Diffuse-reflectance Fourier-transform infrared spectroscopy of vegetable oil triglyceride adsorption on silicic acid

The adsorption of triglyceride by silicic acid from hexane miscellas was observed with diffuse-reflectance Fouriertransform infrared spectroscopy. Triglyceride was adsorbed by hydrogen bonding to silanol groups through the ester carbonyl group. Addition of isopropanol (IPA) to the triglyceride-hexane solution prior to adsorption resulted in unchanged triglyceride adsorption on silicic acid despite IPA's ability to adsorb on silicic acid and hydrogen-bond with triglyceride. Washing the triglyceride, adsorbed on silicic acid, with hexane containing IPA resulted in partial desorption of the triglyceride and a small amount of IPA being adsorbed. Triglyceride desorption into fresh hexane-IPA is due to the establishment of a new equilibrium of lipid and IPA between hexane and silicic acid. The relative strengths of all the possible pairwise interactions among triglyceride, IPA and silicic acid are revealed by the relative amounts of adsorption under various conditions.     

Diffuse reflectance fourier transform infrared spectroscopy of phospholipid adsorption onto silicic acid

Diffuse reflectance Fourier transform infrared spectroscopy was used to study the mode of adsorption of phosphatidylcholine (PC) in hexane onto silicic acid (SA). PC adsorption was mainly through the charged phosphate group with minimal binding through the ester carbonyl. When the SA surface with adsorbed PC is washed with hexane, containing a small concentration of isopropanol, the desorbed PC is recovered without structural change, i.e., there is no evidence of PC hydrolysis in the adsorption process. Adsorbent misture probably promotes PC adsorption due to the increased availability of surface water hydroxyl groups for interaction with the PC phosphate groups. Isopropanol promoted PC binding by destabilizing PC reverse miscelles in solution, thus promoting its adsorption.     

Adsorption of lutein from soybean oil on silicic acid I. Isotherms

Adsorption of lutein from crude soybean oil miscella on dispersed silicic acid resulted in three different Freundlich type isotherms, depending on the amount of adsorbent used. Normally, changing the amount of adsorbent gives a new point on the same isotherm. Further investigation of the lutein adsorption revealed that addition of 1% isopropanol to the hexane solvent and deactivation of the silica acid with water decreased lutein adsorption. Purification of the lutein resulted in increased adsorption, indicating that triglyceride was competing for adsorption sites. The triglyceride competition was confirmed by calculating an adsorption isotherm for triglyceride from crude soybean oil miscella. Use of silicic acid as a column rather than dispersed yielded multiple isotherms for lutein adsorption based on the amount of adsorbent used. Also, lutein adsorption on columns was concentrated at the entrance to the column. Experiments showed that lutein adsorption was not due to partitioning between bound triglyceride and hexane solvent.     

Effects on lutein adsorption of adding polar solvents to silicic acid or to soy oil/hexane miscellas

Polar solvents limit adsorption of lutein from a soy oil miscella on silicic acid by competitive adsorption. Water and selected alcohols were added to miscella and adsorbent to observe if the mode of adding solvent affected lutein adsorption. No differences were produced by the method of addition. However, different mechanisms of limiting lutein adsorption were observed. Isopropanol limited lutein adsorption by competitive adsorption. Water was less competitive because it was less soluble in the miscella and was more thermodynamically stable as free water. Propanediol, a polyol, totally inhibited lutein adsorption by binding silica particles together. This study may have implications for silicic acid adsorption of oil components from hydrolyzed oils in which glycerides and free glycerol are present.     

The effect of added solvents on soy oil lutein adsorption by silicic acid

It has been reported that addition of isopropanol to a soy oil miscella inhibits the binding of soy lutein to added silicic acid by competitive adsorption. It was suggested that the competition was based on the polarity of the miscella constituents. This investigation studied the effects of a homologous series of lower alcohols to competitively inhibit lutein binding to silicic acid from a soy oil hexane miscella. Lutein binding inhibition by molecules of carbon chains with the same lengths, but with different functional groups, was also examined. Minor differences were found between members of a homologous series of alcohols. A similar result was found with short-chain fatty acids. The ability of various functional groups to displace lutein from silicic acid was dependent on the molecules’ ability to form hydrogen bonds, rather than on polarity.     

Regeneration of silicic acid following adsorption of soybean oil pigments

The effectiveness of sequential washes (isopropanol/hexane) of increasing polarity for desorbing soybean oil pigment (lutein) from silica was studied. Increasing the polarity promoted desorption of pigment, as the amount of adsorbed pigment increased. The evidence suggests that silicic acid has adsorption sites of variable accessibility. Lutein adsorption isotherms show that much of the adsorption capacity was regained after desorption.     

An infrared spectroscopy study of lipid adsorption from hexane onto an acid-activated bleaching clay

The mode of adsorption of oleic acid (OA) (0.05 M), triglyceride (TG) (0.05 M) and phosphatidylcholine (PC) (0.5 mM) from hexane solution onto 0.5 g of an acid-activated bleaching clay was investigated using diffuse reflectance Fourier transform infrared spectroscopy. OA was mostly weakly adsorbed by bound water, with some OA adsorbed to silanol sites through carboxyl carbonyl groups. TG was hydrogen- bonded to surface silanol groups through ester carbonyl groups. The CH₂ stretches indicated that TG was oriented perpendicular or at an angle to the surface. PC phosphate groups were bound by the surface moisture with little interaction with silanol groups. The adsorption mechanism of these lipids contrasts with the adsorption of carotenoid and chlorophyll under the same conditions. These pigments are bound by chemisorption, with catalytic modification often occurring before adsorption.     

Effect of extraction methods on lipid yield and fatty acid composition of lipid classes containing γ-linolenic acid extracted from fungi

The effect of extraction procedures on the lipid yield and fatty acid composition of total lipid and main lipid structures (phospholipids, diacylglycerols, triacylglycerols, free fatty acids, and sterol esters) of fungal biomass (Mucor mucedo CCF-1384) containing γ-linolenic acid (GLA) was investigated. Seventeen extraction methods, divided into three groups, were tested: six with chloroform/methanol, five with hexane/alcohols, and six with common solvents or mixtures. The chloroform/methanol procedure (2∶1) was selected as standard, where lipid yield (TL/DCW, total lipid per dry cell weight) was 17.8%, considered to be 100% of lipids present. All chloroform/methanol extractions yielded more than 83% recorvey of lipids. Use of hexane/isopropanol solvent systems led to a maximum of 75% recovery. The best lipid yield was achieved by a two-step extraction with ethanol and hexane (120%). Extraction efficiency of the other solvent systems reached a maximum of 73%. Triacylglycerols were the main structures of lipid isolated; only methanol-extracted lipid contained 58.5% phospholipids. The fatty acid content of total recovered lipid was variable and depended on both the lipid class composition and the solvent system. GLA concentrations in total lipids isolated by hexane/alcohol procedures (7.3–10.7%) are comparable with classical chloroform/methanol systems (6.5–10.0%). The maximal GLA yield was obtained with chloroform/methanol/n-butanol/water/0.1 M ethylenediaminetetraacetic acid (EDTA) (2∶1∶1∶1∶0.1, by vol) and after two-step extraction with ethanol and hexane (14.3 and 13.7 g GLA/kg DCW, respectively). The highest GLA content was analyzed in the phospholipid fraction (16.1%) after using chloroform/methanol/n-butanol/water/0.1 M EDTA (2∶1∶1∶1∶0.1, by vol). Remarkably low concentrations of polyunsaturated fatty acids were determined in the free fatty acid fraction.     

Diffuse reflectance fourier transform infrared spectroscopy of triacylglycerol and oleic acid adsorption on synthetic magnesium silicate

Diffuse reflectance fourier transform infrared (FTIR) was used to observe adsorption complexes of triacylglycerol and oleic acid on silica gel and synthetic magnesium silicate. The spectra provide evidence of the nature of the surface interaction. Triacylglycerol was shown to be physically adsorbed to both adsorbents. Oleic acid was physically adsorbed to the silica gel, but both physically and chemically adsorbed to the magnesium silicate. The FTIR spectrum of magnesium silicate that was used to treat a degraded frying oil was similar to that of oleic acid adsorbed on magnesium silicate.     

Process design and economic analysis of methacrylic acid extraction for three organic solvents

In this work, a techno-economic study for the solvent based extraction of methacrylic acid from an aqueous solution is presented. The involved phase equilibrium calculations in process design are verified by measured experimental data. First, experiments are conducted with different solvent candidates to measure LLE (liquid–liquid equilibrium) data and to establish the effects of extraction temperature and dosage of solvent. Next, the binary interaction parameters for the UNIQUAC model to be used for equilibrium calculations are fine-tuned with measured data. Then, a process for the solvent based extraction of methacrylic acid recovery is designed and verified through simulation with the regressed UNIQUAC model parameters. The optimal configuration of the process flowsheet is determined by minimizing the total annualized cost. Among the three solvent candidates considered-cyclohexane, hexane and toluene-the highest efficiency and the lowest total annualized cost is found with toluene as the solvent.     

A kinetic model for co-oxidation of β-carotene with oleic acid

Oxidation experiments with β-carotene in a lipid solution were conducted under various conditions of temperature, oxygen composition, and lipid content. The experimental results were compared with those using n-decane reported previously. Under all conditions, the oxidation rate in oleic acid was faster than that in n-decane. A novel kinetic model for the co-oxidation of carotene with a lipid was proposed based on the reaction mechanism, which consisted of the oxidation of carotene, the oxidation of oleic acid, and the cross-reaction of carotene with oleic acid. The model quantitatively described the oxidation behavior of carotene over a wide range of temperatures, oxygen compositions, and lipid contents.     

水杨酸和磺基水杨酸在D201树脂上的共吸附行为

采用静态法和动态法研究了水溶液中水杨酸和磺基水杨酸在D201树脂上的共吸附行为和吸附选择性。同时竞争吸附、预负荷竞争吸附和等温吸附的结果均表明:水杨酸的存在对磺基水杨酸的吸附影响较小,而磺基水杨酸的存在则大大削弱了水杨酸的吸附2,种溶质在吸附位点上的竞争为主要作用机制。在双溶质(质量浓度比为1∶1)吸附体系中,初始质量浓度对吸附选择性的影响明显,初始质量浓度≤500 mg/L时,树脂对水杨酸或磺基水杨酸的吸附选择性均很小;初始浓度为1 000—2 000 mg/L时,树脂对磺基水杨酸有很高的吸附选择性,利于二者的选择吸附分离。对初始质量浓度均为2 000 mg/L的双溶质水溶液的动态吸附与脱附表明,以1.000 g树脂装柱,吸附出水在250 mL泄漏点内几乎只含水杨酸,磺基水杨酸被吸附于树脂上。室温下以质量分数5%NaCl+2%NaOH溶液作为脱附剂,可完全洗脱树脂上吸附的磺基水杨酸和水杨酸,其分离系数为300,磺基水杨酸的回收率为96%。应用D201树脂能有效实现磺基水杨酸与水杨酸的选择性吸附分离。     

Separation of phenylalanine by ultrafiltration using D-Phe imprinted polyacrylonitrile-poly(acrylic acid)-poly(acryl amide) terpolymer membrane

A D-phenylalanine (D-Phe) imprinted terpolymer P(AN-AA-AAm) membrane was prepared by the wet phase inversion method. Acrylamide (AAm) and acrylic acid (AA) were used as the functional monomer and acrylonitrile (AN) was used as a physical cross linker. The template molecules were removed from the terpolymer matrix by washing with a 5 percent acetic acid solution. The removal of template molecules from the membrane matrix increased the population of free COOH groups and reduced that of dimerized COOH groups in the membrane matrix, which is an indirect evidence of the formation of recognition sites. The adsorption selectivity of the D-Phe imprinted terpolymer membrane prepared by in-situ implanting method was 0.37 at pH 2 after 3 h batch adsorption using 100 mg Phe/l racemate solution and reached nearly 1 after 24 h. In the ultrafiltration process, the permselectivity was 0.38 at pH 2 after 2.5 min. Separation of D-Phe from the racemate solution was demonstrated by a repeated ultrafiltration batch work.     

Lipid adsorption on commercial silica hydrogels from hexane and changes in triglyceride complexes with time

The structures of and lipid complexes with two commercial silica hydrogels (Trisyl and Sorbsil 40), which contain about 60% moisture, were examined by diffuse reflectance Fourier transform infrared spectroscopy. The spectra suggested that Trisyl contained less moisture than Sorbsil 40. However, the silanol groups of Sorbsil 40 were more active in adsorbing oleic acid, triglyceride, and phosphatidylcholine (PC) from hexane than those of Trisyl. Both adsorbents strongly bound PC through the PC carbonyl and phosphate groups. Lipid adsorption from hexane solution by Trisyl depended solely on trapped moisture, while Sorbsil 40 used moisture and silanol groups on the silica surface. Spectra of triglyceride-silica hydrogel complexes, obtained 24 and 72 h after obtaining the initial spectra, showed that Sorbsil 40 adsorption was by Van der Waals forces, but the triglyceride reoriented over time with an increase in hydrogen bonding. In contrast, Trisyl initially adosorbed triglyceride by hydrogen bonding which was stable for at least 72 h.     

Lipid composition of oats (Avena sativa L.)

Compositions of lipids extracted from a sample of Hinoat oat by seven solvent systems and that extracted with chloroform/methanol (2:1 v/v) from six selected cultivars representing high and low lipid contents are reported. Lipid components (steryl esters, triglycerides, partial glycerides, free fatty acids, glycolipids and phospholipids) were separated by silicic acid column chromatography and thin layer chromatography and quantitated by GLC analysis of fatty acids and phosphorus determinations. Twelve oat cultivars were examined for the fatty acid composition of lipid extracted with n-hexane. Lipids extracted from Hinoat by different solvent systems ranged from 5.6 to 8.8%. Quantitative distribution of lipid components extracted with chloroform/methanol from six cultivars containing 4.6 to 11.6% lipid showed a significant correlation (γ=0.99) between the total lipid and the neutral lipid content. Phospholipid content was similar in all cultivars, but glycolipids showed a two-fold increase in high lipid oats. Triglycerides contained less palmitic and more oleic acid than the glycolipids or phospholipids. Nine glycolipids and 11 phospholipids have been identified, and the polar lipid composition of Hinoat oat is presented.     

Adsorption of 2-naphthalenesulfonic acid/sulfuric acid/sulfurous acid from aqueous solution by iron-impregnated weakly basic resin:Equilibrium and model

Commercial grade weakly basic resin D301 was impregnated with iron through a simple method using ferric chloride. Experiments for single, bisolute and trinary competitive adsorption were carried out to investigate the adsorption behavior of 2-naphthalenesulfonic acid (NSA), sulfuric acid and sulfurous acid from their solution at 298K onto the novel hybrid iron impregnated D301(Fe-D301). Adsorption affinity of NSA on Fe-D301 was found to be much higher than that of sulfuric acid, while adsorption affinity of sulfuric acid was slightly higher than that of sulfurous acid. The data of single-solute adsorption were fitted to the Langmuir model and the Freundlich adsorption model. The non-ideal competitive adsorbed model coupled with the single-solute adsorp-tion models were used to predict the bisolute and trinary-solute competitive adsorption equilibria. The NICM coupled with the Langmuir model yields the favorable representation of the bisolute and trinary-solute compet-itive adsorption behavior.     

Fatty Acid soil detergency performance of poly(sodium α-hydroxyacrylate)

Effects and properties of poly(sodium α-hydroxyacrylate) (PHA) on removal of stearic and oleic acids from cellulosic filter paper under various wash conditions were evaluated and compared with those of sodium dodecyl sulfate (SDS) by using differential scanning calorimetry. PHA had a much greater effect on the removal of stearic and oleic acids than SDS under the same washing conditions. PHA produces complexes with fatty acids on filter paper during the washing process, and in DSC these complexes have endothermic peaks at temperatures higher than the melting point of the fatty acids. The complexes are formed at temperatures both below and above the melting point of the fatty acid and are removed completely from filter paper by rinsing. The conditions of temperature, time, and PHA concentration during washing all affected the formation of the complex and the removal of fatty acid. Whether the fatty acid chain was saturated or not did not affect the formation of a complex.     

Separation and quantitation of mono-, di-, and triglycerides and free oleic acid using thin-layer chromatography with flame-ionization detection

α-Monoolein was prepared from glycidol and oleic acid by the regioselective opening of glycidol in the presence of an anionic resin. During the reaction, the lipochemical synthesis medium becomes enriched in monoolein, the effective emulsifying agent. This mixture can be analyzed by thinlayer chromatography coupled with flame-ionization detection (FID). The products and reagents do not need to be derivatized. Diglyceride and triglyceride by-products affecting the selectivity of the reaction also could be detected using this technique. Cholesterol was used as an internal standard. The factors influencing the separation, including the hydrogen flow rate, scan speed, and the composition of the developing solvent, were investigated. The degree of separation is highly sensitive to the hexane/diethyl ether ratio of the developing solvent. Good separation of triglyceride, oleic acid, the two diglycerides, cholesterol, α-monoolein, and glycidol was obtained with the mixture hexane/diethyl ether/formic acid (65:35:0.04, by vol). Detector response, detection limits, and rod-to-rod variations also were examined. A range of rod loads giving a straightforward relationship between FID response and amount of compound loaded (relative to oleic acid and α-monoolein) was defined. The accuracy of the quantification was illustrated by analysis of a mixture of oleic acid and α-monoolein standards of known composition. Presented at the AOCS conference, New Trends in Lipid and Lippprotein Analysis, La Grande Motte, France, September 1993.     

Separation of fatty acid methyl esters from tall oil by selective adsorption

Fatty acid methyl esters (FAME) and resin acids (RA) were separated from tall oil by selective adsorption. Commercial nonmodified molecular sieve 13X was used as adsorbent. The adsorption isotherms of fatty acids (FA), FAME, and RA on molecular sieve 13X at 25°C were determined using various solvents. The solvents were methanol, ethanol, isopropanol, acetone, benzene, hexane, isooctane, petroleum ether (40–60°C), and petroleum naphtha (80–180°C). With each solvent, FA and RA were adsorbed to a greater extent than FAME. Adsorption isotherms for RA and FAME in binary adsorption systems were also determined using petroleum ether, petroleum naphtha, benzene, and isopropanol. For each component in the binary adsorption, the equilibrium amounts are lower than the values for pure component adsorption. The adsorption of FAME decreased in the presence of RA markedly in petroleum ether and petroleum naphtha. This fact may be the indication of the phenomenon of selective adsorption. Separation was accomplished by adding a solution of esterified tall oil in solvents used in the binary adsorption systems, through a column packed with molecular sieve 13X. With petroleum naphtha, FAME and RA were recovered in yields of 93 and 94%, respectively, from esterified tall oil. Petroleum naphtha gave the best results. The effects of particle size of adsorbent and flow rate of solvent on the efficiency of the separation were also investigated in fixed-bed column studies. The particle size of adsorbent did not apparently alter the results. Changes in the particle size should not significantly change the number of available adsorption sites in a microporous molecular sieve.     

非水介质中表面引发接枝聚合法制备接枝微粒PMAA/SiO2及其对阿魏酸的氢键吸附性能

以偶联剂γ-巯丙基三甲氧基硅烷(MPMS)对微米级硅胶微粒进行表面改性,制得表面键合巯基的改性微粒MPMS-SiO2. 在非水溶剂二甲基甲酰胺(DMF)中使偶氮二异丁腈(AIBN)与MPMS-SiO2表面的巯基(-SH)构成表面引发体系(-SH/AIBN),实现甲基丙烯酸(MAA)在非水介质中的表面引发接枝聚合,制得接枝度为20 g/100 g的接枝微粒PMAA/SiO2,对其进行了表征,考察了主要因素对MAA表面引发接枝聚合的影响规律,研究了PMAA/SiO2对酚酸化合物阿魏酸的氢键吸附作用. 结果表明,-SH/AIBN可顺利引发MAA在非水介质中的接枝聚合,适宜条件为75℃,AIBN用量为单体质量的1.5%. 在PMAA/SiO2与阿魏酸分子之间可产生强氢键作用,包括高强度的多位点常规氢键与p型氢键,导致PMAA/SiO2对阿魏酸有强吸附力,吸附容量达266 mg/g. 质子性溶剂甲醇中的溶剂竞争吸附作用使阿魏酸的吸附容量降低,升高温度吸附容量降低.