Convenient Synthesis of 2,4-Disubstituted Tetrahydrothiophenes from Mannich's Adducts

Ammonium salts of β-functionalized allylic amines 1 were successfully employed as electrophilic agents with functional thiols. The obtained intermediate 2 underwent intramolecular cyclization in the presence of potassium tert-butoxide to afford 2,4-disubstituted tetrahydrothiophenes 3.     

Thermal stability,low gap energy and high Temperature order–disorder Phase Transition in Hybrid Material: [N (CH3)4]2PdCl4

The crystal compound [N (CH₃)₄]₂PdCl₄ was crystallized in the orthogonal system and the space group is P4/mmm and the refined unit cell parameters are a = b = 8.831 Å, c = 11.415 Å. The structure, vibrational spectra and optical properties have been investigated. DSC studies indicate the presence of two phase transitions at higher temperature which confirm the thermal stability of the palladium-based compound. These transitions have been studied by Raman scattering on single crystals as a function of temperature which confirmed their nature. The assignment of the observed bands is discussed based in the theoretical calculated frequencies by the density functional theory (DFT) method using B3LYP/LanL2DZ basis in the GAUSSIAN-09 package of programs. The optical properties in the UV–visible region have been deduced and the energy gap has been determined which is equal to 3.11 eV.     

Higher temperature order–disorder transition,electrical and optical properties of [N(C2H5)4]2Pd2Cl6 compound

[N(C₂H₅)₄]₂Pd₂Cl₆ hybrid compound with semiconducting character was synthetized and characterized by X-ray diffraction, the thermal, optical and electrical properties. X-ray diffraction indicates that the compound crystallize at room temperature in the orthorhombic system and (Immm) space group. Two endothermic peaks at, 343 K and 440 K were observed in the DSC measurements corresponding to the evaporation of water molecules and order-disorder transition, respectively. The optical band gap (E_g = 4.34 eV) was deduced by the Tauc relation. The electrical properties was studied using the impedance spectroscopy in the frequency range of 0.1 Hz to 1 MHz and over the temperature range of 270 K to 480 K. The analysis of Nyquist plots revealed the presence of grains, grain boundaries and the electrode effects. The equivalent circuit was determined. The Ac conductivity was analyzed by the Jonsher low and the conduction mechanism was deduced based in the Elliot theory and indicate that the correlated barrier hopping model (CBH) was described the two regions II and IV and the overlapping polaron model (OLPT) the right model described the conduction in the regions I and III.     

Electrical characterization of the [N(CH<Subscript>3</Subscript>)<Subscript>4</Subscript>][N(C<Subscript>2</Subscript>H<Subscript>5</Subscript>)<Subscript>4</Subscript>]ZnCl<Subscript>4</Subscript> compound

The [N(CH₃)₄][N(C₂H₅)₄]ZnCl₄ compound has been synthesized by a solution-based chemical method. The X-ray diffraction study at room temperature revealed an orthorhombic system with P2₁2₁2 space group. The complex impedance has been investigated in the temperature and frequency ranges 420–520 K and 200 Hz–5 MHz, respectively. The grain interior and grain boundary contribution to the electrical response in the material have been identified. Dielectric data were analyzed using the complex electrical modulus M ^* for the sample at various temperature. The modulus plots can be characterized by full width at half height or in terms of a non-exponential decay function ϕ(t) = exp[(−t/τ) ^β ]. The detailed conductivity study indicated that the electrical conduction in the material is a thermally activated process. The variation of the AC conductivity with frequency at different temperatures obeys the Almond and West universal law.     

Alkylperoxyl spin adducts of pyrroline‐N‐oxide spin traps: Experimental and theoretical CASSCF study of the unimolecular decomposition in organic solvent,potential applications in water

Spin trapping coupled with electron paramagnetic resonance spectroscopy is the most direct method for detection of very low concentrations of free radicals, and it has been intensively used to detect superoxide or alkylperoxyl radicals in biological systems, using cyclic nitrones as spin traps. The half‐life time of the ensuing spin adducts depends dramatically on the spin trap structure; however, their mechanism of decay has never been definitely established. We investigated at the MRMP2/CASSCF (MultiReference second‐order Møller‐Plesset perturbation theory/Complete Active Set Self Consistent Field) level of theory the mechanism of decay of methylperoxyl and tert‐butylperoxyl spin adducts formed with various cyclic nitrones. We showed that no transition state can be located for the O─O homolytic cleavage, which yields an intermediate biradical with the following sequence ^?O─N─C─O^?. Then, homolytic cleavage of the N─C bond yields a nitrosoaldehyde, through an early transition state with a very low activation energy. For each nitrone used as spin trap, electrospray ionization mass spectrometry analysis of the spin trapping mixture allowed to detect the presence of the expected nitrosoaldehyde. We generated tert‐butylperoxyl spin adducts in toluene, and we found a good correlation between their half‐life time and the bond dissociation energy of their peroxidic O─O bond. The theoretical method was then extended to hydroperoxyl spin adducts in water and provided promising results.     

Properties of amorphous carbon nitride prepared by RF reactive sputtering

The local microstructure and optical and electrical properties were investigated of amorphous carbon nitride (a-CN) films deposited by reactive radio-frequency (RF) sputtering. Two series prepared in nitrogen or in a nitrogen and argon mixture were studied. The optical properties were investigated by transmittance/reflectance and photothermal deflection spectroscopies. Combined infrared measurements and Raman scattering spectroscopies were used to investigate the microstructure of a-CN films in terms of nitrogen incorporation within the films and C sp ² content. These experiments were completed by dark electrical conductivity measurements performed in coplanar configuration in the temperature range 50–450?K. The films exhibit semiconductor behaviour and the temperature dependence suggests two types of conduction. An increase in nitrogen incorporation induces an increase with clustering of sp ² phase replacing C=C olefinic groups with aromatic groups.     

Heterodyne detection for Fiber Bragg Grating sensors

In this paper, we present a Fiber-Bragg-Grating-based temperature sensor. The technique employs heterodyne detection using two Fiber Bragg Gratings. One of the gratings is used as a reference (local oscillator) and the second as a sensing arm. This sensor uses a Folded Mach-Zehnder interferometer. As the temperature changes, the Bragg wavelength of the FBG shifts. The heterodyne detection is used to detect the frequency difference between the reference and sensing signals that is caused by the temperature change. The dynamic range and sensitivity of the sensor were analyzed and presented.     

Physicochemical and rheological properties of thickeners produced from Tunisian clays

Modification of two samples of Tunisian clays of the type of natural smectites with organic derivatives of ammonium salts was studied. The physicochemical properties of the modified products and the possibility of their use as components of lubricating oils were analyzed. Published in Russian in Zhurnal Prikladnoi Khimii, 2006, Vol. 79, No. 3, pp. 387–392. This article was submitted by the authors in English.     

Hydrodynamic dimensions, electrophoretic mobility, and stability of hydrophilic quantum dots

Luminescent semiconductor quantum dots (QDs) have great potential for use in biological assays and imaging. These nanocrystals are capped with surface ligands (bifunctional molecules, amphiphilic polymers, phospholipids, etc.) that render them hydrophilic and provide them with functional properties. These coatings alters their hydrodynamic radii and surface charge, which can drastically affect properties such as diffusion within the cell cytoplasm. Heavy atom techniques such as transmission electron microscopy and X-ray scattering probe the inorganic core and do not take into account the ligand coating. Herein we use dynamic light scattering to characterize the hydrodynamic radius (R(H)) of CdSe-ZnS QDs capped with various hydrophilic surface coatings (including dihydrolipoic acid and amphiphilic polymers) and self-assembled QD-protein bioconjugates. Experiments were complemented with measurements of the geometric size and zeta potential using agarose gel electrophoresis and laser Doppler velocimetry. We find that the effects of surface ligands on the hydrodynamic radius and on the nanoparticle mobility are complex and strongly depend on a combination of the inorganic core size and nature and lateral extension of the hydrophilic surface coating. These properties are critical for the design of QD-based biosensing assays as well as QD bioconjugate diffusion in live cells.