Novel liquid crystals based on [1]benzothieno[3,2- b ][1]benzothiophene

Four series of new [1]benzothieno[3,2- b ][1]benzothiophene derivatives have been synthesized. In the non-chiral series a SmA phase occurs, while the chiral series exhibits a rather wide antiferroelectric SmC * A phase just below the SmA phase. The SmA-SmC * A phase transition has been studied using DSC and dielectric spectroscopy. In the SmC * A phase the spontaneous quantities have been measured. The tilt angle shows a typical temperature dependence and the values of spontaneous polarization are rather moderate. The length of the helical pitch increases on increasing the length of the non-chiral alkyl chain.     

Luminescence Properties of New Fused Benzothiophene Derivatives and Their Conductive Oligomers Structural and Solvent Effects

The structural and solvent effects on the electronic absorption and fluorescence spectra, and fluorescence quantum yields, of four new fused benzothiophene derivatives, including benzothieno[3,2b]-thiophene (BTT), benzothieno[3,2-b]benzothiophene (BTBT), 6-methoxy[1]benzothieno[3,2b]-thiophene (MeOBTT), and benzothieno[3,2-b]indole (BTI) were investigated at 295 K. The luminescence properties of the corresponding conductive oligomers, poly(BTT) and poly (MeOBTT), electrosynthesized in acetonitrile, were also studied. Satisfactory McRae, Suppan, and Kawski-Chamma-Viallet solvatochromic correlations were established for the four monomers in most solvents. A weak negative solvatochromic behavior was found for these compounds, indicating that their dipole moments are slightly lower in the excited singlet state than in the ground state. Kamlet-Abboud-Taft multiparametric correlations were also obtained for absorption and fluorescence wave numbers and quantum yields, demonstrating the existence of specific solute-solvent interactions. In the case of the oligomers, important red-shifts of the fluorescence emission maxima ( 90–110 nm) relative to the corresponding monomers were observed, which shows the extent of conjugated segments in the oligomer chains.     

Isolation of Indonesian cananga oil using multi-cycle pressure drop process

New process, instantaneous controlled pressure drop (DIC) was applied on Cananga odorata dry flowers with the aim to isolate essential oil. DIC is based on high temperature, short time heating followed by an abrupt pressure drop into a vacuum. A part of volatile compounds is carried away from flowers in the form of vapor (DIC direct oil) that evolves adiabatically during the pressure drop (proper isolation process) and the other part remains in the DIC-treated flowers (DIC residual oil). In the present paper, the effect of DIC cycle number (1-9) and heating time (4.3-15.7 min) on the availability of oil compounds was investigated at three levels of steam pressure (0.28, 0.4 and 0.6 MPa). The availability was defined as the amount of a compound in direct or residual oil divided by the amount of this compound in the reference oil extracted from non-treated flowers by chloroform during 2h. The total availability and yield of volatiles in the direct oil increased with pressure and cycle number. At a higher pressure, the effect of heating time was insignificant. The amount of oxygenated monoterpenes and other light oxygenated compounds (i.e. predominantly exogenous compounds) in the residual flowers was lower than in the direct oil and this amount decreased with cycle number. On the other hand, the availability of oxygenated sesquiterpenes and other heavy oxygenated compounds (i.e. predominantly endogenous compounds) in residual flowers exhibited a maximum for about five cycles and their quantity at this point was three times as much as in the direct oil. The total availability of each compound at 0.6 MPa was higher than one. The rapid DIC process (0.6 MPa, 8 cycles, 6 min) gave better results than steam distillation (16 h) concerning direct oil yield (2.8%dm versus 2.5%dm) and content of oxygenated compounds (72.5% versus 61.7%).     

Synthesis,crystal structure and magnetic properties of a new tri‐nuclear iron (II,III) complex,a precursor for the preparation of superparamagnetic Fe3O4 nanoparticles applicable in the removal of Cd2+

This study reports the structural and spectroscopic characterization of a novel metal organic compound formulated as [Fe (bpy)₃] [Fe (dipic)₂]₂.7H₂O ( 1 ) (dipic = pyridine‐2,6‐dicarboxylate and bpy = 2,2^′‐bipyridine). 1 was investigated by elemental analysis, FT‐IR spectroscopy, powder X‐ray diffraction and single crystal X‐ray diffraction (SC‐XRD), which revealed a triclinic structure of expected composition. Thermal degradation of 1 was also investigated. Complex 1 was used as a precursor to prepare superparamagnetic nanoparticles of Fe₃O₄ by thermal analysis. The obtained Fe₃O₄ was characterized by Fourier transformed infrared spectroscopy (FT‐IR), powder X‐ray diffraction (XRD) and scanning electron microscopy (SEM). Fe₃O₄ nanoparticles were used as a nano‐adsorbent to remove Cd²⁺ from water at room temperature. The results showed that this nano‐adsorbent is effective in removing Cd²⁺ from contaminated water sources, and that the maximal effectivity of adsorption occurs at pH = 6. Magnetic measurements of complex 1 and Fe₃O₄ nanoparticles at room temperature revealed paramagnetic and superparamagnetic behavior, respectively.     

Caractéristique directionnelle calculée et mesurée d'une sonde électrochimiqueCalculated and measured directional characteristic of an electrochemical probe

The present paper demonstrates how the directional characteristics of an actual three-segment electrodiffusional sensor can be calculated from the probe image. It was shown that utilization of ‘ideal’ directional characteristics lead to an important (up to 15^°) error in flow angle determination. The directional characteristics calculated from the probe image improve significantly (up to 50%) the accuracy of the flow angle measurements. To cite this article: F. Barbeu et al., C. R. Mecanique 330 (2002) 433–436.     

Synthesis of unique cagelike thiacalix[4]arene derivatives in a 1,3-alternate conformation

A novel type of doubly bridged thiacalix[4]arenes in the 1,3-alternate conformation has been prepared by direct aminolysis reaction of easily accessible thiacalix[4]arene tetraacetates with alpha,omega-diamines. Despite the high excess of diamine, both sites of a 1,3-alternate conformer can be intramolecularly bridged to form the cagelike structures in high yields. Optimum results were obtained using 1,2-ethanediamine as bridging units. X-ray analysis of the novel cagelike molecules revealed a highly preorganized array of -C(O)-NH- bonds pointing to the interior of the cavity.     

Meta nitration of thiacalixarenes

Nitration of thiacalix[4]arene, immobilized in the 1,3-alternate conformation, leads regioselectively to meta-substituted products. Depending on the reaction conditions, mono- and dinitro-derivatives can be isolated in acceptable yields. This unique substitution pattern is inaccessible in classical calixarene chemistry, and yields inherently chiral compounds, which makes thiacalixarenes very attractive as building blocks or molecular scaffolds.     

A polymerized calix[6]arene monolayer having gas permeation selectivity that exceeds Knudsen diffusion

A polymerized monolayer of 5,11,17,23,29,35-hexamercaptomethyl-37,38,40,41,42-hexakis-(1-n hexadecyloxy)calix[6]arene (1) has been synthesized on the surface of an ca. 15 mum-thick film derived from poly[1-(trimethylsilyl)-1-propyne] (PTMSP). This monolayer exhibits a permeation selectivity toward He and SF6 that exceeds Knudsen diffusion. Analogous membranes made from a calix[6]arene that contains amidoxime headgroups (i.e., 2) showed Knudsen diffusion characteristics.     

The statistical significance of selected sense–antisense peptide interactions

Sense and antisense peptides, encoded by sense and corresponding antisense DNA strands, are capable of specific interactions that could be a driving force to mediate protein–protein or protein–peptide binding associations. The complementary residue hypothesis suggests that these interactions are founded upon the sum of pairwise interactions between amino acids encoded by corresponding sense and antisense codons. Despite many successful experimental results obtained with the hypothesis, however, the physicochemical basis for these interactions is poorly understood. We examined the potential of the hypothesis for general identification of protein–protein interaction sites, and the possible role of the hypothesis in determining folding in a broad set of protein structures. In addition, we performed a structural study to investigate the binding of a complementary peptide to IL‐1F2. Our results suggest that complementary residue pairs are no more frequent or conserved than average in protein–protein interfaces, and are statistically under‐represented amongst contacting residue pairs in folded protein structures. Although our structural results matched experimental observations of binding between the peptide and IL‐1F2, complementary residue interactions do not appear to be dominant in the bound structure. Overall, our data do not allow us to conclude that the complementary residue hypothesis accounts for specific sense–antisense peptide interactions. © 2012 Wiley Periodicals, Inc.     

Regioselective ipso-nitration of calix[4]arenes

A novel protection/deprotection method leading to the regioselective ipso-substitution of calix[4]arenes is described. The introduction of nosyl (p-nitrobenzenesulfonyl) groups into the lower rim of partly alkylated tert-butylcalix[4]arenes leads subsequently to the exclusive ipso-nitration of the alkylated phenol rings, while the protecting groups can be easily removed in the next step. This method gives dialkoxy- or trialkoxy-substituted calix[4]arenes with nitro groups on the alkylated rings and tert-butyl groups on the remaining ones. The above substitution pattern is complementary to the isomers so far known in the chemistry of calix[4]arenes and could be used in the design of novel type of calixarene-based receptors.