. X-ray fluorescence and neutron activation analysis are the 2 instrumental methods used most widely. Residue data are presented for some typical bromine-containing samples.     

Extraction and characterization of original lignin and hemicelluloses from wheat straw

Original lignin and hemicelluloses were sequentially extracted with high yield/purity, using acidic dioxane/water solution and dimethyl sulfoxide, from ball-milled wheat straw. The acidic dioxane lignin fraction is distinguished by high beta-O-4' structures and by low amounts of condensed units (beta-5', 5-5', and beta-1'). Hemicelluloses contain arabinoxylans as the major polysaccharides, which are substituted by alpha-l-arabinofuranose, 4-O-methylglucuronic acid, acetyl group (DS = 0.1), and xylose at O-3 and/or O-2 of xylans. It was found that arabinoxylans form cross-links with lignins through ferulates via ether bonds, glucuronic acid via ester bonds, and arbinose/xylose via both ether and glycosidic bonds, respectively, in the cell walls of wheat straw. Diferulates are also incorporated into cross-links between lignin and hemicelluloses as well as lignification of wheat straw cell walls. The guaiacyl unit is considered to be a significant condensed structural constructor in extracted lignin and a connector between lignin and carbohydrates.     

Gas-liquid chromatographic determination of adipic acid in crackling candy and soft drinks.

A procedure was developed for the simple and rapid determination of adipic acid in crackling candy and also in soft drinks. An alkaline solution of sample was extracted with ethyl ether to remove fatty substances, and H2SO4 was added to water layer to adjust the pH to less than 2. The acidified layer was saturated with NaCl and then extracted with ether. After drying, the ether layer was concentrated and the adipic acid in the concentrate was methylated using the diazomethane methograph equipped with a flame ionization detector. Recovery of adipic acid from crackling candy and from 2 kinds of soft drinks that had been fortified at the 200 ppm level was 96%. An interlaboratory test was carried out on the determination of adipic acid in orange soft drink. The results obtained by 6 laboratories were between 91 and 100% compared with the theoretical value.     

A method for extraction of pentachlorophenol from plant tissues

Pentachlorophenol (PCP) was extracted from well homogenized and acidified plant samples with diethyl ether. Partial purification was carried out by the partition of PCP between ether extract and aqueous sodium hydroxide (5%), then between the acidified sodium hydroxide solution and benzene. The final purification of PCP was achieved by its good gas chromatographic separation during the quantitative determination. Techniques for optimizing the efficiency of the method were described in detail. The efficiency of the method was found to increase with the increase of the starting quantities of PCP, where it reached 89.2% for amounts greater than 400 ng. The loss of PCP due to its presence in the plant tissues was 29.3 and 21.6% for concentrations of PCP lower than 35.5 and higher than 46.2 ppb in the plant respectively. The overall recovery of PCP from plant tissues was found to be about 60% and 70% at the mentioned low and high concentrations in the plant.     

Iodine and bromine contents of some Austrian soils and relations to soil characteristics

Inductively coupled plasma mass spectrometry (ICP-MS) analysis was used to determine iodine and bromine concentrations in several Austrian agricultural soils. The determined iodine concentrations in topsoils vary between 1.1 and 5.6 mg kg^—1, the arithmetic mean amounted to 3.1 mg kg^—1, bromine contents are always higher than the corresponding iodine values, varying between 2.4 and 11.9 mg kg^—1 with an arithmetic mean of 5.7 mg kg^—1. Due to their different geological origin lime-free soils on average contained significantly less iodine and bromine than calcareous soils. In general the observed values are supported by literature values from other countries far from the sea. A correlation analysis of results with several soil parameters resulted in positive correlations with clay content and a negative relation to sand content. In the group of calcareous soils I and Br correlated positively with organic carbon contents and exchangeable calcium.     

Extraction of chili,black pepper,and ginger with near-critical CO2, propane,and dimethyl ether: analysis of the extracts by quantitative nuclear magnetic resonance

Ginger, black pepper, and chili powder were extracted using near-critical carbon dioxide, propane, and dimethyl ether on a laboratory scale to determine the overall yield and extraction efficiency for selected pungent components. The temperature dependency of extraction yield and efficiency was also determined for black pepper and chili using propane and dimethyl ether. The pungency of the extracts was determined by using an NMR technique developed for this work. The volatiles contents of ginger and black pepper extracts were also determined. Extraction of all spice types was carried out with acetone to compare overall yields. Subcritical dimethyl ether was as effective at extracting the pungent principles from the spices as supercritical carbon dioxide, although a substantial amount of water was also extracted. Subcritical propane was the least effective solvent. All solvents quantitatively extracted the gingerols from ginger. The yields of capsaicins obtained by supercritical CO(2) and dimethyl ether were similar and approximately double that extracted by propane. The yield of piperines obtained by propane extraction of black pepper was low at approximately 10% of that achieved with dimethyl ether and CO(2), but improved with increasing extraction temperature.     

Tetramethylammonium hydroxide (TMAH) thermochemolysis of lignin: behavior of 4-O-etherified cinnamyl alcohols and aldehydes

The thermochemolytic behavior of 4-O-etherified cinnamyl alcohols and aldehydes in lignin was investigated in the presence of tetramethylammonium hydroxide (TMAH) (315 degrees C/4 s), using veratrylglycol-beta-(coniferyl alcohol) ether (1a), veratrylglycol-beta-(sinapyl alcohol) ether (1b), and veratrylglycol-beta-(coniferyl aldehyde) ether (2). The methylated products were monitored with gas chromatography-mass spectrometry. Dimers 1a and 1b provided the coniferyl and sinapyl alcohol dimethyl ethers consisting of three isomers, respectively. Coniferyl alcohol dimethyl ether isomers were also observed in the TMAH thermochemolysis pyrolysates of a bulk dehydrogenation polymer of coniferyl alcohol and a Japanese cedar (Cryptomeria japonica) wood. Coniferyl aldehyde methyl ether was not provided from TMAH thermochemolyses of coniferyl aldehyde, 2, a dehydrogenation polymer of coniferyl aldehyde, and the cedar wood. The former three provided veratryl aldehyde in a large abundance, instead of coniferyl aldehyde methyl ether. Sinapyl aldehyde provided 3,4,5-trimethoxybenzaldehyde in a large abundance and sinapyl aldehyde methyl ether in a trace abundance. The results showed that TMAH thermochemolysis is an effective tool to obtain information on cinnamyl alcohol end groups, but is not applicable to analysis of cinnamyl aldehyde end groups.     

Effects of pH on chemical stability and de-esterification of fenoxaprop-ethyl by purified enzymes, bacterial extracts, and soils

De-esterification is an initial step in the metabolism of certain herbicides, for example, fenoxaprop-ethyl [(+/-)-ethyl 2-[4-[(6-chloro-2-benzoxaolyl)oxy]phenoxy]propanoate] (FE). The ethyl-ester bond cleavage of FE to fenoxaprop acid (FA) by purified enzymes, crude bacterial enzyme preparations, and soils was investigated. In similar experiments fluorescein diacetate (FDA) was used as an alternative substrate. FE stability was pH sensitive in acidic buffered solutions; that is, below pH 4.6, rapid nonenzymatic hydrolysis of the benzoxazolyl-oxy-phenoxy ether linkage occurred, forming 6-chloro-2,3-dihydro-benzoxazol-2-one (CDHB) and ethyl 4-hydroxyphenoxypropanoate or 4-hydroxyphenoxypropanoate. With porcine esterase and cell-free Pseudomonas fluorescens extracts, activity on FE and FDA was most rapid at pH 7.6-8.6 but decreased 80-90% at pH 5.6. Yeast (Candida cylindrica) lipase-mediated de-esterification of FE and FDA was not as sensitive to pH; that is, activity at pH 4.6 was 70% of that at pH 7.6. Short-term incubations (20 h) were conducted in eight soils (pH 4.5-6.9) treated with (14)C-chlorophenyl ring-labeled FE (2 mg kg(-)(1)). In the most acidic soils (pH 4.4-4.5) 25% of the (14)C was recovered as FA, versus 30-40% in moderately acid soils (pH 5.0-5.6) and 55% in neutral soils (pH 6.8-6.9). There was a similar correlation between soil pH and FDA de-esterification. CDHB was formed in all acidic soils with levels 4-fold greater in pH 4.4-4.5 soils than in pH 5. 0-5.6 soils. CDHB was not formed in neutral soils. Results demonstrate some chemical hydrolysis (benzoxazolyl-oxy-phenoxy ether linkage) of FE in acid soils, the sensitivity of enzymatic de-esterification of FE to pH, and the potential of FDA as a colorimetric indicator for esterase hydrolysis of FE.