The “green” image of polyolefins

Polyolefins, because they are produced by non-toxic monomers such as ethylene and propylene and due to the minimum pollution impact during production and use and low-thermal capacity during processing, have achieved a recognized “Green image”. This environmentally friendly image is founded also on the ability of replacing a number of materials and the possibility of contributing to solve the growing problem of recycling plastic parts at the end of their life.     

A novel “green” synthesis of starch-capped CdSe nanostructures

This paper reports a “green” facile, room temperature, one-pot synthesis of starch-capped CdSe nanostructures with an obvious quantum confinement effect via a novel non-organometallic method. It is found that by simply tuning the Cd:Se molar ratio, dots and elongated particles of high aspect ratio could be prepared selectively in the presence of the same ligand concentration without any post-treatment. Spherical particles were produced at 1:1 ratio, while elongated particles were produced at 0.5:1 Cd:Se ratio. The X-ray diffraction (XRD) analysis showed that the particles were predominantly of wurtzite structure, with sharp diffraction patterns regardless of their size and shapes. We inferred that the elongated particles are formed by self-reorganisation occurring via adhesion between the spherical nanoparticles as a result of dipole–dipole interactions.     

Direct synthesis of terminally “clickable” linear and hyperbranched polyesters

1,3‐Dipolar cycloaddition of an organic azide and an acetylenic unit, often referred to as the “click reaction”, has become an important ligation tool both in the context of materials chemistry and biology. Thus, development of simple approaches to directly generate polymers that bear either an azide or an alkyne unit has gained considerable importance. We describe here a straightforward approach to directly prepare linear and hyperbranched polyesters that carry terminal propargyl groups. To achieve the former, we designed an AB‐type monomer that carries a hydroxyl group and a propargyl ester, which upon self‐condensation under standard transesterification conditions yielded a polyester that carries a single propargyl group at one of its chain‐ends. Similarly, an AB₂ type monomer that carries one hydroxyl group and two propargyl ester groups, when polymerized under the same conditions yielded a hyperbranched polymer with numerous “clickable” propargyl groups at its molecular periphery. These propargyl groups can be readily clicked with different organic azides, such as benzyl azide, ω‐azido heptaethyleneglycol monomethylether or 9‐azidomethyl anthracene. When an anthracene chromophore is clicked, the molecular weight of the linear polyester could be readily estimated using both UV–visible and fluorescence spectroscopic measurements. Furthermore, the reactive propargyl end group could also provide an opportunity to prepare block copolymers in the case of linear polyesters and to generate nanodimensional scaffolds to anchor a variety of functional units, in the case of the hyperbranched polymer. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 3200–3208, 2010     

Appraisal of “classic” and “novel” extraction procedure efficiencies for the isolation of polycyclic aromatic hydrocarbons and their derivatives from biotic matrices

In this study the extraction efficiency of pressurized liquid extraction (PLE), employing different extraction solvent mixtures under different extraction conditions, was compared with extraction efficiencies of commonly used procedures, Soxhlet extraction and extraction enhanced by sonication. Spruce needles and fish tissue were selected as test samples. Purification of obtained extracts was carried out by gel permeation chromatography (GPC) employing gel Bio-Beads S-X3. Identification and quantitation of target PAHs was performed by high-performance liquid chromatography with fluorescence detection (HPLC–FLD).

Within optimisation of PLE conditions, temperature of extraction, type of solvent, duration and number of static cycles as well as the influence of sample pre-treatment (drying, homogenisation, etc.) were tested. Comparison of the extraction efficiency of PLE with the efficiencies of the other techniques was done under the optimised conditions, i.e. sample slurry obtained by desiccation with anhydrous sodium sulphate, extracted at 100 °C in 1 cycle lasting 5 min. Hexane:acetone (1:1, v/v) was chosen as the most suitable extraction solvent for isolation of analytes from test samples.

Comparison of mentioned isolation techniques with respect to the amount of co-extracts, procedure blank levels and time and solvent volume demands was also done.     

“Superpermeability” and “pumping” of atomic hydrogen through palladium membranes

Permeation of atomic as well as molecular hydrogen through palladium membranes has been investigated experimentally in the temperature range from room temperature to 200 °C and at a higher incident flux of hydrogen atoms on palladium surface than in previous studies. The results demonstrate that phenomena of ‘superpermeability’ and ‘pumping’ of atomic gases through metal membranes are of a common nature. A theoretical model based on chemical thermodynamics and diffusion theory adequately describes the quantitative relationships observed in experiments. It was found that permeability of atomic hydrogen depends strongly on the magnitude of surface incident flux and membrane temperature.     

“Click polyester”: Synthesis of polyesters containing triazole units in the main chain via safe and rapid “click” chemistry and their properties

Click Cu(I)‐catalyzed polymerizations of diynes that contained ester linkages and diazides were performed to produce polyesters (click polyesters) of large molecular weights [(～1.0–7.0 ) × 10⁴], that contained main‐chain 1,4‐disubstitued triazoles in excellent yields. Incorporation of triazole improved the thermal properties and magnified the even‐odd effect of the methylene chain length. We also found that, by changing the positions of the triazole rings, the thermal properties of the polyesters could be controlled. The use of in situ azidation was a safe reaction, as explosive diazides are not used. In addition, the microwave heating was found to accelerate the polymerization rates. This is the first study that has applied click chemistry for the synthesis of a series of polyesters. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 4207–4218, 2010     

New polymer synthesis. LXXXIII. Synthesis of chiral and cholesteric polyesters from silylated “sugar diols”

A series of polycondensation was conducted with the purpose to optimize the reaction conditions for the polycondensation of silylated 2,3-isopropylidene D -threitol with a dicarboxylic acid dichloride. Polycondensation in o-dichlorobenzene or 1-chloronaphthalene at 180–230°C were found to be most satisfactory. Trifluoroacetic acid/H₂O allow an easy cleavage of the isopropylidene group without hydrolysis of the polyester. Ten cholesteric copolyesters were prepared by polycondensation of mixtures of silylated methylhydroquinone and isosorbide, isomannide, or 2,3-isopropylidene threitol with the dichloride of 1,10-bis(4′-carboxyphenoxy)decane. All these copolyesters form a broad cholesteric phase above 200°C. The copolyesters containing 5 or 10 mol % of a sugar diol display a blue Grandjean texture. © 1996 John Wiley & Sons, Inc.     

Semi‐rigid polyesters analysed using the “strong‐fragile” concept

Semi‐rigid polyesters from diphenyl dicarbonic acid and some branched propyl and butyl spacers have been investigated using Differential Scanning Calorimetry. From Δc_p at Tg and the determination of the fragility index m, we studied the “strong‐fragile” behaviour of these materials. All the samples appear thermodynamically “strong” and “kinetically” fragile. A comparison of these results with those obtained from glass‐forming liquids leading to linear polymers ‐ such as PET, PCT, PEN or poly‐methyl (α‐n‐alkyl) acrylates ‐ shows that a modification of the polymer rigidity leads to change the fragility index m and the Δc_p at the glass transition.