Article

Cascade of coil-globule conformational transitions of single flexible polyelectrolyte molecules in poor solvent.

Institut für Polymerforschung Dresden, Hohe Strasse 6, Germany.
Journal of the American Chemical Society (Impact Factor: 10.68). 12/2002; 124(45):13454-62. DOI: 10.1021/ja0261168
Source: PubMed

ABSTRACT We show that hydrophobic flexible polyelectrolyte molecules of poly(2-vinylpyridine) and poly(methacryloyloxyethyl dimethylbenzylammonium chloride) are trapped and frozen due to adsorption on the mica surface, and the observed AFM single molecule structures reflect the molecular conformation in solution. An increase of the ionic strength of the solution induces the cascade of abrupt conformational transitions due to the intrachain segregation from elongated coil to compact globule conformations through intermediate pearl necklace-globule conformations with different amounts of beads per chain. The length of the necklaces and the number of beads decrease, while the diameter of beads increases with the increase of ionic strength. Coexistence at the same time of extended coils, necklaces with different amounts of beads, and compact globules indicates the cascade of the first-order-type phase transitions.

0 Bookmarks
 · 
48 Views
  • [Show abstract] [Hide abstract]
    ABSTRACT: Water-soluble (1→3)-β-d-glucans with 1,6-linked branches (SBG), originally isolated from the cell walls of Saccharomyces cerevisiae and partially depolymerised to a weight average degree of polymerisation (DP(w)) in the range 120-160 for optimal performance in wound healing applications, were studied by dynamic light scattering (DLS), SEC MALLS and AFM. Results indicate that dilute aqueous SBG solutions (1μg/ml to 3mg/ml) contain higher order structures with a very wide size distribution in water (10-500nm), corresponding to a mixture of single chains, multi-chain aggregates including triple-stranded motifs, and particulate materials. The latter were enriched in longer chains compared to non-particulate fractions. The size distribution of SBG aggregates shifted to slightly lower values upon heating, but showed hysteresis upon cooling. AFM images prepared from very dilute aqueous solution (1-5μg/ml) analysis showed by comparison to other (1→3)-β-d-glucans that some of the structures were the triple helical species coexisting with larger aggregates and single chains, in contrast to carboxymethylated SBG, which contained predominantly single chains. The ability to control the aggregation behaviour of SBG enables tailoring of the physical, and possibly bioactive, properties of SBG preparations.
    Carbohydrate polymers. 02/2013; 92(2):1026-32.
  • [Show abstract] [Hide abstract]
    ABSTRACT: We present the results of variational calculations of a polyelectrolyte solution with low salt in poor solvent conditions for a polymer backbone. By employing the variation method, we quantitatively determined the diagram of the state of the polyelectrolyte in poor solvents as a function of the charge density and the molecular weight. The exact structure and diagram of the polyelectrolyte were compared to the scaling predictions of the necklace model developed by Dobrynin and Rubinstein [Prog. Polym. Sci. 30, 1049-1118 (2005); Dobrynin and Rubinstein, Macromolecules 32, 915-922 (1999); Dobrynin and Rubinstein, Macromolecules 34, 1964-1972 (2001)]. We find that the scaling necklace model may be used as a rather good estimation and analytical approximation of the exact variational model. It is also pointed out that the molecular connection of polymer is crucial for ellipsoid and necklace conformation.
    The Journal of chemical physics. 05/2014; 140(19):194905.
  • [Show abstract] [Hide abstract]
    ABSTRACT: Chitosan macromolecules can be dissolved in water saturated with CO2 under high pressure, i.e. in carbonic acid. This unique biocompatible solvent with acidity regulated by the variation of applied CO2 pressure is rather promising for biomedical applications. In this work the main features of deposition of chitosan structures on the model substrate from solutions in this media were examined. After deposition on the mica surface, the obtained structures have been successfully visualised by atomic force microscopy (AFM). It has been found out that they adsorb as rather peculiar elongated objects with an average length of about 70 nm. Such conformations are believed to appear due to amphiphilic nature of chitosan semiflexible chains in agreement with recent theoretical findings. The well-defined geometry of the elongated monodispersed structures allows them to demonstrate some elements of liquid crystalline-like ordering.
    Colloid and Polymer Science 01/2012; 290(15):1471-1480. · 2.16 Impact Factor