Search results for "Polar"
showing 10 items of 3817 documents
Comment on “Local impermeant anions establish the neuronal chloride concentration”
2014
Glykys et al . (Reports, 7 February 2014, p. 670) proposed that cytoplasmic impermeant anions and polyanionic extracellular matrix glycoproteins establish the local neuronal intracellular chloride concentration, [Cl – ] i , and thereby the polarity of γ-aminobutyric acid type A (GABA A ) receptor signaling. The experimental procedures and results in this study are insufficient to support these conclusions. Contradictory results previously published by these authors and other laboratories are not referred to.
Quantitative characterization of the global electrophilicity pattern of some reagents involved in 1,3-dipolar cycloaddition reactions
2003
Abstract The global electrophilicity power, ω, of a series of dipoles and dipolarophiles commonly used in 1,3-dipolar cycloadditions may be conveniently classified within a unique relative scale. The effects of chemical substitution on the electrophilicity of molecules have been evaluated using a representative set of electron-withdrawing and electron-releasing groups for a series of dipoles including nitrone, nitrile oxide and azide derivatives. The absolute scale of electrophilicity is used to rationalize the chemical reactivity of these species as compared to the static reactivity pattern of the reagents involved in the Diels–Alder reactions.
Understanding the origin of the asynchronicity in bond-formation in polar cycloaddition reactions. A DFT study of the 1,3-dipolar cycloaddition react…
2012
The origin of the asynchronicity in bond-formation in polar cycloadditions has been studied by an ELF analysis of the electron reorganisation along the 1,3-dipolar cycloaddition of Padwa's carbonyl ylide 4 with the 1,2-benzoquinone 8. This reaction presents an unexpected asynchronous bond-formation, which is initialised through the nucleophilic attack of Padwa's carbonyl ylide on the carbonyl oxygen atom of the strongly electrophilically activated 1,2-benzoquinone. The present study allows for the establishment that along an asynchronous bond-formation, the more favourable two-center interaction begins at the most electrophilic center, which is the center with the highest spin density achie…
The triplet excited state of the biocative compound thiabendazole. Characterization and suitability as reporter for cyclodextrin complexation
2012
Fluorescence spectroscopy, laser flash photolysis (LPF), and density functional theory calculations have been performed to characterize the photobehavior of thiabendazole (1). Direct LFP of 1 results in the generation of a transient absorbing at λmax = 570 nm identified as the triplet excited state (31∗). The intersystem crossing quantum yield is 0.91, and the triplet energy is 288 kJ mol−1. The singlet–triplet energy gap is 84 kJ mol−1. The behavior of thiabendazole within CDs results in a marked enhancement of the triplet lifetime, this change is attributed to the mobility restrictions of included 1 imposed by the cyclodextrin cavities.
A DFT study of the Huisgen 1,3-dipolar cycloaddition between hindered thiocarbonyl ylides and tetracyanoethylene
2004
Abstract The mechanism for the 1,3-dipolar cycloaddition between the hindered thiocarbonyl ylide 1 and tetracyanoethylene 2 has been studied at the B3LYP/6-31G ∗ level. Formation of the [3+2] cycloadduct 4 takes place through a stepwise mechanism that is initiated by the nucleophilic attack of the thiocarbonyl ylide 1 to the ethylene derivative 2 to give a zwitterionic intermediate IN . The subsequent cyclization of IN yields a seven-membered cyclic ketene imine 6 , which equilibrates with the thermodynamically more stable [3+2] cycloadduct 4 . The computed free energies are in agreement with the experimental outcomes.
Surface plasmon near-field imaging of very thin microstructured polymer layers.
2004
We report on the near-field imaging of microstructured polymer layers deposited on an homogeneous metal thin film on which a surface plasmon mode is excited. The microstructures in the polymer layers are designed by electron beam lithography, and the near-field imaging is performed with a photon scanning tunneling microscope (PSTM). We show that, despite their very small height, the microstructures can be conveniently imaged with a PSTM thanks to the field enhancement at the surface of the metal thin film supporting the surface plasmon. The influence of the illumination conditions on the contrast of the PSTM images is discussed. In particular, we show that both the field enhancement and the…
Double-quantum nutations in a two-level spin system
1986
The transient oscillatory behavior of the nonlinear response of a two-level electron-spin system is experimentally investigated in a sample of glassy silica with ${E}_{1}^{\mathcal{'}}$ centers (S=(1/2)) at microwave frequency at T=4.2 K. The transient regime, excited by an intense step-modulated radiation tuned to double-quantum (DQ) resonance, is monitored by revealing the second-harmonic (SH) wave radiated by the spins undergoing DQ transitions. Time- and frequency-domain results show that the emitted SH wave has two components: the former, which vanishes at the DQ resonance, exhibits an overdamped transient regime, the latter consists of damped oscillations at a frequency which depends …
Conformational properties of oxazoline-amino acids
2016
Abstract Oxazoline-amino acids (Xaa-Ozn) occur in natural peptides of potentially important bioactivity. The conformations of the model compounds: Ac-(S)-Ala-Ozn(4R-Me), Ac-(S)-Ala-Ozn(4S–Me), and (gauche+, gauche−, anti) Ac-(S)-Val-Ozn(4R-Me) were studied at meta-hybrid M06-2X/6–311++G(d,p) method including solvent effect. Boc- l -Ala- l -Ozn-4-COOMe and Boc- l -Val- l -Ozn-4-COOMe were synthesized and studied by FT-IR and NMR-NOE methods. The conformations in crystal state were gathered from the Cambridge Structural Data Base. The main conformational feature of the oxazoline amino acids is the conformation β2 (ϕ,ψ ∼ −161°, −6°), which predominates in weakly polar environment and still is …
Tetra-alkoxy substituted PPV derivatives: a new class of highly soluble liquid crystalline conjugated polymers
2011
Two first examples of highly soluble tetra-alkoxy substituted PPV derivatives, poly(2,3,5,6-tetrahexyloxy-1,4-phenylene vinylene) (TH-PPV) and poly[2,3,5,6-tetra(2'-ethyl-hexyloxy)-1,4-phenylene vinylene] TEH-PPV, are presented. Both polymers have been fully characterized and the solubility and UV-Vis absorption characteristics have been studied in various organic solvents. Due to the symmetric nature of the repeating unit, TH-PPV and TEH-PPV have an inherently regioregular nature, which is unusual for PPV-type polymers. Observations from polarized light microscopy and differential scanning calorimetry indicate that TH-PPV exhibits thermally induced order resulting in a liquid crystalline m…
Composite soy lecithin–decylpolyglucoside vesicles: A theoretical and experimental study
2008
In the present work, vesicles made with soy lecithin and a commercial mixture of alkyl polyglucosides were prepared and characterized. Vesicles with a constant amount of soy lecithin and an increasing amount of a decylpolyglucoside surfactant, (OrNS10), were formulated and their physicochemical properties were studied with the aim to design a drug delivery system suitable for different applications. To this purpose, morphology, size distribution, ζ-potential and apparent viscosity of the prepared vesicles were studied. Vesicles were also characterized by using optical and light polarized microscopy, transmission electron microscopy and photon correlation spectroscopy. A stability study was …