Organogelation of plant oils and hydrocarbons by long-chain saturated FA,fatty alcohols,wax esters,and dicarboxylic acids

Conversion of oils into gels generally involves altering the chemical characteristics of the liquid. We describe here the gelling of vegetable oils, essential oils, and hydrocarbons at ambient temperature, without changing the chemical characteristics of the liquids, using saturated FA having carbon chain lengths of 10 to 31. The gelling ability of the added FA increased linearly with their chain lengths. Structure-function studies demonstrated that the carboxyl group, position of an additional hydroxyl group, and acyl chain length played an important role in gelation. Long-chain saturated fatty alcohols, wax esters, and dicarboxylic acids also had the ability to gel plant oils and hydrocarbons.     

Structuring of edible oils by mixtures of γ-oryzanol with β-sitosterol or related phytosterols

The relation between molecular structure of oil-structuring agents and their gel-forming capability was investigated for mixtures of the phytosterol ester γ-oryzanol with a series of phytosterols. Dihydrocholesterol, cholesterol, β-sitosterol, and stigmasterol were found to form firm transparent gels with γ-oryzanol in sunflower oil under the conditions used in this work. The mixture of β-sitosterol with γ-oryzanol in sunflower oil does not gel immediately on cooling, but mechanical agitation such as shear promotes gelling. Gels that are formed immediately after cooling show a higher modulus than gels for which there is a time delay between cooling and agitation (150 vs. 100 kPa). The effect of oscillatory shear parameters (amplitude, frequency) is small, as long as the yield stress of the gel is not exceeded. The gels withstand compression very well (up to deformations of 10%), but yield at very small deformations. The enthalpy of melting of the solid phase is estimated to be 26±4 kJ/mol, putting it in the same range as for certain fibrillar steroid-derived organogels.     

Crystal morphology,microstructure, and textural properties of model lipid systems

Mixtures of model lipid systems containing high-melting and low-melting lipid classes were crystallized and microscope images obtained for analysis of crystal morphology and microstructure. Rheological properties of these semisolid systems were tested by use of a texture analyzer. The nature of the highmelting component in a mixture dominated the crystal morphology and, combined with interactions between crystalline and liquid materials, resulted in different microstructures that influenced the rheological properties. In addition to size, shape, and amount (solid fat content) of crystalline material, the crystal packing density, representing how densely the crystalline particles in every level (individual, aggregate, or floc) were arranged, and the nature (or strength) of the link (or bridge) connecting the crystalline particles were important microstructural factors to determine rheological properties. Depending on different crystal packing densities and linking bridges, two different systems were identified in terms of microstructure type—mobile and immobile—in which the relative mobility of microstructural components had different levels. These mobility levels led to different rheological responses.     

Evaluation of olive oils through the fatty alcohols,the sterols and their esters by coupled LC-GC

The analysis of the fatty alcohols, the wax esters, the free and the esterified sterols, as well as that of minor components provides a wealth of information about the quality of an oil or fat, its pretreatment and admixture with other oils. Some results obtained by an easy, nearly fully-automated method are shown for olive oils. More specific information is obtained than by the previous saponification methods.     

Viscosities of fatty acids, triglycerides, and their binary mixtures

Viscosity data have been obtained as a function of temperature for seven fatty acids (pelargonic, capric, lauric, myristic, palmitic, stearic, and oleic) and four triglycerides (tricaprilin, tripalmitin, tristearin, and triolein) and their binary mixtures at temperatures from above their melting points to 90°C. The viscosity measurements were performed by using Cannon Fenske glass capillary kinematic viscometers. Modified versions of the Andrade equation were used to correlate the kinematic viscosities of pure fatty acids and pure triglycerides. The MacAllister method was used for their binary mixtures. The correlation constants are valuable for designing or evaluating chemical process equipment, such as heat exchangers, reactors, distillation columns, and process piping.     

Characterization of edible oils,butters and margarines by Fourier transform infrared spectroscopy with attenuated total reflectance

The combination of attenuated total reflectance (ATR) and mid-infrared spectroscopy (MIRS) with statistical multidimensional techniques made it possible to extract relevant information from MIR spectra of lipid-rich food products. Wavenumber assignments for typical functional groups in fatty acids were made for standard fatty acids: Absorption bands around 1745 cm⁻¹, 2853 cm⁻¹, 2954 cm⁻¹, 3005 cm⁻¹, 966 cm⁻¹, 3450 cm⁻¹ and 1640 cm⁻¹ are due to absorption of the carbonyl group, C−H stretch, =CH double bonds of lipids and O−H of lipids, respectively. In lipid-rich food products, some bands are modified. Water strongly absorbs in the region of 3600–3000 cm⁻¹ and at 1650 cm⁻¹ in butters and margarines, allowing one to rapidly differentiate the foods as function of their water content. Principal component analysis was used to emphasize the differences between spectra and to rapidly classify 27 commercial samples of oils, butters and margarines. As the MIR spectra contain information about carbonyl groups and double bonds, the foods were classified with ATR-MIR, in agreement with their degree of esterification and their degree of unsaturation as determined from gas-liquid chromatography analysis. However, it was difficult to differentiate the studied food products in terms of their average chainlength.     

小晶粒ZSM-22的可控合成及其催化长链正构生物烷烃制航空煤油性能

由生物脱氧油制生物航空煤油具有较大应用潜力和发展前景,为了提高生物航煤的收率,开发性能更好的加氢裂化/异构化催化剂是关键。本文采用水热合成法,在低温陈化、加入晶种、提高合成凝胶的碱度或加入有机碱条件下,合成了平均c轴尺寸在100~330nm的小晶粒ZSM-22分子筛,进行了XRD、SEM、N₂物理吸附、NH₃-TPD和吡啶红外表征,并以生物质油加氢脱氧得到的长链正构生物烷烃为原料,考察了不同晶粒尺寸 ZSM-22催化剂催化裂化和异构化制生物航空煤油的性能。结果表明,通过提高碱度合成的小晶粒H-ZSM-22 具有较强的酸中心,较多可及的强B酸中心数量,其长链正构烷烃转化率可达80%以上。在此基础上,制备的Pt/ZSM-22催化剂具有较高的Pt分散度,表现出很好的加氢裂化/异构化性能,其长链正构烷烃的转化率高达97.79%,生物航煤收率达50.25%,航煤产物异正比为7.55。     

Rapid determination of cis and trans content, iodine value, and saponification number of edible oils by fourier transform near-infrared spectroscopy

Fourier transform near-infrared (FT-NIR) spectroscopy was evaluated as a means of simultaneously determining the cis and trans content, iodine value (IV), and saponification number of neat fats and oils. Reference values for these parameters were obtained from oils using a previously developed mid-FTIR Edible Oil Analysis Package. Two partial least squares calibrations were developed for a 5-mm heated flow cell, the first a process calibration based on hydrogenated soybean samples and the second a more generalized calibration based on an oil samplematrix containing many oil types and designed to remove any correlations among the parameters measured. Each calibration performed well with its own validation samples; however, only the noncorrelated calibration was able to analyze oil samples accurately from a variety of sources. It was found that NIR analysis maintained the internal consistency between cis/trans and IV, and the accuracy and reproducibility of the predictions were on the order of ±1.5 and ±1.0 units, respectively, for all parameters evaluated. FT-NIR is shown to be a very workable means of determining cis/trans/IV values and saponification number for edible fats and oils, and it provides a rapid alternative to the commonly used chemical and physical methods presently employed in the industry.     

Boosting Affinity by Correct Ligand Preorganization for the S2 Pocket of Thrombin: A Study by Isothermal Titration Calorimetry,Molecular Dynamics,and High‐Resolution Crystal Structures

Structural preorganization to fix bioactive conformations at protein binding sites is a popular strategy to enhance binding affinity during late‐stage optimization. The rationale for this enhancement relates to entropic advantages assigned to rigidified versus flexible ligands. We analyzed a narrow series of peptidomimetics binding to thrombin. The individual ligands exhibit at P2 a conformationally flexible glycine, more restricted alanine, N‐methylglycine, N‐methylhomoalanine, and largely rigidified proline moiety. Overall, affinity was found to increase by a factor of 1000, explained partly by an entropic advantage. All ligands adopt the same binding mode with small deviations. The residual mobility of the bound ligands is decreased across the series, and a protein side chain differs in its order/disorder behavior along with changes in the surface‐water network pattern established across the newly generated protein–ligand surfaces. The enthalpy/entropy inventory displays a rather complex picture and emphasizes that thermodynamics can only be compared in terms of relative differences within a structurally similar ligand series.     

Evaluation of the CP-Sil 88 and SP-2560 GC columns used in the recently approved AOCS official method Ce 1h-05: Determination of cis-, trans-, saturated, monounsaturated, and polyunsaturated fatty acids in vegetable or non-ruminant animal oils and fats by capillary GLC method

The AOCS Official Method Ce 1h-05 was recently approved at the 96th AOCS Annual Meeting (2005) by the Uniform Methods Committee as the official method for determining cis and trans FA in vegetable or non-ruminant fats and oils. A series of experiments was undertaken using a margarine (hydrogenated soybean oil) sample containing approximately 34% total trans FA (28% 18∶1 trans, 6% 18∶2 trans, and 0.2% 18∶3 trans), a low-trans oil (ca. 7% total trans FA), and a proposed system suitability mixture (12∶0, 9c−18∶1, 11c−18;1, 9c,12c,15c−18∶3, 11c−20∶1, and 21∶0) in an effort to evaluate and optimize the separation on the 100-m SP-2560 and CP-Sil 88 flexible fused-silica capillary GC columns recommended for the analysis. Different carrier gases and flow rates were used during the evaluation, which eventually lead to the final conditions to be used for AOCS Official Method Ce 1h-05.     

Correlation between growth behavior,internal stress distribution and properties of ZnO:Zn crystals grown by carbon-assisted chemical vapor transport

Internal stress and stress-related defects are considered as the major obstacles that significantly hinder the growth of high-quality ZnO-based crystals. In this work, high-crystalline-quality ZnO:Zn bulk crystals were successfully grown by carbon-assisted chemical vapor transport (CVT). Internal stress in the crystal was directly measured by a neutron beam from a reactor, and stress distributions along the radial direction at different depths were obtained. The stress, temperature, and flow fields in the growth system were simulated by the finite element (FE) method, and the results agreed with the neutron stress analysis. The etch pit density (EPD), Hall properties, and optical transmittances of different crystal regions were studied in detail, and the distribution trend of the crystal properties was consistent with that of internal stress and stress-related defects in the crystal. It is found that the unique temperature filed in the growth system causes the crystal to bend to a slightly convex toward the growth direction and gives rise to a driving force for structural defect formation. The + c and –c faces of the crystal are subjected to tensile and compressive stress, respectively. The maximum stress values are about 280 MPa and -291 MPa near the central regions of ±c faces, while the crystal periphery is basically free of internal stress. The region near the center of +c face has an EPD of 7.5 × 10³ cm^-2 and a transmittance of 79.2% at 800 nm wavelength, while the corresponding carrier concentration and mobility are 2.27 × 10¹⁷ cm^?3 and 159 cm²/V·s, respectively. By comparison, the crystal periphery has an EPD of 10² cm^-2 with an 80.5% transmittance at 800 nm, while the carrier concentration and mobility are 1.85 × 10¹⁷ cm^?3 and 184 cm²/V·s, respectively.