Fatty Esters Research Articles

Initial evaluation of 4-palmitoyloxy butyrate in whole blood as potential biomarker after γ-hydroxybutyric acid intake.

The problem of finding a suitable biomarker to widen the detection window of γ-hydroxybutyric acid (GHB) intake remains a challenge in forensic toxicology. Based on previously published results, the present study deals with the evaluation of a fatty acid ester of GHB (4-palmitoyloxy butyrate (GHB-Pal)) in whole blood as a potential biomarker to extend the detection window of GHB use e.g. in drug-facilitated sexual assaults (DFSA). A liquid chromatography-mass spectrometry (LC-MS/MS) method for the quantification of GHB-Pal in whole blood was validated. Whole blood samples were collected from subjects involed in police roadside controls (n=113) and from narcolepsy patients (n=10) after the controlled administration of Xyrem® (sodium oxybate). Both sample collectives were previously tested for GHB using two different methods: ultra-performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS) and gas chromatography-mass spectrometry (GC-MS). In samples from routine police casework, GHB-Pal was detected in 67 out of 113 analysed GHB-positive samples with a mean concentration of 0.8 ng/mL ± 0.5 ng/mL (standard deviation). Among samples that were tested positive for both compounds, no linear correlation was observed between GHB and GHB-Pal concentrations (r=0.508). In contrast, GHB-Pal was not detected in any of the blood samples analysed from the patients. The absence of GHB and GHB-Pal in the patient cohort may be attributed to the time interval between dose intake and blood collection (approx. 3 and 6 h), during which GHB was eliminated from the body. Furthermore, GHB-Pal was only detectable at a GHB concentration of at least 16 µg/mL, which indicates that endogenous concentrations or low GHB doses may not be sufficient for GHB-Pal formation. Due to missing correlation between both compounds and the lack of GHB-Pal detection several hours after GHB administration, it can be assumed that GHB-Pal in blood is not a suitable biomarker to widen the detection window of GHB.

Selective Lipophilization of Natural Phenolic Alcohols Induced by In Situ Choline Chloride-Based Natural Deep Eutectic Solvents.

In this scientific work, a novel and green method for selective lipophilization of EVOO's bioactive phenolic alcohols (PAs), namely, tyrosol, hydroxytyrosol, and its metabolite homovanillyl alcohol as fatty acid esters, is elucidated. The PAs have been employed as hydrogen bond donors in the formation of natural deep eutectic solvents (NADES) with choline chloride (ChCl). The fast and cheap esterification method by in situ formation of choline chloride-based deep eutectic solvents promotes the derivatization of PAs with various fatty acids as acylating agents in the absence of organic solvents and catalysts. Furthermore, given the growing interest in the application of NADES formed by bioactive molecules in the pharmacological and cosmetic fields, we analyzed the activity of antioxidant enzymes, superoxide dismutase, and glutathione S-transferase of three chemical formulations obtained after the formation of PA-oleate in the H2O2-treated HaCat human keratinocytes cell line, assessing also their toxicity via the MTT assay.

Extracellular Lipases of Yarrowia lipolytica Yeast in Media Containing Plant Oils—Studies Supported by the Design of Experiment Methodology

Lipases are enzymes of great application importance in the food industry, in the cosmetic and detergent industries, in pharmacy and medicine, and in organic chemistry. Among lipases of various origins, those from microorganisms are currently the most commonly used. An excellent producer of lipases seems to be the nonconventional Yarrowia lipolytica yeast, but the biosynthesis of valuable metabolites depends on many factors. This study aimed to investigate the biodiversity of extracellular enzymes produced by four strains of Y. lipolytica, and to determine the optimal conditions of catalysis for the enzymes, according to temperature and pH, in a model hydrolysis reaction. Based on the obtained results, the biodiversity and strain dependence in lipase biosynthesis were observed. Using a Central Composite Design, it was found that temperature is the main factor in determining lipase activity. The enzymes produced by four different strains exhibited other substrate specificity, which was investigated using Latin square design methodology. Only two examined yeast strains, KKP 379 and W29, produced extracellular lipases at a high activity level towards medium- and long-chain fatty acid esters. Moreover, extracellular lipase from wild-type strain KKP 379 was further characterized, followed by exploring the activity of whole-cell biocatalyst and lyophilized enzyme solutions, and it was acknowledged that it was a “true” lipase with the highest affinity to p-nitrophenyl oleate.

Effects of maternal feeding of clofibrate on hepatic fatty acid metabolism in suckling piglet

BackgroundEnergy deficiency is a leading cause of the high pre-weaning mortality of neonatal piglets in the swine industry. Thus, optimal energy metabolism is of crucial importance for improving the survivability of neonatal piglets. The effective utilization of milk fat as primary energy is indispensably required.MethodsPregnant sows (n = 27) were randomly assigned into 3 treatments. Each treatment received a standard diet (3,265 kcal ME/kg) supplemented with either 0, 0.25% or 0.5% clofibrate (w/w) from d 107 of gestation to d 7 of lactation. The effects of maternal clofibrate on their milk fatty acid (FA) and performance of the piglets were evaluated. The evaluations were performed via measuring sow productive performance, milk FA composition, and hepatic FA oxidation of the piglets at birth and d 1, 7, 14 and 19 after birth.ResultsMaternal supplementation of clofibrate had no effect on reproductive performance of the sows at farrowing and weaning (P > 0.05). However, the mortality at weaning was reduced for piglets from sows with 0.25% of clofibrate, and the average weekly (and daily) gain was higher in piglets from sows that received clofibrate than sows without clofibrate in the first week (P < 0.0001). Maternal clofibrate increased percentage of milk C12:0 and C14:0 FAs but decreased C18:2 and n-6 polyunsaturated FAs. Maternal clofibrate also increased plasma ketone body levels and hepatic FA oxidation measured at the first day of birth, but the increase was not detected in piglets on d 7, 14 or 19. Clofibrate was not detected in milk collected from the clofibrate-treated sows. The percentage of FA oxidation decreased, and the percentage of FA esterification increased with increasing in postnatal age. Supplemental carnitine increased FA oxidation regardless of succinate dehydrogenase inhibition, and the increase had no effect on FA esterification.ConclusionsMaternal supplementation of clofibrate during late gestation and early lactation increases hepatic FA oxidative metabolism at birth and improves growth performance of newborn piglets. Maternal clofibrate transfer to suckling piglets via milk was not detected. Carnitine availability is critical for piglets to maintain a high FA oxidation rate during the suckling period.

High-performance bio-based foam from agricultural waste luffa seed oil polyols

The present study aimed to develop eco-friendly polyurethane viscoelastic foam (PVF) with enhanced tear strength while preserving softness, comfort, and safety by utilizing bio-based polyols derived from luffa seed oil (LSO). Two types of bio-based polyols (PLSO-D and PLSO-M) were synthesized through the epoxidation process using diethylene glycol (DEG) and methanol (MeOH), respectively, for the production of LSO-based polyurethane viscoelastic foams (LSO-PVFs). The analyses revealed that these polyols exhibited high dispersion, appropriate hydroxyl values, and contained by-products such as oligomeric esters of fatty acids that facilitated physical and chemical crosslinking. LSO-PVFs demonstrated a uniform and fine cell structure with abundant open-cells, thick cell walls (55.5–76.6µm), and high apparent density (48.7–50.7kg/m3). Moreover, they exhibited enhanced tensile and tear strength (increasing up to 200% compared to petroleum-based PVFs), lower water absorption, excellent mildew resistance at 10% PLSO substitution. Additionally, these factors endowed LSO-PVFs with low indentation hardness and good bottom support performance, characterized by a compressive deflection coefficient of 2.30–3.54. This approach presents a sustainable alternative for foam production that offers comfort, durability while promoting the value-added utilization of agricultural waste.

Anti-ulcerogenic activity of Citrus medica var. sarcodactylis fruit extract nano-emulsion in gastric ulcer rat model through modulating HMBG1/TLR4/NF-κB and Nrf2/HSP70/PGE2 signaling pathways

One of the most prevalent gastrointestinal multi-etiological diseases is gastric ulcer, with several consequences and serious side influences. Nowadays, nanotechnology is one of the advanced tools to enhance drug delivery and bioavailability. Hence, the prime goal of this study was to create safe gastro-protective therapy using methanol fruit extract of Citrus medica var. sarcodactylis (CMF) and its prepared nano formula (Nano-CMF). CMF or its nano form was given to rats at dose 600 mg/kg/day for a week along with a single oral administration of ethanol (5 ml/kg) at the 7th day. The particle size distribution of formulated CMF reflected the successful preparation of nano form, with average size 65 nm. Pretreatment with CMF or its nano formula to ethanol challenged rats significantly controlled the inflammatory response through down-regulated gastric HMBG1/TLR4/NF-κB signaling pathway and its downstream mediators at p<0.001. Moreover, CMF or nano-CMF lessened oxidative stress incidence via modulating Nrf2 signaling pathway, sustaining prostaglandin content, and reducing gastric juice acidity with a significant p value less than 0.001, as compared to the EtOH-intoxicated rats. In addition, nano form effectively preserved the gastric mucosal integrity and alleviated apoptosis in gastric cells as validated by ulcer index (p<0.001), and the histological and immunohistochemical findings, when matched to the EtOH-treated group. The metabolomics analysis revealed the characterization of 36 compounds. GC/MS of CH2Cl2 fraction led to the identification of 34 compounds, the major category was fatty acid esters amounting 43.92%. The TLC technique for methanol extract led to isolation of 8 compounds: (4,5-O-Dicaffeoylquinic acid, ferulic acid, hesperidin, limettin, 5-demethylsinensetin, brassicasterol, campesterol and β-sitosterol). Brassicasterol is newly reported from species while 5-demethylsinensetin was newly reported from the Citrus genus. Furthermore, the docking experiments revealed strong binding affinity interactions of these compounds with TLR-4, Nrf2-Keap1 complex, and pNF-κBp65. In conclusion, mechanism of action of CMF or its nano formula exerting anti-ulcer effect was postulated based on the synergistic action of its reported compounds which possesses anti-inflammatory, antioxidant, and anti-apoptotic activities. To be noted, nano CMF showed a superior potent anti-ulcer activity than CMF and conventional therapy, omeprazole.

Metatranscriptomic insights into the mechanism of 'Multiple Qu' utilization in Jian-flavor Baijiu fermentation

The unique process of “Multiple-qu fermentation” (MF) is essential for the formation of the Jian-flavor Baijiu, but the mechanisms behind its aroma development remain not fully understood. This study compared the effects of “Single-qu fermentation”(SF) and MF on Baijiu production to elucidate the microbial and metabolic interactions responsible for its distinct aroma. Firstly, significant differences were observed in the microbial communities of the two types of Daqu. Medium-temperature Daqu (MT-Daqu) had higher relative abundances of Bacillus, Thermoactinomyces, Thermoascus, and yeasts like Picha and Saccharomycopsis. In contrast, high-temperature Daqu (HT-Daqu) was dominated by thermophilic genera such as Kroppenstedtia, and Thermomyces. In MF, the addition of HT-Daqu promoted an increase in Acetilactobacillus, while simultaneously leading to a decline in Lactobacillus and Kazachstania. Metatranscriptomic analysis revealed that Acetilactobacillus, Lactobacillus, Kazachstania, and Saccharomyces were the primary transcriptionally active genera in Baijiu fermentation. In SF, elevated transcription levels of Lactobacillus promoted the synthesis of ethyl lactate, reaching a concentration of 19.32 µg/L, compared to 7.33 µg/L in MF. Conversely, in MF, elevated transcription levels of Acetilactobacillus, Saccharomyces, and Kazachstania enhanced the synthesis of acetate esters and medium-chain fatty acid (MCFA) ethyl esters, reaching 28.50 µg/L and 195.84 µg/L, compared to 15.77 µg/L and 148.73 µg/L in SF. These differences in microbial communities and transcriptional activity directly shape the synthesis of key flavor compounds, thereby enhancing the distinct sensory characteristics of Jian-flavor Baijiu. This study provides new insights into the microbial and metabolic dynamics driving MF’s role in Jian-flavor Baijiu.

Hierarchical micro-meso-macroporous xAIL@HP UIO-66-NH2 catalysts used for efficient biodiesel production from low-grade acidic oils

The utilization of hierarchical porous supports to fabricate an efficient solid catalyst is a feasible strategy due to their remarkable merit in ameliorating the diffusion of reactants on the catalyst surface and increasing the exposure of active species in particular for the bulky molecule-involving reactions. In this research, to abatement the mass transfer resistance of large triglycerides, the hierarchical porous solid catalyst (xAIL@HP UIO-66-NH2) was prepared by grafting acidic ionic liquid (AIL) with double acidic sites of -SO3H and HSO4- onto micro-meso-macroporous metal-organic gels (HP UIO-66-NH2) through acid-base interactions between -NH2 moiety of HP UIO-66-NH2 and acidic moiety of AILs. The catalyst characterization results showed that the xAIL@HP UIO-66-NH2 catalyst owned the hierarchical porous structure and double Brønsted-Lewis acid centers with large BET surface area and pore volume. This catalyst was adopted for efficient biodiesel production from low-grade acidic oils, exhibiting high catalytic activities for triglyceride transesterification and free fatty acid (FFA) esterification reactions. By using acidic oils as feedstocks, the oil transesterification conversion could reach 91.3 % and the FFAs were completely converted to biodiesel under the conditions of 130 °C for 8 h at methanol-to-oil molar ratio of 35: 1 and catalyst dosage of 8 wt%. Based on the kinetic study, the activation energy Ea of this catalyst was 56.6 kJ/ mol, and the reaction complied with pseudo-first-order kinetics. This solid catalyst demonstrated satisfactory acid and water resistance, with good reusable performance, posing great potential in the efficient biodiesel preparation by the one-pot method using the low-grade acidic oils.

Producing and Testing the Properties of Biodiesel Sourced from Hemp Oil

Organic matter is converted into a variety of fuels, including potential replacements for transport fuels. New sources of raw materials are being sought for their acquisition. One such raw material that is currently attracting a growing degree of attention is hemp. The objective of this study was to produce biodiesel from hemp oil to ascertain its selected properties and to compare them with the properties of biodiesel obtained from rapeseed oil and the properties of diesel fuel. A reactor designed for the non-industrial, local conversion of available raw materials into fatty acid esters was used for the manufacture of biodiesel. The properties of hemp oil biodiesel were evaluated in comparison with those of rapeseed oil biodiesel, with properties of diesel fuel, and with the requirements set forth in the EN 14214 standard, pertaining to the specification of fatty acid methyl esters for utilization in compression-ignition internal combustion engines. The kinematic viscosity value of the hemp oil biodiesel yielded just below the upper limit defined in the standard. Furthermore, research has demonstrated that such biodiesel contains a considerable proportion of esters of linoleic and linolenic acids, which are susceptible to oxidation. The content of linolenic acid ester in esters produced from hemp oil is clearly higher than the content of this ester in esters obtained from rapeseed oil. This higher content contributes to the high value of the iodine number, significantly exceeding the standard requirements. The remaining designated properties of hemp oil biodiesel are in accordance with the requirements laid down in the standard and exhibit similarities to those of rapeseed oil biodiesel. Further research is recommended to enhance the characteristics of hemp oil biodiesel and its utilization in compression-ignition engines.

Enhanced Biodiesel Production with Eversa Transform 2.0 Lipase on Magnetic Nanoparticles.

This research investigated the usefulness of magnetic iron oxide nanoparticles (Fe3O4) as a support to immobilize the lipase Eversa Transform 2.0 (ET 2.0) to obtain an active and stable biocatalyst, easily recoverable from the reaction medium for applications in the production of biodiesel. Biodiesel was an alternative fuel composed mainly of fatty acid esters with strong transesterification and esterification capabilities. The study focused on the esterification of oleic acid with ethanol to synthesize ethyl oleate. Magnetic nanoparticles were prepared by coprecipitation, then activated with glutaraldehyde and functionalized with γ-aminopropyltriethoxysilane (APTES). The optimal conditions for immobilizing ET 2.0 were pH 10, 25 mM sodium carbonate buffer, an enzymatic load of 200 U/g, and 1 h of contact time, obtaining 78% yield and enzymatic activity of 205.9 U/g. Postimmobilization evaluation showed that the immobilized enzyme performed better than its free form. Kinetic studies were conducted under these optimized conditions (2-96 h at 150 rpm and 37 °C). The biocatalyst was tested for the synthesis of ethyl oleate using oleic acid as the substrate and ethanol, achieving a conversion of 88.1%. Subsequent recirculation tests maintained approximately 80% conversion until the fourth cycle, confirming the sustainability of ester production. Molecular docking studies revealed that the binding affinity for the enzyme-docked oil composition was estimated at -5.8 kcal/mol, suggesting that the combination of the substrate and lipase was stable and suitable for esterification.

Amino-acid-functionalized methanesulfonate ionic liquids as effective and reusable catalysts for oleic acid esterification

Five new amino-acid-functionalized methanesulfonate ionic liquids ([AAH][CH3SO3]-ILs) were prepared using methanesulfonic acid and amino acids (AAs). The catalytic performances of the five synthesized [AAH][CH3SO3]-ILs were evaluated for biodiesel synthesis via the esterification of oleic acid with methanol. Among them, IL [GluH][CH3SO3] exhibited the optimal catalytic activity in the oleic acid esterification. An experimental design based on the RSM-BBD was used to optimize the reaction conditions. A conversion rate of 96.8 % was attained using the [GluH][CH3SO3] catalyst for the oleic acid esterification at a catalyst load of 12 wt%, a molar ratio of 19.6:1, a reaction time of 3.5 h and a temperature of 103 °C. The [GluH][CH3SO3]-catalyzed oleic acid esterification followed first-order kinetics with the activation energy and frequency factor of 9.86 kJ·moL−1 and 0.47 min−1, respectively. The catalytic activity of the [GluH][CH3SO3] catalyst did not considerably change during ten consecutive cycles of the esterification reaction. Operational simplicity, high conversion rate along with good reusability makes the IL [GluH][CH3SO3] a promising catalyst for replacing traditional catalysts for the biodiesel preparation via the fatty acids esterification.

Accumulation of Acyl Plastoquinol and Triacylglycerol in Six Cyanobacterial Species with Different Sets of Genes Encoding Type-2 Diacylglycerol Acyltransferase-like Proteins.

Recently, acyl plastoquinol (APQ) and plastoquinone-B (PQ-B), which are fatty acid esters of plastoquinol and plastoquinone-C respectively, have been identified as the major neutral lipids in cyanobacteria. In Synechocystis sp. PCC 6803, Slr2103 having homology with the eukaryotic enzyme for triacylglycerol (TAG) synthesis, diacylglycerol acyltransferase 2 (DGAT2), was identified as responsible for the synthesis of these plastoquinone-related lipids. On the other hand, TAG synthesis in cyanobacteria remains controversial due to the low accumulation level within cyanobacterial cells together with the high contamination level from the environment. In this study, to quantify more precisely and elucidate the relationship between the accumulation of neutral lipids and the presence or absence of DGAT2-like genes, plastoquinone-related lipids and TAG were analyzed directly from total lipids of six cyanobacterial species with different sets of genes encoding DGAT2-like proteins belonging to two distinct subclades. The results showed that the synthesis of these neutral lipids is highly dependent on clade A DGAT2-like proteins under the culture conditions used in this study, although accumulation level of TAG was quite low. In contrast to APQ highly abundant in saturated fatty acids, the fatty acid composition of TAG was species-specific and partly reflected the total lipid composition. Gloeobacter violaceus PCC 7421, which lacks a DGAT2-like gene, accumulated APQ with a high proportion of C18:0, suggesting APQ synthesis by an unidentified acyltransferase.

Modeling high-pressure viscosities of fatty acid esters and biodiesel fuels based on modified rough hard-sphere-chain model and deep learning method

Modeling high-pressure viscosities of fatty acid esters and biodiesel fuels based on modified rough hard-sphere-chain model and deep learning method

Bimetallic Rex-Ru/C catalyst for fatty acid esters to diesel-range alkanes under low temperature

ABSTRACT The hydrogenation of bio-based oil into biodiesel is a key strategy in reducing reliance on fossil fuels. However, efficient catalysts are needed to enable low-temperature hydrogenation reactions due to the current high-temperature requirement for bio-based oil hydrogenation. Here, bimetallic catalysts Rex-Ru/C for low-temperature hydrogenation of bio-based oils were prepared. The presence of Re oxides (ReOx) in the catalyst enhances the abundance of weak and medium acid sites, thereby facilitating the adsorption of H2. The DFT calculation shows the introduction of Re also improved the adsorption capacity of the catalyst for fatty acid methyl ester and H2. The Re0.25-Ru/C catalyst exhibits superior conversion, selectivity, and recyclability at low temperatures compared to the previously reported catalysts, achieving 100% conversion of methyl stearate with 100% selectivity toward n-heptadecane (C17) and n-octadecane (C18) (reaction conditions: 150°C, 4 h, 2.5 MPa H2). Moreover, the catalyst also shows excellent hydrogenation activity toward various fatty acids or esters, including methyl palmitate, stearic acid, and palmitate at low temperatures. The Re0.25-Ru/C catalyst showed consistent recycling performance over 9 cycles. The decline in catalytic performance of the catalyst was primarily caused by a reduction in ReOx content, resulting in a decrease in acid site concentration. Consequently, there was reduced adsorption of H2 and oil on the catalyst.

Serial Re-Pitching of Yeast Impacts Final Flavor Profiles of Commercial Beer

The aroma-active compounds produced by Saccharomyces cerevisiae during the fermentation of wort are key to the unique aroma and flavour profiles of beer. In commercial fermentations, there is batch-to-batch variation depending on yeast “brewing fitness” or the health of the yeast, but how does yeast health impact fermentation performance and metabolite production during fermentation? To address this, daily samples were collected from three full-scale commercial fermentations. The specific gravity was measured immediately, and samples were collected for carbohydrate analysis by High-Performance Liquid Chromatography and volatile compound analysis by Head-Space Gas Chromatography Mass Spectrometry (HS-GC-MS). Acetate esters (3), medium-chain fatty acid ethyl esters (7), hop-derived compounds (3), and an off-flavour (1) were detected and identified, and their relative signal was recorded for each sample. While there did not appear to be an effect of generational age on the duration of fermentation, age, in terms of the number of generations from serial re-pitching, impacted the ratios of volatile compounds. This difference in ratios was observed as early as Day 2, resulting in a difference in the volatile compound profiles of finished beers, therefore resulting in inconsistency in the product. This is important knowledge for brewers as generational age must be considered when fermenting high-quality, consistent products and monitoring fermentation progress/duration may not be enough to determine the ability of yeast to produce balanced flavour profiles.

Discovery of two new long chain fatty acid esters of flavonol glycoside from Pollen Typhae Carbonisatus and their protective effects on HBMECs

ABATRACT Two new compounds, namely, isorhamnenin-3-O-neohesperidin-6′′-linoleic acid ester (1) and isorhamnenin-3-O-neohesperidin-6′′-palmitate (2), along with 17 known compounds, were isolated from Pollen Typhae Carbonisatus (PTC). Their structures were elucidated on the basis of one-dimensional (1D)-, two-dimensional (2D)-nuclear magnetic resonance (NMR), and high-resolution electrospray ionization mass spectrometry (HRESIMS) spectroscopic data analyses. The two new compounds (1 and 2) exhibited a protective effect in a dose-dependent manner and promoted tube generation in the oxygen-glucose deprivation/reoxygenation (OGD/R)-induced human brain microvascular endothelial cells (HBMECs).

Serum metabolite profiles of thyroid autoimmunity patients in early pregnancy.

Research on serum metabolite profiles in thyroid autoimmunity (TAI) patients during early pregnancy is currently limited. The current study aimed to identify differential serum metabolites and assess the relationship between pregnancy outcomes and metabolic abnormalities in individuals with TAI. This research included 26 pregnant women with TAI and 30 healthy controls (HC). We employed a liquid chromatograph mass spectrometer (LC-MS) to analyze changes between the two groups. Newborns in the TAI patients had lower birth weights than those in the control group (P = 0.007). We identified 92 differential metabolites (including 50 upregulated and 42 downregulated) belonging to amino acids, fatty acyls, glycerophosphocholines, steroid and other categories and four significantly enrichment Kyoto Encyclopedia of Genes and Genomes (KEGG) pathways including taurine and hypotaurine metabolism, citrate cycle (TCA cycle), glyoxylate and dicarboxylate metabolism and 2-oxocarboxylic acid metabolism. We further identified 15 characteristic metabolites (6-Methylquinoline, D-erythrose 4-phosphate, 4-Hydroxyisoleucine, phosphatidylcholine (PC)(16:2e/16:0), N3,N4-Dimethyl-L-arginine, N-desmethyltramadol, 3-Methoxybenzaldehyde, sphingomyelin (SM)(d14:3/28:2), gamma-Glutamylleucine, NSI-189, 3-(1-cyano-1,2-dihydroisoquinolin-2-yl)-3-oxopropyl propionate, lysophosphatidylinositol (LPI) 16:0, cis-Aconitic acid, polyamide (PA)(18:1/18:2) and fatty acyl esters of hydroxy fatty acid (FAHFA)(17:0/18:0)) using least absolute shrinkage and selection operator (LASSO) regression. Correlation analyses revealed that 6-Methylquinoline, D-erythrose 4-phosphate, gamma-Glutamylleucine, and LPI 16:0 exhibited a positive correlation with anemia before delivery, while 3-(1-cyano-1,2-dihydroisoquinolin-2-yl)-3-oxopropyl propionate had a negative correlation. LPI 16:0 displayed a positive correlation with uric acid (UA) during both middle and late pregnancy, whereas 3-Methoxybenzaldehyde exhibited a negative correlation with UA in late pregnancy. Cis-Aconitic acid showed a positive correlation with fasting blood glucose (FBG) in middle pregnancy. Conversely, 6-Methylquinoline and 4-Hydroxyisoleucine had a negative correlation with birth weight. Thyroid autoantibodies were found to be associated with 14 metabolites identified using LASSO, with the exception of PA (18:1/18:2). Our findings provide new evidence supporting the early screening of serum metabolites and their potential for predicting adverse pregnancy outcomes in women with TAI.

In vitro skin permeation of flavonoid esters enzymatically derived from natural oils: release mechanism from gel emulsion, stability, and dermatological compatibility

Due to their broad spectrum of biological activities and attractive pharmacological properties, flavonoids are very promising molecules for application in skin care products. In this study, phloridzin and naringin medium- and long-chain fatty acid esters were enzymatically synthesized in reaction with natural oils (coconut and linseed oil) and in vitro transdermal delivery of synthesized esters through artificial Strat-M® membrane was investigated. Experimental results were succesfully fitted using Peppas and Sahlin model which includes the lag phase. Release kinetics of all examined flavonoid esters from gel emulsions through the membrane depended on both diffusion and polymer relaxation effect (0.5<n < 1). The estimated effective diffusion coefficients ranged from 0.168·10-8 to 6.149·10-8 cm2 s-1 for phloridzin esters and from 0.116·10-8 to 4.210·10-8 cm2 s-1 for naringin esters. The effective diffusion coefficients decreased with the increase in ester molecular weight indicating the size-dependent diffusion. All formulation showed good stability, excellent hydration effect, and excellent dermatological compatibility without irritating effect. It can be concluded that gel emulsions with a mixture of flavonoid esters enzymatically synthesized in reaction with vegetable oils can be effectively topically applied as a skin care products.

Ethyl biodiesel production from crude soybean oil using enzymatic degumming-transesterification associated process

Brazil is one of the largest soybean producers in the world. Biodiesel production in Brazil (specially soybean oil biodiesel) has been growing every year and demanding more effective and sustainable technologies, which is the case of enzymatic processes. Enzymatic degumming could be an alternative to provide better quality products, before biodiesel production but also, in a one reaction step as a proposal to reduce time and costs. Therefore, this work was aimed at evaluating enzymatic degumming (previously optimized) of crude soybean oil using a phospholipase cocktail associated with transesterification using lipase from Aspergillus oryzae for ethyl biodiesel production. For this, transesterification was optimized for ethanol:oil (E:O) ratio, water and lipase % through a central composite rotatable design (CCRD). Optimal conditions were used to evaluate two degumming-transesterification associated processes: i) a one-pot reaction (OPR) where degumming and transesterification were performed at the same reactor; and ii) a two-pot reaction (TPR) where oil was first degummed, followed by transesterification. The optimal transesterification condition were achieved for E:O = 4.48:1, water = 3.41 % and lipase = 2.43 %, where 97 % fatty acid ethyl esters (FAEE) were obtained. Both OPR and TPR provided biodiesels with FAEE > 94 %: TPR was the best with 97.5 % and 99.98 % before and after biodiesel purification. Mineral elements (including phosphorus) and other impurities (anions) were low, and within quality standards. Glycerol produced also presented very low content of impurities which is quite advantageous. Although lipase achieves good conversion to FAEE (95.7 ± 0.29 %) using crude oil (Control), the final biodiesel carries many impurities (P=80.07 ± 0.1 mg/kg), thus requiring subsequent biodiesel purification steps. In addition, the high impurity content generates a biodiesel that does not comply with ANP legislative standards, P<10 mg/kg. The use of enzymatic degumming in the biodiesel production process generates a biodiesel with low impurities and higher final quality, in addition to being a process that generates less effluent. Enzymatic degumming was essential for obtaining high quality biodiesel and its association with transesterification showed to be a great option for decreasing time and costs for biodiesel production.

Glycerol esterification of free fatty acids catalyzed by zinc glycerolate for biodiesel production from acidified palm oil: Optimization, kinetic study, and process evaluation

AbstractBiodiesel is an important alternative renewable liquid fuel due to its eco‐friendly, non‐toxic, and lower emissions. In this work, glycerol esterification catalyzed by zinc glycerolate was employed as a pretreatment to prepare biodiesel from acidified palm oil. The effects of stirring rate, catalyst amount, glycerol to free fatty acids (FFAs) molar ratio, and reaction temperature on the conversion of FFAs and concentration of monoglycerides, diglycerides, and triglycerides were investigated and optimized. The results show that the conversion of FFAs could reach 99.16% under the optimized conditions. Moreover, the kinetics of glycerol esterification catalyzed by zinc glycerolate at 160–200°C was obtained. Additionally, a comprehensive evaluation of the new biodiesel production process was also conducted. As a result, higher biodiesel content in the crude biodiesel phase was obtained after transesterification and separation using this new process. Overall, the study contributes to the utilization of waste oils to produce renewable energy and to minimize the waste management problem.