Search results for "Intrinsic"
showing 10 items of 386 documents
Polyelectrolyte Complexes: Phase Diagram and Intrinsic Viscosities of the System Water/Poly(2-vinylpyridinium-Br)/Poly(styrene sulfonate-Na)
2012
In contrast to all earlier work on that subject, measurements are performed at high dilution up to total polymer concentrations wpol of 0.5 wt%. Aqueous solutions of poly(2-vinylpyridinium-Br) and of poly(styrene sulfonate-Na) are only fully miscible if wpol < 0.02 wt%. Decomposition into two liquid phases is observed upon an increase in wpol, where the extension of the miscibility gap is considerably larger at 60 than at 25 °C. Viscosity measurements demonstrate that the formation of the polyelectrolyte complexes may take hours. The intrinsic viscosity of the polyanion turns out to be 20 times larger than that of the polycation and to be much more sensitive toward the addition of extra sal…
Intrinsic viscosities of polyelectrolytes: specific salt effects and viscometric master curves.
2013
Dilute solutions of the sodium salt of polystyrene sulfonic acid (PSS-Na) were measured viscometrically as a function of composition in aqueous solvents of different salinity, where the extra salt was either NaCl or CaCl2. Such experiments yield {η}, the generalized intrinsic viscosities (hydrodynamic specific volume) of the polyelectrolyte for arbitrary polymer concentrations, c. In the limit of infinite dilution {η} becomes identical to the intrinsic viscosity [η]. For NaCl {η} decreases monotonously with rising c, whereas maxima are passed in the case of CaCl2. Condensing c and the concentration of extra salt in the mixed solvent into a single variable enables the establishment of predic…
Viscosity of Polymer Solutions over the Full Range of Composition: A Thermodynamically Inspired Two-Parameter Approach
2015
The approach yields the following relation for the relative viscosity η rel as a function of polymer concentration c (mass/volume): ln ηrel = c/(1 + pc + qc2). Reduced concentrations c (defined as c = c[η], where [η] is the intrinsic viscosity) are used instead of c to incorporate thermodynamic information. The parameters p and q account for changes in the free volume of the solvent caused by the polymer. The analysis of literature data for seven very dissimilar systems discloses the following common feature: p > 0 and q < 0. This means that the curves in the plots of ln ηrel as a function of c are normally located below the tangent at low c and above it at high c. The values of p and q cor…
Coil overlap in moderately concentrated polyelectrolyte solutions: effects of self-shielding as compared with salt-shielding as a function of chain l…
2016
The generalized intrinsic viscosity {η} (hydrodynamic volume of the solute at arbitrary polymer concentration c) – introduced by analogy to the intrinsic viscosity [η] – provides access to the degree of coil overlap Ω for polyelectrolyte solutions in pure water or in saline water. The experimental basis of this investigation consists in viscosity measurements as a function of c for a large number of sodium polystyrene sulfonate (Na-PSS) samples covering the molecular weight range from 0.91 to 1000 kg mol−1. The accurate modeling of these dependencies with a maximum of three parameters yields detailed information on Ω as a function of (c[η]) in the absence and in the presence of extra salt. …
Vinylic polymerization of norbornene by Pd(II)-catalysis in the presence of ethylene
1997
Pd(II) catalysts with nitrilo ligands and BF4− counter ions give the best results in vinylic polymerization of norbornene. Absolute molecular weight determination of polynorbornene (PN) by means of light scattering and the three-dimensional shape of PN were also investigated. By correlation of molecular weights Mw with intrinsic viscosity (Staudinger-index) [η], yield a close to 0.5 exponent for the Mark-Houwink equation with solvents chlorobenzene and cyclohexane at 25°C expected for polymer molecules with confined conformation. The vinylic polymerization of norbornene with [(CH3CN)4Pd][BF4]2 (I) in nitromethane in the presence of ethylene results in PN with narrow molecular weight distrib…
Beiträge zur polymerisation von 2-isopropenylnaphthalin, 3. Anionische homopolymerisation von 2-isopropenylnaphthalin
1981
The anionic homopolymerization of 2-isoprenylnaphthalene with butyllithium in tetrahydrofuran at –78°C is described. The refractive index increment amounts to dn/dc = 0,2084 ml/g for these polymers in toluene at 25°C and wavelength λ = 436 nm. Determination of the molecular weights by light scattering yielded values between 13 000 and 270 000. The second virial coefficients also determined by light scattering measurements are comparable with the corresponding data of poly(α-methylstyrene). A calibration curve is given for gel permeation chromatography of the poly(2-isoprenylnaphthalene)s, whose polymolecularity indexes Mw/Mn lie between 1,06 and 1,2. Their intrinsic viscosity/molecular weig…
A versatile viscometric method for the study of dissolved proteins, exemplified for casein micelles in ammoniacal solutions
2017
Abstract Viscosities of casein solutions were measured within the dilute range in ammoniacal water and in saline solvents containing different amounts and different kinds of salt. All these data are modeled quantitatively by means of an approach accounting for the polyelectrolyte character of casein micelles. Two parameters are required: The intrinsic viscosity [ η ] and a viscometric interaction parameter β . The behavior of casein is compared with that of chain-like polyelectrolytes. For both polymers one observes a pronounced reduction of [ η ] with increasing salt concentration. However, for casein the decline of [ η ] is less pronounced by more than an order of magnitude and depends on…
Controllable membrane remodeling by a modified fragment of the apoptotic protein Bax.
2021
Intrinsic apoptosis is orchestrated by a group of proteins that mediate the coordinated disruption of mitochondrial membranes. Bax is a multi-domain protein that, upon activation, disrupts the integrity of the mitochondrial outer membrane by forming pores. We strategically introduced glutamic acids into a short sequence of the Bax protein that constitutively creates membrane pores. The resulting BaxE5 peptide efficiently permeabilizes membranes at acidic pH, showing low permeabilization at neutral pH. Atomic force microscopy (AFM) imaging showed that at acidic pH BaxE5 established several membrane remodeling modalities that progressively disturbed the integrity of the lipid bilayer. The AFM…
Extension of the Concept of Intrinsic Viscosities to Arbitrary Polymer Concentration: From [η] via {η} to Intrinsic Bulkiness
2019
The capabilities of an alternative definition of intrinsic viscosities [η] published some years ago is being studied by means of comprehensive viscometric data reported in the early days of polymer science. It introduces the generalized intrinsic viscosity {η} as the specific hydrodynamic volume at arbitrary polymer concentration c. {η} quantifies the size of the flow unit and decreases monotonously for T ≫ Tg (glass transition temperature) as a function of c but passes a pronounced minimum as T approaches Tg. In the limit of the pure polymer melt, {η} becomes ; this newly introduced property is termed intrinsic bulkiness, by analogy to the intrinsic viscosity, and provides noncalorimetric …
Role of Solvent Compatibility in the Phase Behavior of Binary Solutions of Weakly Associating Multivalent Polymers
2021
AbstractCondensate formation of biopolymer solutions, prominently those of various intrinsically disordered proteins (IDPs), is determined by “sticky” interactions between associating residues, multivalently present along the polymer backbone. Using a ternary mean field “stickers-and-spacers” model, we demonstrate that if sticker association is of the order of a few times the thermal energy, a delicate balance between specific binding and non-specific polymer-solvent interactions gives rise to a particularly rich ternary phase behavior under physiological circumstances. For a generic system represented by a solution comprising multi-associative scaffold and client polymers, the difference i…