Calix[4]azacrowns: self-assembly and effect of chain length and O-alkylation on their metal ion-binding properties

Both the consequences of 1,3-cyclization of calix[4]arenes by diamide formation, and the effect of 2- and 2,4-alkoxycarbonylmethylation of two 1,3-bridged calix[4]azacrowns on their metal ion-binding capacities have been studied by synthesis of the derivatives in their cone conformation and measurement of the stability constants for their complexation in a range of alkaline earth and transition metal cations. In these two cases, the conformation of the ligand in the solid state has been defined in detail by a crystal structure determination. In the first case, a tubular architecture performing methanol channels is displayed, however, in the second case a zigzag architecture generated by a chloroform network connecting calixarene molecules is present. Speciation in solution appears to be limited to the formation of 1:2 and/or 1:1 and/or 2:1 (M-L) complexes, depending on the system, with values of the stability constants determined by absorption spectroscopy in acetonitrile, lying in the ranges log β₁₂ ca. 10, log β₁₁ ca. 2-5, and log β₂₁ ca. 7-9. There is evidence for selectivity toward Cu(II) and for some unexpected anion effects. None of these ligands appear to be an efficient extractant for the metals as their picrate.     

Dichroisme circulaire d'olefines VI alkylidene-17 androstanes

The Cotton effect of 17-alkylidene (5α) androstanes is discussed. The large variations observed in the C.D. values indicated that the role of olefin torsion in the ground state is not significant. A semi quantitative approach based on A.B.P. model is suggested.     

Variations in Physicochemical Properties and Bioconversion Efficiency of <Emphasis Type="Italic">Ulva lactuca</Emphasis> Polysaccharides After Different Biomass Pretreatment Techniques

Green macroalgae are an abundant and undervalued biomass with a specific cell wall structure. In this context, different pretreatments, namely ethanol organosolv (Org), alkaline, liquid hot water (LHW), and ionic liquid (IL) pretreatments, were applied to the green macroalgae Ulva lactuca biomass and then evaluated. Their effects on chemical composition, biomass crystallinity, enzymatic digestibility, and theoretical ethanol potential were studied. The chemical composition analysis showed that the Org and LHW pretreatments allowed the highest glucan recovery (80.8 ± 3.6 and 62.9 ± 4.4 g/100 g DM, respectively) with ulvan (80.0 and 99.1%) and hemicellulose (55.0 and 42.3%) removal. These findings were in agreement with both thermogravimetric analysis and scanning electron microscopy results that confirm significant structural changes of the pretreated biomasses. It was found that the employed pretreatments did not significantly affect the cellulose crystallinity; however, they both increased the whole crystallinity and the enzymatic digestibility. This later reached 97.5% in the case of LHW pretreatment. Our results showed high efficiency saccharification of Ulva lactuca biomass that will constitute the key step of the implementation of a biorefinery process.     

Well‐defined phosphonate‐functional copolymers through RAFT copolymerization of dimethyl‐p‐vinylbenzylphosphonate

Dibenzyltrithiocarbonate‐mediated RAFT polymerization of dimethyl‐p‐vinylbenzylphosphonate and its copolymerization with styrene are studied in order to access well‐defined statistical and block copolymers containing controlled amounts of dimethylphosphonate groups. NMR and SEC analysis of the (co)polymers confirm the controlled character of the polymerizations. ABA triblock copolymers are treated with TMSiBr/MeOH in order to transform the dimethylphosphonate groups into phosphonic acids while keeping the midchain trithiocarbonate group and triblock nature unaffected. Alternatively, the combination of trithiocarbonate aminolysis with TMSiBr/MeOH treatment of the same triblock copolymers leads to phosphonic acid‐functional diblock copolymer counterparts. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 2616‐2624     

Uniform in bandwidth consistency of the kernel-type estimator of the Shannon's entropy

We establish uniform-in-bandwidth consistency for kernel-type estimators of the differential entropy. Our proofs rely on the methods of Einmahl and Mason (2005) [10].     

A theoretical study of the propagation of Rayleigh waves in a functionally graded piezoelectric material (FGPM)

An exact approach is used to investigate Rayleigh waves in a functionally graded piezoelectric material (FGPM) layer bonded to a semi infinite homogenous solid. The piezoelectric material is polarized when the six fold symmetry axis is put along the propagation direction x₁. The FGPM character imposes that the material properties change gradually with the thickness of the layer. Contrary to the analytical approach, the adopted numerical methods, including the ordinary differential equation (ODE) and the stiffness matrix method (SMM), treat separately the electrical and mechanical gradients. The influences of graded variations applied to FGPM film coefficients on the dispersion curves of Rayleigh waves are discussed. The effects of gradient coefficients on electromechanical coupling factor, displacement fields, stress distributions and electrical potential, are reported. The obtained deviations in comparison with the ungraded homogenous film are plotted with respect to the dimensionless wavenumber. Opposite effects are observed on the coupling factor when graded variations are applied separately. A particular attention has been devoted to the maximum of the coupling factor and it dependence on the stratification rate and the gradient coefficient. This work provides with a theoretical foundation for the design and practical applications of SAW devices with high performance.     

Quasihomogeneous Toeplitz operators on the harmonic Bergman space

In this paper we study the product of Toeplitz operators on the harmonic Bergman space of the unit disk of the complex plane \mathbbC{\mathbb{C}}. Mainly, we discuss when the product of two quasihomogeneous Toeplitz operators is also a Toeplitz operator, and when such operators commute.     

Synthesis of new liquid crystalline diglycidyl ethers

The phenolic Schiff bases I-VI were synthesized by condensation reactions between various diamines, namely o-dianisidine, o-tolidine and ethylenediamine with vanillin or p-hydroxybenzaldehyde and subsequent reactions between these phenolic Schiff bases and epichlorohydrin to produce new diglycidyl ethers Ia-VIa. The structures of these compounds were confirmed by CHN, FT-IR, (1)H-NMR, and (13)C-NMR spectroscopy. Their thermotropic liquid crystalline behavior was studied using differential scanning calorimetry (DSC) and polarizing optical microscopy (POM). All the diglycidyl ethers prepared exhibit nematic mesophases, except for Va and VIa, which did not show any transition mesophases, but simply flow to liquids.     

Kinetics and thermodynamics of sucrose crystallization from pure solution at different initial supersaturations

Growth rates of sucrose crystallization from pure solutions of initial relative supersaturation levels between 0.094 and 0.181 were studied in agitated crystallizer at 313.13 K. Birth and spread model was applicable for the obtained growth rate data in this range of supersaturation and used to estimate the principal growth parameters. The estimated interfacial free energy varied inversely with supersaturation from 0.00842 to 0.00461 J/m², respectively. The obtained kinetic coefficient changed with the initial supersaturation from 9.45 × 10^? 5 to 2.79 × 10^? 7 m/s. The corresponding radius of the 2D (two dimensional) critical nucleus varied from 7.47 × 10^? 9to 1.46 × 10^? 9 m. Predominance of surface integration or volume diffusion mechanism during the growth process was assessed using the calculated activation free energies of the 2D nucleation process. An acceptable confirmation of the calculated radius of the critical 2D nucleus was found using atomic force microscopy (AFM) technique. The calculated interfacial free energy between the saturated sucrose solution and the crystal surface was found to be 0.02325 J/m².