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Journal of Chromatography. A Oct 2022The application of proton transfer ionization reaction mass spectrometry (PTR MS) combined with microscale supercritical fluid extraction (SFE) and supercritical fluid...
Microscale supercritical fluid extraction combined with supercritical fluid chromatography and proton-transfer-reaction ionization time-of-flight mass spectrometry for a magnitude lower limit of quantitation of lipophilic compounds.
The application of proton transfer ionization reaction mass spectrometry (PTR MS) combined with microscale supercritical fluid extraction (SFE) and supercritical fluid chromatography (SFC) aiming to quantitate single-cell fatty acid analysis levels was investigated. Using a microscale extraction vessel, the obtained low limits of quantitation (LLOQs) of arachidonic acid and arachidic acid were 1.2 and 2.7 fmol, respectively, by using less than 1 µL of sample on stainless steel frit. A series of phthalate, vitamin K, and α-tocopherol were also tested, and the LLOQ was less than one femtomole for phthalate and 35 and 13 fmol for vitamin K and α-tocopherol, respectively. A microliter portion of SFE extracts was introduced into the SFC column by split injection, improving the reproducibility of the chromatography and separation efficiency. The method in the present study has great potential to quantitate lipophilic molecules on the nanogram scale of a sample without complex preparation procedures.
Topics: Arachidonic Acid; Chromatography, Supercritical Fluid; Mass Spectrometry; Phthalic Acids; Plant Extracts; Protons; Reproducibility of Results; Stainless Steel; Vitamin K; alpha-Tocopherol
PubMed: 36126560
DOI: 10.1016/j.chroma.2022.463495 -
Environmental Research Dec 2022Organophosphate (OP) insecticides, including chlorpyrifos, have been linked with numerous harmful health effects on maternal and child health. Limited data are available...
INTRODUCTION
Organophosphate (OP) insecticides, including chlorpyrifos, have been linked with numerous harmful health effects on maternal and child health. Limited data are available on the biological mechanisms and endogenous pathways underlying the toxicity of chlorpyrifos exposures on pregnancy and birth outcomes. In this study, we measured a urinary chlorpyrifos metabolite and used high-resolution metabolomics (HRM) to identify biological perturbations associated with chlorpyrifos exposure among pregnant women in Thailand, who are disparately exposed to high levels of OP insecticides.
METHODS
This study included 50 participants from the Study of Asian Women and their Offspring's Development and Environmental Exposures (SAWASDEE). We used liquid chromatography-high resolution mass spectrometry to conduct metabolic profiling on first trimester serum samples collected from participants to evaluate metabolic perturbations in relation to chlorpyrifos exposures. We measured 3,5,6-trichloro-2-pyridinol (TCPy), a specific metabolite of chlorpyrifos and chlorpyrifos-methyl, in first trimester urine samples to assess the levels of exposures. Following an untargeted metabolome-wide association study workflow, we used generalized linear models, pathway enrichment analyses, and chemical annotation to identify significant metabolites and pathways associated with urinary TCPy levels.
RESULTS
In the 50 SAWASDEE participants, the median urinary TCPy level was 4.36 μg TCPy/g creatinine. In total, 691 unique metabolic features were found significantly associated with TCPy levels (p < 0.05) after controlling for confounding factors. Pathway analysis of metabolic features associated with TCPy indicated perturbations in 24 metabolic pathways, most closely linked to the production of reactive oxygen species and cellular damage. These pathways include tryptophan metabolism, fatty acid oxidation and peroxisome metabolism, cytochromes P450 metabolism, glutathione metabolism, and vitamin B3 metabolism. We confirmed the chemical identities of 25 metabolites associated with TCPy levels, including glutathione, cystine, arachidic acid, itaconate, and nicotinamide adenine dinucleotide.
DISCUSSION
The metabolic perturbations associated with TCPy levels were related to oxidative stress, cellular damage and repair, and systemic inflammation, which could ultimately contribute to health outcomes, including neurodevelopmental deficits in the child. These findings support the future development of sensitive biomarkers to investigate the metabolic underpinnings related to pesticide exposure during pregnancy and to understand its link to adverse outcomes in children.
Topics: Biomarkers; Child; Chlorpyrifos; Creatinine; Cystine; Cytochromes; Farmers; Fatty Acids; Female; Glutathione; Humans; Insecticides; Metabolome; NAD; Niacinamide; Organophosphorus Compounds; Pesticides; Pregnancy; Pregnancy Trimester, First; Reactive Oxygen Species; Thailand; Tryptophan
PubMed: 36108722
DOI: 10.1016/j.envres.2022.114319 -
Frontiers in Nutrition 2022Evidence regarding associations of circulating saturated fatty acids (SFAs) with chronic diseases is mixed. The objective of this study was to determine the associations...
BACKGROUND AND AIMS
Evidence regarding associations of circulating saturated fatty acids (SFAs) with chronic diseases is mixed. The objective of this study was to determine the associations between total or individual SFA biomarkers and the risk of cardiometabolic diseases.
METHODS
Four electronic databases were searched from inception to March 2022. Three investigators independently assessed for inclusion and extracted data. Random-effects or fixed-effects models was used to estimate the pooled relative risks (RRs) and corresponding 95% confidence intervals (CIs) for the association of total or individual SFA biomarkers, including even-chain SFAs (e.g., 14:0, myristic acid; 16:0, palmitic acid; 18:0, stearic acid), odd-chain SFAs (e.g., 15:0, pentadecanoic acid; 17:0, margaric acid) and very-long-chain SFAs (VLCSFAs; e.g., 20:0, arachidic acid; 22:0, behenic acid; 24:0, lignoceric acid), with risk of incident type 2 diabetes (T2D), cardiovascular disease [CVD; coronary heart disease (CHD) inclusive of stroke], CHD and stroke.
RESULTS
A total of 49 prospective studies reported in 45 articles were included. Higher concentration of circulating total SFAs was associated with an increasing risk of cardiometabolic diseases, the risk increased significantly by 50% for CVD (95%CI:1.31-1.71), 63% for CHD (95%CI:1.38-1.94), 38% for stroke (95%CI:1.05-1.82), respectively. Similarly, levels of even-chain SFAs were positively associated with higher risk of chronic diseases, with RRs ranging from 1.15 to 1.43. In contrast, the risk of cardiometabolic diseases was reduced with increasing odd-chain SFA levels, with RRs ranging from 0.62 to 0.91. A higher level of VLCSFAs corresponded to 19% reduction in CVD. Further dose-response analysis indicated that each 50% increment in percentage of total SFAs in circulating was associated with an 8% higher risk of T2D (RR: 1.08, 95%CI: 1.02-1.14) and trends toward higher risk of CVD (RR: 1.15, 95%CI: 0.98-1.34). Inverse linear relationships were observed between 17:0 biomarker and T2D or CVD risk.
CONCLUSION
Our findings support the current recommendations of reducing intake of saturated fat as part of healthy dietary patterns. Further studies are needed to confirm our findings on these SFAs in relation to cardiometabolic outcomes and to elucidate underlying mechanisms.
SYSTEMATIC REVIEW REGISTRATION
[https://www.crd.york.ac.uk/prospero/display_record.php?ID=CRD42022329182], identifier [CRD42022329182].
PubMed: 36046138
DOI: 10.3389/fnut.2022.963471 -
Molecular Biology Reports Oct 2022Genetic improvement of soybean oil content depends on in-depth study of the glycerolipid biosynthesis pathway. The first acylation reaction catalysed by...
BACKGROUND
Genetic improvement of soybean oil content depends on in-depth study of the glycerolipid biosynthesis pathway. The first acylation reaction catalysed by glycerol-3-phosphate acyltransferase (GPAT) is the rate-limiting step of triacylglycerol biosynthesis. However, the genes encoding GPATs in soybean remain unknown.
METHODS
We used a novel yeast genetic complementation system and seed-specific heterologous expression to identify GmGPAT activity and molecular function in glycerolipid biosynthesis.
RESULTS
Sixteen GmGPAT genes were cloned by reverse transcription-PCR for screening in yeast genetic complementation. The results showed that GmGPAT9-2 could restore the conditional lethal double knockout mutant strain ZAFU1, and GmGPAT1-1 exhibited low acyltransferase activity in serial dilution assays. In addition, the spatiotemporal expression pattern of GmGPAT9-2 exhibited tissue specificity in leaves, flowers and seeds at different developmental stages. Furthermore, both the proportion of arachidic acid and erucic acid were significantly elevated in Arabidopsis thaliana transgenic lines containing the seed-specific GmGPAT9-2 compared wild type, but the oil content was not affected.
CONCLUSION
Together, our results provide reference data for future engineering of triacylglycerol biosynthesis and fatty acid composition improvement through GPATs in soybean.
Topics: Acyltransferases; Arabidopsis; Fatty Acids; Glycerol; Phosphates; Plant Oils; Plants, Genetically Modified; Saccharomyces cerevisiae; Seeds; Soybean Oil; Glycine max; Triglycerides
PubMed: 36002658
DOI: 10.1007/s11033-022-07852-w -
Frontiers in Nutrition 2022Previous studies have analyzed the associations between the circulating saturated fatty acids (SFAs) and gestational diabetes mellitus (GDM), but no consistent...
BACKGROUND
Previous studies have analyzed the associations between the circulating saturated fatty acids (SFAs) and gestational diabetes mellitus (GDM), but no consistent conclusions have been reached. The aim of this study was to evaluate whether plasma SFAs were in correlation with GDM risks in our in-house women cross-sectional study and to better define their associations on the clinical evidence available to date by a dose-response meta-analysis.
METHODS
We carried out a cross-sectional study of 807 pregnant women in 2018-2019 (Shanghai, China). GDM was defined according to the criteria of the International Association of Diabetes and Pregnancy Study Groups (IADPSG). Gas chromatography was used to determine the plasma fatty acids (FAs) in the 24-28 gestational weeks. The SFAs levels of non-GDM and GDM participants were compared by Mann-Whitney test, and the association between SFAs and GDM was explored by multivariate logistic models. Further, the potential diagnostic value of plasma SFAs was evaluated using the method of receiver operating characteristic (ROC) analysis. For meta-analysis, five databases were systematically searched from inception to March 2022, and we included 25 relevant studies for calculating pooled standard mean differences (SMDs) and 95% CI to describe the differences in SFAs profiles between non-GDM and GDM women. Study-specific, multivariable-adjusted ORs and 95% CI were also pooled using a fixed-effect model or random-effects model according to the heterogeneity to evaluate the associations between circulating SFAs and GDM prevalence.
RESULTS
In our cross-sectional study, we found plasma proportion of palmitic acid (C16:0) was positively associated (aOR: 1.10 per 1% increase; 95% CI: 1.04, 1.17), while plasma stearic acid (C18:0) (aOR: 0.76 per 1% increase; 95% CI: 0.66, 0.89), arachidic acid (C20:0) (aOR: 0.92 per 0.1% increase; 95% CI: 0.87, 0.97), behenic acid (C22:0) (aOR: 0.94 per 0.1% increase; 95% CI: 0.92, 0.97), and lignoceric acid (C24:0) (aOR: 0.94 per 0.1% increase; 95% CI: 0.92, 0.97) were inversely associated with GDM. The area under the receiver operative characteristic curve increased from 0.7503 (the basic diagnostic model) to 0.8178 ( = 0.002) after adding total very-long-chain SFAs (VLcSFAs). A meta-analysis from 25 studies showed the circulating levels of three individual SFAs of GDM women were different from those of normal pregnant women. The summarized ORs for GDM was 1.593 (95% CI: 1.125, 2.255, = 0.009), 0.652 (95% CI: 0.472, 0.901, = 0.010) and 0.613 (95% CI: 0.449, 0.838, = 0.002), respectively, comparing the highest vs. lowest quantile of the concentrations of C16:0, C22:0, and C24:0.
CONCLUSION
Our results, combined with the findings from meta-analysis, showed that women with GDM had a particular circulating SFA profile, characterized by higher levels of palmitic acid, and lower levels of VLcSFAs. Alterations in the chain lengths of blood SFA profile were shown to be associated with the occurrence of GDM.
PubMed: 35978962
DOI: 10.3389/fnut.2022.903689 -
Molecules (Basel, Switzerland) Jul 2022Speciality malts and their extracts have physicochemical characteristics such as colour, flavour, and aroma sorted for in food production. Speciality malts used in food...
Speciality malts and their extracts have physicochemical characteristics such as colour, flavour, and aroma sorted for in food production. Speciality malts used in food production are mostly produced from cereal grains. Hence, this study aimed to produce speciality malts from Bambara groundnut (BGN) seeds and analyse their physicochemical characteristics and metabolites. The base, toasted, caramel, and roasted malt were produced by drying at different temperatures and times. Syrups were produced isothermally from the speciality malts. The speciality malts and syrups were assessed for colour, pH, protein, α and β-amylases, total polyphenols, antioxidants, and metabolite profiling. The BGN speciality malts were assayed for fatty acid methyl esters (FAME), hydrocarbons, sugar alcohols, sugars, acids, amino acids, and volatile components using capillary gas chromatography-mass spectrometry (GC-MS) and gas chromatography with flame ionisation detection (GC-FID). The colours of the speciality malts and syrups were significantly ( = 0.000) different. The protein content of the BGN speciality malts was significantly different ( = 0.000), while the protein content of the syrups was not significantly different. The amylase activities of the BGN speciality malt decreased with the change in kilning temperatures and time. The α- and β-amylase activities for the specialty malts were 1.01, 0.21, 0.29, 0.15 CU/g and 0.11, 0.10, 0.10, 0.06 BU/g. The total polyphenols and antioxidant activities differed for all BGN speciality malts. There were twenty-nine volatiles detected in the BGN speciality malts. Fifteen amino acids consisted of seven essential amino acids, and eight non-essential amino acids were detected in the speciality malts. Fatty acid methyl esters (FAME) identified were palmitoleic, oleic, linolelaidic, linoleic, and arachidic acid. The sugars, organic acids, and sugar alcohols consisted of lactic acid, fructose, sucrose, and myo-inositol. The BGN speciality malts exhibited good physicochemical characteristics and metabolites that can make them useful as household and industrial ingredients for food production, which could be beneficial to consumers.
Topics: Amino Acids; Antioxidants; Edible Grain; Fatty Acids; Gas Chromatography-Mass Spectrometry; Plant Extracts; Polyphenols; Sugar Alcohols; Sugars; Vigna
PubMed: 35889203
DOI: 10.3390/molecules27144332 -
Frontiers in Endocrinology 2022The pathogenesis of the progressive loss of beta cell function latent autoimmune diabetes in adults (LADA) remains still elusive. We aim to study the fatty acid (FA)...
BACKGROUND
The pathogenesis of the progressive loss of beta cell function latent autoimmune diabetes in adults (LADA) remains still elusive. We aim to study the fatty acid (FA) profile in LADA.
SUBJECTS AND METHODS
Data from 116 patients with diabetes and GADA and 249 diabetes controls without GADA selected by Propensity Score Matching were collected. FA was analyzed with liquid chromatography-tandem mass spectrometry analysis.
RESULTS
Principal factor analysis found component 1 explains 82.6% of total variance contained fatty acids from a mixed of lard oil, seafood, and vegetable diet, followed by diet predominantly from vegetable oil, a diet of high fat diet, and a diet of seafood diet. The FA heatmap looked clearly different among the three groups with more similar type 1 (t1dm) and LADA fatty acid profile. n-3 α-linolenic acid (ALA), n-3 long chain polyunsaturated fatty acid (n-3 LC-PUFA), such as Eicosapentaenoic Acid and Docosapentaenoic Acid, n-3/n-6 ratio and triene/tetraene ratio were higher in patients with type 2 diabetes (t2dm) compared with LADA and t1dm. Saturated FAs were lower in t2dm than t1dm and LADA. Arachidic acid and n-6 LC-PUFAs were lower in t2dm than in t1dm and LADA. The characteristics of FAs in LADA were in between of classical t1dm and t2dm. Patients were classified into 6 clusters by FA clusters. Only cluster 2, 3, 5 contained enough patients to be analyzed. Cluster 5 showed an insulin deficient phenotype containing more than 60% of patients with t1dm and LADA and only 12.8% of t2dm. Cluster 2 and 3 were similar. β cell function and glycemic control was better in cluster 3 homing 25% of t2dm. Cluster 2 held 28% of t1dm and LADA, in this cluster more than 60% of patients was t2dm. n-3 linolenic acid, n-3 LC-PUFAs, some n-6 LC-PUFAs, n-3/n-6 ratio and triene/tetraene ratio were negatively associated with GADA positivity while n-6 Arachidonic Acid was associated positively with GADA. Similar findings were found for insulin sensitivity and beta cell function.
CONCLUSION
PUFA are associated with insulin sensitivity and beta cell function, and like other clinical features, FA profile distributed differently, but could not be used as makers to differentiate LADA from t1dm and t2dm.
ETHICS AND DISSEMINATION
This study has been approved by the Ethical Review Committee of Second Hospital of Dalian Medical University (approval number: 2021-005).
CLINICAL TRIAL REGISTRATION
none.
Topics: Autoantibodies; Autoimmunity; Diabetes Mellitus, Type 1; Diabetes Mellitus, Type 2; Fatty Acids; Glucose Intolerance; Glutamate Decarboxylase; Humans; Insulin Resistance; Latent Autoimmune Diabetes in Adults
PubMed: 35846301
DOI: 10.3389/fendo.2022.916981 -
Molecules (Basel, Switzerland) Jun 2022In this study, we investigated and compared the oil yield, physicochemical properties, fatty acid composition, nutrient content, and antioxidant ability of Bunge ()...
In this study, we investigated and compared the oil yield, physicochemical properties, fatty acid composition, nutrient content, and antioxidant ability of Bunge () kernel oils obtained by cold-pressing (CP), hexane extraction (HE), aqueous enzymatic extraction (AEE), and supercritical fluid extraction (SFE). The results indicated that oil contained a high percentage of monounsaturated fatty acids (49.31-50.38%), especially oleic acid (30.73-30.98%) and nervonic acid (2.73-3.09%) and that the extraction methods had little effect on the composition and content of fatty acids. oil is an excellent source of nervonic acid. Additionally, the HE method resulted in the highest oil yield (98.04%), oxidation stability index (9.20 h), tocopherol content (530.15 mg/kg) and sterol content (2104.07 mg/kg). The DPPH scavenging activity rates of the oil produced by SFE was the highest. Considering the health and nutritional value of oils, HE is a promising method for oil processing. According to multiple linear regression analysis, the antioxidant capacity of the oil was negatively correlated with sterol and stearic acid content and positively correlated with linoleic acid, arachidic acid and polyunsaturated fatty acid content. This information is important for improving the nutritional value and industrial production of
Topics: Antioxidants; Fatty Acids; Plant Oils; Sapindaceae; Seeds; Sterols
PubMed: 35807441
DOI: 10.3390/molecules27134185 -
Medicine and Science in Sports and... Oct 2022Metabolomics identifies molecular products produced in response to numerous stimuli, including both adaptive (includes exercise training) and disease processes. We...
PURPOSE
Metabolomics identifies molecular products produced in response to numerous stimuli, including both adaptive (includes exercise training) and disease processes. We analyzed a longitudinal cohort of American-style football (ASF) athletes, who reliably acquire maladaptive cardiovascular (CV) phenotypes during competitive training, with high-resolution metabolomics to determine whether metabolomics can discriminate exercise-induced CV adaptations from early CV pathology.
METHODS
Matched discovery ( n = 42) and validation ( n = 40) multicenter cohorts of collegiate freshman ASF athletes were studied with longitudinal echocardiography, applanation tonometry, and high-resolution metabolomics. Liquid chromatography-mass spectrometry identified metabolites that changed ( P < 0.05, false discovery rate <0.2) over the season. Metabolites demonstrating similar changes in both cohorts were further analyzed in linear and mixed-effects models to identify those associated with left ventricular mass, tissue-Doppler myocardial E ' velocity (diastolic function), and arterial function (pulse wave velocity).
RESULTS
In both cohorts, 20 common metabolites changed similarly across the season. Metabolites reflective of favorable CV health included an increase in arginine and decreases in hypoxanthine and saturated fatty acids (heptadecanoate, arachidic acid, stearate, and hydroxydecanoate). In contrast, metabolic perturbations of increased lysine and pipecolate, reflective of adverse CV health, were also observed. Adjusting for player position, race, height, and changes in systolic blood pressure, weight, and pulse wave velocity, increased lysine ( β = 0.018, P = 0.02) and pipecolate ( β = 0.018, P = 0.02) were associated with increased left ventricular mass index. In addition, increased lysine ( β = -0.049, P = 0.01) and pipecolate ( β = -0.052, P = 0.008) were also associated with lower E ' (reduced diastolic function).
CONCLUSIONS
ASF athletes seem to develop metabolomic changes reflective of both favorable CV health and early CV maladaptive phenotypes. Whether metabolomics can discriminate early pathologic CV transformations among athletes is a warranted future research direction.
Topics: Arginine; Athletes; Eicosanoic Acids; Football; Humans; Hypoxanthines; Lysine; Pulse Wave Analysis; Stearates; Ventricular Function, Left
PubMed: 35617604
DOI: 10.1249/MSS.0000000000002960 -
General Psychiatry 2022Disrupted white matter (WM) microstructure has been commonly identified in youth at clinical high risk (CHR) for psychosis. Several lines of evidence suggest that fatty...
BACKGROUND
Disrupted white matter (WM) microstructure has been commonly identified in youth at clinical high risk (CHR) for psychosis. Several lines of evidence suggest that fatty acids, especially unsaturated fatty acids (UFAs), might play a crucial role in the WM pathology of early onset psychosis. However, evidence linking UFA and WM microstructure in CHR is quite sparse.
AIMS
We investigated the relationship between the plasma UFA level and WM microstructure in CHR participants and healthy controls (HC).
METHODS
Plasma fatty acids were assessed and diffusion tensor imaging (DTI) data were performed with tract-based spatial statistics (TBSS) analysis for 66 individuals at CHR for psychosis and 70 HC.
RESULTS
Both the global and regional diffusion measures showed significant between-group differences, with decreased fractional anisotropy (FA) but increased mean diffusivity (MD) and radial diffusivity (RD) found in the CHR group compared with the HC group. On top of that, we found that in the HC group, plasma arachidic acid showed obvious trend-level associations with higher global FA, lower global MD and lower global RD, which regionally spread over the corpus callosum, right anterior and superior corona radiata, bilateral anterior and posterior limb of the internal capsule, and bilateral superior longitudinal fasciculus. However, there were no associations between global WM measures and any UFA in the CHR group. Conversely, we even found negative associations between arachidic acid levels and regional FA values in the right superior longitudinal fasciculus and right retrolenticular part of the internal capsule in the CHR group.
CONCLUSIONS
Compared with the HC group, CHR subjects exhibited a different pattern of association between WM microstructure and plasma UFA, with a neuroprotective effect found in the HC group but not in the CHR group. Such discrepancy could be due to the excessively upregulated UFAs accumulated in the plasma of the CHR group, highlighting the role of balanced plasma-membrane fatty acids homeostasis in WM development.
PubMed: 35531577
DOI: 10.1136/gpsych-2021-100703