The Osmotic Coefficient of Rod-like Polyelectrolytes: Computer Simulation, Analytical Theory, and Experiment

The osmotic coefficient of solutions of rod-like polyelectrolytes is considered by comparing current theoretical treatments and simulations to recent experimental data. The discussion is restricted to the case of monovalent counterions and dilute, salt-free solutions. The classical Poisson-Boltzmann solution of the cell model correctly predicts a strong decrease in the osmotic coefficient, but upon closer look systematically overestimates its value. The contribution of ion-ion-correlations are quantitatively studied by MD simulations and the recently proposed DHHC theory. However, our comparison with experimental data obtained on synthetic, stiff-chain polyelectrolytes shows that correlation effects can only partly explain the discrepancy. A quantitative understanding thus requires theoretical efforts beyond the restricted primitive model of electrolytes.Comment: 16 pages, 2 figure

Effective field theory approach to Casimir interactions on soft matter surfaces

We utilize an effective field theory approach to calculate Casimir interactions between objects bound to thermally fluctuating fluid surfaces or interfaces. This approach circumvents the complicated constraints imposed by such objects on the functional integration measure by reverting to a point particle representation. To capture the finite size effects, we perturb the Hamiltonian by DH that encapsulates the particles' response to external fields. DH is systematically expanded in a series of terms, each of which scales homogeneously in the two power counting parameters: \lambda \equiv R/r, the ratio of the typical object size (R) to the typical distance between them (r), and delta=kB T/k, where k is the modulus characterizing the surface energy. The coefficients of the terms in DH correspond to generalized polarizabilities and thus the formalism applies to rigid as well as deformable objects. Singularities induced by the point particle description can be dealt with using standard renormalization techniques. We first illustrate and verify our approach by re-deriving known pair forces between circular objects bound to films or membranes. To demonstrate its efficiency and versatility, we then derive a number of new results: The triplet interactions present in these systems, a higher order correction to the film interaction, and general scaling laws for the leading order interaction valid for objects of arbitrary shape and internal flexibility.Comment: 4 pages, 1 figur

Folding and insertion thermodynamics of the transmembrane WALP peptide

The anchor of most integral membrane proteins consists of one or several helices spanning the lipid bilayer. The WALP peptide, GWW(LA)$_n$(L)WWA, is a common model helix to study the fundamentals of protein insertion and folding, as well as helix-helix association in the membrane. Its structural properties have been illuminated in a large number of experimental and simulation studies. In this combined coarse-grained and atomistic simulation study, we probe the thermodynamics of a single WALP peptide, focusing on both the insertion across the water-membrane interface, as well as folding in both water and a membrane. The potential of mean force characterizing the peptide's insertion into the membrane shows qualitatively similar behavior across peptides and three force fields. However, the Martini force field exhibits a pronounced secondary minimum for an adsorbed interfacial state, which may even become the global minimum---in contrast to both atomistic simulations and the alternative PLUM force field. Even though the two coarse-grained models reproduce the free energy of insertion of individual amino acids side chains, they both underestimate its corresponding value for the full peptide (as compared with atomistic simulations), hinting at cooperative physics beyond the residue level. Folding of WALP in the two environments indicates the helix as the most stable structure, though with different relative stabilities and chain-length dependence.Comment: 12 pages, 5 figure

Distributed networks for auditory memory differentially contribute to recall precision

Re-directing attention to objects in working memory can enhance their representational fidelity. However, how this attentional enhancement of memory representations is implemented across distinct, sensory and cognitive-control brain network is unspecified. The present fMRI experiment leverages psychophysical modelling and multivariate auditory-pattern decoding as behavioral and neural proxies of mnemonic fidelity. Listeners performed an auditory syllable pitch-discrimination task and received retro-active cues to selectively attend to a to-be-probed syllable in memory. Accompanied by increased neural activation in fronto-parietal and cingulo-opercular networks, valid retro-cues yielded faster and more perceptually sensitive responses in recalling acoustic detail of memorized syllables. Information about the cued auditory object was decodable from hemodynamic response patterns in superior temporal sulcus (STS), fronto-parietal, and sensorimotor regions. However, among these regions retaining auditory memory objects, neural fidelity in the left STS and its enhancement through attention-to-memory best predicted individuals’ gain in auditory memory recall precision. Our results demonstrate how functionally discrete brain regions differentially contribute to the attentional enhancement of memory representations

Contact lines for fluid surface adhesion

When a fluid surface adheres to a substrate, the location of the contact line adjusts in order to minimize the overall energy. This adhesion balance implies boundary conditions which depend on the characteristic surface deformation energies. We develop a general geometrical framework within which these conditions can be systematically derived. We treat both adhesion to a rigid substrate as well as adhesion between two fluid surfaces, and illustrate our general results for several important Hamiltonians involving both curvature and curvature gradients. Some of these have previously been studied using very different techniques, others are to our knowledge new. What becomes clear in our approach is that, except for capillary phenomena, these boundary conditions are not the manifestation of a local force balance, even if the concept of surface stress is properly generalized. Hamiltonians containing higher order surface derivatives are not just sensitive to boundary translations but also notice changes in slope or even curvature. Both the necessity and the functional form of the corresponding additional contributions follow readily from our treatment.Comment: 8 pages, 2 figures, LaTeX, RevTeX styl

Poisson -- Boltzmann Brownian Dynamics of Charged Colloids in Suspension

We describe a method to simulate the dynamics of charged colloidal particles suspended in a liquid containing dissociated ions and salt ions. Regimes of prime current interest are those of large volume fraction of colloids, highly charged particles and low salt concentrations. A description which is tractable under these conditions is obtained by treating the small dissociated and salt ions as continuous fields, while keeping the colloidal macroions as discrete particles. For each spatial configuration of the macroions, the electrostatic potential arising from all charges in the system is determined by solving the nonlinear Poisson--Boltzmann equation. From the electrostatic potential, the forces acting on the macroions are calculated and used in a Brownian dynamics simulation to obtain the motion of the latter. The method is validated by comparison to known results in a parameter regime where the effective interaction between the macroions is of a pairwise Yukawa form

Structure of Polyelectrolytes in Poor Solvent

We present simulations on charged polymers in poor solvent. First we investigate in detail the dilute concentration range with and without imposed extension constraints. The resulting necklace polymer conformations are analyzed in detail. We find strong fluctuations in the number of pearls and their sizes leading only to small signatures in the form factor and the force-extension relation. The scaling of the peak in the structure factor with the monomer density shows a pertinent different behavior from good solvent chains.Comment: 7 pages, 5 figures. submitted to EP

Connecting brain and behavior in clinical neuroscience: A network approach

In recent years, there has been an increase in applications of network science in many different fields. In clinical neuroscience and psychopathology, the developments and applications of network science have occurred mostly simultaneously, but without much collaboration between the two fields. The promise of integrating these network applications lies in a united framework to tackle one of the fundamental questions of our time: how to understand the link between brain and behavior. In the current overview, we bridge this gap by introducing conventions in both fields, highlighting similarities, and creating a common language that enables the exploitation of synergies. We provide research examples in autism research, as it accurately represents research lines in both network neuroscience and psychological networks. We integrate brain and behavior not only semantically, but also practically, by showcasing three methodological avenues that allow to combine networks of brain and behavioral data. As such, the current paper offers a stepping stone to further develop multi-modal networks and to integrate brain and behavior

Elastic deformation of a fluid membrane upon colloid binding

When a colloidal particle adheres to a fluid membrane, it induces elastic deformations in the membrane which oppose its own binding. The structural and energetic aspects of this balance are theoretically studied within the framework of a Helfrich Hamiltonian. Based on the full nonlinear shape equations for the membrane profile, a line of continuous binding transitions and a second line of discontinuous envelopment transitions are found, which meet at an unusual triple point. The regime of low tension is studied analytically using a small gradient expansion, while in the limit of large tension scaling arguments are derived which quantify the asymptotic behavior of phase boundary, degree of wrapping, and energy barrier. The maturation of animal viruses by budding is discussed as a biological example of such colloid-membrane interaction events.Comment: 14 pages, 9 figures, REVTeX style, follow-up on cond-mat/021242