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     

Synthesis of Organic-Inorganic Hybrid Particles by Sol-Gel Chemistry

The synthesis of ORganically MOdified SILica (ORMOSIL) particles has been carried out using both the hydrolytic and non-hydrolytic sol-gel routes. The hybrid (nano)composites are organically modified with an alkyl or aryl group covalently bonded to silicon. Hybrids have been synthesised in an aqueous sol-gel process by a modified Stöber route, producing spherical nanoparticles with diameters in the range 50–300 nm. The size of the particles can be controlled by control of certain reaction parameters. Smaller ormosil nanoparticles can be synthesised by a base-catalysed emulsion polymerisation route, by varying the type and concentration of surfactant and precursor feed rate. In this case, particles in the size range 3.5–10 nm can be obtained. Hybrids have been synthesised from hyperbranched polyesters by encapsulation in a silica matrix using the hydrolytic sol-gel route. Optimisation of the reaction conditions allows the hybrids to be produced as isolated sub-micron spherical particles. Ormosil particles have also been synthesised using the non-hydrolytic sol-gel route, which may lead to products of different morphologies because of the different polarity of the reaction medium. Different reaction conditions were studied in order to optimise the size and shape of the particles, including choice of solvent, use of surfactants and addition of polystyrene. Dimethylsulfoxide acts as a novel oxygen donor for the catalyst-free formation of colourless silsesquioxanes.     

Adsorption Behaviour of 134Cs and 22Na Ions on Tin and Titanium Ferrocyanides

Tin and titanium ferrocyanides were studied as adsorbents for alkali metal ions, viz., ¹³⁴Cs and ²²Na, which represent radioactive wastes. The ferrocyanides were prepared in granular form. The tin version contained 11.2% water, while the titanium version contained 17.7% water. The exchange capacities for Cs⁺ and Na⁺ in the hydrated tin version were about 1.5 and 0.7 meq/g, respectively, while those in the titanium version were 2.2 and 1.2 meq/g, respectively. Drying at 250°C decimated those capacities. The diffusional time constant of Cs⁺ at 25°C, determined via Fick's second law, was of order of magnitude 1 × 10^–3 s^–1, though there were minor differences due to particle size and the form of ferrocyanide. Similarly, the effective diffusivity was of order of magnitude 1 × 10^–8 cm²/s. The titanium version responded slightly faster than the tin version. Likewise, equilibrium measurements in mixtures with sodium nitrate, potassium nitrate, or uranium oxide, showed that the titanium version exhibited significantly greater selectivity for Cs⁺ than did the tin version. Unfortunately, tests of complete elution of the Cs⁺ from the ferrocyanides were mostly disappointing. Work continues on that subject.     

Planar Chromatography of Some 1-Arylpiperazines Behaving as Dopaminergic Ligands

JPC – Journal of Planar Chromatography – Modern TLC - The chromatographic behavior of fourteen 1-arylpiperazine derivatives has been studied by thin-layer chromatography on both silica...     

Understanding the quality concept in health care

During the past three decades there has been an intense debate on the quality of health care. Errors in medicine, practice variations, competence of physicians, scarcity and lack of resources have all been reasons for discussing the quality of care. A clear definition of quality should explain the nature of the debate, improve uniformity of speech and facilitate meaningful actions such as quality assurance or quality improvement. However, in due course many different definitions have been proposed and principles of quality assurance in health care have been frequently questioned, because of their industrial nature. It raises questions on our understanding of quality in health care. In this paper, we (i) explore the nature of the quality concept, (ii) explain its meaning by Wittgenstein's theory on rule-following, and (iii) argue for understanding medical care as a reflexive practice, in order to integrate the meaning of quality in medical care.     

Analysis of Glycosides and Aglycones of Flavonoid Compounds by Double-Development Thin-Layer Chromatography

JPC – Journal of Planar Chromatography – Modern TLC - Flavonoid glycosides are much more polar than their aglycones and the two groups of compounds are difficult to separate by planar...     

Novel,organosoluble, light‐colored fluorinated polyimides based on 2,2′‐bis(4‐amino‐2‐trifluoromethylphenoxy)biphenyl or 2,2′‐bis(4‐amino‐2‐trifluoromethylphenoxy)‐1,1′‐binaphthyl

Two series of fluorinated polyimides were prepared from 2,2′‐bis(4‐amino‐2‐trifluoromethylphenoxy)biphenyl ( 2 ) and 2,2′‐bis(4‐amino‐2‐trifluoromethylphenoxy)‐1,1′‐binaphthyl ( 4 ) with various aromatic dianhydrides via a conventional, two‐step procedure that included a ring‐opening polyaddition to give poly(amic acid)s, followed by chemical or thermal cyclodehydration. The inherent viscosities of the polyimides ranged from 0.54 to 0.73 and 0.19 to 0.36 dL/g, respectively. All the fluorinated polyimides were soluble in many polar organic solvents, such as N,N‐dimethylacetamide and N‐methylpyrrolidone, and afforded transparent and light‐colored films via solution‐casting. These polyimides showed glass‐transition temperatures in the ranges of 222–280 and 257–351 °C by DSC, softening temperatures in the range of 264–301 °C by thermomechanical analysis, and a decomposition temperature for 10% weight loss above 520 °C both in nitrogen and air atmospheres. The polyimides had low moisture absorptions of 0.23–0.58%, low dielectric constants of 2.84–3.61 at 10 kHz, and an ultraviolet–visible absorption cutoff wavelength at 351–434 nm. Copolyimides derived from the same dianhydrides with an equimolar mixture of 4,4′‐oxydianiline and diamine 2 or 4 were also prepared and characterized. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 2416–2431, 2004     

Synthesis and characterization of well‐defined diblock and triblock copolymers of poly(N‐isopropylacrylamide) and poly(ethylene oxide)

Well‐defined diblock and triblock copolymers composed of poly(N‐isopropylacrylamide) (PNIPAM) and poly(ethylene oxide) (PEO) were successfully synthesized through the reversible addition–fragmentation chain transfer polymerization of N‐isopropylacrylamide (NIPAM) with PEO capped with one or two dithiobenzoyl groups as a macrotransfer agent. ¹H NMR, Fourier transform infrared, and gel permeation chromatography instruments were used to characterize the block copolymers obtained. The results showed that the diblock and triblock copolymers had well‐defined structures and narrow molecular weight distributions (weight‐average molecular weight/number‐average molecular weight < 1.2), and the molecular weight of the PNIPAM block in the diblock and triblock copolymers could be controlled by the initial molar ratio of NIPAM to dithiobenzoate‐terminated PEO and the NIPAM conversion. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 4873–4881, 2004