Effect of chain unsaturation on the self-association of tri- and tetraethylene glycol octyl ethers obtained by butadiene telomerization

2,7-Octadienyl ethers of tri- and tetraethylene glycol (C(8:2)E(3) and C(8:2)E(4)) have been synthesized by the atom-economical butadiene telomerization of the corresponding poly(ethylene glycols). On one hand, this synthetic path is attractive because it is expeditious and environmentally benign, and on the other hand, it provides unconventional amphiphiles for which the lipophilic chains possess two double bonds. These two unsaturations increase the global hydrophilicity of the compound, which is also highlighted by the modelization of the compounds using the conductor-like screening model for real solvents (COSMO-RS). The behavior of C(8:2)E(3) and C(8:2)E(4) in binary amphiphile/water and ternary amphiphile/oil/water systems is therefore greatly modified compared to that of the conventional fully saturated homologues (C(8)E(3) and C(8)E(4)) that are easily obtained after hydrogenation. This results in a lowered efficiency of the unsaturated compounds for oil solubilization. The usual Winsor-type microemulsion systems are formed, and for the same oil, the DLS investigation of the microstructure of the Winsor I microemulsion does not highlight any difference in the self-association between the unsaturated and saturated compounds.     

Group additivity values for estimating the enthalpy of formation of organic compounds: an update and reappraisal. 2. C, H, N, O, S, and halogens

This study extends a previous publication on group additivity values (GAVs) for the elements C, H, and O, to include the elements nitrogen, sulfur, and the halogens. The present state and utility of the Benson additivity schemes for estimating the enthalpy of formation (Δ(f)H(0)) of organic compounds are again described, extending them to include more elements. Old and new GAVs for a wide variety of compounds are provided and are revised where necessary. When new terms are proposed, or old ones are significantly altered, the rationale for so doing is presented. GAV derived ring strain values for benzene and pyridine indicate that the aromatic stabilization of each is essentially the same. As before, the thermochemical consequences of replacing one functional group by another are also shown, thus permitting quick shortcuts to the estimation of new Δ(f)H(0) values.     

Optimal focusing by spatio-temporal inverse filter. I. Basic principles

A focusing technique based on the inversion of the propagation operator relating an array of transducers to a set of control points inside a medium was proposed in previous work [Tanter et al., J. Acoust. Soc. Am. 108, 223-234 (2000)] and is extended here to the time domain. As the inversion of the propagation operator is achieved both in space and time, this technique allows calculation of the set of temporal signals to be emitted by each element of the array in order to optimally focus on a chosen control point. This broadband inversion process takes advantage of the singular-value decomposition of the propagation operator in the Fourier domain. The physical meaning of this decomposition is explained in a homogeneous medium. In particular, a definition of the number of degrees of freedom necessary to define the acoustic field generated by an array of limited aperture in a focal plane of limited extent is given. This number corresponds to the number of independent signals that can be created in the focal area both in space and time. In this paper, this broadband inverse-focusing technique is compared in homogeneous media with the classical focusing achieved by simple geometrical considerations but also with time-reversal focusing. It is shown that, even in a simple medium, slight differences appear between these three focusing strategies. In the companion paper [Aubry et al., J. Acoust. Soc. Am. 110, 48-58 (2001)] the three focusing techniques are compared in heterogeneous, absorbing, or complex media where classical focusing is strongly degraded. The strong improvement achieved by the spatio-temporal inverse-filter technique emphasizes the great potential of multiple-channel systems having the ability to apply completely different signal waveforms on each transducer of the array. The application of this focusing technique could be of great interest in various ultrasonic fields such as medical imaging, nondestructive testing, and underwater acoustics.     

Prolinoamino acids as a tool to stabilize β-turns with the side chain of natural amino acids

Molecular mechanics calculations, X-ray, FT-IR, and NMR analysis performed on Piv-d-Pro^c_l-l-Pro-NHMe (d-Pro^c_l=a proline/leucine chimera) show that it possesses a water stable type II^′ β-turn structure. The isopropyl side chain of d-Pro^c_l compares with the leucine side chain of a typical type I β-turn found in a protein (taken from the PDB). Thus cis-3-substituted prolines with the appropriate side chain can be used to mimic type I, II or II^′ β-turns and incorporate the side chain functionalities on both the i+1 and i+2 positions of β-turns.     

Thermal expansion imaging and finite element simulation of hot lines in high power AlGaN HEMT devices

The temperature and thermo-elastic expansion of the heated area in a high power, high electron mobility transistor (HEMT) device have been investigated by means of finite element calculations and scanning thermal expansion microscopy. With both procedures a hot line is located near the gate line of the transistor. To determine the absolute temperature, the thermo-elastic response was calibrated on the basis of the force–distance curve of the AFM and the thermal expansion of the gold layer on top of the heated areas. The maximum temperatures deduced by the two procedures are in reasonable agreement whereas discrepancies are found for the temperature profile of the hot line, pointing towards a possible influence of the large aspect ratio of the device on the thermo-elastic measurement.     

The effects of pH and alcoholic organic modifiers on the direct separation of some acidic,basic and neutral compounds on a commercially available ovomucoid column

Summary The effects of alcoholic modifiers and pH on the chromatographic properties of an immobilized ovomucoid chiral stationary phase have been investigated using acidic, basic and neutral solutes. A series of primary, secondary and tertiary alcohols and pH's ranging from 3.5 to 6.0 were used in this study. The results indicate that both the shape and the hydrophobicity of the alcoholic modifier affect retention (k') and enantioselectivity (). In general, an increase in the hydrophobicity of the modifier results in a decrease in k's and 's. However, this is not the case whent-butanol is the modifier, suggesting that the size of the alkyl moiety attached to the carbinol carbon also contributes to the chromatographic results. The pH studies indicated that Coulombic interactions play a role in the retention of the acidic and basic solutes. The results also suggest that in addition to ethanol and 1-propanol,t-butanol should be considered during optimization and that maximum efficiencies may be obtained at pH 5.0.     

Scaling properties of a structure intermediate between quasiperiodic and random

We consider a one-dimensional structure obtained by stringing two types of beads (short and long bonds) on a line according to a quasiperiodic rule. This model exhibits a new kind of order, intermediate between quasiperiodic and random, with a singular continuous Fourier transform (i.e., neither Dirac peaks nor a smooth structure factor). By means of an exact renormalization transformation acting on the two-parameter family of circle maps that defines the model, we study in a quantitative way the local scaling properties of its Fourier spectrum. We show that it exhibits power-law singularities around a dense set of wavevectorsq, with a local exponent(q) varying continuously with the ratio of both bond lengths. Our construction also sheds some new light on the interplay between three characteristic properties of deterministic structures, namely: (1) a bounded fluctuation of the atomic positions with respect to their average lattice; (2) a quasiperiodic Fourier transform, i.e., made of Dirac peaks; and (3) for sequences generated by a substitution, the number-theoretic properties of the eigenvalue spectrum of the substitution.     

Dielectrophoresis of nanoparticles

A numerical scheme based on the distributed Lagrange multiplier method (DLM) is used to study the motion of nano-sized particles of dielectric suspensions subjected to uniform and nonuniform electric fields. Particles are subjected to both electrostatic and hydrodynamic forces, as well as Brownian motion. The results of the simulations presented in this paper show that uniform electric fields the evolution of the particle structures depends on the ratio of electrostatic particle-particle interactions and Brownian forces. When this ratio is of the order of 100 or greater, particles form stable chains and columns, whereas when it is of the order of 10 or smaller the particle distribution is random. For the nonuniform electric field cases considered in this paper, the relative magnitude of Brownian forces is in the range such that it does not influence the eventual collection of particles by dielectrophoresis and the particular locations where the particles are collected. However, Brownian motion is observed to influence the transient particle trajectories. The deviation of the particle trajectories compared to those determined by the electrostatic and hydrodynamic forces alone is characterized by the ratio of Brownian and dielectrophoretic forces.