On-line coupling of flow field-flow fractionation and multi-angle laser light scattering

Abstract This paper describes the first successful coupling of a flow field-flow fractionator with a multi-angle laser light-scattering photometer in order to carry out absolute measurements of even high molar mass and radius of gyration distributions. Two standards with broad molar mass distributions, polystyrene particles and coil-shaped dissolved dextrans were investigated in order to establish the efficiency of this experimental apparatus. The distribution functions of molar mass and radius of gyration were determined for the samples. The results calculated for the dextran sample from the distribution functions were a weight-average molar mass of 2 730 000 g mol and a z-average radius of gyration of 47 nm. Comparison with results obtained from a conventional apparatus, consisting of size-exclusion chromatography and a light-scattering photometer, showed that field-flow fractionation is able to separate molecules in the range where size-exclusion chromatography fails owing to the existence of an exclusion boundary. The polystyrene latex sample gave results of 13 400 000 g mol for the weight-average molar mass and 15 nm for the z-average radius of gyration. In addition, a structure-property relationship in the form of an 〈R2G〉 1 2 versus M relationship was calculated for each substance. For the polystyrene latex standard in water an exponent of 0.33 ± 0.02 was found. The corresponding value for the dextran in 0.1 M sodium nitrate solution was 0.50 ± 0.01.

[1]  B. Zimm Molecular Theory of the Scattering of Light in Fluids , 1945 .

[2]  P. Wyatt Light scattering and the absolute characterization of macromolecules , 1993 .

[3]  J. Giddings,et al.  Improved flow field-flow fractionation system applied to water-soluble polymers: programming, outlet stream splitting, and flow optimization. , 1986, Analytical chemistry.

[4]  P. Debye Light Scattering in Solutions , 1944 .

[5]  M. N. Myers,et al.  Hydrodynamic relaxation in flow field-flow fractionation using both split and frit inlets. , 1991, Analytical chemistry.

[6]  J. Giddings,et al.  Separation of particles in aqueous suspensions by thermal field-flow fractionation. Measurement of thermal diffusion coefficients , 1992 .

[7]  B. Hunt Analysis of polymers: T. R. Crompton Pergamon, Oxford, 1989, viii + 362 pages, £45.00 ISBN 0-08-033942-5 , 1990 .

[8]  W. Kulicke,et al.  Preparation and characterization of a series of poly(acrylamide-co-acrylates), with a copolymer composition between 0–96.3 mol-% acrylate units with the same degree and distribution of polymerization , 1985 .

[9]  J. J. Kirkland,et al.  Molecular weight distributions of water-soluble polymers by flow field-flow fractionation , 1992 .

[10]  J. Giddings,et al.  Extension of sedimentation/steric field-flow fractionation into the submicrometer range: size analysis of 0.2-15-.mu.m metal particles , 1992 .

[11]  W. Kulicke,et al.  Molecular characterization of water‐soluble, cationic polyelectrolytes , 1992 .

[12]  Dierk Roessner,et al.  Characterization of hydroxyethyl starch by polymer analysis for use as a plasma volume expander , 1993 .

[13]  J. J. Kirkland,et al.  Comparison of sedimentation field flow fractionation with chromatographic methods for particulate and high-molecular-weight macromolecular characterizations , 1981 .

[14]  R. Kniewske,et al.  Preparation, characterization, solution properties and rheological behaviour of polyacrylamide , 1982 .

[15]  J. J. Kirkland,et al.  Polymer molecular weight distributions by thermal field flow fractionation using Mark-Houwink constants , 1992 .

[16]  P. Wyatt Mean square radius of molecules and secondary instrumental broadening , 1993 .

[17]  R. Beckett,et al.  Calibration of thermal field-flow fractionation using broad molecular weight standards , 1993 .

[18]  J. Giddings,et al.  Separation and molecular weight distribution of anionic and cationic water-soluble polymers by flow field-flow fractionation , 1992 .

[19]  J. J. Kirkland,et al.  Flow field-flow fractionation of polymers in organic solvents , 1992 .

[20]  P. Flory,et al.  Treatment of Intrinsic Viscosities , 1951 .

[21]  W. Kulicke,et al.  Bestimmung der Molmassenverteilung sowie der Stabilitätsgrenze von Polyacrylamiden unter Benutzung einer kombinierten Ausschlußchromatographie/Kleinwinkel-Laser-Streulichtphotometer Anlage , 1984 .

[22]  K. Gekko,et al.  Physicochemical studies of oligodextran. I. Molecular weight dependence of intrinsic viscosity, partial specific compressibility and hydrated water , 1971, Biopolymers.

[23]  M. N. Myers,et al.  Programmed thermal field-flow fractionation , 1976 .

[24]  J. J. Kirkland,et al.  Asymmetric-channel flow field-flow fractionation with exponential force-field programming , 1992 .

[25]  W. Kulicke,et al.  Characterization of water-soluble, cationic polyelectrolytes as exemplified by poly(acrylamide-co-trimethylammoniumethylethacryate chloride) and the establishment of structure-property relationships , 1991 .