Electrostatic Effects in Soft Matter and Biophysics NATO Series

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Series II: Mathematics, Physics and Chemistry - Voi. 46 Electrostatic Effects in Soft Matter and Biophysics

edited by

Christian Holm Max-Planck-Institut fur Polymerforschung, Mainz, Germany

Patrick Kekicheff Institut Charles Sadron, C.N.R.S., , and Rudolf Podgornik Department of Physics, University of Ljubljana, Ljubljana, Slovenia

SPRINGER-SCIENCE+BUSINESS MEDIA, B.V. Proceedings of the NATO Advanced Research Workshop on Electrostatic Effects in Soft Matter and Biophysics Les Houches, France 1-13 October 2000

A C.I.P. Catalogue record for this book is available from the Library of Congress.

ISBN 978-1-4020-0197-0 ISBN 978-94-010-0577-7 (eBook) DOI 10.1007/978-94-010-0577-7

Printed on acid-free paper

AII Rights Reserved ©2001 Springer Science+Business Media Dordrecht Originally published by Kluwer Academic Publishers in 2001 Softcover reprint of the hardcover 1st edition 2001 No part of the material protected by this copyright notice may be reproduced or utilized in any form or by any means, electronic or mechanical, including photocopying, recording or by any information storage and retrieval system, without written permission from the copyright owner. Preface

Recently theoretical interest in soft matter has finally caught up with its undisputed practical and technological relevance (high- and elastomers, polyelectrolyte hydrogels, food processing and storage, waste management, new tailored materials, etc.). But even more importantly charged soft matter appears to be at the heart of biotechnologies that are widely believed to be the most important technologies of this century and that already figure in many countries' technological strategies. Recent impetus in the elucidation of the structure of synthetic genosomes, com• plexes of negatively charged DNA and positively charged lipids, reveals all the subtleties that one has to master in order to be able to study and understand materials that are both soft and charged. Soft charged matter is dominated by the interplay of thermal fluctua• tions and long-range electrostatic effects on different length and time scales which results in complicated phase diagrams. The range of expertise that one needs to study charged soft matter is so wide, encompassing contin• uum mechanics, statistical mechanics, field theory, molecular simulations on the theoretical side and sophisticated experimental techniques such as direct force measurements, laser tweezers, light, X-ray and neutron scat• tering, atomic force microscopy, that it is quite unusual for any university department to be proficient in all its facets. The idea to organize the NATO Advanced Study Institute "Electrostatic Effects in Soft Matter and Biophysics" grew out of a workshop organized by W. Gelbart, A. Parsegian and P. Pincus in Santa Barbara at the ITP in 1998 with a similar theme. While there it was devoted to active researchers, mainly theorists, already familiar with the subject, we felt that it was time to do our share in educating young people to foster the development of this exciting and rapidly growing field. Our aim was to bring together theorists, computer simulators and ex• perimentalists from research areas as diverse as macromolecular charged colloids and biological materials like DNA. We tried to cover most ba• sic investigative tools on soft charged materials: analytical methods and approaches, computational tools and tricks of the trade, as well as experi• mental methods in their different ranges of applicability. The lectures were divided into three thematic blocks: The first block consisted of modern analytical methods used to describe electrostatic interactions between charged soft bodies with fixed charges vi PREFACE

immersed in a solution of mobile charge carriers. H. Wennerstrom intro• duced us to the intermolecular interactions specifically concentrating on the dielectric description in the condensed phase and the Lifshitz theory. R. Kjellander and R. Netz covered in depth the introduction to integral equation theories for the electric double layer and the mean-field Poisson• Boltzmann equation and all its varied consequences respectively. They also introduced us to the various modern theoretical approaches that go beyond the mean-field approximation. B. Shklovskii introduced us to his approach to electrostatic correlations based on the Wigner crystal model and showed us how different physical problems can be treated with this theory. R. Podgornik reviewed the work on the equation of state in charged macromolecular arrays motivated by recent experimental findings on or• dered DNA arrays and ordered multilamellar lipid arrays. B. Gelbart and A. Khokhlov reviewed some recent experimental and theoretical insights into DNA condensation and complexation, cationic histone proteins, and chromatin, and told us about new analytical and experimental approaches to understand these biologically important structures. J.-F. Joanny showed us how many problems in the physics of polyelectrolytes and polyam• pholytes in dilute and semi-dilute solutions can be treated with simple scaling theories. The second block consisted of an introduction to simulational methods of molecular dynamics and Monte Carlo approaches to soft matter sys• tems with long-range Coulombic interactions. B. Jonsson introduced us to protein electrostatics and compared theoretical approaches to Monte Carlo simulations. We also learned about correlation effects between plates and spheres and the collapse of DNA-like systems due to correlation interaction• s. K. Kremer prepared a grand tour of simulations, showed us how poor solvent modifies the behavior of polyelectrolytes and gave examples for deviations between theory and simulations for stiff rod polyelectrolytes. The last thematic block treated experimental methods. In depth cover• age of light, neutron, and X-rays scattering was performed by M. Caffrey, M. Rawiso, and C. Williams. They emphasized new type of experiments like real-time measurements, neutron spin echo, standing X-ray waves, reflectivity, photon correlation spectroscopy, X-ray speckles, and use of X-ray microbeams. A comparison between the main techniques of direct force measurements was presented by P. Kekicheff.These include tech• niques based on osmotic equilibria, surface force balances, surface force apparatus, atomic force microscope and force measurement techniques on individual freely moving particles (total internal reflection microscopy, etc). The advantages but also the limitations of each technique were underlined and discussed in different systems. In addition new methods applicable to charged systems (colloidal dispersions, polyelectrolytes, DNA assemblies) PREFACE vii

were presented (video microscopy, fluorescent microscopy, etc) by D. Grier in conjunction with structural and chemical inhomogeneities, defects and microphases either already present or induced upon confinement or under stress. The chapters in this book do not necessarily follow the courses presented at the school. The authors rather focus on a specific part of the lectures' content, giving adequate background material, trying to provide a reference chapter for further reading. Exactly for this purpose we also added an in• troductory chapter on the Poisson-Boltzmann description of the cell model, because it lies at the basis of many theoretical advances, and which was not treated in this way in the school. Unfortunately other urgent activities did not allow M. Rawiso to prepare a full version of his contribution in time, but he included a guide to the literature of his lectures. We think that all participants will agree that the Les Houches School provided a unique learning environment for all of us. We had enjoyable mountain trips with the daring experience of how long a return trip through the French Alps can be, if the guide gets lost, and a great cultural experience by visiting the van Gogh exhibition in Martigny. We spent a whole day without running water, thus testing the dedication and passion for science of the students as well as the lecturers. The students discussed eagerly their work at the poster sessions, and were willing to ask for more at the tutoring sessions that we organized after the lectures. We obtained a total of 140 applications for the 57 available positions from people of more than 19 different countries. We agreed only to accept a very limited number of senior scientists, and gave full priority to young scientists. For all of those that could not make it to Les Houches, and also because there is no single one textbook covering all the different facets of soft charged matter, it is our hope to service the science community with these proceedings. We would like to thank the people who helped us finish this project. At various stages those were T. Caramico, M. Karttune, and M. Richter. Many thanks go also to the staff at Les Houches, the members of the pep group at Mainz, and of course to all authors who accepted the heavy workload of contributing to this volume. Finally we gratefully acknowledge generous financial support by the NATO as ASI PST.ASI.976196 and the European Community under grant HPCFCT -1999-0130, with supplementary funds by the Max-Planck-Institut fur Polymerforschung which made this meeting possible.

Christian Holm, Patrick Kekicheff, Rudi Podgornik

Mainz, Strasbourg, Ljubljana, August 2001.

List of Participants

Directors

Holm, Christian Max-Planck-Institut fur Polymerforschung, Ackermannweg 10, 55128 Mainz, Germany. E-Mail: [email protected] Kekicheff, Patrick Institut Charles Sadron, C.N.R.S., 6 rue Boussingault, 67083 Strasbourg, France. E-Mail: [email protected] Podgornik, Rudolf Department of Physics, University of Ljubljana, Jadranska 19 SI-1000 Ljubljana, Slovenia. E-Mail: [email protected]

Lecturers

Caffrey, Martin Ohio State University, Department of Chemistry, 100 West 18th Avenue Columbus, OR 43210-1173, USA. E-Mail: [email protected] Gelbart, William Department of Chemistry, U.C.L.A. University of California, Los Angeles, CA 90095-1569, USA. E-Mail: [email protected] Grier, David G. University of Chicago, James Franck Institute, 5640 South Ellis Ave. Chicago, IL 60637-1433, USA. E-Mail: [email protected] Joanny, Jean-Franr;ois Physicochimie Curie, Institut Curie Section Recherche, 11 rue P.et M.Curie, 75231 Cedex 05. E-Mail: jean-francois.joanny@curieJr Jonsson, Bo Physical Chemistry Depart., Lund University Chern. Center, POB 124, 22100 Lund, Sweden. E-Mail: [email protected] Khokhlov, Alexei R. Moscow State University, Physics Department Moscow, 117234 Russia. E• Mail: polly.phys.msu.su x LIST OF PARTICIPANTS

Kjellander, Roland Physical Chemistry Dep., Goteborg University Fysikalisk kemi, 41296 Gote• borg, Sweden. E-Mail: [email protected] Kremer, Kurt Max-Planck-Institut fUr Polymerforschung, Ackermannweg 10, 55128 Mainz, Germany. E-Mail: [email protected] Netz, Roland R. Max-Planck-Institut fur Kolloid- und Grenzflachenforschung, 14424 Pots• dam, Germany. E-Mail: [email protected] Radler, Joachim O. Max-Planck-Institut fur Polymerforschung, Ackermannweg 10, 55128 Mainz, Germany. E-Mail: [email protected] Rawiso, Michel Institut Charles Sadron, C.N.R.S., 6 rue Boussingault, 67083 Strasbourg, France. E-Mail: [email protected] Shklovskii, Boris 1. University of Minnesota School of Physics and Astronomy, 116 Church St. SE, Minneapolis, MN 55455, USA. E-Mail: [email protected] Wennerstrom, Hdkan Department of Physical Chemistry, 1 Box 124 Chemical Center, 22100 Lund, Sweden. E-Mail: [email protected] Williams, Claudine E. CNRS-CollE~ge de France, 11 Place Marcellin-Berthelot, 75321 Paris, France. E-Mail: [email protected]

ASI Students

Baigl, Damien, CNRS-College de France, Physique de la Matiere Conden• see, 11, place Marcelin Berthelot, 75005 Paris, France. E-Mail: [email protected] Barbosa, Marcia, Instituto de Fisica, UFRGS, Caixa Postal 15051, RS 91501-970 Porto Alegre, Brazil. E-Mail: [email protected] Behrens, Sven Holger, University of Chicago, The James Franck Institute, 5640 S. Ellis Avenue, Chicago, IL 60637, USA. E-Mail: [email protected] Bergenholtz, Johan, University ofGothenburg, Dept. of Physical Chemistry, 41296 Goteborg, Sweden. E-Mail: [email protected] LIST OF PARTICIPANTS Xl

Betterton, Meredith, Curie Institute UMR CNRSjIC, 1b8 11 rue Pierre et Marie Curie, 75248 Paris Cedex 05, France. E-Mail: [email protected] Borukhov, Itamar, UCLA, Dept. of Chemistry and Biochemistry, 607 C. Young Dr. East, Los Angeles, CA 90095-1569, USA. E-Mail: [email protected] Burak, Yoram, Tel Aviv University, School of Physics and Astronomy, Tel Aviv, 69978, Israel. E-Mail: [email protected] Castelnovo, Martin, Institut Charles Sadron, 6 Rue Boussingault, 67083 Strasbourg, France. E-Mail: [email protected] Cepic, Mojca, Jozef Stefan Institute, Jamova 39, 1000 Ljubljana, Slovenia. E-Mail: [email protected] Deserno, Markus, UCLA, Dept. of Chemistry, 405 Hilgard Ave. Los Ange• les, CA 90095-1569, USA. E-Mail: [email protected] Dzeshkouski, Aliaksandr, University of North Carolina, Chemistry Dept., CBU3290, Chapel Hill, NC 27599-3290, USA. E-Mail: [email protected] Fleck, Christian, Universitat Konstanz, Fachbereich Physik, 78457 Kon• stanz, Germany. E-Mail: [email protected] Forsberg, Bjorn, University of Gothenburg, Dept. of Physical Chemistry, 41296 Goteborg, Sweden. E-Mail: [email protected] HiiujJler, Wolfgang, Max-Planck-Institut fur Polymerforschung, Acker• mannweg 10, 55128 Mainz, Germany. E-Mail: [email protected] Hagberg, Daniel, Lund University, Theoretical Chemistry Chem. Center, POB 124,22100 Lund, Sweden. E-Mail: [email protected] Hansen, Per Lyngs, National Institutes of Health, LPSBjNICHD, Bldg. 12A Rm. 2041, 12 South Drive, Bethesda, MD 20892-5626, USA. E-Mail: [email protected] Jonsson, Marie, Physical Chemistry 1, Box. 124, 22100 Lund, Sweden. E-Mail: [email protected] Jusufi, Arben, Heinrich-Heine-Universitat Dusseldorf, Institut fur Theo• retische Physik II, Universitatsstr. 1, 40225 Dusseldorf, Germany. E-Mail: [email protected] Karttunen, Mikko, Helsinki University of Technology, Laboratory of Com• putational , P.O. Box, 9400 02015 Hut Helsinki, Finland. E• Mail: [email protected] XlI LIST OF PARTICIPANTS

Khan, Malek, Lund University, Theoretical Chemistry, Box 124, 22100 Lund, Sweden. E-Mail: [email protected] Kramarenko, Elena, Moscow State University, Physics Dept. Moscow, 117234, Russia. E-Mail: [email protected] Kranenburg, Marieke, University of Amsterdam, Dept. Chemical • ing Nieuwe, Achtergracht 166, 1018 WV Amsterdam, The Netherlands. E-Mail: [email protected] Kunze, Karl-Kuno, Max-Planck-Institut fur Kolloid- und Grenzflachen• forschung, 14424 Potsdam, Germany. E-Mail: [email protected] Ligoure, Christian, CNRS GDPC CC26, University Montpellier, 2 Mont• pellier, 34095 CEDEX 05, France. E-Mail: [email protected] Limbach, Hans Jorg, Max-Planck-Institut fur Polymerforschung, Acker• mannweg 10, 55128 Mainz, Germany. E-Mail: [email protected] Lobaskin, Vladimir, Physics Dept. Chelyabinsk, State University, 454136 Chelyabinsk, Russia. E-Mail: [email protected] Loison, Claire, CECAM, ENS Lyon, 46 Allee d'Italie, 69364 Lyon Cedex 07, France. E-Mail: [email protected] Lopes, Antonio, ITQB-Institute for Techonological Chemistry and , New University of Lisbon Ap. 127, 2781-901 Oeiras, Portugal. E-Mail: [email protected] Lukatsky, Dmitry, Department of Materials and Interfaces, Weizmann, In• stitute of Science, Rehovot, 76100, Israel. E-Mail: [email protected] Martin-Molina, Alberto, Dept. Of Applied Physics, Campus de Fuente• nueva Univ. of Granada, 18071 Granada, Spain. E-Mail: [email protected] Messina, Rene, Max-Planck-Institut fur Polymerforschung, Ackermann• weg 10, 55128 Mainz, Germany. E-Mail: [email protected] Migliorini, Gabriele, Max-Planck-Institut fur Polymerforschung, Acker• mannweg 10, 55128 Mainz, Germany. E-Mail: [email protected] Moldakarimov, Samat, Institute of Polymer Materials and Technology, Sat• paev Str. 18a, 480013 Almaty, Kazakhstan. E-Mail: [email protected] Moreira, Andre Guerin, Max-Planck-Institut fur Kolloid- und Grenz• flachenforschung, 14424 Potsdam, Germany. E-Mail: [email protected] LIST OF PARTICIPANTS Xlll

Nguyen, The Toan, University of Minnesota, School of Physics, 116 Church Street S.E., Minneapolis, MN 55455, USA. E-Mail: [email protected] Oksana, Ismailova, Heat Physics Dept., Uzbek Academy of Sciences, Katar• tal 28, 700135 Tashkent, Uzbekistan. E-Mail: [email protected] Patkowski, Adam, A. Mickiewicz University, Umultowska 85, 61-614 Poz• nan, Poland. E-Mail: [email protected] Pinchuk, Anatoliy, Kyiv Shevchenko University, Eugene Potje 9/43, 03057 Kyiv, Ukraine. E-Mail: [email protected] Ramirez, Rosa, CECAM. ENS-Lyon 46, Allee d'Italie, 69007 Lyon, France. E-Mail: [email protected] Rastegar, Abbas, University of Nijmegen, Research Institute for Materi• als, Toernooiveld 1, 6525ED Nijmegen, The Netherlands. E-Mail: raste• [email protected] Rescic, Jurij, University of Ljubljana Faculty of Chemistry and Chemical Technology, Askerceva 5,1000 Ljubljana, Slovenia. E-Mail: jurij.rescic@uni• lj.si Schiessel, Helmut, Max-Planck-Institut fur Polymerforschung, Acker• mannweg 10, 55128 Mainz, Germany. E-Mail: [email protected] Sens, Pierre, Institut Charles Sadron, 6 Rue Boussingault, 67083 Stras• bourg, France. E-Mail: [email protected] Smith, Benjamin A., McGill University-Condensed matter Physics 3600 University st. Montreal, PQ H3A 2TB Canada. E-Mail: [email protected] Squires, Todd, Harvard Physics Department, Cambrigde, MA 02138, USA. E-Mail: [email protected] Tchoukov, Plamen Hristov, Institute of Physical Chemistry, Bulgarian Academy of Science Acad. G. Bonchev Str. bl. 11, 1113 Sofia, Bulgaria. E-Mail: [email protected] Tsori, Yoav, Tel Aviv University, School of Physics and Astronomy, Tel Aviv, 69978, Israel. E-Mail: [email protected] Vilfan, Andrej, Cavemdish Laboratory, TCM Group, Madingley Road, CB3 OHE Cambridge, UK. E-Mail: [email protected] Volk, Nicole Helena, Universitiit Mainz , Institut fur Physikalische Chemie, Welder Weg 11, 55099 Mainz, Germany. E-Mail: [email protected] XIV LIST OF PARTICIPANTS von Gruenberg, Hans-Henning, Universitat Konstanz, PF 5560, 78457 Kon• stanz, Germany. E-Mail: [email protected] Whiting, Carole Jo, University of Leeds, Polymer IRC, Physics Department Leeds, LS2 9JT West Yorkshire, UK. E-Mail: [email protected] Wilk, Agnieszka, Adam Mickiewicz University Poznan, Institute of Physics, ul. Umultowoska 85, 61-614 Poznan, Poland. E-Mail: [email protected] Zakharova, Svetlana, Leiden University, HB 325, LIC 7, Gorlaeus Labora• tories, Einteinweg 55, RA 2300 Leiden, The Netherlands. E-Mail: [email protected] Zeldovich, Konstantin, Moscow State University, Physics Dept. Moscow, 117234, Russia. E-Mail: [email protected] Zhumadilova, Gulmira, Institute of Polymer Materials and Technology, Satpaev str. 18a, 480013 Almaty, Kazakhstan. E-Mail: [email protected] Ziherl, Primoz, University of Pennsilvania, 209 South 33rd Street, Philadel• phia, PA 19104-6396, USA. E-Mail: [email protected] Contents

Preface...... v

List of Participants...... IX Structure and dynamic properties of membrane lipid and protein Martin Caffrey...... 1 Cell model and Poisson-Boltzmann theory: A brief introduction Markus Deserno, Christian Holm...... 27 DNA Condensation And Complexation William M. Gelbart...... 53 Interactions in Colloidal Suspensions David G. Grier and Sven H. Behrens...... 87 Computer Simulations of charged systems Christian Holm, Kurt Kremer...... 117 Scaling description of charged polymers Jean-Fran~ois Joanny ...... 149 When -Ion Correlations Are Important in Charged Colloidal Systems Bo Jonsson and Hiikan Wennerstrom. 171 Direct Surface Force Measurement Techniques Patrick Kekicheff ...... 205 Counterions in polyelectrolytes Alexei R.Khokhlov, Konstantin B.Zeldovich and Elena Yu. Kramarenko ...... 283 Distribution function theory of electrolytes and electrical double layers Roland Kjellander ...... 317 Field-Theoretic Approaches to Classical Charged Systems Andre G. Moreira and Roland R. Netz...... 367 xvi CONTENTS

Interactions and conformational fluctuations in macromolecular arrays Rudolf Podgornik ...... 409 Structure and phasebehavior of cationic-lipid DNA complexes Joachim O. Radler...... 441 Small angle scattering methods applied to polyelectrolyte solutions Michel Rawiso ...... 461 Lateral correlation of multivalent counterions is the universal mechanism of charge inversion Toan T. Nguyen, Alexander Yu. Grosberg and Boris I. Shklovskii .. 469 Highly Charged Polyelectrolytes : experimental aspects Claudine E. Williams...... 487 Index...... 507