An Efficient Synthesis of Substituted 2H-Pyran-2-one Derivatives via the Conjugated Addition of the Enolates of Carbonyl Compounds to Enaminoesters

Short simple synthesis of alkenoic acid esters and their intramolecular cyclization products, 2H-Pyran-2-ones from enolates of carbonyl compounds and enaminoesters are described.     

Photo-SRM: laser-induced dissociation improves detection selectivity of Selected Reaction Monitoring mode

Selected Reaction Monitoring (SRM) carried out on triple‐quadrupole mass spectrometers coupled to liquid chromatography has been a reference method to develop quantitative analysis of small molecules in biological or environmental matrices for years and is currently emerging as a promising tool in clinical proteomic. However, sensitive assays in complex matrices are often hampered by the presence of co‐eluted compounds that share redundant transitions with the target species. On‐the‐fly better selection of the precursor ion by high‐field asymmetric waveform ion mobility spectrometry (FAIMS) or increased quadrupole resolution is one way to escape from interferences. In the present work we document the potential interest of substituting classical gas‐collision activation mode by laser‐induced dissociation in the visible wavelength range to improve the specificity of the fragmentation step. Optimization of the laser beam pathway across the different quadrupoles to ensure high photo‐dissociation yield in Q2 without detectable fragmentation in Q1 was assessed with sucrose tagged with a push‐pull chromophore. Next, the proof of concept that photo‐SRM ensures more specific detection than does conventional collision‐induced dissociation (CID)‐based SRM was carried out with oxytocin peptide. Oxytocin was derivatized by the thiol‐reactive QSY® 7 C₅‐maleimide quencher on cysteine residues to shift its absorption property into the visible range. Photo‐SRM chromatograms of tagged oxytocin spiked in whole human plasma digest showed better detection specificity and sensitivity than CID, that resulted in extended calibration curve linearity. We anticipate that photo‐SRM might significantly improve the limit of quantification of classical SRM‐based assays targeting cysteine‐containing peptides. Copyright © 2011 John Wiley & Sons, Ltd.     

Chemoselective direct amidation of fatty acids with furfurylamine without coupling reagents in reversed micellar microenvironment

Furan heterocyclic compounds derived from renewable sources are popular versatile candidates for the production of multifunctional macromolecular materials. These compounds are also used as hydrophobilization monomers for reversible polyadducts or as versatile building blocks in Diels-Alder reactions. In the present study, an efficient approach to chemoselective acylation of furfurylamine with a series of non-preactivated monocarboxylic or dicarboxylic long-chain fatty acids and some of their functionalized derivatives has been achieved via catalytic direct amidation in reversed micellar medium. A convenient and environmentally friendly method has been developed for furfurylamides via a dehydrative coupling reaction. For this purpose, a new cationic Brønsted-type sulfonic acid catalyst containing a hexadecyl alkyl chain was synthesized and fully characterized. The present catalytic reaction produced the respective N-furfurylamides materials in good to excellent yields. This study also confirms that the direct amidation of carboxylic acids with selected amine compounds can be successfully catalyzed by Brønsted acids. Its simplicity and high atom economy are the main advantages of this method.     

Effects of higher-order dispersion on pulse splitting in the normal dispersion regime

By solving numerically the extended nonlinear Schrödinger equation we investigate the influence of higher-order dispersion effects on the propagation of optical pulses in the normal dispersion regime in a highly nonlinear fiber. Already a small amount of third-order dispersion can lead to a pulse-breakup above a certain pulse power. The splitting is followed by an expansion of the spectrum towards longer wavelengths without any impact of Raman scattering. The transfer of energy to longer wavelengths strongly depends on the dispersion profile of the fiber.     

The nonlinear refraction and absorption dependence on the thermal effect for 4 ns pulse duration in binuclear Zn(II) phthalocyanine solution

The influence of thermal effect on the third-order nonlinear optical properties of binuclear Zn(II) phthalocyanine in chloroform solution was studied. The nonlinear refraction and absorption of the sample was measured by using Z-scan technique with 4 ns laser pulses at 532 nm wavelength. The opposite signs of the effective nonlinear refraction index were observed by changing the focal length of focusing lens from 10 cm to 20 cm in the experimental setup. Changing the focusing lens increased the beam waist radius from 7 μm to 20 μm. The nonlinear absorption coefficient was reduced about 200 times based on changing the fluence or beam waist radius. The drastic changes in the third-order nonlinear optical parameters were attributed to thermal effect. To investigate the role of thermal effects even further the effective nonlinear refraction and absorption coefficients were studied by using different repetition rates, input powers and concentrations.     

Single-ion conductivity enhancement for the composite polymer electrolytes based on Li(PVAOB)/PPEGMA for lithium-ion batteries

In the present work, a series of single-ion conducting composite polymer electrolytes based on lithium polyvinyl alcohol oxalate borate (Li(PVAOB)) and poly(polyethylene glycol methacrylate) (PPEGMA) were produced. PEGMA was polymerized into PPEGMA, and the Li(PVAOB) was prepared from poly (vinyl alcohol) (PVA), oxalic acid, and boric acid. Li(PVAOB) was blended with PPEGMA at different stoichiometric ratios to obtain a single-ion conducting system. All the electrolytes were characterized by Fourier transformation infrared spectroscopy (FT-IR), thermogravimetry analysis (TGA), differential scanning calorimeter (DSC), and scanning electron microscopy (SEM) techniques. These results verified the interaction between host and guest polymers, sufficient thermal stability within the measured conductivity domain, and the homogeneity of the composite electrolytes. The effect of PPEGMA onto the ionic conductivity was investigated using impedance spectroscopy. The Li(PVAOB)-60PPEGMA is the optimum content, and this sample has a maximum ionic conductivity of 3 × 10^?4 S/cm at 100 °C which is approximately five orders of magnitude higher than neat Li(PVAOB). Activation energy (E _a ) of ionic transport decreased from 11.9 to 0.27 kJ/mol, suggesting a much faster ionic mobility for higher PPEGMA-containing samples.