Temperature effect on thin lipid film elasticity and phase separation: insights from Langmuir monolayer and fluorescence microscopy techniques

Langmuir monolayer pressure isotherms and compressibility modulus measurements of phospholipid mixtures in several Langmuir monolayer systems at the air/water interface were investigated in this study. The ultimate aim was to carry out a comparison of the elasticity modulus for monolayers with different mixtures of l,2-dioleoyl-sn-glycero-3-phosphocholine (DOPC), l,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC) and chicken egg yolk sphingomyelin (eSM), in the presence/absence of cholesterol (Chol). In particular, we were able to propose that the leading force beyond the phase separation into liquid expanded (LE-) and liquid condensed (LC-) phases emerges from the increasing barrier to incorporate DOPC molecules into a highly ordered LC-phase. In addition, our findings suggest that DOPC lipid molecules have a priority to incorporate in a disordered LE-phase, while DPPC and eSM prefer the ordered one. Also, Chol seems to split almost equally into both phases, indicating that Chol has no priority for either phase and there are no particular interactions between Chol and saturated lipid molecules.     

Capillary electrochromatography with monolithic silica columns. IV. Electrochromatographic characterization of polar bonded monolithic stationary phases having surface-bound cyano functionalities

Two polar ligands, namely 3-hydroxypropionitrile and 1H-imidazole-4,5-dicarbonitrile (IDCN) were covalently attached to epoxy-activated silica-based monolithic capillary columns via an epoxide ring-opening reaction to yield CN-OH-Monolith and 2CN-OH-Monolith, respectively. The silica monolith was prepared by a sol-gel process, and the resulting "rod-like" stationary phase was subjected to pore tailoring with an alkaline solution to convert small pore domains to mesopore domains, thus yielding a monolith with bimodal pore structure consisting of flow through pores (i.e., flow channels for mobile-phase flow) and mesopores that provide most of the adsorption capacity of the monolith toward the separated solutes. The two polar monoliths, CN-OH-Monolith and 2CN-OH-Monolith, were evaluated in normal-phase CEC with organic-rich mobile phases less polar than the stationary phase. The 2CN-OH-Monolith bearing more polar functions than the CN-OH-Monolith exhibited more retention and improved selectivity toward model polar solutes.     

NMR Studies and electrophilic properties of triphenylphosphine-trifluoromethanesulfonic anhydride; a remarkable dehydrating reagent system for the conversion of aldoximes into nitriles

NMR Studies on the reaction of triphenylphosphine with various amounts of triflic anhydride at 0 °C is described. The reagent structure resulting from mixing 1.3 equiv of Ph₃P with Tf₂O (1.0 mmol) has been established as an equilibrium mixture consisting mainly of triphenyl(trifluoromethylsulfonyloxy)phosphonium trifluoromethanesulfinate and the corresponding bis(triphenyl)oxodiphosphonium trifluoromethanesulfinate dimer. The electrophilic properties of the system have been exploited in the development of a mild method for converting aldoximes into nitriles. The dehydration occurs at 0 °C under very mild conditions by initial activation of the oxime oxygen, followed by treatment with a base and subsequent elimination of triphenylphosphine oxide. The substrate scope and functional group tolerance of this useful method are explored.     

EPR and solid-state NMR studies of poly(dicarbon monofluoride) (C2F)n

Poly(dicarbon monofluoride) (C2F)n was studied by electron paramagnetic resonance (EPR) and solid-state nuclear magnetic resonance (NMR). The effects of physisorbed oxygen on the EPR and NMR relaxation were underlined and extrapolated to poly(carbon monofluoride) (CF)n and semi-covalent graphite fluoride prepared at room temperature. Physisorbed oxygen molecules are shown to be an important mechanism of both electronic and nuclear relaxations, resulting in apparent spin-lattice relaxation time and line width during NMR and EPR measurements, respectively. The effect of paramagnetic centers on the 19F spin-lattice relaxation was underlined in accordance with the high electron spin density determined by EPR. 19F magic angle spinning (MAS) NMR, 13C MAS NMR, and 13C MAS NMR with 19F to 13C cross polarization (CP) underline the presence of two types of carbon atoms, both sp3 hybridized: some covalently bonded to fluorine and the others linked exclusively to carbon atoms. Finally, a C-F bond length of 0.138 +/- 0.002 nm has been determined thanks to the re-introduction of dipolar coupling using cross polarization.     

Nitric oxide measurements in biological samples

The crucial role of nitric oxide (NO) in controlling many physiological functions in mammals is now established. To aid understanding this crucial role, sensitive and selective methods for its in vivo and in vitro detection are vital. The unique chemical and physical properties of NO set the tone for its detection strategies. This review summarizes different techniques and methodologies used in measuring NO in biological samples. Those include gas and liquid phase chemiluminescence, electron spin resonance spectroscopy, UV-visible spectroscopy, fluorescence, electrochemical sensors, and reporter cell assay. The principles, applications, merits, and limitations of each technique are discussed.     

Capillary electrophoresis and fluorescence studies on molecular beacon-based variable length oligonucleotide target discrimination

Molecular beacons (MBs) are oligonucleotide probes having a compact hairpin structure, with a fluorophore attached to one end and a quencher molecule attached to the other end. In its native state, the fluorophore is quenched by virtue of its proximity to the quencher molecule. Upon hybridization with its complementary oligonucleotide target, fluorescence is elicited due to a conformational change that results in separation of the fluorophore and quencher molecule. The present study describes the hybridization interaction of an MB to various complementary target sequences. The effects of temperature and length of complementary target sequences on hybridization were investigated using capillary electrophoresis and solution-based fluorescence techniques. Hybridization efficiency was dependent on the ability of the target sequences to destabilize the stem region by binding directly to the stem region. Optimal hybridization occurred between 40 and 50 degrees C for all targets tested, with the true target forming a more stable hybrid complex.     

Fundamental and vortex solitons in a two-dimensional optical lattice

Fundamental and vortex solitons in a two-dimensional optically induced waveguide array are reported. In the strong localization regime the fundamental soliton is largely confined to one lattice site, whereas the vortex state comprises four fundamental modes superimposed in a square configuration with a phase structure that is topologically equivalent to the conventional vortex. However, in the weak localization regime, both the fundamental and the vortex solitons spread over many lattice sites. We further show that fundamental and the vortex solitons are stable against small perturbations in the strong localization regime.     

Abstract capacitary estimates and the completeness and separability of certain classes of non-locally convex topological vector spaces

We are concerned with establishing completeness and separability criteria for large classes of topological vector spaces which are typically non-locally convex, including Lebesgue-like spaces, Lorentz spaces, Orlicz spaces, mixed-normed spaces, tent spaces, and discrete Triebel–Lizorkin and Besov spaces. For vector spaces of measurable functions we also derive pointwise convergence results. Our approach relies on abstract capacitary estimates and works in certain cases of interest even in the absence of a background measure space and/or of a vector space structure.     

Mimetics of the Selenoenzyme Glutathione Peroxidase: Novel Structures and Unusual Catalytic Mechanisms

Glutathione peroxidase (GPx) mimetics comprise an important class of selenium-containing antioxidants that catalyze the destruction of biologically harmful peroxides in the presence of stoichiometric thiol reductants. The synthesis of two novel cyclic selenium compounds and their evaluation as GPx mimetics was achieved. The first is a cyclic seleninate ester that is formed in situ from the oxidation of allyl 3-hydroxypropyl selenide. The second is a spirodioxyselenurane that is similarly formed from di(3-hydroxypropyl) selenide. Both compounds were shown to be remarkably active catalysts in an assay based on the reduction of t-butyl hydroperoxide with benzyl thiol. The mechanisms of the catalytic cycles of the two novel selenium compounds were elucidated and were found to be distinct from each other and from that of GPx.