508
WATER-SOLUBLE POLYMERS
Affiliation Index Clemson University, 74,502 Columbia Research Laboratories, 350 Ethicon, Inc., 74,468 Exxon Research and Engineering Company, 57 Halliburton Services, 446 INSA de Rouen, 405 Louisiana State University, 189 McMaster University, 82,105 Macrophile Associates, 232 Medical College of Virginia, 367 NASA-Marshall Space Flight Center, 418 Polytechnic University, 493 Protan A/S (Norway), 430 Protan, Inc. (USA), 430
Purdue University, 484 Seton Hall University, 202 Stanford University, 303 Université Pierre et Marie Curie (Paris), 218 University of Alabama—Huntsville, 418 University of Florida—Gainesville, 25,151,159,175 University of Massachusetts—Amherst, 249,261 University of Southern California, 159 University of Southern Mississippi, 2,119,130,276,291,320,338 University of Wisconsin—Madison, 350 University of the Witwatersrand (South Africa), 394
Subject Index Acidic fibroblast growth factor, effect of heparin, 377-378 Acrylamide, mechanism and kinetics of persulfate-initiated polymerization, 82-101 Acrylamide-3-(2-acrylamido-2methylpropyl-dimethylammonio)-1 propanesulfonate copolymers added electrolytes, effect, 124,126/,127 characterization, 122 compositions, 123f,124,125/ macromolecular structure, 122,123r microstructure, 124* molecular weight, 123/ monomer synthesis, 120,121/ pH, effects, 127,128/ polymer concentration, effect, 127,128/ polymerization, degree, 123r reaction parameters for copolymerization, 122f reactivity ratios, 123,124f,125/ synthesis, 120,122 viscosity measurements, 122
Acrylamide-based polyelectrolytes, hydrophobically modified, See Hydrophobically modified acrylamidebased polyelectrolytes Acrylamide-/i-decylacrylamide copolymer system, effect of concentration on apparent viscosity, 130,131/ Acrylamide polymerization inverse emulsion polymerization, 64,65/66 inverse microemulsion polymerization, 66 precipitation polymerization, 67 solution polymerization, 60-63; Acrylamide polymerization using persulfate initiation cage-effect theory, 87-88 complex theory, 87-88 inhibition, 85 initiation mechanism elucidation, 91-98,100 generalization to other water-soluble monomers, 98-99,100f,101 kinetics, 85-91 radical addition mechanism, 85 redox pairs, use, 83,84r
509
INDEX Acrylamide polymerization using persulfate ïrûûauon—Continued
reduction oxidation, 83 solvents), effects, 83,85 solvent-transfer theory, 85 Acrylamide polymerization using persulfate initiation at high monomer concentration comparison of kinetic model to experimental data, 112,114-117/ consumption rate of initiator, effect on initial monomer concentration, 112,117/ conversion time and weight-average molecular weight conversion data and model predictions, 112,114-116/ experimental conditions, 109,11 Of experimental method of polymerization, 107,108/ experimental procedure, 107 limiting conversions, 109,110r,lll/ molecular-weight determination, 106-107 parameter estimation, 109,112,113* rate order vs. monomer concentration, 109 residual monomer concentration determination, 106 thermal and monomer-enhanced decomposition of potassium persulfate, relative magnitudes, 112,117/ Acrylamide polymer synthesis, See Acrylamide polymerization Acrylamide-sulfobetaine amphoteric monomer copolymers, See Acrylamide-3-(2-acrylamido-2-methylpropyldimethylammonio)-1 -propanesulfonate copolymers 3-(Acrylamido)-3methylbutyltrimethylammonium chloride, synthesis, 35 2- (Acrylamido)-2-methylpropanesulfonic acid, synthesis, 44 3- (2-Acrylamido-2-methylpropyldimethylammonio)-1 -propanesulfonate-acrylamide copolymers, See Acrylamide-3-[2-(acrylamido)-2-methylpropyldimethylammonio]1-propanesulfonate copolymers Aggregation diffusion-limited cluster-cluster aggregation model, 315-317 process, 315
Albumin-cross-linked polyvinylpyrrolidone hydrogels albumin functionalization, 486* bulk degradation mechanism, 487,490 enzyme digestion, 487,488-485^ equilibrium swelling properties, 485,487,488/ hydrogel synthesis, 485 in vivo experiment, 486,490,491/ procedure for albumin functionalization, 485 procedure for enzyme digestion of hydrogels, 486 radiographic image, 490,491/ surface-degradation mechanism, 487,490 ultrasonographic image, 490,491/ Alginate, 76-77 Algorithm development for molecularweight-distribution determination choice of function-fit method, 279-280,281/282 regression algorithm, 284 series use for integration, 282-284 Aliphatic polyesters, application, 405-406 Alkyldiallylamine characterization procedure, 153 C-NMR spectra of copolymers, 153,154/ C-NMR spectrum, 153/ cyclocopolymerization procedure, 153 reaction, 152 homocyclopolymerization, 152 polymeric micelles, formation, 157/ side-chain crystallization of copolymers, 155,156/ synthesis, 152 Alkyldiallylmethylammomum chloride characterization procedure, 153 C-NMR spectra of copolymers, 153/154,155-156/ cyclocopolymerization procedure, 153 reaction, 152 homocyclopolymerization, 152 polymeric micelles, formation, 157/ synthesis, 152 Amine-functionalized water-soluble polyamides as drug carriers anchoring reactions, 399-400 experimental procedure, 400403 13
13
13
510 Amine-runctionalized water-soluble polyamides as drug carrière—Continued structural prerequisites, 395-396 synthetic approaches, 396-399 Amine imides, 46-47 6-Amino-6-deoxycellulose, synthesis, 190 6-Amino-6-deoxycellulose acetate 6-azido-6-deoxycellulose acetate, synthesis, 191 azido groups, reduction to amino groups, 193,196 cellulose-g-peptide graft copolymers, use in synthesis, 196-197 C-NMR spectra of cellulose acetate precursors, 193,195/ experimental procedure, 190-191,192* graft copolymers copolymerization procedure, 191,192* synthetic scheme, 191,193 Ή-NMR spectra of ^-peptide graft copolymer, 196,198/ IR spectra cellulose acetate precursors, 193,194/ g-peptide graft copolymer, 196,19^ synthesis, 191 6-0-tosylcellulose acetate, synthesis, 191 Ammonium imides, 46-47 Amphiphilic associating polymers, use in thickening of aqueous solutions, 218-219 Amphiphilic polyelectrolytes containing aromatic chromophores, 291-292 Amphoteric polymers aminimide synthesis, 46-47 commercial applications, 21 examples, 17,20/21 polyampholytic synthesis, 47 properties, 21 quaternary ammonium carboxylate synthesis, 46 Angiogenesis, effect of heparin, 384 Anionic dyes, clinical applications, 370 Anionic monomers, application of persulfate-initiated polymerization, 99,100*,101 Anionic polyelectrolytes, synthesis, 17 Anionic polymers polyphosphonic acid and salt synthesis, 45-46 polysulfonic acid and salt synthesis, 43-45 13
WATER-SOLUBLE POLYMERS Antibody localization, polyanionic polymers, 375 Antigen localization, polyanionic polymers, 375 Antipolyelectrolytic effect, description, 119 Antiviral action of polyanions, 371-373 Aqueous solutionis), roles of molecular structure and solvation on drag reduction, 320-335 Aqueous solution behavior, hydrophobically modified poly(acrylic acid), 218-231 Aqueous solution properties of naphthalene-pendent acrylic copolymers added urea concentration, effect, 294,296/ copolymer structure, 293 diamine copolymers solution pH, effect, 300,301/ structure, 297 experimental materials, 292-293 fluorescent spectroscopy, 293 hydrophobic methyl groups, effect, 300,301/ polymer characterization, 293 polymer concentration, effect, 294,297,298/ solution pH, effect, 294,296/ solution pH for diamine copolymers, effect, 300,301/ steady-state fluorescent spectra, 294,295/ steady-state spectra of diamine copolymers, 297,298-299/300 structure copolymer, 293 diamine copolymers, 297 viscosity measurements, 293 Aryl cyclic sulfonium zwitterions, synthesis, 41 ASi-containing polyacrylamides, synthesis and properties, 165*, 166 Associative copolymer systems behavior, role of liaisons, 239-245 free energies of hydrophobic bonding between alkyl chains, 242,243/,244*,245 Associative polymers thickening of solutions, use, 218 water viscosity, increase, 446 Atherosclerosis, role of heparin, 383-384 6-Azido-6-deoxycellulose acetate, synthesis, 189-190
INDEX Β Basic fibroblast growth factor, inhibition by heparin, 378 Beclomethasone dipropionate, nasal delivery, 356 y-Benzyl-a,L-glutamate rt-carboxyanhydride cellulose copolymer, synthesis, 196-197,198-199/ experimental procedure, 190-191,192* graft copolymerization procedure, 191,192* synthetic scheme, 191,193 Bioadhesive drug delivery advantages, 350-351 bioadhesive parameters, 351,353 buccal drug delivery, 357-358 cervical and vaginal drug delivery, 350 colon and rectal drug delivery, 359 components, 351,352/ epithelium, 354-355 mucus layer, 353-354 nasal drug delivery, 356 ocular drug delivery, 355-356 stomach and intestinal drug delivery, 358-359 strategies, 355-360 Bioadhesive parameters chain segment mobility, 353 charges, 351,353 hydration and expanded nature of polymer, 353 Bioadhesive screening techniques, 351 Biodegradable hydrogels, 484 Biopolymers, water soluble, See Water-soluble biopolymers Bioresorbable polymers, 405-406 2,3-0-Bis(phenylcarbamoyl)-6-azido6-deoxycellulose, synthesis, 196 Block copolymers antithrombogenicity, 469 electron micrographs, 469,470/ hemocompatibility, 470,471* platelet adhesion and aggregation on surface, 471* properties, 474 schematic representation, 471,472/ synthesis, 469,472,475 wettability, 469,470f Brain, role of polyanionic polymers, 380
511 Buccal drug delivery, 357-358 Bulk degradation, definition, 484 Bulk polymerization of /i-vinylpyrrolidone reactivity ratios, 69* typical recipe, 69 C Cage-effect theory, description, 87-88 Calcium metabolism, role of heparin, 380-381 Carbetimer, antitumor application, 370-371 Cat-Floe, synthesis, 27 Cathepsin, vascular effects, 376 Cationic antibiotics, detoxification, 369-370 Cationic guar, effect on solution viscosity of polysaccharides, 453,455*,456,457-458/ Cationic monomers, application of persulfateinitiated polymerization, 99,100*,101 Cationic polyelectrolytes, synthesis, 17,\9f Cationic polymer synthesis oxonium polymer, 43 phosphonium polymer, 41,42/43 quaternary ammonium polymer, 27-40 sulfonium polymer, 4(M1 Cationic quaternary ammonium monomers, 34 Cell membrane transduction, role of heparin, 381 Cellulose, chemical modification for increased water solubility, 75 Cervical drug delivery, 360 Chain-growth polymerization, synthesis of water-soluble copolymers, 2,4 Charge-density parameter, theory for polyelectrolytes, 203-204 Charged polymers amphoteric polymers, 17,2(y,21 classification, 17 examples anionic monomers for polyelectrolytic synthesis, 17,19/ quaternary ammonium salts for cationic polyelectrolytic synthesis, 17,19/ properties, effect of structure, 17 Charged polysaccharides, effect on solution viscosity of polysaccharides, 453,455f,456,457-458/
512 Charge-transfer interactions, liaisons, 234 Chelation, role of heparin, 381 Chemical modification of natural polymers alginate, 76-77 cellulose, 75 chitosan, 74-75 hyaluronic acid, 77 pectin, 76 proteins, 77-78 starch, 75-76 Chitin extraction process, 431,432/ structure, 430,432/ Chitosan biological properties, 434,435* canonic properties, 431,434* certificate of analysis for purified materials, 431,433/ chemical modification for increased water solubility, 74-75 chemical properties, 434* commercial sources, 431 fibers, 438,440-441/ films, 435,436/437 forms aqueous, 435,436/ physical, 435,437*,438 powder, 435 shaped, 437-438,439^44Qf key properties relating to biomedical applications, 431,434-435* manufacturing scheme, 431,432/ paper, 438,442/ purification scheme, 431,433/ sponge, 438,442/ structure, 430,432/ Cluster-cluster aggregation, description, 315 Colon drug delivery, factors affecting residence time, 359 Comblike cyclopolymers of alkyldiallylamines and alkyldiallylmethylammonium chlorides, synthesis and characterization, 151-157 Complex theory application to persulfate-initiated acrylamide polymerization, 88-90 description, 87-88 evaluation for acrylamide polymerization, 88
WATER-SOLUBLE POLYMERS Complexation reactions between synthetic polymers, objectives of investigations, 303 Condinine, polymerization, 39 Conformational behavior, effect of extra liaisons, 237-239 Connective tissue, role of polyanionic polymers, 379-380 Contact, definition, 233 Coordination-complex forces, baisons, 234 Copoly(a,^D,L-aspaitamides), synthesis, 401-402 Copoly(imide-amides), synthesis, 396-397 Cosolute-binding systems, role of liaisons in behavior, 244,246 Coulombic forces, liaisons, 234 Cross-link, definition, 233 Cycle-polymerization, description, 27
D Derivatized polysaccharides, examples, 16 Detoxification, use of polyanionic polymers, 369-370 Dextran sulfate, oral absorption, 385 Diacetone acrylamide, 33 /t-[(Dialkylamino)alkyl]acrylamides, synthesis, 35 Dialkyldiallylammonium salts, synthesis of water-soluble cyclopolymers, 151-152 Dialkyl(2-methylene-3-butenyl)sulfonium chloride, synthesis of monomers and polymers, 4041 Diallyldecylmethylammonium chloride hydrophobically associating copolymers applications, 188 Brookfield viscosity measurement, 179 C-NMR spectrum, effect of solvent, 182f,183 copolymerization procedure, 178,179* copolymerization with diallyldimethylammonium chloride, 183* experimental materials, 176 NMR measurements, 179-180 shear rate, effect on viscosity vs. concentration, 185,186-187/188 viscosity of copolymer comonomer content, effect, 185/ concentration effects, 183,184/185 13
INDEX
513
WaUylmemyl(p-propionamido)ammomum chloride monomer and homopolymers, 31-32 Diffusion, study of Na ion interactions with polyions in aqueous salt-free solutions by diffusion, 202-216 Diffusion coefficient calculation, 203 relationship to molecular weight, 278 Diffusion-limited aggregation, description, 315 Diffusion-limited cluster-cluster aggregation, model, 315-317 [P-(Dimethylamino)ethyl]acrylamide, 33 p-[(Dimethylamino)ethyl]styrene, 32 [(Dimethylammo)memyl]aciylamide, 32-33 p-[(Dimethylamino)methyl]styrene, 32 (Y-Dimethylaminopropyl)acrylamide, 33 Dimethyldiallylammonium chloride, 27-28,29/ Dimethyldiallylammonium chloride polymer electroconductivity, 50,51* fractionation and characterization by size exclusion chromatography, 30,31/ intrinsic viscosity vs. ionic strength, 29,3Qf mtrinsic viscosity vs. temperature and molecular weight, 28,29/ N-NMR spectrum, 28,29/ structure, 27 synthesis, 27 n-[ 1,1 -Dimethyl-3-(dimethylamino)propyl]acrylamide, 33 DNAs, molecular structure, 15 Drag reduction classification of models, 320-321 coil size vs. drag reduction efficiency, 321 discovery, 320 influencing factors, 320 Drag reduction in aqueous solutions associations, effects, 334,335/ composition, effect, 323,328/329 experimental materials, 321 experimental results, agreement with theoretical models, 334 friction factor vs. Reynolds number, plot, 323,326/ hydrodynamic volume changes, effect, 329,332-333/ measurements, 321-322 molecular weight, effect, 329,330-331/ +
14
Drag reduction in aqueous solutions— Continued
percent drag reduction, definition, 323 percent drag reduction values, 323,327* percent drag reduction vs. polymer volume fraction, 323,326/ polymer characterization, 321 solvent ordering, effect, 334,335/ tailored copolymers, 322-323,324-325* universal calibration for diverse polymer types, 334,335/ Drug and enzyme conjugates, examples of use with polyanionic polymers, 368-369 Drug carriers, amine-functionalized, water-soluble polyamides, 394-403 Drug delivery, bioadhesive, See Bioadhesive drug delivery Dynamic light scattering for molecularweight-distribution determination of water-soluble macromolecules algorithm development, 279-284 data collection, 285,287 data processing, 285-287 experimental procedure, 284-287 polyacrylamide molecular-weight distribution, 288,289/ polyethylene oxide molecular-weight distribution, 288,289/ sample preparation, 284-285 series approximations, 288 terminology, 277 theory, 277-279
Ε Electroconductivity in electrophotography, use of water-soluble polymers, 50,51*/ Encephalomyocarditis viruses, effect of pyrans, 373 Endothelial cell growth factor, effect of heparin, 377-378 Enhanced oil recovery, use of water-soluble polymers, 175 Enzyme(s), applications for chemically modified water-soluble compounds, 77-78 Enzyme-catalyzed hydrolysis, network degradation, 485
514 Epidermal growth factor, applications for chemically modified water-soluble compounds, 77-78 Epithelium, bioadhesion, 354-355 Ethylene oxide polymers, classes, 26 F Fibronectin, description, 354-355 First-order normalized autocorrelation function, definition, 277-278 Flocculation, use of water-soluble polymers, 48/ Fluorescent probes of complexation between poly(rt-isopropylacrylamide) and sodium n-dodecyl sulfate, comparison, 261-273 Fluorocarbon surfactants, hydrophobic bonding to β-cyclcdextrins, 159-160 Fractal dimensionality, description, 316-317 Free-radical polymerization kinetics scheme, practical consequences, 57-58,59* reactions, 57-58 Friction factor, definition, 322 Friend leukemia, protection by pyran, 372 FX-13-containing polyacrylamide Brookfield viscosities vs. mole percent comonomer, 161-162,164/ synthesis, 161,162* FX-14-containing polyacrylamide Brookfield viscosities vs. mole percent comonomer, 161-162,164/ synthesis, 161,162* G Gastric and intestinal mucosa, role of heparinoids and heparin, 384-385 Gastrointestinal tract, motility pattern, 358 Gel degradation, mechanisms, 484 Generalized exponential distribution adjustable parameters, 280,281/ function, 279-280 integrability, 280 molecular-weight distribution, effect of choice of function, 280 Glycocalyx, description, 354
WATER-SOLUBLE POLYMERS Graft copolymers electron micrograph, 476/ synthesis, 474,477-478 thrombogenicity, 476,477* H Heparanase, inhibition, 371 Heparan sulfate, role in brain, 380 Heparan sulfate proteoglycans, role in brain, 380 Heparin affinity for superoxide dismutase, 368 angiogenesis, effect, 384 detoxification of cationic antibiotics, 369-370 glomerular effects, 376-377 growth, effect, 377-378 inhibition of heparanase, 371 oral absorption, 385 proteinase inhibition, 375-376 role(s) atherosclerosis, 383-384 brain, 380 cell membrane transduction, 381 connective tissue, 379-380 gastric and intestinal mucosa, 384-385 immunity, 374 inflammation, 383 lipids, 383 structure, 385 transcription inhibition, 382 tumor inhibition, 378 vascular effects, 376 Heparinoids gastric and intestinal mucosa, role, 384-385 immunity, role, 374 vascular effects, 376 Heparin sulfate, antigen or antibody localization, 375 Heterochain-type polymers, use as drug carriers, 394-395 Ή-NMR characterization of polyethylene glycol derivatives degrees of substitution, comparison with those from titration, 420* end-group conversion, determination, 420 impurity detection, 421
515
INDEX Ή-NMR characterization of polyethylene glycol derivatives—Continued molecular-weight determination, 42It problems, 420 Homogeneous precipitation, example, 237 Homopolymer solutions, role of liaisons in behavior, 234-236 Hyaluronan biomedical applications, 493 description, 493 function, 493 structural comparisons, 495-499 structure, 493,494/,495 viscoelasticity, 493 Hyaluronic acid, applications for chemically modified water-soluble compounds, 77 Hydrodynamic radius, definition, 279 Hydrodynamic volume definition, 4 dimension of macromolecular chain in solution vs. repeating unit structure, 4-5,6-7/ methods for increasing, 5,8/ Hydrogels, 468 Hydrogen bond(s), liaisons, 234 Hydrogen bonding, prerequisites, 304 Hydropmhc-hydrophobic domain polymer systems advantages, 468-469 block copolymers, 469-475 graft copolymers, 474,476/,477r,478 networks, 482/ polymer blends, 478,479f,480r,481/ Hydrophobically associating ionic copolymers, typical hydrophobic association, 175-176 Hydrophobically associating ionic copolymers of methyldialryl-(l,ldihydropentadecafluorooctoxyethyl)ammonium chloride, effect of perfluoro carbon groups on water solubility, 176-188 Hydrophobically associating polyacrylamides, synthesis, 67,68/ Hydrophobically associating polymers apparent viscosity vs. concentration, 339,34Qf hydrocarbon replacement by perfluoroalkyl groups, 159 proposed model, 339,340/
Hydrophobically associating systems, role of liaisons in behavior, 242 Hydrophobically modified acrylamide-based polyelectrolytes, 338-347 Hydrophobically modified hydroxyethylcellulose, role of liaisons in behavior, 240,241/ Hydrophobically modified poly(acrylic acid) aqueous solution behavior alkyl chain content and length, effect, 221,222/ comparison to hydrophobically modified nonionic polymers, 228-229 ionic strength, effect, 221,222/228-229 pH, effect, 223,224/ shear rate, effect, 223,224/229-230 experimental apparatus, 220 experimental conditions, 220-221 experimental materials, 219 mixed aggregates, formation, 229 modification of poly(acrylic acid), procedure, 219,220/ solubilization of hydrophobic additives, 226,227/230 surfactants, effect, 223,225/226 viscosity vs. interchain association, 226,228 Hydrophobically modified polymer(s), 21-22 Hydrophobically modified polymer systems, examples, 468 Hydrophobically modified water-soluble polymers applications, 130 examples, 130 water viscosity, increase, 446 Hydrophobic bond, description of term, 338 Hydrophobic bonding, free energies between alkyl chains of associative copolymer systems, 242,243/,244/,245 Hydrophobic effects on complexation and aggregation in water-soluble polymers chain configuration, 308,311 complexation measurements fluorescent measurements, 306,307/ interpretation, 308,31(^,311-312 pH measurements, 308,309/ complexation mechanism, experimental support, 311-312 diffusion-limited cluster-cluster aggregation model, 315-317
516 Hydrophobic effects on complexation and aggregation in water-soluble polymers— Continued
dynamic-light-scattering measurements of aggregation, 312,313-314/,315 experimental procedure, 305-306 Hydrophobic interactions, liaisons, 234 Hydrosoluble polymeric drug carriers derived from citric acid and L-lysine catalytic hydrogenolysis, procedure, 416 coupling of amine-type compounds, procedure, 416 hydrogenolysis of protecting groups, 408,41Qf,411 hydrolysis of imide functions, 411,412-413/,414,416 interfacial polycondensation, 407-408,409/416 IR spectra procedure, 417 molecular-weight determination, 417 monomer synthesis, 406-407 self-coupling of amine-type compounds, 414,415/ Hypercoils, formation, 291
Icebergs, description, 339 Immunity, role of polyanionic polymers, 374 Indifferent solvent, definition, 234 Inflammation, role of heparin, 383 Initiation mechanism for persulfate-initiated acrylamide polymerization chain initiation, 95 complex-cage equivalence, 91 historically used mechanism, 91-94 initiator reactions, 94 propagation, 95 proposed mechanism, 94-97 rate equation, derived, 97-98,100* swollen cage formation and decomposition, 94-95 termination, 95 transfer to monomer, 95 Inorganic polymers, 16-17 Insulin, nasal delivery, 356 Intensity-time autocorrelation function, definition, 277
WATER-SOLUBLE POLYMERS Interacting polymers, viscosity behavior and oil-recovery properties, 446-464 Intestinal drug delivery, description, 358-359 Intraparticle interference factor approximation, 279 occurrence, 278-279 Intrinsic viscosity, measurement, 9,11 Inverse emulsion polymerization of acrylamide advantages, 64,66 schematic diagram, 64,65/ typical recipe, 64 Inverse microemulsion polymerization of acrylamide, 66 Ionenes, synthesis, 35-36 Ionomers, description, 218 Isotactic polyacrylamide, synthesis, 83
Κ
Kinetics, free-radical polymerization, 57-58,59* Kinetics of persulfate-initiated acrylamide polymerization cage-effect theory, 87-88 complex theory, 87-88 rate dependence, 85,86* solvent-transfer theory, 85-86
L Large-scale aggregates, occurrence, 303-304 Laurylacrylate-containing polyacrylamides, synthesis and properties, 161,163* Lectins, description, 355 Liaisons associative copolymer systems, effect on behavior, 23£-245 bimolecular formation, 238-239 characteristics, 233 charge-transfer interactions, 234 conformational behavior, effect of extra liaisons, 237-239 coordination-complex forces, 234 cosolute-binding systems, effect on behavior, 244,246 Coulombic forces, 234 description, 232-233
INDEX Liaisons—Continued equilibrium constant for simple homopolymer solutions, 235-236 estimation of average number in simple homopolymer solutions, 235 Flory-Huggins interaction parameter, 236 hydrogen bonds, 234 hydrophobic interactions, 234 interaction forces, types, 233-234 simple homopolymer solutions, effect on behavior, 234-236 solubility behavior, effect of extra liaisons, 237 spectroscopic behavior, effect of extra liaisons, 237 unimolecular formation, 238 van der Waals forces, 234 Linear crystalline polyethylenimine, 37 Lipids, role of heparin, 383 Lower critical solution temperature probes of poly(/i-isopropylacrylamide) cloud-point measurements, 253,255/ experimental materials, 250-251 fluorescent probes, 254,256,257/258 hydrogen bonding, effect, 249-250 measurements, 252-253 microcalorimetry, 253-254,255/ nonradiative energy transfer, 258-259 polymer synthesis, 253 sample preparation, 252 synthesis of fluorene-labeled poly(rt-isopropylacrylamide), 251-252 synthesis of poly(nisopropylacrylamide), 251 thermal response in aqueous media for practical applications, use, 250 Lymphocyte mobilization, effect of polyanionic polymers, 373-374
Macromolecular systems, importance of molecular-weight characterization, 276 2-(Methacryloyloxy)ethyl]sulfonate, structure, 44 [3-(Methacryloyloxy)-2-hydroxypropyl]sulfonate structure, 45 synthesis, 44
517 Methacryloylurea derivatives containing quaternary ammonium groups, synthesis, 38 MethyldiaUyl-(l,l-dmydropentadecafluon)octoxyethyl)ammonium chloride (FX-15) hydrophobically associating copolymers applications, 188 Brookfield viscosity measurement, 179 Br vs. F group, effect on polymerization, 18Qf C-NMR spectrum, effect of solvent, 181-182/ copolymerization with diallyldimethylammonium chloride, 183* experimental materials, 176 homopolymerization procedure, 13
178M79 NMR measurements, 179-180 synthesis 2-(bromoethyl)-l, 1-dihydropentadecafluoro-rt-octyl ether, 176-177 di allyl-( 1,1 -dihydropentadecafluorooctoxyethyl)amine, 177 FX-15,177-178 viscosity of copolymers comonomer content, effect, 185/ concentration, effect, 183,184/185 viscosity vs. concentration, effect of shear rate, 185,186-187/188 Λ-Methylolacrylamide, 32-33 Microemulsion, definition, 66 Mobility of injected fluid and crude oil in reservoir rock, definition, 462 Molecular studies, role in drag reduction in aqueous solutions, 320-335 Molecular weight, determination, 106-107 Molecular-weight characterization of macromolecular systems, 276-277 Molecular-weight distribution, determination for water-soluble macromolecules by dynamic light scattering, 276-289 Molecular weight maximum, determination, 280 Mucus layer charge, effect on bioadhesion, 354 presence, 353-354 thickness, effect on bioadhesion, 354
518 Ν Naphthalene-pendent acrylic copolymers, photophysical and rheological studies of aqueous solution properties, 291-301 Nasal drug delivery, 356 Natural polymers, chemical modification, 74-78 Neocarzinostatin, 369 Networks of polymers, copolymerization, 482/ Nonionic polymers applications, 17 repeating units, 17,18/ Nonpolyelectrolytic water-soluble polymers, 25-26 Nonradiative energy transfer between species in solution, investigation, 258-259 N-substituted a,p-D,L-aspartamide polymers, synthesis, 396-399 Nucleic acids, 15 Nucleus,roleof polyanionic polymers, 381-382
Ο Ocular drug delivery, 355-356 Oil-recovery properties of interacting polymers copolymer-crude oil ratio, effect, 460,46If experimental results, 459/ quaternary ammonium salt organic polymer, effect, 459,460/ Organic polymers, functional groups that impart water solubility, 25,26/ Osteoporosis, role of heparin, 380-381 Oxonium monomers and polymers, 43
Ρ Particle-cluster aggregation, description, 315 Pectins, applications for chemically modified water-soluble compounds, 76 Peptide graft copolymers, synthesis using soluble aminodeoxycellulose acetate, 188-199 Percent drag reduction, definition, 323
WATER-SOLUBLE POLYMERS Persulfate-initiated polymerization of acrylamide, mechanism and kinetics, 82-101 Persulfate-initiated polymerization of acrylamide at high monomer concentration comparison of kinetic model to experimental data, 112,114-117/ conversion time and weight-average molecular weight conversion data and effect of consumption rate of initiator on initial monomer concentration, 112,117/ experimental conditions, 109,110/ experimental procedure, 107 limiting conversions, 109,110/, 111/ model predictions, 112,114-116/ molecular-weight determination, 106-107 parameter estimation, 109,112,113/ polymerization, experimental method, 107,108/ rate order vs. monomer concentration, 109 relative magnitudes of thermal and monomer-enhanced decomposition of potassium persulfate, 112,117/ residual monomer concentration determination, 106 Phosphonated polyethylene, synthesis, 45 Phosphonium monomers and polymers, viscosity data, 41,42/43 Piloplex, function, 356 Polyacrylamide(s) applications, 82 degradation, 82 intrinsic viscosity, effect of time, 83 molecular-weight distribution, 288,289/ polyvinyl alcohol) synthesis, 26 synthesis, 25-26 Polyacrylamide-perfluorocarbon group containing water-soluble polymers Brookfield viscosities, 161-166 Brookfield viscosity-comonomer content profiles, 168,172 characterization, 166/,167/ diffusion coefficient vs. polymer concentration, 166,167/172-173 experimental procedure, 160-161 NaCI concentration, effect on Brookfield viscosity, 168,169/
INDEX Polyacrylamide-perfluorocarbon group containing water-soluble polymère— Continued
nonionic surfactants, effect on Brookfield viscosity, 168,171/473 rheology, 168,169-171/ shear, effect on Brookfield viscosity, 168,169/ structures of comonomers, 160 surfactant concentration, effect on Brookfield viscosity, 168,17Qf temperature, effect on Brookfield viscosity, 168,170/ viscosity vs. concentration, 161,164/ Poly(acrylic acid) hydrophobically modified, See Hydrophobically modified poly(acrylic acid) synthesis, 26 Polyampholytes, 47 Polyampholytic polymers, 119-120 Polyanionic polymers angiogenesis, effect, 384 antigen or antibody localization, 375 antitumor application, 370-371 antiviral activity, 371-373 applications anionic dyes, 370 drug carriers and enhancers, 368 detoxification, use, 369-370 drug and enzyme conjugates, use, 368-369 glomerular effects, 376-377 growth, effect, 377-378 heparanase inhibition, 371 immunoadjuvancy, 371-373 interest, 367 lymphocyte mobilization, 373-374 oral absorption, 385 proteinase inhibition, 375-376 reviews, 367-368 role(s) atherosclerosis, 383-384 brain, 380 cell membrane transduction, 381 chelation, 381 connective tissue, 379-380 gastric and intestinal mucosa, 384-385 immunity, 374-375 inflammation, 383 lipids, 383
519 Polyanionic polymers role(s)—Continued nucleus, 381-382 osteoporosis, 380-381 respiration, 385 structure, 384 transcription inhibition, 382 tumor inhibition, 378-379 tumor necrosis factor, isolation, 379 vascular effects, 376 Poly(a,p-D,L-aspartamides) side chain modification procedure, 402 synthesis, 401 Poly(a,p-D,L-asparmydrazide-c0-D,Lornithine, synthesis, 400-401 Poly(diallyldimethylammonium chloride), cyclocopolymerization reaction, 152 Polyelectrolytic water-soluble polymers amphoteric polymer synthesis, 46-47 anionic polymer synthesis, 43-46 cationic polymer synthesis, 27-43 Polyethylene glycol(s) analysis, 419 biotechnical and biomedical applications, 418 properties, 418 selectivity, 419 solubility, 418 superoxide dismutase, use as carrier, 368 Polyethylene glycol aldehydes, 422-425 Polyethylene glycol benzaldehyde characterization, 423 reactivity, 423-424 synthesis, 422 Polyethylene glycol derivatives Ή-NMR characterization, 419,420-421* properties, ideal, 422 Polyethylene glycol propionaldehyde, 424-425 Polyethylene oxide, molecular-weight distribution, 288,289/ Polyethylene sulfonate, antitumor application, 370-371 Polyiminodiacetamides, synthesis, 396-399 Poly [imino-2,1 -propyleneoxy-poly(ethyleneoxy)-1,2-propyleneiminocarbonylmethyleneiminomethylenecarbonyl], synthesis, 401
520 Poly(n-isopropylacrylamide) applications for complexation with surfactants, 262 probes of lower critical solution temperature, 249-259 structure, 249,261 Poly(n-isopropylacrylamide>-sodium n-dodecyl sulfate complexes bound probes of critical micelle concentration, 269,270^272/ characterization, 264,265/ cloud points, 265,267 critical micelle concentration vs. lower critical solution temperature, 272/ experimental materials, 262-263 free probes of critical micelle concentration, 267,269,27Qf lower critical solution temperatures, 272,273/ measurements, 264 modeling of complexation, 269,271-272 polymer synthesis, 264 sample preparation, 263-264 sodium dodecyl sulfate, effect on lower critical solution temperature, 265,266/267,268/ structures, 264,266/ synthesis, 263 Puly(|3-malic acid), synthesis, 406 Polymer behavior, effect of extra liaisons, 237 Polymer blends equilibrium hydration, 480,481/ interpolymer hydrogen bond formation, 478,479/480 mechanical properties, 480/ Polymer-bound aminosalicylic acid, synthesis, 402 Polymer-bound cw-dichloroplatinum(II) complexes, synthesis, 403 Polymer-bound drugs, smooth solubility as prerequisite of efficacious administration, 394-395 Polymer-bound ferrocenylpropanoic acid, synthesis, 403 Polymer-bound phenylacetic acid, synthesis, 402 Polymer complexation degree of acid dissociation, effect, 305 molecular weight, effect, 305 study methods, 304-305
WATER-SOLUBLE POLYMERS Polymerization, acrylamide, 83,84/,85 Polymer solution viscosity, vs. oil recovery, 462 Polymers used as mobility control agents, 447 Poly(methacrylic acid), synthesis, 26 Poly(methyl vinyl ether), synthesis, 26 Polypeptides, 15-16 Polyphosphonic acids and salts, synthesis, 45 Polysaccharides, 16 Poly(styrene sulfonate) blends applications, 462 oil-recovery properties, 459,460-461/ viscosity behavior, 448-459 Polysulfonic acids and salts, synthesis, 43-45 Polyvinyl acetate-ctf-vinyl alcohol), role of liaisons in behavior, 239-240,241/ Polyvinyl alcohol), synthesis, 26 Precipitation polymerization of acrylamide, 67 Primary recombination, définition, 88 Primary structure, influencing factors, 2,3/ Proteins applications for chemically modified water-soluble compounds, 77-78 commercial applications, 16 molecular structure, 15 properties, effect of structure, 15-16 synthesis, 16 Pyran antiviral action, 371-372 immunity,role,374 vaccine adjuvancy, 371 Pyran copolymer antitumor application, 370-371 superoxide dismutase, use as carrier, 368 Pyrene, solubilization, 226,227/230 Pyrene-labeled polyacrylamides absorption spectrum, 141,142/ characterization methods, 132 decay profiles, 146,148-149/ excimer-monomer intensity ratios vs. concentration, 141,145/, 146 excitation spectra, 146,147/ experimental materials, 132 fluorescence emission spectra, 141,142-143/ instrumentation, 132
INDEX Pyrene-labeled polyacrylamides—Continued model-compound synthesis, 135-136,138 monomer synthesis, 132-135 photophysical characterization, 141-149 rheological characterization, 138,141 solution-polymerized microstructure, 141,144/ solution techniques for copolymerization, 135,137-138,139/ surfactant-polymerized microstructure, 141,143/ surfactant technique for copolymerization, 135-136,14Qf
521 Rheological properties of hydrophobically modified acrylamide-based polyelectrolytes—Continued conceptual model, 342 electrostatic repulsions, shielding by added electrolyte, 346,347/ experimental procedure, 339,341/342 monomer synthesis, 339,341/ polymer synthesis, 339 solution studies, 342,343-345/ terpolymers, comparison, 342,346,347/ viscometric measurement, 339,342 Rheology, 11,13/ RNAs, molecular structure, 15
Q Quaternary ammonium carboxylates, 46 Quaternary ammonium polymers, synthesis, 27-40 Quaternary ammonium salt organic polymers, effect on solution viscosity of polysaccharides, 456r,459 Quaternary ammonium salt-polyacrylamide blends oil-recovery properties, 463i polymer interactions giving rise to large viscosity increases, 463-464 viscosity behavior, 462-463 Quaternary structure, influencing factors, 2 R Reaction-limited aggregation, description, 315 Rectal drug delivery, factors affecting residence time, 359 Reduction activation, development, 83 Residual monomer concentration, determination, 106 Respiration, role of polyanionic polymers, 385 Reynolds number, definition, 322 RF-4 and RF-8 containing polyacrylamides, synthesis and properties, 163,165/ Rheological properties of hydrophobically modified acrylamide-based polyelectrolytes apparent viscosity vs. polymer concentration, 342,343-345/
S Secondary recombination, definition, 88 Secondary structure, influencing factors, 2 Second-order temporal correlation function, determination, 305-306 Sedimentation of suspended polymers, use of water-soluble polymers, 49/50 Sensitivity, definition, 43 Serpins, 375-376 Silanization of silica importance, 425 percent Ν vs. reaction conditions and silanating reagent, 426-427/ problems, 425 reactive amino groups, availability on surfaces, 427-428 Silica, silanization, 425 Size exclusion chromatography, advantages and disadvantages for molecular-weightdistribution determination, 277 Sludge dewatering, use of water-soluble polymers, 48,4
