Static Light Scattering Studies of Suspensions of Charged Rodlike Tobacco Mosaic Virus

Maier, Erich E.; Schulz, Susanne; Weber, R.

doi:10.1021/ma00183a600

Cited by 52 publications

(21 citation statements)

References 1 publication

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“…9,49,50,54 Most experiments for linear chain polyelectrolytes show that qpeak ~ ρpμ scales with a power law exponent near μ ≈1 / 3 in semidilute solutions and approximately μ ≈ 1 / 2 i n semidilute solutions. 49,55 The exponent 1 / 3 represents the tendency of particles spatially localizing at interparticle distances. Since the particle concentration being proportional to their volume fraction, this behavior is typical in charged colloidal-like particles.…”

Section: Resultsmentioning

confidence: 99%

Polyelectrolyte association and solvation

Chremos

Douglas

2018

The Journal of Chemical Physics

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There has been significant interest in the tendency of highly charged particles having the same charge to form dynamic clusters in solution, but an accepted theoretical framework that can account for this ubiquitous phenomenon has been slow to develop. The theoretical difficulties are especially great for flexible polyelectrolytes due to the additional complex coupling between the polyelectrolyte chain configurations and the spatial distribution of the ionic species in solution. For highly charged polyelectrolytes, this leads to the formation of a di use “polarizable” cloud of counter-ions around these polymers, an effect having significant implications for the function of proteins and other natural occurring polyelectrolytes, as emphasized long ago by Kirkwood and coworkers. To investigate this phenomenon, we perform molecular dynamics simulations of a minimal model of polyelectrolyte solutions that includes an explicit solvent and counterions, where the relative affinity of the counter-ions and the polymer for the solvent is tunable through the variation of the relative strength of the dispersion interactions of the polymer and ions. In particular, we find that these dispersion interactions can greatly influence the nature of the association between the polyelectrolyte chains under salt-free conditions. We calculate static and dynamic correlation functions to quantify the equilibrium structure and dynamics of these complex liquids. Based on our coarse-grained model of polyelectrolyte solutions, we identify conditions in which three distinct types polyelectrolyte association arise. We rationalize these types of polyelectrolyte association based on the impact of the selective solvent affinity on the charge distribution and polymer solvation in these solutions. Our findings demonstrate the essential role of the solvent in the description of the polyelectrolyte solutions, as well as providing a guideline for the development of a more predictive theory of the properties of the thermodynamic and transport properties of these complex fluids.

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Section: Resultsmentioning

confidence: 99%

Polyelectrolyte association and solvation

Chremos

Douglas

2018

The Journal of Chemical Physics

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“…Most experiments for linear chain polyelectrolytes show that q peak scales with a power law exponent near 1/3 in dilute solutions and approximately 1/2 in semidilute solutions. 64,68 The exponent 1/3 represents the tendency of particles spatially localizing at interparticle distances. Since the particle concentration being proportional to their volume fraction, this behavior is typical in charged colloidal-like particles (as discussed below).…”

Section: Resultsmentioning

confidence: 99%

Solution properties of star polyelectrolytes having a moderate number of arms

Chremos

Douglas

2017

The Journal of Chemical Physics

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We investigate polyelectrolyte stars having a moderate number of arms by molecular dynamics simulations of a coarse-grained model over a range of polyelectrolyte concentrations, where both the counter-ions and solvent are treated explicitly. This class of polymeric materials is found to exhibit rather distinct static and dynamic properties from linear and highly branched star polyelectrolyte solutions emphasized in past studies. Moderately branched polymers are particle-like in many of their properties, while at the same time they exhibit large fluctuations in size and shape as in the case of linear chain polymers. Correspondingly, these fluctuations suppress crystallization at high polymer concentrations, leading apparently to an amorphous rather than crystalline solid state at high polyelectrolyte concentrations. We quantify the onset of this transition by measuring the polymer size and shape fluctuations of our model star polyelectrolytes and the static and dynamic structure factor of these solutions over a wide range of polyelectrolyte concentration. Our findings for star polyelectrolytes are similar to those of polymer-grafted nanoparticles having a moderate grafting density, which is natural given the soft and highly deformable nature of both of these ‘particles’.

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“…From the analysis of the peak evolution in Figure 6 one can observe that its position changes only slightly with the pronounced increase (1-20%) of the polymer concentration. For monodisperse homogeneously distributed particle Q max ∼ Φ 1/3 or Φ 1/2 in the case of spherical 23,24 or rodlike [25][26][27] objects. The observed behavior does not fulfill any of these scaling relations.…”

Section: Spp-p(e-co-p) Diblockmentioning

confidence: 99%

A SANS Study of the Self-Assembly in Solution of Syndiotactic Polypropylene Homopolymers, Syndiotactic Polypropylene-block-poly(ethylene-co-propylene) Diblock Copolymers, and an Alternating Atactic−Isotactic Multisegment Polypropylene

et al. 2004

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We have studied by small-angle neutron scattering (SANS) the crystallization of syndiotactic polypropylene (sPP) homopolymer in dilute hydrocarbon solution in parallel with the self-assembling behavior of crystalline-amorphous block copolymers of (syndiotactic propylene)-block-poly(ethylene-copropylene) [sPP-P(E-coP)] and atactic-isotactic multiblock polypropylene copolymers (aPP-iPP). Homopolymers and diblock copolymers of various molecular weights and volume fractions were investigated in decane over a wide temperature range (between 160 and-20°C) while the temperature evolution of the aPP-iPP aggregates was studied in dodecane starting from 175°C. The homopolymer crystallizes by forming platelets of a thickness of about 60-65 Å, independent of the molecular weight or polymer volume fraction in solution. The diblock copolymers aggregate by forming a complex morphology that shows a multilevel structure. This was investigated with SANS and ultra-SANS (USANS) over 3 orders of magnitude in size scale. At small scale (tens of angstroms) an overall 2-dimensional structure seems to be formed. It evolves at intermediate scale (hundreds of angstroms) into a rodlike structure. The rods associate in bundles that at a micrometric scale form supramolecular structures like networks. Such an association could be promoted by the PE sequences present within the P(E-coP) block. The multiblock copolymer forms very open rodlike aggregates and demonstrates that the general morphology of self-assembling materials with multiple alternating crystalline-amorphous blocks appears to be 1-dimensional. 2.1. Samples. The syndiotactic polypropylene homopolymer, sPP, and the crystalline-amorphous diblock polymers, sPP-P(E-coP), were prepared via a living polymerization in toluene at 0°C using a bis(salicylaldiminato)titanium complex. 8 All air-and moisture-sensitive chemistry was carried out in a Braun Labmaster drybox or using standard Schlenk line techniques. The solvents were dried on solvent columns containing molecular sieves, alumina, and activated copper. Propylene (Matheson, Polymer Grade) was purified by a column containing molecular sieves and alumina.. Ethylene (Matheson, Polymer Grade) was used as received. Methylaluminoxane (MAO-IP, 12.9 wt % Al in toluene, Akzo Nobel) was dried under vacuum at 60°C for 24 h. The alternating aPP/iPP multisegment polypropylene was made with a hafnium tert-butyl catalyst with the structure [(2-(3,5-(t-Bu) 2PhInd)2-HfCl2)]. The polymerization was performed in liquid propylene under pressure at 50°C using MAO with [Al/Hf]) 1000. 9 The polymer 1 H NMR spectra were recorded on a Varian Inova 500 MHz spectrometer and referenced to nondeuterated † Jü lich GmbH.

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Static Light Scattering Studies of Suspensions of Charged Rodlike Tobacco Mosaic Virus

Cited by 52 publications

References 1 publication

Polyelectrolyte association and solvation

Polyelectrolyte association and solvation

Solution properties of star polyelectrolytes having a moderate number of arms

A SANS Study of the Self-Assembly in Solution of Syndiotactic Polypropylene Homopolymers, Syndiotactic Polypropylene-block-poly(ethylene-co-propylene) Diblock Copolymers, and an Alternating Atactic−Isotactic Multisegment Polypropylene

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