Molecular mass distribution analysis of ethyl(hydroxyethyl)cellulose by size-exclusion chromatography with dual light-scattering and refractometric detection

Dual low-angle light scattering and refractometric detection coupled to size-exclusion chromatography provided proof for the presence of a low amount of stable aggregates/particles in ethyl(hydroxyethyl)cellulose. Unlike the correct size-exclusion chromatographic behavior of the parent polysaccharide itself, the aggregates exhibit variable size-dependent weak retention as a function of flow-rate and of ionic strength of the aqueous mobile phase. Therefore, determination of the molecular mass of non-aggregated polymer is possible in aqueous mobile phase containing 0.1 M NaCl under conditions at which aggregates are completely adsorbed on the column packing irrespective of the flow-rate used. Flow-rate and ionic strength-dependent variations of aggregate behavior as well as model size-exclusion experiments with latex particles indicate that they partly carry a minute charge and have a compact structure. Their weak retention under the separation conditions used suggests a difference in their surface chemistry when compared with the dissolved polymer coils which exhibit a correct size-exclusion behavior.     

Ion exchange resins in steel analysis

The metals vanadium, chromium and molybdenum may be separated from the other constituents of steel by passing an acetate buffered solution of the steel through a strongly basic onion exchanger and selectively eluting the above metals from the resin column with aqueous solutions of 0.6 N sodium hydroxide, 8 N hydrochloric acid and 1 N hydrochloric acid, respectively.     

Molar mass characterization of cationic methyl methacrylate-ethyl acrylate copolymers using size-exclusion chromatography with online multi-angle light scattering and refractometric detection

Size-exclusion chromatography (SEC) combined with online multi-angle light scattering (MALS) and refractometric (RI) detection has been employed for the molar mass characterisation of water-insoluble cationic methyl methacrylate-ethyl acrylate copolymers (Eudragit RS and RL). Due to their positive charge, cationic polymers are particularly difficult to separate on a SEC column, in worst cases being completely adsorbed on the oppositely charged packing material. This work has examined how a careful addition of salt (LiCl) to the copolymer solution in ethanol decreases the electrostatic interactions, clearly seen as a decrease in elution volume from the SEC column as well as an improved recovery. At a certain level of ionic strength, typically about 50 mM, the copolymer recovery from the SEC column reached 100% and molar mass distributions corresponding to the complete sample could be obtained. The combined MALS/RI detection gives the opportunity to measure the absolute molar mass independent of recovery and retention. Thus, in this study, it turned out to be a favourable tool for tracing the changes in elution behaviour of the charged copolymer as the ionic strength was increased.     

SPECTROSCOPIC STUDIES OF CUTANEOUS PHOTOSENSITIZING AGENTS–XV. ANTHRALIN and ITS OXIDATION PRODUCT 1,8-DIHYDROXYANTHRAQUINONE

The photochemistry (Type I and II) of anthralin and its photo-oxidation product 1,8-dihydroxyanthraquinone (1,8-DHAQ) has been studied in ethanol, acetonitrile and dimethylsulfoxide using spin-trapping and direct detection of singlet oxygen (1O2) luminescence techniques. In ethanol, where it exists in its neutral form (AN), anthralin does not undergo either Type I or II reactions upon UV-irradiation. In contrast, irradiation of anthralin in acetonitrile, a solvent in which anthralin is partially converted to its corresponding mono-anion (AN-), generates both superoxide and singlet oxygen. Irradiation of anthralin in dimethylsulfoxide, where the AN- form is present in substantial quantity, generates superoxide and solvent derived radicals but no detectable singlet oxygen. UV-irradiation of 1,8-DHAQ in ethanol and acetonitrile produces both superoxide and singlet oxygen in significant yields. In dimethylsulfoxide, on the other hand, only superoxide and solvent derived radicals are observed. The 1O2 quantum yield for AN- and 1,8-DHAQ in acetonitrile were determined to be 0.14 and 0.88 relative to rose bengal in the same solvent. These findings suggest that the AN photosensitization occurs via Type I and II pathways, is solvent dependent and involves AN- as well as its oxidation product 1,8-DHAQ, which is a more potent generator of both singlet oxygen and superoxide.     

New gem-dicyanocyclobutane-containing hydroxyesters

Six new gem-dicyanocyclobutanes containing carbomethoxy and hydroxyl/acetoxy functions were synthesized by cycloaddition of the appropriate vinyl ethers or alkoxystyrenes to methyl β,β-dicyanoacrylate. They proved to be too thermally labile to allow polycondensation to potentially piezoelectric linear polyesters.     

Parametric studies of interaction strengths in polymer/CO2 systems: discontinuous molecular dynamics simulations

Discontinuous molecular dynamics simulations are performed on homopolymer/solvent and surfactant/solvent systems. The homopolymer and surfactant molecules are modeled as freely jointed square-well chains. Solvent molecules are modeled as both hard spheres and square-well spheres. We explore how the various interaction parameters affect the types of phase behavior and micellization observed in the homopolymer/solvent and surfactant/solvent systems. Increasing the packing fraction of homopolymers in both hard-sphere solvents and square-well solvents increases the solvent's ability to dissolve homopolymers only when the segment-solvent interaction strength exceeds a critical value. Although only upper critical solution temperature (UCST) behavior is observed for homopolymers in hard-sphere solvents, both UCST and lower critical solution temperature (LCST) behavior are observed for homopolymers in square-well solvents, depending upon the interaction strengths and chain length. This indicates that it is necessary to account for the solvent-solvent attraction to model LCST behavior in supercritical CO2. Our simulation results on surfactants in hard-sphere solvents show that it is necessary to account for the interactions experienced by both the head and tail blocks in order to capture the essential features of surfactant/supercritical CO2 systems.