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Preface xiii
Contributors xv
Polyelectrolytes. Physicochemical Aspects and Biological Significance Magnus Ullner 1
Introduction 1
Polyelectrolytes and Biological Function 1
Electrostatic Interactions 3
Ion Distributions and the Poisson-Boltzmann Equation 3
Debye-Huckel Theory 9
Solution Properties 13
Flexibility 17
The Concept of Persistence Length 17
Interactions and the Separation of Length Scales 23
Polyelectrolyte Behavior: Electrostatic Persistence Length 26
DNA Persistence Length 29
References 31
Solution Behavior of Nucleic Acids Rita S. Dias 41
Biological Function of Nucleic Acids 41
Discovery of DNA 41
Structure of Nucleic Acids 43
DNA 43
RNA 47
Analogues of Nucleic Acids 48
Nuclei Acids Nanostructures 48
DNA 48
RNA 50
Behavior of DNA in Solution 51
Ionization Equilibrium 51
Flexibility of NucleicAcids 51
Melting of Double-Stranded DNA 52
Effect of Base Composition 53
Effect of Ionic Strength 53
Effect of pH 53
Dependence on DNA Chain Length 54
Dependence on DNA Concentration 54
Acknowledgments 55
References 55
Single DNA Molecules: Compaction and Decompaction Anatoly A. Zinchenko Olga A. Pyshkina Andrey V. Lezov Vladimir G. Sergeyev Kenichi Yoshikawa 59
Introduction 59
Condensation and Compaction of DNA by Surfactants 60
Linear DNA Condensation/Compaction by Positively Charged Surfactants 60
Compaction of Plasmid DNA with Surfactants 63
Non-ionic Surfactants 64
Zwitterionic Surfactants 64
Decompaction of DNA-Surfactant Complex 65
DNA Condensation by Cationic Liposomes 65
DNA Compaction and Decompaction by Multivalent Cations 74
DNA Compaction by Polycations 77
Compaction of DNA in a Crowded Environment of Neutral Polymer 81
Conclusion 82
References 82
Interaction of DNA with Surfactants in Solution Rita S. Dias Kenneth Dawson Maria G. Miguel 89
Introduction 89
Surfactants 89
Polymer-Surfactant Interactions 93
Polyelectrolyte-Oppositely Charged Surfactant Interactions 94
DNA-Surfactant Interactions 95
DNA-Cationic Surfactant Interactions 96
Solution Behavior 96
Effect of the Surfactant Chain Length 99
Effect of the Surfactant Head-group 101
Structure of DNA-Surfactant Complexes 102
DNA Is an Amphiphilic Polyelectrolyte 105
DNA Covalent Gels and Their Interaction with Surfactants 106
Applications 108
Control of DNA Compaction/Decompaction 108
Purification 110
Gene Transfection 110
Acknowledgments 111
References 111
Interaction of DNA with Cationic Polymers Eric Raspaud Adriana C. Toma Francoise Livolant Joachim Radler 119
Introduction 119
Theory of DNA Interacting with Polycations 120
Manning Condensation 120
Counterion Release 121
Short-Range Attractive Force due to Ion Correlations 121
Phase Diagrams of Condensed DNA-Polycation Phases 121
Finite-Size Aggregates 122
Condensation of DNA, Phase Diagram, and Structure 122
Short Polycations and Multivalent Cations 123
Long Polycations and Basic Proteins 123
Formation of Polycation-DNA Complexes: Polyplexes 125
DNA-Nanoparticles for Gene Delivery 126
Artificial Viruses 126
Cytotoxicity 127
Cellular Uptake and Intracellular Interactions of Polyplexes 127
Conclusion 129
Acknowledgment 129
References 129
Interactions of Histones with DNA: Nucleosome Assembly, Stability, Dynamics, and Higher Order Structure Karsten Rippe Jacek Mazurkiewicz Nick Kepper 135
Introduction 135
Histones 136
Core Histones 136
Linker Histones 137
Histone Variants 138
Posttranslational Modifications of Histones 141
Structure of Histone-DNA Complexes 142
Nucleosome 142
Chromatosome 144
Assembly of Nucleosomes and Chromatosomes 144
Chaperone-Guided Nucleosome Assembly 146
Chromatin Remodeling Complexes 147
Stability and Dynamics of Nucleosomes 148
Accessibility of Nucleosomal DNA 148
DNA Sequence Specificity of Nucleosome Binding 149
Thermodynamic and Kinetic Parameters for Nucleosome Formation under Physiological Conditions 150
Higher Order Chromatin Structures 154
Assembly of Chromatin Fibers 154
Higher Order Folding of Chromatin Fibers 157
Acknowledgments 158
References 158
Opening and Closing DNA: Theories on the Nucleosome Igor M. Kulic Helmut Schiessel 173
Introduction 173
Unwrapping Nucleosomes 176
Nucleosome Sliding 180
Transcription Through Nucleosomes 187
Tail Bridging 194
Discussion and Conclusion 202
Acknowledgment 204
References 204
DNA-DNA Interactions Lars Nordenskiold Nikolay Korolev Alexander P. Lyubartsev 209
Introduction 209
The Statistical Polymer Solution Model Predicts DNA Collapse/Aggregation Phase Behavior 211
DNA in Solution is Condensed to a Compact State by Multivalent Cationic Ligands 214
DNA Compaction in Solution 214
Experimental Studies on Chromatin and Nucleosome Condensation 219
Measurement of DNA-DNA Forces from Osmotic Stress 221
Ion Correlation Effects Included in Theory and in Computer Modeling Explain DNA-DNA Attraction 222
Analytical Theories of DNA-DNA Interactions 222
Computer Simulations of DNA-DNA Interactions 224
Modeling DNA-DNA Interactions in Chromatin and NCP 227
Conclusions and Future Prospects 230
References 231
Hydration of DNA-Amphiphile Complexes Cecilia Leal Hakan Wennerstrom 239
Introduction 239
General Properties of DNA Double Helices and Cationic Aggregates 240
Thermodynamics of DNA-Amphiphile Complexes 243
Molecular Properties of DNA-Amphiphile Complexes 247
Concluding Remarks 249
References 250
DNA-Surfactant/Lipid Complexes at Liquid Interfaces Dominique Langevin 253
Introduction 253
Soluble Surfactants 255
DNA-DTAB Surface Layers 255
Other DNA-Cationic Surfactants Systems 261
DNA Surfactants 262
Insoluble Surfactants 262
DNA-DODAB Surface Layers 263
DNA-TODAB Surface Layers 267
DNA-ODA Surface Layers 271
DNA Binding with Other Surfactant Layers 273
Lipids 274
Cationic Lipids-DNA Surface Layers 275
DSPC-Divalent Ion-DNA Surface Layers 276
DPPC-Divalent Ion-DNA Surface Layers 278
DMPE-Divalent Ion-DNA Surface Layers 279
Other Types of Binding 283
Mixtures of Surfactants and Lipids 284
Conclusion 285
References 286
DNA and DNA-Surfactant Complexes at Solid Surfaces Marite Cardenas Tommy Nylander 291
Introduction 291
Adsorption of DNA at Surfaces 292
Attachment of DNA Surfaces-Strategies and Challenges 294
DNA Structure on Surfaces-Comparison with Highly Charged Polyelectrolytes 297
Regulating the DNA Compaction by Compaction Agents at Interfaces to Control the Structure 297
Cationic Surfactants and DNA at Hydrophobic Surfaces 298
Cationic Surfactants and DNA at Negatively Charged Surfaces 304
Some Applications-Arrays and Nanostamping 307
Acknowledgments 310
References 310
Role of Correlation Forces for DNA-Cosolute Interactions Malek O. Khan 317
Introduction 317
Experimental Evidence of DNA Condensation Induced by Electrostatic Agents 317
Simulations Used to Characterize the DNA Compaction Mechanism 319
Ion Correlations Limiting the Validity of DLVO Theory 320
Ion Correlations Driving the Compaction of DNA 322
Conformation of Compact DNA-The Coil to Toroid Transition 328
Conclusions 332
References 334
Simulations of Polyions: Compaction, Adsorption onto Surfaces, and Confinement A.A.C.C. Pais P. Linse 337
Introduction 337
Models 339
Solutions of Polyions with Multivalent Counterions 340
Polyion Conformation 340
Small-Ion Distribution 341
Other Aspects 343
Polyion Adsorption onto Charged Surfaces 343
Surfaces with Homogeneous Surface Charge Densities 344
Surfaces with Heterogeneous Surface Charge Densities 344
Polyions in Confined Geometries 346
Structural Aspects 347
Free Energies 347
Concluding Remarks 349
References 349
Cross-linked DNA Gels and Gel Particles Diana Costa M. Carmen Moran Maria G. Miguel Bjorn Lindman 353
Introduction 353
Covalently Cross-Linked DNA Gels 354
Volumetric Behavior of DNA Gel Probes DNA-Cosolute Interactions 354
Swelling Reversibility 357
ds-DNA versus ss-DNA: Skin Formation 357
DNA Gel Particles 358
Particle Characterization 358
Particle Swelling and Deswelling Kinetics 359
Kinetics of DNA Release 360
Physical DNA Gels 361
Phase Behavior 361
Rheological Studies 362
References 363
DNA as an Amphiphilic Polymer Rita S. Dias Maria G. Miguel Bjorn Lindman 367
Some General Aspects of Self-Assembly 367
Illustrations 369
Solubilization of Hydrophobic Molecules in ds-DNA 370
Adsorption on Hydrophobic Surfaces 372
Effects of Hydrophobic Cosolutes on DNA Melting 372
Differences in Interactions (Phase Separation) of Cationic Surfactants between ss-DNA and ds-DNA 373
DNA-Protein Interaction 374
Dependence of DNA Melting on Base Sequence 374
DNA Physical and Chemical Gels 374
References 375
Lipid-DNA Interactions: Structure-Function Studies of Nanomaterials for Gene Delivery Kai K. Ewert Charles E. Samuel Cyrus R. Safinya 377
Introduction 377
Formation and Structures of CL-DNA Complexes 378
Effect of the Lipid-DNA Charge Ratio ([rho subscript chg]) on CL-DNA Complex Properties 383
Physicochemical Effects and Phase Behavior of CL-DNA Lipids 383
Biological Effects 386
Effect of the Membrane Charge Density ([sigma subscript M]) on CL-DNA Complex Properties 387
Effect of Nonlamellar CL-DNA Complex Structure on the Transfection Mechanism 391
Model of Transfection with Lamellar CL-DNA Complexes 393
Model of Transfection with Inverted Hexagonal CL-DNA Complexes 395
PEGylated CL-DNA Complexes: Surface Functionalization and Distinct DNA-DNA Interaction Regimes 396
DNA-DNA Interaction Regimes in PEG-Lipid CL-DNA Complexes 396
Surface Functionalization of CL-DNA Complexes with PEG-Lipids 397
Conclusion and Summary 400
Acknowledgments 400
References 401
Index 405
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