Bicontinuous Liquid Crystals (Surfactant Science)

Cover......Page 1
BICONTINUOUS LIQUID CRYSTALS......Page 10
Preface......Page 12
Introduction......Page 16
REFERENCES......Page 18
The Editors......Page 22
Contributors......Page 24
Acknowledgments......Page 26
Contents......Page 28
Section 1: Theoretical Aspects and Modeling of Bicontinuous Phases......Page 31
1.1 INTRODUCTION......Page 33
1.2 MONOOLEIN FORMS A CONTINUOUS BILAYER, WITH A MINIMAL SURFACE CONFORMATION, SEPARATING TWO CONTINUOUS WATER COMPARTMENTS......Page 35
1.3 THE NODAL SURFACE DESCRIPTION OF CUBIC MINIMAL SURFACE STRUCTURES......Page 37
1.4 SOLUBILIZATION OF AMPHIPHILIC MOLECULES INTO THE MONOOLEIN–WATER PHASE......Page 38
1.5 COLLOIDAL DISPERSIONS OF CUBIC PHASES......Page 39
Nanostructures based on dispersed cubic phases......Page 41
REFERENCES......Page 42
2.1 INTRODUCTION......Page 45
2.2 RIBBON OR RECTANGULAR PHASES......Page 50
2.3 MESH AND BICONTINUOUS PHASES......Page 52
2.4 THEORETICAL IDEAS......Page 60
2.5 CONCLUSION......Page 64
REFERENCES......Page 65
3.1 INTRODUCTION......Page 71
3.2 ELECTRICAL CHARACTERIZATION OF TOPICAL CUBOSOMAL GELS......Page 74
3.3 CUBIC “PHASES” IN THE SKIN......Page 78
3.4 SUMMARY......Page 84
ACKNOWLEDGMENTS......Page 85
REFERENCES......Page 86
CONTENTS......Page 89
4.1 INTRODUCTION......Page 90
4.2 RELATIONSHIP OF MEMBRANE FUSION TO LAMELLAR/INVERTED PHASE TRANSITION MECHANISMS......Page 92
4.3.1 Ways in Which Exogenous Additives Move Lamellar/Inverted Phase Boundaries: Effects of Lipid Additives......Page 100
4.3.1.1 Spontaneous Curvature......Page 101
4.3.1.2 Chain-Packing Energy......Page 102
4.3.2 Effects of Peptides and Enzymes on Inverted Phase Behavior and Fusion......Page 103
4.3.2.1 Enzymatic Production of Lipids that Change Spontaneous Curvature and Chain-Packing Energy of Membrane Lipids......Page 104
4.3.2.2 Effects of Viral Fusion Peptides......Page 105
4.3.2.3 Membrane-Spanning Peptides......Page 108
4.4 STUDYING LAMELLAR/QII PHASE TRANSITIONS TO REFINE MODELS OF FUSION INTERMEDIATE ENERGETICS......Page 114
4.4.1 Evaluation of the Gaussian Curvature Elastic Coefficient by Measurement of TQ......Page 115
4.4.2 Implications for Membrane Fusion......Page 117
4.4.3 Implications for the Effects of Peptides on Membrane Fusion and QII Phase Formation......Page 118
4.5 CONCLUSION......Page 119
REFERENCES......Page 120
CONTENTS......Page 129
ABSTRACT......Page 130
5.1 INTRODUCTION AND HISTORICAL CONTEXT......Page 131
5.2 CURVATURE......Page 132
5.3 PERIODICITY......Page 133
5.4 MINIMAL SURFACES......Page 135
5.5 TRIPLY PERIODIC MINIMAL SURFACES (TPMS)......Page 137
5.6 TOPOLOGY OF TPMS......Page 139
5.7 PARAMETRIZATION OF SURFACES USING THE GAUSS MAP AND THE COMPLEX PLANE......Page 140
5.8 HOMOGENEITY OF CURVATURE ON SURFACES......Page 143
5.9 MOLECULAR SHAPE AND THE SURFACTANT PACKING PARAMETER......Page 144
5.10 BENDING ENERGY AND RELATIVE STABILITIES......Page 145
5.11 TPMS SURFACE SYMMETRIES AND PHASE TRANSFORMATIONS......Page 147
5.12 NETWORKS EMBEDDED IN TPMS......Page 148
5.13 A BRIEF INTRODUCTION TO THE HYPERBOLIC CRYSTALLOGRAPHY OF BICONTINUOUS MESOMORPHS AND THEIR USE IN GENERATING SURFACE RETICULATIONS......Page 149
5.14 POLYCONTINUOUS LIQUID CRYSTALS......Page 151
5.15 FINAL REMARKS......Page 155
REFERENCES......Page 156
Section 2: Physical Chemistry and Characterization......Page 159
CONTENTS......Page 161
6.1 INTRODUCTION......Page 162
6.2 THE “CLASSIC” SPONGE PHASE......Page 163
6.3 THE NOVEL L3 PHASE......Page 167
6.3.1 Phase Behavior and Conductivity......Page 169
6.3.1.1 The System Calciumtetradecylmethylester-alpha-Sulfonate (Ca(C14-alphaMES)2)/2-Ethyl-hexyl-Monoglycerinether (EHG) (3) in Water......Page 170
6.3.1.2 The System Calciumdodecylsulfates (Ca(DS)2)/1-Phenylpropyl-1-Amine (PPA) in Water......Page 173
6.3.1.3 Magnesiumdodecylsulfates (Mg(DS)2)/EHG/Water in Mixtures with Na(DS)2 and C12DMAO......Page 174
6.3.1.4 Discussion......Page 177
6.3.2 Phase Transition Lalpha to L3......Page 180
6.3.2.2 Small-Angle Neutron Scattering......Page 182
6.3.2.3 NMR Characterization from an Ordered to a Disordered State......Page 184
6.3.3 Electric Birefringence and Scaling Laws......Page 185
6.3.4 Rheological Properties......Page 189
6.4 OUTLOOK AND CONCLUSION......Page 192
REFERENCES......Page 194
CONTENTS......Page 199
7.1 INTRODUCTION......Page 200
7.2 STRUCTURAL FEATURES OF THE PROTEIN-CONTAINING BICONTINUOUS CUBIC PHASES OF LIPIDS......Page 201
7.2.1 MO/Lysozyme/Water System......Page 203
7.2.2 MO/Cytochrome c/Water System......Page 205
7.2.3 MO/Hemoglobin/Water System......Page 206
7.2.4 MO/Glucose Oxidase/Water System......Page 208
7.2.5 Concluding Remarks......Page 210
7.3 MOLECULAR FEATURES OF THE BICONTINUOUS QII PHASES OF LIPIDS WITH ENTRAPPED PROTEINS — SPECTROSCOPIC STUDIES......Page 211
7.3.1 Raman Spectroscopy of the MO/Lysozyme/Water Q229 Phase......Page 212
7.3.2 Fourier-Transform Infrared Spectroscopy of the MO/Cytochrome c/Water Q224 Phase......Page 216
7.3.3 Fourier-Transform Infrared Spectroscopy of the MO/Hemoglobin/Water Q230 and Q224 Phases......Page 219
7.3.4 Concluding Remarks......Page 221
7.4 ELECTROCHEMICAL STUDIES AND BIOANALYTICAL APPLICATIONS OF THE PROTEIN-CONTAINING BICONTINUOUS QII PHASES OF LIPIDS......Page 222
7.4.1 Amperometric Bioelectrodes Based on the Protein-Containing Bicontinuous QII Phases of Lipids......Page 224
7.4.2 Potentiometric Biosensors Based on the Enzyme-Containing Bicontinuous QII Phases of Lipids......Page 233
7.4.3 Concluding Remarks......Page 236
REFERENCES......Page 238
ABSTRACT......Page 243
8.1 INTRODUCTION AND SOME HISTORICAL REMARKS......Page 244
8.2.1 Introduction......Page 250
8.2.3 Dynamic NMR Parameters......Page 251
8.2.4 NMR Diffusometry......Page 252
8.3.1 Introduction......Page 254
8.3.2.1 Bandshape Studies......Page 257
8.3.2.2 NMR Relaxation......Page 259
8.3.3 Diffusion Studies of Bicontinuous Cubic Phases and Sponge Phases......Page 262
REFERENCES......Page 268
Section 3: Applications......Page 271
CONTENTS......Page 273
9.1 INTRODUCTION......Page 274
9.2.1 Gyroid Structure (Ia3d Symmetry)......Page 277
9.2.2 Three-Dimensional Hexagonal Structure (P63/mmc Symmetry)......Page 280
9.2.3 Other Cubic Structures......Page 283
9.2.4 Disordered Bicontinuous Networks......Page 284
9.3.1.1 Liquid Crystal Templating?......Page 285
9.3.1.2 Cooperative Assembly......Page 286
9.3.1.3 Bicontinuous Structures by PDA......Page 289
9.3.2 Evaporation-Driven Assembly (EDA)......Page 294
9.3.2.1 Acidic Sol–Gel Silica......Page 295
9.3.2.3 Coating Flow Effects......Page 296
9.3.2.4 In Situ Studies of EDA Mechanism......Page 297
9.4 CONCLUSIONS AND SYNTHESIS CONDITIONS......Page 302
REFERENCES......Page 306
CONTENTS......Page 315
10.1 INTRODUCTION......Page 316
10.2.1 In Vitro Studies......Page 318
10.2.2 In Vivo Studies......Page 319
10.3 DRUG RELEASE FROM BULK NONDISPERSED CUBIC PHASE IN RELATION TO CUBOSOMES......Page 320
10.4.1 Dialysis as a Method for Measuring Drug Release from Cubosomes......Page 323
10.4.2 Pressure Ultrafiltration—A Proposed Method for Measuring Drug Release from Colloidal Particles Such As Cubosomes......Page 324
10.4.2.1.1 Diazepam......Page 326
10.4.2.1.2 Rifampicin, Propofol, and Griseofulvin......Page 327
10.4.2.2.1 Glucose......Page 328
10.5 THE FUTURE FOR CUBOSOMES AS A CONTROLLED-RELEASE DELIVERY SYSTEM......Page 330
REFERENCES......Page 331
CONTENTS......Page 337
11.1 INTRODUCTION......Page 338
11.2.1 Form, Function, and Rational Design......Page 339
11.3 HOW CRYSTALS GROW IN MESO......Page 341
11.4.1 Salt......Page 344
11.4.3 Screen Compatibility......Page 345
11.5.1 The Microgravity Analogy......Page 346
11.6 QUO VADIS......Page 347
REFERENCES......Page 348
CONTENTS......Page 351
12.2 SWELLING BEHAVIOR OF MONOGLYCERIDES......Page 352
12.3 DRUG RELEASE FROM MONOGLYCERIDES......Page 353
12.4 INFLUENCE OF pH ON SWELLING AND DRUG RELEASE......Page 355
12.5 FORMULATION FACTORS AFFECTING DRUG RELEASE FROM MONOGLYCERIDES......Page 362
12.6 BINDING OF VARIOUS DRUGS TO MONOGLYCERIDES......Page 365
12.7 EFFECT OF DRUGS ON THE PHASE TRANSITION OF MONOGLYCERIDES......Page 368
12.8.1 Oral Delivery......Page 369
12.8.2 Topical Delivery......Page 372
12.8.3 Depot Drug Delivery Systems......Page 374
12.8.5 Ophthalmic Application......Page 378
12.9 CONCLUSION......Page 379
REFERENCES......Page 380
CONTENTS......Page 383
13.1 INTRODUCTION......Page 384
13.2 PREPARATION OF THE LIQUID FORMULATION AND SIZE DISTRIBUTION OF THE DISPERSED PARTICLES......Page 385
13.3 ENCAPSULATION EFFICIENCY......Page 390
13.4 SMALL-ANGLE X-RAY DIFFRACTION......Page 391
13.5 CUBOSOMES AND LIPID CUBIC PARTICLES......Page 392
13.7 PHYSICAL AND CHEMICAL STABILITY OF THE LIQUID FORMULATION......Page 394
13.8 STABILITY OF CUBOSOME DISPERSION PREPARED FROM LIQUID FORMULATION......Page 395
13.9 ABILITY TO FORM CUBOSOME FROM LIQUID FORMULATION AFTER STORAGE......Page 396
13.10 IN VITRO DRUG RELEASE......Page 397
13.11 IN VITRO AND IN VIVO TOXICITY OF CUBOSOME PREPARED FROM A LIQUID FORMULATION......Page 400
13.12 IN VITRO CELLULAR ASSOCIATION OF DRUGS FROM CUBOSOME......Page 403
13.13 SOLUBILIZATION OF CUBOSOME BY BILE SALT AND ABSORPTION OF MIXED MICELLES......Page 406
13.14 ORAL DELIVERY OF CUBOSOME ENCAPSULATING PYRENE......Page 409
13.15 ORAL DELIVERY OF CUBOSOME ENCAPSULATING INSULIN......Page 410
13.16 ORAL VACCINATION BY ANTIGEN LOADED IN CUBOSOME......Page 411
13.17 CONCLUSIONS......Page 413
REFERENCES......Page 414
CONTENTS......Page 417
ABSTRACT......Page 418
14.1 INTRODUCTION......Page 419
14.2 SOME RELEVANT COMMENTS ON THE CHARACTERISTICS OF CUBIC PHASES......Page 420
14.2.1 Mesomorphism......Page 421
14.3.1 Solubilization and Controlled Release......Page 427
14.3.1.1 Drugs......Page 428
14.3.1.3 Enzymes......Page 432
14.3.1.4 Vitamins......Page 433
14.3.2.1 Membrane Protein Crystal Formation......Page 436
14.3.3.1 Maillard Reactions in Cubic Phases......Page 439
14.3.3.2 Polymerization in Lyotropic Liquid Crystal Mesophases......Page 443
14.3.3.4 Electrochemical Behavior of Ferrocene......Page 444
14.3.3.5 Encapsulation and Diffusion of Dendrimers in Cubic Phases......Page 446
14.3.3.6 Lipase Action on the Interfacial Monoolein in a Monoolein/Sodium Oleate Cubic Phase (Auto Hydrolysis)......Page 448
14.4 CONCLUSIONS......Page 449
REFERENCES......Page 450
CONTENTS......Page 455
15.2 BICONTINUOUS LIPIDIC CUBIC PHASES: COMPATIBILITY WITH MEMBRANE PROTEINS......Page 456
15.3 SPECTROSCOPY ON PROTEINS SOLUBILIZED IN LIPIDIC CUBIC PHASES......Page 459
15.4 CRYSTALLIZATION OF SOLUBLE AND MEMBRANE PROTEINS IN LIPIDIC CUBIC PHASES......Page 461
15.5.1 Bacteriorhodopsin......Page 466
15.5.1.1 K Intermediate......Page 471
15.5.1.2 L Intermediate......Page 473
15.5.1.3 M Intermediate......Page 474
15.5.2 Halorhodopsin......Page 475
15.5.3 Sensory Rhodopsin II......Page 478
15.5.3.1 K Intermediate......Page 479
15.5.5 Photosynthetic Reaction Center......Page 480
ACKNOWLEDGMENTS......Page 481
REFERENCES......Page 482
CONTENTS......Page 487
16.2.1 Formation and Phase Behavior......Page 488
16.2.2.1 Amphiphilic Nature of the Cubic Phase......Page 489
16.2.2.2 Bio/Muco-Adhesive Properties of the Cubic Phase......Page 490
16.2.2.3 Physicochemical Stabilization of Incorporated Drugs......Page 492
16.3.1 Oral Delivery......Page 493
16.3.2 Oral Mucosal Delivery......Page 494
16.4 FUTURE DIRECTIONS FOR THE CUBIC PHASE DELIVERY SYSTEM......Page 496
REFERENCES......Page 497
Index......Page 501