Pluronic copolymer liquid crystals: unique, replaceable media for capillary gel electrophoresis

Abstract

Liquid crystalline solutions of Pluronic copolymers are versatile alternatives to solutions of entangled, random coil polymers as replaceable media for capillary gel electrophoresis (CGE). Pluronic copolymers are tri-block polymers of poly(ethylene oxide) [(EO) x ] and poly(propylene oxide) [(PO) y ] with the general formula (EO) x (PO) y (EO) x . Large micelles form in aqueous solutions in which central, hydrophobic cores of (PO) y segments are surrounded by “brushes” of hydrated (EO) x tails. Solutions of Pluronic F127 (BASF Performance Chemicals) in a concentration range of about 18–30% are liquids at refrigerator temperatures (≤5°C) and are easily introduced into capillaries. A self-supporting, gel-like liquid crystalline phase is formed as the temperature is raised to ≥20°C. This liquid crystalline phase consists of spherical micelles with diameters of 17–18 nm which pack with local cubic symmetry. CGE in Pluronic F127 liquid crystals separates species within several chemical classes as varied as nucleoside monophosphates and organic dyes, oligonucleotides of 4–60 nucleotides, DNA fragments of 50–3000 base pairs (bp), and supercoiled plasmid DNAs of 2000–10 000 bp. Mechanisms of molecular sieving in polymer liquid crystals must differ in fundamental ways from separations in random polymer gels because molecules move around uncrosslinked obstacles that are larger than the smallest dimensions of typical analytes. Molecular sieving in Pluronic liquid crystals is envisioned to occur as molecules squeeze between hydrated (EO) x strands of micelle brushes, or through brushtips and interstitial spaces between micelles. Small molecules such as nucleotides appear to separate by a different mechanism involving partitioning between hydrophilic and hydrophobic environments. This process is termed “hydrophobic interaction electrophoresis”. The unique structures of Pluronic copolymers and their liquid crystalline phases provide new challenges and opportunities in separations science.