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1.
Int J Pharm ; 595: 120266, 2021 Feb 15.
Artigo em Inglês | MEDLINE | ID: mdl-33486017

RESUMO

Partitioning tests in water are early-stage standard experiments during the development of pharmaceutical formulations, e.g. of lipid-based drug delivery system (LBDDS). The partitioning behavior of the active pharmaceutical ingredient (API) between the fatty phase and the aqueous phase is a key property, which is supposed to be determined by those tests. In this work, we investigated the API partitioning between LBDDS and water by in-silico predictions applying the Perturbed-Chain Statistical Associating Fluid Theory (PC-SAFT) and validated these predictions experimentally. The API partitioning was investigated for LBDDS comprising up to four components (cinnarizine or ibuprofen with tricaprylin, caprylic acid, and ethanol). The influence of LBDDS/water mixing ratios from 1/1 up to 1/200 (w/w) as well as the influence of excipients on the API partitioning was studied. Moreover, possible API crystallization upon mixing the LBDDS with water was predicted. This work showed that PC-SAFT is a strong tool for predicting the API partitioning behavior during in-vitro tests. Thus, it allows rapidly assessing whether or not a specific LBDDS might be a promising candidate for further in-vitro tests and identifying the API load up to which API crystallization can be avoided.


Assuntos
Lipídeos/química , Preparações Farmacêuticas/química , Água/química , Caprilatos/química , Química Farmacêutica/métodos , Cinarizina/química , Cristalização , Composição de Medicamentos , Sistemas de Liberação de Medicamentos , Etanol/química , Excipientes/química , Ibuprofeno/química , Solubilidade , Termodinâmica , Triglicerídeos/química
2.
Food Chem ; 338: 128067, 2021 Feb 15.
Artigo em Inglês | MEDLINE | ID: mdl-32950871

RESUMO

Kainth fruit, as traditional medicine, has been used in the Himalayan region for its health-promoting properties. However, the phytochemicals and lipidomes of Kainth Seed Oil (KSO) are still scarce. Here, we investigated the physicochemical characterization of KSO and its nutraceuticals, antioxidant potentials. Kainth seeds contain 19-20% oil rich in polyunsaturated fatty acids (PUFA, 82.22%), particularly linoleic acid (C18:2). Lipidome analysis of KSO using high-resolution mass spectrometry showed that trilinoleate (C54:6) was the dominant triacylglycerol (TAG) species. Further, the characteristics of PUFA-rich oil were validated by Fourier transforms infrared spectroscopy (FTIR) and Differential Scanning calorimetry (DSC). The nutraceuticals profiling of KSO depicted the presence of tocopherols (86.72 mg) and phytosterols (32.25 mg) in 100 g oil with significant antioxidant activity. The oil cake contained 19.09% protein and minerals and can be a source for dietary protein. Collectively these results suggest that KSO will be a suitable source for PUFA and nutraceuticals potential.


Assuntos
Antioxidantes/química , Suplementos Nutricionais/análise , Óleos Vegetais/química , Pyrus/química , Ácidos Graxos Insaturados/análise , Lipidômica , Espectrometria de Massas , Fitosteróis/análise , Pyrus/metabolismo , Sementes/química , Sementes/metabolismo , Tocoferóis/análise , Triglicerídeos/análise , Triglicerídeos/química
3.
Food Chem ; 334: 127588, 2021 Jan 01.
Artigo em Inglês | MEDLINE | ID: mdl-32721837

RESUMO

A mixture of sphingoid bases (SPGs) was prepared from butter serum, a by-product of anhydrous milk fat production. The mixture comprised seven types of SPGs with C16 to C19 alkyl chains. These milk SPGs inhibited the oxidation of fish oil triacylglycerol (TAG) more effectively than did a standard SPG (d18:1) with α-tocopherol. Reaction products were prepared from the combination of d18:0 or d18:1 with acrolein and propanal. Both sets of reaction products showed antioxidant activity toward fish oil TAG. Antioxidant activity of reaction products from d18:0 was stronger than that of reaction products from d18:1, suggesting that the molecule d18:0 may be a significant focus of the difference in antioxidant activity between milk SPGs and d18:1. To use SPGs as food additives in the future, an appropriate source of SPGs will be needed, and butter serum appears to have promise as a source of functional SPGs with strong antioxidant activity.


Assuntos
Antioxidantes/química , Óleos de Peixe/química , Leite/química , Esfingolipídeos/química , Triglicerídeos/química , Acroleína/química , Aldeídos/química , Animais , Aditivos Alimentares/química , Hidrólise , Oxirredução , alfa-Tocoferol/química
4.
Food Chem ; 339: 127808, 2021 Mar 01.
Artigo em Inglês | MEDLINE | ID: mdl-32829241

RESUMO

This paper reports an experimental study of the formation and properties of dark chocolate prepared using novel CB alternative fats (CBAs): symmetric (OSatO) and asymmetric (SatSatO) mixed-acid triacylglycerols (TAGs), in which Sat and O represent saturated fatty acids (stearic:S + palmitic:P) and oleic acid moieties, respectively. It was found that the ternary fat mixtures of CB/SatSatO/OSatO with a ratio of CB/(SatSatO + OSatO) of 1:1 formed the most stable ß-form of the double chain length (DCL) structure (ß-2), which revealed sufficient hardness and sharp melting profiles around body temperature without tempering processes. Fat bloom formation was not observed in dark chocolate with CBAs at ratios of CB/SatSatO/OSatO of 50/20/30-50/0/50 during the one-year storage test at temperatures between 15 °C and 30 °C. Overall, the present study has shown that fat mixtures made of CB/SatSatO/OSatO, which are rich in oleic acid moieties, can be employed as a cocoa butter equivalent (CBE) fat without tempering procedures.


Assuntos
Chocolate , Gorduras na Dieta , Triglicerídeos/química , Varredura Diferencial de Calorimetria , Cristalização , Ácidos Graxos/química , Ácido Oleico/química , Ácido Palmítico/química , Ácidos Esteáricos/química
5.
J Oleo Sci ; 69(11): 1359-1366, 2020 Nov 01.
Artigo em Inglês | MEDLINE | ID: mdl-33055442

RESUMO

For the very first time, the nutritional and physicochemical properties of the oil extracted from hackberry Celtis australis fruit were investigated with the aim of possible applications of such wild fruit oil. The physicochemical properties such as peroxide value, acidity, saponification, iodine value and total fat content of the extracted oil were examined extensively. The obtained results showed that peroxide value, acidity, saponification, iodine value and total fat content of the extracted oil were found to be 4.9 meq O2/kg fat, 0.9 mg KOH/g fat, 193.6 mg KOH/g fat, 141.52 mg I2/g fat and ~5%, respectively. The predominant fatty acid found in this wild fruit is linoleic acid which was calculated to be 73.38%±1.24. In addition, gamma-tocopherol (87%) and ß-sitosterol (81.2%±1.08) were the major tocopherol and sterol compositions found in Celtis australis seed oil. Moreover, equivalent carbon number (ECN) analysis has indicated that the three linoleic acids are the main composition of the triacylglycerols extracted from Celtis australis. Also, the high value of omega 6 and ß-sitosterol make this oil applicable in cosmetics and pharmaceutical applications.


Assuntos
Carbono/análise , Ésteres/análise , Ácidos Graxos/análise , Ácido Linoleico/análise , Fitosteróis/análise , Óleos Vegetais/química , Sementes/química , Tocoferóis/análise , Triglicerídeos/análise , Ulmaceae/química , Biofarmácia , Fenômenos Químicos , Cosméticos , Peróxidos/análise , Sitosteroides/análise , Triglicerídeos/química , gama-Tocoferol/análise
6.
Yakugaku Zasshi ; 140(8): 1051-1061, 2020.
Artigo em Japonês | MEDLINE | ID: mdl-32741863

RESUMO

It has been reported that medium-chain triglyceride (MCT) have various physiological functions, such as anti-obesity and hypolipidemic effects. They can also elicit increased disaccharidase activity and intestinal cell proliferation. However, a meta-analysis of randomized controlled trials, comparing the effects of MCT on weight loss and body composition, detected commercial bias. Additional research on the physiological functions is needed in order to have conclusive evidence. Thus, we sought to evaluate the various functions of MCT by conducting a feeding study in rats. Rats fed a diet containing 15% (w/w) MCT, had significantly lower visceral fat weight, plasma and liver lipid concentrations; they had significantly higher intestinal maltase and glucoamylase activities; and they had a greater number of Ki-67 positive cells/crypt, compared to the rats fed a diet containing 15% (w/w) lard. The effects of a diet containing 5% (w/w) MCT was observed only for plasma cholesterol levels and the number of Ki-67 positive cells/crypt; in which some results were found to be inconsistent with previous reports. These results indicate that physiological functions of MCT are numerous and need to be confirmed by additional research.


Assuntos
Glucana 1,4-alfa-Glucosidase/metabolismo , Intestino Delgado/enzimologia , Metabolismo dos Lipídeos/efeitos dos fármacos , Triglicerídeos/administração & dosagem , Triglicerídeos/farmacologia , alfa-Glucosidases/metabolismo , Animais , Fármacos Antiobesidade , Proliferação de Células/efeitos dos fármacos , Dieta , Hipolipemiantes , Intestino Delgado/citologia , Gordura Intra-Abdominal , Antígeno Ki-67/metabolismo , Masculino , Tamanho do Órgão/efeitos dos fármacos , Ratos Sprague-Dawley , Triglicerídeos/química
7.
J Food Sci ; 85(9): 2923-2932, 2020 Sep.
Artigo em Inglês | MEDLINE | ID: mdl-32839962

RESUMO

Benzyl isothiocyanate (BITC) was encapsulated in oil-in-water emulsions stabilized by Pseudosciaena crocea roe protein isolate (PRPI). The stability, lipid digestion, BITC bioavailability, and retention rate of the emulsions were characterized using a simulated gastrointestinal tract model. Tween-corn and PRPI-medium-chain triglycerides (MCT) emulsions were used as controls. The membrane permeability and BITC absorption from these emulsions were investigated by in situ single-pass intestinal perfusion. The results showed that the PRPI-stabilized emulsions were stable under nonacidic environment conditions. Moreover, the PRPI-corn emulsion had more obvious protective effects than PRPI-MCT and Tween-corn emulsions. Atomic force and confocal laser scanning microscopy images showed that the protein hydrolyzed and oil droplets aggregated during simulated gastric phase digestion. Following the exposure of oil droplets in the small intestine phase, the PRPI-corn emulsion had a high rate of free fatty acid release (99.13 ± 2.49%), and the retention rate and bioavailability of BITC from the PRPI-corn emulsion were 75.93 ± 7.17% and 77.32 ± 5.36%, respectively, which were significantly higher than those measured for the other emulsions (P < 0.05). Moreover, the Ka and Peff of the PRPI-corn emulsion reached the maximum value at 45 min and then decreased slowly. These results suggest that the PRPI-corn emulsion delivery system is effective in encapsulating, delivering, and protecting BITC. PRACTICAL APPLICATION: This study provides some useful information for the food industry to develop a Pseudosciaena crocea roe protein isolate (PRPI) emulsion that could be successfully used to construct a BITC delivery system and improve benzyl isothiocyanate (BITC) bioavailability. The protective effect on BITC assessed in vitro simulated gastrointestinal tract and in situ single-pass intestinal perfusion are discussed.


Assuntos
Sistemas de Liberação de Medicamentos/métodos , Proteínas de Peixes/química , Mucosa Intestinal/metabolismo , Isotiocianatos/química , Animais , Disponibilidade Biológica , Digestão , Sistemas de Liberação de Medicamentos/instrumentação , Emulsões/química , Emulsões/metabolismo , Proteínas de Peixes/metabolismo , Trato Gastrointestinal/metabolismo , Humanos , Hidrólise , Isotiocianatos/metabolismo , Tamanho da Partícula , Perciformes , Triglicerídeos/química , Triglicerídeos/metabolismo , Zea mays/química
8.
Nat Commun ; 11(1): 3944, 2020 08 07.
Artigo em Inglês | MEDLINE | ID: mdl-32769983

RESUMO

Triacylglycerols (TG) are synthesized at the endoplasmic reticulum (ER) bilayer and packaged into organelles called lipid droplets (LDs). LDs are covered by a single phospholipid monolayer contiguous with the ER bilayer. This connection is used by several monotopic integral membrane proteins, with hydrophobic membrane association domains (HDs), to diffuse between the organelles. However, how proteins partition between ER and LDs is not understood. Here, we employed synthetic model systems and found that HD-containing proteins strongly prefer monolayers and returning to the bilayer is unfavorable. This preference for monolayers is due to a higher affinity of HDs for TG over membrane phospholipids. Protein distribution is regulated by PC/PE ratio via alterations in monolayer packing and HD-TG interaction. Thus, HD-containing proteins appear to non-specifically accumulate to the LD surface. In cells, protein editing mechanisms at the ER membrane would be necessary to prevent unspecific relocation of HD-containing proteins to LDs.


Assuntos
Membrana Celular/metabolismo , Bicamadas Lipídicas/metabolismo , Gotículas Lipídicas/metabolismo , Proteínas de Membrana/metabolismo , Triglicerídeos/metabolismo , Dicroísmo Circular , Retículo Endoplasmático/metabolismo , Proteínas de Membrana/química , Simulação de Dinâmica Molecular , Domínios Proteicos , Transporte Proteico , Triglicerídeos/química
9.
J Chromatogr A ; 1629: 461474, 2020 Oct 11.
Artigo em Inglês | MEDLINE | ID: mdl-32823012

RESUMO

A 'heart-cut' multidimensional gas chromatography‒mass spectrometry (H/C MDGC‒MS) method for separation and identification of triacylglycerols (TAGs) in extra virgin olive oil was developed. A GC configuration, comprising a non-polar first dimension (1D) column (15 m length) and a mid-polarity second dimension (2D) column (9 m length), was employed. Standard TAGs were used to test and demonstrate the H/C MDGC method, for identification of TAG components and to validate the method. Various chromatographic conditions such as column flow and temperature program were evaluated. The 1D separation resulted in overlap of some standard TAG peaks. These overlapped 1D regions of the standard TAGs were H/C to 2D for further separation and resulted in clearly distinguished individual TAG component peaks. The 1D separation of olive oil TAGs displayed three major peaks and four minor peaks. The application of the H/C MDGC method to olive oil TAGs resulted in the separation of each sampled 1D region into two or more TAG peaks. TAG components in olive oil resolved on the 2D column were identified based on characteristic mass fragment ions such as [M-RCO2]+, [RCO+128]+, [RCO+74]+ and RCO+ and comparison of their mass spectra with that of the standard TAGs. Sixteen olive oil TAGs were identified by MS after 2D separation. The repeatability of the H/C method was evaluated in terms of retention time shift and area response in the 2D and found to be <0.02% and <8% RSD respectively.


Assuntos
Cromatografia Gasosa-Espectrometria de Massas/métodos , Azeite de Oliva/química , Triglicerídeos/isolamento & purificação , Limite de Detecção , Padrões de Referência , Reprodutibilidade dos Testes , Processamento de Sinais Assistido por Computador , Temperatura , Triglicerídeos/química
10.
J Oleo Sci ; 69(8): 825-835, 2020 Aug 06.
Artigo em Inglês | MEDLINE | ID: mdl-32641606

RESUMO

The development of human milk fat substitutes (HMFSs), rich in palmitic acid (16:0) at the sn-2 position of triacylglycerol (TAG) and rich in unsaturated fatty acids (FAs) (oleic acid, 18:1 and linoleic acid, 18:2) at the sn-1(3) positions, has gained popularity. In this study, HMFSs containing polyunsaturated fatty acids (PUFAs) predominantly at the sn-2 position were prepared, and their oxidation stabilities were compared. First, a non-PUFA-containing HMFS (NP-HMFS) was produced by enzymatic reactions using Novozyme® 435 and Lipozyme® RM-IM as the enzymes and lard as the raw material. Second, HMFSs, containing 10 % PUFA at the sn-2 or sn-1(3) position, were individually prepared by enzymatic reactions using lard and fish oil as raw materials. Here, sn-2-PUFA-monoacylglycerol (MAG) was extracted from the reaction solution using a mixture of hexane and ethanol/water (70:30, v/v) to produce high-purity sn-2-PUFA-MAG with 78.1 % yield. For the PUFA-containing HMFS substrates, comparable oxidation stability was confirmed by an auto-oxidation test. Finally, HMFSs containing 10 % or 2 % sn-1,3-18:1-sn-2-PUFA-TAG species were prepared by enzymatic reactions and subsequent physical blending. The oxidative stability of sn-1,3-18:1-sn-2-PUFA-HMFS was two-fold higher than that of 1/2/3-PUFA-HMFS in which each PUFA was located without stereospecific limitations in TAG. The removal of PUFA-TAG molecular species with higher concentrations of unsaturated units had a significant effect. In addition, the oxidation stability increased with the addition of tocopherol as an antioxidant. Thus, the combined use of two strategies, that is, the removal of PUFA-TAG molecular species with high concentrations of unsaturated units and the addition of antioxidants, would provide a PUFA-containing HMFS substrate with high oxidative stability.


Assuntos
Substitutos da Gordura/química , Ácidos Graxos Insaturados/química , Ácidos Graxos Insaturados/isolamento & purificação , Leite Humano , Triglicerídeos/química , Triglicerídeos/isolamento & purificação , Antioxidantes , Gorduras na Dieta , Óleos de Peixe/química , Humanos , Ácido Linoleico , Lipase/química , Ácido Oleico , Oxirredução , Ácido Palmítico , Tocoferóis
11.
J Oleo Sci ; 69(8): 801-807, 2020 Aug 06.
Artigo em Inglês | MEDLINE | ID: mdl-32641609

RESUMO

The health benefits of conjugated linoleic acid (CLA), a functional lipid with anti-cancer, anti-obesity, and hypotensive activity, have garnered increasing attention. The current study was conducted to determine the oxidative stability of CLA in the form of triacylglycerol (CLA-TAG) and phosphatidylcholine (CLA-PC) at the sn-2 position. Oxidation was performed at 30°C or 40°C in the dark. Hydroperoxides, as the primary oxidation products, were analyzed using diphenyl-1-pyrenylphosphine. Thiobarbituric acid reactive substances (TBARS) and volatile compounds were monitored as secondary oxidation products. The results suggest that CLA-PC was more stable against oxidation than CLA-TAG from the perspective of suppression of the generation of hydroperoxides and TBARS. However, CLA-PC produced more volatile compounds than CLA-TAG. We suggest that choline was released during the oxidation of CLA-PC, and acted as an antioxidant. The ensuing reaction between choline and hydroperoxide induced the generation of volatile compounds such as pentanal, hexanal, and heptanal.


Assuntos
Ácido Linoleico/química , Fosfatidilcolinas/química , Triglicerídeos/química , Aldeídos/análise , Antioxidantes , Colina/química , Estabilidade de Medicamentos , Peróxido de Hidrogênio/análise , Peróxido de Hidrogênio/química , Oxirredução , Temperatura , Substâncias Reativas com Ácido Tiobarbitúrico/análise
12.
Food Chem ; 333: 127448, 2020 Dec 15.
Artigo em Inglês | MEDLINE | ID: mdl-32663748

RESUMO

Antarctic krill oil (AKO) is an emerging dietary supplement containing metal ions that influence oil oxidation. Thus, this study focuses on the effect and mechanism of metal ions on phospholipid oxidation in AKO. Firstly, AKO containing Mg2+, Mn2+, Cu2+, Fe2+ and Fe3+ (200 µmol/kg) were prepared separately and incubated at 60 °C for 6 days. Peroxide value (POV) and malondialdehyde (MDA) content showed that Fe3+ exhibited the most effective prooxidative activity, with the prooxidative activity of Fe2(SO4)3 (water-soluble) being stronger than that of ferric oleate (FeOl, fat-soluble). In addition, phosphatidylethanolamine (PE) oxidation degree (more than 90%) was considerably greater than phosphatidylcholine (PC) oxidation degree (about 15%) in AKO. Differences in the structure of head group hindered chelation of PC with metal ions than PE due to electrostatic repulsion and steric hindrance. Therefore, PC significantly inhibited, while PE promoted, the oxidation of polyunsaturated triacylglycerol (TAG), like fish oil (p < 0.01).


Assuntos
Euphausiacea/química , Metais/química , Óleos/química , Fosfolipídeos/química , Animais , Regiões Antárticas , Cátions/química , Suplementos Nutricionais , Malondialdeído/química , Oxirredução , Fosfatidilcolinas/química , Fosfatidiletanolaminas/química , Triglicerídeos/química
13.
Food Chem ; 328: 126991, 2020 Oct 30.
Artigo em Inglês | MEDLINE | ID: mdl-32512466

RESUMO

A previously developed direct inlet tandem mass spectrometric method for analysis of triacylglycerol (TAG) regioisomers was updated and validated for operation with current instrumentation with improved sensitivity and throughput. TAG regioisomers in pooled Chinese and Finnish human milk samples, two bovine milk samples and 11 infant formulas were identified and quantified. A total of 241 TAG regioisomers were identified and quantified, consisting of over 60 mol% of all TAGs in the human milk samples. The infant formulas deviated largely from human milk in regioisomeric composition of TAGs. In the Finnish and Chinese human milks, the most abundant ones were 1,3-dioleoyl-2-palmitoylglycerol (OPO; 7.4 and 8.8 mol% of all TAGs) and 1(3)-linoleoyl-2-palmitoyl-3(1)-oleoylglycerol (LPO; 4.7 and 8.3 mol% of all TAGs). In the infant formulas 1,2(2,3)-dioleoyl-3(1)-palmitoylglycerol (OOP) and 1(3)-linoleoyl-2-oleoyl-3(1)-palmitoylglycerol/1(3)-palmitoyl-2-linoleoyl-3(1)-oleoylglycerol (LOP/PLO) were more abundant than OPO and LPO. The differences between human milk and infant formula prompt for further development of current formulas.


Assuntos
Fórmulas Infantis/análise , Leite Humano/química , Espectrometria de Massas em Tandem/métodos , Triglicerídeos/química , Animais , Bovinos , Humanos , Lactente , Peso Molecular , Estereoisomerismo
14.
J Oleo Sci ; 69(6): 597-604, 2020.
Artigo em Inglês | MEDLINE | ID: mdl-32493885

RESUMO

The aim of the present research is to investigate the effect of three harvest date on the composition of apricot seed. Indeed, triacylglycerols (TAGs) content and composition were studied in developing Tunisian apricot varieties bitter (Bargoug), semi-sweet (Oud Rhayem) and sweet (Chechi Bazza) cultivars at intervals of early (14 DAP), mid phase (28 DAP) and full phase (55 DAP) of oil accumulation by UHPLC-ESI-MS method. Eleven molecular species of triacylglycerols were detected and identified as LLL, LLO, LLP, LOO, LLS/LOP, LPP, OOO, LOS, OOP, POP and OOS. At 14 DAP, LLO was the major TAGs molecular species with 35.4-52.6% (maximum reached in semi-sweet apricot). Others major TAGs were founded at lower content as LOO (17.5-40.3%) and OOO (5.7-12.7%). However, among maturity, three distinct profiles of TAGs molecular species were observed: bitter apricot was significantly richer in OOO molecular species than cultivars ones. However, semi-sweet and sweet cultivars were richer in LLO and LOO molecular species at different time-dates. These latter may provide a schedule for harvesting Tunisian apricot seeds with high quality of oil content.


Assuntos
Cromatografia Líquida de Alta Pressão/métodos , Prunus armeniaca/química , Prunus armeniaca/crescimento & desenvolvimento , Sementes/química , Sementes/crescimento & desenvolvimento , Espectrometria de Massas por Ionização por Electrospray/métodos , Espectrometria de Massas em Tandem/métodos , Triglicerídeos/química , Triglicerídeos/isolamento & purificação
15.
J Chromatogr A ; 1623: 461161, 2020 Jul 19.
Artigo em Inglês | MEDLINE | ID: mdl-32376015

RESUMO

Triacylglycerols (TAGs) containing less common fatty acids (FAs) were isolated from the seeds of three plants (Santalum album, Crepis foetida, and Leucas aspera). These FAs had allenic (laballenic acid, Lb) and acetylenic (crepenynic, C; ximenynic acids, Xi) bonds. TAGs were analyzed on reversed-phase and chiral columns. High-resolution tandem mass spectrometry identified TAGs by positive electrospray ionization (ESI+). Twenty-two molecular species of TAGs isolated from the seed oil of Santalum album were separated by RP-HPLC and chiral HPLC methods and identified by positive electrospray ionization tandem MS detection (ESI+-MS). Two major enantiomers, i.e., sn-OOLb and sn-LLLb (O represents oleic acid; and L represents linoleic acid), were synthesized from the appropriate phosphatidylcholines. This allowed the identification of enantiomers after separation by chiral chromatography by tandem mass spectrometry. Similarly, TAGs from the seeds of Crepis foetida, and Leucas aspera were analyzed by reversed-phase chromatography and identified by mass spectrometry. Four enantiomers (sn-OOC, sn-LLC, sn-OOXi, and sn-LLXi) were synthesized. A total of six and three enantiomers of TAGs containing crepenynic and ximenynic acids, respectively, were identified by chiral column analysis. The retention times of TAGs containing allenic and acetylenic bonds were always greater on the reversed-phase column than TAGs with the same number of carbon atoms and the same unsaturation (e.g., LLL versus LLLb). From the chiral column, the regioisomers and enantiomers were eluted in the order of symmetric-asymmetric-asymmetric (i.e., sn-OCO, sn-COO, and sn-OOC). Through tandem mass spectrometry, we were able to identify and distinguish regioisomer [DAG]+-type ions, i.e., [MNH4NH3RCOOH]+, that can be considered diagnostic. Unfortunately, enantiomers and TAGs with the same numbers of carbon atoms and the same unsaturation levels have identical mass spectra, such as LLL and LLLb.


Assuntos
Cromatografia Líquida de Alta Pressão , Ácidos Graxos/análise , Sementes/química , Espectrometria de Massas em Tandem , Triglicerídeos/química , Alquinos/análise , Alquinos/química , Cromatografia Líquida , Cromatografia de Fase Reversa , Ácidos Graxos/química , Ácido Linoleico/análise , Ácidos Oleicos/análise , Fosfatidilcolinas/química , Espectrometria de Massas por Ionização por Electrospray , Estereoisomerismo , Triglicerídeos/análise , Triglicerídeos/isolamento & purificação
16.
Food Chem ; 324: 126816, 2020 Sep 15.
Artigo em Inglês | MEDLINE | ID: mdl-32344337

RESUMO

Identification and quantification of triacylglycerols (TAGs) in salmon muscle tissue were conducted using electrospray ionization (ESI)-MS/MS in a triple quadrupole mass spectrometer. The confirmation of three fatty acid moieties of individual TAGs was determined using the multiple neutral loss (NL) scanning mode. A total of 98 TAGs were identified, and the predominant TAG species were 16:0-18:0-20:5 (10.4%), 18:1-18:2-22:6 (9.0%), and 18:0-18:1-22:6 (16.4%) in salmon muscle tissue. NL scanning was an effective means to confirm the three fatty acid moieties of the TAGs, leading to the rapid and accurate identification of individual TAGs. To the best of our knowledge, this is the first application of multiple neutral loss scanning to identify TAGs in salmonoid tissue, and many TAG species have been newly identified (i.e., 18:1-18:2-22:6, 16:0-18:2-20:5, 18:1-18:2-20:5, etc.). This study showed that the shotgun lipidomic approach along with NL scans is a useful means for studying TAG metabolism in fish.


Assuntos
Músculo Esquelético/química , Salmão , Espectrometria de Massas por Ionização por Electrospray/métodos , Espectrometria de Massas em Tandem/métodos , Triglicerídeos/análise , Animais , Ácidos Graxos/análise , Triglicerídeos/química
17.
J Chromatogr A ; 1622: 461103, 2020 Jul 05.
Artigo em Inglês | MEDLINE | ID: mdl-32317104

RESUMO

Triacylglycerols (TAGs) containing cyclofatty acids (cycloFAs) from two oilseeds of Sterculia foetida and Hydnocarpus wightiana were analysed using both reversed-phase (RP18) and chiral phase columns. TAGs were identified using high-resolution electrospray ionization mass spectrometry in the positive ion mode. Fifty-five molecular species of TAGs have been identified in sterculic oil, 27 of which contained at least one cyclopropenyl-FA (e.g., malvalic or sterculic acids). The structures of regioisomers and enantiomers were determined for five major TAGs with cyclopropenyl-FAs. One hundred thirty-six TAGs were identified in chaulmoogra oil, 71 of which contained at least one cyclopentenyl-FA (e.g., gorlic, chaulmoogric, and hydnocarpic acids, etc.). Furthermore, in three molecular species, regioisomers and enantiomers were identified using HPLC on a chiral phase column. Eight molecular species of TAGs were prepared through organic synthesis to facilitate the identification of enantiomers. Retention times of fatty acid-containing triacylglycerols with one ring and one double bond are very similar to triacylglycerols with a dienoic fatty acid, but elution times are shorter. For example, dimalvaloylpalmitate elutes earlier than dilinoleylpalmitate. The order of elution of TAGs on the chiral column differs. In TAGs with 2 degrees of unsaturation (ring and double bond, e.g. PStP-StPP-PPSt), the order of elution is symmetric-asymmetric-asymmetric TAGs. TAGs with 4 degrees of unsaturation (one ring and three double bonds or two rings and two double bonds) present a different pattern. When TAGs contain two rings and two double bonds, the order of elution TAGs is asymmetric-symmetric-asymmetric (StStP-StPSt-PStSt); when TAGs contain a ring and 3 double bonds, the elution order is symmetric-asymmetric-asymmetric TAGs (OStO-StOO-OOSt). In species with a higher degree of unsaturation (e.g., 5), the elution order of the TAGs is asymmetric-asymmetric-symmetric (e.g. CCO-OCC-COC).


Assuntos
Ácidos Graxos/análise , Triglicerídeos/química , Cromatografia Líquida de Alta Pressão , Cromatografia de Fase Reversa , Ciclopropanos/análise , Ácidos Graxos/química , Ácidos Graxos/isolamento & purificação , Ácidos Graxos Monoinsaturados/análise , Óleos Vegetais/química , Espectrometria de Massas por Ionização por Electrospray , Sterculia/química , Estereoisomerismo
18.
Biochim Biophys Acta Biomembr ; 1862(7): 183254, 2020 07 01.
Artigo em Inglês | MEDLINE | ID: mdl-32135144

RESUMO

BACKGROUND: Oxidation of small dense low-density lipoprotein (sdLDL) and membranes is causally related to atherosclerosis. The omega-3 fatty acid (FA) eicosapentaenoic acid (EPA, 20:5, ω-3) significantly reduced oxidized LDL in patients with hypertriglyceridemia by unknown mechanisms. We compared EPA effects to related FAs of varying chain length and unsaturation on oxidation of sdLDL and model membranes, and on cholesterol crystal domains. We compared EPA to the FAs: stearic (SA, 18:0), oleic (OA, 18:1, ω-9), linoleic (LA, 18:2, ω-6), alpha-linolenic (ALA, 18:3, ω-3), eicosanoic (EA, 20:0), eicosatrienoic (ETE, 20:3, ω-3), arachidonic (AA, 20:4, ω-6), docosapentaenoic (DPA, 22:5, ω-3), and docosahexaenoic (DHA, 22:6, ω-3). METHODS: Human sdLDL or model membranes of cholesterol and 1,2-Dilinoleoyl-sn-glycero-3-phosphocholine [18:2(cis)PC or DLPC] were preincubated with FAs followed by copper-induced oxidation. Malondialdehyde (MDA) or lipid hydroperoxides (LOOH) levels measured oxidation; small-angle X-ray diffraction assessed cholesterol domain formation. RESULTS: After 40 min, EPA reduced MDA levels 70% compared to vehicle (p < 0.001). Lesser inhibition was observed with DHA, DPA, ETE, and ALA (33%, 34%, 32%, and 16%, respectively; all p < 0.001 versus vehicle). Similar relative FA effects were observed in model membranes where EPA more substantially inhibited cholesterol crystal domain formation. CONCLUSION: We observed relationships between hydrocarbon length and unsaturation with antioxidant activity and membrane cholesterol domain formation. EPA had the most favorable molecular structure, likely contributing to membrane stability, improved lipoprotein clearance, and reduced inflammation. GENERAL SIGNIFICANCE: Insight is provided into FA hydrocarbon length and unsaturation relationships with antioxidant activity in lipoproteins and membranes, and cholesterol crystal domains formation.


Assuntos
Colesterol/química , Ácido Eicosapentaenoico/química , Ácidos Graxos Ômega-3/química , Ácidos Graxos/química , Ácidos Docosa-Hexaenoicos/química , Ácido Eicosapentaenoico/metabolismo , Humanos , Lipoproteínas LDL/química , Oxirredução , Triglicerídeos/química
19.
Anal Bioanal Chem ; 412(10): 2315-2326, 2020 Apr.
Artigo em Inglês | MEDLINE | ID: mdl-32198533

RESUMO

The intestinal microbiome plays an important role in human health and disease and fecal materials reflect the microbial activity. Thus, analysis of fecal metabolites provides insight in metabolic interactions between gut microbiota and host organism. In this work, we applied flow injection analysis coupled to Fourier transform mass spectrometry (FIA-FTMS) to identify and quantify lipid species in human fecal samples. Fecal homogenates were subjected to lipid extraction and analyzed by FIA-FTMS. The analysis of different subjects revealed a vast heterogeneity of lipid species abundance. The majority of samples displayed prominent signals of triacylglycerol (TG) and diacylglycerol (DG) species that could be verified by MS2 spectra. Therefore, we focused on the quantification of TG and DG. Method validation included limit of quantification, linearity, evaluation of matrix effects, recovery, and reproducibility. The validation experiments demonstrated the suitability of the method, with exception for approximately 10% of samples, where we observed coefficients of variation higher than 15%. Impaired reproducibility was related to sample inhomogeneity and could not be improved by additional sample preparation steps. Additionally, these experiments demonstrated that compared with aqueous samples, samples containing isopropanol showed higher amounts of DG, presumably due to lysis of bacteria and increased TG lipolysis. These effects were sample-specific and substantiate the high heterogeneity of fecal materials as well as the need for further evaluation of pre-analytic conditions. In summary, FIA-FTMS offers a fast and accurate tool to quantify DG and TG species and is suitable to provide insight into the fecal lipidome and its role in health and disease.


Assuntos
Diglicerídeos/química , Fezes/química , Análise de Injeção de Fluxo/métodos , Espectrometria de Massas/métodos , Triglicerídeos/química , Humanos , Espectrometria de Massas/instrumentação
20.
J Food Sci ; 85(4): 964-971, 2020 Apr.
Artigo em Inglês | MEDLINE | ID: mdl-32222051

RESUMO

Oil migration (OM) has been an immense issue in fat-based foods such as peanut butter and chocolate fillings. The objective of this study was to evaluate the effect of high-intensity ultrasound (HIU) on OM in a palm kernel oil-based fat used in chocolate fillings, coatings, and confectionery applications. The sample was crystallized at 30 °C for 90 min and stored for 48 hr at 25 °C. HIU was applied after 20 min at 30 °C using a 3.2-mm diameter tip operating at an amplitude of 216 µm (90 W) for 10 s. OM was measured using a centrifuge- and a filter paper-based method. Crystal morphology and size, solid fat content (SFC), melting behavior, and hardness were evaluated after 90 min, 48 hr, and after OM. Results showed that HIU reduced OM (P < 0.05) by 52.0% when measured using the filter paper method while a reduction of 97.4% was observed when measured with the centrifuge method. HIU also reduced the crystal size (P < 0.05) and formed a more organized crystalline network. A reduction in peak temperature (Tp ) after 90 min of crystallization and 48 hr of storage was observed in sonicated samples without affecting the enthalpy. However, enthalpy and Tp were higher in the sample without HIU analyzed after OM due to the migration of low melting point triacylglycerols out of the crystalline network. HIU also increased the hardness (P < 0.05) from 1.37 N and 3.17 N. But no differences (P > 0.05) were found on SFC due to sonication. Overall, HIU changed the crystalline structure of the fat allowing for a better entrapment of liquid oil in the crystalline matrix. Results from this study will benefit food producers that are looking for fat sources with better capacity to entrap oil. PRACTICAL APPLICATION: OM is one of the main problems facing the fat industry, especially since the elimination of partially hydrogenated fats from foods. Efforts are being focused on finding new technologies to reduce OM and therefore to improve the shelf life of the product. This study introduces for the first time, a new processing technology to reduce OM in a palm kernel fat with high content of saturated fatty acids that is commonly used in confectionery applications.


Assuntos
Manipulação de Alimentos/métodos , Óleo de Palmeira/química , Sonicação/métodos , Cristalização , Gorduras/química , Ácidos Graxos/química , Dureza , Cinética , Sementes/química , Temperatura , Triglicerídeos/química
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