The Electrostatic Basis of Diacylglycerol Pyrophosphate—Protein Interaction

Diacylglycerol pyrophosphate (DGPP) is an anionic phospholipid formed in plants, yeast, and parasites under multiple stress stimuli. It is synthesized by the phosphorylation action of phosphatidic acid (PA) kinase on phosphatidic acid, a signaling lipid with multifunctional properties. PA functions in the membrane through the interaction of its negatively charged phosphomonoester headgroup with positively charged proteins and ions. DGPP, like PA, can interact electrostatically via the electrostatic-hydrogen bond switch mechanism but differs from PA in its overall charge and shape. The formation of DGPP from PA alters the physicochemical properties as well as the structural dynamics of the membrane. This potentially impacts the molecular and ionic binding of cationic proteins and ions with the DGPP enriched membrane. However, the results of these important interactions in the stress response and in DGPP’s overall intracellular function is unknown. Here, using 31P MAS NMR, we analyze the effect of the interaction of low DGPP concentrations in model membranes with the peptides KALP23 and WALP23, which are flanked by positively charged Lysine and neutral Tryptophan residues, respectively. Our results show a significant effect of KALP23 on the charge of DGPP as compared to WALP23. There was, however, no significant effect on the charge of the phosphomonoester of DGPP due to the interaction with positively charged lipids, dioleoyl trimethylammonium propane (DOTAP) and dioleoyl ethyl-phosphatidylcholine (EtPC). Divalent calcium and magnesium cations induce deprotonation of the DGPP headgroup but showed no noticeable differences on DGPP’s charge. Our results lead to a novel model for DGPP—protein interaction.

A Potassium Based Fluorine Containing Bioactive Glass for Use as a Desensitizing Toothpaste

Potassium releasing bioactive glasses (BAGs) may offer improved relief for dentine hypersensitivity compared to conventional sodium containing BAGs by releasing K+ ions for nerve desensitization and occluding dentinal tubules to prevent fluid flow within dentinal tubules. Potassium oxide was substituted for sodium oxide on a molar basis in a fluoride containing BAG used in toothpastes for treating dentine hypersensitivity. The BAG powders were then immersed in an artificial saliva at pH 7 and tris buffer and the pH rise and ion release behavior were characterized by ICP-OES and ISE. The potassium and sodium containing BAGs were characterized by XRD, DSC, FTIR and NMR. Both BAGs presented amorphous diffraction patterns and the glass transition temperature of the potassium glass was higher than that of the sodium glass. The 31P MAS-NMR spectra indicated a peak at 2.7 ppm corresponding to apatite and a small peak at −103 ppm indicated crystallization to fluorapatite. Both BAGs dissolved and formed apatite at similar rates, although the dissolution of the potassium glass was slightly slower and it released less fluoride as a result of partial nanocrystallization to fluorapatite upon quenching. The potassium release from the potassium ions could potentially result in nerve deactivation when used in toothpastes.

Support Effect on the Performance of Ni2P Catalysts in the Hydrodeoxygenation of Methyl Palmitate

The effect of support nature, SiO2 and γ-Al2O3, on physicochemical and catalytic properties of nickel phosphide catalysts in methyl palmitate hydrodeoxygenation (HDO) has been considered. Firstly, alumina-supported nickel phosphide catalysts prepared by temperature-programmed reduction method starting from different precursors (phosphate–Ni(NO3)2 and (NH4)2HPO4 or phosphite–Ni(OH)2 and H3PO3) were compared using elemental analysis, N2 physisorption, H2-TPR, XRD, TEM, NH3-TPD, 27Al and 31P MAS NMR techniques and catalytic experiments. The mixture of nickel phosphide phases was produced from phosphate precursor on alumina while using of phosphite precursor provides Ni2P formation with the higher activity in methyl palmitate HDO. Besides, the comparative study of the performances of Ni2P/SiO2 and Ni2P/Al2O3 catalysts demonstrates the apparent superiority of alumina-supported Ni2P in the methyl palmitate hydrodeoxygenation. Considering the tentative scheme of methyl palmitate transformation, we proposed that cooperation of Ni2P and acid sites on the surface of alumina provides the enhanced activity of alumina-supported Ni2P through the acceleration of acid-catalysed hydrolysis.