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Chemical Science May 2021Surface-sensitive vibrational spectroscopy is a common tool for measuring molecular organization and intermolecular interactions at interfaces. Peak intensity ratios are...
Surface-sensitive vibrational spectroscopy is a common tool for measuring molecular organization and intermolecular interactions at interfaces. Peak intensity ratios are typically used to extract molecular information from one-dimensional spectra but vibrational coupling between surfactant molecules can manifest as signal depletion in one-dimensional spectra. Through a combination of experiment and theory, we demonstrate the emergence of vibrational exciton delocalization in infrared reflection-absorption spectra of soluble and insoluble surfactants at the air/water interface. Vibrational coupling causes a significant decrease in peak intensities corresponding to C-F vibrational modes of perfluorooctanoic acid molecules. Vibrational excitons also form between arachidic acid surfactants within a compressed monolayer, manifesting as signal reduction of C-H stretching modes. Ionic composition of the aqueous phase impacts surfactant intermolecular distance, thereby modulating vibrational coupling strength between surfactants. Our results serve as a cautionary tale against employing alkyl and fluoroalkyl vibrational peak intensities as proxies for concentration, although such analysis is ubiquitous in interface science.
PubMed: 34221313
DOI: 10.1039/d1sc01276b -
Biology Jun 2021Seasonal variations in the fatty acid (FA) compositions of pollen loads collected from the Al-Ahsa Oasis in eastern Saudi Arabia throughout one year were determined to...
Seasonal variations in the fatty acid (FA) compositions of pollen loads collected from the Al-Ahsa Oasis in eastern Saudi Arabia throughout one year were determined to identify the optimal season for harvesting bee pollen rich in essential fatty acids (EFAs) and unsaturated fatty acids (UFAs). The highest values (%) of lipids, linolenic acid (C), stearic acid (C), linoleic acid (C), arachidic acid (C), the sum of the C18:0, C18:1, C18:2, and C18:3 concentrations, and EFAs were obtained from bee pollen harvested during autumn. The maximum values (%) of oleic acid (C), palmitic acid (C), UFAs, and the UFA/saturated fatty acid (SFA) ratio were found in bee pollen harvested during summer. The highest concentrations (%) of behenic acid (C), lignoceric acid (C), and SFAs were found in bee pollen harvested during winter. Bee pollen harvested during spring ranked second in its oleic, palmitic, linolenic, stearic, arachidic, behenic, and lignoceric acid concentrations and for EFAs, UFAs, and the UFA/SFA ratio. The lowest SFA concentration was found in bee pollen harvested during summer. Oleic, palmitic, and linolenic acids were the most predominant FAs found in bee pollen. It was concluded that the FA composition of bee pollen varied among the harvest seasons due to the influence of the dominant botanical origins. We recommend harvesting pollen loads during spring and summer to feed honeybee colonies during periods of scarcity and for use as a healthy, nutritious food for humans.
PubMed: 34199497
DOI: 10.3390/biology10060495 -
The Journal of Nutrition Sep 2021Metabolic flexibility is the responsiveness to heterogeneous physiological conditions, such as food ingestion. A key unresolved question is how inflammation affects...
BACKGROUND
Metabolic flexibility is the responsiveness to heterogeneous physiological conditions, such as food ingestion. A key unresolved question is how inflammation affects metabolic flexibility.
OBJECTIVES
Our study objective was to compare metabolic flexibility, specifically the metabolomic response to a standardized meal, by fasting inflammation status.
METHODS
Participants in Guatemala (n = 302, median age 44 y, 43.7% men) received a standardized, mixed-macronutrient liquid meal. Plasma samples (fasting, 2 h postmeal) were assayed by dual-column LC [reverse phase (C18) and hydrophilic interaction LC (HILIC)] with ultra-high-resolution MS, for concentrations of 6 inflammation biomarkers: high-sensitivity C-reactive protein (hsCRP), leptin, resistin, IL-10, adiponectin, and soluble TNF receptor II (TNFsR). We summed the individual inflammation biomarker z-scores, after reverse-coding of anti-inflammation biomarkers. We identified features with peak areas that differed between fasting and postmeal (false discovery rate-adjusted q <0.05) and compared median log2 postprandial/fasting peak area ratios by inflammation indicators.
RESULTS
We found 1397 C18 and 974 HILIC features with significant postprandial/fasting feature ratios (q <0.05). Overall inflammation z-score was directly associated with the postprandial/fasting feature ratios of arachidic acid, and inversely associated with the feature ratio of lysophosphatidic acid (LPA), adjusting for age and sex (all P < 0.05). The postprandial/fasting ratio of arachidic acid was negatively correlated with resistin, IL-10, adiponectin, and TNFsR concentrations (all P < 0.05). Feature ratios of several fatty acids-myristic acid [m/z 227.2018, retention time (RT) 229], heptadecanoic acid (m/z 269.2491, RT 276), linoleic acid (m/z 280.2358, RT 236)-were negatively correlated with fasting plasma concentrations of leptin (nanograms per milliliter) and adiponectin (micrograms per milliliter), respectively (all P < 0.05). The postprandial/fasting ratio of LPA was positively correlated with IL-10 and adiponectin (both P < 0.05); and the ratio of phosphatidylinositol was positively correlated with hsCRP (P < 0.05).
CONCLUSIONS
Postprandial responses of fatty acids and glycerophospholipids are associated with fasting inflammation status in adults in Guatemala.
Topics: Adult; Fasting; Fatty Acids; Female; Glycerophospholipids; Humans; Inflammation; Male; Postprandial Period
PubMed: 34113999
DOI: 10.1093/jn/nxab183 -
Cancer Immunology, Immunotherapy : CII Jan 2022Lipids have immunomodulatory functions and the potential to affect cancer immunity. (Observational Study)
Observational Study
BACKGROUND
Lipids have immunomodulatory functions and the potential to affect cancer immunity.
METHODS
The associations of pretreatment serum cholesterol and long-chain fatty acids with the objective response rate (ORR), progression-free survival (PFS), and overall survival (OS) were evaluated in 148 patients with non-small cell lung cancer who received nivolumab.
RESULTS
When each lipid was separately evaluated, increased low-density lipoprotein (LDL)-cholesterol (P < 0.001), high-density lipoprotein (HDL)-cholesterol (P = 0.014), total cholesterol (P = 0.007), lauric acid (P = 0.015), myristic acid (P = 0.022), myristoleic acid (P = 0.035), stearic acid (P = 0.028), linoleic acid (P = 0.005), arachidic acid (P = 0.027), eicosadienoic acid (P = 0.017), dihomo-γ-linolenic acid (P = 0.036), and behenic acid levels (P = 0.032) were associated with longer PFS independent of programmed death ligand 1 (PD-L1) expression. Meanwhile, increased LDL-cholesterol (P < 0.001), HDL-cholesterol (P = 0.009), total cholesterol (P = 0.036), linoleic acid (P = 0.014), and lignoceric acid levels (P = 0.028) were associated with longer OS independent of PD-L1 expression. When multiple lipids were evaluated simultaneously, LDL-cholesterol (P = 0.003), HDL-cholesterol (P = 0.036), and lauric acid (P = 0.036) were independently predictive of PFS, and LDL-cholesterol (P = 0.008) and HDL-cholesterol (P = 0.031) were predictive of OS. ORR was not associated with any serum lipid.
CONCLUSIONS
Based on the association of prolonged survival in patients with increased serum cholesterol and long-chain fatty acid levels, serum lipid levels may be useful for predicting the efficacy of immune checkpoint inhibitor therapy.
Topics: Aged; Antineoplastic Agents, Immunological; Carcinoma, Non-Small-Cell Lung; Cholesterol; Cholesterol, HDL; Cholesterol, LDL; Disease-Free Survival; Fatty Acids; Female; Gene Expression Regulation, Neoplastic; Humans; Immune Checkpoint Inhibitors; Lipids; Lung Neoplasms; Male; Middle Aged; Nivolumab; Prospective Studies; Treatment Outcome
PubMed: 34091744
DOI: 10.1007/s00262-021-02979-4 -
International Journal of Molecular... May 2021Bacterial symbionts associated with insects are often involved in host development and ecological adaptation. , a common facultative endosymbiont harbored in pea aphids,...
Bacterial symbionts associated with insects are often involved in host development and ecological adaptation. , a common facultative endosymbiont harbored in pea aphids, improves host fitness and heat tolerance, but studies concerning the nutritional metabolism and impact on the aphid host associated with carrying are limited. In the current study, we showed that -infected aphids had a shorter nymphal developmental time and higher body weight than -free aphids when fed on detached leaves. Genes connecting to fatty acid biosynthesis and elongation were up-regulated in -infected aphids. Specifically, elevated expression of fatty acid synthase 1 () and diacylglycerol-o-acyltransferase 2 () could result in accumulation of myristic acid, palmitic acid, linoleic acid, and arachidic acid in fat bodies. Impairing fatty acid synthesis in -infected pea aphids either by a pharmacological inhibitor or through silencing and expression prolonged the nymphal growth period and decreased the aphid body weight. Conversely, supplementation of myristic acid (C14:0) to these aphids restored their normal development and weight gain. Our results indicated that promoted development and growth of its aphid host through enhancing fatty acid biosynthesis. Our discovery has shed more light on nutritional effects underlying the symbiosis between aphids and facultative endosymbionts.
Topics: Animals; Aphids; Fatty Acids; Host Microbial Interactions; Serratia; Symbiosis
PubMed: 34073039
DOI: 10.3390/ijms22115951 -
Foods (Basel, Switzerland) May 2021Authentication of extra virgin olive oils is a key strategy for their valorization and a way to preserve olive biodiversity. Physical and thermal analysis have been...
Authentication of extra virgin olive oils is a key strategy for their valorization and a way to preserve olive biodiversity. Physical and thermal analysis have been proposed in this study as fast and green techniques to reach this goal. Thirteen extra virgin olive oils (EVOOs) obtained from minor olive cultivars, harvested at three different ripening stages, in four Italian regions (Abruzzo, Apulia, Sardinia, and Calabria) have been studied. Thermal properties, viscosity and color, as influenced by fatty acid composition and chlorophyll content, have been investigated. The thermal curves of EVOOs, obtained by differential scanning calorimetry, were mostly influenced by the oleic acid content: a direct correlation with the cooling and heating enthalpy and an indirect correlation with the cooling transition range were observed. The minor fatty acids, and particularly arachidic acid, showed an influence, mostly on the heating thermograms. Viscosity and color showed respectively a correlation with fatty acids composition and chlorophyll content, however they didn't result able to discriminate between the samples. Thanks to the principal component analysis, the most influencing thermal parameters and fatty acids were used to cluster the samples, based on their botanical and geographical origin, resulting instead the harvesting time a less influential variable.
PubMed: 34064430
DOI: 10.3390/foods10051004 -
The American Journal of Clinical... Aug 2021Several individual studies have shown that circulating levels of odd-chain SFAs and very-long-chain SFAs (VLSFAs) may have beneficial effects, but the results are mixed....
The associations between individual plasma SFAs, serine palmitoyl-transferase long-chain base subunit 3 gene rs680379 polymorphism, and type 2 diabetes among Chinese adults.
BACKGROUND
Several individual studies have shown that circulating levels of odd-chain SFAs and very-long-chain SFAs (VLSFAs) may have beneficial effects, but the results are mixed. While the dietary and metabolic factors that may influence VLSFAs are not well-known, a previous study observed associations of VLSFA concentrations with variants in serine palmitoyl-transferase long-chain base subunit 3 (SPTLC3) gene.
OBJECTIVES
We investigated the associations of individual plasma SFAs and SPTLC3 gene rs680379 polymorphism with metabolic risk factors and type 2 diabetes (T2D).
METHODS
We measured plasma SFAs using gas chromatography among 898 T2D cases and 1618 matched controls, and genotyped the SPTLC3 gene rs680379 polymorphism using the MassArray System among 1178 T2D cases and 1907 matched controls. Conditional logistic regression was used to estimate ORs and 95% CIs.
RESULTS
We found that plasma odd-chain SFAs and VLSFAs were correlated with favorable blood lipids and insulin resistance marker profiles. After multivariable adjustment, pentadecanoic acid (15:0) was inversely associated with the odds of T2D (OR per 1 SD difference: 0.63; 95% CI: 0.57, 0.70), as were measurements of 3 individual VLSFAs [arachidic acid (20:0), behenic acid (22:0), and lignoceric acid (24:0)], with ORs ranging from 0.60 to 0.72 (95% CIs ranging between 0.52 and 0.79). The associations between 3 individual VLSFAs and T2D were attenuated after further adjustment for triglycerides. Meanwhile, compared with the rs680379 GG genotype carriers, the ORs of T2D for the GA and AA genotype carriers were 0.81 (95% CI: 0.68-0.97) and 0.76 (95% CI: 0.61-0.96), respectively.
CONCLUSIONS
Plasma 15:0 and VLSFAs were inversely associated with T2D. Meanwhile, compared with the rs680379 GG genotype carriers, subjects with GA and AA genotypes were associated with decreased odds of T2D. More investigations are warranted to confirm our findings.
Topics: Aged; Asian People; Blood Glucose; Case-Control Studies; China; Diabetes Mellitus, Type 2; Fatty Acids, Volatile; Female; Genotype; Glucose; Humans; Insulin Resistance; Male; Middle Aged; Polymorphism, Single Nucleotide; Risk Factors; Serine C-Palmitoyltransferase
PubMed: 33964854
DOI: 10.1093/ajcn/nqab102 -
AIDS (London, England) Aug 2021HIV infection and antiretroviral therapy (ART) have both been linked to dyslipidemia and increased cardiovascular disease (CVD). The relationships among the lipidome,...
OBJECTIVE
HIV infection and antiretroviral therapy (ART) have both been linked to dyslipidemia and increased cardiovascular disease (CVD). The relationships among the lipidome, immune activation, and subclinical vascular disease in children with perinatally acquired HIV (PHIV) have not been investigated.
METHODS
Serum lipid composition, including 13 lipid classes constituting 850 different lipid species were measured by direct infusion-tandem mass spectrometry in samples from 20 ART-treated PHIV and 20 age-matched and sex-matched HIV- Ugandan children. All participants were between 10 and 18 years of age with no other known active infections. PHIVs had HIV-1 RNA level 50 copies/ml or less. In addition, common carotid artery intima--media thickness (IMT), as well as plasma marker of systemic inflammation (hsCRP, IL6, sTNFRa I), monocyte activation (soluble CD14 and CD163), and T-cell activation (expression of CD38 and HLA-DR on CD4+ and CD8+) were evaluated.
RESULTS
Median age (Q1, Q3) of study participants was 13 years (11, 15), 37% were boys, 75% were on an NNRTI-based ART regimen. The concentrations of cholesterol ester, LCER, phosphatidylcholines, and sphingomyelin lipid classes were significantly increased in serum of PHIV compared with HIV (P≤0.04). Biomarkers associated with CVD risk including hsCRP, sCD163, and T-cell activation were directly correlated with lipid species in PHIV (P ≤ 0.04). Contents of free fatty acids including palmitic (16 : 0), stearic (18 : 0), and arachidic acid (20 : 0) were positively correlated with IMT in PHIV.
CONCLUSION
Serum lipidome is altered in young virally suppressed PHIV on ART. A direct association between inflammation and lipid species known to be associated with CVD was observed.
Topics: Adolescent; Child; HIV Infections; Humans; Inflammation; Lipidomics; Male; Uganda; Vascular Diseases
PubMed: 33878042
DOI: 10.1097/QAD.0000000000002923 -
Marine Drugs Mar 2021This study was designed to profile the metabolites of , an indigenous and less explored microalgae species. H Nuclear Magnetic Resonance (NMR) spectroscopy and Liquid...
This study was designed to profile the metabolites of , an indigenous and less explored microalgae species. H Nuclear Magnetic Resonance (NMR) spectroscopy and Liquid Chromatography-Mass Spectrometry (LCMS) were used to establish the metabolite profiles of five different extracts of this microalga, which are hexane (Hex), ethyl acetate (EtOAc), absolute ethanol (EtOH), EtOH:water 1:1 (AqE), and 100% water (Aq). Partial least square discriminant analysis (PLS-DA) of the generated profiles revealed that EtOAc and Aq extracts contain a diverse range of metabolites as compared to the other extracts with a total of twenty-one metabolites, comprising carotenoids, polyunsaturated fatty acids, and amino acids, that were putatively identified from the NMR spectra. Meanwhile, thirty-two metabolites were successfully annotated from the LCMS/MS data, ten of which (palmitic acid, oleic acid, α-linolenic acid, arachidic acid, cholesterol, DHA, DPA, fucoxanthin, astaxanthin, and pheophytin) were similar to those present in the NMR profile. Another eleven glycerophospholipids were discovered using MS/MS-based molecular network (MN) platform. The results of this study, besides providing a better understanding of 's chemical make-up, will be of importance in exploring this species potential as a feed ingredient in the aquaculture industry.
Topics: Amino Acids; Carotenoids; Chromatography, Liquid; Fatty Acids, Unsaturated; Haptophyta; Magnetic Resonance Spectroscopy; Mass Spectrometry; Metabolomics; Tandem Mass Spectrometry
PubMed: 33801258
DOI: 10.3390/md19030139 -
Anais Da Academia Brasileira de Ciencias 2021The immobilization of the enzyme tyrosinase (Tyr) in lipid matrices can be explored to produce biosensors for detecting polyphenols, which is relevant for the food...
The immobilization of the enzyme tyrosinase (Tyr) in lipid matrices can be explored to produce biosensors for detecting polyphenols, which is relevant for the food industry. Herein, we shall demonstrate the importance of the lipid composition to immobilize the enzyme tyrosinase in Langmuir-Blodgett (LB) films. Tyr could be incorporated into Langmuir monolayers of arachidic acid (AA), 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC) and 1,2-dipalmitoyl-sn-glycero-3-phospho-(1'-rac-glycerol) (sodium salt) (DPPG), having as the main effect an expansion in the monolayers. Results from polarization-modulated infrared reflection-absorption spectroscopy (PM-IRRAS) pointed to electrostatic interactions between the charged residues of Try and the lipid headgroups, in addition to changes in the order of lipid chains. The interaction between Tyr and DPPC in Langmuir monolayers can be correlated with the superior performance of DPPC/Tyr LB films used as biosensors to detect catechol by cyclic voltammetry. The molecular-level interactions assessed via PM-IRRAS are therefore believed to drive an immobilization process for Tyr in the lipid LB matrix and may serve as a general criterion to identify matrices that preserve enzyme activity.
Topics: Biosensing Techniques; Monophenol Monooxygenase; Phospholipids; Spectrophotometry, Infrared; Surface Properties
PubMed: 33787687
DOI: 10.1590/0001-3765202120200019