Jenkinswren0203

Health benefits have been associated with the consumption of omega-3 polyunsaturated fatty acids (PUFA). Linseed oil is rich in long chain omega-3 PUFA, but can generate toxic compounds due to its high susceptibility to oxidation. The nature of the emulsifier can affect both lipolysis and oxidation during digestion since these phenomena occur at the oil-water interface. The objective of this study was to compare the effect of low-molecular weight surfactants (cetyltrimethylammonium bromide (CTAB), Citrem), protein (sodium caseinate, fish gelatin) and polysaccharides (gum arabic, modified starch) on the structure of linseed oil emulsions, lipolysis and formation of reactive oxidation species during in vitro digestion. The emulsion stabilized with Citrem underwent extensive coalescence in the gastric phase, which strongly decreased the extent of lipid digestion and reduced the formation of oxidation markers relative to other emulsions. GSK-3 activity Emulsions stabilized by proteins and modified starch showed aggregation with partial coalescence in the gastric phase, but protein-stabilized emulsions showed better resistance to oxidation. This study shows that emulsifier properties affect the susceptibility of the emulsion to aggregation and coalescence in the gastrointestinal environment, and strongly influence the extent of lipid digestion and the formation of reactive oxidation products. These findings point out the importance of the choice of the emulsifier to control the lipid digestibility and the protection of sensible lipids thus promoting optimal nutritional properties in omega-3-enriched foods.Trodusquemine is an aminosterol known to prevent the binding of misfolded protein oligomers to cell membranes and to reduce their toxicity in a wide range of neurodegenerative diseases. Its precise mechanism of action, however, remains unclear. To investigate this mechanism, we performed confocal microscopy, fluorescence resonance energy transfer (FRET) and nuclear magnetic resonance (NMR) measurements, which revealed a strong binding of trodusquemine to large unilamellar vesicles (LUVs) and neuroblastoma cell membranes. Then, by combining quartz crystal microbalance (QCM), fluorescence quenching and anisotropy, and molecular dynamics (MD) simulations, we found that trodusquemine localises within, and penetrates, the polar region of lipid bilayer. This binding behaviour causes a decrease of the negative charge of the bilayer, as observed through ζ potential measurements, an increment in the mechanical resistance of the bilayer, as revealed by measurements of the breakthrough force applied with AFM and ζ potential measurements at high temperature, and a rearrangement of the spatial distances between ganglioside and cholesterol molecules in the LUVs, as determined by FRET measurements. These physicochemical changes are all known to impair the interaction of misfolded oligomers with cell membranes, protecting them from their toxicity. Taken together, our results illustrate how the incorporation in cell membranes of sterol molecules modified by the addition of polyamine tails leads to the modulation of physicochemical properties of the cell membranes themselves, making them more resistant to protein aggregates associated with neurodegeneration. More generally, they suggest that therapeutic strategies can be developed to reinforce cell membranes against protein misfolded assemblies.DNAzymes were previously identified by in vitro selection for a variety of chemical reactions, including several biologically relevant peptide modifications. However, finding DNAzymes for peptide lysine acylation is a substantial challenge. By using suitably reactive aryl ester acyl donors as the electrophiles, here we used in vitro selection to identify DNAzymes that acylate amines, including lysine side chains of DNA-anchored peptides. Some of the DNAzymes can transfer a small glutaryl group to an amino group. These results expand the scope of DNAzyme catalysis and suggest the future broader applicability of DNAzymes for sequence-selective lysine acylation of peptide and protein substrates.To investigate the effects of chirality on the phase behavior of ionic plastic crystals and ionic liquids, salts of a chiral sandwich complex with various anions were synthesized. The synthesized salts have the general chemical formula [Ru(C5H5)(C6H5CHCH3OCH3)]X (X = CB11H12, CF3BF3, PF6, CPFSA (= [double bond, length as m-dash]CF2(SO2CF2)2N)), where the ruthenium complex possesses a chiral substituent. The racemates of the salts with the CB11H12, CF3BF3, and PF6 anions crystallized as a solid solution, racemic compound, and conglomerate, respectively. The (S)-enantiomer and the racemate of the CB11H12 salt exhibited phase transitions to the ionic plastic phase and melted at high temperatures. Further, this salt exhibited polymorphism, as crystallographically investigated. Most of the other salts were ionic liquids exhibiting no plastic phase. The CPFSA salt was liquid and exhibited glass transition at low temperatures.Ultrafast intersystem crossing (ISC) in transition metal complexes leads to a long-lived active state with a high yield, which leads to efficient light energy conversion. The detailed mechanism of ISC may lead to a rational molecular design of superior transition metal complexes. Coherent nuclear wave packets observed in femtosecond time-resolved spectroscopies provide important information on the excited-state dynamics. In particular, analyzing the nuclear wave packets in both the reactant and the product may unveil the molecular dynamics of an ultrafast reaction. In this study, experimental evidence proving the reaction coordinates of the ultrafast ISC of ruthenium(ii) complexes is presented using coherent vibrational spectroscopy with a quantum chemical simulation of coherent vibrational motion. We observed vibrational modes strongly coupled to the ISC, whose vibrational coherences undergo remarkable attenuation after the ISC. The coupled modes contain metal-ligand stretching or symmetry breaking components, and the faster ISC rates of lower-symmetry ruthenium(ii) complexes support the significance of the latter.