Conformational study of a single molecule of poly para phenylene ethynylenes in dilute solutions

The conformation of single molecules of dialkyl poly para phenylene ethynylenes (PPEs), electro-active polymers, is studied in solutions using molecular dynamics simulations. The conformation of conjugated polymers affects their electro-optical properties and therefore is critical to their current and potential uses, though only limited theoretical knowledge is available regarding the factors that control their configuration. The present study investigates the affects of molecular parameters including molecular weight of the polymer and chemical structure of the side chains of PPEs in different solvents on the conformation of the polymers. The PPEs are modeled atomistically where the solvents are modeled both implicitly and explicitly. The study finds that PPEs assume extended configuration which is affected by the length of the polymer backbone and the nature and length of substituting side chains. While the polymer remains extended, local dynamics is retained and no long range correlations are observed within the backbone. The results are compared with scattering experiments.     

Solution behavior of polyimide‐graft‐polystyrene copolymers in selective solvents

A polyimide‐graft‐polystyrene (PI‐g‐PS) copolymer with a polyimide backbone and polystyrene side chains was synthesized by the “grafting from” method using styrene polymerization on a polyimide multicenter macroinitiator via ATRP mechanism. The side chain grafting density z = 0.86 of PI‐g‐PS is rather high for graft‐copolymers synthesized by the ATRP method. Molecular characteristics and solution behavior of PI‐g‐PS were studied in selective solvents using light scattering and viscometry methods. In all solvents, the backbone tends to avoid contact with a poor solvent. To describe the conformation and hydrodynamic properties of PI‐g‐PS macromolecules in thermodynamically good solvents for side chains and PI‐g‐PS, the wormlike spherocylinder model is used. Macromolecules of the studied graft‐copolymer are characterized by high equilibrium rigidities (Kuhn segment length >20 nm). In Θ‐conditions, PI‐g‐PS macromolecules may be modeled by a rigid prolate ellipsoid of revolution with a low asymmetry form and a collapsed backbone as the ellipsoid core. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2014 , 52, 1539–1546     

Polyaniline copolymers with solvent‐mimic side chains

We investigated new polyaniline copolymers with solvent‐mimic side chains for enhanced processability in various solvents. The solvent‐mimic side chains, benzyloxypropoxy (BOP), phenoxybutoxy (POB), and dihydroxypropoxy (DHP), were introduced into copolymers and used with nonpolar aromatic and polar alcoholic solvents, respectively. Compared to a polyaniline homopolymer, polyaniline copolymers with a small amount of side chains (<4 mol %) exhibit different physical properties, including film‐forming ability. This can be attributed to the solvent‐mimic side chains strongly interacting with the solvent and/or the polyaniline backbone. Especially, in nonpolar aromatic solvents, polyaniline copolymers with nonpolar aromatic BOP and POB side chains exhibit good film‐forming ability leading to high electrical conductivity, while the polyaniline homopolymer did not form a film. Therefore, introducing solvent‐mimic side chains in conducting polymers is a very attractive method of enhancing their processability and physical properties. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 1986–1995     

Synthesis of biodegradable conjugated polymers with controlled backbone flexibility

A series of flexible, highly bright fluorescent poly(p‐phenyleneethynylene)s (PPEs) was prepared by employing a disulfide containing nonconjugated monomer at various ratios under Sonogashira reaction conditions. PPEs with flexible linkers exhibited fluorescence properties comparable to those of a fully conjugated PPE when less than 50% of flexible monomers were incorporated into the backbone. To evaluate the self‐assembly properties of PPEs, a series of conjugated polymer nanoparticles (CPNs) was fabricated by treating PPEs with organic acids followed by dialysis. CPNs containing linkers exhibited different complexation behavior with polysaccharides, warranting further investigation into how flexibility and biodegradability of CPNs influence their cellular interaction and entry. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 1403–1412     

Helical Folding of Conjugated Oligo(phenyleneethynylene): Chain‐Length Dependence,Solvent Effects,and Intermolecular Assembly

As a representative folding system that features a conjugated backbone, a series of monodispersed (o‐phenyleneethynylene)‐alt‐(p‐phenyleneethynylene) (PE) oligomers of varied chain length and different side chains were studied. Molecules with the same backbone but different side‐chain structures were shown to exhibit similar helical conformations in respectively suitable solvents. Specifically, oligomers with dodecyloxy side chains folded into the helical structure in apolar aliphatic solvents, whereas an analogous oligomer with tri(ethylene glycol) (Tg) side chains adopted the same conformation in polar solvents. The fact that the oligomers with the same backbone manifested a similar folded conformation independent of side chains and the nature of the solvent confirmed the concept that the driving force for folding was the intramolecular aromatic stacking and solvophobic interactions. Although all were capable of inducing folding, different solvents were shown to bestow slightly varied folding stability. The chain‐length dependence study revealed a nonlinear correlation between the folding stability with backbone chain length. A critical size of approximately 10 PE units was identified for the system, beyond which folding occurred. This observation corroborated the helical nature of the folded structure. Remarkably, based on the absorption and emission spectra, the effective conjugation length of the system extended more effectively under the folded state than under random conformations. Moreover, as evidenced by the optical spectra and dynamic light‐scattering studies, intermolecular association took place among the helical oligomers with Tg side chains in aqueous solution. The demonstrated ability of such a conjugated foldamer in self‐assembling into hierarchical supramolecular structures promises application potential for the system.     

Small‐angle neutron scattering analysis of bottlebrush backbone and side chain flexibility

Bottlebrush polymers have densely tethered side chains grafted to a linear polymer backbone, resulting in stretching of both the side chains and backbone. Prior studies have reported that the side chains are only weakly stretched while the backbone is highly elongated. Here, scaling laws for the bottlebrush backbone and side chains are determined through small‐angle neutron scattering analysis of a systematic series of poly(lactic acid) bottlebrush polymers synthesized via a “grafting‐through” ring‐opening polymerization. Scattering profiles are modeled with the empirical Guinier–Porod, rigid cylinder, and flexible cylinder models. Side chains are found to be only weakly stretched, with an end‐to‐end distance proportional to N^0.55, while the overall bottlebrush increases in size proportional to N^0.77. These results demonstrate that the bottlebrush backbone is not fully extended and that both side chains and backbone have significant conformational flexibility in solution. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2017 , 55, 104–111     

Synthesis and application of poly(phenylene ethynylene)s for bioconjugation: a conjugated polymer-based fluorogenic probe for proteases

A set of carboxylate-functionalized poly(phenylene ethynylene)s (PPEs) has been synthesized in which the carboxylic acid groups are separated from the polymer backbone by oligo(ethylene glycol) spacer units. These polymers are soluble in water and organic solvents and have photophysical properties that are sensitive to solvent conditions, with high salt content and the absence of surfactant promoting the formation of aggregates of relatively low quantum yield and long fluorescence lifetime. Quenching of these materials by the dinitrophenyl (DNP) chromophore (K(SV) approximately 10(4)) is also highly solvent-dependent. The presence of carboxylate groups far from the polymer backbone appended to each repeating unit allows for the postpolymerization modification of these PPEs with peptides by methods analogous to those described for carboxylate-functionalized small-molecule dyes. Covalent attachment of the fluorescence-quenching 14-mer Lys(DNP)-GPLGMRGLGGGGK to the PPE results in a nonemissive substrate whose fluorescence is restored upon treatment with trypsin. The rate of fluorescence turn-on in this case is increased 3-fold by the presence of surfactant, though the actual rate of peptide hydrolysis remains the same. A small-molecule mimic of the polymer-peptide system shows a smaller fluorescence enhancement upon treatment with trypsin, illustrating the value of polymer-based amplification in this sensory scheme.     

Novel fluorescent (p‐phenylene ethynylene)‐calix[4]arene‐based polymer: Design,synthesis, and properties

A novel fluorescent (p‐phenylene ethynylene)‐calix[4]arene‐based polymer ( CALIX‐PPE ) has been successfully synthesized by cross‐coupling polymerization of bis‐calix[4]arene 1 with 1,4‐diethynylbenzene. The polycondensation was carried out in toluene/NEt₃ at 35 °C for 24 h, using PdCl₂(PPh₃)₂/CuI as the catalytic system, furnishing CALIX‐PPE in excellent isolated yields (higher than 95%, several runs). The yellow polymer is freely soluble in several nonprotic organic solvents. The GPC trace of the isolated polymer showed a monomodal distribution and a number‐average molecular weight of 23,300 g mol^?1 (M_w/M_n = 2.05). No evidence was found in the structural analysis (FTIR and ¹H/¹³C NMR) regarding the formation of alkyne homocoupled segments along the polymer chain. For comparative purposes, the synthesis of an analogous poly(p‐phenylene ethynylene) containing p‐t‐butyl‐phenoxymethyl side chains ( TBP‐PPE ) was also undertaken. A great similarity was found between the photophysical properties of CALIX‐PPE and TBP‐PPE in solution (UV–vis and laser induced luminescence), clearly demonstrating their unique dependence on the structure and conformation of the conjugated PPE backbone. The fluorescence spectra of polymers are of nearly identical shape, displaying their maximum emission around 420 nm. The calculated solution photoluminescence quantum yields of CALIX‐PPE and TBP‐PPE are of similar magnitude (?_{F( CALIX‐PPE )} = 0.43; ?_{F( TBP‐PPE )} = 0.51). © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 6477–6488, 2008     

Synthesis,characterization, and structure–property investigation of conformationally rigid regioisomers of poly(p‐phenylene ethynylene)s

A series of rigid poly(p‐phenylene ethynylene)s ( PPE1 – PPE4 ) with biphenyl‐ ( M1–M3 ) and phenyl‐ ( M4 ) side groups is prepared from appropriately functionalized monomers. Herein, the solution and solid state absorption studies show the polymers have adopted twisted and rigid conformations, as supported by deep HOMO energy levels (?5.76 to ?5.81 eV). The absorption maxima of PPE1–PPE3 are shifted to shorter wavelength (λ_max = 375–381 nm) as compared to linear poly(p‐phenylene ethynylene)s (446 nm), implying a nonplanar conformation. The self‐assembly of polymers into fibers is examined using scanning electron microscopy. The fibers are not observed in PPE4 with short phenyl side group, suggesting the important role of the interplay between rigidity, position, and size of the side chains toward the formation of fibers. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 3652–3662     

Structure—Property relationships for exciton transfer in conjugated polymers

The ability of conjugated polymers to function as electronic materials is dependent on the efficient transport of excitons along the polymer chain. Generally, the photophysics of the chromophore monomer dictate the excited state behavior of the corresponding conjugated polymers. Different molecular structures are examined to study the role of excited state lifetimes and molecular conformations on energy transfer. The incorporation of rigid, three‐dimensional scaffolds, such as iptycenes and cyclophanes, can encourage an oblique packing of the chromophore units of a conjugated polymer, thus allowing the formation of electronically‐coupled aggregates that retain high quantum yields of emission. Rigid iptycene scaffolds also act as excellent structural directors that encourage complete solvation of PPEs in a liquid crystal (LC) solvent. LC‐PPE mixtures display both an enhanced conformational alignment of polymer chains and extended effective conjugation lengths relative to isotropic solutions, which leads to enhanced energy transfer. Facile exciton migration in poly(p‐phenylene ethynylene)s (PPEs) allows energy absorbed over large areas to be funneled into traps created by the binding of analytes, resulting in signal amplification in sensory devices. © 2011 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2011     

Cononsolvency of poly(N‐isopropylacrylamide) in methanol aqueous solution—insight by dielectric spectroscopy

Both water and methanol are good solvents for poly(N‐isopropylacrylamide) (PNIPAM), while PNIPAM does not dissolve in their mixed solvents, this phenomenon is called cononsolvency. Cononsolvency is closely related to many phenomena in life but so far, its mechanism is still controversial. In this work, the dielectric behavior of PNIPAM methanol aqueous solution was studied in the frequency of 40Hz–40GHz. From lower frequency to higher frequency, four relaxations were found. They are, respectively, from global chain motion, local motion of backbone, motion of side chain group, and the dipole orientation of the solvent molecule. The solvent dependence of dielectric parameters for the chain motion implied that the PNIPAM chain has undergone the coil‐globule‐coil transition. Dielectric analysis to microwave frequency showed that the volume of the bound solvent units on PNIPAM chain increases with the increasing methanol concentration, which suggested that the structure of solvation units bound on PNIPAM side chains undergo a changing process experience from water to water‐methanol cluster to the ternary methanol cluster. This work reveals the structure and dynamics of the PNIPAM chain and the solvent unit that involved in the solvation of PNIPAM, and provides some new insight into the cononsolvency phenomenon. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2017 , 55, 1227–1234     

Conformational behavior of comb-like polyelectrolytes in selective solvent: computer simulation study

In this work, we present molecular dynamics simulations of comb-like polyelectrolytes in selective solvent. The studied polymers have a neutral backbone and polyelectrolyte side chains. The solvent is poor for the backbone and the theta solvent for the side chains. The polymers are modeled on a coarse-grained level with implicit solvent. The simulations show that the comb-like polyelectrolytes tend to form intramolecular self-organized structures of the pearl necklace type. This type of conformational behavior has been predicted by Borisov and Zhulina (Borisov, O. V.; Zhulina, E. B. Macromolecules 2005, 38, 2506) for neutral comb-like copolymers in selective solvent. The present study shows that comb-like polyelectrolytes in selective solvent exhibit the same type of behavior; however, it can be controlled by one additional parameter, the degree of dissociation of the grafts. The local conformational characteristics are studied using the ensemble-averaged bond angle cosines as functions of monomer position in the chain, which reveal structural details invisible by other means.     

Intramolecular mobility of side chains of poly(methacrylic acid) in regularly grafted copolyimides in solution

A “dark” copolyimide with regularly grafted side chains of polymethacrylic acid and a luminescence-labeled copolyimide containing an anthracene label covalently attached to side chains with an average polycondensation degree of the polyimide backbone of ～16 and an average polymerization degree of side poly(methacrylic acid) chains of ～100 are synthesized. Relaxation times τ_IMM characterizing the mobility of parts of side chains in solvents of different thermodynamic qualities for the backbone and side chains are determined through the polarized luminescence method. It is shown that, in a “common” solvent for the backbone and side chains, the values of τ_IMM are close to those characterizing the mobility of linear polymethacrylate chains. In selective solvents, changes in τ_IMM are related to not only changes in intramolecular interactions but also changes in the heterogeneity of the dynamic characteristics of parts of grafted chains arranged at different distances from the grafting point.     

Efficient synthesis of well‐defined amphiphilic cylindrical brushes polymer with high grafting density: Interfacial “Click” chemistry approach

Reported here is a novel approach toward efficient preparation of well‐defined cylindrical brushes polymer (CBPs) with both hydrophobic and hydrophilic side chains connected to the linear backbone by interfacial “click” chemistry in two immiscible solvents. The CBPs with high grafting density of more than 95% and molecular polydispersity (M_w/M_n) less than 1.12 can be readily synthesized using present approach. On contrary, the CBPs synthesized from the “click” reaction in a single solvent in homogenous state have low grafting density of less than 55% and molecular polydispersity (M_w/M_n) more than 1.78. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Structure‐property relationships in densely grafted π‐stacked polymers

Three methyl end‐capped oligo(ethylene glycol) (MOEG) ethers ( 1b‐d ) and a methoxyderivative ( 1a ) of benzofulvene monomer BF3k were synthesized and induced to polymerize spontaneously by solvent removal to obtain soluble π‐stacked polymers bearing densely grafted MOEG side chains (poly‐ 1b – d ) and model polymer poly‐ 1a. The physicochemical features (e.g., solubility, NMR, MALDI‐TOF, and absorption/emission spectra, as well as MWD, conformation plot, and thermal properties) of the synthesized polymers were compared in a structure‐property relationship study. This approach afforded the following evidence. The structure of poly‐ 1a – d is very similar to that of BF3k , suggesting that the polymerization mechanism is not affected by the presence of the electron‐rich methoxy group or bulkier MOEG side chains. However, the latter appear to be capable of affecting the conformational behavior of the polymer backbone. The solubility of poly‐ 1a – d depends on the number of the oligo(ethylene glycol) monomeric units. In particular, poly‐ 1d , featuring a long MOEG side chain (n = 9), shows an amphiphilic character and is soluble in a number of organic solvents, whereas it interacts with water to give isolated macromolecules in equilibrium with nanosized water‐soluble aggregates. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 2446–2461, 2010     

β-1,3-Glucan (Schyzophyllan) Can Act as a One-Dimensional Host for Creating Chirally Twisted Poly(p-phenylene Ethynylene)

It has been demonstrated that a chiral, insulated poly(p-phenylene ethynylene) (PPE) nano-wire can be created by a polymer wrapping method utilizing natural β-1,3-glucan polysaccharide schizophyllan (SPG). Spectroscopic and microscopic measurements have revealed that PPE adopts a rigid conformation and exists as one piece in the helical hollow constructed by two SPG chains. Moreover, the inherent helical structure of SPG can induce the chiral twisting of the insulated PPE backbone. It is believed that the present system is really applicable for designing novel chiral sensors based on PPE.     

Novel amphiphilic graft copolymers bearing hydrophilic poly(acrylic acid) backbones and hydrophobic poly(butyl methacrylate) side chains

A novel amphiphilic graft copolymer consisting of hydrophilic poly(acrylic acid) backbones and hydrophobic poly(butyl methacrylate) side chains was synthesized by successive atom transfer radical polymerization followed by hydrolysis of poly‐(methoxymethyl acrylate) backbone. A grafting‐from strategy was employed for the synthesis of graft copolymers with narrow molecular weight distributions (polydispersity index < 1.40). Hydrophobic side chains were connected to the backbone through stable C? C bonds instead of ester connections. Poly(methoxymethyl acrylate) backbone was easily hydrolyzed to poly(acrylic acid) backbone with HCl without affecting the hydrophobic side chains. The amphiphilic graft copolymer could form stable micelles in water. The critical micelle concentration in water was determined by a fluorescence probe technique. The morphology of the micelles was preliminarily explored with transmission electron microscopy and was found to be spheres. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 6857–6868, 2006     

Effects of alkyl side chains positioning and presence of fused aromatic units in the backbone of low‐bandgap diketopyrrolopyrrole copolymers on the optoelectronic properties of organic solar cells

The systematic optimization of the chemical structure of low‐bandgap (LBG) donor‐acceptor polymeric semiconductors is a challenging task for which accurate guidelines are yet to be determined. Several different structural and molecular parameters are crucial ingredients for obtaining LBG polymers that simultaneously possess high power conversion efficiencies, good processability in common organic solvents, and enhanced stability in organic photovoltaic devices. In this work, we present an extensive structure–optoelectronic properties–solar cell performance study on the emerging class of diketopyrrolopyrrole‐based LBG polymers. In particular, we investigate alkyl side chain positioning by introducing linear alkyl side chains into two different positions (α‐ and β‐), and the distance of the electron rich and electron deficient monomers within the repeat units of the polymer chain. We demonstrate that anchoring linear alkyl side chains to the α‐positions and introducing fused moieties into the polymer backbone, can be beneficial toward maintaining photocurrents similar to the unsubstituted derivative, and concurrently exhibit better processabiliy in common organic solvents. These results can provide a design rationale towards further optimization of semiconducting polymers. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018 , 56, 138–146     

Successive SET‐LRP and ATRP synthesis of ferrocene‐based PPEGMEA‐g‐PAEFC well‐defined amphiphilic graft copolymer

A series of ferrocene‐based well‐defined amphiphilic graft copolymers, consisting of hydrophilic poly[poly(ethylene glycol) methyl ether acrylate] (PPEGMEA) backbone and hydrophobic poly(2‐acryloyloxyethyl ferrocenecarboxylate) (PAEFC) side chains were synthesized by successive single‐electron‐transfer living radical polymerization (SET‐LRP) and atom transfer radical polymerization (ATRP). The backbone was prepared by SET‐LRP of PEGMEA macromonomer, and it was then treated with lithium di‐isopropylamide and 2‐bromopropionyl bromide at ?78 °C to give PPEGMEA‐Br macroinitiator. The targeted well‐defined graft copolymers with narrow molecular weight distributions (M_w/M_n ≤ 1.32) were synthesized via ATRP of AEFC initiated by PPEGMEA‐Br macroinitiator, and the molecular weights of the backbone and side chains were both controllable. The electro‐chemical behaviors of graft copolymers were studied by cyclic voltammetry, and it was found that graft copolymers were more difficult to be oxidized, and the reversibility of electrode process became less with raising the content of PAEFC segment. The effects of the preparation method, the length of hydrophobic PAEFC segment, and the initial water content on self‐assembly behavior of PPEGMEA‐g‐PAEFC graft copolymers in aqueous media were investigated by transmission electron microscopy. The morphologies of micelles could transform from cylinders to spheres or rods with changing the preparation condition and the length of side chains. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Synthesis and Solution Properties of Loose Polymer Brushes Having Polyimide Backbone and Methylmethacrylate Side Chains

Summary: Graft-copolymers with polyimide backbone and PMMA side chains are synthesized by ATRP of methylmethacrylate on the polyimide macroinitiator. The obtained copolymers, macroinitiator, and cleaved side chains are investigated by ¹H NMR, SEC, static and dynamic light scattering, sedimentation, and viscosimetry in solutions. The synthesized copolymer is relatively loose polymer brushes: the average distance between grafted PMMA chains is ∼11 nm (4 repeat units of the backbone). The hydrodynamic and conformational characteristics of graft-copolymers change on passage from ethylacetate to chloroform due to difference in the thermodynamic quality of the solvents with respect to the copolymer components. The backbone is characterized more extended conformation than individual polyimide macromolecule.