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Beilstein Journal of Organic Chemistry 2024Tandem Diels-Alder reactions are often used for the straightforward formation of complex natural compounds and the fused polycyclic systems contained in their...
Tandem Diels-Alder reactions are often used for the straightforward formation of complex natural compounds and the fused polycyclic systems contained in their precursors. In the second step of this reaction, regio- and stereochemically controlled intramolecular cyclization leads to the formation of versatile nitrogen-containing tricyclic systems. However, these useful organic transformations are usually carried out in highly toxic organic solvents such as benzene, toluene, chloroform, etc. Despite recent efforts by 'green chemists', synthetic chemists still use these traditional toxic organic solvents in many of their reactions, even though safer alternatives are available. However, in addition to the harmful effects of these petrochemical solvents on the environment, the prediction that their resources will run out in the near future has led 'green chemists' to explore solvents that can be derived from renewable resources and used effectively in various organic transformations. In this context, we have shown for the first time that the 100% atom-economical tandem Diels-Alder reaction between aminofuranes and maleic anhydride can be carried out successfully in vegetable oils and waxes. The reaction was successfully carried out in sunflower seed oil, olive oil, oleic acid and lauryl myristate under mild reaction conditions. A series of epoxyisoindole-7-carboxylic acid and bisepoxyisoindole-7-carboxylic acids were obtained in good yields after a practical isolation procedure. The results obtained in this study demonstrate the potential of vegetable oils and their renewable materials to provide a reaction medium that is more sustainable than conventional organic solvents in cascade Diels-Alder reactions and can be used repeatedly without significant degradation. These materials also allow the reaction to be completed in less time, with less energy consumption and higher yields.
PubMed: 38887569
DOI: 10.3762/bjoc.20.114 -
Metabolomics : Official Journal of the... Jun 2024The coral holobiont is underpinned by complex metabolic exchanges between different symbiotic partners, which are impacted by environmental stressors. The chemical...
The coral holobiont is underpinned by complex metabolic exchanges between different symbiotic partners, which are impacted by environmental stressors. The chemical diversity of the compounds produced by the holobiont is high and includes primary and secondary metabolites, as well as volatiles. However, metabolites and volatiles have only been characterised in isolation so far. Here, we applied a paired metabolomic-volatilomic approach to characterise holistically the chemical response of the holobiont under stress. Montipora mollis fragments were subjected to high-light stress (8-fold higher than the controls) for 30 min. Photosystem II (PSII) photochemical efficiency values were 7-fold higher in control versus treatment corals immediately following high-light exposure, but returned to pre-stress levels after 30 min of recovery. Under high-light stress, we identified an increase in carbohydrates (> 5-fold increase in arabinose and fructose) and saturated fatty acids (7-fold increase in myristic and oleic acid), together with a decrease in fatty acid derivatives in both metabolites and volatiles (e.g., 80% decrease in oleamide and nonanal), and other antioxidants (~ 85% decrease in sorbitol and galactitol). These changes suggest short-term light stress induces oxidative stress. Correlation analysis between volatiles and metabolites identified positive links between sorbitol, galactitol, six other metabolites and 11 volatiles, with four of these compounds previously identified as antioxidants. This suggests that these 19 compounds may be related and share similar functions. Taken together, our findings demonstrate how paired metabolomics-volatilomics may illuminate broader metabolic shifts occurring under stress and identify linkages between uncharacterised compounds to putatively determine their functions.
Topics: Animals; Anthozoa; Metabolomics; Light; Stress, Physiological; Volatile Organic Compounds; Photosystem II Protein Complex
PubMed: 38886248
DOI: 10.1007/s11306-024-02136-9 -
Cancer Research Jun 2024The genetic landscape of cancer cells can lead to specific metabolic dependencies for tumor growth. Dietary interventions represent an attractive strategy to restrict...
The genetic landscape of cancer cells can lead to specific metabolic dependencies for tumor growth. Dietary interventions represent an attractive strategy to restrict the availability of key nutrients to tumors. In this study, we identified that growth of a subset of melanoma was severely restricted by a rationally designed combination therapy of a stearoyl-CoA desaturase (SCD) inhibitor with an isocaloric low-oleic acid diet. Despite its importance in oncogenesis, SCD underwent monoallelic co-deletion along with PTEN on chromosome 10q in about 47.5% of melanoma, and the other SCD allele was methylated, resulting in very low SCD expression. While this SCD deficient subset was refractory to SCD inhibitors, the subset of PTEN wildtype melanoma that retained SCD was sensitive. As dietary oleic acid could potentially blunt the effect of SCD inhibitors, a low-oleic acid custom diet was combined with SCD inhibitor. The combination reduced monounsaturated fatty acids and increased saturated fatty acids, inducing robust apoptosis and growth suppression and inhibiting lung metastasis with minimal toxicity in preclinical mouse models of PTEN wildtype melanoma. When combined with anti-PD1 immunotherapy, the SCD inhibitor improved T cell functionality and further constrained melanoma growth in mice. Collectively, these results suggest that optimizing SCD inhibitors with diets low in oleic acid may offer a viable and efficacious therapeutic approach for improving melanoma treatment.
PubMed: 38885087
DOI: 10.1158/0008-5472.CAN-23-1635 -
Journal of Pharmacy & Bioallied Sciences Apr 2024The scientific validity of contemporary and alternative medicinal practices, such as Ayurveda and Siddha, holds significant importance in today's context.
BACKGROUND
The scientific validity of contemporary and alternative medicinal practices, such as Ayurveda and Siddha, holds significant importance in today's context.
AIM AND OBJECTIVE
The present study employs gas chromatography-mass spectrometry (GC-MS) analysis to investigate a pain-relieving Ayurvedic oil, Dhanwantharam Thailam, aiming to establish correlations between its medicinal activity and the biomolecules it contains.
MATERIALS AND METHODS
Procured sample from a reputable Ayurvedic vendor in Chennai, Dhanwantharam Thailam underwent GC-MS analysis using standard procedures.
RESULTS AND DISCUSSION
The resulting profile revealed the presence of crucial molecules like oleic acid, dodecanoic acid, 1,2,3-propanetriyl ester, ethenyl ester, and 9,12-octadecadienoyl chloride (Z, Z), aligning with the medicinal properties attributed to Dhanwantharam Thailam.
CONCLUSION
The identification of these biomolecules supports the role of Dhanwantharam Thailamas an effective pain-relieving oil.
PubMed: 38882853
DOI: 10.4103/jpbs.jpbs_14_24 -
Heliyon Jun 2024Erucic acid, more than 2 %, in mustard seed oil is considered unhealthy as edible oil, and also anti-nutritional for human consumption. The existing mustard varieties...
Erucic acid, more than 2 %, in mustard seed oil is considered unhealthy as edible oil, and also anti-nutritional for human consumption. The existing mustard varieties of Bangladesh contain 40-48 % erucic acid, which is a big concern for the country's nutritional, and food security and safety. Hence, to improve the seed oil quality of the existing variety, six popular cultivars of mustard were crossed with a canola-grade line in 7 × 7 half diallel fashion, and the developed 21 F hybrids were assessed for yield contributing traits, and fatty acids composition. Variables with significant variations were found, while days to siliquae maturity, plant height, days to first flowering, and seeds per siliquae have moderate narrow sense heritability. The estimated gene action indicated that dominant or over-dominant gene action was more prominent in governing the traits. The parents, P, P, and P were discovered the best general combiners for early maturity and short phenology, whereas P and P were found to be the best general combiners for yield-attributing traits. Moreover, the hybrids P × P, P × P P × P, P × P and P × P were chosen as the promising hybrids due to their best specific combining ability, and desired heterotic effects on yield contributing traits. In addition, a significant decrease, on average 30-40 %, in erucic acid, but an approximately 20-25 % increase of oleic acid was found among the hybrids, in which the hybrids P × P-S1, P × P-S2 and P × P-S4 demonstrated a better stability index. Overall, the obtained findings suggested that the hybrids, viz. P × P, P × P, P × P, P × P, P × P, P × P, and P × P were promising based on their early maturity, high-yielding, reduced erucic acid, and high oleic acid contents.
PubMed: 38882389
DOI: 10.1016/j.heliyon.2024.e31977 -
Cell Biochemistry and Function Jun 2024The prevalence of metabolic dysfunction-associated steatotic liver disease (MASLD) is increasing rapidly due to the obesity epidemic. In the inflammatory stages of MASLD...
The prevalence of metabolic dysfunction-associated steatotic liver disease (MASLD) is increasing rapidly due to the obesity epidemic. In the inflammatory stages of MASLD (MASH), activation of hepatic stellate cells (HSCs) leads to initiation and progression of liver fibrosis. Extracellular vesicles (EVs) are released from all cell types and play an important role in intercellular communication. However, the role of EVs released from hepatocytes in the context of MASLD is largely unknown. Therefore, the present study aimed to investigate the role of EVs derived from both normal and steatotic (free fatty acid-treated) hepatocytes on the phenotype of HSCs via the senescence pathway. Primary rat hepatocytes were treated with free fatty acids (FFAs: oleic acid and palmitic acid). EVs were collected by ultracentrifugation. EVs markers and HSCs activation and senescence markers were assessed by Western blot analysis, qPCR and cytochemistry. Reactive oxygen species (ROS) production was assessed by fluorescence assay. RNA profiles of EVs were evaluated by sequencing. We found that EVs from hepatocytes treated with FFAs (FFA-EVs) inhibit collagen type 1 and α-smooth muscle actin expression, increase the production of ROS and the expression of senescence markers (IL-6, IL-1β, p21 and senescence-associated β-galactosidase activity) in early activating HSCs via the AKT-mTOR pathway. Sequencing showed differentially enriched RNA species between the EVs groups. In conclusion, EVs from FFA-treated hepatocytes inhibit HSC activation by inducing senescence via the AKT-mTOR signaling pathway. Determining the components in EVs from steatotic hepatocytes that induce HSC senescence may lead to the identification of novel targets for intervention in the treatment of MASLD in the future.
Topics: Animals; Extracellular Vesicles; Hepatic Stellate Cells; Rats; Proto-Oncogene Proteins c-akt; Cellular Senescence; TOR Serine-Threonine Kinases; Hepatocytes; Signal Transduction; Male; Fatty Liver; Reactive Oxygen Species; Cells, Cultured; Rats, Sprague-Dawley
PubMed: 38881228
DOI: 10.1002/cbf.4077 -
Journal of Colloid and Interface Science Jun 2024Binary superparticles formed by self-assembling two different types of nanoparticles may utilize the synergistic interactions and create advanced multifunctional...
Binary superparticles formed by self-assembling two different types of nanoparticles may utilize the synergistic interactions and create advanced multifunctional materials. Bi-magnetic superparticles with a core-shell structure have unique properties due to their specific spatial configurations. Herein, we built MnO@Ni core-shell binary superparticles via an emulsion self-assembly technique. The superparticles are generated with a spherical morphology, and have a typical average size of about 240 nm. By altering the ratio of the two magnetic nanoparticles, the thickness of Ni shells can be adjusted. Oleic acid ligands are crucial for the formation of core-shell structure. Magnetic analysis suggests that core-shell superparticles display dual-phase magnetic interactions, contrasting with the single-phase magnetic behaviors of commonly core-shell magnetic nanoparticles. The calculation on the effective magnetic anisotropy constants indicates that the presence of Ni shell layers reduces the dipole interactions among the MnO core particles. Due to the presence of Ni nanoparticle shells, the blocking temperature of MnO is reduced, while the Curie temperature of MnO is independent on Ni content. Tunable magnetic properties can be achieved by modulating the Ni nanoparticle shell thickness. This study offers insights for the development of core-shell superparticles with varied magnetic characteristics.
PubMed: 38879993
DOI: 10.1016/j.jcis.2024.06.103 -
Nitric Oxide : Biology and Chemistry Jun 2024Obesity is commonly linked with adipose tissue (AT) dysfunction, setting off inflammation and oxidative stress, both key contributors to the cardiometabolic...
Obesity is commonly linked with adipose tissue (AT) dysfunction, setting off inflammation and oxidative stress, both key contributors to the cardiometabolic complications associated with obesity. To improve metabolic and cardiovascular health, countering these inflammatory and oxidative signaling processes is crucial. Offering potential in this context, the activation of nuclear factor erythroid 2-related factor 2 (Nrf2) by nitro-fatty acids (NO-FA) promote diverse anti-inflammatory signaling and counteract oxidative stress. Additionally, we previously highlighted that nitro-oleic acid (NO-OA) preferentially accumulates in white adipose tissue (AT) and provides protection against already established high fat diet (HFD)-mediated impaired glucose tolerance. The precise mechanism accounting for these protective effects remained largely unexplored until now. Herein, we reveal that protective effects of improved glucose tolerance by NO-OA is absent when Nrf2 is specifically ablated in adipocytes (ANKO mice). NO-OA treatment did not alter body weight between ANKO and littermate controls (Nrf2) mice on both the HFD and low-fat diet (LFD). As expected, at day 76 (before NO-OA treatment) and notably at day 125 (daily treatment of 15 mg/kg NO-OA for 48 days), both HFD-fed Nrf2 and ANKO mice exhibited increased fat mass and reduced lean mass compared to LFD controls. However, throughout the NO-OA treatment, no distinction was observed between Nrf2 and ANKO in the HFD-fed mice as well as in the Nrf2 mice fed a LFD. Glucose tolerance tests revealed impaired glucose tolerance in HFD-fed Nrf2 and ANKO compared to LFD-fed Nrf2 mice. Notably, NO-OA treatment improved glucose tolerance in HFD-fed Nrf2 but did not yield the same improvement in ANKO mice at days 15, 30, and 55 of treatment. Unraveling the pathways linked to NO-OA's protective effects in obesity-mediated impairment in glucose tolerance is pivotal within the realm of precision medicine, crucially propelling future applications and refining novel drug-based strategies.
PubMed: 38879114
DOI: 10.1016/j.niox.2024.06.002 -
Applied Biochemistry and Biotechnology Jun 2024This study explores the nutritional and phytochemical profiling of twenty-three genotypes of Vicia faba L. var. minor seeds cultivated in the experimental field of the...
This study explores the nutritional and phytochemical profiling of twenty-three genotypes of Vicia faba L. var. minor seeds cultivated in the experimental field of the Arid Lands Institute of Medenine. Our comprehensive analysis encompasses fatty acid composition, sugar content, phytochemical composition, and antioxidant potential, providing a nuanced understanding of the seeds' nutritive quality. The investigation revealed substantial variations among genotypes, showcasing the potential for targeted nutritional enhancement. Quantification of total polyphenols, flavonoids, condensed tannins, and radical scavenging activities revealed average values of 16.46 mg GAE/g DW, 6.27 mg CTE/g DW, 0.47 mg CE/g DW, and 0.146 mM TEAC, respectively. Notably, the seeds exhibited a low tannin content, a desirable trait for animal feed applications. Liquid chromatography-mass spectrometry (LC-MS) was employed for the identification of phenolic compounds, unearthing the prevalence of quinic acid and flavanols, including catechin (+) and epicatechin. Sugar analysis identified the presence of glucose and sucrose, emphasizing the seeds' unique carbohydrate composition. Gas chromatography elucidated the fatty acid profile, spotlighting prominent components such as palmitic acid (13.87%), stearic acid (3.37%), oleic acid (27.66%), linoleic acid (45.83%), and linolenic acid (3.53%). The findings underscore the seeds' nutritive significance, positioning them as rich sources of natural antioxidants, fatty acids, and phenolic compounds. Moreover, the extracts' favorable tannin content positions them as potential candidates for functional food applications, showcasing their promise as sources of bioactive molecules with diverse applications.
PubMed: 38878163
DOI: 10.1007/s12010-024-04993-5 -
Journal of Dairy Science Jun 2024Nutrition and physiological state affect hepatic metabolism. Our objective was to determine if feeding flaxseed oil (∼50% C18:3n-3 cis), high oleic soybean oil (∼70%...
Nutrition and physiological state affect hepatic metabolism. Our objective was to determine if feeding flaxseed oil (∼50% C18:3n-3 cis), high oleic soybean oil (∼70% C18:1 cis-9), or milk fat (∼50% C16:0) alters hepatic expression of PC, PCK1, and PCK2 and the flow of carbons from propionate and pyruvate into the TCA cycle in preruminating calves. Male Holstein calves (n = 40) were assigned to a diet of skim milk with either: 3% milk fat (MF; n = 8), 3% flaxseed oil (Flax; n = 8), 3% high oleic soybean oil (HOSO; n = 8), 1.5% MF + 1.5% high oleic soybean oil (MF-HOSO; n = 8), or 1.5% MF + 1.5% flaxseed oil (MF-Flax; n = 8) from d 14 to d 21 postnatal. At d 21 postnatal, a liver biopsy was taken for gene expression and metabolic flux analysis. Liver explants were incubated in [U-C] propionate and [U-C] pyruvate to trace carbon flux through TCA cycle intermediates or with [U-C] lactate, [1-C] palmitic acid, or [2-C] propionate to quantify substrate oxidation to CO and acid soluble products. Compared with other treatments, plasma C18:3n-3 cis was 10 times higher and C18:1 cis-9 was 3 times lower in both flax (Flax and MF-Flax) treatments. PC, PCK1, and PCK2 expression and flux of [U-C] pyruvate as well as [U-C] propionate were not different between treatments. PC expression was negatively correlated with the enrichment of citrate M+5 and malate M+3, and PCK2 was negatively correlated with citrate M+5, suggesting that when expression of these enzymes is increased, carbon from pyruvate enters the TCA cycle via PC mediated carboxylation, and then OAA is converted to phosphoenolpyruvate via PCK2. Acid soluble product formation and PC expression were reduced in HOSO (MF-HOSO and HOSO) treatments compared with flax (MF-Flax and Flax), indicating that fatty acids regulate PC expression and carbon flux, but that fatty acid flux control points are not connected to PC, PCK1, or PCK2. In conclusion, fatty acids regulate hepatic expression of PC, PCK1, and PCK2, and carbon flux, but the point of control is distinct.
PubMed: 38876219
DOI: 10.3168/jds.2023-24500