Mesomorphic Order in Polymers

INDEX A 4-AcryloyIoxy-4-cyanobiphenyl 88 Actin filaments 248 Adenine stacks 215 Alkylacrylates 50 Alkylethers 28, 29 Alkylmethacrylates 50, 57 a-Amino acids, random and block copolymers of 165,169 Amorphous polymers 22 Amphiphilic pattern 182,195 Apparent viscosity 158,162 Arnott-Bond-Felsenfeld triplexes 204 Aromatic polymerization, formation of planar molecules by 111 Arthropod cuticle 245 Analogues, nematic 245 Analogues, structural 205 Anisodiametric groups, polymers with side 34 Anisotropic to isotropic state, transition from 44 Anisotropy, dielectric 88 Annealed films east on glass 82 Annealed films east on lead 81 Annealing treatment 79 Antiviral(s) activities of fluoramides 185 monomeric 207 oligomerie and polymeric 208 states 228

Downloaded by 185.106.104.109 on October 13, 2016 | http://pubs.acs.org Publication Date: June 1, 1978 | doi: 10.1021/bk-1978-0074.ix001

,

Block copolymers of two α-amino acids 165,169 with a polyvinyl and polypeptide .. 166 with a saccharide and peptide ........ 165 Bulk polymerization 32, 86, 88 n-Butylmethacrylate (BMA) 59 C

Calf-thymus DNA 181 Cano's experiments 240 Carboaromatie systems 204, 206 Carbobenzoxy-L-lysine 171,172 Carbonfibersfrom mesophase pitches 118 Carbonaceous mesophase 109, 111 Carbons in side chains, interplanar spacings vs 46 Cell for thermal polymerization of 4-cyano-4'-acryloyloxybiphenyl .. 91 L-Cells with polynucleotide triplexes, preincubation of mouse 228 Cellular information transfer from nucleic acids to proteins 206 Cholesteric ( s ) mesophase characteristics of long chain terminated estrogen 200 to nematic structure 142 order in biopolymers 237 pitch with time, change of 140 side groups 64 liquid crystalline order in poly mers and copolymers with .... 56 Β structure 136,238 twist 241 Backbone of cytochrome C 187 Backbones, methacrylic 14 Cholesterol -containing liquid crystalline Base-base recognition schemes in polymers, thermotropic 33 polynucleotides 189 esters of N-methacryloyl-o>-aminoBase-pair analogues 183,204,205 carbonic acids (ChMAA-n) .... 37 Benzene 146 in the formation of a liquid crystal Benzoic acid, phenylesters of 24 line structure, role of 49 Benzoic acid side groups 56 Benzyl-L-glutamate 169,172 Cholesteryl p-acryoyloxybenzoate (ChAB) 58 Biological tests 185 30, 31 Biomesogens and their models 178 Cholesteryl derivatives 97 Biopolymers, cholesteric order in 237 C h oies terylacrylate monomer Cholesterylmethacrylate (ChMA) 38,57,58 Bioregulations, metastabilitles and hysteresis in 181 Cholesterylvinyl succinate, polymer/ monomer state diagram of 98 Birefringence 77, 245 243 Blends, thin films of 66 Chromosome, dinoflagellate

257

Blumstein; Mesomorphic Order in Polymers ACS Symposium Series; American Chemical Society: Washington, DC, 1978.


258

M E S O M O R P H I C

Circular dichroism 144 Coil conformations, polypeptide chains in random 128 Coil radius 129 Comb-like polymers 35, 127 Comonomers into vinyl nucleobasestack matrices, hypothetical insertion of vinyl 216 Complementary matrix fits in nucleoproteinic systems 187 Composition, glass transition tem perature as a function of 67 Concentration, Onsager critical 130 Connective tissue, stacked series of nested arcs in 238 Contractile apparatus in striated muscle, liquid crystalline 248 Copolyesters 119-121 Copolymerization 59 reactions, vinvlmonomers for 183 Copolymers 27, 41, 63, 184 from α-amino acids, block 165, 169 of carbobenzoxy-L-lysine and benzyl-L-glutamate 172 with cholesteric side groups 56 of cholesteryl derivatives 31 of cholesterylmethacrylate (PChMA) with n-alkylmethacrylates 57 or L-leucine and benzyl-L-glutamate 172 with a polyvinyl block and a polypeptide block 166 with a saccharide block and a peptide block 165 thin films of 66 with varied nucleobase design, vinyl 217 with varied strand polarity pattern, 9-vinyladenine 218 x-ray scattering intensity vs. scattering angle for 53 Counterrotation in poly (γ-benzyl glutamate) liquid crystals 157 Crayfish striated muscle 248, 250 Critical angle 159 Critical concentration, Onsager 130 Crystalline, liquid ( see Liquid crystalline ) Crystalline polymers, comparison with 10 Crystallization temperature, melting temperature vs 74 Crystals, liquid (see Liquid crystals) Cuticle, Arthropod 245 4-Cyano-4 -acryloyloxybiphenyl 91 4-Cyano-4 -biphenyl(η -j- 2)alkenoates 86, 87 Cytochrome C, backbone of 187 Cytokinines 204 /

,

ORDER

I N

P O L Y M E R S

D Dichloroethane 151 Dichloromethane , 157 Dielectric anisotropy 88 Dielectric constant during polymerization, static 92 Differential scanning calorimetry 73 Diffraction from polymers with mesomorphic order, x-ray 1 Diffraction studies on mesomorphic order in polymers, x-ray 12 Dilatometric measurements 138 Dinoflagellate chromosome 243 Dioxane 146,171 Diphenyl derivatives 17,28,29 DNA calf-thymus 181 -interaction measurements 185 intercalators 203 n-Dodecylmethacrylate (DMA) 59 DSC 98 Duplexes, Watson-Crick 204

Ε Electron-microscopic studies Enantiotropic (liquid crystalline) polymers Energy, interaction Energy of nematic and isotropic phases of rigid rod solution, free .. Enthalpy (ies) change for the 4-cyano-4'-biphenyl(η + 2)alkenoates of transition Equilibrium separation Ester-aniles of estrone Estrogen cholesterics, long chain terminated Estrone, ester-aniles of Excluded volume effects

183 22 130 132 104 87 87 158 202 200 202 127

F Falling sphere method Fibers from isotropic pitches from mesophase pitches, carbon myofilament lattice of long tonic .... Fibrous arrangements, twisted Filament(s) actin and myosin lattice, effect of ionic strength on .. spacing, effect of pH on Films cast on glass, annealed cast on lead, annealed of copolymers and blends, thin


158 115 118 250 237 248 253 253 82 81 66

259

INDEX

Flexible spacer group 24, 27 Flow temperatures of transition from anisotropic to isotropic state 44 Fluoramides as stereoelectronic simulations of tilerone 210 Fluorenes and flu or en one in classical thermotropics 210 Folds of the polypeptide chains 167 Free energy of nematic and isotropic phases of rigid rod solution 132


G Glass ( es ) annealed films cast on 82 isotropic 16 temperatures of transition from anisotropic to isotropic state .... 44 transition 16 temperature 22, 67 Glycoproteins 239 H Half pitch Heats, transition Helical ambitions of simple vinyl polymers α-Helical conformation Helices, double Hélicoïdal model Helix-coil transition of a polypeptide chain Heteroaromatie systems 204, n-Hexadecylmethacrylate (HMA) ... Hexagonal structure Homopolymers 24, of benzyl-L-glutamate of carbobenzoxy-L-lysine of cholesteryl derivatives Homopolymerization reactions, vinylmonomers for Hypothetical insertion of vinyl comonomers into vinyl nucleobase-stack matrices Hysteresis experiments in the melting profile, thermal phenomena in bioregulations in polynucleotide triplexes, molecular

139 98 215 157 242 245 129 206 59 171 184 169 171 31 183 216 183 192 181 186

I "Infective" compounds, "strangening" nucleic acids by Information transfer from nucleic acids to proteins, cellular

197 206

Inosine stacks Interaction energy Intercalations, Sobell visualization of Intercalative fit, hypothetical Intercalators, DNA Interferon priming Interhybrid arrangements and interactions, speculative Intermediate organization Interplanar spacings vs. carbons in side chains Interplanar spacings and melting points Investigation techniques Ionic strength onfilamentlattice, effect of Ising model Isomorphous solid solution of poly ( cetylvinyl ether ) Isotropic glasses phases of rigid rod solution, free energy of pitches,fibersfrom state, glass temperatures, flow temperatures, flow temperatures of transition from anisotropic to

216 130 203 212 203 228 223 7, 9 46 41 39 253 129 95 16 132 115

44

L Lamellar liquid crystal model of the carbonaceous mesophase Ill Lamellar structure 167 Lattice, effect of ionic strength on filament 253 Lattice stability, forces affecting 254 Layers, polypeptide 168 Layers, superimposed 242 Lead, annealed films cast on 81 Length, persistence 132 L-Leu cine 172 Linkage groups 118 Liquid crystalline contractile apparatus in striated muscle 248 order in polymers and copolymers with cholesteric side groups .... 56 phase transition of synthesized polymers 29 polyesters 117 polymers, thermotropic cholesterolcontaining 33 segments, copolyesters containing .. 119 side chains 122 state, polymerization in the 95 structures 12, 49,167 textures 21


260

M E S O M O R P H I C ORDER I N P O L Y M E R S


Liquid crystals magnetic reorientation and counterrotation in poly ( y-benzyl glutamate) model of the carbonaceous mesophase, lamellar nematic structure of Low angle x-ray diffraction peak

Mesophase ( continued ) lamellar liquid crystal model of the carbonaceous Ill 157 pitch 109,118 reactions, thermotropic 108 Ill sphere 112 93 spherules 110 118 Metastabilities in Deregulations 181 66 Methacrylic backbones 14 N-Methacrvloyl-to-aminocarbonic acids (ChMAA-n) 35-38,41 M Methylmethaerylate (MMA) 58 Mixing curves of polynucleotide/ Macromolecules polymer interactions 221, 222 with mesogenic groups 40 models of 48 Model(s) biomesogens and their 178 in oriented samples, packing of 48 considerations 23 Magnetic reorientation and countermacromole eu le 48 rotation 157 191, 213 Main chain polymers 12 Modelling nucleic acids Molecular hystereses in polynucleo Matrix fits in nucleoproteinic tide triplexes 186 systems, complementary 187 Mean field theory 130 Molecules by aromatic polymeriza tion, formation of planar Ill Mechanical properties of copolyesters 121 129 Melt viscosity of copolyesters 120 Molecules, isolated Monomer(s) 39,58,60,61,86 Melting characterization of 59 vs. crystallization temperatures 74 cholestervlaerylate 97 curves of polynucleotide/polymer elemental analyses of ChMAA-n .... 38 interactions 221, 222 mesomorphic 86 points of ChMAA-II 41 phase transitions of 28 points of N-methacryloyl-o)-polymer interactions 95 aminocarbonie acids (MAA-n) 37 -polymer state diagram of profiles, thermal 211 eholesterylvinyl succinate 98 profiles, thermal hysteresis in 192 synthesis of 37 Membranes, amphiphilic pattern 207 development in 182 Monomeric antivirals 181 Mesogenic groups 13, 27, 34, 40 Monomeric thermotropics Mesogenic side chains 23 Mouse L-eel Is with polynucleotide triplexes 228 Mesomorphic 244 monomers, new series of 86 Mucilage Muscle, striated 248, 250 order in block copolymers from Myofilament lattices of long tonic α-amino acids 165 fibers 250 on the physical properties of Myosin filaments 248 poly ( p-biphenyl a cry late ), influence of 71 Ν in polymers, x-ray diffraction studies on 12 7, 56 in polynucleotide analogues 178 Nematic analogues 245 x-ray diffraction from polymers liquid crystal 93 with 1 phases of rigid rod solution, free pattern, superhelical 202 energy of 132 properties 87 polymers 17,29 Mesophase excluded volume effects 127 characteristics of long chain termi smectic polymers 24 nated estrogen cholesterics 200 structure 142 characteristics of 2-pyridine-5temperature 142 carboxylic esters, smectic 198 238 formation 115 Nested arcs in connective tissue


261

INDEX

Poly-benzyl-L-glutamate (PBLG) .127, 168 Poly ( γ-L-benzylglutamate ) 57 Poly-y-benzyl-L-glutamates 137 Poly ( p-biphenyl aery late ) (PPBA) 71,74,80 Polybutadiene 168 Poly ( N-p-butoxybenzylidene-paminostyrene ) (PBBAS) 7 Ροΐν-γ-buty 1 -L-glutamate 151 Poly ( cetyl vinyl ether ) 95 Poly ( cholesteryl p-acryloyloxybenzoate) (PChAB) 5 Poly ( cholesteryl mcthacrylate ) (PChMA) 5 Polycholesteryl-II-methacryloyloxyΟ undecanoate 37 η -Ο cty 1 m eth aery 1 ate (OMA) 59 Poly ( Λ - ( p-cyanobenzylidene )-paminostyrene ) (PCBAS) 7 Oligomeric antivirals 208 Onsager critical concentration 130 Poly ( p-cvclohexvlphenylacrylate ) (PPCPA) ..' 71 Optical techniques 157 ORD characteristics 211 Poly ( di ( A -p-acryloyloxybenzyliORD spectra of polynucleotide/ dene ) - ρ - d i am in oben zen e polymer interactions 221, 222 (PdiABAB) 5 Oriented samples, macromolecule Polv ( di ( N-p-acryloyloxvbenzvlipacking in 48 ' dene)hydrazine) (PdiABH) ...... 10 Polyesters, development of liquid crystalline 117 Ρ Poly glutamates 136 Poly-y-heptyl-L-glutamate 151 Packing of macromolecules in 151 oriented samples 48 Poly-y-hexyl-L-glutamate 41,61 Peptide block, copolymers with a 165 Polymer(s) amorphous 22 Persistence length 132 characterization of 59 pH onfilamentspacing, effect of 253 with cholesteric side groups, liquid Phase crystalline order in 56 boundry 131 comb-like 35 diagram 89 crystalline 10 separation 32 enantiotropic (liquid crystalline) .. 22 transitions with flexible spacer groups 15,16 of cholesteryl derivatives 30, 31 withoutflexiblespacer groups 16, 19 of monomers 28 helical ambitions of simple vinyl .... 215 points 98 with intermediate organization 9 of synthesized polymers, liquid crystalline phase transition liquid crystalline 29 of synthesized 29 Phenylesters of benzoic acid 24 with liquid crystalline side chains .. 122 Pitch, cholesteric 140 main chain 12 Pitches, fibers from 115, 118 with mesomorphic order, x-ray Planar molecules, formation of Ill Planar texture 43 diffraction from 1 Polarity patterns, strand 218 -monomer interactions 95 Polarizing microscopy 98 -monomer state diagram of Poly ( p-acryloyloxyazobenzene ) cholesterylvinyl succinate 98 (PPAAB) 71 nematic 17,24,29,127 Poly ( acryloyloxybenzoic acid ) physical properties on poly(p(PABA) 3 biphenyl acrylate) and related 71 Poly-y-alkyl-L-glutamates 137 -polynucleotide interactions 221, 222 Poly-y-amyl-L-glutamate 151 with side anisodiametric groups 34 Poly ( γ-benzyl glutamate ) 157 side chain 13 Poly-y-benzyl-D-glutamates 137 smectic 4,17, 29


Nuclear magnetic resonance (NMR) 72,144,157,161 Nucleic acids 239 amphiphilic pattern development in 182 modelling 191,213 to proteins, cellular information transfer from 206 "strangening" 197,213 Nucleobase design, vinyl copolymer with varied 217 Nucleobase-stack matrices, vinyl 216 Nucleoproteinic systems, comple mentary matrix fits in 187

7

7


M E S O M O R P H I C ORDER I N P O L Y M E R S

262 Polymer ( s ) ( continued ) synthesis of 38 tacticity , 73 thermal properties of selected 17 thermotropic cholesterol-containing liquid crystalline 33 x-ray diffraction studies on meso morphic order in 12 Polymeric antivirals 208 Polymerization 59 of 4-aeryloyloxy-4 -cyanobiphenyl, thin layer 88 bulk 32, 86, 88 of 4-cyano-4 -acryloyloxybiphenyl, cell for thermal 91 formation of planar molecules by aromatic Ill in the liquid crystalline state 95 static dielectric constant during 92 Polv ( m eth a cry 1 oy 1 oxy ben zo i c ' acid) ( P M B A ) 3 Poly ( N-p-m eth aery 1 oy 1 oxyben zy l i dene-p-aminobenzoic acid ) (PMBABA) 3 Polynucleotides 181 amphiphilic pattern of 195 analogues, mesomorphic order in .... 178 base-base recognition schemes in .. 189 pattern, triple standard 190 —polymer interactions 221, 222 strand analogues 183 effects of 226, 227 modelling and "strangening" nucleic acids by 213 triplexes molecular hystereses in 186 preincubation of mouse L-cells with 228 triplet parts of 193 Poly-y-octyl-L-glutamate 151 Polypeptide(s) 136 block, copolymers with a 166 chains folds of the 167 helix-coil transition of 129 in random coil conformations 128 layers 168 Poly ( p-phenylene-bis ( N-methylenep-aminostyrene ) ) ( P P M A S ) 10 Polyvinyl block, copolymers with a .... 166 Preincubation of mouse L-cells with polynucleotide triplexes 228 Propylmethacrylate ( P M A ) 58 Proteins 239 amphiphilic pattern development in 182 cellular information transfer from nucleic acids to 206 2-Pyridine-5-carboxylic esters 198 /


/

?j

Q

Quadratic structure

.171 R

Random copolymers of α-amino acids Reduced temperature Reorientation curves, N M R Reorientation in poly ( γ-benzyl glutamate) liquid crystals, magnetic Rigidity, induced Rod(s) concentration solution, nematic and isotropic phases of rigid supramolecular Rundall's model

169 142 161 157 128 128 132 245 241

S Saccharide block, copolymers with a .. 165 Sarcomeric unit cell in crayfish striated muscle 250 Scattering angle for copolymer, x-ray scattering intensity vs 53 S eh iff base side groups 56 Sedimentation experiments 183 Separation, equilibrium 158 Side chain(s) conformation 154 interplanar spacings vs. carbons in . 46 length, effect of 151 mesogenic 23 polymers 13 with liquid crystalline 122 steric hindrance between 149 Side groups anisodiametric 34 benzoic acid 56 cholesteric 56, 64 Schiff base 56 Simulations of tilerone, fluoramides as stereoelectric

210

Smectic 3, 56 mesophase chracteristics of 2pyridine-5-carboxylie esters ... 198 organization 4, 64 polymers 17, 24, 29 S obeli visualization of intercalations .. 203 Solid solution of poly( cetylvinylether ), isomorphous 95 Solution, nematic and isotropic phases of rigid rod 132 Solutions, polyglutamates in concentrated 136 Solvents on T and twisting angle, effect of 146 x


263

INDEX

Spacer groups flexible 24,27 polymers with flexible 15, 16 polymers without flexible 16, 19 Spacings vs. carbons in side chains, interplanar 46 Spacings of ChMAA-II, interplanar .... 41 Specific heat for atactic and isotactic PPBA 74 Spherules, mesophase 110 Spherulites, sequential growth of solid 42 Splitting width 144


Stack(s)

adenine 2.15 inosine 216 matrices, hypothetical insertion of vinyl comonomers into vinyl nucleobase216 Stacked series of nested arcs in connective tissue 238 State diagram of cholesterylvinyl succinate, polymer—monomer 98 Stereoelectric simulations of tilerone 210 Steric hindrance between side chains .. 149 Steroids 205 Strand analogues, polynucleotide .226,227 Strand polarity patterns, 9-vinyladenine copolymers with varied 218 "Strangening" nucleic acids 197,213 Striation ..." 136 Structural anologues 205 Structure(s) 166,167,169 cholesteric 142,238 hexagonal 171 lamellar 167 liquid crystalline .167 of polyglutamates in concentrated solutions 136 quadratic 171 triplex 186 Superhelical mesomorphic pattern .... 202 Supramolecular rods 245 Synthesis 38, 86,165,166, 169

Thermal hysteresis in the melting profile melting profiles optical analysis polymerization of 4-eyano-4'-

aeryloyloxybiphenyl 91 properties 15, 17 Thermogravimetric analysis 83 Thermomechanical methods 98 Thermotropic(s) cholesterol-containing liquid crystalline polymers 33 classical 195,196,210 fluorenes and fluorenones in

classical mesophase reactions modelling nucleic acids by simple .. monomeric Thin layer polymerization of 4-acr\Toyloxy-4'-cyanobiphenyl . Tilerone, stereoelectric simulations of Time, apparent viscosity vs Time, change of cholesteric pitch with Tissue, stacked series of nested arcs in connective Tonic fibers, mvofilament lattice of long Transition enthalpies of heats of a polypeptide chain, helix-coil .... sharpness of the temperatures and enthalpies for the 4-cyano-4'-biphenyl(n + 2)alkenoates Triple standard polynucleotide pattern Triplet parts of polynucleotide triplexes Triplexes Arnott-Bond-Felsenfeld

molecular hystereses in poly nucleotide preincubation of mouse L-cells with polynucleotide

structures

Tacticity, polymer Temperature ( s ) for the 4-eyano-4'-biphenyl ( η + 2 ) alkenoates, transition flow temperatures and temperatures of transition from anisotropic to isotropic state, glass nematic reduced vs. twist angle Terminal groups Texture, planar

73 87 44 142 142 153 118 43

192 211 75

triplet parts of polynucleotide Twist angle vs. temperature Twist, cholesteric Twisted fibrous arrangements structure systems due to viruses Twisting angle

9-Vinyladenine copolymers with varied strand polarity pattern


210 108 191 181 88 210 162 140 238 250 87 98 129 129 87 190 193 204

186 228 186

193 153 241 237 136 239 142,146

218


264

M E S O M O R P H I C ORDER IN P O L Y M E R S

Vinyl comonomers into vinyl nucleobase-stack matrices, hypothetical insertion of Vinylcopolymer with varied nucleobase design 9 - Vi ny 1 h y pox an th i η e Vinylmonomers for homo- and eopolym eri zation reactions Vinyl nucleobase-stack matrices, hypothetical insertion comono mers into Vinyl polymers, helical ambitions of simple Viruses, twisted systems due to Viscometric techniques Viscosities, apparent 158, Volume effects, nematic polymers: excluded Volume measurement, specific

216 217 216 183 216 215 239 157 162 127 142

Watson-Crick duplexes

204

X X-ray diffraction from atactic PPBA peak, low angle from polymers with mesomorphic order studies on mesomorphic order in polymers diffractograms investigations scattering intensity vs. scattering angle for copolymer


79 80 66 1 12 98 16 53

Mesomorphic Order in Polymers

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