Multilayer thin films: sequential assembly of nanocomposite materials
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IMAGE 1
V
CONTENTS
LIST O F CONTRIBUTORS XXV
VOLUME 1
1 LAYER-BY-LAYER ASSEMBLY (PUTTING MOLECULES T O WORK) 1
GERO DECHER
1.1 T H E W H O L E IS M O R E T H A N T H E S U M O F ITS PARTS 1
1.2 F R O M SELF-ASSEMBLY TO DIRECTED ASSEMBLY 1
1.3 HISTORY A N D DEVELOPMENT O F T H E LAYER-BY-LAYER ASSEMBLY METHOD 4
1.4 LBL-ASSEMBLY IS T H E SYNTHESIS O F FUZZY SUPRAMOLECULAR OBJECTS 6
1.5 REPRODUCIBILITY A N D CHOICE O F DEPOSITION CONDITIONS 7
1.6 MONITORING MULTILAYER BUILD-UP 10
1.7 SPRAY- A N D SPIN-ASSISTED MULTILAYER ASSEMBLY 13
1.8 RECENT DEVELOPMENTS 14
1.8.1 SELF-PATTERNING LBL-FILMS 14
1.8.2 DEPOSITION O F LBL-FILMS O N VERY SMALL PARTICLES 15
1.8.3 PURELY INORGANIC LBL-"FILMS" 37
1.9 FINAL R E M A R K S 18
REFERENCES 19
PART I PREPARATION A N D CHARACTERIZATION 2 3
2 LAYER-BY-LAYER PROCESSED MULTILAYERS: CHALLENGES A N D OPPORTUNITIES 2
5 MICHAEL F. RUBNER A N D ROBERT E. COHEN 2.1 INTRODUCTION 2 5
2.2 F U N D A M E N T A L CHALLENGES A N D OPPORTUNITIES 2 5
2.2.1 LBL ASSEMBLY O N NANOSCALE ELEMENTS A N D I N CONFINED GEOMETRIES
2 5 2.2.2 LIVING CELLS AS FUNCTIONAL ELEMENTS O F POLYELECTROLYTE
MULTILAYERS 28 2.2.3 MULTILAYER CELLULAR BACKPACKS 2 8
2.2.4 DIRECT LBL PROCESSING O F LIVING CELLS 2 9
2.3 TECHNOLOGICAL CHALLENGES A N D OPPORTUNITIES 31
2.3.1 IMPROVING PROCESSING T I M E A N D VERSATILITY 31
2.3.2 TOWARDS MECHANICALLY ROBUST MULTILAYER COATINGS 3 2 2.4 T H E PATH
FORWARD 3 6
REFERENCES 36
HTTP://D-NB.INFO/1016558333
IMAGE 2
VI CONTENTS
3 LAYER-BY-LAYER ASSEMBLY: FROM CONVENTIONAL T O
UNCONVENTIONAL METHODS 43 CUANGLU W U A N D XI ZHANG
3.1 INTRODUCTION 43
3.2 CONVENTIONAL LBL METHODS 4 4
3.2.1 ELECTROSTATIC LBL ASSEMBLY 4 4
3.2.2 HYDROGEN-BONDED LBL ASSEMBLY 4 7
3.2.3 LBL ASSEMBLY DRIVEN BY COORDINATION INTERACTION 5 0
3.2.4 TO C O M B I N E LBL ASSEMBLY A N D POST-CHEMICAL REACTION FOR T H
E FABRICATION O F ROBUST T H I N FILMS 5 0 3.3 UNCONVENTIONAL LBL
METHODS 5 2
3.3.1 ELECTROSTATIC COMPLEX FOR UNCONVENTIONAL LBL ASSEMBLY 5 2 3.3.1.1
NANOREACTORS WITH E N H A N C E D Q U A N T U M YIELD 53 3.3.1.2 "ION
TRAPS" FOR E N H A N C I N G T H E PERMSELECTIVITY A N D PERMEABILITY 53
3.3.1.3 SURFACE I M P R I N T E D LBL FILMS 5 4
3.3.1.4 CATION-SELECTIVE |ICP BASED O N SMILBL FILM 58 3.3.2
HYDROGEN-BONDED COMPLEX FOR UNCONVENTIONAL LBL ASSEMBLY 5 8 3.3.3 BLOCK
COPOLYMER MICELLES FOR UNCONVENTIONAL LBL ASSEMBLY 61 3.3.4 RC-JC
INTERACTION COMPLEX FOR ELECTROSTATIC LBL ASSEMBLY 62 3.4 S U M M A R Y
A N D OUTLOOK 64
REFERENCES 6 4
4 NOVEL MULTILAYER THIN FILMS: HIERARCHIC LAYER-BY-LAYER (HI-LBL)
ASSEMBLIES 6 9
KATSUHIKO ARIGA, QINGMIN JI, A N D JONATHAN P. HILL 4.1 INTRODUCTION 6 9
4.2 HI-LBL FOR MULTI-CELLULAR MODELS 70
4.3 HI-LBL FOR U N U S U A L D R U G DELIVERY MODES 72
4.4 HI-LBL FOR SENSORS 7 5
4.4.1 MESOPOROUS C A R B O N HI-LBL 7 5
4.4.2 MESOPOROUS C A R B O N CAPSULE HI-LBL 76
4.4.3 GRAPHENE/IONIC-LIQUID HI-LBL 78
4.5 FUTURE PERSPECTIVES 7 9
REFERENCES 8 0
5 LAYER-BY-LAYER ASSEMBLY USING HOST-GUEST INTERACTIONS 83
JANNEKE VEERBEEK, DAVID N. REINHOUDT, ANDJURRIAAN HUSKENS 5.1
INTRODUCTION 83
5.2 SUPRAMOLECULAR LAYER-BY-LAYER ASSEMBLY 8 4
5.3 3D PATTERNED MULTILAYER ASSEMBLIES O N SURFACES 8 5
5.4 3D SUPRAMOLECULAR NANOPARTICLE CRYSTAL STRUCTURES 88
5.5 POROUS 3D SUPRAMOLECULAR ASSEMBLIES I N SOLUTION 9 0
5.6 CONCLUSIONS 9 5
REFERENCES 9 5
IMAGE 3
CONTENTS VII
6 LBL ASSEMBLIES USING VAN D E R WAALS O R AFFINITY INTERACTIONS A N D
THEIR
APPLICATIONS 99
TAKESHI SERIZAWA, MITSURU AKASHI, MICHIYA MATSUSAKI, HIOHARU AJIRO, AND
TOSHIYUKI KIDA 6.1 INTRODUCTION 9 9
6.2 STEREOSPECIFIC TEMPLATE POLYMERIZATION O F METHACRYLATES BY
STEREOCOMPLEX FORMATION I N NANOPOROUS LBL FILMS 100 6.2.1 INTRODUCTION
100
6.2.2 LBLIT-PMMA/ST-PMMA STEREOCOMPLEX UULTRATHIN FILM 102 6.2.3
FABRICATION O F TEMPLATE NANOSPACES I N FILMS 104
6.2.4 POLYMERIZATION W I T H I N TEMPLATE NANOSPACES U S I N G A
DOUBLE-STRANDED ASSEMBLY 106
6.2.5 STUDIES O N T H E POROUS STRUCTURE O B T A I N E D BY LBL ASSEMBLY
111
6.3 PREPARATION A N D PROPERTIES O F HOLLOW CAPSULES C O M P O S E D O F
LAYER-BYLAYER POLYMER FILMS CONSTRUCTED T H R O U G H V A N D E R WAALS
INTERACTIONS 113
6.3.1 INTRODUCTION 113
6.3.2 PREPARATION O F HOLLOW NANOCAPSULES C O M P O S E D O F
POLY(METHYL
METHACRYLATE) STEREOCOMPLEX FILMS 114 6.3.3 PREPARATION A N D FUSION
PROPERTIES O F NOVEL HOLLOW NANOCAPSULES
C O M P O S E D O F POLY (LACTIC ACID)S STEREOCOMPLEX FILMS 116 6.4
FABRICATION O F THREE-DIMENSIONAL CELLULAR MULTILAYERS U S I N G
LAYER-BYLAYER PROTEIN NANOFILMS CONSTRUCTED T H R O U G H AFFINITY
INTERACTION 120 6.4.1 INTRODUCTION 120
6.4.2 HIERARCHICAL CELL MANIPULATION 121
6.4.3 H I G H CELLULAR ACTIVITIES I N D U C E D BY 3D-LAYERED CONSTRUCTS
124 6.4.4 QUANTITATIVE 3D-ANALYSES O F NITRIC OXIDE DIFFUSION I N A
3D-ARTERY
MODEL 124
6.5 CONCLUSION 129
REFERENCES 129
7 LAYER-BY-LAYER ASSEMBLY O F POLYMERIC COMPLEXES 135
JUNQI SUN, XIAOKONG LIU, A N D JIACONG SHEN 7.1 INTRODUCTION 135
7.2 CONCEPT O F LBL ASSEMBLY O F POLYMERIC COMPLEXES 136
7.2.1 LBL ASSEMBLY O F POLYELECTROLYTE COMPLEXES FOR T H E RAPID A N D
DIRECT
FABRICATION O F F O A M COATINGS 136 7.2.2 LBL ASSEMBLY O F
HYDROGEN-BONDED POLYMERIC COMPLEXES 138 7.2.3 LBL ASSEMBLY O F
POLYELECTROLYTE-SURFACTANT COMPLEXES 139 7.3 STRUCTURAL TAILORING O F
LBL-ASSEMBLED FILMS O F POLYMERIC
COMPLEXES 140
7.3.1 MIXING RATIO O F PECS 140
7.3.2 LBL CODEPOSITION O F PECS A N D FREE POLYELECTROLYTES 142 7.3.3
SALT EFFECT 143
7.4 LBL-ASSEMBLED FUNCTIONAL FILMS O F POLYMERIC COMPLEXES 144
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VIII CONTENTS
7.4.1 SELF-HEALING SUPERHYDROPHOBIC COATINGS 144
7.4.2 MECHANICALLY STABLE ANTIREFLECTION- A N D ANTIFOGGING-INTEGRATED
COATINGS 146 7.4.3 TRANSPARENT A N D SCRATCH-RESISTANT COATINGS WITH
WELL-DISPERSED NANOFILLERS 147 7.5 S U M M A R Y 149
REFERENCES 149
8 MAKING AQUEOUS NANOCOLLOIDS FROM LOW SOLUBILITY MATERIALS: LBL SHELLS
O N NANOCORES 151
YURI LVOV, PRAVIN PATTEKARI, AND TATSIANA SHUTAVA 8.1 INTRODUCTION 151
8.2 FORMATION O F NANOCORES 153
8.2.1 STABILIZERS V E R S U S LAYER-BY-LAYER POLYELECTROLYTE SHELL 153
8.3 ULTRASONICATION-ASSISTED LBL ASSEMBLY 154
8.3.1 TOP-DOWN APPROACH 154
8.3.2 BOTTOM-UP APPROACH 158
8.4 SOLVENT-ASSISTED PRECIPITATION INTO PREFORMED LBL-COATED SOFT
ORGANIC NANOPARTICLES 159 8.5 WASHLESS (TITRATION) LBL TECHNIQUE 161
8.6 F O R M A T I O N O F LBL SHELLS O N NANOCORES 163
8.7 D R U G RELEASE STUDY 165
8.8 CONCLUSIONS 168
REFERENCES 168
9 CELLULOSE FIBERS A N D FIBRILS A S TEMPLATES FOR T H E LAYER-BY-LAYER
(LBL)
TECHNOLOGY 171 LARS WDGBERG
9.1 BACKGROUND 171
9.2 FORMATION O F LBLS O N CELLULOSE FIBERS 172
9.3 T H E U S E O F LBL TO IMPROVE ADHESION BETWEEN WOOD FIBERS 176
9.4 T H E U S E O F LBL TO PREPARE ANTIBACTERIAL FIBERS 179
9.5 T H E U S E O F NFC/CNC TO PREPARE INTERACTIVE LAYERS U S I N G T H
E LBL
APPROACH 182
9.6 CONCLUSIONS 185
REFERENCES 186
1 0 FREELY STANDING LBL FILMS 189
CHAOYANGJIANG AND VLADIMIR V. TSUKRUK 10.1 INTRODUCTION 189
10.2 FABRICATION O F FREELY STANDING ULTRATHIN LBL FILMS 189
10.2.1 LBL FILMS WITH GOLD NANOPARTICLES A N D SILVER NANOWIRES 10.2.2
LBL FILMS WITH QUANTUM DOTS 193
10.2.3 LBL FILMS WITH NANOCRYSTALS 194
10.2.4 LBL FILMS WITH GRAPHENE OXIDES A N D C A R B O N N A N O T U B E
S
191
195
IMAGE 5
CONTENTS
IX
10.2.5 LBL WITH BIOMATERIALS 198
10.2.6 MECHANICAL A N D OPTICAL PROPERTIES 199
10.2.7 SURFACE MORPHOLOGY A N D INTERNAL MICROSTRUCTURE 201 10.3 POROUS
A N D PATTERNED FREELY STANDING LBL FILMS 204
10.3.1 NANOPOROUS LBL FILMS 204
10.3.2 PATTERNED LBL FILMS 205
10.3.3 SCULPTURED LBL FILMS 207
10.4 FREELY STANDING LBL FILMS WITH WEAK INTERACTIONS 208
10.4.1 RESPONSIVE LBL FILMS 2 0 8
10.4.2 ANISOTROPIC LBL MICROCAPSULES 209
10.4.3 LBL-SHELLS FOR CELL ENCAPSULATION 2 1 0
REFERENCES 214
11 NEUTRON REFLECTOMETRY A T POLYELECTROLYTE MULTILAYERS 219
REGINE VON KLITZING, RALF KOHLER, A N D CHLOE CHENIGNY 11.1 INTRODUCTION
219
11.2 N E U T R O N REFLECTOMETRY 219
11.2.1 SPECULAR REFLECTOMETRY 220
11.2.2 CONTRAST VARIATION: INTERESTING FEATURES FOR PEMS 2 2 2
11.2.2.1 SUPERLATTICE STRUCTURE 2 2 2
11.2.2.2 BLOCK STRUCTURE 223
11.2.3 FITTING 223
11.3 PREPARATION TECHNIQUES FOR POLYELECTROLYTE MULTILAYERS 224 11.3.1
DIPPING 224
11.3.2 SPRAYING 228
11.3.3 SPIN-COATING 231
11.3.4 C O M P A R I S O N O F T H E TECHNIQUES A N D MODEL 231
11.4 TYPES O F POLYELECTROLYTES 233
11.4.1 A STRONG POLYANION A N D A W E A K POLYCATION 233
11.4.2 TWO STRONG POLYELECTROLYTES 235
11.4.3 TWO W E A K POLYELECTROLYTES 2 3 7
11.4.4 MULTILAYERS WITH NON-ELECTROSTATIC INTERACTIONS 238 11.5
PREPARATION PARAMETERS 238
11.5.1 ION EFFECTS 238
11.5.1.1 IONIC STRENGTH 238
11.5.1.2 C O U N T E R I O N S 2 3 9
11.5.2 P H 241
11.5.3 TEMPERATURE 241
11.6 INFLUENCE O F EXTERNAL FIELDS AFTER PEM ASSEMBLY 242
11.6.1 SCALAR FIELDS: IONIC STRENGTH 2 4 2
11.6.2 SCALAR FIELDS: T E M P E R A T U R E 244
11.6.3 SCALAR FIELDS: WATER 246
11.6.3.1 SWELLING I N WATER 2 4 7
11.6.3.2 MODELS FOR DETERMINATION O F T H E WATER C O N T E N T 2 5 2
IMAGE 6
X | CONTENTS
11.6.3.3 EFFECT O F POLYMER C H A R G E DENSITY A N D I O N S D U R I N
G PREPARATION O N
SWELLING I N WATER 254
11.6.3.4 ODD-EVEN EFFECT 256
11.6.4 DIRECTED EXTERNAL FIELDS: MECHANICAL A N D ELECTRICAL FIELDS 2 5
7 11.6.4.1 MECHANICAL STRESS 2 5 7
11.6.4.2 ELECTRIC FIELD 2 5 8
11.7 PEM AS A STRUCTURAL U N I T 259
11.7.1 C U S H I O N 2 5 9
11.7.1.1 CELL-MEMBRANE M I M I C SYSTEMS 260 11.7.1.2 MULTILAYERS BEYOND
POLYELECTROLYTES 261
11.7.2 MATRIX 261
11.8 CONCLUSION A N D OUTLOOK 261
REFERENCES 2 6 2
12 POLYELECTROLYTE CONFORMATION IN A N D STRUCTURE O F POLYELECTROLYTE
MULTILAYERS 2 6 9 STEPHAN BLOCK, O L A F SOLTWEDEI, PETER NESTLER, A N D
CHRISTIANE A. H E L M 12.1 INTRODUCTION 2 6 9
12.2 RESULTS 2 7 0
12.2.1 T H E FIRST POLYELECTROLYTE LAYER BRUSH A N D / O R FLATLY
ADSORBED C H A I N S 2 7 0
12.2.2 ADSORPTION O F ADDITIONAL LAYERS A N D INTERDIFFUSION 2 7 5
12.2.3 T H E O U T E R M O S T LAYER FROM O D D - E V E N TO
E V E N - O D D EFFECT 2 7 7 12.3 CONCLUSION A N D OUTLOOK 279
REFERENCES 280
13 C H A R G E BALANCE A N D TRANSPORT IN ION-PAIRED POLYELECTROLYTE
MULTILAYERS 281 JOSEPH B. SCHLENOFF 13.1 INTRODUCTION 281
13.2 ASSOCIATION MECHANISM: COMPETITIVE ION PAIRING 283
13.2.1 INTRINSIC VS. EXTRINSIC CHARGE C O M P E N S A T I O N 2 8 5
13.2.1.1 KEY EQUILIBRIA 285
13.2.1.2 INTERACTION ENERGIES 2 8 7
13.2.1.3 MULTILAYER DECOMPOSITION 290 13.2.1.4 DOPING-MODERATED
MECHANICAL PROPERTIES 2 9 2 13.3 SURFACE VERSUS BULK POLYMER CHARGE 2 9
2
13.3.1 DISTRIBUTION O F SURFACE CHARGE I N LAYER-BY-LAYER BUILD-UP: M E
C H A N I S M 297
13.4 POLYELECTROLYTE INTERDIFFUSION 301
13.4.1 EQUILIBRIUM VERSUS NON-EQUILIBRIUM CONDITIONS FOR SALT A N D
POLYMER SORPTION 304
13.5 I O N TRANSPORT THROUGH MULTILAYERS: T H E "RELUCTANT" EXCHANGE M E
C H A N I S M 305
IMAGE 7
CONTENTS XI
13.5.1 PRACTICAL CONSEQUENCES: TRAPPING A N D SELF-TRAPPING 313
13.6 CONCLUDING REMARKS 3 1 5
REFERENCES 3 1 5
14 CONDUCTIVITY SPECTRA O F POLYELECTROLYTE MULTILAYERS REVEALING ION
TRANSPORT PROCESSES 321 MONIKA SCHONHOFF A N D CORNELIA CRAMER 14.1
INTRODUCTION TO CONDUCTIVITY STUDIES O F LBL FILMS 321
14.2 PEM SPECTRA: OVERVIEW 323
14.3 DC CONDUCTIVITIES O F PEMS 3 2 4
14.4 MODELING O F PEM SPECTRA 3 2 8
14.5 ION C O N D U C T I O N I N POLYELECTROLYTE COMPLEXES 3 2 9
14.6 SCALING PRINCIPLES I N CONDUCTIVITY SPECTRA: F R O M T I M E - T E
M P E R A T U R E TO T I M E - H U M I D I T Y SUPERPOSITION 3 3 2
14.6.1 GENERAL ASPECTS O F SCALING 3 3 2
14.6.2 T I M E - T E M P E R A T U R E SUPERPOSITION PRINCIPLE I N PEC
SPECTRA 333 14.6.3 ESTABLISHMENT O F A T I M E - H U M I D I T Y
SUPERPOSITION PRINCIPLE 334 REFERENCES 3 3 5
15 RESPONSIVE LAYER-BY-LAYER ASSEMBLIES: DYNAMICS, STRUCTURE A N D
FUNCTION 3 3 7
SVETLANA SUKHISHVILI
15.1 INTRODUCTION 337
15.2 C H A I N DYNAMICS A N D FILM LAYERING 338
15.2.1 LESSONS F R O M PECS 338
15.2.1.1 P H A S E DIAGRAMS O F PECS A N D LBL FILM DEPOSITION 338
15.2.1.2 POLYELECTROLYTE TYPE A N D EQUILIBRIUM A N D DYNAMICS I N PECS
3 4 0
15.2.2 P H - I N D U C E D C H A I N DYNAMICS A N D FILM STRUCTURE 3 4 2
15.3 RESPONSIVE SWELLABLE LBL FILMS 348
15.3.1 LBL-DERIVED HYDROGELS 348
15.3.1.1 PREPARATION A N D SWELLING 3 4 8
15.3.1.2 MECHANICAL PROPERTIES 3 5 0
15.3.1.3 LBL HYDROGELS AS MATRICES FOR CONTROLLED RELEASE O F BIOACTIVE
MOLECULES 351 15.3.2 LBL FILMS O F MICELLES WITH RESPONSIVE CORES 353
15.4 CONCLUSION A N D OUTLOOK 358
REFERENCES 3 5 9
16 TAILORING T H E MECHANICS O F FREESTANDING MULTILAYERS 3 6 3
ANDREAS FERY AND VLADIMIR V. TSUKRUK 16.1 INTRODUCTION 3 6 3
16.2 M E A S U R E M E N T S O F MECHANICAL PROPERTIES O F
FLAT LBL FILMS 364
16.2.1 MICROMECHANICAL PROPERTIES F R O M BULGING EXPERIMENTS 3 6 4
IMAGE 8
XII | CONTENTS
16.2.2 BUCKLING M E A S U R E M E N T S O F LBL FILMS 3 6 7
16.2.3 LOCAL MECHANICAL PROPERTIES PROBED WITH FORCE SPECTROSCOPIES 3 6
9 16.2.4 S U M M A R Y O F MECHANICAL PROPERTIES O F FLAT LBL FILMS 3 7
0
16.3 MECHANICAL PROPERTIES O F LBL MICROCAPSULES 3 7 2
16.3.1 THEORY A N D M E A S U R E M E N T O F MECHANICAL PROPERTIES O F
MICROCAPSULES 3 7 3 16.3.2 BASIC CONCEPTS O F SHELL THEORY 3 7 3
16.3.3 EXPERIMENTAL M E A S U R E M E N T S 3 7 4
16.3.4 SMALL DEFORMATION M E A S U R E M E N T S 3 7 5
16.4 PROSPECTIVE APPLICATIONS UTILIZING MECHANICAL PROPERTIES 3 7 8
16.4.1 FLAT FREESTANDING LBL FILMS FOR S E N S I N G APPLICATIONS 378
16.4.2 MICROCAPSULES FOR CONTROLLED DELIVERY PROCESSES 3 8 2 16.4.2.1
EXPLODING CAPSULES 3 8 2
16.4.2.2 ASYMMETRIC CAPSULES 3 8 2
16.4.2.3 MECHANICAL STABILITY A N D INTRACELLULAR DELIVERY 3 8 5
REFERENCES 3 8 6
17 DESIGN A N D TRANSLATION O F NANOLAYER ASSEMBLY PROCESSES:
ELECTROCHEMICAL ENERGY T O PROGRAMMABLE PHARMACIES 3 9 3 MD. NASIM
HYDER, NISARG J. SHAH, AND PAULA T. H A M M O N D 17.1 INTRODUCTION 3 9
3
17.2 CONTROLLING TRANSPORT A N D STORING C H A R G E I N MULTILAYER T H
I N FILMS:
IONS, ELECTRONS A N D MOLECULES 3 9 5 17.2.1 LBL SYSTEMS FOR PROTON
EXCHANGE FUEL CELLS 3 9 5
17.2.2 C H A R G E STORAGE U S I N G LBL ASSEMBLIES 3 9 8
17.2.2.1 C A R B O N N A N O T U B E LBL ELECTRODES 3 9 8 17.2.2.2 C A R
B O N N A N O T U B E / C O N J U G A T E D POLYMER SYSTEM 4 0 0 17.2.3
COMPOSITE SYSTEMS 4 0 2
17.2.3.1 VIRUS BATTERY 4 0 2
17.2.3.2 DSSC LBL ELECTRODES 4 0 2
17.2.3.3 MULTICOLOR ELECTROCHROMIC DEVICES 404
17.3 LBL FILMS FOR MULTI-AGENT D R U G DELIVERY - OPPORTUNITIES FOR
P R O G R A M M A B L E RELEASE 406 17.3.1 PASSIVE CONTROLLED RELEASE
407
17.3.1.1 RELEASE O F PROTEINS 408
17.3.1.2 SMALL MOLECULE DELIVERY 4 1 2 17.3.2 MULTI-AGENT DELIVERY A N D
CONTROL O F SEQUENCE 418
17.4 AUTOMATED SPRAY-LBL - ENABLING FUNCTION A N D
TRANSLATION 4 2 2
17.4.1 MEANS O F ACHIEVING N E W ARCHITECTURES 425
17.4.2 COATING O F COMPLEX SURFACES 4 2 7
17.4.3 U S I N G KINETICS TO MANIPULATE C O M P O S I T I O N 4 2 9
17.5 CONCLUDING REMARKS 431
REFERENCES 4 3 1
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CONTENTS XIII
18 SURFACE-INITIATED POLYMERIZATION A N D LAYER-BY-LAYER FILMS 4 3 7
NICEL ESTILLORE A N D RIGOBERTO C. ADVINCULA 18.1 INTRODUCTION 4 3 7
18.2 OVERVIEW O F SURFACE-GRAFTED POLYMER BRUSHES 438
18.2.1 SYNTHESIS O F POLYMER BRUSHES 4 3 9
18.2.2 SURFACE-INITIATED A T O M TRANSFER RADICAL POLYMERIZATION
(SI-ATRP) 4 3 9 18.3 LAYER-BY-LAYER (LBL) SELF-ASSEMBLY 4 4 0 18.3.1.1
WATER-SOLUBLE ATRP MACROINITIATORS 4 4 0 18.4 C O M B I N E D LBL-SIP
APPROACH 441
18.4.1 SINGLE ADSORPTION O F A POLYELECTROLYTE ATRP MACROINITIATOR O N T
O A C H A R G E D SURFACE 4 4 2 18.4.2 ADSORPTION O F OPPOSITELY C H A R
G E D ATRP MACROINITIATOR(S) O N T O A N LBL DEPOSITED MULTILAYER
ASSEMBLY 4 4 3
18.4.3 MULTIPLE ADSORPTION O F OPPOSITELY C H A R G E D ATRP
MACROINITIATORS FOR ENHANCED INITIATOR DENSITY 4 4 7
18.5 APPLICATIONS O F T H E C O M B I N E D LBL-SIP APPROACH 4 4 9
18.5.1 DUAL STIMULI-RESPONSE O F T H E LBL-SIP B R U S H MODIFIED
SURFACES 4 4 9 18.5.2 FUNCTIONAL FREE-STANDING B R U S H FILMS 4 5 0
18.5.3 CELL ADHESION 451
18.5.4 STIMULI RESPONSIVE FREE-STANDING FILMS 451
18.6 CONCLUDING REMARKS 4 5 3
REFERENCES 4 5 3
19 QUARTZ CRYSTAL RESONATOR A S A TOOL FOR FOLLOWING T H E BUILD-UP O F
POLYELECTROLYTE MULTILAYERS 4 5 5 MIKKO SALOMAKI ANDJOUKO KANKARE 19.1
INTRODUCTION 4 5 5
19.2 BASIC CONCEPTS 4 5 6
19.3 GROWTH PROCESSES 461
19.3.1 EFFECT O F T E M P E R A T U R E 4 6 2
19.4 EXPERIMENTAL TECHNIQUES 4 6 3
19.5 ANALYSIS O F Q C R DATA 4 6 5
REFERENCES 4 6 9
VOLUME 2
PART II APPLICATIONS 471
20 ELECTROSTATIC A N D COORDINATIVE SUPRAMOLECULAR ASSEMBLY O F
FUNCTIONAL FILMS FOR ELECTRONIC APPLICATION A N D MATERIALS SEPARATION 4
7 3 BERND TIEKE, ASHRAF EL-HASHANI, KRISTINA HOFFMANN, A N D ANNA MAIER
20.1 INTRODUCTION 4 7 3
20.2 POLYELECTROLYTE MULTILAYER M E M B R A N E S 4 7 4
20.2.1 WATER DESALINATION 4 7 4
20.2.2 SIZE- A N D CHARGE-SELECTIVE TRANSPORT O F AROMATIC C O M P O U N
D S 4 7 6
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XIV CONTENTS
20.2.3 ION SEPARATION F R O M POLYELECTROLYTE BLEND
MULTILAYER M E M B R A N E S 479 20.2.4 M E M B R A N E S CONTAINING
MACROCYDIC C O M P O U N D S 4 8 0 20.2.4.1
P-SULFONATO-CALIX[N]ARENE-CONTAINING M E M B R A N E S 4 8 0 20.2.4.2
AZACROWN ETHER-CONTAINING M E M B R A N E S 483
20.2.4.3 M E M B R A N E S CONTAINING HEXACYCLEN-HEXAACETIC ACID 486
20.2.5 LBL-ASSEMBLED FILMS O F P R U S S I A N BLUE A N D ANALOGUES 4 8
7 20.2.6 COORDINATIVE ASSEMBLY O F FUNCTIONAL T H I N FILMS 493 20.2.6.1
FILMS O F COORDINATION POLYMERS BASED O N SCHIFF-BASE-METAL ION
COMPLEXES 493
20.2.6.2 FILMS O F COORDINATION POLYMERS BASED O N TERPYRIDINE-METAL I O
N COMPLEXES 495
20.2.6.3 FILMS O F COORDINATION POLYMERS BASED O N
BISIMIDAZOLYLPYRIDINE-METAL ION COMPLEXES 5 0 2
20.3 S U M M A R Y A N D CONCLUSIONS 504
REFERENCES 506
21 OPTOELECTRONIC MATERIALS A N D DEVICES INCORPORATING POLYELECTROLYTE
MULTILAYERS 511
H.D. ROBINSON, REZA MONTAZAMI, CHALONGRAT DAENGNGAM, ZIWEI ZUO, WANG
DONG, JONATHAN METZMAN, A N D RANDY HEFIIN 21.1 INTRODUCTION 511
21.2 SECOND O R D E R NONLINEAR OPTICS 5 1 2
21.3 PLASMONIC E N H A N C E M E N T O F SECOND O R D E R NONLINEAR
OPTICAL
RESPONSE 515
21.4 NONLINEAR OPTICAL FIBERS 519
21.5 OPTICAL FIBER BIOSENSORS 521
21.6 ANTIREFLECTION COATINGS 525
21.7 ELECTROCHROMIC DEVICES 5 2 7
21.8 ELECTROMECHANICAL ACTUATORS 5 3 0
REFERENCES 5 3 3
22 NANOSTRUCTURED ELECTRODES ASSEMBLED FROM METAL NANOPARTICLES A N D Q
U A N T U M DOTS IN POLYELECTROLYTES 5 3 9 LARA HALAOUI 22.1
INTRODUCTION 5 3 9
22.2 NANOSTRUCTURED PT ELECTRODES F R O M ASSEMBLIES O F PT
NANOPARTICLES I N POLYELECTROLYTES 5 4 0
22.2.1 ASSEMBLY O F POLYACRYLATE-CAPPED PT N P S I N POLYELECTROLYTES 5
4 0 22.2.2 SURFACE CHARACTERIZATION BY H Y D R O G E N UNDERPOTENTIAL
DEPOSITION 541
22.2.3 H 2 0 2 S E N S I N G AT ARRAYS O F PT N P S I N POLYELECTROLYTE
AT LOW SURFACE COVERAGE 545
22.2.4 BIOSENSING AT ASSEMBLIES O F GLUCOSE OXIDASE MODIFIED PT N P S I
N POLYELECTROLYTES 548
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CONTENTS XV
22.2.5 SURFACE OXIDATION A N D STABILITY O F PT N P ASSEMBLIES 5 4 9
22.2.6 OXYGEN REDUCTION AT PT N P ASSEMBLIES 5 5 0
22.3 NANOSTRUCTURED PHOTOELECTRODES F R O M ASSEMBLIES O F Q-CDS I N
POLYELECTROLYTES 552 22.3.1 DIP VERSUS D I P - S P I N ASSEMBLY O F
Q-CDS I N POLYELECTROLYTES 553 22.3.2 PHOTOELECTROCHEMISTRY A T
PDDA/Q-CDS ASSEMBLY I N T H E PRESENCE O F
HOLE SCAVENGERS 5 5 5 22.3.3 PHOTOCURRENT POLARITY-SWITCHING AT Q-CDS
PHOTOELECTRODES 556 22.4 CONCLUSIONS 5 5 8
REFERENCES 5 5 9
23 RECORD PROPERTIES O F LAYER-BY-LAYER ASSEMBLED COMPOSITES 5 7 3 MING
YANG, PAUL PODSIADLO, BONG SUP SHIM, A N D NICHOLAS A. KOTOV 23.1
INTRODUCTION 573
23.2 LBL ASSEMBLIES O F CLAYS 5 7 4
23.2.1 STRUCTURE A N D PROPERTIES O F CLAY PARTICLES 5 7 4
23.2.2 STRUCTURAL ORGANIZATION I N CLAY MULTILAYERS 5 7 5
23.2.3 CLAY MULTILAYERS AS HIGH-PERFORMANCE NANOCOMPOSITES 576 23.2.4
APPLICATIONS O F CLAY MULTILAYERS I N BIOTECHNOLOGY 5 7 8 23.2.5
ANISOTROPIC TRANSPORT I N CLAY MULTILAYERS 5 8 0
23.2.6 CLAY MULTILAYERS FOR OPTICAL A N D ELECTRONIC APPLICATIONS 581
23.3 LBL ASSEMBLIES O F C A R B O N NANOTUBES 5 8 2
23.3.1 STRUCTURE A N D PROPERTIES O F CNTS 5 8 2
23.3.2 STRUCTURAL ORGANIZATION A N D MECHANICAL PROPERTIES I N
MULTILAYERS O F C A R B O N NANOTUBES 583 23.3.3 ELECTRICAL C O N D U C
T O R APPLICATIONS 5 8 4
23.3.4 SENSOR APPLICATIONS 5 8 5
23.3.5 FUEL CELL APPLICATIONS 5 8 7
23.3.6 NANO-/MICRO-SHELL LBL COATINGS 5 8 7
23.3.7 BIOMEDICAL APPLICATIONS 5 8 8
23.4 CONCLUSIONS A N D PERSPECTIVES 5 8 9
REFERENCES 5 9 0
24 CARBON NANOTUBE-BASED MULTILAYERS 5 9 5
YONG TAE PARK A N D JAIME C. CRUNLAN 24.1 INTRODUCTION 5 9 5
24.2 CHARACTERISTICS O F C A R B O N N A N O T U B E LAYER-BY-LAYER
ASSEMBLIES 5 9 6
24.2.1 GROWTH O F CARBON NANOTUBE-BASED MULTILAYERS 5 9 6 24.2.2
ELECTRICAL PROPERTIES 6 0 0
24.2.3 MECHANICAL BEHAVIOR 601
24.3 APPLICATIONS O F C A R B O N N A N O T U B E LAYER-BY-LAYER
ASSEMBLIES 602 24.3.1 TRANSPARENT ELECTRODES 602
24.3.2 SENSOR APPLICATIONS 604
24.3.3 ENERGY-RELATED APPLICATIONS 6 0 7
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XVI CONTENTS
24.3.4 BIOMEDICAL APPLICATIONS 608
24.4 CONCLUSIONS 6 0 9
REFERENCES 609
25 NANOCONFINED POLYELECTROLYTE MULTILAYERS: FROM NANOSTRIPES T O
MULTISEGMENTED FUNCTIONAL NANOTUBES 613 C6CI!E J. ROY, CIDRIC C. BURON,
SOPHIE DEMOUSTIER-CHAMPAGNE, AND ALAIN M.JONAS 25.1 INTRODUCTION 613
25.2 ESTIMATION O F T H E SIZE O F POLYELECTROLYTE C H A I N S I N
DILUTE
SOLUTIONS 6 1 4
25.3 CONFINING LBL ASSEMBLY O N FLAT SURFACES 618
25.3.1 LBL ASSEMBLY TEMPLATED BY CHEMICALLY NANOPATTERNED SURFACES 619
25.3.2 LBL LIFT-OFF 621
25.4 CONFINING LBL ASSEMBLY I N NANOPORES 624
25.4.1 PECULIARITIES O F LBL ASSEMBLY I N NANOPORES 6 2 7
25.4.2 MULTISEGMENTED LBL NANOTUBES 630
25.5 CONCLUSIONS 633
REFERENCES 634
2 6 T H E DESIGN O F POLYSACCHARIDE MULTILAYERS FOR MEDICAL APPLICATIONS
6 3 7
BENJAMIN THIERRY, DEWANG MA, A N D FRANGOISE M. WINNIK 26.1 INTRODUCTION
637
26.2 POLYSACCHARIDES AS MULTILAYERED FILM C O M P O N E N T S : A N
OVERVIEW O F
T H E I R STRUCTURE A N D PROPERTIES 6 3 8 26.2.1 POLYCATIONS 639
26.2.2 POLYANIONS 641
26.3 MULTILAYERS F O R M E D BY ASSEMBLY O F WEAK POLYANIONS A N D
CHITOSAN O R CHITOSAN DERIVATIVES 642 26.3.1 H Y A L U R O N A N 642
26.3.2 POLYGALACTURONIC ACID 646
26.3.3 ALGINATE 6 4 7
26.4 MULTILAYERS F O R M E D BY ASSEMBLY O F STRONG POLYANIONS A N D
CHITOSAN O R CHITOSAN DERIVATIVES 6 4 7 26.4.1 H E P A R I N 6 4 7
26.4.2 CHONDROITIN SULFATE 649
26.5 CARDIOVASCULAR APPLICATIONS O F POLYSACCHARIDE MULTILAYERS 6 5 0
26.5.1 ANTI-THROMBOGENIC PROPERTIES O F POLYSACCHARIDE MULTILAYERS 6 5 0
26.5.2 PREPARATION O F POLYSACCHARIDE MULTILAYERS O N BLOOD VESSELS 651
26.5.3 D R U G DELIVERY TO T H E VASCULAR WALL F R O M POLYSACCHARIDE
MULTILAYERS 652
26.6 CONCLUSIONS 654
REFERENCES 655
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CONTENTS XVII
27 POLYELECTROLYTE MULTILAYER FILMS BASED O N POLYSACCHARIDES: FROM
PHYSICAL
CHEMISTRY T O T H E CONTROL O F CELL DIFFERENTIATION 659 THOMAS BOUDOU,
KEFENG REN, THOMAS CROUZIER, A N D CATHERINE PICART 27.1 INTRODUCTION
659
27.2 FILM INTERNAL COMPOSITION A N D HYDRATION 6 6 0
27.2.1 FILM GROWTH 6 6 0
27.2.2 HYDRATION A N D SWELLABILITY 662
27.2.3 INTERNAL C O M P O S I T I O N 665
27.3 FILM CROSS-LINKING: RELATION BETWEEN COMPOSITION A N D MECHANICAL
PROPERTIES 666
27.3.1 IONIC PAIRING 666
27.3.2 COVALENT A M I D E BONDS 6 6 8
27.3.3 MECHANICAL PROPERTIES O F FILMS A N D CORRELATION WITH CROSS-LINK
DENSITY 669
27.4 CELL ADHESION O N T O CROSS-LINKED FILMS: CELL ADHESION,
CYTOSKELETAL
ORGANIZATION A N D C O M P A R I S O N WITH O T H E R MODEL MATERIALS
671 27.4.1 FILM CROSS-LINKING MODULATES MYOBLAST ATTACHMENT,
PROLIFERATION A N D CYTOSKELETAL ORGANIZATION 671 27.4.2 CORRELATION
BETWEEN T H E CELL SPREADING AREA A N D YOUNG'S
M O D U L U S E 0 6 7 5
27.4.3 C O M P A R I S O N WITH O T H E R MATERIAL SUBSTRATES:
POLYACRYLAMIDE (PA) A N D POLYDIMETHYSILOXANE (PDMS) 6 7 7 27.5 CELL
DIFFERENTIATION: ESC A N D MYOBLASTS 6 7 9
27.5.1 FILM CROSS-LINKING INFLUENCES T H E MYOGENIC DIFFERENTIATION
PROCESS MORPHOLOGICALLY B U T N O T T H E EXPRESSION O F MUSCLE-SPECIFIC
PROTEINS 679
27.5.2 FILM CROSS-LINKING DRIVES T H E FATE O F M O U S E EMBRYONIC S T
E M 681 27.6 CONCLUSIONS 684
REFERENCES 6 8 5
28 DIFFUSION O F N A N O P A R T I D E S A N D BIOMOLECULES INTO
POLYELECTROLYTE MULTILAYER FILMS: TOWARDS N E W FUNCTIONAL MATERIALS 691
MARC MICHEL A N D VINCENT BALL 28.1 INTRODUCTION 691
28.2 LBL FILMS I N W H I C H N A N O P A R T I D E S A R E INCORPORATED
STEP-BY-STEP 693
28.3 LBL FILMS M A D E UNIQUELY F R O M N A N O P A R T I D E S 693
28.4 N A N O P A R T I D E S PRODUCED BY POST-TREATMENT O F DEPOSITED
FILMS 694
28.5 DIFFUSION O F COLLOIDS I N ALREADY DEPOSITED FILMS 6 9 8
28.5.1 PERMEABILITY O F LBL FILMS TOWARDS IONS, SMALL D R U G S A N D
DYES 6 9 8
28.5.2 DIFFUSION O F N A N O P A R T I D E S I N A N D O U T O F LBL
FILMS 700
28.6 EMERGING PROPERTIES O F FILMS FILLED WITH N A N O P A R T I D E S
BY T H E
POST-INCUBATION METHOD 7 0 5 28.6.1 PRODUCTION O F
ANISOTROPICALLY-COATED COLLOIDS 705
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XVIII CONTENTS
28.6.2 SENSING A N D CONTROLLED RELEASE APPLICATIONS 705
28.6.3 ELECTRICAL CONDUCTIVITY 705
28.7 CONCLUSIONS A N D PERSPECTIVES 706
REFERENCES 707
29 COUPLING CHEMISTRY A N D HYBRIDIZATION O F DNA MOLECULES O N
LAYER-BY-LAYER MODIFIED COLLOIDS 711 JING KANG A N D LARS DAHNE 29.1
INTRODUCTION 711
29.2 MATERIALS A N D M E T H O D S 712
29.2.1 MATERIALS 712
29.2.2 METHODS 713
29.2.2.1 COUPLING O F OLIGONUCLEOTIDES ONTO LBL-COATED COLLOIDAL
PARTICLES 713 29.2.2.2 HYBRIDIZATION O F C O M P L E M E N T A R Y
OLIGOS O N T O T H E LBL-OLIGO PARTICLES 716
29.3 RESULTS 716
29.3.1 ONE-STEP VERSUS T W O - S T E P COUPLING PROCESS BY EDC 716
29.3.2 SELECTION O F POLYELECTROLYTES 716
29.3.2.1 SELECTION O F POLYCATIONS 717
29.3.2.2 SELECTION O F POLYANIONS 718 29.3.3 NON-SPECIFIC BINDING A N D
ITS MINIMIZATION 718
29.3.4 COUPLING BY L.L'-CARBONYLDIIMIDAZOL I N ORGANIC SOLVENT 721
29.3.5 N U M B E R O F COATING LAYERS 722
29.3.6 C O U P L I N G A N D HYBRIDIZATION EFFICIENCY 722
29.3.6.1 C O U P L I N G EFFICIENCY 722 29.3.6.2 HYBRIDIZATION
EFFICIENCY 723 29.3.7 C O M P A R I S O N O F LBL PARTICLES WITH
CONVENTIONAL CARBOXYLATED PARTICLES 724
29.3.8 A R R A N G E M E N T O F T H E COUPLED OLIGO MOLECULES 724
29.3.8.1 ANALYSIS BY FRET INVESTIGATIONS 724 29.3.8.2 FRET O F DSOLIGOS
FREE IN SOLUTION 725 29.3.8.3 FRET O F DSOLIGOS O N LBL PARTICLES 726
29.3.9 STABILITY O F T H E LBL-OLIGO PARTICLES 7 2 7
29.4 S U M M A R Y 7 2 7
REFERENCES 729
3 0 A "MULTILAYERED" APPROACH T O T H E DELIVERY O F DNA: EXPLOITING
T H E STRUCTURE O F POLYELECTROLYTE MULTILAYERS T O PROMOTE
SURFACE-MEDIATED CELL TRANSFECTION A N D MULTI-AGENT DELIVERY 731 DAVID
M. LYNN 30.1 INTRODUCTION 731
30.2 SURFACE-MEDIATED DELIVERY O F DNA: MOTIVATION A N D CONTEXT,
OPPORTUNITIES A N D CHALLENGES 732 30.3 FILMS FABRICATED USING
HYDROLYTICALLY DEGRADABLE CATIONIC POLYMERS 734
IMAGE 15
CONTENTS XIX
30.4 TOWARD SPATIAL CONTROL: RELEASE O F DNA F R O M T H E SURFACES O F
I M P L A N T S
A N D DEVICES 736
30.5 TOWARD TEMPORAL CONTROL: TUNABLE RELEASE A N D SEQUENTIAL RELEASE
739
30.5.1 APPROACHES BASED O N INCORPORATION O F DIFFERENT HYDROLYTICALLY
DEGRADABLE POLYAMINES 740
30.5.2 APPROACHES BASED O N INCORPORATION O F CATIONIC "CHARGE-SHIFTING"
POLYMERS 742
30.5.3 NEW APPROACHES TO RAPID RELEASE 744
30.6 CONCLUDING REMARKS 745
REFERENCES 746
31 DESIGNING LBL CAPSULES FOR DRUG LOADING A N D RELEASE 749
BRUNO C. DE CEEST A N D STEFAAN C. DE S M E D T 31.1 INTRODUCTION 749
31.2 ENGINEERING MICROPARTICULATE TEMPLATES TO DESIGN LBL CAPSULES FOR
CONTROLLED D R U G RELEASE 750 31.3 ENGINEERING T H E SHELL TO DESIGN
LBL CAPSULES FOR CONTROLLED D R U G
RELEASE 753
31.4 INTERACTION O F LBL CAPSULES WITH LIVING CELLS IN VITRO A N D
IN VIVO 759
31.5 CONCLUSIONS 761
REFERENCES 761
32 STIMULI-SENSITIVE LBL FILMS FOR CONTROLLED DELIVERY O F PROTEINS A N
D DRUGS 7 6 5
KATSUHIKO SATO, SHIGEHIRO TAKAHASHI, A N D JUN-ICHI ANZAI 32.1
INTRODUCTION 765
32.2 AVIDIN-CONTAINING LBL FILMS 7 6 5
32.3 CONCANAVALIN A-CONTAINING LBL FILMS 768
32.4 DENDRIMER-CONTAINING LBL FILMS 771
32.5 INSULIN-CONTAINING LBL FILMS 772
32.6 CONCLUSIONS 774
REFERENCES 776
33 ASSEMBLY O F MULTILAYER CAPSULES FOR DRUG ENCAPSULATION A N D
CONTROLLED RELEASE 7 7 7
JINBO FEI, YUE CUI, QIANG HE, ANDJUNBAI LI 33.1 INTRODUCTION 7 7 7
33.2 MAGNETICALLY SENSITIVE RELEASE 779
33.3 ULTRASOUND-STIMULATED RELEASE 780
33.4 PHOTO-STIMULATED RELEASE 781
33.5 THERMO-STIMULATED RELEASE 783
33.6 PH-SENSITIVE RELEASE 785
33.7 REDOX-CONTROLLED RELEASE 787
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XX | CONTENTS
33.8 BIO-RESPONSIVE RELEASE 788
33.9 EXTENSION 792
33.10 CONCLUDING REMARKS 794
REFERENCES 794
34 ENGINEERED LAYER-BY-LAYER ASSEMBLED CAPSULES FOR BIOMEDICAL
APPLICATIONS 801 ANGUS P.R.JOHNSTON, GEORGINA K. SUCH, SARAH J. DODDS, A
N D FRANK CARUSO 34.1 INTRODUCTION 801
34.2 TEMPLATE SELECTION 801
34.3 MATERIAL ASSEMBLY 804
34.4 LOADING 809
34.4.1 PRELOADING O N / I N TEMPLATE 8 1 0
34.4.2 LOADING W I T H I N LAYERS 811
34.4.3 POST-LOADING 813
34.5 DEGRADATION A N D RELEASE 813
34.6 APPLICATIONS 816
34.6.1 MICROREACTORS 816
34.6.2 TARGETING 818
34.6.3 THERAPEUTIC DELIVERY 819
34.6.3.1 SMALL MOLECULES 8 1 9
34.6.3.2 VACCINES 821
34.6.3.3 DNA 8 2 2
34.7 CONCLUSIONS 823
REFERENCES 8 2 4
35 ASSEMBLY O F POLYMER MULTILAYERS FROM ORGANIC SOLVENTS FOR
BIOMOLECULE ENCAPSULATION 831 SEBASTIAN BEYER, JIANHAO BAI, A N D DIETER
TRAU 35.1 INTRODUCTION 831
35.1.1 BIO-TEMPLATE-BASED LBL ENCAPSULATION I N T H E A Q U E O U S
PHASE 831 35.1.2 LOADING-BASED LBL BIOMOLECULE ENCAPSULATION I N T H E A
Q U E O U S PHASE 8 3 2
35.1.3 DIFFUSION-BASED LBL BIOMOLECULE ENCAPSULATION I N T H E A Q U E O
U S PHASE 833
35.2 LIMITATIONS O F LBL-BASED BIOMOLECULE ENCAPSULATION I N A Q U E O U
S PHASE 834
35.3 LBL BIOMOLECULE ENCAPSULATION I N T H E ORGANIC PHASE 835
35.3.1 REVERSE-PHASE LBL 8 3 6
35.3.1.1 M E C H A N I S M 836
35.3.1.2 TECHNIQUE 8 3 9
35.3.1.3 ENCAPSULATION O F BIOMOLECULES 8 4 0 35.3.2 "INWARDS BUILD-UP
SELF-ASSEMBLY" O F POLYMERS FOR BIOMOLECULE ENCAPSULATION I N T H E
ORGANIC PHASE 845 35.3.2.1 M E C H A N I S M A N D TECHNIQUE 845
IMAGE 17
CONTENTS
35.3.2.2 ENCAPSULATION O F BIOMOLECULES 846
35.4 CONCLUSION A N D OUTLOOK 8 4 7
REFERENCES 8 4 9
36 STIMULI-RESPONSIVE POLYMER COMPOSITE MULTILAYER MICROCAPSULES A N D
MICROCHAMBER ARRAYS 851 MARIA N. ANTIPINA, MAXIM V. KIRYUKHIN, A N D
CLEB B. SUKHORUKOV
36.1 INTRODUCTION 8 5 2
36.2 FABRICATION O F STIMULI-RESPONSIVE LBL MICROCAPSULES 853 36.2.1
PH-RESPONSIVE CAPSULES 855
36.2.2 SALT-RESPONSIVE CAPSULES A N D CAPSULE FUSION 8 5 8 36.2.3
REDOX-RESPONSIVE CAPSULES 8 6 2 36.2.4 CHEMICAL-RESPONSIVE CAPSULES 8 6
2 36.2.4.1 SOLVENT 8 6 2
36.2.4.2 GLUCOSE 863
36.2.4.3 C 0 2 8 6 3
36.2.4.4 ENZYMES 8 6 4
36.2.5 TEMPERATURE-RESPONSIVE CAPSULES 8 6 5 36.2.6 REMOTE RESPONSIVE
CAPSULES 866
36.2.6.1 MAGNETIC LBL CAPSULES 8 6 6 36.2.6.2 ULTRASOUND-TRIGGERED
RELEASE 8 6 7 36.2.6.3 OPTICALLY ADDRESSABLE CAPSULES 8 6 8 36.2.7
MECHANICAL ADDRESSING O F INDIVIDUAL CAPSULES 8 6 9 36.2.8 PATTERNING
POLYELECTROLYTE CAPSULES 8 7 2 36.3 MICROCHAMBER ARRAYS 8 7 3
36.3.1 FABRICATION O F MICROCHAMBERS B Y LBL ASSEMBLY O N I M P R I N T
E D SURFACES 873
36.3.1.1 LBL ASSEMBLY O F T H E PEMS I N CONFINED GEOMETRIES 874
36.3.1.2 DISSOLVING T H E TEMPLATE A N D M A K I N G A FREE-STANDING PEM
FILM W I T H A N ARRAY O F S T A N D I N G HOLLOW M I C R O C H A M B E
R S 874 36.3.2 MICROCHAMBER LOADING WITH SUBSTANCES O F INTEREST 8 7 7
36.3.3 RESPONSIVENESS O F C H A M B E R S TO LIGHT A N D MECHANICAL LOAD
8 7 9 36.4 CONCLUSION 881
REFERENCES 8 8 2
37 DOMAIN-CONTAINING FUNCTIONAL POLYELECTROLYTE FILMS: APPLICATIONS T O
ANTIMICROBIAL COATINGS A N D ENERGY TRANSFER 891 AURDLIE GUYOMARD,
BERNARD NYSTEN, ALAIN M. JONAS, A N D KARINE GLINEL 37.1 INTRODUCTION
891
37.2 POLYELECTROLYTE FILMS INCORPORATING RANDOMLY DISTRIBUTED
HYDROPHOBIC N A N O D O M A I N S FOR ANTIMICROBIAL APPLICATIONS 893
37.2.1 HYDROPHOBIC N A N O D O M A I N S I N HYDROPHILIC PEMS WITH A M P
H I P H I L I C MACROMOLECULES 893 37.2.2 E N T R A P M E N T O F A N
ANTIBACTERIAL PEPTIDE I N HYDROPHOBIC
N A N O D O M A I N S 8 9 5
IMAGE 18
XXII | CONTENTS
37.3 MULTICOMPARTMENTALIZED STRATIFIED POLYELECTROLYTE FILMS FOR CONTROL
O F ENERGY TRANSFER 898 37.3.1 H O W PRECISELY C A N T H E
STRATIFICATION O F A LBL FILM BE CONTROLLED? 898 37.3.2 FABRICATION O F
DYE-IMPERMEABLE POLYELECTROLYTE BARRIERS 901
37.3.3 CONTROL O F A CASCADE O F EVENTS I N A MULTICOMPARTMENTALIZED
STRATIFIED POLYELECTROLYTE FILM 902 37.4 CONCLUSIONS A N D PERSPECTIVES
903
REFERENCES 904
38 CREATING FUNCTIONAL MEMBRANES THROUGH POLYELECTROLYTE ADSORPTION 907
MERLIN L. BRUENING 38.1 INTRODUCTION 9 07
38.2 FUNCTIONALIZATION O F T H E INTERIOR O F MEMBRANES 908
38.2.1 DEPOSITION O F PEMS I N POROUS MEDIA 908
38.2.2 FUNCTIONALIZATION O F M E M B R A N E S WITH PROTEINS 910
38.2.2.1 PROTEIN ADSORPTION I N M E M B R A N E S 910 38.2.2.2
TRYPSIN-CONTAINING POLYELECTROLYTE FILMS FOR PROTEIN DIGESTION 911
38.2.3 CATALYTIC FILMS A N D M E M B R A N E S 914
38.2.3.1 CATALYTIC, NANOPARTICLE-CONTAINING FILMS 914 38.2.3.2 CATALYTIC
M E M B R A N E S 915
38.3 LBL FILMS AS M E M B R A N E SKINS 918
38.3.1 EARLY STUDIES 918
38.3.2 REMOVAL O F DYES A N D SMALL ORGANIC MOLECULES F R O M WATER 918
38.3.3 SELECTIVE REJECTION O F F~ A N D PHOSPHATE 920
38.3.4 VARIATION O F PSS/PDADMAC FILM PROPERTIES WITH T H E N U M B E R
O F
ADSORBED LAYERS 921 38.4 CHALLENGES 922
REFERENCES 922
3 9 REMOTE A N D SELF-INDUCED RELEASE FROM POLYELECTROLYTE MULTILAYER
CAPSULES A N D FILMS 9 2 5
ANDRE C. SKIRTACH, DMITRY V. VOLODKIN, AND HELMUTH MOHWALD REFERENCES
940
4 0 CONTROLLED ARCHITECTURES IN LBL FILMS FOR SENSING A N D
BIOSENSING 951 OSVALDO N. OLIVEIRA JR., PEDRO H.B. AOKI, FELIPPE J.
PAVINATTO, AND CARLOS J . L CONSTANTINO 40.1 I N T R O D U C T I O N 951
40.2 LBL-BASED SENSORS A N D BIOSENSORS 952
40.2.1 OPTICAL DETECTION METHODS 952
40.2.2 MASS C H A N G E METHODS 954
40.2.3 ELECTROCHEMICAL METHODS 955
IMAGE 19
CONTENTS XXIII
40.2.4 METHODS INVOLVING ELECTRICAL M E A S U R E M E N T S 956
40.2.5 E-TONGUES A N D E-NOSES 958
40.2.6 EXTENDING T H E CONCEPT O F E-TONGUE TO BIOSENSING 963 40.3
SPECIAL ARCHITECTURES FOR SENSING A N D BIOSENSING 964
40.4 STATISTICAL A N D COMPUTATIONAL METHODS TO TREAT T H E DATA 969
40.4.1 ARTIFICIAL NEURAL NETWORKS A N D REGRESSION METHODS 970 40.4.2
OPTIMIZATION O F BIOSENSING PERFORMANCE U S I N G MULTIDIMENSIONAL
PROJECTIONS 971 40.5 CONCLUSIONS A N D PERSPECTIVES 977
REFERENCES 9 7 8
41 PATTERNED MULTILAYER SYSTEMS A N D DIRECTED SELF-ASSEMBLY O F
FUNCTIONAL NANO-BIO MATERIALS 985 LLSOON LEE 41.1 NEW APPROACHES A N D
MATERIALS FOR MULTILAYER FILM PATTERNING
TECHNIQUES 985
41.2 CELL ADHESION A N D PATTERNING U S I N G PEMS 9 8 8
41.3 PEMS INCORPORATING PROTEINS A N D T H E I R PATTERNING 990
41.4 METAL/GRAPHENE CONDUCTIVE PATTERNING VIA PEM FILMS 992
41.5 O R D E R E D A N D DISORDERED PARTICLES O N PEMS 995
41.6 MECHANICAL ASPECTS O F PEM FILMS A N D DEGRADABLE FILMS 997
REFERENCES 999
42 ELECTROCHEMICALLY ACTIVE LBL MULTILAYER FILMS: FROM BIOSENSORS T O
NANOCATALYSTS 1003
ERNESTO. J. CALVO
42.1 INTRODUCTION 1003
42.2 ELECTROCHEMICAL RESPONSE 1004
42.3 DYNAMICS O F C H A R G E EXCHANGE 1012
42.3.1 PROPAGATION O F REDOX C H A R G E (ELECTRON HOPPING) 1012 42.3.2
ION EXCHANGE 1018
42.3.3 APPLICATIONS 1024
42.3.4 BIOSENSORS 1026
42.3.5 CORE-SHELL NANOPARTICLES 1030
42.3.6 NANOREACTORS 1030
42.3.7 BIOFUEL CELL CATHODES 1031
42.4 CONCLUSIONS 1033
REFERENCES 1034
43 MULTILAYER POLYELECTROLYTE ASSEMBLY IN FEEDBACK ACTIVE COATINGS
A N D FILMS 1039
DMITRY C. SHCHUKIN AND HELMUTH MOHWAID 43.1 INTRODUCTION. T H E CONCEPT
O F FEEDBACK ACTIVE COATINGS 1039
43.2 POLYELECTROLYTE-BASED SELF-HEALING ANTICORROSION COATINGS 1040
43.2.1 PASSIVE PROTECTION ACTIVITY O F POLYELECTROLYTE MULTILAYERS 1042
IMAGE 20
XXIV | CONTENTS
43.2.2 CONTROLLED RELEASE O F INHIBITING AGENTS 1044
43.3 COATINGS WITH ANTIBACTERIAL ACTIVITY 1045
43.4 CONCLUSIONS A N D OUTLOOK 1050
REFERENCES 1050
INDEX 1053 |
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spelling | Multilayer thin films sequential assembly of nanocomposite materials ed. by Gero Decher ... 2., completely rev. and enl. ed. Weinheim Wiley-VCH txt rdacontent n rdamedia nc rdacarrier Mehrschichtsystem (DE-588)4244347-7 gnd rswk-swf (DE-588)4143413-4 Aufsatzsammlung gnd-content Mehrschichtsystem (DE-588)4244347-7 s DE-604 Decher, Gero 1956- Sonstige (DE-588)1022460250 oth X:MVB text/html http://deposit.dnb.de/cgi-bin/dokserv?id=3902504&prov=M&dok_var=1&dok_ext=htm Inhaltstext DNB Datenaustausch application/pdf http://bvbr.bib-bvb.de:8991/F?func=service&doc_library=BVB01&local_base=BVB01&doc_number=024986553&sequence=000001&line_number=0001&func_code=DB_RECORDS&service_type=MEDIA Inhaltsverzeichnis |
spellingShingle | Multilayer thin films sequential assembly of nanocomposite materials Mehrschichtsystem (DE-588)4244347-7 gnd |
subject_GND | (DE-588)4244347-7 (DE-588)4143413-4 |
title | Multilayer thin films sequential assembly of nanocomposite materials |
title_auth | Multilayer thin films sequential assembly of nanocomposite materials |
title_exact_search | Multilayer thin films sequential assembly of nanocomposite materials |
title_full | Multilayer thin films sequential assembly of nanocomposite materials ed. by Gero Decher ... |
title_fullStr | Multilayer thin films sequential assembly of nanocomposite materials ed. by Gero Decher ... |
title_full_unstemmed | Multilayer thin films sequential assembly of nanocomposite materials ed. by Gero Decher ... |
title_short | Multilayer thin films |
title_sort | multilayer thin films sequential assembly of nanocomposite materials |
title_sub | sequential assembly of nanocomposite materials |
topic | Mehrschichtsystem (DE-588)4244347-7 gnd |
topic_facet | Mehrschichtsystem Aufsatzsammlung |
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