Alternating copolymers consisting of arylalkyl methacrylates. II. Effect of coil collapse on fluorescence spectra of alternating copolymers of 2-(9-carbazolyl)ethyl methacrylate and aromatic vinyl monomers

Alternating and random copolymers of 2-(9-carbazolyl)ethyl methacrylate with aromatic vinyl monomers were synthesized and their fluorescence properties were compared in good and poor solvents. Contraction of the polymer coils induced the hypochromic effect, i.e., the mutual interaction of the ground-state chromophores, but caused little quenching of their excited state. This is sharp in contrast with the vinyl-type of polymers, exhibiting large interactions in both the ground and excited states. Introduction of bulky groups on the comonomers in the alternating copolymers further suppressed these interactions. © 1996 John Wiley & Sons, Inc.     

Alternating Copolymers Consisting of Arylalkyl Methacrylates III: Phosphorescence of Poly(arylalkyl methacrylate-alt-styrene) in a Rigid Solution

Delayed emission was observed for alternating and random copolymers of 9-phenanthrylmethyl methacrylate and 2-(9-carbazolyl)ethyl methacrylate with styrene in a rigid solution at 77 K. All the copolymers showed monomeric phosphorescence and delayed fluorescence, indicating the absence of deep trap sites in either the excited singlet or triplet states. The delayed fluorescence was more pronounced for the random copolymers with higher chromophore contents than that for the alternating copolymers. Hence, the interchromophore distance is crucial for efficient triplet-state energy migration. © 1997 John Wiley & Sons, Ltd.     

Photophysics of carbazole-containing systems. 1. Dilute solution behavior of poly(N-vinyl carbazole) and N-vinyl carbazole/methyl acrylate copolymers

Steady-state and time-resolved fluorescence techniques have been used to study the photophysical behaviors of poly(N-vinyl carbazole), PNVCz and a series of N-vinyl carbazole-methyl acrylate (NVCz-co-MA) copolymers in dilute solution as a function of both NVCz composition and temperature. A kinetic scheme, intended to describe intramolecular excimer formation across the entire NVCz composition range, is proposed. In low aromatic content copolymers, two monomer species (unquenched and quenched monomer) and two excimer species (the sandwich-like excimer and a higher energy excimer) exist. The contribution from monomer emission to the overall fluorescence decreases with increasing NVCz content through increased excimer formation: this is likely to be consequent upon (1) an increase in the number of excimer forming sites, and (2) increasing efficiency of energy transfer from the excited monomers to the excimer forming sites. In the homopolymer, PNVCz, the only emission that can be observed on a nanosecond timescale is excimeric. This fluorescence appears to originate from three excimer species (the sandwich-like excimer, and two higher energy forms). For the homopolymer, the current observations are consistent with the model proposed by Vandendriessche and De Schryver [Polym. Photochem. 7 , 153 (1986)]. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35 : 963–978, 1997     

Syntheses and some fluorescence properties of poly(2-methacrylamido-3-arylpropionic acid)

2-Methacrylamido-3-arylpropionic acid, where aryl is 1-naphthyl (M1NpPA), 2-naphthyl (M2NpPA), or 1-pyrenyl (M1PyPA), was synthesized. Free radical polymerization gave polymers which were soluble in water at pH > 6. In aqueous solution, poly(M1NpPA) and poly(M2NpPA) exhibited strong excimer fluorescence as a dominant component, whereas poly(M1PvPA) showed weak monomer fluorescence as a main component. Excitation spectra and fluorescence quenching by Tl⁺ ions suggested that naphthyl groups in poly(M1NpPA) and poly(M2NpPA) interacted so as to form excimer sites, by which migrating excited singlets were trapped, leading to the strong excimer emission. It was suggested, however, that pyrenyl groups in poly(M1PyPA) were sterically so constrained that they could not attain the full-overlap excimer conformation but could only interact to form self-quenching sites, to which energy migration occurred, leading to weak fluorescence. © 1993 John Wiley & Sons, Inc.     

Energy migration in poly(N‐vinyl carbazole) and its copolymers with methyl methacrylate: Fluorescence polarization,quenching, and molecular dynamics

Fluorescence polarization and quenching measurements were used to examine intramolecular energy migration for poly(N‐vinyl carbazole) and copolymers of N‐vinyl carbazole with methyl methacrylate. Quenching measurements of the carbazole fluorescence by CCl₄ were performed in dilute solution in toluene, and fluorescence anisotropy, r, was measured for the chains dispersed in a solid matrix of poly(methyl methacrylate) (PMMA). The results suggested that the chains with a high carbazole content, that is, a high content of excimer trapping sites, do not show the highest values of the singlet energy‐migration rate. Isotropies, r^?1, of the samples in vitrified PMMA corroborated such conclusions. Molecular dynamics simulations on isotactic and syndiotactic trichromophoric copolymer fragments were used to obtain parameters related to the energy‐transfer process as a function of the methyl methacrylate content. The parameters from the simulations supported the interpretation of the experiments. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 1615–1626, 2003     

Photochemistry of amphiphilic copolymers: Fluorescence spectra of copolymers of 1-(2-naphthyl)ethyl methacrylate and sodium 2-acrylamido-2-methylpropanesulfonate in solution

Amphiphilic copolymers containing 1-(2-naphthyl)ethyl ester groups were prepared and their fluorescence properties were examined. The fluorescnce spectra of the copolymers with a higher naphthyl content showed predominantly a broad monomer emission with λ_max at 340 nm in methanol, whereas a structured emission with λ_max at 344 and 362 nm was observed in aqueous solution. The former spectra changed rapidly to the latter ones upon UV irradiation. Photolysis of the copolymers and the monomeric model compound in methanol gave 2-vinylnaphthalene, whose fluorescence agreed with those of copolymers in water, together with methyl ether, alkylnaphthalenes, and other products. These results indicate that the copolymers hold vinylnaphthalene-like traps, which may emit preferentially in water because of efficient sensitization. © 1995 John Wiley & Sons, Inc.     

Configurations conducive to the formation of intramolecular excimers in poly(N‐vinyl carbazole) and its copolymers

The ratios of the intensity of excimer and monomer emissions, denoted I_E/I_M, in poly(N‐vinyl carbazole) and copolymers of N‐vinyl carbazole and methyl methacrylate were measured with steady‐state fluorescence. Measurements were performed in dilute solutions of several fluid solvents at 25 °C and in a solid matrix of poly(methyl methacrylate) at room temperature. The values of I_E/I_M depended on the nature of the solvent, the emission wavelength, and the copolymer composition. Molecular dynamics simulations were performed for diastereoisomers of 2,4‐di(N‐carbazolyl)pentane and for isotactic and syndiotactic trichromophoric copolymer fragments to assist in the identification of the thermally accessible conformations capable of forming intramolecular excimers and the configurational relationship of the carbazole units in these complexes. Nearest neighbor carbazole groups made the dominant contribution to the excimers. Excimers were more likely in isotactic sequences than in syndiotactic sequences, as was also the case for the low‐energy excimer arising from the complete overlap of two carbazole units. © 2001 John Wiley & Sons, Inc. J Polym Sci Part B: Polym Phys 39: 1272–1281, 2001     

Alternating copolymerization of N-(alkyl-substituted phenyl)maleimides with isobutene and thermal properties of the resulting copolymers

Radical copolymerization of N-(alkyl-substituted phenyl)maleimides (RPhMI) with isobutene (IB) was carried out with an initiator in various solvents at 60°C. The copolymerization of N-(2,6-diethylphenyl)maleimide (2,6-DEPhMI) with IB in benzene proceeded readily in a homogeneous system to give an alternating copolymer over a wide range of the comonomer compositions in the feed. Whereas the alternating tendency of the copolymerization of other RPhMI with IB decreased depending on the alkyl substituents of RPhMI in the following order: 2,6-DEPhMI > N-(2,6-dimethylphenyl)maleimide ≥ N-(2-methylphenyl)maleimide >. N-(4-ethylphenyl)maleimide. The copolymerization reactivities were discussed based on the rate constants for the homo-propagations and cross-propagations. Subsequently, the effect of the solvent on the rate and the reactivity ratios was examined. It was revealed that the copolymerization in chloroform proceeded with higher alternating tendency at a higher copolymerization rate than in the copolymerizations in benzene or dioxane. The copolymers of RPhMI with IB showed excellent thermal stability, i.e., high glass transition temperature and initial decomposition temperature over 200 and 350°C, respectively. © 1996 John Wiley & Sons, Inc.     

Ferroelectric and piezoelectric properties of a quenched poly(vinylidene fluoride-trifluoroethylene) copolymer

The ferroelectric and piezoelectric properties of melt-quenched unoriented poly(vinylidene fluoride-trifluoroethylene) (73 : 27) copolymer films as a function of the number of poling cycles have been studied. The investigation revealed that quenched films exhibit a decrease in D-E hysteresis behavior as the number of poling cycles increases when the samples are poled at room temperature. Corresponding decreases in remanent polarization, Pr, as well as small increases in the coercive field, Ec, were observed as the material was subjected to successive poling cycles. The piezoelectric coefficients, d₃₁ and e₃₁, also decreased as the number of poling cycles increased. In addition, a clear reduction in the “apparent” Curie transition temperature between unpoled and poled material was observed. Preliminary evidence indicates that films quenched from the melt to below T_c do not form a stable ferroelectric crystal phase as previously believed. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35: 2671–2679, 1997     

Synthesis and properties of poly(aryl ether ether ketone) copolymers with pendant methyl groups

Polyether ether ketone and polyether ether ketone copolymers were prepared by the nucleophilic substitution reaction of 4,4′-difluorobenzophenone with hydroquinone and with varying mole proportions of hydroquinone and methyl hydroquinone using sulfolane solvent in the presence of anhydrous K₂CO₃. The polymers were characterised by different physico-chemical techniques. The crystallinity of the polymers was found to decrease with increase in concentration of the methyl hydroquinone units in the polymer. Thermogravimetric studies showed that all the polymers were stable upto 430 °C with a char yield above 49% at 900 °C in N₂ atmosphere. The glass transition temperature was found to increase and the crystalline melting temperature and activation energy were found to decrease with increase in concentration of the methyl hydroquinone units in the polymer.     

Effect of stereocomplex formation between enantiomeric poly(l,l-lactide) and poly(d,d-lactide) blocks on self-organization of amphiphilic poly(lactide)-block-poly(ethylene oxide) copolymers in dilute aqueous solution

The effect of crystallization of a hydrophobic poly(lactide) block on the self-organization of biocompatible and biodegradable amphiphilic poly(lactide)-block-poly(ethylene oxide) (PLA-b-PEO) copolymers in a dilute aqueous solution has been investigated. It was demonstrated that the co-crystallization of poly(L,L-lactide) [P(L,L)LA] and poly(d,d-lactide) [P(d,d)LA] chains under equimolar mixing of P(L,L)LA₄₆-b-PEO₁₁₃ and P(d,d)LA₅₆-b-PEO₁₁₃ copolymers resulted in the formation of stable and spontaneously water-redispersible stereocomplex micelles with semicrystalline P(L,L)LA/P(d,d)LA cores. It was shown that the P(L,L)LA₄₆ / P(d,d)LA₅₆-b-PEO₁₁₃ stereo-complex micelles produced by dialysis can be potential vehicles for the anticancer agent oxaliplatin     

Synthesis and properties of multiblock copolymers consisting of poly(L‐lactic acid) and poly(oxypropylene‐ co‐oxyethylene) prepared by direct polycondensation

A multiblock copoly(ester–ether) consisting of poly(l ‐lactic acid) (PLLA) and poly(oxypropylene‐co‐oxyethylene) (PN) was prepared and characterized. Preparation was done via the solution polycondensation of a thermal oligocondensate of l ‐lactic acid, a commercially available telechelic polyether (PN: Pluronic‐F68), and dodecanedioic acid as a carboxyl/hydroxyl adjusting agent. When stannous oxide was used as the catalyst, the molecular weight of the resultant PLLA/PN block copolymers became very high (even with a high PN content) under optimized reaction conditions. The refluxing of diphenyl ether (solvent) at reduced pressure allowed the efficient removal of the condensed water from the reaction system and the feed‐back of the intermediately formed l ‐lactide at the same time in order to successfully bring about a high degree of condensation. The copolymer films obtained by solution casting became more flexible with the increasing PN content as soft segments. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 1513–1521, 1999     

Effect of bovine serum albumin on the micellization of poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) block copolymers in aqueous solutions by fluorescence spectroscopy

Effect of bovine serum albumin (BSA) on the temperature-dependent association behavior of poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) (PEO-PPO-PEO) block copolymers was investigated using pyrene fluorescence spectroscopy. The critical micellization temperature (CMT) of pluronics in aqueous solution was increased by the addition of BSA. A closed association model was used to obtain the standard free energies (△G0), enthalpies (△H 0), and entropies (△S 0) of micellization. The standard enthalpy and entropy of micellization for pluronic polymers in water were decreased with an increase of the BSA content. The more PPO component in the pluronic polymer, the higher the changed values of micellization enthalpy and entropy. The hydrophobic part of the pluronics, PPO, was responsible for the interaction between pluronics and BSA. Hydrophobic interaction between PPO and BSA was correlated to the alternation of the PPO-PPO interaction by the addition of BSA, which would shift the CMT toward higher temperature and alter the thermodynamic parameters of micellization for pluronics in aqueous solutions.     

Association of stereoregular poly(methyl methacrylates) in dilute solution. Proton NMR study

By measurement of integrated intensities of high-resolution proton nuclear magnetic resonance (NMR) bands, associated structures of isotactic (i) and syndiotactic (s) poly(methyl methacrylate) (PMMA) in dilute toluene-d₈ and dimethylformamide-d₇ solutions were detected and characterized. In 1% (w/v) solutions of highly stereoregular s-PMMA in toluene-d₈ at 27°C, 76% of the monomer units are present in the form of compact aggregates. Consequences of this finding for the polymerization of methyl methacrylate in toluene in the presence of s-PMMA are discussed.     

A fluorine-containing hydrophobically associating polymer. I. Synthesis and solution properties of copolymers of acrylamide and fluorine-containing acrylates or methacrylates

Fluorine-containing hydrophobically associating polymers have been synthesized by copolymerization of acrylamide with a small amount of an acrylate or methacrylate having a fluorocarbon containing ester group. It was found that hydrophobic associations occurring between these fluorocarbon chains was stronger than the interactions of the corresponding hydrocarbon comonomers and depend on the length of the fluorocarbon chain. The rheological properties of the copolymer solutions were studied. The solutions were found to be highly pseudoplastic but the viscosity loss was completely reversible upon removal of shear. Evidence for hydrophobic association of the fluorocarbon groups was obtained by the dependence of the Brookfield viscosity on temperature, the addition of NaCl, and the addition of organic solvents, urea, and surfactants.     

Micellization and gelation of aqueous solutions of star-shaped PEG-PCL block copolymers consisting of branched 4-arm poly(ethylene glycol) and polycaprolactone blocks

Star-shaped block copolymers consisting of non-toxic poly(ethylene glycol) and biodegradable polycaprolactone ((PEG5K-PCL)₄) were synthesized by ring-opening polymerization of the ε-caprolactone monomer with hydroxyl-terminated 4-armed PEG as initiator. These biodegradable, amphiphilic star block copolymers showed micellization and sol-gel transition behaviors in aqueous solution with varying concentration and temperature. In the dilute aqueous solutions of star block copolymers, micellization behavior occurred over specific concentration. The 1,6-diphenyl-1,3,5-hexatriene (DPH) solubilization method was used to determine the critical micellization concentration (CMC) of star block copolymers. The obtained micelle size increased with increasing hydrophobic PCL block length. In high-concentration solutions, the star block copolymers showed temperature-sensitive sol-gel transition behavior. The morphology of the micelle and gel was investigated by atomic force microscopy (AFM). As a result, the micelles showed a core-corona spherical structure at concentration near CMC, while the gel showed a mountain-chain-like morphology picture. It was proposed that with increasing the micelle concentration the worm-like micelle clusters formed firstly and the gel was constructed by the packing of micelle clusters.     

Fluorescence emission of amphiphilic copolymers bearing benzimidazole groups: Stimuli‐responsive behaviors in aqueous solution

A stimuli‐responsive amphiphilic copolymer poly(NIPAM_m‐b‐VBNBI_n), including N‐isopropylacrylamide (NIPAM) as a thermoresponsive unit and 1‐(4‐vinyl benzyl)‐2‐naphthyl‐benzimidazole (VBNBI) as a sensitive fluorophore unit, was designed and synthesized by reversible addition‐fragmentation chain transfer polymerization. The aqueous solutions of the copolymers exhibited reversible fluorescent response to pH and temperature. In addition, the copolymers showed aggregation‐induced fluorescence enhancement in THF/water mixture. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 4459–4466     

Properties of poly(vinyl alcohol)-graft-polyacrylamide copolymers depending on the graft length. 2. Thermal properties in the bulk state

Thermal behavior of poly(vinyl alcohol)-graft-polyacrylamide copolymers (PVA-g-PAA), so-called intramolecular polymer-polymer complexes (intraPC), with variable M̄ _vPAA and constant average number N of grafts is considered in this report. Complete compatibility of PVA and PAA through hydrogen bonding is realized in the range of the graft lengths not exceeding some critical value. The content of adsorbed and trapped water in graft copolymers reflects some features of PVA-g-PAA_N structure depending on the graft lengths. The first thermal decomposition region in air for copolymers begins at higher temperatures with growing M̄ _vPAA, but the total destruction interval reduces. Formal kinetic decomposition parameters of the first decomposition stage appear to be the largest for the PVA-g-PAA with the largest quantity of H-bonds between the main and graft chains. Chemical transformations in graft copolymers, PVA and PAA during thermal decomposition are discussed.     

Molecular modeling of poly(p‐phenylenevinylene): Synthesis and photophysical properties of oligomers

A series of oligo(phenylenevinylene)s (OPVs) of different lengths containing aldehyde and dialdehyde groups on the ends were synthesized and characterized. Their photophysical properties were also investigated via ultraviolet–visible, steady‐state, and time‐resolved fluorescence spectra. The results indicated that the absorption maximum, radiative rate constant, and excitation maximum of an OPVnCHO oligomer series (where n represents the oligomeric length) showed linear relationships with the reciprocal number of conjugated units. Similarly, the absorption maximum and emission lifetime of the oligomers of an OPVn–2CHO series showed linear relationships with the reciprocal number of conjugated units. The dependence of the fluorescence intensities of the OPVs on the concentration of the quencher C₆₀ was evaluated. Apparently, upon photoexcitation, the OPVs underwent significant fluorescence quenching. The results for different OPV derivatives and a quenching mechanistic discussion showed that the static quenching contribution was indeed responsible for the significant upward curvature. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 911–924, 2007     

Copper(I)-mediated radical polymerization of methacrylates in aqueous solution

α-Methoxypolyethylene oxide methacrylate was polymerized by copper(I)-mediated living radical polymerization in aqueous solution to give polymers with controlled number-average molecular masses and narrow polydispersities. When equimolar quantities of initiator with respect to copper(I) bromide were used, the reaction was extremely fast with quantitative conversion achieved in less than 5 min at ambient temperature. However, the molecular weight distribution was broad, and control over the number-average molecular weight (M_n) growth was extremely poor; this is ascribed to an increase in termination because of the increased rate as a result of the coordination of water at the copper center. The complex formed between copper(I) bromide and N-(n-propyl)-2-pyridylmethanimine, bis[N-(n-propyl)-2-pyridylmethanimine]copper(I), was demonstrated to be stable in aqueous solution by ¹H NMR over 10 h at 25 °C. However, on increasing the temperature to 50 °C, decomposition occurred rapidly. Thus, polymerization temperatures were maintained at ambient temperature. When longer alkyl chains were utilized in the ligand, that is, pentyl and octyl, the complex acted as a surfactant leading to heterogeneous solutions. When the catalyst concentration was reduced by two orders of magnitude, the rate of polymerization was reduced with 100% conversion achieved after 60 min with the M_n of the final product being higher than that predicted and the polydispersity equal to 1.43. Copper(II) was added as an inhibitor to circumvent these problems. When 10% of Cu(I) was replaced by Cu(II) {[Cu(I)] + [Cu(II)]/[I] = 1/100}, the mass distribution showed a bimodal distribution, and the rate of polymerization decreased significantly. With a catalyst composition [Cu(I)]/[Cu(II)] = 0.5/0.5 {[Cu(I)] + [Cu(II)]}/[I] = 1/100, polymerization proceeded slowly with 80% conversion reached after 22 h. Thus, the concentration of Cu(I) was further reduced with [Cu(I)]/[Cu(II)] = 10/90, {[Cu(I)] + [Cu(II)]}/[I] = 1/100. The system then contained [Initiator]/[Cu(I)] = 1000/1 and [I]/[Cu(II)] = 1000/9. Under these conditions, the reaction reached 50% after 5 h with the polymer having both an M_n close to the theoretical value and a narrow polydispersity of PDi = 1.15. Optimum results were obtained by increasing the amount of catalyst. When a ratio of [Cu(I)]/[Cu(II)] = 10/90 with a ratio of [Cu]/[I] = 1/1, a conversion of 100% was achieved after less than 20 h, leading to a product having M_n = 8500 and PDi = 1.15. Decreasing the amount of Cu(II) relative to Cu(I) to [Cu(I)]/[Cu(II)] = 0.5/0.5 (maintaining the overall amount of copper) led to 100% conversion after 75 min: M_n = 9500, PDi = 1.10. Block copolymers have been demonstrated by sequential monomer addition with excellent control over M_n and PDi. © 2001 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 39: 1696–1707, 2001