Number Of Double Bonds Research Articles

Chemical Composition of Aerosols from the E-Cigarette Vaping of Natural and Synthetic Cannabinoids.

Vaping cannabinoids in electronic (e)-cigarette devices is rapidly increasing in popularity, particularly among adolescents, although the chemistry affecting the composition of the vape aerosol is not well understood. This work investigates the formation of aerosol mass, bioactive hydroxyquinones, and harmful or potentially harmful carbonyls from the e-cigarette vaping of natural and synthetic cannabinoids e-liquids in propylene glycol and vegetable glycerin (PG/VG) solvent at a 50 mg/mL concentration in a commercial fourth-generation vaping device. The following cannabinoids were studied: cannabidiol (CBD), 8,9-dihydrocannabidiol (H2CBD), 1,2,8,9-tetrahydrocannabidiol (H4CBD), cannabigerol (CBG), and cannabidiolic acid (CBDA). Quantification of analytes was performed using liquid chromatography coupled to accurate mass spectrometry. The addition of cannabinoids significantly increased aerosol and carbonyl formation compared with the PG/VG solvent alone. All cannabinoids in the study formed hydroxyquinones during vaping (up to ∼1% mass conversion) except for CBDA, which primarily decarboxylated to CBD. Hydroxyquinone formation increased and carbonyl formation decreased, with a decreasing number of double bonds among CBD and its synthetic analogues (H2CBD and H4CBD). During the vaping process, ∼3-6% of the cannabinoid mass can be observed as carbonyls under the study conditions. Oxidation of the terpene moiety on the cannabinoids is proposed as a major contributor to carbonyl formation. CBD produced significantly higher concentrations of formaldehyde, acetaldehyde, acrolein, diacetyl, and methylglyoxal compared with the other cannabinoid samples. CBG produced significantly higher levels of acetone, methacrolein, and methylglyoxal. Conversion of CBD to tetrahydrocannabinol (THC) was not observed under the study conditions. The chemical mechanism basis for these observations is discussed. Compared with other modalities of use for CBD and other cannabinoids, vaping has the potential to adversely impact human health by producing harmful products during the heated aerosolization process.

Exploring lipidomic profiles and their correlation with hormone receptor and HER2 status in breast cancer.

Dysregulated lipid metabolism promotes the progression of various cancer types, including breast cancer. The present study aimed to explore the lipidomic profiles of patients with breast cancer, providing insights into the correlation between lipid compositions and tumor subtypes characterized by hormone receptor (HR) and human epidermal growth factor receptor 2 (HER2) status. Briefly, 30 patients with breast cancer were categorized into four groups based on their HR and HER2 status: HR+ no HER2 expression (HER2-0), HR+ HER2-low; HR+ HER2-positive (pos) and HR- HER2-pos. The lipidomic profiles of these patients were analyzed using high-throughput liquid chromatography-mass spectrometry. The data were processed through principal component analysis (PCA), partial least squares-discriminant analysis (PLS-DA) and random forest (RF) classification to assess the lipidomic variations and significant lipid features among these groups. The profiles of the lipids, particularly triglycerides (TG) such as TG(16:0-18:1-18:1)+NH4, were significantly different across the groups. PCA and PLS-DA identified unique lipid profiles in the HR+ HER2-pos and HR+ HER2-0 groups, while RF highlighted phosphatidylinositol-3,4,5-trisphosphate(21:2)+NH4 as a crucial lipid feature for accurate patient grouping. Advanced statistical analysis showed significant correlations between lipid carbon chain length and the number of double bonds within the classifications, providing insights into the role of structural lipid properties in tumor biology. Additionally, a clustering heatmap and network analysis indicated significant lipid-lipid interactions. Pathway enrichment analysis showed critical biological pathways, such as the 'Assembly of active LPL and LIPC lipase complexes', which has high enrichment ratio and statistical significance. In conclusion, the present study underscored that lipidomic profiling is crucial in understanding the metabolic alterations associated with different breast cancer subtypes. These findings highlighted specific lipid features and interactions that may serve as potential biomarkers for breast cancer classification and target pathways for therapeutic intervention. Furthermore, advanced lipidomic analyses can be integrated to decipher complex biological data, offering a foundation for further research into the role of lipid metabolism in cancer progression.

Kinetic Investigation of the Emulsion Polymerization of Vinylidene Fluoride

AbstractPoly(vinylidene fluoride) (PVDF) is among the most produced fluoropolymers, second only to polytetrafluoroethylene. Despite its popularity, the complex microstructural properties achieved during the polymerization are not well documented in the literature. In particular, available models only track the chain length distribution of the polymer, while neglecting the distribution of other important properties, affecting the final behavior of the product. In this work, a 2D kinetic model, evaluating not only the chain length but also the number of terminal double bonds (TDBs) per chain, is developed. The numerical solution of the model is achieved by fractionating the population of polymer chains into classes with a specific number of TDBs and using the method of moments for each class. The model results are compared with experimental evidences for the amount of produced polymer, moles of main chain‐ends, number, and weight average molecular weight as well as full molecular weight distribution. Based on this comparison, kinetic parameters are estimated by optimization using genetic algorithm. The model reliability is finally verified using additional experimental data at different temperatures and amounts of initiator.

Determination of double bond positions in unsaturated fatty acids by pre-column derivatization with dimethyl and dipyridyl disulfide followed by LC-SWATH-MS analysis.

Comprehensive in-depth structural characterization of free mono-unsaturated and polyunsaturated fatty acids often requires the determination of carbon-carbondouble bond positions due to their impact on physiological properties and relevance in biological samples or during impurity profiling of pharmaceuticals. In this research, we report on the evaluation of disulfides as suitable derivatization reagents for the determination of carbon-carbondouble bond positions of unsaturated free fatty acids by UHPLC-ESI-QTOF-MS/MS analysis and SWATH (sequential windowed acquisition of all theoretical mass spectra) acquisition. Iodine-catalyzed derivatization of C = C double bonds with dimethyl disulfide (DMDS) enabled detection of characteristic carboxy-terminal MS2 fragments for various fatty acids in ESI negative mode. The determination of double bond positions of fatty acids with up to three double bonds, the transfer of the method to plasma samples, and its limitations have been shown. To achieve charge-switching for positive ion mode MS-detection, derivatization with 2,2'-dipyridyldisulfide (DPDS) was investigated. It enabled detection of both corresponding characteristic omega-end- and carboxy-end-fragments for fatty acids with up to two double bonds in positive ion mode. It provides a straightforward strategy for designing MRM transitions for targeted LC-MS/MS assays. Both derivatization techniques represent a simple and inexpensive way for the determination of double bond positions in fatty acids with low number of double bonds. No adaptation of MS hardware is required and the specific isotopic pattern of resulting sulfur-containing products provides additional structural confirmation. This reaction scheme opens up the avenue of structural tuning of disulfide reagents beyond DMDS and DPDS using reagents like cystine and analogs to achieve enhanced performance and sensitivity.

Multiple tail ionizable lipids improve in vivo mRNA delivery efficiency with biosafety

Ionizable lipid-based lipid nanoparticles (LNP) play a crucial role in the delivery of mRNA. The hydrophobic tail of ionizable lipid affects the formation of LNP and the release of mRNA. In this report, we focus on the effect of the number, chain length, and double bond number of the hydrophobic tail on the delivery efficiency. First, a series of ionizable lipids with two, three and four tails were synthesized and characterized featured with imidazole group as the head. The ionizable lipids derived LNP were prepared using a microfluidic co-mixing device, yielding particles primarily in the size range of 100 to 150 nm, with a polydispersity index (PDI) below 0.2. Screening identified ionizable lipids with four tails exhibiting superior delivery efficiency, of which U-15, U-17, U-18 and U-19 demonstrated the highest performance. Additionally, the U-19 significantly prolongs mRNA expression duration, and along with specific extrahepatic delivery effect compared to ALC-0315. Tissue slice tests on representatives (U-06: two tails, U-19: four tails, U-29: three tails) revealed no notable abnormalities. Analysis of immunogenicity, liver and kidney function tests indicated that all samples exhibited no evident immunogenicity or in vivo toxicity. Findings from tests on lysosome escape, cell transfection, and cytotoxicity revealed excellent in vitro delivery effectiveness. In summary, among the 35 imidazole-based ionizable lipids screened, optimal effects were exhibited by four tails, which providing a new strategy for the development of ionizable lipids.

High-Fat Feeding Alters Circulating Triglyceride Composition: Roles of FFA Desaturation and ω-3 Fatty Acid Availability.

Hypertriglyceridemia is a risk factor for type 2 diabetes and cardiovascular disease (CVD). Plasma triglycerides (TGs) are a key factor for assessing the risk of diabetes or CVD. However, previous lipidomics studies have demonstrated that not all TG molecules behave the same way. Individual TGs with different fatty acid compositions are regulated differentially under various conditions. In addition, distinct groups of TGs were identified to be associated with increased diabetes risk (TGs with lower carbon number [C#] and double-bond number [DB#]), or with decreased risk (TGs with higher C# and DB#). In this study, we examined the effects of high-fat feeding in rats on plasma lipid profiles with special attention to TG profiles. Wistar rats were maintained on either a low-fat (control) or high-fat diet (HFD) for 2 weeks. Plasma samples were obtained before and 2.5 h after a meal (n = 10 each) and subjected to lipidomics analyses. High-fat feeding significantly impacted circulating lipid profiles, with the most significant effects observed on TG profile. The effects of an HFD on individual TG species depended on DB# in their fatty acid chains; an HFD increased TGs with low DB#, associated with increased diabetes risk, but decreased TGs with high DB#, associated with decreased risk. These changes in TGs with an HFD were associated with decreased indices of hepatic stearoyl-CoA desaturase (SCD) activity, assessed from hepatic fatty acid profiles. Decreased SCD activity would reduce the conversion of saturated to monounsaturated fatty acids, contributing to the increases in saturated TGs or TGs with low DB#. In addition, an HFD selectively depleted ω-3 polyunsaturated fatty acids (PUFAs), contributing to the decreases in TGs with high DB#. Thus, an HFD had profound impacts on circulating TG profiles. Some of these changes were at least partly explained by decreased hepatic SCD activity and depleted ω-3 PUFA.

Dependence of photophysical properties on stereoisomers: The case of nonsymmetric 2-aryl(benz)imidazole-annulated derivatives

Nonsymmetric 2-aryl (benz)imidazole derivatives were previously synthesized via C-H/N-H annulation of imidazole derivatives from lapachol moieties with internal alkynes as an efficient tool to increase the π-system of lapimidazole derivatives. To investigate their photophysical properties, time-resolved and steady-state fluorescence measurements were carried out on dropcast film, powder, and diluted solution. Despite having the same number of single and double bonds, slight differences in their structures lead to distinct photophysical properties. The time-correlated single-photon counting measurements also demonstrated that the aspects of the temporal decay curves are dependent on the treatment of the samples during the measurements. The decay curves were relatively well fitted using an alternative method based on the exponentially modified Gaussian function, giving rise to a more complete set of fitting parameters. Finally, theoretical calculations corroborate that small structural changes in molecules can significantly alter their conformational dynamics, electronic spectra, and overall electronic behavior and stability.

Improved moisture barrier and mechanical properties of rice protein/sodium alginate films for banana and oil preservation: Effect of the type and addition form of fatty acid

Attenuating the moisture sensitivity of hydrophilic protein/polysaccharide-based films without impairing other properties remains a challenge. Fatty acid dispersed in Pickering emulsion was proposed to overcome such issue. An increase in fatty acid chain length slightly reduced the water vapor permeability (WVP) of emulsion films. As the number of fatty acid double bonds increased from 0 to 1, the WVP of emulsion films was significantly decreased by 14.02% while mechanical properties were significantly enhanced. More hydrogen bonds and stronger electrostatic interactions in the presence of fatty acids were observed by molecular dynamics simulation. The weight loss of bananas coated with oleic acid-incorporated film-forming emulsion was 6.81% lower than that of uncoated group after 4 days, and the corresponding film was more effective to delay oil oxidation than the commercial polypropylene film, indicating that the film is a promising alternative to food coating and packaging material.

Synthesis and Biological Evaluations of Granulatamide B and its Structural Analogues.

While granulatamides A and B have been previously isolated, their biological activities have been only partially examined. The aim of this study was to synthesize granulatamide B (4b), a tryptamine-derivative naturally occurring in Eunicella coral species, using the well-known procedure of Sun and Fürstner and its 12 structural analogues by modifying the side chain, which differs in length, degree of saturation as well as number and conjugation of double bonds. The prepared library of compounds underwent comprehensive assessment for their biological activities, encompassing antioxidative, antiproliferative, and antibacterial properties, in addition to in vivo toxicity evaluation using a Zebrafish model. Compound 4i, which consists of a retinoic acid moiety, exhibited the strongest scavenging activity against ABTS radicals (IC50 = 36 ± 2 μM). In addition, 4b and some of the analogues (4a, 4c and 4i), mostly containing an unsaturated chain and conjugated double bonds, showed moderate but non-selective activity with certain IC50 values in the range of 20-40 μM. In contrast, the analogue 4l, a derivative of alpha-linolenic acid, was the least toxic towards normal cell lines. Moreover, 4b was also highly active against Gram-positive Bacillus subtilis with an MIC of 125 μM. Nevertheless, both 4b and 4i, known for the best-observed effects, caused remarkable developmental abnormalities in the zebrafish model Danio rerio. Since modification of the side chain did not significantly alter the change in biological activities compared to the parent compound, granulatamide B (4b), the substitution of the indole ring needs to be considered. Our group is currently carrying out new syntheses focusing on the functionalization of the indole core.

The gut-facial aging axis: A two-sample Mendelian randomization and mediation analysis of gut microbiota, gut microbiota metabolic pathways, and blood metabolites.

Facial aging (FA) is a complex process influenced by both genetic and environmental factors. Gut microbiota (GM), gut microbiota metabolic pathways (GMMPs), and blood metabolites (BMs) have been implicated in the regulation of FA, but the causal and mediating effects of these factors remain unclear. We used summary-level data from genome-wide association studies (GWAS) of 16S rRNA gene sequencing data for GM (n=18 340), GWAS of GMMPs (n=7738), BMs (n=24 925), and GWAS of FA (n=423 999). We applied Mendelian randomization (MR) methods to estimate the causal effects of GM, GMMPs, and BMs on FA. We performed mediation analysis to quantify the proportion of the effects mediated by blood metabolites. We identified nine genus, two phylum, two families of GM, nine GM metabolic pathways, and 73 BMs that showed potential causal effects on FA. After Bonferroni correction, three BMs remained causally associated with FA, including average number of methylene groups per double bond (β, -0.023; 95% CI, -0.032∼-0.014; p=3.120×10-7) and average number of methylene groups in a fatty acid chain (β, -0.031; 95% CI, -0.045∼-0.016; p=2.062×10-5), which had strong negative causal effects on FA, and ratio of bisallylic groups to total fatty acids (β, 0.023; 95% CI, 0.017∼-0.029; p=8.441×10-15), which had a strong positive causal effect on FA. Mediation analysis revealed that histidine, average number of methylene groups in a fatty acid chain, and triglycerides in chylomicrons and largest VLDL particles mediated the effects of anaerofilum and/ or superpathway of Laspartate and Lasparagine biosynthesis on FA. Our study provides novel insights into the causal and mediating effects of GM, GMMPs, and BMs on FA. These findings may have implications for the development of new strategies for preventing or delaying FA.

The effect of fat model variation on muscle fat fraction quantification in a cross-sectional cohort.

Spectroscopic imaging, rooted in Dixon's two-echo spin sequence to distinguish water and fat, has evolved significantly in acquisition and processing. Yet precise fat quantification remains a persistent challenge in ongoing research. With adequate phase characterization and correction, the fat composition models will impact measurements of fatty tissue. However, the effect of the used fat model in low-fat regions such as healthy muscle is unknown. In this study, we investigate the effect of assumed fat composition, in terms of chain length and double bond count, on fat fraction quantification in healthy muscle, while addressing phase and relaxometry confounders. For this purpose, we acquired bilateral thigh datasets from 38 healthy volunteers. Fat fractions were estimated using the IDEAL algorithm employing three different fat models fitted with and without the initial phase constrained. After data processing and model fitting, we used a convolutional neural net to automatically segment all thigh muscles and subcutaneous fat to evaluate the fitted parameters. The fat composition was compared with those reported in the literature. Overall, all the observed estimated fat composition values fall within the range of previously reported fatty acid composition based on gas chromatography measurements. All methods and models revealed different estimates of the muscle fat fractions in various evaluated muscle groups. Lateral differences changed from 0.5% to 5.3% in the hamstring muscle groups depending on the chosen method. The lowest observed left-right differences in each muscle group were all for the fat model estimating the number of double bonds with the initial phase unconstrained. With this model, the left-right differences were 0.64% ± 0.31%, 0.50% ± 0.27%, and 0.50% ± 0.40% for the quadriceps, hamstrings, and adductors muscle groups, respectively. Our findings suggest that a fat model estimating double bond numbers while allowing separate phases for each chemical species, given some assumptions, yields the best fat fraction estimate for our dataset.

Effect of number of intramolecular double bonds on photophysical properties and ESIPT processes for Cha-NH2 and its derivatives: A theoretical study

In recent years, the research on excited-state intramolecular proton transfer (ESIPT) reactions has aroused increasingly attention theoretically and experimentally. For a deep exploration, we designed three derivatives of Cha-NH2 with different numbers of carbon–carbon double bonds: Cha-NH2-1, Cha-NH2-2, and Cha-NH2-3. Using density functional theory and time-dependent density functional theory methods, we systematically studied the photophysical properties and ESIPT processes of Cha-NH2 and its derivatives. Detailed analysis revealed that the number of carbon–carbon double bonds within the molecule has a significant impact on the ESIPT behavior and spectral properties of Cha-NH2 and its derivatives. Specifically, as the number of carbon–carbon double bonds increases, the strength of intramolecular hydrogen bond is gradually weakened, leading to a red shift in the spectrum and a increase in the forward energy barrier for ESIPT, which is unfavorable for the occurrence of the ESIPT reaction. Therefore, this finding opens up broad application prospects for the adjustment and optimization of future ESIPT process.

Activation of hTREK-1 by polyunsaturated fatty acids involves direct interaction

TREK-1 is a mechanosensitive channel activated by polyunsaturated fatty acids (PUFAs). Its activation is supposed to be linked to changes in membrane tension following PUFAs insertion. Here, we compared the effect of 11 fatty acids and ML402 on TREK-1 channel activation using the whole cell and the inside-out configurations of the patch-clamp technique. Firstly, TREK-1 activation by PUFAs is variable and related to the variable constitutive activity of TREK-1. We observed no correlation between TREK-1 activation and acyl chain length or number of double bonds suggesting that the bilayer-couple hypothesis cannot explain by itself the activation of TREK-1 by PUFAs. The membrane fluidity measurement is not modified by PUFAs at 10 µM. The spectral shift analysis in TREK-1-enriched microsomes indicates a KD,TREK1 at 44 µM of C22:6 n-3. PUFAs display the same activation and reversible kinetics than the direct activator ML402 and activate TREK-1 in both whole-cell and inside-out configurations of patch-clamp suggesting that the binding site of PUFAs is accessible from both sides of the membrane, as for ML402. Finally, we proposed a two steps mechanism: first, insertion into the membrane, with no fluidity or curvature modifications at 10 µM, and then interaction with TREK-1 channel to open it.

Machine Learning for Characterizing Biofuels Based on Femtosecond Laser Ionization Mass Spectrometry.

A sample mixture of fatty acid methyl esters (FAMEs) was measured by femtosecond laser ionization mass spectrometry (fsLIMS) using the fifth (206 nm) and fourth (257 nm) harmonic emissions of an ytterbium (Yb) laser (1030 nm). Molecular ions were observed as the major signals in this technique, providing valuable information concerning the molecular weight and the number of double bonds in the molecule. The mass spectral data were then used as explanatory variables in machine learning based on artificial intelligence (AI) to correlate with objective variables such as the cetane number, kinematic viscosity, specific gravity, a higher heating value, an iodine value, flash point, oxidative stability index, and a cloud point measured for reference biofuel samples containing various FAMEs. The properties of biofuels, i.e., the objective variables, were evaluated from the mass spectral data obtained for unknown samples. The errors in the evaluation were a few percent when the distribution of the FAMEs in the unknown biofuel sample was similar to those of the biofuels used for machine learning. As demonstrated herein, the present approach, involving a combination of fsLIMS and AI, has the potential for use in evaluating the properties of a biofuel and then in solving of environmental issues associated with global warming.

Feasibility of omega-3 fatty acid fraction mapping using chemical shift encoding-based imaging at 3 T.

The aim of this work is to develop an ω-3 fatty acid fraction mapping method at 3 T based on a chemical shift encoding model, to assess its performance in a phantom and in vitro study, and to further demonstrate its feasibility in vivo. A signal model was heuristically derived based on spectral appearance and theoretical considerations of the corresponding molecular structures to differentiate between ω-3 and non-ω-3 fatty acid substituents in triacylglycerols in addition to the number of double bonds (ndb), the number of methylene-interrupted double bonds (nmidb), and the mean fatty acid chain length (CL). First, the signal model was validated using single-voxel spectroscopy and a time-interleaved multi-echo gradient-echo (TIMGRE) sequence in gas chromatography-mass spectrometry (GC-MS)-calibrated oil phantoms. Second, the TIMGRE-based method was validated in vitro in 21 adipose tissue samples with corresponding GC-MS measurements. Third, an in vivo feasibility study was performed for the TIMGRE-based method in the gluteal region of two healthy volunteers. Phantom and in vitro data was analyzed using a Bland-Altman analysis. Compared with GC-MS, MRS showed in the phantom study significant correlations in estimating the ω-3 fraction (p < 0.001), ndb (p < 0.001), nmidb (p < 0.001), and CL (p = 0.001); MRI showed in the phantom study significant correlations (all p < 0.001) for the ω-3 fraction, ndb, and nmidb, but no correlation for CL. Also in the in vitro study, significant correlations (all p < 0.001) between MRI and GC-MS were observed for the ω-3 fraction, ndb, and nmidb, but not for CL. An exemplary ROI measurement in vivo in the gluteal subcutaneous adipose tissue yielded (mean ± standard deviation) 0.8% ± 1.9% ω-3 fraction. The present study demonstrated strong correlations between gradient-echo imaging-based ω-3 fatty acid fraction mapping and GC-MS in the phantom and in vitro study. Furthermore, feasibility was demonstrated for characterizing adipose tissue in vivo.

Structural elucidation of complex polyesters polyols from bio-lubricant using off-line liquid chromatography x supercritical fluid chromatography coupled with Orbitrap mass spectrometry

Synthetic complex esters and polyol esters are incorporated as partially bio-based and biodegradable alternatives to petroleum base oils in lubricant formulations, to provide specific properties or performance and to help reducing their carbon footprint in certain cases. A sample can contain over 400 molecules of high chemical similarity including numerous isomers. To resolve such complexity, a separation technique with large peak capacity coupled to high-resolution mass spectrometry (HRMS) is essential. In this study, comprehensive off-line LCxSFC hyphenated with an Orbitrap analyzer was used for the structural elucidation of a synthetic bio-lubricant composed of a polyol reacted with fatty acids of varying length or with repetitive units of polyesters of ricinoleic acid. Retention in the LC first dimension was mostly due to the degree of oligomerization of ricinoleic acid within the polyester and to the chain length of the fatty acid. The SFC second dimension highlighted the esterification degree of the polyalcohol and the number and positions of fatty acids double bonds. The combination of both dimensions permitted the separation of isomers. The coupling of SFC with Orbitrap analyzer allowed an accurate assignment of molecular formulas. Finally, the fragmentation in the ionization source confirmed the attributed structures. By introducing a clear distribution of the chemical structures in the retention space, LCxSFC-HRMS provided a powerful analytical method for the comprehensive molecular characterization of the complex polyester polyols sample.

Different lateral packing stress in acyl chains alters KcsA orientation and structure in lipid membranes

The molecular structures of the various intrinsic lipids in membranes regulate lipid-protein interactions. These different lipid structures with unique volumes produce different lipid molecular packing stresses/lateral stresses in lipid membranes. Most studies examining lipid packing effects have used phosphatidylcholine and phosphatidylethanolamine (PE), which are the main phospholipids of eukaryotic cell membranes. In contrast, Gram-negative or Gram-positive bacterial membranes are composed primarily of phosphatidylglycerol (PG) and PE, and the physical and thermodynamic properties of each acyl chain in PG at the molecular level remain unresolved. In this study, we used 1-palmitoyl-2-oleoyl-sn-glycero-3-phospho-(1′-rac-glycerol) (POPG, 16:0–18:1 PG) and 1-palmitoyl-2-arachidonoyl-sn-glycero-3-phospho-(1′-rac-glycerol) (PAPG, 16:0–20:4 PG) to prepare lipid bilayers (liposome) with the rod-type fluorescence probe DPH. We measured the lipid packing conditions by determining the rotational freedom of DPH in POPG or PAPG bilayers. Furthermore, we investigated the effect of different monoacyl chains on a K+ channel (KcsA) structure when embedded in POPG or PAPG membranes. The results revealed that differences in the number of double bonds and carbon chain length in the monoacyl chain at sn-2 affected the physicochemical properties of the membrane and the structure and orientation of KcsA.

Optimized quantification of fatty acids in complex media using advanced analytical techniques.

Various medium formulations contain essential fatty acids at concentrations ranging from 10 to 100 mg/L. Accurate and precise lipid measurement in media is crucial for monitoring media quality and conducting studies on lipids in the context of cell culture. This study employed two-dimensional gas chromatography (GC × GC) analyses to offer enhanced resolution, sensitivity, and separation performance compared to GC. Quantification of fatty acid methyl esters (FAMEs) in a medium was conducted using GC × GC combined with a high-resolution mass spectrometer and flame ionization detector, considering potential interference from nonionic surfactant Tween 80, which was precipitated and removed by optimizing the concentration of cobalt thiocyanate (CTA) solution during pretreatment. This advanced analytical approach enabled identification of cis and trans isomers of identical molecular weights and determination of the location and number of double bonds in the same carbon number structure. Our analysis identified 36 FAMEs within the C6-C24 region, and a 5% CTA solution was optimal for efficient removal of Tween 80 during lipid extraction. Additionally, this advanced method minimized FAME contamination and loss during pretreatment, thereby significantly reducing the sample volume required to detect trace levels of FAMEs. This improvement led to a fatty acid recovery rate of 106% while maintaining the average relative standard deviation for the target FAMEs of about 3%. Our research paves the way for future investigation into medium quality control and the role of fatty acids in cell culture. This offers the possibility for economical and effective trace quantification of fatty acids in complex media.

Metabolism of 11'-α- and 11'-γ-Tocomonoenols in HepG2 Cells Favors the γ-Congener and Results Predominantly in Carboxymethylbutyl-Hydroxychromans.

Tocomonoenols (T1) are little-known vitamin E derivatives naturally occurring in foods. Limited knowledge exists regarding the cellular uptake and metabolism of α-tocomonoenol (αT1) and none about that of γ-tocomonoenol (γT1). The study investigates the cytotoxicity, uptake, and metabolism of αT1 and γT1 in HepG2 cells compared to the α- and γ-tocopherols (T) and -tocotrienols (T3). None of the studied tocochromanols are cytotoxic up to 100µmolL-1. The uptake of the γ-congeners is significantly higher than that of the corresponding α-forms, whereas no significant differences are observed based on the degree of saturation of the sidechain. Carboxymethylbutyl-hydroxychromans (CMBHC) are the predominant short-chain metabolites of all tocochromanols and conversion is higher for γT1 than αT1 as well as for the γ-congeners of T and T3. The rate of metabolism increases with the number of double bonds in the sidechain. The rate of metabolic conversion of the T1 is more similar to tocopherols than to that of the tocotrienols. This is the first evidence that both αT1 and γT1 follow the same sidechain degradation pathway and exert similar rates of metabolism than tocopherols. Therefore, investigation into the biological activities of tocomonoenols is warranted.

The role of C18 fatty acids in improving the digestion and retrogradation properties of highland barley starch

In this study, five C18 fatty acids (FA) with different numbers of double bonds and configurations including stearic acid (SA), oleic acid (OA), elaidic acid (EA), linoleic acid (LA), and α-linolenic acid (ALA), were selected to prepare highland barely starch (HBS)-FA complexes to modulate digestibility and elaborate the underlying mechanism. The results showed that HBS-SA had the highest complex index (34.18 %), relative crystallinity (17.62 %) and single helix content (25.78 %). Furthermore, the HBS-C18 FA complexes were formed by EA (C18 FA with monounsaturated bonds) that had the highest R1047/1022 (1.0509) and lowest full width at half-maximum (FWHM, 20.85), suggesting good short-range ordered structure. Moreover, all C18 FAs could form two kinds of V-type complexes with HBS, which can be confirmed by the results of CLSM and DSC measurements, and all of them showed significantly lower digestibility. HBS-EA possessed the highest resistant starch content (20.17 %), while HBS-SA had the highest slowly digestible starch content (26.61 %). In addition, the inhibition of HBS retrogradation by fatty acid addition was further proven, where HBS-SA gel firmness (37.80 g) and aging enthalpy value were the lowest, indicating the most effective. Overall, compounding with fatty acids, especially SA, could be used as a novel way to make functional foods based on HBS.