Transesterification
Dotaz
Zobrazit nápovědu
A combination of two chromatographic and two enzymatic methods was used for the analysis of molecular species of lipids from Gram-positive bacteria of the genus Kocuria. Gram-positive bacteria contain a majority of branched fatty acids (FAs), especially iso- and/or anteiso-FAs. Two strains K. rhizophila were cultivated at three different temperatures (20, 28, and 37°C) and the majority phospholipid, i.e., the mixture of molecular species of phosphatidylglycerols (PGs) was separated by means of hydrophilic interaction liquid chromatography (HILIC). After enzymatic hydrolysis of PGs by phospholipase C and derivatization of the free OH group, the sn-1,2-diacyl-3-acetyl triacylglycerols (AcTAGs) were separated by reversed phase HPLC. Molecular species such as i-15:0/i-15:0/2:0, ai-15:0/ai-15:0/2:0, and 15:0/15:0/2:0 (straight chains) were identified by liquid chromatography-positive electrospray ionization mass spectrometry. The tandem mass spectra of both standards and natural compounds containing iso, anteiso and straight chain FAs with the same carbons were identical. Therefore, for identification of the ratio of two regioisomers, i.e. i-15:0/ai-15:0/2:0 vs. ai-15:0/i-15:0/2:0, they were cleavage by pancreatic lipase. The mixture of free fatty acids (FFAs) and 2-monoacylglycerols (2-MAGs) was obtained. After their separation by TLC and esterification and/or transesterification, the fatty acid methyl esters were quantified by GC-MS and thus the ratio of regioisomers was determined. It has been shown that the ratio of PG (containing as majority i-15: 0 / i-15: 0, i-15: 0 / ai-15: 0 and / or ai-15: 0 / i-15: 0 and ai-15: 0 / ai-15: 0 molecular species) significantly affected the membrane flow of bacterial cells cultured at different temperatures.
- MeSH
- chemické techniky analytické metody MeSH
- chromatografie kapalinová * MeSH
- diglyceridy chemie izolace a purifikace MeSH
- fosfolipidy chemie MeSH
- hmotnostní spektrometrie s elektrosprejovou ionizací * MeSH
- hydrofobní a hydrofilní interakce MeSH
- mastné kyseliny chemie MeSH
- Micrococcaceae chemie MeSH
- plynová chromatografie s hmotnostně spektrometrickou detekcí MeSH
- vysokoúčinná kapalinová chromatografie MeSH
- Publikační typ
- časopisecké články MeSH
The successfulness of a lipase-catalyzed industrial process depends on a proper lipase selection. In this work, an alternative screening platform for industrially important biotransformations catalyzed by microbial lipases was proposed. Thus, the reactivity of sixty lipase activities from spore-forming microorganisms towards hydrolytic and transesterification reactions by using p-nitrophenyl palmitate as a chromogenic acyl donor substrate was explored. Only three biocatalysts were capable of catalyzing all reactions tested. Fourteen biocatalysts did not show hydrolytic activity at all; however, they displayed transesterification activities using ethanol, starch, low-methoxyl (LM) pectin, high-methoxyl (HM) pectin, or vitamin C as acyl acceptors. Using heat-treated biocatalysts, hydrolytic activities were not highly correlated with the corresponding transesterification activities using ethanol (r = -0.058, p = 0.660), starch (r = 0.431, p = 0.001), LM pectin (r = -0.010, p = 0.938), HM pectin (r = 0.167, p = 0.202), and vitamin C (r = -0.048, p = 0.716) as acyl acceptor. In addition, to the best of our knowledge, several transesterification activities produced from microorganisms of the genus Bacillus, Brevibacillus, Lysinibacillus, Geobacillus, or Sporosarcina were reported for first time. Finally, the global lipase market was presented and segmented by date, application, geography and player highlighting the commercial contribution of microbial lipases.
- MeSH
- biotransformace MeSH
- esterifikace MeSH
- hydrolýza MeSH
- katalýza MeSH
- lipasa * metabolismus MeSH
- Publikační typ
- časopisecké články MeSH
The potential of new trimetallic (Ce, Cu, La) loaded montmorillonite clay catalyst for synthesizing biodiesel using novel non-edible Celastrus paniculatus Willd seed oil via two-step transesterification reaction has been reported along with catalyst characterization. Transesterification reaction was optimized and maximum biodiesel yield of 89.42% achieved under optimal operating reaction states like; 1:12 oil to methanol ratio, 3.5% of catalyst amount, 120 °C of reaction temperature for 3 h. The predicted and experimental biodiesel yields under these reaction conditions were 89.42 and 89.40%, which showing less than 0.05% variation. Additionally, optimum biodiesel yield can be predicted by drawing 3D surface plots and 2D contour plots using MINITAB 17 software. For the characterization of the obtained biodiesel, analysis including the GC/MS, FT-IR, 1H NMR and 13C NMR were applied. The fuel properties of obtained biodiesel agrees well with the different European Union (EU-14214), China (GB/T 20828), and American (ASTM-951, 6751) standards.
- MeSH
- bentonit * MeSH
- biopaliva * analýza MeSH
- esterifikace MeSH
- katalýza MeSH
- oleje rostlin analýza MeSH
- spektroskopie infračervená s Fourierovou transformací MeSH
- Publikační typ
- časopisecké články MeSH
- Geografické názvy
- Čína MeSH
Branched esters of palmitic acid and hydroxy stearic acid are antiinflammatory and antidiabetic lipokines that belong to a family of fatty acid (FA) esters of hydroxy fatty acids (HFAs) called FAHFAs. FAHFAs themselves belong to oligomeric FA esters, known as estolides. Glycerol-bound FAHFAs in triacylglycerols (TAGs), named TAG estolides, serve as metabolite reservoir of FAHFAs mobilized by lipases upon demand. Here, we characterized the involvement of two major metabolic lipases, adipose triglyceride lipase (ATGL) and hormone-sensitive lipase (HSL), in TAG estolide and FAHFA degradation. We synthesized a library of 20 TAG estolide isomers with FAHFAs varying in branching position, chain length, saturation grade, and position on the glycerol backbone and developed an in silico mass spectra library of all predicted catabolic intermediates. We found that ATGL alone or coactivated by comparative gene identification-58 efficiently liberated FAHFAs from TAG estolides with a preference for more compact substrates where the estolide branching point is located near the glycerol ester bond. ATGL was further involved in transesterification and remodeling reactions leading to the formation of TAG estolides with alternative acyl compositions. HSL represented a much more potent estolide bond hydrolase for both TAG estolides and free FAHFAs. FAHFA and TAG estolide accumulation in white adipose tissue of mice lacking HSL argued for a functional role of HSL in estolide catabolism in vivo. Our data show that ATGL and HSL participate in the metabolism of estolides and TAG estolides in distinct manners and are likely to affect the lipokine function of FAHFAs.
- MeSH
- bílá tuková tkáň metabolismus MeSH
- estery chemie MeSH
- HEK293 buňky MeSH
- kyselina palmitová metabolismus MeSH
- kyseliny stearové metabolismus MeSH
- lidé MeSH
- lipasa metabolismus MeSH
- lipolýza fyziologie MeSH
- mastné kyseliny metabolismus MeSH
- metabolismus fyziologie MeSH
- myši knockoutované MeSH
- myši MeSH
- sterolesterasa metabolismus MeSH
- triglyceridy metabolismus MeSH
- tuková tkáň metabolismus MeSH
- zvířata MeSH
- Check Tag
- lidé MeSH
- myši MeSH
- ženské pohlaví MeSH
- zvířata MeSH
- Publikační typ
- časopisecké články MeSH
- práce podpořená grantem MeSH
The paper describes transesterification of oil by methanol with use of cosolvents such as ethyl acetate, tetrahydrofuran, hexane, acetone and diethyl ether at catalyst homogeneous (potassium hydroxide) and heterogeneous (mixed oxides). The cosolvents dissolve oil and methanol to form a single (homogeneous) phase, which increases the reaction rate. Therefore, the biodiesel production will be environmentally friendly because less energy is consumed, which increases sustainability. The whole binodal curve of ternary plots of oil, methanol and cosolvent was determined to find the molar ratio, in which the reaction mixture forms a single phase. The ethyl acetate and tetrahydrofuran have relatively small heterogeneous region, because of the similarity of their electric dipole moment with methanol. After transesterification, the detailed analysis of ester and also glycerol phase was carried out. For homogeneous catalyst, the highest esters content in the ester phase was achieved with tetrahydrofuran. For heterogeneous catalyst, the ester content was lower with cosolvent than without cosolvent, probably due to dilution of reaction components by cosolvent or bonding of cosolvent to the active sites of the catalyst.
- MeSH
- biopaliva * MeSH
- esterifikace MeSH
- estery * MeSH
- katalýza MeSH
- methanol MeSH
- oleje rostlin MeSH
- Publikační typ
- časopisecké články MeSH
Fatty acid esters of long-chain hydroxy fatty acids or (O-acyl)-hydroxy fatty acids (OAHFAs) were identified for the first time in vernix caseosa and characterized using chromatography and mass spectrometry. OAHFAs were isolated from the total lipid extract by a two-step semipreparative TLC. The general structure of OAHFAs was established using high-resolution and tandem mass spectrometry of intact lipids and their transesterification and derivatization products. Two isomeric lipid classes were identified: O-acyl esters of ω-hydroxy fatty acids (ωOAHFA) and O-acyl esters of α-hydroxy fatty acids (αOAHFAs). To the best of our knowledge, αOAHFAs have never been detected in any biological sample before. Chromatographic separation and identification of OAHFAs species were achieved using non-aqueous reversed-phase HPLC coupled to electrospray ionization hybrid linear ion trap-Orbitrap mass spectrometry. The lipid species were detected as deprotonated molecules, and their structures were elucidated using data-dependent fragmentation in the negative ion mode. More than 400 OAHFAs were identified in this way. The most abundant ωOAHFAs species were 28:0/ω-18:2, 29:0/ω-18:2, 30:0/ω-18:2, 32:0/ω-18:2, and 30:0/ω-18:3, while αOAHFAs comprised saturated species 21:0/α-24:0, 22:0/α-24:0, 23:0/α-24:0, 24:0/α-24:0, and 26:0/α-24:0. OAHFAs were estimated to account for approximately 0.04% of vernix caseosa lipids. Graphical Abstract.
A new method for the preparation of anhydrous ethyl ester of lactic acid was studied. The selected method is based on catalytic transesterification of lactic acid oligomers, which were prepared for this purpose by autocatalytic oligomerization of lactic acid. In this work, a kinetic model for the case of catalytic alcoholysis of oligoesters was derived assuming a first-order reaction and equimolar content of reactants in the reaction mixture. The model makes it possible to obtain the values of the reaction rate and equilibrium constants and the equilibrium alcohol concentration by regression analysis at one time. The model was verified by measuring the rate of consumption of ethanol over the time at various reaction temperatures with anhydrous FeCl₃ as the catalyst. The reaction was studied at overpressure under autogenous conditions in the temperature range of 100⁻180 °C. For the catalyst concentration of 1 mol %, the activation energy value was 64.35 kJ·mol-1. The dependence of equilibrium composition and rate constant on the temperature was obtained. The derived model is generally applicable to all first-order equilibrium reactions. The presumption is that the forward and reverse reactions are of the same order and have the same stoichiometry and equivalent amounts of reactants at the beginning of the reaction.
Biodiesel is a mixture of esters of fatty acids (most often palmitic, stearic and oleic) and lower alcohols (in our work butanol) produced by transesterification. It is a renewable source of energy, prepared from triacylglycerides, which are contained in vegetable oils and animal fats. This work focuses on alkaline catalyzed transesterification of rapeseed oil with butanol and comparison of two catalysts (potassium hydroxide and potassium tert-butoxide). In industry is usually transesterification of rapeseed oil carried out like reaction catalyzed by potassium hydroxide. Potassium hydroxide have high content of K2CO3, KHCO3 and water. Moreover water is formed by neutralization of potassium hydroxide with free fatty acids contained in oil. In cause of tert-butoxide catalyzed reaction, it is not possible because tert-butoxide have not a OH- aniont, which is needed for water forming. The influence of various conditions (addition of water, temperature of separation, intensity of stirring and type of catalyst) on butanolysis process was studied for both catalysts. For both catalysts dependence of conversions on time were plotted. When tert-butoxide was used, satisfactory phase separation was not achieved. The only way was separation of hot crude reaction mixture without adding water. Ester formed by this method had high content of free glycerol and soaps, but reached higher conversion. The best results were obtained with KOH and subsequent separation of cold crude reaction mixture with the addition of water and slow stirring. The difference between reactions catalyzed by potassium hydroxide and potassium tert-butoxide was described.
- MeSH
- biopaliva * MeSH
- butanoly * MeSH
- hydroxidy * MeSH
- katalýza MeSH
- kyseliny mastné mononenasycené MeSH
- olej z řepky MeSH
- oleje rostlin MeSH
- sloučeniny draslíku * MeSH
- zvířata MeSH
- Check Tag
- zvířata MeSH
- Publikační typ
- časopisecké články MeSH
Cholesteryl esters of ω-(O-acyl)-hydroxy FAs (Chl-ωOAHFAs) were identified for the first time in vernix caseosa and characterized using chromatography and MS. Chl-ωOAHFAs were isolated using adsorption chromatography on silica gel and magnesium hydroxide. Their general structure was established using high-resolution and tandem MS of intact lipids, and products of their transesterification and derivatizations. Individual molecular species were characterized using nonaqueous reversed-phase HPLC coupled to atmospheric pressure chemical ionization. The analytes were detected as protonated molecules, and their structures were elucidated in the negative ion mode using controlled thermal decomposition and data-dependent fragmentation. About three hundred molecular species of Chl-ωOAHFAs were identified in this way. The most abundant Chl-ωOAHFAs contained 32:1 ω-hydroxy FA (ω-HFA) and 14:0, 15:0, 16:0, 16:1, and 18:1 FAs. The double bond in the 32:1 ω-HFA was in then-7 andn-9 positions. Chl-ωOAHFAs are estimated to account for approximately 1-2% of vernix caseosa lipids.
- MeSH
- estery cholesterolu metabolismus MeSH
- lidé MeSH
- mastné kyseliny chemie metabolismus MeSH
- novorozenec MeSH
- vernix caseosa metabolismus MeSH
- Check Tag
- lidé MeSH
- novorozenec MeSH
- Publikační typ
- časopisecké články MeSH
Annually, a great amount of waste fats and oils not suitable for human consumption or which cannot be further treated are produced around the world. A potential way of utilizing this low-cost feedstock is its conversion into biodiesel. The majority of biodiesel production processes today are based on the utilization of inorganic alkali catalysts. However, it has been proved that an organic base - tetramethylammonium hydroxide - can be used as a very efficient transesterification catalyst. Furthermore, it can be employed for the esterification of free fatty acids - reducing even high free fatty acid contents to the required level in just one step. The work presented herein, is focused on biodiesel production from waste frying oils and animal fats using tetramethylammonium hydroxide at the pilot-plant level. The results showed that the process performance in the pilot unit - using methanol and TMAH as a catalyst, is comparable to the laboratory procedure, even when the biodiesel is produced from waste vegetable oils or animal fats with high free fatty acid content. The reaction conditions were set at: 1.5% w/w of TMAH, reaction temperature 65°C, the feedstock to methanol molar ratio to 1:6, and the reaction time to 120min. The conversion of triglycerides to FAME was approximately 98%. The cloud point of the biodiesel obtained from waste animal fat was also determined.
- MeSH
- biopaliva * MeSH
- esterifikace MeSH
- estery chemie MeSH
- katalýza MeSH
- kvartérní amoniové sloučeniny chemie MeSH
- kyseliny mastné neesterifikované MeSH
- mastné kyseliny chemie MeSH
- methanol MeSH
- odpadky - odstraňování metody MeSH
- oleje rostlin chemie MeSH
- oleje chemie MeSH
- průmyslový odpad MeSH
- teplota MeSH
- triglyceridy chemie MeSH
- tuky chemie MeSH
- zvířata MeSH
- Check Tag
- zvířata MeSH
- Publikační typ
- časopisecké články MeSH
- práce podpořená grantem MeSH
