Deviations from the mean field predictions for the phase behaviour of random copolymers melts

We investigate the phase behaviour of random copolymers melts via large scale Monte Carlo simulations. We observe macrophase separation into A and B--rich phases as predicted by mean field theory only for systems with a very large correlation lambda of blocks along the polymer chains, far away from the Lifshitz point. For smaller values of lambda, we find that a locally segregated, disordered microemulsion--like structure gradually forms as the temperature decreases. As we increase the number of blocks in the polymers, the region of macrophase separation further shrinks. The results of our Monte Carlo simulation are in agreement with a Ginzburg criterium, which suggests that mean field theory becomes worse as the number of blocks in polymers increases.Comment: 6 pages, 4 figures, Late

Correlated disorder in random block-copolymers

We study the effect of a random Flory-Huggins parameter in a symmetric diblock copolymer melt which is expected to occur in a copolymer where one block is near its structural glass transition. In the clean limit the microphase segregation between the two blocks causes a weak, fluctuation induced first order transition to a lamellar state. Using a renormalization group approach combined with the replica trick to treat the quenched disorder, we show that beyond a critical disorder strength, that depends on the length of the polymer chain, the character of the transition is changed. The system becomes dominated by strong randomness and a glassy rather than an ordered lamellar state occurs. A renormalization of the effective disorder distribution leads to nonlocal disorder correlations that reflect strong compositional fluctuation on the scale of the radius of gyration of the polymer chains. The reason for this behavior is shown to be the chain length dependent role of critical fluctuations, which are less important for shorter chains and become increasingly more relevant as the polymer length increases and the clean first order transition becomes weaker.Comment: 11 pages, 5 figures, submitted to PR

Polyelectrolyte multilayer formation: electrostatics and short-range interactions

We investigate the phenomenon of multilayer formation via layer-by-layer deposition of alternating charge polyelectrolytes. Using mean-field theory, we find that a strong short-range attraction between the two types of polymer chains is essential for the formation of multilayers. The dependence of the required short-range attraction on the polymer charge fraction and salt concentration is calculated. For weak short-range attraction between any two adjacent layers, the adsorbed amount (per added layer) decays as the distance from the surface increases, until the chains stop adsorbing altogether. For strong short-range attraction, the adsorbed amount per layer increases after an initial decrease, and finally it stabilizes in the form of a polyelectrolyte multilayer that can be repeated many times.Comment: 8 pages, 7 figure

Separation of VUV/UV photons and reactive particles in the effluent of a He/O2 atmospheric pressure plasma jet

Cold atmospheric pressure plasmas can be used for treatment of living tissues or for inactivation of bacteria or biological macromolecules. The treatment is usually characterized by a combined effect of UV and VUV radiation, reactive species, and ions. This combination is usually beneficial for the effectiveness of the treatment but it makes the study of fundamental interaction mechanisms very difficult. Here we report on an effective separation of VUV/UV photons and heavy reactive species in the effluent of a micro scale atmospheric pressure plasma jet ($\mu$-APPJ). The separation is realized by an additional flow of helium gas under well-defined flow conditions, which deflects heavy particles in the effluent without affecting the VUV and UV photons. Both components of the effluent, the photons and the reactive species, can be used separately or in combination for sample treatment. The results of treatment of a model plasma polymer film and vegetative Bacillus subtilis and Escherichia coli cells are shown and discussed. A simple model of the He gas flow and reaction kinetics of oxygen atoms in the gas phase and at the surface is used to provide a better understanding of the processes in the plasma effluent. The new jet modification, called X-Jet for its appearance, will simplify the investigation of interaction mechanisms of atmospheric pressure plasmas with biological samples.Comment: 10 pages, 7 figures, submitted to Journal of Physics D: Applied Physic

Localization transition of random copolymers at interfaces

We consider adsorption of random copolymer chains onto an interface within the model of Garel et al. Europhysics Letters 8, 9 (1989). By using the replica method the adsorption of the copolymer at the interface is mapped onto the problem of finding the ground state of a quantum mechanical Hamiltonian. To study this ground state we introduce a novel variational principle for the Green's function, which generalizes the well-known Rayleigh-Ritz method of Quantum Mechanics to nonstationary states. Minimization with an appropriate trial Green's function enables us to find the phase diagram for the localization-delocalization transition for an ideal random copolymer at the interface.Comment: 5 page

A Model Ground State of Polyampholytes

The ground state of randomly charged polyampholytes is conjectured to have a structure similar to a necklace, made of weakly charged parts of the chain, compacting into globules, connected by highly charged stretched `strings'. We suggest a specific structure, within the necklace model, where all the neutral parts of the chain compact into globules: The longest neutral segment compacts into a globule; in the remaining part of the chain, the longest neutral segment (the 2nd longest neutral segment) compacts into a globule, then the 3rd, and so on. We investigate the size distributions of the longest neutral segments in random charge sequences, using analytical and Monte Carlo methods. We show that the length of the n-th longest neutral segment in a sequence of N monomers is proportional to N/(n^2), while the mean number of neutral segments increases as sqrt(N). The polyampholyte in the ground state within our model is found to have an average linear size proportional to sqrt(N), and an average surface area proportional to N^(2/3).Comment: 8 two-column pages. 5 eps figures. RevTex. Submitted to Phys. Rev.

Conformational transitions of heteropolymers in dilute solutions

In this paper we extend the Gaussian self-consistent method to permit study of the equilibrium and kinetics of conformational transitions for heteropolymers with any given primary sequence. The kinetic equations earlier derived by us are transformed to a form containing only the mean squared distances between pairs of monomers. These equations are further expressed in terms of instantaneous gradients of the variational free energy. The method allowed us to study exhaustively the stability and conformational structure of some periodic and random aperiodic sequences. A typical phase diagram of a fairly long amphiphilic heteropolymer chain is found to contain phases of the extended coil, the homogeneous globule, the micro-phase separated globule, and a large number of frustrated states, which result in conformational phases of the random coil and the frozen globule. We have also found that for a certain class of sequences the frustrated phases are suppressed. The kinetics of folding from the extended coil to the globule proceeds through non-equilibrium states possessing locally compacted, but partially misfolded and frustrated, structure. This results in a rather complicated multistep kinetic process typical of glassy systems.Comment: 15 pages, RevTeX, 20 ps figures, accepted for publication in Phys. Rev.

Bulk and Boundary Critical Behavior at Lifshitz Points

Lifshitz points are multicritical points at which a disordered phase, a homogeneous ordered phase, and a modulated ordered phase meet. Their bulk universality classes are described by natural generalizations of the standard $\phi^4$ model. Analyzing these models systematically via modern field-theoretic renormalization group methods has been a long-standing challenge ever since their introduction in the middle of the 1970s. We survey the recent progress made in this direction, discussing results obtained via dimensionality expansions, how they compare with Monte Carlo results, and open problems. These advances opened the way towards systematic studies of boundary critical behavior at $m$-axial Lifshitz points. The possible boundary critical behavior depends on whether the surface plane is perpendicular to one of the $m$ modulation axes or parallel to all of them. We show that the semi-infinite field theories representing the corresponding surface universality classes in these two cases of perpendicular and parallel surface orientation differ crucially in their Hamiltonian's boundary terms and the implied boundary conditions, and explain recent results along with our current understanding of this matter.Comment: Invited contribution to STATPHYS 22, to be published in the Proceedings of the 22nd International Conference on Statistical Physics (STATPHYS 22) of the International Union of Pure and Applied Physics (IUPAP), 4--9 July 2004, Bangalore, Indi

Ground States of Two-Dimensional Polyampholytes

We perform an exact enumeration study of polymers formed from a (quenched) random sequence of charged monomers $\pm q_0$, restricted to a 2-dimensional square lattice. Monomers interact via a logarithmic (Coulomb) interaction. We study the ground state properties of the polymers as a function of their excess charge $Q$ for all possible charge sequences up to a polymer length N=18. We find that the ground state of the neutral ensemble is compact and its energy extensive and self-averaging. The addition of small excess charge causes an expansion of the ground state with the monomer density depending only on $Q$. In an annealed ensemble the ground state is fully stretched for any excess charge $Q>0$.Comment: 6 pages, 6 eps figures, RevTex, Submitted to Phys. Rev.