Transport coefficients, Raman spectroscopy, and computer simulation of lithium salt solutions in an ionic liquid

Lithium salt solutions of Li(CF3SO2)2N, LiTFSI, in a room-temperature ionic liquid (RTIL), 1-butyl-2,3-dimethyl-imidazolium cation, BMMI, and the (CF3SO2)2N(-), bis(trifluoromethanesulfonyl)imide anion, [BMMI][TFSI], were prepared in different concentrations. Thermal properties, density, viscosity, ionic conductivity, and self-diffusion coefficients were determined at different temperatures for pure [BMMI][TFSI] and the lithium solutions. Raman spectroscopy measurements and computer simulations were also carried out in order to understand the microscopic origin of the observed changes in transport coefficients. Slopes of Walden plots for conductivity and fluidity, and the ratio between the actual conductivity and the Nernst-Einstein estimate for conductivity, decrease with increasing LiTFSI content. All of these studies indicated the formation of aggregates of different chemical nature, as it is corroborated by the Raman spectra. In addition, molecular dynamics (MD) simulations showed that the coordination of Li+ by oxygen atoms of TFSI anions changes with Li+ concentration producing a remarkable change of the RTIL structure with a concomitant reduction of diffusion coefficients of all species in the solutions.     

A strong bound on the integral of the central path curvature and its relationship with the iteration-complexity of primal-dual path-following LP algorithms

The main goals of this paper are to: i) relate two iteration-complexity bounds derived for the Mizuno-Todd-Ye predictor-corrector (MTY P-C) algorithm for linear programming (LP), and; ii) study the geometrical structure of the LP central path. The first iteration-complexity bound for the MTY P-C algorithm considered in this paper is expressed in terms of the integral of a certain curvature function over the traversed portion of the central path. The second iteration-complexity bound, derived recently by the authors using the notion of crossover events introduced by Vavasis and Ye, is expressed in terms of a scale-invariant condition number associated with m × n constraint matrix of the LP. In this paper, we establish a relationship between these bounds by showing that the first one can be majorized by the second one. We also establish a geometric result about the central path which gives a rigorous justification based on the curvature of the central path of a claim made by Vavasis and Ye, in view of the behavior of their layered least squares path following LP method, that the central path consists of long but straight continuous parts while the remaining curved part is relatively “short”. R. D. C. Monteiro was supported in part by NSF Grants CCR-0203113 and CCF-0430644 and ONR grant N00014-05-1-0183. T. Tsuchiya was supported in part by Japan-US Joint Research Projects of Japan Society for the Promotion of Science “Algorithms for linear programs over symmetric cones” and the Grants-in-Aid for Scientific Research (C) 15510144 of Japan Society for the Promotion of Science.     

Et3N-induced demethylation-annulation of 3-alkynyl-4-methoxy-2-pyridones and structurally related compounds in the synthesis of furan-fused heterocycles

Various 3-iodo-4-methoxypyridin-2-ones and related pyrone and coumarin derivatives have been demonstrated as readily available precursors of 2-substituted furan-fused heterocycles by means of in situ sequential Sonogashira-acetylide coupling, dealkylation, and regioselective furan annulation reactions. A Et3N-induced S(N)2 process has been established that accounts for the dealkylation process.     

Bimolecular radical termination: New perspectives and insights

The reversible addition‐fragmentation chain transfer‐chain length dependent termination (RAFT‐CLD‐T) method has allowed us to answer a number of fundamental questions regarding the mechanism of diffusion‐controlled bimolecular termination in free‐radical polymerization (FRP). We carried out RAFT‐mediated polymerizations of methyl acrylate (MA) in the presence of a star matrix to develop an understanding of the effect of polymer matrix architecture on the termination of linear polyMA radicals and compared this to polystyrene, polymethyl methacrylate, and polyvinyl acetate systems. It was found that the matrix architecture had little or no influence on termination in the dilute regime. However, due to the smaller hydrodynamic volumes of the stars in solution compared to linear polymer of the same molecular weight, the gel onset point occurred at greater conversions, and supported the postulate that chain overlap (or c*) is the main cause for the observed autoacceleration observed in FRP. Other theories based on “short–long” termination or free‐volume should be disregarded. Additionally, since our systems are well below the entanglement molecular weight, entanglements should also be disregarded as the cause of the gel onset. The semidilute regime occurs over a small conversion range and is difficult to quantify. However, we obtain accurate dependencies for termination in the concentrated regime, and observed that the star polymers (through the tethering of the arms) provided constriction points in the matrix that significantly slow the diffusion of linear polymeric radicals. Although, this could at first sight be postulated to be due to reptation, the dependencies showed that reptation could be considered only at very high conversions (close to the glass transition regime). In general, we find from our data that the polymer matrix is much more mobile than what is expected if reptation were to dominate. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 3155–3173, 2008     

Validation of a high-performance liquid chromatographic method with fluorescence detection for the simultaneous determination of tetracyclines residues in bovine milk

A high-performance liquid chromatography-fluorescence detection method was optimized and validated to determine tetracyclines residues in bovine milk. Post-column derivatization using metal complexation in non-aqueous reagent increased the fluorescence of chelates by a factor up to 2.54 compared to water (signal-to-noise ratio enhancement). Overall recoveries ranged from 61 to 115%, with RSD_r from 5 to 15% (n = 54). Detection limits ranged from 5 to 35 μg kg⁻¹. Limits of quantification were established at 50 μg kg⁻¹. Decision limits (CCα) were 109, 108 and 124 μg kg⁻¹ and detection capabilities (CCβ) 119, 117 and 161 μg kg⁻¹ for oxytetracycline, tetracycline and chlortetracycline, respectively. The method was applied successfully in a national monitoring program.     

Initiation mechanisms in copolymerization: Reaction of t-butoxyl radicals with co-monomers ethyl vinyl ether and methyl methacrylate

The radical trapping technique employing 1,1,3,3-tetramethyl-1,3-dihydro-1H-isoindol-2-yloxyl as a scavenger has been used to investigate the reaction of t-butoxyl radicals with mixtures of ethyl vinyl ether and methyl methacrylate. The range of identified products includes those from both addition and hydrogen abstraction with both monomers, head addition with ethyl vinyl ether, and some second monomer addition products. Relative rate constants have been obtained for various pairs of constituent reactions. t-Butoxyl radicals add to ethyl vinyl ether one to two times faster than to methyl methacrylate, depending on which monomer is in excess. The ratio is less than 1 in nonolefinic solvents and as high as 6 in t-butanol. This solvent effect is thought to be due to the radicals complexing to either methyl methacrylate or t-butanol (H-bonding), thereby increasing its electrophilic character. © 1997 John Wiley & Sons, Inc.     

The influence of the amount of hardener on the tensile mechanical behavior of an epoxy system

The tensile mechanical behavior of an epoxy/amine system, with varying amounts of hardener, was evaluated. The results showed that a brittle to ductile transition occurs as the amount of hardener is increased. This behavior was associated with the change in the number of molecular segments that present mobility in the macromolecular network. The epoxy-rich formulations are brittle due to the total consumption of the functional groups on the hardener molecule. On the other hand, the amine-rich formulations showed a fracture behavior characteristic of materials with large deformation capacity. This behavior was associated with the presence of unreacted points on the hardener molecule which introduce a new mobile molecular segment in the macromolecular network formed. © 1998 John Wiley & Sons, Ltd.     

Properties of Charmonium States in a Phenomenological Approach

We investigate the spectrum and decay rates of charmonium states within the framework of the non relativistic quark model by employing a Coulomb like potential from the perturbative one gluon exchange and the linear confining potential along with the potential derived from instanton vacuum to account for the hyperfine mass splitting of charmonium states in variational approach. We predict radiative E1, M1, two-photon, lepton and two-gluon decay rates of low lying charmonium states. An overall agreement is obtained with the experimental masses and decay widths.We have estimated the branching ratio of two gluons decaying into light hadrons.     

Design and Synthesis In Silico Drug-like Prediction and Pharmacological Evaluation of Cyclopolymethylenic Homologous of LASSBio-1514

Acylhydrazones are still an important framework to the design of new bioactive compounds. As treatment of chronic pain represents a clinical challenge, we decided to modify the structure of LASSBio-1514 (1), previously described as anti-inflammatory and analgesic prototype. Applying the homologation as a strategy for molecular modification, we designed a series of cyclopentyl- (2a–e), cyclobutyl- (3a–e), and cyclopropylacylhydrazones (4a–e) that were synthetized and evaluated in murine models of inflammation and pain. A comparison of their in silico physicochemical and drug-like profile was conducted, as well as their anti-inflammatory and analgesic effect. Compounds 4a (LASSBio-1755) and 4e (LASSBio-1757) displayed excellent in silico drug-like profiles and were identified as new analgesic lead-candidates in acute and chronic model of pain, through oral administration.     

Mechanism of base-catalyzed autooxidation of corticosteroids containing 20-keto-21-hydroxyl side chain

Corticosteroids and related compounds containing the 20-keto-21-hydroxyl side chain such as betamethasone, betamethasone 9,11-epoxide, dexamethasone, and dexamethasone 9,11-epoxide have been found to undergo facile autooxidation on the 1,3-dihydroxyacetone side chain of their D-rings under strong alkaline conditions to yield five main degradants (17-formyloxy-17-acid, 17-acid, 21-aldehyde, 20-hydroxy-21-acid, and 17-ketone). The rate of the autooxidation was correlated with the strength and concentration of the base used in the reaction. A novel mechanism for the observed autooxidation is proposed, in which the facile oxidation of the presumed enolate (resulting from the carbanion at the 21-position) by molecular oxygen is the key step. The proposed autooxidation mechanism, supported by LC-MS isotope experiments using ¹⁸O₂ as the oxidant, can satisfactorily explain the oxidative degradation patterns observed for corticosteroids containing the 20-keto-21-hydroxyl side chain.