Disassembly via an environmentally friendly and efficient fluorous phase constructed with dendritic architectures

Traditionally the fluorous phase is generated with perfluorinated alkyl groups that are usually perfluorooctyl or longer and are bioaccummulative and biopersistent and therefore, are considered environmentally unfriendly. Here we report a new concept for the construction of the fluorous phase. This concept is based on the amplification of the fluorous effect with the help of dendritic architectures containing very short semifluorinated groups on their periphery. This new concept was demonstrated by the convergent synthesis of the first and second generation AB₃ and AB₂ benzyl ether dendrons functionalized on their periphery via catalytic nucleophilic addition of their phenolates to perfluoropropyl vinyl ether. The resulting dendrons are liquids. Their fluorous phase affinity was analyzed and demonstrated that the dendritic architecture amplifies the fluorous phase at a specific generation by the number of functional groups on the dendron periphery, and at different generations by increasing their generation number. Therefore, this concept is very efficient for the design and synthesis of new fluorous materials. In addition, by contrast with dendrons containing perfluoroalkyl groups on their periphery, the current dendrons mediate the disassembly of their parent building blocks but do not mediate the self‐assembly in a supramolecular architecture. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 2498–2508, 2010     

A new insight in the dynamo-mechanical behavior of poly(ethylene terephthalate)

Dynamic mechanical experiments performed on a semicrystalline sample of poly(ethylene terephthalate) evidenced the relaxation processes (α and β) that occur in the polymer. Multifrequency experiments were used both in order to calculate the apparent activation energy of relaxation and to point out how the dynamic conditions alter not only the main relaxations, but the overlapping melting/recrystallization events that succeed after the glass transition. Heating rate seems to affect these phenomena in a way similar to frequency. Also, a consecutive heating step was carried out to support the statements.     

Locally supported rational spline wavelets on a sphere

In this paper we construct certain continuous piecewise rational wavelets on arbitrary spherical triangulations, giving explicit expressions of these wavelets. Our wavelets have small support, a fact which is very important in working with large amounts of data, since the algorithms for decomposition, compression and reconstruction deal with sparse matrices. We also give a quasi-interpolant associated to a given triangulation and study the approximation error. Some numerical examples are given to illustrate the efficiency of our wavelets.

     

Widely tunable optical parametric oscillator driven by a pulsed diode-pumped nonlinear-mirror mode-locked Nd:YAG laser

We report on the development of a pulsed diode end-pumped Nd:YAG laser mode-locked by a nonlinear mirror and stabilized by an acousto-optical modulator. With the introduction of appropriate intracavity loss, the laser is able to generate 22.8 ps pulses with the energy of 4.5 μJ. After amplification and frequency doubling stages, the second harmonic radiation is used to non-collinearly synchronously pump a β-barium borate optical parametric oscillator in a walk-off compensated scheme. The system demonstrates a wide-tuning range from 635 nm to 2.55 μm for the signal output, with maximum average conversion efficiency as high as 42%.     

Mild and reliable cleavage sequence for phenoxy acetates

A novel combination of reliable transformations like ester saponification and subsequent Curtius-rearrangement employing mild reaction conditions, offers the first synthetically interesting strategy for the removal of methoxycarbonylmethyl groups from phenolic oxygens. This methodology gives also access to labile iodosubstituted phenols.     

A convenient synthesis of iminosugar-C-glycosides via organometallic addition to N-benzyl-N-glycosylhydroxylamines

N-Benzyl-N-glycosylhydroxylamines were prepared in very good yield via condensation of furanoses and pyranoses with N-benzylhydroxylamine at 110°C for 30 min under solvent-free conditions. These anomeric sugar-hydroxylamines exist in equilibrium with the open-chain nitrone form. In fact upon treatment with various organometallic reagents, the corresponding adducts were obtained with good to high diastereoselectivity. These adducts were converted into iminosugar-C-glycosides by reductive dehydroxylation and intramolecular cyclization.