Macromolecular Complexes in Chemistry and Biology

ISBN-13: 9783642784712 / Angielski / Miękka / 2011 / 361 str.

Paul Dubin; J. Bock; Richie Davis

Opis

Throughout most of this century, progress in Polymer Science took place by way of studies of dilute polymer solutions and of the solid state. More recently, attention has been focused on the semi-dilute regime. The elucidation of transi- ent network and temporal gel states under conditions of moderate concentra- tion by numerous hydrodynamic and optical techniques is now well established and a solid theoretical underpinning for these phenomena is in place. However, in most of the systems studied, interpolymer interactions are relatively weak forces, because in solutions oftypical polymers, strong interpolymer interactions lead to bulk phase separation. However, polymers that form highly associating structures in equilibrium solution now constitute an important class of synthetic macromolecules, and it is evident that strong intermacromolecular interactions - without accompanying phase separation - are prevalent in biopolymer sys- tems as well. This behavior is generally characteristic of amphiphilic polymers, which contain both hydrophilic and hydrophobic repeat units.It is also charac- teristic of systems in which two macromolecular species are complementary, such as hydrogen-bond-donating and hydrogen-bond-accepting polymers, or polycations and polyanions. Interest in associating polymer systems currently derives from both applied and fundamental questions. Synthetic water-soluble polymers bearing hydro- phobic groups exhibit special rheological properties that make them well-suited as thickeners and viscosity-modifiers. Drag-reduction effects may arise in such polymer solutions, and may also be observed in polymer complexes based on hydrogen-bonding.

Spis treści

I. Hydrophobically Associating Polymers.- 1 Synthesis and Characterization of Hydrophobically Associating Water-Soluble Polymers.- 1.1 Introduction.- 1.2 Synthesis.- 1.3 Copolymerization.- 1.4 Postpolymerization Modification.- 1.5 Characterization-Hydrophobe Incorporation.- 1.6 Summary.- 1.7 References.- 2 Analysis of Hydrophobically Associating Copolymers Utilizing Spectroscopic Probes and Labels.- 2.1 Introduction.- 2.2 Emission Probes and Labels.- 2.3 Absorption Probes.- 2.4 Concluding Remarks.- 2.5 References.- 3 Solution Properties of Hydrophobically Associating Water-Soluble Polymers.- 3.1 Introduction.- 3.2 Polymer Systems.- 3.3 Solubility Characteristics.- 3.4 Solution Stability.- 3.5 Solution Rheological Properties.- 3.6 Summary.- 3.7 References.- 4 Aggregation of Hydrophobically Modified Polyelectrolytes in Dilute Solution: Tonic Strength Effects.- 4.1 Introduction.- 4.2 Experimental.- 4.3 The Polymers.- 4.4 Dilute Solution Viscosity.- 4.5 Fluorescence Spectroscopy.- 4.6 Intrinsic Viscosity.- 4.7 Concluding Remarks.- 4.8 References.- 5 Microdomain Composition in Two-Phase Hydrogels.- 5.1 Introduction.- 5.2 Background.- 5.2.1 Microphase Separation in Polymers.- 5.2.2 Importance of Graft Polymers.- 5.3 Results.- 5.3.1 Hydrogels from Surfactant Solutions.- 5.3.2 Hydrogels from Ethanol/Water Solutions.- 5.3.3 Solute Uptake by Gels.- 5.4 Conclusions.- 5.5 References.- 6 Molecular Association and Polymerization of 1-Alkyl-4-vinylpyridinium Ions.- 6.1 Complexation in 1-Alkyl-4-vinylpyridinium Ions and Related Polymers.- 6.2 Homopolymerization of 1-Alkyl-4-vinylpyridinium Ions.- 6.3 Copolymerization of 1-Alkyl-4-vinylpyridinium Ions.- 6.4 Conclusion.- 6.5 References.- 7 Fluorocarbon-Modified Water Soluble Polymers.- 7.1 Introduction.- 7.2 Experimental.- 7.3 Results and Discussion.- 7.4 Conclusions.- 7.5 References.- II. Polyelectrolyte Complexes.- 8 Static Light Scattering of Polyelectrolyte Complex Solutions.- 8.1 Introduction.- 8.2 Survey of Static Light Scattering Studies on PEC Solutions.- 8.3 Interpretation of Light Scattering Experiments.- 8.4 Experimental.- 8.4.1 Materials.- 8.4.2 Methods of Investigation.- 8.5 Results and Discussion.- 8.6 Conclusion.- 8.7 References.- 9 Interaction Between Oppositely Charged Low Ionic Density Polyelectrolytes: Complex Formation or Simple Mixture?.- 9.1 Introduction.- 9.2 Material and Techniques.- 9.2.1 Polymer Synthesis.- 9.2.2 Polymer Characterization.- 9.2.3 Other Techniques.- 9.3 Phase Diagram.- 9.3.1 Phase Diagram Representation.- 9.3.2 Influence of the Charge Density.- 9.3.3 Influence of the Ionic Strength.- 9.3.4 Influence of the Molecular Weight of the Samples.- 9.3.5 Phase Diagram and Complex Formation.- 9.4 Polymer-Polymer Affinity and Phase Diagram.- 9.5 Conclusion.- 9.6 References.- 10 Basic Properties of Soluble Interpolyelectrolyte Complexes Applied to Bioengineering and Cell Transformations.- 10.1 Introduction.- 10.2 Kinetic and Equilibrium Properties of Interpolyelectrolyte Complexes.- 10.3 Interpolyelectrolyte Complexes as Protein Carriers.- 10.4 Complexes of DNA with Synthetic Polycations for Cell Transformation.- 10.5 Conclusion.- 10.6 References.- 11 Conformation Presumption for Polysaccharide-Polylysine Complexation.- 11.1 Introduction.- 11.2 Complex Formation.- 11.3 Pectate-Polylysine Interaction.- 11.4 Polyguluronate Rich Alginate-Polylysine Interaction.- 11.5 Polymannuronate Rich Alginate-Polylysine Interaction.- 11.6 Conclusion.- 11.7 References.- 12 Interpolymer Complexes and their Ion-Conduction.- 12.1 Introduction.- 12.2 Classification of Interpolymer Complexes.- 12.3 Formation of Interpolymer Complexes from PAA with POE.- 12.4 Thermodynamics of Interpolymer Complexes from PAA (or PMMA) with POE.- 12.5 Selective and Substitution Interpolymer Complexation.- 12.6 Solid Properties of a Hydrogen-Bonding Complex.- 12.7 Ion Conduction and Solid Polymer Electrolytes.- 12.8 Ion Conduction of Hydrogen-Bonding Complexes.- 12.9 References.- 13 Fluorescence Probe Studies of Poly(acrylic acid) Interchain Complexation Induced by High Shear Flow and Influence of Cationic Surfactants on the Complexation.- 13.1 Introduction.- 13.2 Experimental.- 13.2.1 Materials.- 13.2.2 Flow Processing.- 13.2.3 Fluorescence Measurements.- 13.3 Results and Discussion.- 13.3.1 Drag Reduction (DR) and PAA Conformation.- 13.3.2 Local Chain Rigidity.- 13.3.3 Hydrophobic Association.- 13.3.4 Hydrophobe-Assisted Rigidity.- 13.4 References.- III. Biopolymer Systems.- 14 Water-Soluble Biospecific Polymers for New Affinity Purification Techniques.- 14.1 Introduction.- 14.2 Discrimination on the Basis of High Molecular Weight.- 14.2.1 Biospecific Ultrafiltration.- 14.2.2 Biospecific Gel Filtration.- 14.3 Discrimination on the Basis of High Density of Charges: Affinophoresis.- 14.4 Discrimination on the Basis of Surface Tension Properties: Affinity Partition.- 14.5 Discrimination on the Basis of Reversible Solubility: Affinity Precipitation.- 14.6 Advantages and Drawbacks of Techniques Involving Water-Soluble Biospecific Polymers.- 14.7 References.- 15 Protein-Polyelectrolyte Complexes.- 15.1 Introduction.- 15.2 Investigation Methods.- 15.3 Factors Influencing Protein-Polyelectrolyte Complexation and Structures of the Protein-Polyelectrolyte Complexes.- 15.4 Protein Separation by Polyelectrolytes.- 15.5 Enzymes in Polyelectrolyte Complexes.- 15.6 Conclusion.- 15.7 References.- 16 Precipitation of Proteins with Polyelectrolytes: Role of Polymer Molecular Weight.- 16.1 Introduction.- 16.2 Materials and Methods.- 16.3 Results and Discussion.- 16.4 Conclusions.- 16.5 References.- 17 Complex Coacervation: Micro-Capsule Formation.- 17.1 Introduction and Terminology.- 17.2 Simple Coacervation.- 17.3 Complex Coacervation.- 17.4 Theory of Complex Coacervation.- 17.5 Coacervation as a Method of Microencapsulation.- 17.6 Materials and Methods.- 17.7 Results.- 17.8 Conclusions.- 17.9 References.- 18 Complexation of Proteins with Polyelectrolytes in a Salt-Free System and Biochemical Characteristics of the Resulting Complexes.- 18.1 Introduction.- 18.2 Experimental Section.- 18.3 Results and Discussion.- 18.4 Conclusions and Topics for Future Research.- 18.5 References.- IV. Ionomers in Solution.- 19 Ionomer Solutions: Polyelectrolyte or Ionomer behavior.- 19.1 Introduction.- 19.2 Sulfonated Polystyrene Ionomer Solutions in Nonpolar Solvents.- 19.3 Sulfonated Polystyrene Ionomer Solutions in Polar Solvents.- 19.4 Perfluorinated Ionomer Solutions.- 19.5 Conclusion.- 19.6 References.- 20 Scattering Studies of Ionomer Aggregates in Nonpolar Solvents.- 20.1 Introduction.- 20.2 Experimental.- 20.3 Light Scattering Analysis.- 20.4 Results and Discussion.- 20.5 References.

O autorze

The current book describes the chemical and physical behavior of polymers and biopolymers that form highly associating structures in equilibrium solution. It summons the established results known of polymer complexes in solution taking into account also the recent developments. It covers the whole range from synthesis and fundamental aspects to applications and technology of associated polymers.