Permeability of some fat products to moisture

Summary Films of cocoa butter, highly hydrogenated cottonseed oil, mixtures of highly hydrogenated cottonseed oil and cottonseed oil, chocolate liquor, and sweet milk chocolate were prepared; and their permeability to water vapor was determined by the cup method. The permeability constant was calculated in terms of grams of water diffusing through a centimeter cube in one second under a vapor pressure gradient of one millimeter of mercury across the cube. Under the test conditions employed, the permeability constant for cocoa butter at room temperature was found to vary from 5.8×10⁻¹² to 81.6×10⁻¹². The permeability constants for the highly hydrogenated cottonseed oil and the cocoa butter, under comparable conditions at room temperature, was found to be approximately 1.3×10⁻¹² and 33×10⁻¹², respectively. From data obtained with cocoa butter it was concluded that the permeability constant increased with moderate increases in film thickness. Polymorphism was found to have a large effect on permeability, an approximately 15-fold difference was found between quickly chilled and tempered films of cocoa butter at 3°C. (37.4°F.). The percentage of liquid component in the fat was found to have a large effect on permeability. The increasing of the percentage of liquid cottonseed oil in highly hydrogenated cottonseed oil from 0 to 40% increased the permeability constant from 1.3×10⁻¹² to about 420×10⁻¹². The permeability of chocolate liquor and sweet milk chocolate at room temperature was increased greatly when the relative humidity on the wet side of the films was increased to 100%. The nonfat components absorbed enough moisture to impair the structure of the film. Presented at the 32nd Fall Meeting of the American Oil Chemists' Society, Chicago, Ill., October 20–22, 1958. Fellow, National Confectioners' Association. One of the laboratories of the Southern Utilization Research and Development Division, Agricultural Research Service, U. S. Department of Agriculture.     

Homogeneous catalytic hydrogenation of canola oil using a ruthenium catalyst

Dichlorodicarbonylbis (triphenylphosphine) ruthenium (II), RuCl₂ (CO)₂ (PPh₃)₂, was investigated as a catalyst for edible oil hydrogenation in a preliminary screening of potential catalysts for producing partially hydrogenated fats with lowtrans-isomer content. Refined, bleached and deodorized canola oil was hydrogenated using 1.77 × 10⁻⁵ − 6.64 × 10⁻⁴ mol/kg-oil of ruthenium catalyst equivalent to 1.79 × 10⁻⁴ − 6.71 × 10⁻³ wt% Ru. The effects of temperature (50–180 C) and pressure (50–750 psig) on reaction rate,trans-isomer content and fatty acid composition were examined. The activities of RuCl₂ (CO)₂ (PPh₃)₂ and nickel (Nysel HK-4 and AOCS standard nickel catalyst) were compared on a molar basis. At 4.40 × 10⁻⁴ mol/kg-oil (0.0026 wt/Ni or 0.0044 wt% Ru), 140 C and 50 psig, the nickel catalysts were completely inactive, but the ruthenium catalyst produced an IV drop of 40 units in 60 min. At 110 C, 750 psig and 1.34 × 10⁻⁴ mol/kg-oil (1.35 × 10⁻³ wt% Ru), a hydrogenation rate of 0.89 ΔIV/min and a maximumtrans-isomer content of 10.4% (IV=45.0) was obtained with the ruthenium catalyst.     

Optical application of poly(HEMA-<Emphasis Type="Italic">co</Emphasis>-MMA) containing silver nanoparticles and N,N-dimethylacrylamide

High functional ophthalmic lens materials, poly(HEMA-co-MMA)s, were prepared by the copolymerization of HEMA, MMA, NVP, EDGMA, and N,N-dimethylacrylamide in the presence of silver nanoparticles. Silver nanoparticles have antimicrobial properties and a hydrophilic monomer N,N-dimethylacrylamide has excellent biocompatibility and oxygen transmissibility. The water content was in the range of 36.63–44.45%, indicating the characteristics of general water-content contact lenses, and the refractive index was measured to be in the range of 1.423–1.435. Meanwhile, the oxygen transmissibility ranged from 10.63×10⁻¹¹ to 18.85×10⁻¹¹ (cm²/sec)(mlO₂/ml×mmHg) increasing with increasing the addition ratio of N,N-dimethylacrylamide. The polymeric materials satisfied the basic characteristics required for ophthalmic contact lenses. The polymers can be used to fabricate antimicrobial hydrogel contact lenses with high oxygen transmissibility.     

Kinetic study of the reaction between tocopheroxyl radical and unsaturated fatty acid esters in benzene

A kinetic study of the reaction between a tocopheroxyl radical and unsaturated fatty acid esters has been undertaken. The rates of allylic hydrogen abstraction from various unsaturated fatty acid esters (ethyl oleate2, ethyl linoleate3, ethyl linolenate4, and ethyl arachidonate5) by the tocopheroxyl radical (5,7-diisopropyltocopheroxyl6) in benzene have been determined spectrophotometrically. The second-order rate constants, k₃, obtained are 1.04×10⁻⁵ M⁻¹s⁻¹ for2, 1.82×10⁻² M⁻¹s⁻¹ for3, 3.84×10⁻² M⁻¹s⁻¹ for4, and 4.83×10⁻² M⁻¹s⁻¹ for5 at 25.0°C. Thus, the rate constants, k_abstr/H, given on an available hydrogen basis are k₃/4=2.60×10⁻⁶ M⁻¹s⁻¹ for2, k₃/2=9.10×10⁻³ M⁻¹s⁻¹ for3, k₃/4=9.60×10⁻³ M⁻¹s⁻¹ for4, and k₃/6=8.05×10⁻³ M⁻¹s⁻¹ for5. The k_abstr/H values obtained for the polyunsaturated fatty acid esters3,4, and5 containing H-atoms activated by two π-electron systems are similar to each other, and are about three orders of magnitude higher than that for the ethyl oleate2 containing H-atoms activated by a single π-system. From these results, it is suggested that the prooxidant effect of α-tocopherol in edible oils and fats may be induced by the above hydrogen abstraction reaction.     

Development of a new biosensor for mediatorless voltammetric determination of hydrogen peroxide and its application in milk samples

A new biosensor for the voltammetric detection of hydrogen peroxide was developed based on immobilization of catalase on a clinoptilolite modified carbon paste electrode using bovine serum albumin and glutaraldehyde. The biosensor response was evaluated according to electrode composition, reaction time, solution pH and temperature. The voltammetric signals were linearly in proportion to H₂O₂ concentration in the range 5.0 × 10⁻⁶–1.0 × 10⁻³ M with a correlation coefficient of 0.9975. The detection limit is 8.0 × 10⁻⁷ M and the relative standard deviation for 4.0 × 10⁻⁴ M hydrogen peroxide was 1.83% (n = 6). The biosensor exhibited high sensitivity, and it was determined that it could be used for more than 2 months. In addition, the biosensor was successfully applied for the determination of hydrogen peroxide in milk samples.     

Effects of quenching mechanisms of carotenoids on the photosensitized oxidation of soybean oil

The effects of 0, 1.0 × 10”⁻⁵, 2.5 × 10⁻⁵, and 5.0 × 10⁻⁵ M β-apo-8'-carotenal, β-carotene, and canthaxanthin on the photooxidation of soybean oil in methylene chloride containing 3.3 × 10⁻⁹ M chlorophyll b were studied by measuring peroxide values and conjugated diene content. β-Apo-8'-carotenal, β-carotene, and canthaxanthin contain 10,11, and 13 conjugated double bonds, respectively. The peroxide values and conjugated diene contents of oils containing the carotenoids were significantly lower (P<0.05) than those of control oil containing no carotenoid. As the number of conjugated double bonds of the carotenoids increased, the peroxide values of soybean oils decreased significantly (P<0.05). The quenching mechanisms and kinetics of the carotenoids in the photosensitized oxidation of soybean oil were studied by measuring peroxide values. The steady-state kinetics study showed that carotenoids quenched singlet oxygen to reduce chlorophyll-sensitized photooxidation of soybean oil. The singlet-oxygen quenching rate constants ofβ- apo-8'-carotenal, β-carotene, and canthaxanthin were 3.06 × 10⁹, 4.60 × 10⁹, and 1.12 × 10¹⁰ M⁻¹sec⁻¹, respectively.     

Sorption kinetics of carbon dioxide onto rubidium carbonate

Rubidium carbonate was used as an adsorbent to capture carbon dioxide from gaseous stream of carbon dioxide, nitrogen, and moisture in a fixed-bed to obtain the breakthrough data of CO₂. Experiments were carried out at flow rates of carbon dioxide and nitrogen (5×10⁻⁶–35×10⁻⁶ m³/min), moisture (0.5×10⁻⁶–3.0×10⁻⁶ m³/h), amount of adsorbent (0.5×10⁻³–1.8×10⁻³ kg), mole fraction of carbon dioxide (0.03–0.22), and different sorption temperatures (323–353 K) at atmospheric pressure. The deactivation model in the non-catalytic heterogeneous reaction systems was used to analyze the sorption kinetics among carbon dioxide, carbonate, and moisture, employing the experimental breakthrough data that fit the deactivation model better than the adsorption isotherm models in the literature.     

Drying kinetics and effective moisture diffusivity of purslane undergoing microwave heat treatment

The effects of microwave drying on moisture content, moisture ratio, drying time and effective moisture diffusivity of purslane leaves (Portulaca oleracea L.) were investigated. By increasing the microwave output power (180–900W) and the sample amounts (25–100 g), the drying time decreased from 43 to 12.5 minutes and increased from 27 to 54 minutes, respectively. To determine the kinetic parameters, the drying data were fitted to various models based on the ratios of the differences between the initial and final moisture contents and equilibrium moisture content versus drying time. Among the models proposed, the semi-empirical Midilli et al. model gave a better fit for all drying conditions applied. By increasing the microwave output power and decreasing the sample amount, the effective moisture diffusivity values ranged from 5.913×10⁻¹¹ to 1.872×10⁻¹⁰ m²/s and from 9.889×10⁻¹¹ to 3.292×10⁻¹¹ m²/s, respectively. The activation energy was calculated using an exponential expression based on the Arrhenius equation.     

Electrochemical determination of ascorbic acid at the surface of a graphite electrode modified with multi-walled carbon nanotubes/tetradecyltrimethylammonium bromide

A multi-walled carbon nanotubes (MWCNTs)–tetradecyltrimethylammonium bromide (TTAB) film-coated graphite electrode (GE) was fabricated, and the electrochemical oxidation of ascorbic acid (AA) was studied in Britton–Robinson (B–R) buffer (pH 7.0) using cyclic, square wave, and differential pulse voltammetry (CV, SWV, and DPV). An electroanalytical study of AA and acetaminophen (ACOP) and of several mixtures of these compounds in different ratios was made. A sensitive linear voltammetric response for AA was obtained for the concentration range of 5 × 10⁻⁷ to 1.7 × 10⁻⁴ mol L⁻¹, with a correlation coefficient of 0.992, and the detection limit for AA was found to be 1.1 × 10⁻⁷ mol L⁻¹ using DPV. The relative standard deviation (RSD) was 2.7%, suggesting that the film electrode has excellent day-to-day reproducibility. The proposed voltammetric approach was also applied to the determination of the AA concentration in commercial tablets.     

Bile Acids Conjugation in Human Bile Is Not Random: New Insights from <Superscript>1</Superscript>H-NMR Spectroscopy at 800 MHz

Bile acids constitute a group of structurally closely related molecules and represent the most abundant constituents of human bile. Investigations of bile acids have garnered increased interest owing to their recently discovered additional biological functions including their role as signaling molecules that govern glucose, fat and energy metabolism. Recent NMR methodological developments have enabled single-step analysis of several highly abundant and common glycine- and taurine- conjugated bile acids, such as glycocholic acid, glycodeoxycholic acid, glycochenodeoxycholic acid, taurocholic acid, taurodeoxycholic acid, and taurochenodeoxycholic acid. Investigation of these conjugated bile acids in human bile employing high field (800 MHz) ¹H-NMR spectroscopy reveals that the ratios between two glycine-conjugated bile acids and their taurine counterparts correlate positively (R ² = 0.83–0.97; p = 0.001 × 10⁻²–0.006 × 10⁻⁷) as do the ratios between a glycine-conjugated bile acid and its taurine counterpart (R ² = 0.92–0.95; p = 0.004 × 10⁻³–0.002 × 10⁻¹⁰). Using such correlations, concentration of individual bile acids in each sample could be predicted in good agreement with the experimentally determined values. These insights into the pattern of bile acid conjugation in human bile between glycine and taurine promise useful clues to the mechanism of bile acids’ biosynthesis, conjugation and enterohepatic circulation, and may improve our understanding of the role of individual conjugated bile acids in health and disease. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Fluorescence Enhancement Effect for the Determination of Nucleic Acids With Morin–NanoTiO<Subscript>2</Subscript>

It is found that nucleic acids can greatly enhance the fluorescence intensity of morin–nanoTiO₂. Under optimum conditions, the enhanced fluorescence intensity of the system is in proportion to the concentration of nucleic acids in the range of 2.0 × 10⁻⁸ to 2.2 × 10⁻⁷ g mL⁻¹ for calf thymus DNA (ctDNA) and 1.0 × 10⁻⁸ to 2.5 × 10⁻⁷ g mL⁻¹ for yeast RNA (yRNA). The detection limits are 4.8 × 10⁻⁹ g mL⁻¹ for ctDNA and 1.2 × 10⁻⁹ g mL⁻¹ for yRNA, respectively. This method has satisfactorily been used for the determination of nucleic acids in actual sample.     

Kinetic Study of the Prooxidant Effect of α-Tocopherol. Hydrogen Abstraction from Lipids by α-Tocopheroxyl Radical

A kinetic study of the prooxidant effect of α-tocopherol was performed. The rates of allylic hydrogen abstraction from various unsaturated fatty acid esters (ethyl stearate 1, ethyl oleate 2, ethyl linoleate 3, ethyl linolenate 4, and ethyl arachidonate 5) by α-tocopheroxyl radical in toluene were determined, using a double-mixing stopped-flow spectrophotometer. The second-order rate constants (k _p) obtained are <1 × 10⁻² M⁻¹ s⁻¹ for 1, 1.90 × 10⁻² M⁻¹ s⁻¹ for 2, 8.33 × 10⁻² M⁻¹ s⁻¹ for 3, 1.92 × 10⁻¹ M⁻¹ s⁻¹ for 4, and 2.43 × 10⁻¹ M⁻¹ s⁻¹ for 5 at 25.0 °C. Fatty acid esters 3, 4, and 5 contain two, four, and six –CH₂– hydrogen atoms activated by two π-electron systems (–C=C–CH₂–C=C–). On the other hand, fatty acid ester 2 has four –CH₂– hydrogen atoms activated by a single π-electron system (–CH₂–C=C–CH₂–). Thus, the rate constants, k _abstr/H, given on an available hydrogen basis are k _p/4 = 4.75 × 10⁻³ M⁻¹ s⁻¹ for 2, k _p/2 = 4.16 × 10⁻² M⁻¹ s⁻¹ for 3, k _p/4 = 4.79 × 10⁻² M⁻¹ s⁻¹ for 4, and k _p/6 = 4.05 × 10⁻² M⁻¹ s⁻¹ for 5. The k _abstr/H values obtained for 3, 4, and 5 are similar to each other, and are by about one order of magnitude higher than that for 2. From these results, it is suggested that the prooxidant effect of α-tocopherol in edible oils, fats, and low-density lipoproteins may be induced by the above hydrogen abstraction reaction.     

Chia seeds as a source of natural lipid antioxidants

Chia (Salvia sp) seeds were investigated as a source of natural lipid antioxidants. Methanolic and aqueous extracts of defatted chia seeds possessed potent antioxidant activity. Analysis of 2 batches of chia-seed oils demonstrated marked difference in the fatty acid composition of the oils. In both batches, the oils had high concentrations of polyunsaturated fatty acids. The major antioxidant activity in the nonhydrolyzed extract was caused by flavonol glycosides, chlorogenic acid (7.1 × 10⁻⁴ mol/kg of seed) and caffeic acid (6.6 × 10⁻³ m/kg). Major antioxidants of the hydrolyzed extracts were flavonol aglycones/kaempferol (1.1 × 10⁻³ m/kg), quercetin (2.0 × 10⁻⁴ m/kg) and myricetin (3.1 × 10⁻³ m/kg); and caffeic acid (1.35 × 10⁻² m/kg). Two methods were used to measure antioxidant activities. Both were based on measuring bleaching ofβ-carotene in the coupled oxidation ofβ-carotene and linoleic acid in the presence of added antioxidants.     

Synthesis and Electrical Properties of Three Novel Poly(Ferrocenyl-Schiff Bases) and Their Charge Transfer Complexes with Iodine

Three ferrocenyl-Schiff base monomers were synthesized by the condensation of ferrocenecarboxaldehyde and phenylenediamine under neutral conditions, and then used to produce copolymer materials with terephthaloyl chloride monomer by the Friedel–Crafts method. The model compound and copolymers of three novel poly(ferrocenyl-Schiff bases) and their charge transfer complexes with iodine were successful obtained and their structures were characterized by ¹H-NMR, infrared, and ultraviolet spectra. The effect of degree of iodine doping on their structures was studied. It appears that poly-p-bis(ferrocenyl-Schiff base) can be doped to a higher iodine level than the other two prepared materials. Electrical measurement results showed that the conductivity can be increased several orders of magnitude after doping with iodine. The maximum conductivity at room temperature is 3.17 × 10⁻⁴ S cm⁻¹ indicating that the conducting polymer has potential as a semiconductor material.     

Simple Determination of Deoxycholic and Ursodeoxycholic Acids by Phenolphthalein-β-Cyclodextrin Inclusion Complex

An expeditious colorimetric methodology for the determination of the deoxycholic acid (DCA) and of the ursodeoxycholic acid (UDCA) in pharmaceutical formulations is reported. The method is based on their competitive complexation reaction with a color indicator to form β-cyclodextrin-inclusion complexes. Several pH color indicators were tested, but phenolphthalein (PHP) showed the best interaction with the β-cyclodextrin (β-CD) with an inclusion yield higher than 95%. The best concentrations of β-cyclodextrin to form inclusion complexes were 1.24 × 10⁻³ and 6.2 × 10⁻⁴ M at pH 9.5 and 10.5. Statistical analysis of the results showed that the pH had a significant effect on the DCA determination and that high β-CD-PHP inclusion complex concentrations had a significant negative effect on the UDCA determination (p < 0.05). The limit of detection and limit of quantification were 3.94 × 10⁻⁵ and 1.31 × 10⁻⁴ M for DCA (range: 6.1 × 10⁻⁶–3.13 × 10⁻³ M), 4.08 × 10⁻⁵  and 1.36 × 10⁻⁴ M for UDCA (range: 6.05 × 10⁻⁶–3.88 × 10⁻⁴ M). This simple and cheap method showed high stability and feasible instrumentation.     

Composite materials with the use of shale phenols

Polymer materials with cohesion strengths from 2.9 to 5.4 MPa and adhesion to steel 3 from 2.6 to 3.1 MPa were prepared based on compositions of shale phenols. The specific elongation varied from 75 to 125%. In the use of compositions for the immobilization of industrial wastes, the leachability of strontium and cesium was 1 × 10⁻¹⁰ and 1 × 10⁻¹² cm²/s, respectively, whereas the leachability of cobalt and ruthenium was 1 × 10⁻¹³ cm²/s, which is several orders of magnitude lower than the leachability of 1 × 10⁻⁸ cm²/s from Portland cement.     

Inhibition by cardiolipins of platelet-activating factor-induced rabbit platelet activation

Evidence is presented that cardiolipin, a naturally occurring phospholipid, inhibits the aggregatory effect of platelet-activating factor (paf) on rabbit plateletsin vitro. Bovine heart cardiolipin was shown to inhibit the aggregation of washed rabbit platelets induced by 1×10⁻¹⁰ M and 2×10⁻¹⁰ M paf with IC₅₀ values (doses for half-maximal inhibition) of 8.4±0.8×10⁻⁷ M and 2.6±0.6×10⁻⁶ M, respectively. Phosphonocardiolipin was also able to inhibit platelet aggregation induced by 1× 10⁻¹⁰ M paf with an IC₅₀ value of 3±1×10⁻⁷M. Both compounds, in concentrations up to 1×10⁻⁵ M, were unable to aggregate washed rabbit platelets and failed to inhibit the aggregation induced by 0.9 and 1.8 μM adenosine diphosphate or 0.2–1.0 μM arrchidonic acid. By contrast, the acetylated derivative of cardiolipin exerted an aggregatory effect on aspirin-treated rabbit platelets in the presence of creatine phosphate/creatine phosphokinase. This aggregation was inhibited by the specific paf antagonists BN 52021 and WEB 2086. Also, platelets treated with acetyl-cardiolipin were insensitive to the aggregatory effect of paf. Phosphatidic acid, phosphatidylglycerol,bis(dipalmitoylglycero)phosphate and their phosphono analogues were totally inactive. Similar data were obtained when platelet-rich plasma was used instead of washed rabbit platelets. Our results support the hypothesis that the effect of cardiolipin is mediated through specific paf receptors that act on the rabbit platelet membrane.     

Kinetic model of asymmetric reduction of 3-oxo-3-phenylpropionic acid ethyl ester using <Emphasis Type="Italic">Saccharomyces cerevisiae</Emphasis> CGMCC No.2266

The kinetic model of asymmetric reduction of 3-oxo-3-phenylpropionic acid ethyl ester using Saccharomyces cerevisiae CGMCC No.2266 with 10% glucose as co-substrate to realize the regeneration of NADPH was established. The effect factors on reduction, the type and the content of co-substrate and coenzyme, and the changes of the substrate and product content vs. time during the reaction process were investigated. The results indicate that 10% glucose can increase the reaction conversion from 23.0% to 98.4% and NADPH is reducer. The reduction process conforms with sequence mechanisms. The model parameters are as follows: v _m =5.0×10⁻⁴ mol·L⁻¹·h⁻¹, k₁=1.5×10⁻⁶ mol·L⁻¹·h⁻¹, k₂=3.0×10⁻³ mol·L⁻¹·h⁻¹. The kinetic model is in good agreement with the experimental data.     

Production of α-galactosidase fromAspergillus awamori: Properties and action on para-nitrophenyl α-D-galactopyranoside and galacto-Oligosaccharides of soy milk

Soybean products including soy milk can provide needed protein for human consumption. Soybean flour contains raffinose and stachyose considered responsible for flatulence often associated with soy products. A partially purified preparation of α-galactosidase and invertase, prepared fromAspergillus awamori NRRL 4869 cultured on wheat bran, hydrolyzes the oligosaccharides of soy milk. The α-galactosidase exhibited its maximum activity at pH 5.0 and was stable in that pH range. The optimum temperature was 50 C; however, 8% of α-galactosidase activity was lost after 15 min at 55 C., and complete inactivation was observed after 14 min at 70 C. Parachloromercuribenzoate, AgNO₃, HgCl₂, and iodine exhibited strong inhibitory effects on the enzymes. Km values of the α-galactosidase with melibiose and raffinose as substrates were 3.0 and 3.6 × 10⁻² M, respectively, and the molecular weights of both enzymes were estimated to be about 130,000 on the basis of Sephadex and sodium dodecyl sulfate (SDS)-polyacrylamide gel electrophoresis.     

Homogeneous electrocatalytic oxidation of <Emphasis Type="SmallCaps">d</Emphasis>-penicillamine with ferrocyanide at a carbon paste electrode: application to voltammetric determination

The electrooxidation of d-penicillamine (d-PA) was studied in the presence of ferrocyanide as a homogeneous mediator at the surface of a carbon paste electrode in aqueous media using cyclic voltammetry (CV) and chronoamperometry. Under optimum pH in CV the oxidation of d-PA occurs at a potential about 380 mV less positive than that in the absence of ferrocyanide. The catalytic oxidation peak current was dependent on the d-PA concentration and a linear calibration curve was obtained in the ranges 4.0 × 10⁻⁵–2.0 × 10⁻³ M and 8.0 × 10⁻⁶–1.8 × 10⁻⁴ M of d-PA with CV and differential pulse voltammetry (DPV) methods, respectively. The detection limits (3σ) were determined as 1.9 × 10⁻⁵ and 3.2 × 10⁻⁶ M by CV and DPV methods. This method was also used for the determination of d-PA in pharmaceutical preparations by the standard addition method.