Heterograft copolymers of poly(ε‐caprolactone) prepared by combination of ATRA “grafting onto” and ATRP “grafting from” processes

This paper aims at reporting on the synthesis of a heterograft copolymer by combining the “grafting onto” process based on atom transfer radical addition (ATRA) and the “grafting from” process by atom transfer radical polymerization (ATRP). The statistical copolymerization of ε‐caprolactone (εCL) and α‐chloro‐ε‐caprolactone (αClεCL) was initiated by 2,2‐dibutyl‐2‐stanna‐1,3‐dioxepane (DSDOP), followed by ATRA of parts of the chlorinated units of poly(αClεCL‐co‐εCL) on the terminal double bond of α‐MeO,ω‐CH₂?CH? CH₂? CO₂‐poly(ethylene oxide) (PEO). The amphiphilic poly(εCL‐g‐EO) graft copolymer collected at this stage forms micelles as supported by dynamic light scattering (DLS) and transmission electron microscopy (TEM). The unreacted pendant chloro groups of poly(εCL‐g‐EO) were used to initiate the ATRP of styrene with formation of copolymer with two populations of randomly distributed grafts, that is PEO and polystyrene. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 6015–6024, 2006     

Study on the retention behaviour of low-molar-mass polystyrenes and polyesters in reversed-phase liquid chromatography by evaluation of thermodynamic parameters

Polymers can be characterized under sorption conditions, to obtain information on molar mass and chemical composition. In order to get a better understanding of their retention behaviour under such conditions, the evaluation of thermodynamic parameters obtained from van't Hoff analyses on low-molar-mass polystyrenes (PS) and polyesters (PE) in various THF–water mixtures on a C₁₈ column is described in this study. Linear van't Hoff behaviour was observed in almost all cases. Negative values for both ΔH and ΔS were found for both PS and PE oligomers, which increase with increasing %THF. For ΔS this is explained from multi-site attachment effects. For PS, the non-linear relations between ΔH and ΔS, and degree of polymerization (p) could be properly described by the Stockmayer–Fixman equation. Although less clear, similar trends were found for PE. For PS, evidence for penetration effects of oligomer chains into the bonded chains was obtained. Martin plots for both PS and PE were shown to be non-linear in all investigated eluent compositions. The extent of non-linearity is suggested to depend on the conformation of a polymer in solution. No distinct enthalpy–entropy-compensation temperature (EECT) independent of p was found for PS, thus confirming the findings of an earlier study in which no exact molar mass independence was found under critical conditions. Further evaluation of EECT for PS oligomers revealed a retention mechanism independent of the binary eluent composition. This indicates that conclusions from this study can also be used for a qualitative understanding of sorption mechanisms in the gradient elution mode. Finally, for PS it was shown that ΔG equals zero under critical conditions, thus confirming theoretical predictions.     

Etude de la réaction de l'acétylacétone avec les diamines hétéroaromatiques

The inluence of the starting o-diamine on the reaction products is shown in the condensation of heteroaromatic o-diamines with acetylacetone; 2,3- and 3,4-diaminopyridines gave only a crotonic intermediate providing imidazopyridines. On the other hand, 1,5-diaminoimidazoles gave tow types of compounds, imidazotriazepines and imidazopyridines. Triazolopyridazines were formed from 3,4-diaminotriazoles.     

Gamma-ray spectroscopy with relativistic exotic heavy-ions

Feasibility of gamma-ray spectroscopy at relativistic energies with exotic heavy-ions and new generation of germanium detectors (segmented Clover) is discussed. An experiment with such detector array and radioactive is discussed.     

A multipotential hydrolytic reactor using the yeast strainKluyveromyces marxianus

In previous publications, we described the continuous production of D-fructose from enzymatic hydrolysis of inulin with immobilized permeabiliized cells ofKluyveromyces marxianus and the increase of productivity obtained by using a mutant selected by NTG action on the wild-type strain. By improving reactor performance, it has been possible to reach 2000 g/L/d of liberated sugar from an inulin solution with the mutant strain.

In addition, it has been shown that the KF 28 mutant was an invertase and pectinase hyperproducer. These enzymatic activities are also secreted by the speciesKluyveromyces marxianus. Therefore, we investigated the possibility of using immobilized cells of this yeast as a multipotential hydrolysis reactor. A sucrose hydrolysis reactor and a pectin hydrolysis reactor were set up. It is shown here that the majority of the optimized parameters from the inulin hydrolysis reactor can be transported directly to the other reactors. However, some parameters have to be adapted, especially for pectin hydrolysis.