Controlled synthesis of amphiphilic biodegradable polylactide‐grafted dextran copolymers

The whole controlled synthesis of novel amphiphilic polylactide (PLA)‐grafted dextran copolymers was achieved. The control of the architecture of such biodegradable and potentially biocompatible copolymers has required a three‐step synthesis based on the “grafting from” concept. The first step consisted of the partial silylation of the dextran hydroxyl groups. This protection step was followed by the ring‐opening polymerization of D ,L ‐lactide initiated from the remaining OH functions of the partially silylated polysaccharide. The third step involved the silylether group deprotection under very mild conditions. Based on previous studies, in which the control of the first step was achieved, this study is focused on the last two steps. Experimental conditions were investigated to ensure a controlled polymerization of D ,L ‐lactide, in terms of grafting efficiency, graft length, and transesterification limitation. After polymerization, the final step was studied in order to avoid degradation of both polysaccharide backbone and polyester grafts. The chemical stability of dextran backbone was checked throughout each step of the synthesis. PLA‐grafted dextrans and PLA‐grafted (silylated dextrans) were proved to adopt a core‐shell conformation in various solvents. Furthermore, preliminary experiments on the potential use of these amphiphilic grafted copolymers as liquid/liquid interface stabilizers were performed. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 2577–2588, 2004     

Working Methods Paper: Critical considerations with respect to the identification of tin species in the environment

Biogeochemical pathways of tin species in the environment are still controversial, e.g. with regard to methylation and transmethylation phenomena, owing to the fact that the identification of methylated tin-compounds is often difficult. The previous tentative identification of a mixed methylbutyltin compound in sediment and biological samples by GC/AAS after hydride generation gave an illustration of this problem. This compound was previously identified in sediments by other authors and also suspected to occur in a contaminated sediment sample from the Boyardville Marina, France. The retention time obtained by GC/AAS corresponded to the actual retention time of a mixed methylbutyltin calibrant. However, additional checks demonstrated that the compound detected was actually monophenyltin. This evidence was produced by a thorough analysis of a selected sediment sample by alternative techniques such as GC/AAS and GC/AES after pentylation, GC/FPD and GC/MS. The results presented highlight the need for a full identification of compounds to avoid mis-interpretation.     

Complex polymer architectures through dimethoxymethyl 1,1‐diphenylethylene derivatives

The reactions of polystyryllithium and potassium on dimethoxymethyl 1,1‐diphenylethylene derivatives were studied in different solvents. In a polar medium, A₃ and A₆ star types were formed according to the stoichiometry, whereas in a nonpolar medium, hyperbranched structures were synthesized. Extensions of an already proposed mechanism in polar and nonpolar media were examined. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 3329–3335, 2003     

351 nm, 0.7 ns laser damage thresholds of monomeric liquid-crystalline systems

The 351 nm laser-damage thresholds (at 0.7 nm pulse length) of monomeric liquid crystals are reported and results from aromatic-core samples are compared with those from fully saturated systems. The role of π-electron conjugation is examined and identified as the key cause for laser damage. For UV laser compatibility of devices, the damage behaviour of an alignment-layer polymer (nylon 6/6) was also investigated.     

Comprehensive study on the formation of polyelectrolyte complexes from (quaternized) poly[2‐(dimethylamino)ethyl methacrylate] and poly(2‐acrylamido‐2‐methylpropane sodium sulfonate)

Polyelectrolyte complexes (PECs) have been prepared from well‐defined (quaternized) poly[2‐(dimethylamino)ethyl methacrylate] (PDMAEMA) and high molecular weight poly(2‐acrylamido‐2‐methylpropane sodium sulfonate) (PAMPSNa) after a thorough study of their viscometric properties. The effect of pH and quaternization degree of PDMAEMA on PECs stoichiometry has been examined. PEC‐based materials have been characterized in terms of thermal stability, equilibrium swelling degree, and free/bound water composition. The stoichiometry and swellability of the physically crosslinked hydrogels obtained from fully quaternized PDMAEMA/PAMPSNa complexes do not depend on pH. In contrast, PECs made of non quaternized PDMAEMA and PAMPSNa are highly affected by pH, and could reversibly disintegrate at pH ≥ 9. Partially quaternized PDMAEMA/PAMPSNa PECs exhibit intermediate properties and form stable loose structures in the whole investigated pH range. Finally, stable dispersions of PECs nanoparticles have been successfully produced from dilute solutions of the complementary polyelectrolytes. The nanoparticle average diameter as determined by dynamic light scattering proved to depend on the molar fraction of DMAEMA‐based subunits and on the initial polyelectrolyte concentration. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 5468–5479, 2006     

Kristallstruktur von Hexamincyclotriphosphazen,P3N3(NH2)6

Crystal Structure of Hexamine Cyclotriphosphazene, P₃N₃(NH₂)₆ In the presence of KNH₂ hexamine cyclotriphosphazene semi ammoniate (molar ratio 12:1) in NH₃ gives crystals of solvent free P₃N₃(NH₂)₆ within 5 d at 130°C and p(NH₃) = 110 bar. The structure was solved by X-rax methods: P₃N₃(NH₂)₆: P2₁/c, Z = 4, a = 10.889(6) Å, b = 5.9531(6) Å, c = 13.744(8) Å, β = 97.83(3)°, Z(F_o) = 1 721 with (F_o)² ≥ 3σ(F_o)², Z(var.) = 157, R/R_w = 0,036/0,041 The structure contains columns of molecules P₃N₃(NH₂)₆ all in the same orientation. The six-membered rings within one molecule have boat conformation. The columns are stacked together in a way that one is surrounded by four others shifted by half a lattice constant in direction [010]. Strong hydrogen bridge-bonds N? H…?N connect molecules within the columns and between them.     

MECHANISM OF PHOTOREDUCTION OF THIAZINE DYES BY EDTA STUDIED BY FLASH PHOTOLYSIS-II. pH DEPENDENCE OF ELECTRON ABSTRACTION RATE CONSTANT OF THE DYES IN THEIR TRIPLET STATE

Abstract— The pH dependence of the apparent reactivity of thiazine dyes in their triplet states has been studied in aqueous solutions, using as electron donor HY^-3, the trianionic species of ethylene diamine tetraacetic acid (EDTA), in the pH range 4–8. The pH dependence is found to be related to a change in the degree of protonation of the triplet excited dye. The apparent reactivity and lifetime of two differently protonated forms of thionine, azur B and methylene blue were determined by classical and dye-laser flash techniques, making it possible to evaluate the rate constant for electron abstraction of these molecules in their triplet states. It is found that: (a) protonation on the ring nitrogen increases the electron-abstraction rate constant of the triplet-state species about twenty-fold, and (b) methylation on the side amino groups decreases it.     

Glass and polymeric membrane electrodes for the measurement of pH in milk and cheese

While there is a considerable interest in the food industry in determining various analytes using ion-selective electrodes (ISEs), only few reports describe their use for direct measurements in food. In this study, the suitability of glass electrodes and ionophore-based solvent polymeric ISEs for the determination of pH in Process cheese, Cheddar cheese and milk was investigated. The liquid junction potential between a 3 M KCl bridge electrolyte and diluted as well as undiluted Process cheese was found to be negligible. Reference electrodes with ceramic plug and sleeve-type junctions performed well, although precautions needed to be taken to prevent plugging at the junctions. While the protein rennet casein posed no problems in pH measurements, the extraction of neutral lipophilic compounds or hydrophobic peptides into solvent polymeric membranes was evident, resulting in some loss of selectivity for monovalent cations upon exposure to cheese. However, it was found that ISEs based on tridodecylamine (R₃N) as ionophore and o-nitrophenyl octyl ether (oNPOE) as plasticizer can be used to accurately measure the pH of milk and, after desensitization of the electrodes in a cheese emulsion, of diluted Process cheese. Since pH measurements with a glass electrode showed that emulsions of cheese moderately diluted to a cheese content of 70% have the same pH as undiluted cheeses, it is possible to determine the pH in cheese with ionophore-based ISEs. R₃N membranes also performed well in undiluted milk.     

Darstellung und Kristallstruktur von K3La(NH2)6

Preparation and Crystal Structure of K₃La(NH₂)₆. Single crystals of K₃La(NH₂)₆ were obtained by the reaction of the metals (3 K + 1 La) during five days at 200°C and 4000 atm NH₃ pressure. The compound crystallizes monoclinic with a = 6.74, b = 11.67, c = 7.23 Å and β = 108.1°; the space group is C2/m (No. 12). The lattice contains 2 formula units. The amide ions are arranged in a strongly distorted cubic closepacking. All cations occupy edging anion-octahedra.     

The solid state and solution chemistry of dichlorobis(α-picoline)-cobalt(II)

Summary The thermal decomposition of [CoCl₂(-pic)₂] was investigated over the 108°C to 222°C range and the Intennediates CoCl₂(-pic) (s) and CoCl₂ (s) were observed, with the evolution of (-pic) (g). Quantitative thermodynamic and kinetic data were obtained by performing dynamic and isothermal studies on the complex Additional thermodynamic data were obtained by studying the CoCl₂/-pic system in acetone. The effect of the methylsubstituent on the metal-donor-N bond as well as on the thermodynamic quantities were discussed.