The influence of food emulsifiers on fat and sugar dispersions in oils. II. Rheology,colloidal forces

The influence of food emulsifiers on the viscoelastic properties (storage modulus and yield value) of fat and sugar dispersions in vegetable oils has been investigated. It was found that almost all of the emulsifiers tested influence the rheology of the dispersions. The magnitude and the direction of the rheological changes depend on both the type and the amount of emulsifier. In most cases the changes are relatively small, especially for fat crystals. Generally speaking, the largest changes are caused by lecithins and saturated monoglycerides. The magnitudes of colloidal forces and equilibrium distances between the particles have been estimated from the rheological network model of van den Tempel [J. Colloid Sci. 16:284 (1964)] and from the correlation of the yield value to the interaction energy by Gillespie [J. Colloid Sci. 15:219 (1960)] and Tadros [Langmuir 6:28 (1990) andChemistry and Industry 7:210 (1985)]. The results indicate that van der Waals forces alone cannot be responsible for the interparticle interaction in fat or sugar dispersions. The formation of water bridges is discussed as a probable source of interaction in both cases. Furthermore, the validity of the network model for fat and sugar dispersions in oils is questionable.     

The influence of food emulsifiers on fat and sugar dispersions in oils. III. Water content,purity of oils

The influence of water on the interactions between fat and sugar crystals dispersed in triglyceride (vegetable) oils was qualitatively estimated from sedimentation and rheological experiments. The experiments were performed both with and without food emulsifiers (monoglycerides and lecithins) present in the oil. The effects of minor natural oil components (nontriglycerides) on the interactions and on emulsifier adsorption to the crystals were examined by comparing a commercial refined oil and a chromatographically purified oil. The results show that water generally increases the adhesion between fat and sugar crystals in oils and also increases the surface activity of the oil-soluble food emulsifiers. Minor oil components give a small increase in the adhesion between fat and sugar crystals in oils, but do not influence the adsorption of food emulsifiers in any systematic way.     

Polymorphism of stabilized and nonstabilized tristearin,pure and in the presence of food emulsifiers

The polymorphism of tristearin (SSS) was studied by means of differential scanning calorimetry and powder X-ray diffraction. The influence of 5% in weight of different food emulsifiers—i.e., 1-monostearin, sorbitan tristearate, and sugar monostearate—was also studied. Because polymorphism is sensitive to thermal treatment, two thermal conditionings were applied. According to the dynamic process (melting, quenching, and heating at 5°C/min), SSS showed three polymorphic forms: α, β′, and β₁. The presence of the emulsifiers hindered the β′→β transformation, and a destructured β₂ form was recorded. According to the stabilization process (stabilization at 57°C for various periods of time), SSS showed two β′ forms: β ₂ ^′ and β ₁ ^′ . Three hours of stabilization were necessary to recover the whole triglyceride under the β form. The emulsifiers slowed down the polymorphic transition rates. Indeed, after six hours of stabilization, mixtures of β′ and β were observed. Sugar monostearate seemed to have the most powerful effect on the transition kinetics because large amounts of α form were detected. Presented at the 86th AOCS Annual Meeting & Expo, in San Antonio, Texas, in May 1995.     

Weak gels of fat crystals in oils at low temperatures and their fractal nature

The formation of fat crystal gels in soybean oil has been studied by sedimentation in a low concentration region at 10–25°C. At 10°C, weak gels were formed with 1% crystals, and no gels formed at concentrations of 2–5%. At temperatures of 15–25°C, no gels were formed at concentrations of 1–5%, and samples sedimented. Stronger gels of fat crystals were formed with ∼10% fat crystals at all temperatures examined. Formation of weak gels is a consequence of the fractal nature of fat crystal aggregates and sediments. At low temperature, the interaction is weak. The fractal dimension is then high, and the floc size is large for low crystal concentrations. These large flocs form a three-dimensional network that act as a weak gel and withstand gravitational force. When the temperature is increased, the fat crystal interaction becomes stronger, fractal dimension decreases, and floc size decreases. Smaller flocs have a higher density, pack more easily, and sediment. Similar effects are observed when the concentration of fat crystals is increased at low temperature due to a decrease in floc size.     

Wetting of fat crystals by triglyceride oil and water. 1. The effect of additives

Wetting of fat crystals has been extensively examined in this work by contact angle (θ) measurements of fat crystal, oil, and water in three-phase contact. Contact angle was measured in oil. The crystals were nonpolar and wetted by oil for a contact angle equal to 0°, and polar and wetted by water for an angle equal to 180°. Fat crystals are expected to contribute to the stability of margarine emulsions if they are preferentially wetted by the oil phase (0°<θ<90°), but result in instability if they are preferentially wetted by the water phase (90°<θ<180°). In the absence of oil and water additives, fat crystals in α and β' polymorphs were introduced to the oil/water interface from the oil side (contact angle θ ∼ 30°). β Polymorphs were completely wetted by oil (θ ≈ 0°). The contact angle for β' crystals decreased with increasing temperature and was slightly lower in butter oil than in soybean oil. Emulsifiers in the oil phase (lecithins, monoglycerides and their esters, ethoxylated emulsifiers) and surface-active proteins in the water phase (milk proteins) made the crystals more polar (higher θ). Nonsurface-active proteins, sugar, and citric acid had no significant effect, although concentrations of salt lowered θ. Contact angle increased with temperature for emulsifiers of limited solubility in the oil, e.g., saturated monoglyceride.     

Water-in-triglyceride oil emulsions. Effect of fat crystals on stability

The influence of low concentrations (0.1-5%) of fat crystals on the stability of water-in-soybean oil emulsions was examined by light scattering and sedimentation experiments. Both the initial flocculation/coalescence rate and long-term stability against water separation were determined. The initial flocculation/coalescence rate increased upon addition of small amounts of fat crystals. When the crystal concentration was increased above a critical concentration (specific to a system), a decrease in the flocculation/coalescence rate occurred. The increased flocculation/coalescence rate is likely the effect of bridging of water droplets by fat crystals. Fat crystal wetting by water is an important criterion for this phenomenon to occur. Emulsion stabilization for crystal concentrations above critical is caused by a mechanical screening of water droplets. The presence of considerable amounts of crystals in oil also lowered the density difference between droplet and medium, and enhanced viscosity. The degree of increase in viscosity depended upon the emulsifier. Both a decrease in density difference and an increase in viscosity play a role in hindering flocculation/coalescence of droplets. In long-term studies of water separation, all concentrations of fat crystals stabilized the water-in-oil emulsions. The droplet size of these emulsions increased until the critical droplet size was approached where the screening effect of crystals on the droplets no longer stabilized the emulsions. The stabilizing effect for emulsions with monoolein was continuously improved by increasing the amount of crystals up to 5%. For lecithin-stabilized emulsions, an optimal effect was achieved for fact crystal concentrations of 1–2%.     

The influence of temperature on interactions and structures in semisolid fats

The strength of fat crystal networks in oil increases at elevated temperatures due to increased adhesion between partially melted crystal surfaces. This strong adhesion, in combination with low oil viscosity (weak hydrodynamic force), is the reason for extensive fat crystal flocculation at elevated temperatures. The crystal flocs likely sinter, dramatically increasing the thickness of semisolid fats. Crystal growth also occurs. The described temperature-induced crystal changes may be suppressed by a controlled sintering process at low temperature. Emulsifiers, such as sorbitan esters of tristearate, also suppress the temperature-induced changes. Fat crystals can be used as thickeners or gelling agents for triglyceride oils in various applications. It is possible to direct the thickening to a specific temperature, and to control the degree of thickening, by choice of fat phase composition, additives, tempering conditions, and crystallization technique.     

Equilibrium,Kinetics, and Thermodynamics of Bovine Serum Albumin Adsorption on Single-Walled Carbon Nanotubes

We investigated the equilibrium, kinetics, and thermodynamics of bovine serum albumin (BSA) adsorption on single-walled carbon nanotubes (SWNTs) from aqueous solutions with different pH and temperatures. We analyzed the experimental adsorption equilibrium and kinetic data to evaluate the adsorption characteristics of SWNTs for BSA. The results show that the effects of pH and temperature were important. Moreover, the adsorption isotherm data of BSA on SWNTs are consistent with the Langmuir and Freundlich models, while the kinetics can be expressed by the pseudo-first-order and the intraparticle diffusion rate models. The maximum protein adsorption capacity of SWNTs, which have a surface area of 191.2 m²/g, was found to be 609.8 mg g^?1 at pH 4 and 40°C, and this was the highest value obtained among our previous studies examined with various metal oxides. In addition, the zeta potential measurements were examined to understand the effects of charge density of the surface and the protein on the adsorption process. Thermodynamic analysis results indicate that the nature of adsorption changes with pH. SWNTs were found to be effective for BSA adsorption.     

Simplified gravimetric determination of total fat in food composites after chloroform-methanol extraction

A modification of Association of Official Analytical Chemists (AOAC) method 983.23 for the quantitative determination of total lipid in food composites was evaluated for the measurement of total fat. The procedure is based on the Bligh and Dyer chloroform/methanol total lipid extraction. Relative to AOAC 983.23, the proposed method is less labor-intensive and is applicable to batch analysis of a larger number of samples, thus reducing the cost of analysis and increasing sample throughput. Total lipid values from the proposed method are comparable to those from AOAC 983.23 and slightly higher than total fat determined by acid hydrolysis (AOAC 954.02, 945.44, or 922.06). Recoveries of standard additions of different food-grade oils from a mixed food composite were essentially quantitative, ranging from 96 to 101%. Total lipid measured in Total Diet Standard Reference Material 1548 (SRM 1548, National Institute of Standards and Technology) was 101% of the certified mean total fat content and within the certified range. The method is to be suitable for analysis of food composites with between 0.15 and 1.5 g total fat (3 to 30% by weight). More than 600 samples of a variety of total diet composites were collected and assayed as diet quality control samples for two National Heart, Lung and Blood Institute-sponsored multicenter clinical feeding trials: DELTA (Dietary Effects on Lipoproteins and Thrombogenic Activity) and DASH (Dietary Approaches to Stop Hypertension). The mean coefficient of variation was 1.2% for duplicate assays of these samples over the course of two years and multiple analysts. In addition, total lipid values for more than 200 samples of a diet composite quality control material, used in this laboratory over a two-year period, had a 3.99% coefficient of variation. Although the accuracy of all gravimetric total fat methods with respect to the U.S. Food and Drug Administration’s Nutritional Labeling and Education Act (NLEA) definition of total fat as the sum of triglycerides remains to be determined, the reported modification of AOAC 983.23 yields a total fat content of acceptable accuracy relative to other gravimetric methods, and with proper quality control the method has excellent precision.     

Kinetics,Isotherms and Equilibrium Study of Co(II) Adsorption from Single and Binary Aqueous Solutions by Acacia nilotica Leaf Carbon

The removal of cobalt ion from aqueous solution by Acacia nilotica leaf carbon (HAN), is described. Effect of pH, agitation time and initial concentration on adsorption capacities of HAN was investigat...     

Triglyceride composition of ewe,cow, and goat milk fat

The separation and identification of the components in milk fat, which are mainly triglycerides, is a challenge due to its complex composition. A reverse-phase high-performance liquid chromatography (HPLC) method with gradient elution and light-scattering detection is described in this paper for the triglyceride analysis in ewes’ milk fat. Triglyceride identification was carried out by combining HPLC, gas-liquid chromatography (GLC), and the calculated equivalent carbon numbers of several triglyceride standards. Quantitation of partially resolved peaks in the HPLC chromatogram was accomplished by applying a peak deconvolution program. Forty-four fatty acids were identified by GLC analysis, but only 19 were used for the following prediction of triglyceride molecular species; 181 triglycerides were identified, some of which were grouped at the same peak and needed application of the deconvolution program. Consequently, coefficients of variation were close to or lower than 5%. Moreover, the triglyceride composition of ewe, cow, and goat milk fat were compared by using these methods. These results show that ewe milk fat is richer in short- and medium-chain triglycerides, and cow milk fat is richer in long-chain and unsaturated triglycerides.     

Adsorption of tannic acid on chitosan-montmorillonite as a function of pH and surface charge properties

Chitosan, a natural biopolymeric cation, is a candidate to modify montmorillonite for the adsorption of anions. As an anionic organic pollutant the adsorption of tannic acid was studied. Because of protonation/deprotonation reactions of both chitosan-montmorillonite and tannic acid, the adsorption process is strongly pH-dependent. The objective of this work is to characterize the pH dependency of adsorption in combination with surface charge determinations.Montmorillonite was modified with different amounts of chitosan, corresponding to 20–1000% of the cation exchange capacity (CEC). The deacetylation degree of chitosan was determined by polyelectrolyte titration and was found to be 74%. The uptake of chitosan was determined by the C-content. The interlayer expansion was investigated by X-ray powder diffraction. The adsorption capacity for tannic acid was investigated with the batch technique at pH 3, 4, 5 and 8. As a measure for the adsorption properties, the electrokinetic surface charge was determined with a particle charge detector.The uptake of chitosan by montmorillonite is up to 152% (1.69 mol_c kg^− 1) of the CEC. The resulting anion exchange capacity of chitosan-montmorillonite calculated from C-content is 0.43 mol_c kg^− 1. At low loadings with chitosan (24.7 and 49.5% uptake), a monolayer is formed in montmorillonite. At an uptake of 96.8%, a bilayer structure is observed, which becomes more dominant at higher loadings. On the external surface, a monolayer of chitosan was formed. From pH 4 to 8, the surface charge of all modified montmorillonites is with − 9 to 8 mmol_c kg^− 1 close to the point of zero charge. The maximal adsorption capacity for tannic acid is found with 240 g kg^− 1 (0.14 mol_c kg^− 1) at pH 4. The adsorption process fits in well with the Freundlich isotherm. At lower as well as higher pH values the adsorption capacity decreases up to about 25%. Most probably the exchange sites in the interlayer do not contribute to the adsorption of tannic acid. The observed surface charge is lower than the adsorbed amount of tannin. It is thought that tannin is adsorbed also by van der Waals forces besides ionic forces.     

Adsorption Behavior of Halogenated Anesthetic and Water Vapor on Cr‐Based MOF (MIL‐101) Adsorbent. Part I. Equilibrium and Breakthrough Characterizations

A synthesized chromium‐based metal organic framework (Cr‐MOF) was used for the adsorption of halogenated anesthetics, i.e., sevoflurane (SF). Adsorption isotherm and breakthrough experiments involving SF (reference sorbate) and water vapor were measured at 298 K and atmospheric pressure on both Cr‐MOF and a commercially used reference adsorbent. The Cr‐MOF MIL‐101 showed a significantly higher SF adsorption capacity and much higher selectivity relative to water vapor compared to the reference adsorbent. Binary‐mixture breakthrough tests demonstrated a “roll‐up effect” for SF on the reference adsorbent while no such effect was observed on MIL‐101.     

The chemical bonding of copper ions on kaolin from Suzhou, China

Reactions of copper with kaolin are important in determining copper fate in the environment. Adsorption characteristics of Cu by the kaolin from Suzhou, China were investigated at varying Cu concentrations (0 to 100 mg/l), pH values (approximately 2 to 11) and temperature (25, 40 and 50 °C). Cu adsorption by the kaolin was well described by the Langmuir and Freundlich adsorption equations. The kaolin did not exhibit the adsorption maximum, 666.67 mg/kg, as determined by the linearized form of the Langmuir equation. The k_d values decreased exponentially with increasing initial Cu concentrations in the solution. A unit increase in pH resulted in approximately 8.47, 9.61 and 10.82% increase in Cu adsorption by the kaolin at the initial Cu concentration 5, 50, 100 mg/l, respectively. The pH₅₀ values increase with increasing initial Cu concentration. Desorption of Cu was well described by the linear model (y = 0.0917x + 0.7136) with correlation coefficient R² = 0.9994. Most of the adsorbed Cu is nonspecific adsorption; the mobility of Cu in the kaolin from Suzhou, China is high under low pH conditions.     

Sintering of fat crystal networks in oil during post-crystallization processes

Several foods contain semi-solid fats that consist of solid crystals dispersed in a liquid oil. In oil-continuous margarine, butter, and chocolate, fat crystals determine properties such as consistency, stability against oiling-out, and emulsion stability. Trends toward foods with less fat and/or less saturated fat create a need for understanding and controlling the properties of fat crystal dispersions. Fat crystals form a network in oil due to mutual adhesion. One source of strong adhesion is formation of solid bridges (sintering), which has been studied in this work through sedimentation and rheological experiments. Results indicate that sintering may be created by crystallization of a fat phase with a melting point between that of the oil and the crystal. Generally speaking, β′ crystals were sintered by β′ fat bridges, favored by rapid cooling, and β crystals by β fat bridges, favored by slow cooling. The existence of the same polymorphic form of the crystal and bridge indicated that solid bridges, rather than bridges formed by small crystal nuclei, were formed. A maximum in sintering ability for an optimal sintering fat concentration occurred due to competition between bridge formation and other crystallization processes. Some emulsifiers influenced the sintering process. For example, monooolein made it more pronounced, while technical lecithin had the opposite effect.     

Production,health implications and applications of oleogels as fat replacer in food system: A review

Various food formulations widely utilized solid fats to provide specific textural properties and sensory attributes. Partially hydrogenated oil was commonly used as solid fat before being banned by FDA recently because of the existence of trans fats. Oleogels, semi-solid gel typically prepared from liquid vegetable oil and food-grade oleogelators, is developed as an alternative for solid fats that is free of trans fat and low in saturated fats. Oleogels are prepared via indirect or direct oleogelation technology by which the liquid oil is entrapped in a three-dimensional network with the aid of low molecular weight oleogelators (LMOGs) and high molecular weight oleogelators (HMOGs). Oleogels received tremendous attention from food scientists to be used in various food applications, particularly high-fat products such as comminuted meat, chocolates, ice cream, shortening and margarine and even as a deep-frying medium. They satisfy not only the current trends of consumers for healthy food products (free of trans fat and low in saturated fat) but also provide viscoelastic solid- and gel- like properties to structure high fat food products. More importantly, recent studies showed that oleogels tend to be metabolized differently from conventional fats and oils giving them an additional advantage in improving the nutritional value of high-fat foods. Therefore, this review aims to provide an overview that captures the latest studies on oleogels from their production via direct dispersion and indirect dispersion methods, processing conditions that influence the physical properties, metabolism and health attributes as well as recent application in food products.     

Single component and competitive adsorption of propane, carbon dioxide and butane on Vycor glass

Equilibrium of gas phase adsorption on Vycor glass has been investigated. Adsorption isotherms for propane, carbon dioxide and butane as pure gases, binary mixtures and ternary mixtures were determined experimentally as a function of temperature using a volumetric method. The single-component isotherms were described with the Langmuir and Freundlich equations. Additionally, a second order isotherm based on statistical thermodynamics and an isotherm equation based on vacancy solution theory taking into account real phase behavior were used for fitting single-component equilibrium data. In order to describe the measured partial isotherms for binary mixtures, at first simple extensions of the single-component isotherm models were used, i.e., the conventional competitive Langmuir model and a multi-Freundlich equation based on the ideal adsorbed solution theory (IAS). Since these two simple isotherm models failed to represent the unusual competitive behavior observed, three model extensions using additional mixture parameters were applied, i.e., two modified multi-Langmuir equations based on: (a) statistical thermodynamics and (b) vacancy solution theory and a modified multi-Freundlich IAS model correcting spreading pressure uncertainties. These three model equations were found to be capable to describe the observed behavior better. Finally, the measured partial adsorption equilibrium data of the ternary system were correlated based on the extended equations using the determined additional binary parameters. The results obtained reveal the difficulty to predict accurately multi-component adsorption equilibria.     

D5MC沉降式离心机的应用与改进

介绍了D5MC沉降式离心机的结构特点、主要技术参数及使用方法,指出了其在实际生产过程中出现的问题及采取的改进措施。     

The influence of chemical interesterification on physicochemical properties of complex fat systems 1. Melting and crystallization

The effects of blending palm oil (PO) with soybean oil (SBO) and lard with canola oil, and subsequent chemical interesterification (CIE), on their melting and crystallization behavior were investigated. Lard underwent larger CIE-induced changes in triacylglycerol (TAG) composition than palm oil. Within 30 min to 1 h of CIE, changes in TAG profile appeared complete for both lard and PO. PO had a solid fat content (SFC) of ∼68% at 0°C, which diminished by ∼30% between 10 and 20°C. Dilution with SBO gradually lowered the initial SFC. CIE linearized the melting profile of all palm oil-soybean oil (POSBO) blends between 5 and 40°C. Lard SFC followed an entirely different trend. The melting behavior of lard and lard-canola oil (LCO) blends in the 0–40°C range was linear. CIE led to more abrupt melting for all LCO blends. Both systems displayed monotectic behavior. CIE increased the DP of POSBO blends with ≥80% PO in the blend and lowered that of blends with ≤70% PO. All CIE LCO blends had a slightly lower DP vis-à-vis their noninteresterified counterparts.     

The Adsorption of Pollutants by Peat,Lignite and Activated Chars

The ability of peat, lignite and activated chars made from peat and lignite to adsorb dyes and metals from wastewater and NO₂ from air was investigated. Equilibrium isotherms were determined to assess the maximum adsorption capacity of the adsorbents for the pollutants. Kinetic studies for the adsorption of dyes and metal ions onto the adsorbents were undertaken in agitated batch adsorbers. Mass transport models were tested to predict the concentration decay curves in batch adsorbers. The models tested were single resistance models based on the assumption of a single external mass transfer coefficient and two resistance models which included an internal diffusion coefficient and an external mass transfer coefficient. The surface phenomena which influence the extent and the rate of uptake have been studied. The equilibrium capacity data conform to Langmuir plots. A previously proposed model was used to evaluate the external single resistance mass transfer model and was successfully applied to predict the adsorption of metal ions in single component systems under batch conditions. It has been shown that the assumption of negligible intraparticle diffusion is valid and that external film diffusion is the rate limiting step in describing the adsorption processes at high sorbent loadings. The same type of result is not observed for the adsorption of coloured organic matter onto peat where the sorption processes cannot be successfully modelled by use of a single resistance model and a two resistance model incorporating internal diffusion is required. The surface phenomena which influence the extent and the rate of uptake of NO₂ have been studied. The type of chars produced and the activation processes affect the adsorption. As activation increases, micropore volume and surface area increase and the maximum capacity of the adsorbent increases. Surface area alone is not the only parameter which affects equilibrium uptake. © 1997 SCI.