1.Carbonate phosphonium salts as catalysts for the transesterification of dialkyl carbonates with diols. The competition between cyclic carbonates and linear dicarbonate products.
Selva M1, Caretto A, Noè M, Perosa A. Org Biomol Chem. 2014 Jun 28;12(24):4143-55. doi: 10.1039/c4ob00655k.
At 90-120 °C, in the presence of methylcarbonate and bicarbonate methyltrioctylphosphonium salts as catalysts ([P8881][A]; [A] = MeOCO2 and HOCO2), the transesterification of non-toxic dimethyl- and diethyl-carbonate (DMC and DEC, respectively) with 1,X-diols (2 ≤ X ≤ 6) proceeds towards the formation of cyclic and linear products. In particular, 1,2-propanediol and ethylene glycol afford propylene- and ethylene-carbonate with selectivity and yields up to 95 and 90%, respectively; while, the reaction of DMC with higher diols such 1,3-butanediol, 2-methyl-1,3-propanediol, 1,3-propanediol, 2,2-dimethyl, 1,3-propanediol, 1,4-butanediol and 1,6-hexanediol produce linear C8-C10 dicarbonates of general formula MeOC(O)O∼∼∼OC(O)OMe as the almost exclusive products. Of note, these dicarbonate derivatives are not otherwise accessible in good yields by other conventional base catalyzed methods. Among 1,3-diols, the only exception was 2-methyl 2,4-pentandiol that yields the corresponding cyclic carbonate, i.
2.A study of the methylene/perfluormethylene selectivity of porous polymer monolithic stationary phases exhibiting different fluorous/hydrophobic content.
Xu Z1, Oleschuk RD2. J Chromatogr A. 2014 Feb 14;1329:61-70. doi: 10.1016/j.chroma.2013.12.032. Epub 2014 Jan 8.
Porous polymer monolithic columns are prepared from a variety of monomers and cross-linkers and can be customized to exhibit different selectivities for separate analyte classes. The composition of the monolith can be precisely controlled by selecting different monomers and or cross-linker ratios. In this work monoliths exhibiting both fluorous and hydrophobic character were prepared using butyl methacrylate and its fluorous analogue (monomer) and 1,3-butanediol diacrylate and its fluorous analogue (cross-linker) in different ratios. The selectivity of the monoliths was probed using capillary electrochromatography with several fluorous and alkyl benzene analytes. Hydrophobic stationary phases exhibited greater methylene selectivity ( [Formula: see text] ) while those with increasing fluorous character show enhanced pefluoromethylene selectivity ( [Formula: see text] ). The Gibbs free energy change associated with the sorption of the analytes on each stationary phase composition can be calculated from migration times (i.
3.The metabolism of (R)-3-hydroxybutyrate is regulated by the enhancer-binding protein PA2005 and the alternative sigma factor RpoN in Pseudomonas aeruginosa PAO1.
Lundgren BR1, Harris JR1, Sarwar Z1, Scheel RA1, Nomura CT2. Microbiology. 2015 Nov;161(11):2232-42. doi: 10.1099/mic.0.000163. Epub 2015 Aug 25.
A variety of soil-dwelling bacteria produce polyhydroxybutyrate (PHB), which serves as a source of energy and carbon under nutrient deprivation. Bacteria belonging to the genus Pseudomonas do not generally produce PHB but are capable of using the PHB degradation product (R)-3-hydroxybutyrate [(R)-3-HB] as a growth substrate. Essential to this utilization is the NAD+-dependent dehydrogenase BdhA that converts (R)-3-HB into acetoacetate, a molecule that readily enters central metabolism. Apart from the numerous studies that had focused on the biochemical characterization of BdhA, there was nothing known about the assimilation of (R)-3-HB in Pseudomonas, including the genetic regulation of bdhA expression. This study aimed to define the regulatory factors that govern or dictate the expression of the bdhA gene and (R)-3-HB assimilation in Pseudomonas aeruginosa PAO1. Importantly, expression of the bdhA gene was found to be specifically induced by (R)-3-HB in a manner dependent on the alternative sigma factor RpoN and the enhancer-binding protein PA2005.
4.Anticonvulsant properties of an oral ketone ester in a pentylenetetrazole-model of seizure.
Viggiano A1, Pilla R2, Arnold P3, Monda M4, D'Agostino D5, Coppola G6. Brain Res. 2015 Aug 27;1618:50-4. doi: 10.1016/j.brainres.2015.05.023. Epub 2015 May 27.
The ketogenic diet is known to have an anti-epileptic effect; in fact it is currently used to treat drug resistant epilepsies. The efficacy of this diet is thought to be correlated to the elevation of blood ketone bodies. Because of problems with compliance to this diet, there is an interest in evaluating alternative pharmacological treatments that can have anti-seizure effects by elevating ketone bodies. In the present experiment, an orally administered synthetic ketone ester (R,S - 1,3-butanediol acetoacetate diester, or BD-AcAc2) was evaluated for its anti-seizure efficacy in a rat model. The threshold for seizure induction with progressive intravenous infusion of pentylenetrazole (PTZ) was evaluated in anesthetized Wistar rats two hours after a single 1 ml intragastric administration of BD-AcAc2 (i.e. 4 g/kg b.w., treated group) or water (control group). After correction for the dose of anesthetic, the results showed that the administration of BD-AcAc2 induced an elevation of the PTZ threshold (140 ± 11 mg/kg for the treated group, 122 ± 6 mg/kg for the control group), along with an increased level of blood β-hydroxybutyrate (2.
