Changes in triacylglycerol composition during ripening of sea buckthorn (Hippophaë rhamnoides L.) seeds

Changes in the quantitative composition of triacylglycerols (TAGs) in maturing sea buckthorn (Hippopha? rhamnoides L.) seeds were determined by lipase hydrolysis. As a whole, the rate of synthesis of separate TAG classes increased in proportion to both their unsaturation and relative content (weight percent) in total TAGs. Up to the 80th day of maturation, the formation of triunsaturated TAGs was predominant. Subsequently, at the terminal stage of seed ripening, the absolute content (in nanomoles per seed) of a major group of these TAGs containing linolenic and linoleic acyls decreased by approximately 7%, and the increase in the total TAG content was mainly due to the synthesis of TAG molecules including stearic and palmitic acyls in the rac-1,3 positions, as well as those containing oleate in the sn-2 position. At each maturation stage, the composition of the TAGs formed was controlled both by the composition of fatty acids available for TAG synthesis and by the rate of incorporation of a particular fatty acid into the sn-2 position of the TAGs.     

Influence of Cultivar and Environmental Conditions on the Triacylglycerol Profile of Hazelnut (Corylus avellana L.)

The oil of several hazelnut (Corylus avellana L.) samples was extracted and evaluated for their triacylglycerol (TAG) composition. Trials were conducted in two Portuguese localities (Vila Real and Felgueiras) during three consecutive years and involved a total of 19 cultivars. The samples were analyzed by reversed-phase high-performance liquid chromatography with evaporative light-scattering detection. Sample preparation was fast and simple, consisting only of the dissolution of the oil in acetone, homogenization, and filtration, allowing this technique to be suitable for routine analyses. All samples presented a similar qualitative profile composed of eleven compounds: LLL, OLL, PLL, OOL, POL, PPL, OOO, POO, PPO, SOO and PSO (P, palmitoyl; S, stearoyl; O, oleoyl; and L, linoleoyl). The main components were OOO, LOO, and POO, reflecting the high content of oleic acid in hazelnut oils. A total of 79 different samples were studied, and the obtained data were statistically analyzed. Significant differences were verified in canonical variate plots when cultivars were grouped by country of origin. In general, the American cultivars were richer in TAGs with saturated fatty acids moieties, and the group of French, German, and English cultivars was richer in TAGs containing linoleic acid moieties. Differences were also significant when cultivars were grouped by year of production, showing that besides genetic factors, the TAG composition can be influenced by environmental factors.     

Regioisomerism of triacylglycerols in lard, tallow, yolk, chicken skin, palm oil, palm olein, palm stearin, and a transesterified blend of palm stearin and coconut oil analyzed by tandem mass spectrometry.

Triacylglycerols (TAG) of lard, tallow, egg yolk, chicken skin, palm oil, palm olein, palm stearin, and a transesterified blend of palm stearin and coconut oil (82:18) were investigated by chemical ionization and collision-induced dissociation tandem mass spectrometry. Accurate molecular level information of the regioisomeric structures of individual TAGs was achieved. When existing in a TAG molecule of lard, palmitic acid occupied 90-100% of the sn-2 position. Within the major fatty acid combinations in tallow TAGs, the secondary position sn-2 was preferentially occupied in the decreasing order by oleoyl > palmitoyl > stearoyl residues, the order in saturated TAGs being myristoyl > stearoyl = palmitoyl. TAGs in egg yolk were more asymmetric than in chicken skin, with linoleic acid highly specifically attached in the yolk sn-2 carbon. Nearly 50% of yolk TAGs contained 52 carbon atoms with two or three double bonds. Linoleic, oleic, and palmitic acids were in the sn-2 location in decreasing quantities in palm oil and its fractions. Triacylglycerols of equal molecular weight behaved similarly in the fractionation process. Randomization of the parent oil TAGs was seen in the transesterified oil. The tandem mass spectrometric analysis applied provided detailed information of the distribution of fatty acids in individual combinations in TAGs.     

Triacylglycerol composition of coffee beans (Coffea canephora P.) by reversed phase high-performance liquid chromatography and positive electrospray tandem mass spectroscopy

The triacylglycerol (TAG) composition of coffee beans (Coffea canephora P.) was determined by reversed phase liquid chromatography-mass spectrometry and tandem mass spectrometry. The TAGs were separated on a Microsorb RP C-18 column in series with a Supelcosil RP C-18 column using isocratic elution with acetonitrile/2-propanol/hexane (v/v/v, 57:38:5) as the mobile phase at a flow rate of 1 mL/min for 100 min. Under these conditions, 13 TAGs were identified (elution order): trilinoleyl-glycerol (LLL, 11.76%), dilinolenoyl-palmitoyl-glycerol (PLnLn, 2.94%), dilinoleyl-oleyl-glycerol (OLL, 7.77%), dilinoleyl-palmitoyl-glycerol (PLL, 25.90%), dipalmitoyl-linolenoyl-glycerol (PPLn, 1.66%), dioleoyl-linoleyl-glycerol (OOL, 1.68%), dilinoleyl-stearyl-glycerol (SLL, 8.28%), palmitoyl-oleyl-linoleyl-glycerol (POL, 8.76%), dipalmitoyl-linoleyl-glycerol (PPL, 13.74%), dilinoleyl-arachidyl-glycerol (ALL, 3.51%), trioleoyl-glycerol (OOO, 2.33%), palmitoyl -linoleyl-stearyl -glycerol (PLS, 8.73%), and distearoyl-linolenonyl-glycerol (SSLn, 2.91%). The relative composition (%) was obtained directly from the data system with the photodiode array detector.     

Authentication of animal fats using direct analysis in real time (DART) ionization-mass spectrometry and chemometric tools

A combination of direct analysis in real time (DART) ionization coupled to time-of-flight mass spectrometry (TOFMS) and chemometrics was used for animal fat (lard and beef tallow) authentication. This novel instrumentation was employed for rapid profiling of triacylglycerols (TAGs) and polar compounds present in fat samples and their mixtures. Additionally, fat isolated from pork, beef, and pork/beef admixtures was analyzed. Mass spectral records were processed by principal component analysis (PCA) and stepwise linear discriminant analysis (LDA). DART-TOFMS profiles of TAGs were found to be more suitable for the purpose of discrimination among the examined fat types as compared to profiles of polar compounds. The LDA model developed using TAG data enabled not only reliable classification of samples representing neat fats but also detection of admixed lard and tallow at adulteration levels of 5 and 10% (w/w), respectively. The presented approach was also successfully applied to minced meat prepared from pork and beef with comparable fat content. Using the DART-TOFMS TAG profiles of fat isolated from meat mixtures, detection of 10% pork added to beef and vice versa was possible.     

Variability in fatty acid and triacylglycerol composition of the oil of coconut (Cocos nucifera L.) hybrids and their parentals

The fatty acid profiles and triacylglycerol (TAG) compositions of oils from the solid endosperm of different Philippine coconut hybrids and their parentals were determined by using gas chromatography (GC) and high-performance liquid chromatography (HPLC). In general, varietal differences in fatty acid composition were observed. Lauric acid (C12) content was significantly higher in the hybrids PCA 15-8 (50.45%) and PCA 15-9 (50.26%) by about 3.16% points as compared to other hybrids, and higher in Tacunan Green Dwarf (50.50%) among the parentals. Among the fatty acids, lauric acid exhibited the least variation. In general, none of the hybrids had higher fatty acid content than their parentals. The HPLC chromatogram of triacylglycerols (TAG) showed 8 major peaks which differ in carbon number (CN) by two: identified as TAG CN 30, 32, 34, 36, 38, 40, 42, and 44. TAGs CN 30 (4.08%) and CN 34 (19.20%) were found to be significantly higher in PCA 15-9 than in the other hybrids. CN 36 was highest (21.94-23.66%) in all hybrids and parentals. The TAG CNs varied significantly among hybrids and parents, i.e., in CN 30, 32, and 34, which are high in medium chain triacylglycerols (MCTs), and in CN 30 (for parentals only), 40, 42, and 44 (the latter two for parentals only), and none in CN 36. MCTs calculated for two hybrids and their parents ranged from 13.81% to 20.55%.     

Analysis of isomeric forms of oxidized triacylglycerols using ultra-high-performance liquid chromatography and tandem mass spectrometry

Detailed studies on the regioisomeric structures of oxidized species of triacylglycerols (TAG), formed in food during storage and processing, have not been published thus far. In this study, an analytical approach based on efficient ultra-high-performance liquid chromatographic (UHPLC) separation of different isomers of oxidized TAG species and their tandem mass spectrometric analysis was created. A linear solvent gradient based on acetonitrile and acetone was used in the UHPLC method. A novel method utilizing positive ion ESI using ammonia supplemented in the nebulizer gas was used to produce ammonium adduct ions for mass spectrometric analysis. With the UHPLC method used, different regioisomers of TAG species containing oxidized linoleic or oleic acid could be efficiently resolved. Differences in the fragmentation patterns of many of the oxidized TAG isomers could be demonstrated by the tandem mass spectrometric method. On the basis of the results, the approach enables regiospecific analysis of oxidized TAG molecules.     

Oils from improved high stearic acid sunflower seeds

Seed oils from new recombinant high-stearic sunflower lines (Helianthus annuus L.) have been characterized. These new lines were generated by crossing high stearic acid lines between themselves or by crossing them with standard and high-oleic sunflower lines. Of the novel lines generated, the lines CAS-29 and CAS-30 are on a standard background and contain up to 34.5% of stearic acid. In contrast, CAS-15 and CAS-33 are on a high oleic acid background and contain only 24.9 and 17.4% of stearic acid, respectively. The stearic acid contents of lines CAS-19 and CAS-20 are 10.0 and 21.5%, respectively, and they have only one of the two genes that control the high stearic acid trait. In accordance with their vegetable origin, these lines have a low percentage of stearic acid in the sn-2 position of the TAGs, from 0.6 to 2.1%. The amount of disaturated TAGs increases with the stearic acid content, from 1.8% in the standard line to between 5.1% in CAS-20 and 38.5% in CAS-29. There was also a concomitant reduction in triunsaturated TAGs, which were reduced to levels as low as 8.4% in CAS-29, as opposed to the 67.9% that they constitute in the standard line RHA-274. The asymmetrical distribution of the saturated fatty acids between the sn-1 and sn-3 TAG positions ranges from 0.26 to 0.36, being lower in those lines with higher oleic acid content.     

Slow recrystallization of tripalmitoylglycerol from MCT oil observed by 2H NMR

The crystallization and recrystallization of fats have a significant impact on the properties and quality of many food products. While crystallization has been the subject of a number of studies using pure triacylglycerols (TAG), recrystallization in similarly pure systems is rarely studied. In this work, perdeuterated tripalmitoylglycerol ( (2)H-PPP) was dissolved in medium chain triacylglycerol oil (MCT) to yield a saturated solution. The solution was heated to cause partial melting of the solid and dissolution of the molten fraction of (2)H-PPP in MCT and was then cooled to the original temperature to induce recrystallization from the supersaturated solution. (2)H NMR was used to monitor the disappearance of (2)H-PPP from the solution and showed that recrystallization occurred in two steps. The first step was rapid, taking place over a few minutes, and accounted for more than two-thirds of the total recrystallization. The second step was much slower, taking place over a remarkably long timescale of hours to days. It is proposed that dissolution occurs from all parts of the crystals, leaving an etched and pitted surface. The first step of crystallization is the infilling of these pits, while the second step is the continued growth on the smoothed crystal faces.     

Diacylglycerol and triacylglycerol as responses in a dual response surface-optimized process for diacylglycerol production by lipase-catalyzed esterification in a pilot packed-bed enzyme reactor

Diacylglycerol (DAG) and triacylglycerol (TAG) as responses on optimization of DAG production using a dual response approach of response surface methodology were investigated. This approach takes the molecular equilibrium of DAG into account and allows for the optimization of reaction conditions to achieve maximum DAG and minimum TAG yields. The esterification reaction was optimized with four factors using a central composite rotatable design. The following optimized conditions yielded 48 wt % DAG and 14 wt % TAG: reaction temperature of 66.29 degrees C, enzyme dosage of 4 wt %, fatty acid/glycerol molar ratio of 2.14, and reaction time of 4.14 h. Similar results were achieved when the process was scaled up to a 10 kg production in a pilot packed-bed enzyme reactor. Lipozyme RM IM did not show any significant activity losses or changes in fatty acid selectivity on DAG synthesis during the 10 pilot productions. However, lipozyme RM IM displayed higher selectivity toward the production of oleic acid-enriched DAG. The purity of DAG oil after purification was 92 wt %.     

Mass Transfer of Carbaryl from Pure Water to Salt Aqueous Solution: Result Comparison Between Sea and Lab-Made Water

It is well known that mass transfer of a solid compound into a liquid phase is characterized by mutual properties of both sides. Solubilization capacity of the liquid phase is primary affected by its composition in inorganic species inducing salting in/out effect evaluated by Setschenow constant, generally defined at 298.15 K. On the other hand, the equilibrium process is highly influenced by polar compatibility issue. Therefore, the study of such transfer is essential in order to set the role of each party participating in the solid–liquid equilibrium. Thus, a comparison of transfer magnitude and feasibility of carbaryl from pure water, to seawater, and lab-made seawater was held. To do so, solubility of the compound was experimented at different temperature in multiple media. Solubility determination is based on the saturation of a specific heated fluid passing through a saturation cell. The solute transported is subsequently trapped in a specific extraction column. Back flashing method is then applied to dissolve the compound. After validation, aqueous solubility of carbaryl was studied as function of temperature ranging from (273.15 to 318.15 K) at atmospheric pressure. In addition, solubility was determined in pure, seawater, and corresponding lab-made water, thus solubility values ranged from 3.57E-06 to 3.49E-05 in pure water, from 3.04E-06 to 2.53E-05 in seawater and from 6.51E-06 to 3.61E-05 in lab-made water. As a result, thermophysical properties of transfer and usage of lab-made water on the mass transfer properties divergence was spotted. The Salting out phenomenon observed for carbaryl was interpreted by the internal pressure theory that suggests the reduction of internal cavities in the presence of salt, making solubilization process more difficult to achieve. Thus, showing an overall endogenic process with a positive Gibbs free energy of transfer that is highly affected by the magnitude of salting out effect and the temperature. The molar entropy of transfer increases versus temperature caused by the disorder of solvent molecules due to the dissolution process.     

Identification of triacylglycerol species from high-saturated sunflower (Helianthus annuus) mutants

The triacylglycerol (TAG) composition of oils from new high-saturated sunflower lines has been studied by means of GLC. The TAG profiles have been compared with the TAG reconstruction made after lipase hydrolysis (according to the 2-random 1,3-random theory). New TAG species with asclepic (cis,Delta11-octadecenoic acid, isomer of oleic acid), araquidic, or behenic acids have been synthesized and identified in oils from mutant lines. The TAG molecular species that contain asclepic acid instead of oleic acid have a longer retention time. Because each mutant oil has a specific TAG GLC pattern, this method could be used for a more precise validation of oil type than current fatty acid methyl ester analysis. The comparison of the results obtained by GLC with the reconstruction after pancreatic lipase hydrolysis shows, in general, a good agreement between both methods. However, results shown in this paper show that this is not always the case. TAG species containing two molecules of linoleic acid show a higher presence of palmitic or stearic acid than could be expected from a random distribution. The abundance of SLL increased in proportion to the stearic acid content of the oil, and the amount of TAG species with three unsaturated fatty acids (LLL or OLL) was therefore reduced.     

The destruction of quartz, amorphous silica minerals, and feldspars in model experiments and in soils: Possible mechanisms, rates, and diagnostics (the analysis of literature)

The dissolution of quartz and amorphous SiO₂ proceeds via the adsorption of water molecules on the surface of these minerals with the further formation of four silanol groups around the silicon atom and the detachment of the molecules of orthosilicic acid from the surface. The rates of quartz dissolution at pH 7 and 3 constitute 10^?15.72 and 10^?16.12 mol/m² s, respectively. They increase by three orders of magnitude upon the rise in pH from 7 to 10; they also increase in the solutions of strong electrolytes and in the presence of the anions of polybasic organic acids. The dissolution of feldspars begins from the release of alkali metals and calcium from the surface of crystal lattices of these minerals into the solution in the course of the cation exchange reaction. This is a fast process, and it does not control the rate of the feldspar dissolution that depends on the concentrations of protonated (in the acid medium) and deprotonated (in the alkaline medium) complexes with participation of the surface Si-O-Si and Al-O-Si groups of the mineral lattices. The rate of dissolution of K-Na feldspars decreases from n × 10^?11 to n × 10^?12 mol/m² s upon the rise in pH from 3 to 5; it also increases in the plagioclase series with an increase in the portion of anorthite molecules and in the presence of the anions of polybasic organic acids in the solution. The rate of dissolution of feldspars in the model experiments is by 1–3 orders of magnitude higher than that obtained by different methods for native soils. This may be related to the adequacy of determination of the specific surface and its changes with time in native soils.     

太阳能除湿系统中混合盐溶液的性能

溶液除湿和太阳能再生技术,是解决高温高湿地区蒸发降温技术难题的关键。该文利用建立的太阳能再生溶液除湿实验台,实验测量研究了氯化钙（CaCl2）和氯化锂（LiCl）混合盐溶液（物质的量比1∶1）的密度与不同质量分数之间的关系;研究了进口空气的温度、湿度、流量,盐溶液的流量,溶液的质量分数、水汽压差等参数与除湿量之间的关系。结果表明：混合溶液的密度与其中的某一组分的溶液（CaCl2）密度非常近似,两者有很好的线性关系;影响除湿量的关键因素是传热传质过程中混合盐溶液和空气的水汽压差的大小。根据Ertas的实验研究,论文得到了氯化钙（CaCl2）和氯化锂（LiCl）混合溶液质量分数为20%～40%的溶液水汽压的计算公式,以及水汽压差和除湿量之间的关系式。该研究为禽畜舍、温室等设施除湿技术提供了新的研究思路。     

Effects of a meal rich in 1,3-diacylglycerol on postprandial cardiovascular risk factors and the glucose-dependent insulinotropic polypeptide in subjects with high fasting triacylglycerol concentrations

It was previously reported that compared to triacylglycerol (TAG) oil, diacylglycerol (DAG) oil improves postprandial lipid response. However, the effects of DAG oil on postprandial hyperglycemia and incretin response have not yet been determined. In this study, the effects of DAG oil on both postprandial hyperlipidemia and hyperglycemia and the response to the glucose-dependent insulinotropic polypeptide (GIP) were studied. This randomized, double-blind, crossover study analyzed data for 41 individuals with high fasting triacylglycerol concentrations. The subjects ingested test meals (30.3 g of protein, 18.6 g of fat, and 50.1 g of carbohydrate) containing 10 g of DAG oil (DAG meal) or TAG oil (TAG meal) after fasting for at least 12 h. Blood samples were collected prior to and 0.5, 2, 3, 4, and 6 h after ingestion of the test meal. Postprandial TAG concentrations were significantly lower after the DAG meal compared with the TAG meal. Postprandial TAG, insulin, and GIP concentrations were significantly lower after the DAG meal compared with the TAG meal in 26 subjects with fasting serum TAG levels between 1.36 and 2.83 mmol/L. DAG-oil-based meals, as a replacement for TAG oil, may provide cardiovascular benefits in high-risk individuals by limiting lipid and insulin excursions.     

鄂西溇水上游碳酸盐岩分布区岩石的溶蚀试验研究

对碳酸盐岩类岩石样品的溶蚀试验表明,岩性对溶蚀的影响主要表现为各类岩石在启动溶蚀速率上的差异.在相同温压、相同比表面积的条件下,灰岩类岩石样品的启动溶蚀速率大于白云岩类岩石样品的启动溶蚀速率.但当样品在水岩反应过程中有不同的比表面积时,溶蚀作用的强弱或快慢就取决于岩石溶蚀速率与水岩反应有效接触面积的消长关系.     

pH对酸性土壤中铝的溶出和铝离子形态分布的影响

ＰＨ对酸性土壤中铝的溶出和土壤溶液中铝离子形态分布的影响的研究结果表明,土壤中铝的溶出量随ＰＨ降低而增加,ＰＨ对不同土壤中铝的溶出的影响不同,三种土壤中铝的溶出量受ＰＨ影响的大小顺序是：红壤〉赤红壤〉砖红壤,说明不同类型土壤中铝的溶出对外来酸的敏感和程度不同。     

Metabolism of triacylglycerol species during seed germination in fatty acid sunflower (Helianthus annuus) mutants

Sunflower mutant lines with high saturated fatty acid content (palmitic or stearic) in the oil have a completely different set of triacylglycerols (TAG), some of which were not found in standard sunflowers. For optimum seed germination, all of these new TAG species must be effectively catabolized. The behavior of the TAG composition during germination in cotyledons of all these mutant lines showed two different phases: an initial phase (between 0 and 2 days after sowing) with a higher catalytic activity and a preference for TAG containing at least two oleic acid molecules and a second phase with lower TAG degradation rate and a low preference for TAG containing two saturated fatty acids usually accompanied by linoleic acid. Despite the elevated content of saturated fatty acids in some TAG species, the total TAG degradation rate and germination process were similar in these lines, suggesting that sunflower seed lipases do not show a marked preference for any TAG species.     

Hypolipidemic effect of oils with balanced amounts of fatty acids obtained by blending and interesterification of coconut oil with rice bran oil or sesame oil

Blended oils comprising coconut oil (CNO) and rice bran oil (RBO) or sesame oil (SESO) with saturated fatty acid/monounsaturated fatty acid/polyunsaturated fatty acid at a ratio of 1:1:1 and polyunsaturated/saturated ratio of 0.8-1 enriched with nutraceuticals were prepared. Blended oils (B) were subjected to interesterification reaction using sn-1,3 specific Lipase from Rhizomucor miehei. Fatty acid composition and nutraceutical contents of the blended oil were not affected by interesterification reaction. Male Wistar rats were fed with AIN-76 diet containing 10% fat from CNO, RBO, SESO, CNO+RBO blend (B), CNO+SESO(B), CNO+RBO interesterified (I), or CNO+SESO(I) for 60 days. Serum total cholesterol (TC), low-density lipoprotein cholesterol, and triacylglycerols (TAGs) were reduced by 23.8, 32.4, and 13.9%, respectively, in rats fed CNO+RBO(B) and by 20.5, 34.1, and 12.9%, respectively, in rats fed CNO+SESO(B) compared to rats given CNO. Rats fed interesterified oils showed a decrease in serum TC, low-density lipoprotein cholesterol (LDL-C), and TAGs in CNO+RBO(I) by 35, 49.1, and 23.2 and by 33.3, 47, and 19.8% in CNO+SESO(I), respectively, compared to rats given CNO. Compared to rats fed CNO+RBO blended oils, rats on CNO+RBO interesterified oil showed a further decrease of 14.6, 24.7, and 10% in TC, LDL-C, and TAG. Rats fed CNO+SESO interesterified oils showed a decrease in serum TC, LDL-C, and TAG by 16.2, 19.6, and 7.8%, respectively, compared to rats given blended oils of CNO+SESO (B). Liver lipid analysis also showed significant change in the TC and TAG concentration in rats fed blended and interesterified oils of CNO+RBO and CNO+SESO compared to the rats given CNO. The present study suggests that feeding fats containing blended oils with balanced fatty acids lowers serum and liver lipids. Interesterified oils prepared using Lipase have a further lowering effect on serum and liver lipids even though the fatty acid composition of blended and interesterified oils remained same. These studies indicated that the atherogenic potentials of a saturated fatty acid containing CNO can be significantly decreased by blending with an oil rich in unsaturated lipids in appropriate amounts and interesterification of blended oil.     

Adsorbed protein secondary and tertiary structures by circular dichroism and infrared spectroscopy with refractive index matched emulsions

The secondary structure of protein adsorbed at the emulsion interface has been studied in refractive index matched emulsions using the techniques of circular dichroism (CD) and Fourier transform infrared spectroscopy. Bovine serum albumin (BSA) and bovine beta-lactoglobulin (betalg) stabilized emulsions were studied, and the refractive index was altered by the addition of glycerol or polyethylene glycol. The effect of additive on the solution and adsorbed protein structure in addition to the effect of adsorption time was considered. Both adsorption and glycerol addition alter protein secondary structure; however, the majority of secondary structure remains. Small changes are observed in the secondary structure of adsorbed protein with time. Near-ultraviolet CD studies showed the effect of glycerol and adsorption on the aromatic groups. BSA showed small changes both upon the addition of glycerol to protein in solution and upon adsorption. betalg showed slightly larger changes upon the addition of glycerol to protein in solution and a larger change upon adsorption.