Fragmentation of conjugate bases of esters derived from multifunctional alcohols including triacylglycerols

Enolate anions of esters from 1,2 and 1,3 diols undergo an internal nucleophilic substitution reaction that produces a β-ketoester and an alkoxide ion within the molecular species. These intermediate ions undergo two competitive fragmentation pathways. The first pathway corresponds to a second nucleophilic substitution of the ketoester by the alkoxide that yields a neutral cyclic ether and the β-ketoacid carboxylate. The latter then loses carbon dioxide and produces the enolate anion of the corresponding ketone. The second proposed pathway is stepwise: it starts with a proton transfer from the methylene group between the two carbonyls to the alkoxide anion that produces an alcohol and the enolate ion of the β-ketoester inside the molecular species. The latter undergoes cleavage of the ester bond induced by the negative charge to yield an ion-dipole complex composed of a neutral acylketene and an alkoxide ion. The direct dissociation of this ion-dipole complex competes with an internal proton exchange to yield a new complex that consists of an alcohol molecule and the anion of the acylketene, which can also dissociate. The fragmentation pathway that leads to the ketone enolate is sensitive to the relative positions (1,2 or 1,3) of the esters on the molecular backbone. This position-sensitive reaction is useful for the assignment of the primary and secondary positions in triacylglycerols, even in mixtures, as shown by some examples.     

Enhancing Ocular Bioavailability of Ciprofloxacin Using Colloidal Lipid-Based Carrier for the Management of Post-Surgical Infection

Conjunctivitis and endogenous bacterial endophthalmitis mostly occurred after ophthalmic surgery. Therefore, the present study aimed to maximize the ocular delivery of ciprofloxacin (CPX) using colloidal lipid-based carrier to control the post-surgical infection. In this study, CPX was formulated as ophthalmic liposomal drops. Two different phospholipids in different ratios were utilized, including phosphatidylcholine (PC) and dimyrestoyl phosphatidylcholine (DMPC). The physiochemical properties of the prepared ophthalmic liposomes were evaluated in terms of particle size, entrapment efficiency, polydispersity index, zeta potential, and cumulative CPX in-vitro release. In addition, the effect of sonication time on particle size and entrapment efficiency of CPX ophthalmic drops was also evaluated. The results revealed that most of the prepared formulations showed particle size in nanometer size range (460–1047 nm) and entrapment efficiency ranging from 36.4–44.7%. The antibacterial activity and minimum inhibitory concentration (MIC) were investigated. Ex vivo antimicrobial effect of promising formulations was carried out against the most common causes of endophthalmitis microorganisms. The pharmacokinetics of the prepared ophthalmic drops were tested in rabbit aqueous humor and compared with commercial CPX ophthalmic drops (Ciloxan^®). Observed bacterial suppression was detected in rabbit’s eyes conjunctivitis with an optimized formulation A3 compared with the commercial ophthalmic drops. CPX concentration in the aqueous humor was above MIC against tested bacterial strains. The in vivo data revealed that the tested CPX drops showed superiority over the commercial ones with respect to peak aqueous humor concentration, time to reach peak aqueous humor concentration, elimination rate constant, half-life, and relative bioavailability. Based on these results, it was concluded that the prepared ophthalmic formulations significantly enhanced CPX bioavailability compared with the commercial one.     

Contribution to the Modelling of Coupled Heat and Mass Transfers on 3D Real Structure of Heterogeneous Building Materials: Application to Hemp Concrete

Hydraulic flow, electrical flow and the passage of elastic waves through porous media are all linked by electrokinetic processes. In its simplest form, the passage of elastic waves through the porous medium causes fluid to flow through that medium and that flow gives rise to an electrical streaming potential and electrical counter-current. These processes are frequency-dependent and governed by coupling coefficients which are themselves frequency-dependent. The link between fluid pressure and fluid flow is described by dynamic permeability, which is characterised by the hydraulic coupling coefficient (C_hp). The link between fluid pressure and electrical streaming potential is characterised by the streaming potential coefficient (C_sp). While the steady-state values of such coefficients are well studied and understood, their frequency dependence is not. Previous work has been confined to unconsolidated and disaggregated materials such as sands, gravels and soils. In this work, we present an apparatus for measuring the hydraulic and streaming potential coefficients of high porosity, high permeability consolidated porous media as a function of frequency. The apparatus operates in the range 1 Hz to 2 kHz with a sample of 10 mm diameter and 5–30 mm in length. The full design and validation of the apparatus are described together with the experimental protocol it uses. Initial data are presented for three samples of Boise sandstone, which present as dispersive media with the critical transition frequency of 918.3?±?99.4 Hz. The in-phase and in-quadrature components of the measured hydraulic and streaming potential coefficients have been compared to the Debye-type dispersion model as well as theoretical models based on bundles of capillary tubes and porous media. Initial results indicate that the dynamic permeability data present an extremely good fit to the capillary bundle and Debye-type dispersion models, while the streaming potential coefficient presents an extremely good fit to all of the models up to the critical transition frequency, but diverges at higher frequencies. The streaming potential coefficient data are best fitted by the Pride model and its Walker and Glover simplification. Characteristic pore size values calculated from the measured critical transition frequency fell within 1.73% of independent measures of this parameter, while the values calculated directly from the Packard model showed an underestimation by about 12%.

     

LW-compact operators and domination problem

Positivity - This paper introduces a ‘new’ class of operators. An operator T from a Banach lattice E into a Banach space Y will be called an LW-compact if T carries L-weakly compact...