Spontaneous chirality via long-range electrostatic forces

We consider a model for periodic patterns of charges constrained over a cylindrical surface. In particular we focus on patterns of chiral helices, achiral rings or vertical lamellae, with the constraint of global electroneutrality. We study the dependence of the patterns' size and pitch angle on the radius of the cylinder and salt concentration. We obtain a phase diagram by using numerical and analytic techniques. For pure Coulomb interactions, we find a ring phase for small radii and a chiral helical phase for large radii. At a critical salt concentration, the characteristic domain size diverges, resulting in macroscopic phase segregation of the components and restoring chiral symmetry. We discuss possible consequences and generalizations of our model.Comment: Revtex, 4 pages, 4 figure

Electrostatic attraction between cationic-anionic assemblies with surface compositional heterogeneities

Electrostatics plays a key role in biomolecular assembly. Oppositely charged biomolecules, for instance, can co-assembled into functional units, such as DNA and histone proteins into nucleosomes and actin-binding protein complexes into cytoskeleton components, at appropriate ionic conditions. These cationic-anionic co-assemblies often have surface charge heterogeneities that result from the delicate balance between electrostatics and packing constraints. Despite their importance, the precise role of surface charge heterogeneities in the organization of cationic-anionic co-assemblies is not well understood. We show here that co-assemblies with charge heterogeneities strongly interact through polarization of the domains. We find that this leads to symmetry breaking, which is important for functional capabilities, and structural changes, which is crucial in the organization of co-assemblies. We determine the range and strength of the attraction as a function of the competition between the steric and hydrophobic constraints and electrostatic interactions.Comment: JCP June/200

Pattern formation on the surface of cationic-anionic cylindrical aggregates

Charged pattern formation on the surfaces of self--assembled cylindrical micelles formed from oppositely charged heterogeneous molecules such as cationic and anionic peptide amphiphiles is investigated. The net incompatibility $\chi$ among different components results in the formation of segregated domains, whose growth is inhibited by electrostatics. The transition to striped phases proceeds through an intermediate structure governed by fluctuations, followed by states with various lamellar orientations, which depend on cylinder radius $R_c$ and $\chi$. We analyze the specific heat, susceptibility $S(q^*)$, domain size $\Lambda=2\pi/q^*$ and morphology as a function of $R_c$ and $\chi$.Comment: Sent to PRL 11Jan05 Transferred from PRL to PRE 10Jun0

An alternative method for phase-unwrapping of interferometric data

In this paper we present a novel algorithm for phase unwrapping where only a subset of data from the wrapped phase map is used to reconstruct the unwrapped phase map as a linear combination of radial basis functions (RBF’s). For noisy phase maps this algorithm gives better results than three reference algorithms based on radial basis functions, Zernike polynomials and path dependent phase unwrapping strategies

Dynamics of Collapse of flexible Polyelectrolytes and Polyampholytes

We provide a theory for the dynamics of collapse of strongly charged polyelectrolytes (PEs) and flexible polyampholytes (PAs) using Langevin equation. After the initial stage, in which counterions condense onto PE, the mechanism of approach to the globular state is similar for PE and PA. In both instances, metastable pearl-necklace structures form in characteristic time scale that is proportional to N^{4/5} where N is the number of monomers. The late stage of collapse occurs by merger of clusters with the largest one growing at the expense of smaller ones (Lifshitz- Slyozov mechanism). The time scale for this process T_{COLL} N. Simulations are used to support the proposed collapse mechanism for PA and PE.Comment: 14 pages, 2 figure

CO and C 3

ZnSb2O6 has been synthesized by a microwave-assisted solution method in order to test its possible application as a gas sensor. Zinc nitrate, antimony trichloride, and ethylenediamine were used as precursors and deionized water as solvent. Microwave radiation, with a power of ~350 W, was applied for solvent evaporation. The thermal decomposition of the precursors leads to the formation of ZnSb2O6 at 600°C. This oxide crystallized in a tetragonal structure with cell parameters a=4.66 Å, c=9.26 Å and space group P42/mnm. Microwires and microrods formed by nanocrystals were observed by means of scanning and transmission electron microscopies (SEM and TEM, resp.). Pellets of the oxide were tested as gas sensors in flowing atmospheres of carbon monoxide (CO) and propane (C3H8). Sensitivity increased with the gas concentration (0–300 ppm) and working temperatures (ambient, 150 and 250°C) increase. The results indicate high sensitivity of ZnSb2O6 in both gases at different concentrations and operating temperatures

Collapse of Stiff 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.Comment: 4 pages RevTex, 3 ps figures included using epsf, final version as appeared in PR

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

A Modified Random Phase Approximation of Polyelectrolyte Solutions

We compute the phase diagram of salt-free polyelectrolyte solutions using a modified Debye-Huckel Approach. We introduce the chain connectivity via the Random Phase Approximation with two important modifications. We modify the electrostatic potential at short distances to include a bound on the electrostatic attractions at the distance of closest approach between charges. This modification is shown to act as a hard core in the phase diagram of electrolyte solutions. We also introduce a cut-off on the integration of the modes of wave length smaller than the size over which the chains are strongly perturbed by the electrostatic interactions. This cut-off is shown to be essential to predict physical phase diagram in long chain solutions