Transient electric birefringence study of agarose aggregates in water-dimethyl sulphoxide mixtures

The dynamical behavior of agarose aggregates in a mixture of water and dimethyl sulphoxide (DMSO) has been investigated using a Transient Electric Birefringence (TEB) set up. Different agarose concentrations for different water/DMSO proportions were considered. The relaxation of the birefringence curves can be fitted with a stretched exponential of the form Δn(t) = Δn0 exp(-(Dt)^0.5). The exponent 0.5 suggests a high polydispersity of the aggregates. The rotational diffusion coefficient, D, depends strongly on the water/DMSO proportion. For small values of the applied electric field it presents a maximum for a water volume fraction equal to 0.5. A strong dependence of D on the applied electric field is also observed. However, the same kind of behavior as for weak fields is recovered when a subtle representation of the data is used. Differential Scanning Calorimetry (DSC) results also show a maximum in the temperature of fusion of the aggregates for a water volume fraction of 0.5. This set of results suggest strongly that « complexes » of water/DMSO/agarose are formed in the mixture and that the process of aggregate formation is more « efficient » for a water/DMSO mixture of same proportions.     

Improvement of Ethanol Yield from Glycerol via Conversion of Pyruvate to Ethanol in Metabolically Engineered <Emphasis Type="Italic">Saccharomyces cerevisiae</Emphasis>

The conversion of low-priced glycerol to higher value products has been proposed as a way to improve the economic viability of the biofuels industry. In a previous study, the conversion of glycerol to ethanol in a metabolically engineered strain of Saccharomyces cerevisiae was accomplished by minimizing the synthesis of glycerol, the main by-product in ethanol fermentation processing. To further improve ethanol production, overexpression of the native genes involved in conversion of pyruvate to ethanol in S. cerevisiae was successfully accomplished. The overexpression of an alcohol dehydrogenase (adh1) and a pyruvate decarboxylase (pdc1) caused an increase in growth rate and glycerol consumption under fermentative conditions, which led to a slight increase of the final ethanol yield. The overall expression of the adh1 and pdc1 genes in the modified strains, combined with the lack of the fps1 and gpd2 genes, resulted in a 1.4-fold increase (about 5.4 g/L ethanol produced) in fps1Δgpd2Δ (pGcyaDak, pGupCas) (about 4.0 g/L ethanol produced). In summary, it is possible to improve the ethanol yield by overexpression of the genes involved in the conversion of pyruvate to ethanol in engineered S. cerevisiae using glycerol as substrate.     

Identification de la relation de dispersion dans les barresIdentification of the dispersion relation in rods

Dispersion and attenuation of longitudinal waves in elastic or weakly viscoelastic rods are measured by analysing the resonant frequencies present in the strain spectrum due to an unknown loading. The method takes the finite measuring time of the test into account. It is applied to an aluminium bar, in which the dispersion relation is identified very accurately at frequencies up to 60 kHz. To cite this article: R. Othman et al., C. R. Mecanique 330 (2002) 849–855.     

Ternary complexes in gels from agarose and from chemically‐modified agarose

Thermodynamic data and mechanical measurements are shown for gels prepared in aqueous binary solvents (water/DMSO, water/DMF, water/methyl formamide and water/formamide). When electrostatic interactions, as opposed to hydrogen bonding, can be established with the cosolvent (DMSO, DMF, methyl formamide) we come to the conclusion that ternary complexes are formed (agarose/water/cosolvent). In the case of chemically‐modified agarose (OH groups replaced by OCH₃ groups) we suggest that these cosolvents are directly involved in the formation of the gel.     

Poly(ethylene glycol)--oligolactates with monodisperse hydrophobic blocks: preparation, characterization, and behavior in water

Methoxypoly(ethylene glycol)-b-oligo-L-lactate (mPEG-b-OLA) diblock oligomers with monodisperse OLA blocks were obtained by fractionation of polydisperse block oligomers using preparative HPLC. The fractionated oligomers were composed of an mPEG block with a molecular weight of 350, 550, or 750 and an OLA block with a degree of polymerization of 4, 6, 8, or 10. The diblock oligomers with a low PEG content were fully amorphous, with glass transition temperatures ranging from -60 to -20 degrees C, indicating that the blocks were miscible. Upon heating aqueous dispersions of the block oligomers, cloud points, depending on the PEG/OLA ratio of the block oligomer, were observed at temperatures above 40 degrees C. The monodispersity of the hydrophobic block enabled the amphiphilic molecules to form nanoparticles in water with a hydrodynamic radius of 130-300 nm, at concentrations above the critical aggregation concentration (0.4-1 mg/mL), whereas polydisperse mPEG-b-OLAs gave formation of large aggregates. Static light scattering measurements showed that the nanoparticles have a low density (0.6-25 mg/mL), indicating that the particles are highly hydrated. In agreement herewith, the (1)H NMR spectra of nanoparticles in D2O closely resembled spectra in a good solvent for both blocks (CDCl3). It is therefore suggested that the nanoparticles contain a hydrated core of mPEG-b-OLA block oligomers, stabilized by a thin outer PEG layer. The particles were stable for two weeks, except for the mPEG350 series and mPEG750-b-OLA4, indicating that both the PEG block size and the PEG weight fraction of the oligomers determine their stability. The evident self-emulsifying properties of mPEG-b-oligo-l-lactates with monodisperse hydrophobic blocks as demonstrated in this study, together with their expected biocompatibility and biodegradability, make these systems well suitable for pharmaceutical applications.     

Diastereoselective preparation of novel tetrahydrooxazinones via heterocycloaddition of N-Boc, O-Me-acetals

Under Lewis acid conditions, reaction of N-Boc, O-Me acetals with the (R)-(+)-O-vinyl-pantolactone does not lead to the expected dihydrooxazine, but to the corresponding tetrahydrooxazinone, as a result of the loss of the t-Bu group. A diastereoselective and asymmetrical way to these new heterocyclic compounds is described, together with the first evidence of their ability to undergo N-acylation.     

Soft Polymer Janus Nanoparticles at Liquid–Liquid Interfaces

Soft polymeric Janus nanoparticles (JNPs), made from polystyrene‐b‐poly(butadiene)‐b‐poly(methylmethacrylate), PS‐PB‐PMMA, triblock terpolymers, assemble into a monolayer at the water–oil interface to reduce interfacial tension. The extent to which the polymer chains can deform influences the packing density of the JNPs at the interface. The longer the polymer chains are relative to the core, the softer are the JNPs, resulting in a JNPs assembly with a lower initial lateral packing density. The interfacial activity of JNPs can be further tuned by complexation of the PMMA chains with lithium ions that are introduced into the water phase. This work provides a fundamental understanding of soft JNPs packing at the water–oil interface and provides a strategy to tailor the areal density of soft JNPs at liquid–liquid interface, enabling the design of smart responsive structured‐liquid systems.     

Uniqueness for the Navier–Stokes equations and multipliers between Sobolev spaces

We re-prove various uniqueness theorems for the Navier–Stokes equations, stating the assumptions in terms of multipliers between Sobolev spaces instead of Lebesgue or Lorentz spaces.