title: Combination of SEC/MALS experimental procedures and theoretical analysis for studying the solution properties of macromolecules.
abstract: Size-exclusion chromatography (SEC) with dual detection, i.e., employing refractive index (RI) and multiangle light-scattering (MALS) detectors, has been applied to study the solution properties of two very different polymer-solvent systems at 25 degrees C: poly(N-vinylcarbazole) (PVCz) in an organic solvent THF that is a very good solvent and a system under theta conditions that is formed by polyvinylpyrrolidone (PVP) in water containing a 0.1 M concentration of NaNO(3). In both cases, the analysis of a single highly polydisperse sample obtained by free radical polymerization is enough for obtaining molecular weight and radius of gyration calibration curves, molecular weight distributions (MWD) (and thus, molecular weight averages), molecular dimensions, scaling laws coefficients and unperturbed dimensions. Extrapolation to theta conditions produces values of the characteristic ratio of the unperturbed dimensions C(n)=<r(2)>(o)/nl(2)=15.9 and 14, respectively, for PVCz and PVP. Unperturbed dimensions are also theoretically calculated with different models such as Kuhn equivalent chain, worm-like chain and rotational isomeric states model. Conformational parameters required for this last model were taken from the literature in the case of PVCz; however, they are calculated by molecular dynamics simulations in the case of PVP. Theoretical values obtained with the RIS model are in good agreement with the experimental results.
authors.affiliation: Departamento de Química Física, Universidad de Alcalá, 28871 Alcalá de Henares, Spain. mpilar.tarazona@uah.es
authors.forename: M Pilar
authors.initials: MP
authors.lastname: Tarazona
authors.forename: Enrique
authors.initials: E
authors.lastname: Saiz
mesh_terms: D002850:Chromatography, Gel / Q000379:methods*; D003198:Computer Simulation; D046911:Macromolecular Substances; D008956:Models, Chemical; D008958:Models, Molecular; D008970:Molecular Weight; D010783:Photometry / Q000379:methods*; D011145:Polyvinyls / Q000032:analysis* / Q000737:chemistry; D011205:Povidone / Q000032:analysis* / Q000737:chemistry; D015203:Reproducibility of Results; D012680:Sensitivity and Specificity; D012996:Solutions / Q000737:chemistry*
chemical_list: D046911:Macromolecular Substances; D011145:Polyvinyls; D012996:Solutions; C035125:poly-N-vinylcarbazole; D011205:Povidone