Etudes sur les fibres naturelles et de synthèse

Résumé Nous avons mesuré, en fonction de la température, le degré de gonflement dans l'eau de fibres de collagène amorphes qui ont été tannées différemment, ceci dans le but de pouvoir déterminer, pour chaque degré de tannage (pontage chimique) la chaleur de mélange du collagène amorphe sec avec l'eau de gonflement. En utilisant la théorie relative au gonflement des réseaux polymériques amorphes dans un excès de diluant, on a pu montrer que le paramètre thermodynamiqueχ ₁ caractéristique du système collagène-eau (paramètre deFlory-Huggins) varie avec la composition du réseau gonflé. Par contre, le paramètre ?enthalpique? correspondantϰ ₁=− =−0,34 est indépendant de cette composition. La chaleur de mélangeΔH _mél/V ₀ d'un cm³ de collagène amorphe sec avec l'eau de gonflement peut être calculée pour les différents degrées de tannage. Elle a le signe deϰ ₁, i. e. elle est négative et est donnée par:ΔH _mél/V ₀=RT gK₁(1−v₂ ^éq). Sa valeur absolue est donc d'autant moins importante que le degré de tannage des fibres est poussé; v₂ ^éq augmente en effet avec la concentration en liens intermoléculaires introduits dans les échantillons. La variation d'enthalpie accompagnant la transformation d'une fibre de collagène cristalline sèche en fibre amorphe gonflée (enthalpie de rétraction dans l'eau) diminuée de la chaleur de mélange correspondant au gonflement de la fibre amorphe sèche dans l'eau donne la chaleur de fusion du collagène sec. Cette quantité est égale à:ΔH/V ₀=28±1,5 cal./cm³ et est indépendante du degré de tannage comme on doit s'y attendre.

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Summary We have measured the temperature dependence of the swelling of amorphous collagen fibres of different degrees of tanning in an excess of water. This was done for the purpose of determining the heat of mixing of amorphous dry collagen with the equilibrium swelling water for each degree of tanning (chemical crosslinking). Using the theory of swelling of polymeric networks in an excess of diluent we were able to show that the parameterχ ₁ of the system collagen-water (Flory-Huggins parameter) is a function of the composition of the swollen network. On the other hand, the energy parameterϰ ₁=− =−0,34 is found to be concentration independent. The heat of mixingΔH _mél/V ₀ of 1 cm³ of dry amorphous collagen with the equilibrium swelling water can be calculated for the different degrees of tanning. It has the same sign asϰ ₁, i. e. is negative, and is given byΔH _mél/V ₀=RTϰ ₁ (1−v₂ ^éq). Its absolute value decreases therefore with increasing degrees of tanning, sincev ₂ ^éq increases with the density of the cross-links in the sample. The change in heat content on transforming 1 cm³ of dry crystalline collagen fibre into amorphous swollen fibre (heat of shrinking in water), decreased by the heat of swelling of the dry amorphous fibre in water, gives the heat of fusion of dry collagen. This latter equalsΔH/V ₀=28±1.5 cal/cm³ and is, as expected, independent of the degree of tanning.

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Zusammenfassung Um die Mischungsw?rme des amorphen trockenen Kollagens mit dem Quellungswasser zu bestimmen, wurde die Temperaturabh?ngigkeit des Quellungsgrades von verschieden stark gegerbten amorphen Kollagenfasern gemessen. Auf Grund der Theorie der Quellung von amorphen polymeren Netzwerken in einem überschu? von Quellungsmittel konnte gezeigt werden, da? der thermodynamische (Flory- Huggins) Parameterχ ₁ für das System Kollagen-Wasser vom Quellungsgrad des Netzwerkes abh?ngt. Hingegen ist der Enthalpieparameterϰ ₁=− =−0,34 davon unabh?ngig. Die Mischungsw?rmeΔH _mél/V₀ eines cm³ trockenen amorphen Kollagens mit dem Quellungswasser kann für verschiedene Gerbungsgrade (Vernetzungsgrade) berechnet werden. Sie hat das gleiche Vorzeichen wieϰ ₁ d. h. ist negativ, und gehorcht der Gleichung:ΔH _mél/V ₀=RTϰ ₁ (1−v₂ ^éq). Der Betrag der Mischungsw?rme ist um so kleiner, je h?her der Gerbungsgrad der Faser ist; in der Tat w?chstv ₂ ^éq mit der Konzentration der Vernetzungspunkte an. Wenn von der Enthalpie?nderung, welche mit dem übergang von einer trockenen kristallinen Faser zu einer gequollenen amorphen verbunden ist, (Schrumfungsenthalpie im Wasser), die oben definierte QuellungsenthalpieΔH _mél/V ₀ abgezogen wird, so bleibt die Schmelzw?rme des trockenen Kollagens übrig. Diese Schmelzw?rme betr?gt:ΔH/V ₀=28±1,5 cal./cm³ und ist, wie zu erwarten, vom Vernetzungsgrad (Gerbungsgrad) des Fadens unabh?ngig.

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Travail effectué au Laboratoire de Chimie-Physique de l'Université de Liège, Liège (Belgique).     

Reaction of 5-allyl-2,5-dichloro-4,4-dimethoxy-3-morpholinocyclopent-2-enone with Me3SiI

5-Allyl-2,5-dichloro-4,4-dimethoxy-3-morpholinocyclopent-2-enone reacts with Me₃SiI in MeCN to give the corresponding product of reductive vinylic monodechlorination. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1660–1661, August, 1998.     

Nonlinear schrödinger equations and intermolecular interactions

Nonlinear time-independent Schr6dinger equations arise if the model Hamiltonian depends on the wave function. This may occur if certain interactions are accounted for in an averaged manner, for example, if a moleule is embedded into a polarizable medium. Arguments are given in favor of the perturbational solution which facilitate the treatment of nonlinearity effects. Two examples are discussed: the case of a polarizable environment and the effective correction of the basis set superposition error.     

Influence de la structure sur les proprietes mesomorphes de polyesters—III

A new homogous series of thermotropic mesomorphic polyesters with high inherent viscosity has been synthesized. Mesogenic elements

are separated by flexible spacers CO(CH₂)_nCO in the backbone. A study of their mesomorphic properties is reported.     

Styrene emulsion polymerization: Particle-size distributions

Data are presented on the time evolution of particle-size distributions (PSDs) in seeded and ab initio styrene emulsion polymerization systems. Initiation was by chemical reagent (potassium persulfate) or γ-radiation. The unswollen PSDs at various times during interval II of the polymerization were obtained by direct measurement of calibrated electron micrographs. Experimental results were fitted with the equations that describe the time evolution of an initial PSD. Analytic solutions to these equations that allow for entry, exit, and propagation of free radicals were obtained. The values of the rate coefficients for these processes used to fit the experimental data were in excellent agreement with those obtained from dilatometric kinetics experiments.     

A COMPARISON OF MAMMALIAN CELL SENSITIVITY TO EITHER 254 nm OR ARTIFICIAL "SOLAR" SIMULATED RADIATION

The sensitivity of six mammalian cell strains to either germicidal (254 nm) or artificial "solar" simulated radiation was tested. The solar simulator used had an output similar, in some respects, to natural sunlight. Cellular capacity for Herpes simplex virus production was used as the assay procedure. The tested cells were a strain of African green monkey kidney cells and five human skin fibroblast cell strains. The latter included a "normal" cell strain, and four photosensitive cell strains; three of which were strains of xeroderma pigmentosum cells, and one strain of Bloom's syndrome cells. When comparing the D¹⁰ values, the different cell strains varied by a factor of six in response to germicidal radiation, but only by a factor of two to artificial "solar" simulated radiation. The relative sensitivity of the cells to either type of radiation also varied from 1.7 to 10.9. Large variations in response occurred even among the xeroderma pigmentosum cell strains. These responses suggest that mammalian cell sensitivity to 254 nm radiation may not be a true indicator of a cell's responses to natural sunlight.     

Detection of toluene diisocyanate with a coated quartz piezoelectric crystal: Part 3. Practical coatings for a humidity-corrected detector

Dithizone and tri-n-octylphosphine oxide (TOPO) were tested as coatings for quartz piezoelectric crystals to be used in a detector for touene diisocyanate (TDI). Cobalt(II) chloride and polyethylene glycol (PEG) with molecular weights of 400 and 1540 were tested for suitability as coatings for detecting humidity variations so that correction for humidity could be obtained from a two-crystal system. Sensitivities for TDI of 12 and 75 Hz ppm^?1 were found with dithizone and TOPO, respectively, between 0 and 1 ppm TDI. Cobalt chloride-coated crystals showed a sensitivity for water of 0.053 Hz ppm^?1 at 8000 ppm water and about 40 Hz ppm^?1 for TDI at the 2 ppm level. PEG-400 and PEG-1540 provided sensitivities to water of 0.038 and 0.051 Hz ppm^?1 respectively, and the response was linear over the range 9000—13 000 ppm water. All coatings showed irreversible behaviour towards TDI.     

Polysaccharides ofEremurus. X. Characteristics of the polysaccharides ofEremurus lactiflorus andE. luteus

Water-soluble polysaccharides have been isolated from two species ofEremurus — E. lactiflorus andE. luteus — with yields of 13.5% and 20.5%, respectively. They contained mainly glucose and mannose in ratios of 1:5 and 1:3.1. The polysaccharides ofE. lactiflorus were separated from a column of DEAE-cellulose. The yield of neutral fraction was 10.3%. Gel filtration of the polysaccharides on Sephadex G-200 showed their polydispersity. Homogeneous fractions were obtained by fractional precipitation with ethanol. They have been characterized with respect to monosaccharide composition, molecular weight, and IR spectra.     

Decarbonylation of N-carbazolylacetyl chloride in the friedel-crafts acylation reaction

Reaction products of N-carbazolylacetyl chloride under Friedel-Crafts reaction conditions include carbon monoxide, the reaction product from carbazole and formaldehyde (CF condensate), and carbazole. It is postulated that decarbonylation of N-carbazolylacetyl chloride involves intermediate formation of a N-carbazolylmethyl cation.