106 research outputs found
Segregation versus interdigitation in highly dynamic polymer/surfactant layers
Many polymer/surfactant formulations involve a trapped kinetic state that provides some beneficial character to the formulation. However, the vast majority of studies on formulations focus on equilibrium states. Here, nanoscale structures present at dynamic interfaces in the form of air-in-water foams are explored, stabilised by mixtures of commonly used non-ionic, surface active block copolymers (Pluronic®) and small molecule ionic surfactants (sodium dodecylsulfate, SDS, and dodecyltrimethylammonium bromide, C12TAB). Transient foams formed from binary mixtures of these surfactants shows considerable changes in stability which correlate with the strength of the solution interaction which delineate the interfacial structures. Weak solution interactions reflective of distinct coexisting micellar structures in solution lead to segregated layers at the foam interface, whereas strong solution interactions lead to mixed structures both in bulk solution, forming interdigitated layers at the interface
Dynamic self-assembly of DNA minor groove-binding ligand DB921 into nanotubes triggered by an alkali halide.
We describe a novel self-assembling supramolecular nanotube system formed by a heterocyclic cationic molecule which was originally designed for its potential as an antiparasitic and DNA sequence recognition agent. Our structural characterisation work indicates that the nanotubes form via a hierarchical assembly mechanism that can be triggered and tuned by well-defined concentrations of simple alkali halide salts in water. The nanotubes assembled in NaCl have inner and outer diameters of ca. 22 nm and 26 nm respectively, with lengths that reach into several microns. Our results suggest the tubes consist of DB921 molecules stacked along the direction of the nanotube long axis. The tubes are stabilised by face-to-face π-π stacking and ionic interactions between the charged amidinium groups of the ligand and the negative halide ions. The assembly process of the nanotubes was followed using small-angle X-ray and neutron scattering, transmission electron microscopy and ultraviolet/visible spectroscopy. Our data demonstrate that assembly occurs through the formation of intermediate ribbon-like structures that in turn form helices that tighten and compact to form the final stable filament. This assembly process was tested using different alkali-metal salts, showing a strong preference for chloride or bromide anions and with little dependency on the type of cation. Our data further demonstrates the existence of a critical anion concentration above which the rate of self-assembly is greatly enhanced
Counterion adsorption on flexible polyelectrolytes: comparison of theories
Counterion adsorption on a flexible polyelectrolyte chain in a spherical
cavity is considered by taking a "permuted" charge distribution on the chain so
that the "adsorbed" counterions are allowed to move along the backbone. We
compute the degree of ionization by using self-consistent field theory (SCFT)
and compare with the previously developed variational theory. Analysis of
various contributions to the free energy in both theories reveals that the
equilibrium degree of ionization is attained mainly as an interplay of the
adsorption energy of counterions on the backbone, the translational entropy of
the small ions, and their correlated density fluctuations. Degree of ionization
computed from SCFT is significantly lower than that from the variational
formalism. The difference is entirely due to the density fluctuations of the
small ions in the system, which are accounted for in the variational procedure.
When these fluctuations are deliberately suppressed in the truncated
variational procedure, there emerges a remarkable quantitative agreement in the
various contributing factors to the equilibrium degree of ionization, in spite
of the fundamental differences in the approximations and computational
procedures used in these two schemes. Nevertheless, since the significant
effects from density fluctuations of small ions are not captured by the SCFT,
and due to the close agreement between SCFT and the other contributing factors
in the more transparent variational procedure, the latter is a better
computational tool for obtaining the degree of ionization
Conformational Instability of Rodlike Polyelectrolytes due to Counterion Fluctuations
The effective elasticity of highly charged stiff polyelectrolytes is studied
in the presence of counterions, with and without added salt. The rigid polymer
conformations may become unstable due to an effective attraction induced by
counterion density fluctuations. Instabilities at the longest, or intermediate
length scales may signal collapse to globule, or necklace states, respectively.
In the presence of added-salt, a generalized electrostatic persistence length
is obtained, which has a nontrivial dependence on the Debye screening length.
It is also found that the onset of conformational instability is a re-entrant
phenomenon as a function of polyelectrolyte length for the unscreened case, and
the Debye length or salt concentration for the screened case. This may be
relevant in understanding the experimentally observed re-entrant condensation
of DNA.Comment: 8 pages, 4 figure
Structure and dynamics of balanced supercritical CO2-microemulsions
Balanced scCO(2)-microemulsions contain equal volumes of water and CO2 and are a novel class of microemulsions of substantial interest for both fundamental research and technical applications. One existing feature of these systems is that the solvent quality of scCO(2), and hence the overall microemulsion properties, is tuned simply by adjusting pressure, which is not possible with "classical" microemulsions containing oil instead of CO2. Motivated by this, we systematically investigated the phase behavior, the microstructure, and the dynamics of balanced microemulsion systems of the type H2O-CO2-Zonyl FSO 100/Zonyl FSN 100. In systematic phase behavior studies, we found that upon increasing pressure, CO2 and water are more efficiently solubilized. Small angle neutron scattering (SANS) experiments were conducted in order to determine the topology and the length scales of the underlying microstructure. The results obtained strongly suggest the existence of bicontinuously structured microemulsions with an adjustable characteristic length scale of up to 330 angstrom. From a quantitative analysis of the SANS data, we found that at a fixed microemulsion composition the stiffness of the surfactant membrane is increased solely by increasing the pressure, whereby the renormalization corrected (i.e. bare) bending rigidity kappa(0), SANS rises from kappa(0,SANS) 0.88 k(B)T at 200 bar to 0.93 k(B)T at 300 bar. These findings were confirmed with high pressure neutron spin echo experiments
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