Soft Matter Characterization

front-matter......Page 1
Basic Concepts - Scattering and Time Correlation Functions......Page 36
2 Basic Scattering Theory - Interference......Page 38
3 Fundamentals of Time Correlation Functions......Page 42
3.2 Time Averages......Page 43
3.2.1 Basic Definitions......Page 44
3.3.2 Long Time Limit......Page 45
3.3.4 Other Common Forms for Time Correlation Functions......Page 46
3.4 Ensemble-Averaged Time Correlation Functions......Page 47
3.5 Spectral Densities of Time Correlation Functions......Page 49
4.1 Spatial Fourier Transforms......Page 50
4.3 Space Time Correlation Function of the Local Density......Page 51
4.4 The Van Hove Space Time Correlation Function......Page 52
4.6 Physical Interpretation, Limiting Values and the Radial Distribution Function......Page 53
4.7 The Structure Factor......Page 54
4.9 Space Time Correlation Functions for Perfect.Gases......Page 55
5.1 Derivation of the Diffusion Equation......Page 58
5.2 Random Walk......Page 60
5.4 Solution of Partial Differential Equations......Page 61
5.5 Expression for the Diffusion Coefficient......Page 63
5.6 The Langevin Equation......Page 64
5.7 The Stokes-Einstein Relation......Page 65
6.1 Translational Motion of Small Molecules in Liquids - The Gaussian Approximation......Page 66
6.2 Molecular Dynamics Simulations......Page 67
6.4 Molecular Dynamics Tests of the Stokes-EinsteinRelation for Hard Sphere Fluids......Page 68
6.6 Diffusion in Quasi-Two Dimensional Systems......Page 69
7.1 The Hydrodynamic Radius......Page 70
7.2.1 Ellipsoids of Revolution......Page 71
7.3 Non-Dilute Dispersions......Page 72
8 Conclusion......Page 73
References......Page 74
Total Intensity Light Scattering from Solutions of Macromolecules......Page 76
1 Introduction......Page 884
2 What Does SAXS Measure?......Page 1094
3.1 The Basic Relation......Page 84
3.2 Identical Scattering Elements......Page 85
3.3 Optically Diverse Scattering Elements......Page 86
3.4 Optically Anisotropic Scattering Elements......Page 88
3.5 Scattering Beyond the RGD Regime......Page 90
4.2 Identical Scattering Elements......Page 92
4.3 Optically Diverse Scattering Elements......Page 97
4.4 Optically Anisotropic Scattering Elements......Page 99
4.5 Scattering Beyond the RGD Regime......Page 101
5 Gelation Versus Crystallization......Page 551
5.2 Identical Scattering Elements......Page 103
5.3 Optically Diverse Scattering Elements......Page 114
5.4 Optically Anisotropic Scattering Elements......Page 116
5.5 Scattering Beyond the RGD Regime......Page 117
A Material Properties of Fluid Membranes......Page 120
6.2 Monodisperse Solute, Identical Optically Isotropic Scattering Elements......Page 122
6.3 Heterodisperse Solute, Identical Optically Isotropic Scattering Elements......Page 124
6.4 Optically Diverse, Isotropic Scattering Elements......Page 127
7.1 The Basic Relation......Page 129
7.2 Low Concentrations: the Third Virial Coefficient......Page 130
7.3 Concentrated Solutions......Page 131
7.4 Moderately Concentrated Solutions......Page 135
8.1 The Basic Relation......Page 139
8.2 Dilute to Low Concentrations......Page 140
8.3 Concentrated Solutions......Page 141
8.4 Moderately Concentrated Solutions......Page 142
8.5 Behavior for a Charged Solute......Page 147
9.1 Intermolecular Association in Polymer Solutions......Page 149
9.2 Intermolecular Association in Micelle Solutions......Page 153
9.3 Online Monitoring of Polymerization Systems......Page 154
References......Page 157
Small-Angle Scattering from Surfactants and Block Copolymer Micelles......Page 167
1 Introduction......Page 169
2 Description of SANS Instruments......Page 170
2.2 Experimental Evidence......Page 175
2.2.1 Sample Preparation, Equipment and Data Analysis......Page 176
2.3.1 Linear Coil-Coil Diblock Copolymer Solution......Page 177
2.3.2 Cyclic Coil-Coil and Linear Rod-Coil Diblock Copolymer Solutions......Page 180
2.4.1 Cyclic Coil-Coil Diblock Copolymer......Page 181
2.4.2 Linear Rod-Coil Diblock Copolymer......Page 186
2.5.1 Ring Cod-Coil Diblock Copolymer......Page 188
2.5.2 Linear Rod-Coil Diblock Copolymer......Page 191
2.6 Extension to the Diblock Copolymer in the Melt Case......Page 193
3 Self-Organization of Block Copolymers......Page 194
3.1 Self-Assembly in Bulk......Page 196
3.1.1 Morphology......Page 197
3.1.2.1 Solvent Evaporation Under Controlled Conditions......Page 200
3.1.2.2 Spin- and Dip-Coating......Page 201
3.2 Self-Assembly in Solution......Page 202
3.2.1 Morphology......Page 203
3.2.2 Micelle Structure......Page 204
3.2.3 Micelle Dynamics......Page 206
3.2.3.2 Unimers Exchange and Micelle Hybridization......Page 207
3.2.4 Methods of Micelle Preparation......Page 209
3.2.4.1 Direct Dissolution......Page 210
3.2.4.2 Indirect Dissolution, Co-solvent or Dialysis Method......Page 211
3.2.4.3 Stimulus-Induced Self-Organization......Page 212
3.2.4.4 Film Casting/Film Re-hydratation......Page 213
3.2.5 Control of Micelle Behavior at Core and Corona Levels......Page 214
4 Towards Water-Soluble Dendrigrafts [34]......Page 1369
References......Page 218
4. Small-Angle Scattering from Surfactants and Block Copolymer Micelles......Page 224
1 Introduction......Page 225
2 The Various Preparation Methods......Page 1120
3 Disorder under Coherent Illumination......Page 229
3.2 Globular Core-Shell Micellar Models......Page 236
3.3 Cylindrical Elongated and Disk-Like Core-Shell Micelles......Page 240
3.4 Long Cylindrical and Worm-Like Micelles......Page 241
4 Manipulation for Single Molecule Measurements......Page 250
4.1 Models with Non-Interacting Gaussian Chains......Page 251
4.2 Models with Interacting Excluded-Volume Chains......Page 252
4.3 Calculation of Radial Profiles......Page 258
5.2 Concentrated Solutions and Suspensions......Page 657
Acknowledgements......Page 263
B The ADE Phase Diagram......Page 264
Brush-Like Polymers......Page 267
2 Theoretical Models for Brush-Like Polymers......Page 270
2.1.2 Scattering Function......Page 271
2.1.3 Hydrodynamic Radius......Page 273
2.2.1 Radius of Gyration......Page 274
2.2.2 Scattering Function......Page 277
2.2.3 Hydrodynamic Radius......Page 280
2.2.4 Intrinsic Viscosity......Page 282
2.3.1 Radius of Gyration......Page 284
2.3.2 Scattering Function......Page 286
2.3.3 Hydrodynamic Radius......Page 287
2.4.1 Radius of Gyration......Page 288
2.4.2 Scattering Function......Page 290
3.1 Motivation: Why  \"Tweeze \"?......Page 1169
3.1 Polymacromonomers......Page 292
3.1.1 Solvents......Page 294
3.1.2 Radius of Gyration......Page 296
3.1.3.1 Cross-Section Plot......Page 302
3.1.3.2 Kratky Plot......Page 303
3.1.3.3 Holtzer Plot......Page 305
3.1.4 Steady Transport Coefficients......Page 306
3.1.5 Backbone Stiffness......Page 309
3.2 Combs and Centipedes......Page 311
Appendix A Characteristic Function for WormLike Chains......Page 314
References......Page 315
Polyelectrolytes-Theory and Simulations......Page 319
1 Introduction......Page 1148
2 Principle and Operating of AFM......Page 321
3.1 Specification of the Cell Model......Page 324
3.2 Poisson-Boltzmann Theory......Page 326
3.3 Solution of the Poisson-Boltzmann Equation for the Cylindrical Case......Page 327
3.5 Limiting Laws of the Cylindrical PB-Solution......Page 329
4 Methodology......Page 331
5 Solutions of Block Copolymers Forming Lyotropic Liquid Crystal Phases......Page 334
5.1 Simulations of Osmotic Coefficients and Counterion Induced Attractions......Page 336
5.2 Simulations of Rods of Finite Length......Page 339
6 Conclusion......Page 1439
7.1 Introduction......Page 346
7.2 Pearl-Necklace Conformation......Page 347
7.3.1 Fluctuations......Page 349
7.3.2 Single Chain Form Factor S1(q)......Page 353
7.3.3 Scaling of the Correlation Length with Density......Page 355
7.3.4 Stretching Pearl Necklaces......Page 356
8 Polyelectrolyte Networks......Page 357
8.1 Conformation in Poor Solvent......Page 360
Acknowledgments......Page 361
References......Page 362
7. Dynamic Light Scattering......Page 366
Small-Angle Scattering of Block Copolymers......Page 1031
1.2 Dynamic Light Scattering and Laser Light Scattering......Page 367
1.3 Laser Light Scattering and X-Ray/Neutron Scattering......Page 368
2.1 Energy Transfer versus Momentum Transfer......Page 370
2.2 Siegert Relation and Time Correlation Functions.[11]......Page 371
2.3 Diffusions and Internal Motions......Page 373
2.4 Practice of (Single-Scattering) Photon Correlation Experiments......Page 375
2.4.1 Coherence Consideration via the Phase Integral......Page 376
2.4.2 Angular Apertures and Field Stops [11]......Page 377
3 The Size of a Biomolecule: Radius-of-Gyration Measurements......Page 379
3.2.1 Scattering Geometries for Photon Correlation and Cross-Correlation......Page 381
3.2.2 Cross-Correlation Functions......Page 384
4.1 General Considerations [10]......Page 386
4.2.1 Fiber-Optic Dynamic Light Scattering......Page 387
4.3 Practice of Photon Cross-Correlation Spectroscopy......Page 390
Acknowledgments......Page 906
5.1.1 Ensemble-Averaging of a Slow Relaxing System......Page 392
5.1.2 Theory......Page 393
5.2.1 Laser Doppler Velocimetry......Page 395
5.2.2 Phase Analysis Light Scattering [94, 98-102]......Page 396
Acknowledgments......Page 400
References......Page 401
8. Light Scattering from Multicomponent Polymer Systems......Page 404
Single Molecule Microscopy......Page 733
1 Introduction......Page 910
1.1 General Background......Page 409
1.2 Principles of Rheo-Optics......Page 410
2.1 Background of Shear Rheo-Optics......Page 411
2.2 Shear-Induced Phase Transition: Two Opposing Phenomena, Mixing and Demixing......Page 414
3.1 Pullulan......Page 507
3.1 Dynamical Asymmetry Versus Dynamical Symmetry......Page 416
3.2 Some Anticipated Effects of Dynamical Asymmetry on Self-Assembly in the Quiescent State......Page 418
3.3 Basic Time-Evolution Equation and a Theoretical Analysis of the Early Stage Self-Assembly in Dynamically Asymmetric Syste......Page 424
3.4 General Background on the Effects of Shear Flow on Self-Assembly of Both Dynamically Symmetric and Asymmetric Systems......Page 428
4.1 Simultaneous Measurements of Stress, Optical Microscopy, Light Scattering, Transmittance, Birefringence, etc......Page 430
4.2 Examples: Simultaneous Measurements of Stress, Shear-SALS, and Shear-Microscopy......Page 438
5.1 Shear-Rate Dependence of Steady-State Structures......Page 447
5.2 Uniformity of Droplet Size in Regime II......Page 450
5.3 String Structure in Regime IV......Page 452
5.4 Shear-Induced Phase Transition......Page 455
5.5 Small Molecules Versus Polymers......Page 460
5.6 Tracing Back the Growth History of Phase-Separated Structures......Page 463
6 Three-Dimensional Reconstruction of Molecule Shapes......Page 465
6.1 Observation of Shear-Induced Dissipative Structures......Page 466
6.2 Origin of Shear-Induced Formation of Dissipative Structures......Page 468
6.3 Shear-Rate Dependence......Page 470
6.4 Time-Evolution of Transient Dissipative Structures......Page 477
6.5 Further Remarks......Page 481
6.6 Shear-Induced Dissipative Structures Formed for Semidilute Crystallizable Polymer Solutions......Page 486
7 Crystallization of Adsorbed Polymer Monolayers......Page 1280
References......Page 489
9. Light Scattering from Polysaccharrides as Soft Materials......Page 494
1.1 Polysaccharides are Archetypes for Soft Materials......Page 496
2 Some General Considerations......Page 499
2.1 Can Static Light Scattering Shed some Light onto the Reasons for Softness?......Page 500
2.2.1 Relevance of the Translational Diffusion Coefficient......Page 503
2.2.2 Segmental Mobility......Page 504
2.2.3 Effect of Finite Concentration......Page 505
3.2 Homoglucans of the a(1-4) and ß(1-4) Type......Page 511
3.2.1  Cellulose-(CTC) and Amylose Tri-Carbanilate (ATC)......Page 512
3.2.2 Aqueous Metal Complexes as Solvents......Page 516
3.2.3 Solutions of Amylose......Page 526
3.3.3 Cellulose and Amylose in FeTNa......Page 531
4 Single- and Multiple Helices. Exocellular Polysaccharides......Page 534
4.1 Xanthan......Page 535
4.2 Gellan and Polysaccharides from the Rhizobia Family......Page 540
4.3 Schizoplylan......Page 546
4.4 rho-Parameter and Second Virial Coefficient......Page 548
4.5 Effects of Coulomb Charges and of Flexible Side Chains......Page 549
5.1 Alginates: Evidence for Bundle Formation......Page 555
5.2 The Carrageenans: Evidence for Double Helix Formation......Page 559
5.3 Summary of the Dispute on Double or Single Helices as Unimers......Page 566
6 Thickeners - What Inhibits Gel Formation?......Page 567
6.1 Galactomannans and Xyloglucans......Page 568
6.2 Properties of Nonheated Tamarind Polysaccharides......Page 572
6.3 Properties of Enzymatically Oxidized Tamarind Polysaccharides......Page 574
References......Page 577
7.1.2 Hyperbranching......Page 580
7.2.1 Suggested Amylopectin Structures......Page 583
7.2.2 Amylopectin Fragments by Controlled Degradation......Page 584
7.2.3 Starches of Different Origin......Page 593
8 Chain Dynamics......Page 595
8.1 Effects of Segmental Concentration in the Particle......Page 596
8.2.1 Some General Relationships for Flexible Particles......Page 599
8.2.2 Effect of Chain Stiffness......Page 601
8.2.3 Effect of Branching on the TCF......Page 604
8.3.1 Gelation of Hyperbranched Polysaccharides Forced by Small Molecular Weight Compounds......Page 605
8.3.2 Hydrodynamic Correlation Length......Page 606
8.3.3 Shape of the Time Correlation Function in the Course of Sol-gel Transformation......Page 608
8.3.4 Heterodyne or Nonergodic Scattering Behavior......Page 610
9.1 Objectives of this Section......Page 612
9.2 Static Light Scattering......Page 613
9.2.1 Significance of Appropriate Plots......Page 615
9.2.2 Concentration Dependence......Page 618
9.3.1 Time Correlation Function and Hydrodynamic Radius......Page 620
9.3.2 Effect of Polydispersity and Internal Segmental Motion......Page 622
References......Page 624
Fluorescence Photobleaching Recovery......Page 635
1 Introduction......Page 637
2 General Principle......Page 638
3 Comparison of Theory and Experiment......Page 741
3.1 General Considerations......Page 639
3.3 Cleanup......Page 641
3.4 Validating the Labeled Macromolecule......Page 643
3.5 Recipes......Page 644
References......Page 645
4.2 Single-Beam FPR Devices......Page 648
4.3 Two-Beam Instruments......Page 654
5.4 Liquid Crystals......Page 658
5.5 Gels......Page 659
5.7 Thin Films and Surfaces......Page 660
5.8 Other Applications......Page 661
Acknowledgments......Page 662
References......Page 663
Fluorescence Correlation Spectroscopy......Page 667
1 Introduction......Page 668
2 Coherent X-Rays from a Synchrotron Source......Page 966
2.1 One-Photon Excitation......Page 670
2.2 Two-Photon Excitation......Page 672
2.3 Fluorescent Dyes......Page 674
3.1 Autocorrelation Analysis......Page 676
3.2 Cross-Correlation Analysis......Page 685
4 Monomer, Dimer, or Multimer?......Page 1099
4.1 Concentration and Aggregation Measurements......Page 687
4.2.1 Diffusion Analysis......Page 688
4.2.2 Confined and Anomalous Diffusion......Page 689
4.2.3 Active Transport Phenomena in Tubular Structures......Page 690
4.2.4 Determination of Molecular Interactions......Page 692
4.2.5 Conformational Changes......Page 693
4.3 Consideration of Cross-Correlation Amplitudes: A.Direct Way to Monitor Association/Dissociation and Enzyme Kinetics......Page 694
4.3.1 Two-Photon Cross-Correlation Analysis......Page 696
4.3.2 Scanning Cross-Correlation......Page 698
4.4 Consideration of Fast Flickering: Intramolecular Dynamics and Probing of the Microenvironment......Page 701
References......Page 703
Forced Rayleigh Scattering - Principles and Application (Self Diffusion of Spherical Nanoparticles and Copolymer Micelle......Page 706
1 Introduction......Page 707
2.1 Experimental Setup......Page 708
2.2.1 Single Grating and Detection of Translational Diffusion Coefficients......Page 711
2.2.2 Detection of Rotational Diffusion Coefficients in FRS Experiments......Page 713
2.2.3 Complementary Grating Phenomena......Page 715
2.2.4 Thermal Diffusion Coefficients......Page 716
3 Applications......Page 718
3.1 Self Diffusion of Colloidal Particles in HighlyConcentrated Colloidal Dispersions......Page 719
3.2 Self Diffusion of Copolymer Micelles in a Homopolymer Melt......Page 722
3.2.1 Rotational Self Diffusion of Frozen Copolymer Micelles......Page 723
3.2.2 Self Diffusion of Copolymer Micelles in a Homopolymer Melt of Varying Molar Mass......Page 725
3.2.3 Complementary Grating Effects Detected by FRS on Copolymer Micelles in a Homopolymer Melt close to the Liquid-Solid Tran......Page 728
4 Instabilities of a Moving Dewetting Rim......Page 938
6 Instrument Resolution and Polydispersity......Page 773
1 Introduction......Page 735
2.1 The Steady-State Instrument D22......Page 736
2.2 The Time-of-Flight Instrument LOQ......Page 737
2.3 Detectors for SANS Instruments......Page 739
3.2 Choice of Configurations and Systematic Required Measurements......Page 742
3.2.3 .Beam-Stop Alignment......Page 743
3.2.6 Transmission......Page 744
3.3 Conclusion......Page 745
4 From Raw Data to Absolute Scaling......Page 746
4.2 Normalization with a Standard Sample......Page 747
4.3 Solid Angle DeltaOmega(Q)......Page 749
4.4.1 Definition......Page 750
4.4.2 Numerical Applications and Examples......Page 751
4.4.3 Transmission at Large Angles......Page 752
4.5 Multiple Scattering......Page 753
4.5.1 Transmission at Large Angles......Page 754
4.6 Subtraction of Incoherent Background......Page 755
References......Page 756
5.2 SLD, Contrast Variation, and Isotopic Labeling......Page 759
5.2.1 The Zero Average Contrast Method......Page 760
5.2.2 Contrast Variation Technique......Page 761
5.2.4 Limits of Isotopic Labeling......Page 762
5.3 Analytical Expressions of Particle Form Factors......Page 763
5.3.2 Concentric Shells and Hollow Sphere......Page 764
5.3.4 Ellipsoid......Page 765
5.3.7 Fractals......Page 766
5.3.8 Concentrated Surfactant Phases......Page 767
5.3.10 Case of Interfaces......Page 768
5.4 Indirect Fourier Transform Method......Page 769
5.5 Structure Factors of Colloids......Page 771
6.2 Effect of the lambda Distribution......Page 775
6.3.1 Evidence of Wavelength Spread on Bragg Peaks......Page 777
6.3.2 Importance of the Choice of Instrument Configurations......Page 778
6.4 Polydispersity......Page 779
6.5 Instrumental Resolution and Polydispersity......Page 780
6.6 Conclusion......Page 781
6.7.1 Wavelength Distribution......Page 782
6.7.2 Angular Distribution......Page 783
7.1 Recent Developments......Page 784
7.2.1 Interactive Instrument Control......Page 785
7.2.3 Ultra Small-Angle Scattering (USANS)......Page 786
7.3 General Conclusion......Page 787
References......Page 788
Small Angle Neutron Scattering on Gels......Page 793
1 General Introduction......Page 1388
2 Single Molecule Fluorescence Imaging......Page 797
2.2 Scattering Functions for Polymer Gels......Page 799
2.3 Phenomenological Scattering Theories of Polymer Gels......Page 800
2.4 Inhomogeneities in Gels......Page 801
2.5 Statistical Theory of Polymer Gels......Page 803
3 Quantitative Analysis of Dewetting Experiments......Page 805
3.2 Swollen and Deswollen Gels......Page 811
3.3.1 Non-Charged Gels......Page 814
3.3.2 Charged Gels......Page 817
3.4 Critical Phenomena and Volume Phase Transition......Page 819
3.4.1 Isobar and Isochore Lines [15]......Page 820
3.4.2 Critical Phenomena with Respect to Temperature......Page 821
3.4.3 Critical Phenomena with Respect to Pressure......Page 823
3.5 Charged Gels and Microphase Separation......Page 825
3.5.1 Borue-Erukhimovich (BE) Theory for Weakly Charged Polymer Solutions......Page 826
3.5.3 Scattering Inflection......Page 830
3.6.1 Biopolymer Gels......Page 833
3.6.2 Physical Gels Formed with Microcrystallites......Page 834
3.6.4 Ion-Complexed Gels......Page 835
3.7 Oil Gelators......Page 836
4 Concluding Remarks......Page 837
References......Page 839
Complex Melts under Extreme Conditions: From Liquid Crystal to Polymers......Page 843
2 Instabilities of Thin Liquid Films Induced by Long-Range Forces......Page 1033
2.1.2 From Liquid Crystals to Side-Chain Liquid Crystal Polymers......Page 847
2.2.1 The Smectic Phase of SCLC-Polymers under Flow......Page 849
2.2.2 From Flow-Aligning to Non-Flow Aligning Behavior in SCLC-Polymers......Page 856
2.3.1 Discovery of the Shear Induced Isotropic-Nematic Phase Transition in SCLC-Polymer Melts......Page 861
2.3.2 Time-Dependent Study......Page 865
2.3.3 Origin of the Melt Cohesion - Origin of the Shear Induced Phase Transition......Page 868
2.3.4 Viscoelastic Characteristic Times in SCLC-Polymers......Page 869
2.3.5 Chain Conformation in the Shear Induced Nematic Phase......Page 870
2.3.6 Discovery of the Low Frequency Elastic Regime......Page 871
2.3.7 Epilog......Page 872
3 Adsorption Results......Page 874
3.2 Definition of the Relevant Parameters......Page 875
3.4 Influence of the Pressure on the Smectic Order Parameter......Page 877
3.5 Influence of the Pressure on the Smectic Phase Correlation Lengths......Page 878
Acknowledgments......Page 880
16. In Situ Investigation of Adsorbded Amphiphilic Block Copolymers by......Page 883
Structural Studies of Proteins and Nucleic Acids in Solution Using Small Angle X-Ray Scattering (SAXS)......Page 1092
2 Ellipsometry......Page 885
2.1 Analysis of Thin, Adsorbed films at the Brewster Angle......Page 886
2.2 Data Collection and Interpretation......Page 888
2.3 Limits of Model Applicability......Page 889
3.1 Materials and Experimental......Page 890
3.2 Adsorption of PS-b-PVP Copolymers......Page 891
3.3 Adsorption of NaPSS-b-PtBS Copolymers......Page 895
4 Neutron Reflection......Page 900
4.2 Results......Page 902
Synchrotron Small-Angle X-Ray Scattering......Page 909
2.1 Momentum Transfer and Differential Scattering Cross Section......Page 911
2.2 Form Factor and Polydispersity......Page 914
2.3 Limiting Form of I(q)......Page 916
2.4 Structure Factor......Page 919
3 Experimental Setup......Page 924
3.1 Source......Page 926
3.2 Impacts of Third Generation Sources......Page 927
3.2.2 Microbeam SAXS......Page 928
3.3 Optics......Page 929
3.4 Detectors......Page 931
3.5 Sample Environments......Page 934
4.1 Intensity Normalization......Page 939
4.2 Angular and Intensity Calibrations......Page 940
4.3 Instrumental Smearing Effects......Page 941
4.4 Influence of Radiation Damage......Page 942
5.1 Combined Small-Angle and Wide-Angle X-ray Scattering......Page 943
5.2 Ultra Small-Angle X-ray Scattering......Page 947
5.3 Anomalous Small-Angle X-ray Scattering......Page 952
5.4 Time-Resolved Experiments......Page 956
Summary and Outlook......Page 958
References......Page 960
X-Ray Photon Correlation Spectroscopy (XPCS)......Page 963
1 Introduction......Page 964
4 X-Ray Photon Correlation Spectroscopy (XPCS)......Page 975
5 Experimental Set-Up......Page 977
6 XPCS in Soft Condensed Matter Systems......Page 979
7 Liquid Surface Dynamics Studied by XPCS......Page 988
8 Slow Dynamics in Hard Condensed Matter Systems......Page 995
Acknowledgments......Page 1000
References......Page 1001
19. Analysis of Polyelectrolytes by Small-Angle X-Ray Scattering......Page 1007
AFM Imaging in Physiological Environment: From Biomolecules to Living Cells......Page 1386
1 Introduction......Page 1008
2.1 Poisson-Boltzmann Cell Model......Page 1010
2.2 Beyond the Poisson-Boltzmann Cell Model......Page 1012
2.3 Calculation of the Scattering Intensity I(q) Using the PB-Cell Model......Page 1013
2.4 Anomalous Small Angle X-Ray Scattering......Page 1015
3.1 Systems......Page 1017
3.2 Solution Properties: Electric Birefringence......Page 1018
3.3 Osmotic Coefficient......Page 1019
3.4.1 SAXS......Page 1021
3.4.2 ASAXS......Page 1022
3.4.2.2 Comparison of ASAXS Data with the PB-cell Model......Page 1025
4 Conclusion......Page 1027
References......Page 1029
2.2 Structure Characterization......Page 1034
2.3 Phase Transitions: Mechanisms and Kinetics......Page 1040
3.1 Theory......Page 1043
3.1.1 Form Factors......Page 1044
3.1.2 Structure Factors......Page 1047
3.1.4 Instrumental Effects......Page 1048
3.2 Recent Experimental Examples......Page 1049
4.1.1 Form Factors......Page 1052
4.1.3 Polydispersity......Page 1053
4.2 Recent Experimental Examples......Page 1054
5.1 Introduction......Page 1056
5.2 Lyotropic Phases Formed by Block Copolymers in Solution......Page 1058
5.3.1 Lamellar Phase......Page 1065
5.3.2 Hexagonal Phase......Page 1067
5.3.3 Cubic Micellar Phases......Page 1068
6.1 Morphology Probed by SAXS and WAXS......Page 1075
6.2 Crystal/Chain Orientation Probed by SAXS and WAXS......Page 1080
6.3 SAXS/WAXS Studies of Crystallization Kinetics......Page 1082
References......Page 1085
1 Introduction......Page 1093
5 Probing Intermolecular Forces Between Biomolecules......Page 1101
7 Modeling States with Conformational Diversity......Page 1108
8 Anomalous Small-Angle X-Ray Scattering of Biomolecules......Page 1110
9 Time-Resolved SAXS......Page 1111
References......Page 1115
22. TEM Imaging of Block Copolymer Aggregates in Solutions......Page 1118
3.1 The Area-Difference-Elasticity (ADE) Model......Page 1314
3.3 Other Rod Like Morphologies......Page 1123
3.4 Bilayers......Page 1125
3.5 Hexagonally Packed Hollow Hoops......Page 1127
4.1 Block Length......Page 1129
4.2 Water Content......Page 1130
4.3 Initial Polymer Concentration......Page 1134
4.4 Presence of Additives......Page 1135
4.4.2 Acids......Page 1137
4.4.3 Bases......Page 1138
4.5 Nature and Composition of the Common Solvent......Page 1139
4.6 Homopolymer......Page 1140
4.8 Polydispersity......Page 1142
5 Conclusion......Page 1143
Acknowledgments......Page 1144
Single-Molecule Studies of DNA......Page 1147
2.2 Basic Single DNA Imaging Methods......Page 1150
2.3 Single DNA Dynamics: Theory Meets Experiment......Page 1152
2.4 Single DNA Dynamics in Fluid Flow......Page 1155
2.5 Entangled Polymer Dynamics......Page 1160
2.6 DNA Electrophoresis......Page 1161
2.7 Dynamics of DNA Molecules Confined to Two Dimensions......Page 1163
2.8 Fluorescence Imaging of Protein-DNA Interactions......Page 1165
2.9 Single Pair Fluorescence Resonance Energy Transfer (spFRET)......Page 1166
3.3 Principles of Optical Tweezers......Page 1170
3.4 Optical Tweezers Instrumentation......Page 1173
3.5 Mechanical Properties of DNA......Page 1176
3.6 Protein-DNA Interactions......Page 1185
3.7 DNA Translocating Molecular Motors......Page 1188
24. Single Molecule Microscopy......Page 1195
2.1 Fluorescence Measurements......Page 1198
2.2 Single Molecule Imaging......Page 1199
2.3 Fluorescence from Single Molecules......Page 1204
2.4 Determination of the Number of Molecules and Proof of Single Molecules......Page 1206
2.5 Time Resolution of Single Molecule Imaging and Analysis of Dynamic Data......Page 1207
2.6 Space Resolution of Single Molecule Imaging......Page 1210
2.7 Spectroscopy of Single Molecule Fluorescence......Page 1211
2.8 Fluorescence Labeling of Biomolecules for Single Molecule Measurements......Page 1215
3.1 Imaging Movement of Molecular Motors......Page 1217
3.2 Movement of Single Molecules in Biosystems......Page 1219
3.3 Association and Dissociation of Biomolecules......Page 1221
3.4 Kinetic Processes of Single Molecules......Page 1223
3.6 Dynamic Changes in Structural State of Biomolecules......Page 1225
4.1 Immobilization of Biomolecules......Page 1228
4.2 Manipulation Techniques for Single Molecule Detection......Page 1230
4.3 Nanometry by Manipulation Techniques......Page 1233
5.1 Mechanical Properties of Protein Polymers......Page 1235
5.2 Mechanically Induced Unfolding of Single Protein Molecules......Page 1237
5.3 Interaction of Biomolecules......Page 1238
5.4 Manipulation and Molecular Motors - Processive Motors......Page 1239
5.5 Nonprocessive Muscle Myosin Motors......Page 1242
5.6 Rotary Motors and ATP Synthesis......Page 1244
5.7 DNA-Based Molecular Motors......Page 1245
5.8 Simultaneous Measurement of Chemical and Mechanical Reactions......Page 1247
Visualizing Properties of Polymers at Interfaces......Page 1251
1.1 Why are Interfacial Phenomena of Interest?......Page 1252
1.2 What Can Be Learned by Visualizing Polymers at Interfaces?......Page 1253
5 Entropically Caused Interfacial Tension between Chemically Identical Molecules......Page 1271
6 Dewetting and Aging of (Almost) Glassy Polymer Films......Page 1275
8 Morphological Changes in Polymer Crystals......Page 1286
9 Coupled Growth in Superposed Polymer Lamellae......Page 1291
10 Polymer Crystallization in Nanometer-Sized Spherical Compartment......Page 1294
11 Conclusions......Page 1297
References......Page 1298
Optical Microscopy of Fluctuating Giant Vesicles and Motile Cells......Page 1301
1.2 From Passive to Active Systems......Page 1303
2 Optical Methods and Image Analysis......Page 1305
2.1 Phase Contrast and Real Time Image Analysis......Page 1306
2.3 Total Internal Reflection Fluorescence......Page 1311
3.2 Physical Chemistry of Membrane Curvature......Page 1316
3.2.1 Transversal Membrane Asymmetry......Page 1317
3.2.2 Effective Elastic Layers......Page 1318
3.3 Experimental Spectra and Monte Carlo Simulations......Page 1319
4.2 Dynamic Phase Transition in Cell Spreading......Page 1324
4.3 The Phase Model of Cell Motility......Page 1328
5 Perspectives for Biological Physics......Page 1329
A1 Amphiphiles and Vesicles......Page 1330
A2 The Fluid-Gel Transition......Page 1332
A3.2 Bending Elasticity......Page 1333
A3.5 Volume and Area Constraints......Page 1335
A4.2 Permeability......Page 1336
B1 The Budding Transition......Page 1338
B2 The Prolate-Oblate Transition......Page 1341
C Organization of a Motile Cell: The Story of Actin......Page 1342
Acknowledgments......Page 1343
References......Page 1344
Highly-Branched Polymers: From Comb to Dendritic Architectures......Page 1347
1 Introduction......Page 1349
2.1 Combs with Homopolymer Branches [6-9]......Page 1350
2.2 Combs with Randomly Distributed A and B Branches......Page 1355
2.3 Combs with A-B Diblock Branches......Page 1356
2.4 Stars with Comb Branches [26, 27]......Page 1357
3.1 Controlled Branching [25]......Page 1362
3.2 Combs-on-Combs......Page 1364
5.1 Encapsulation of Molecules into Water-Soluble Dendrigrafts......Page 1377
6 Viral Diagnostic using Dendrigraft-Oligonucleotides [34]......Page 1379
Acknowledgments......Page 1383
References......Page 1384
2.1 Principal Components of the Microscope......Page 1390
2.2 Imaging Modes......Page 1392
2.2.1 The Static Mode......Page 1393
2.2.2 The Dynamic Mode......Page 1394
2.3 Biological Sample Preparation......Page 1396
2.4 AFM Tip Modifications......Page 1397
3 Imaging of Biological Systems......Page 1398
3.1 Biomolecules......Page 1399
3.2.1 Model Membranes......Page 1402
3.2.2 Reconstituted or Native Membranes......Page 1403
4.1 Topography of Intact Cells......Page 1408
4.2 Cell Mechanical Properties......Page 1410
4.3 Example 1: Local Nanomechanical Motion of the Cell Wall of Saccharomyces cerevisiae......Page 1412
4.4 Example 2: Cell Adhesion......Page 1415
4.4.1 Morphological Evaluation of Cell Adhesion-Images Analysis......Page 1416
4.4.2 Section Analysis......Page 1418
4.4.3 Modeling of the Cell Mechanical Properties......Page 1422
5 Developments and Perspective of the Dynamic Mode in Liquid Medium for Imaging Biological Systems......Page 1425
5.1.1 The Use of Small Cantilevers......Page 1426
5.1.2 Fast AFM Imaging......Page 1429
5.2 Example of Improvement of Dynamic AFM in Liquid: Small Amplitudes......Page 1430
5.2.1 Viscous Hydrodynamic Damping of Cantilever in Water Medium......Page 1431
5.2.2 Improving the Acoustic Excitation of the Cantilever-Tip......Page 1434
5.3.3 AFM Study of the Molecular Ordering of a Confined Liquid......Page 1435
References......Page 1440