1,878 research outputs found

    Variational theory for a single polyelectrolyte chain revisited

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    We reconsider the electrostatic contribution to the persistence length, e\ell_e, of a single, infinitely long charged polymer in the presence of screening. A Gaussian variational method is employed, taking e\ell_e as the only variational parameter. For weakly charged and flexible chains, crumpling occurs at small length scales because conformational fluctuations overcome electrostatic repulsion. The electrostatic persistence length depends on the square of the screening length, eκ2\ell_e\sim\kappa^{-2}, as first argued by Khokhlov and Khachaturian by applying the Odijk-Skolnick-Fixman (OSF) theory to a string of crumpled blobs. We compare our approach to previous theoretical works (including variational formulations) and show that the result eκ1\ell_e\sim\kappa^{-1} found by several authors comes from the improper use of a cutoff at small length scales. For highly charged and stiff chains, crumpling does not occur; here we recover the OSF result and validate the perturbative calculation for slightly bent rods.Comment: 11 pages, 6 figure

    Counterion Condensation and Fluctuation-Induced Attraction

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    We consider an overall neutral system consisting of two similarly charged plates and their oppositely charged counterions and analyze the electrostatic interaction between the two surfaces beyond the mean-field Poisson-Boltzmann approximation. Our physical picture is based on the fluctuation-driven counterion condensation model, in which a fraction of the counterions is allowed to ``condense'' onto the charged plates. In addition, an expression for the pressure is derived, which includes fluctuation contributions of the whole system. We find that for sufficiently high surface charges, the distance at which the attraction, arising from charge fluctuations, starts to dominate can be large compared to the Gouy-Chapmann length. We also demonstrate that depending on the valency, the system may exhibit a novel first-order binding transition at short distances.Comment: 15 pages, 8 figures, to appear in PR

    Conformational Instability of Rodlike Polyelectrolytes due to Counterion Fluctuations

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    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

    Collapse of Stiff Polyelectrolytes due to Counterion Fluctuations

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    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

    Personalisation and recommender systems in digital libraries

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    Widespread use of the Internet has resulted in digital libraries that are increasingly used by diverse communities of users for diverse purposes and in which sharing and collaboration have become important social elements. As such libraries become commonplace, as their contents and services become more varied, and as their patrons become more experienced with computer technology, users will expect more sophisticated services from these libraries. A simple search function, normally an integral part of any digital library, increasingly leads to user frustration as user needs become more complex and as the volume of managed information increases. Proactive digital libraries, where the library evolves from being passive and untailored, are seen as offering great potential for addressing and overcoming these issues and include techniques such as personalisation and recommender systems. In this paper, following on from the DELOS/NSF Working Group on Personalisation and Recommender Systems for Digital Libraries, which met and reported during 2003, we present some background material on the scope of personalisation and recommender systems in digital libraries. We then outline the working group’s vision for the evolution of digital libraries and the role that personalisation and recommender systems will play, and we present a series of research challenges and specific recommendations and research priorities for the field

    The Persistence Length of a Strongly Charged, Rod-like, Polyelectrolyte in the Presence of Salt

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    The persistence length of a single, intrinsically rigid polyelectrolyte chain, above the Manning condensation threshold is investigated theoretically in presence of added salt. Using a loop expansion method, the partition function is consistently calculated, taking into account corrections to mean-field theory. Within a mean-field approximation, the well-known results of Odijk, Skolnick and Fixman are reproduced. Beyond mean-field, it is found that density correlations between counterions and thermal fluctuations reduce the stiffness of the chain, indicating an effective attraction between monomers for highly charged chains and multivalent counterions. This attraction results in a possible mechanical instability (collapse), alluding to the phenomenon of DNA condensation. In addition, we find that more counterions condense on slightly bent conformations of the chain than predicted by the Manning model for the case of an infinite cylinder. Finally, our results are compared with previous models and experiments.Comment: 13 pages, 2 ps figure
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