Folding a Polymer via Two-Point Interaction with an External Folding Agent: Use of H-Bonding and Charge-Transfer Interactions

A polymer containing electron-rich aromatic donors (1,5-dialkoxynaphthalene (DAN)) was coerced into a folded state by an external folding agent that contained an electron-deficient aromatic acceptor (pyromellitic diimide (PM)) unit. The donor-containing polymer was designed to carry a tertiary amine moiety in the linking segment, which served as an H-bonding site for reinforcing the interaction with the acceptor containing folding agent that also bore a carboxylic acid group. The H-bonding interaction of the carboxylic acid and the tertiary amine brings the PDI unit between two adjacent DAN units along the polymer backbone to induce charge-transfer (C-T) interactions, and this in turn causes the polymer chain to form a pleated structure. Evidence for the formation of such a pleated structure was obtained from NMR titration studies and also by monitoring the C-T band in their UV-visible spectra. By varying the length of the segment that links the PDI acceptor to the carboxylic acid group, we showed that the most effective folding agent was the one that had a single carbon spacer, as evident from the highest value of the association constant. Control experiments with propionic acid clearly demonstrated the importance of the additional C-T interactions for venerating the folded structures. Further, solution viscosity measurements in the presence of varying amounts of the folding agent revealed a gradual stiffening of the chain in the case of the PDI carrying carboxylic acid, whereas no such affect was seen in the case of simple propionic acid. These observations were supported by D FT calculations of the interactions of a dimeric model of the polymer with the various folding agents; here too the stability of the complex was seen to be highest in the case of the single carbon spacer.

A new diketopyrrolopyrrole-based co-polymer for ambipolar field-effect transistors and solar cells

A new thieno3,2-b]thiophenediketopyrrolopyrrole-benzo1,2-b:4,5-b']dithio phene based narrow optical gap co-polymer (PTTDPP-BDT) has been synthesized and characterized for field-effect transistors and solar cells. In field-effect transistors the polymer exhibited ambipolar charge transport behaviour with maximum hole and electron mobilities of 10(-3) cm(2) V-1 s(-1) and 10(-5) cm(2)V(-1) s(-1), respectively. The respectable charge transporting properties of the polymer were consistent with X-ray diffraction measurements that showed close molecular packing in the solid state. The difference in hole and electron mobilities was explained by density functional theory calculations, which showed that the highest occupied molecular orbital was delocalized along the polymer backbone with the lowest unoccupied molecular orbital localized on the bis(thieno3,2-b]thiophene)diketopyrrolopyrrole units. Bulk heterojunction photovoltaic devices with the fullerene acceptor PC70BM were fabricated and delivered a maximum conversion efficiency of 3.3% under AM1.5G illumination. (C) 2012 Elsevier B.V. All rights reserved.

Understanding the folding process of synthetic polymers by small-molecule folding agents

Two acceptor containing polyimides PDI and NDI carrying pyromellitic diimide units and 1,4,5,8-naphthalene tetracarboxy diimide units, respectively, along with hexa(oxyethylene) (EO6) segments as linkers, were prepared from the corresponding dianhydrides and diamines. These polyimides were made to fold by interaction with specifically designed folding agents containing a dialkoxynaphtha-lene (DAN) donor linked to a carboxylic acid group. The alkali-metal counter-ion of the donor carboxylic acid upon complexation with the EO6 segment brings the DAN unit in the right location to induce a charge-transfer complex formation with acceptor units in the polymer backbone. This two-point interaction between the folding agent and the polymer backbone leads to a folding of the polymer chain, which was readily monitored by NMR titrations. The effect of various parameters, such as structures of the folding agent and polymer, and the solvent composition, on the folding propensities of the polymer was studied.

Hyperbranched polyurethanes with varying spacer segments between the branching points

Hyperbranched polyurethanes, with varying oligoethyleneoxy spacer segments between the branching points, have been synthesized by a one-pot approach starting from the appropriately designed carbonyl azide that incorporates the different spacer segments. The structures of monomers and polymers were confirmed by IR and H-1-NMR spectroscopy. The solution viscosity of the polymers suggested that they were of reasonably high molecular weight. Reversal of terminal functional groups was achieved by preparing the appropriate monohydroxy dicarbonyl azide monomer. The large number of terminal isocyanate groups at the chain ends of such hyperbranched macromolecules caused them to crosslink prior to its isolation. However, carrying out the polymerization in the presence of 1 equiv of a capping agent, such as an alcohol, resulted in soluble polymers with carbamate chain ends. Using a biphenyl-containing alcohol as a capping agent, we have also prepared novel hyperbranched perbranched polyurethanes with pendant mesogenic segments. These mesogen-containing polyurethanes, however, did not exhibit liquid crystallinity probably due to the wholly aromatic rigid polymer backbone. (C) 1996 John Wiley & Sons, Inc.

Catalytic oxidative polymerization of 1,1-diphenylethylene at ambient temperature and potential application of peroxide macroinitiator

The Co(II)TPP(Py) complex was used as an efficient dioxygen carrier for the radical polymerization of 1,1-diphenylethylene (DPE), which has a low ceiling temperature, at ambient temperature and low oxygen pressure. The mechanism of polymerization is discussed' on the basis of kinetic data, W-vis, ESR, and H-1 NMR studies. The rate of polymerization (RP) and number-average molecular weights (M) of poly(1,1-diphenylethylene peroxide) (PDPEP) are higher and the polydispersity is lower than in 2,2'-azobis(isobutyronitrile) (AIBN) initiated polymerization. PDPEP was further. used as a macroinitiator for the polymerization of MMA. The polymerization obeys classical kinetics. The K-2 value of the PDPEP has been determined from the slope of R-P(2) VS [M](2)[I], which reveals that it can also be used at higher temperature for the polymerization. An "active" PMMA was also synthesized, containing initiating segments in the polymer backbone.

Single-step synthesis of internally functionalizable hyperbranched polyethers

Radical catalyzed thiol-ene reaction has become a useful alternative to the Huisgen-type azide-yne click reaction as it helps expand the variability in reaction conditions as well as the range of clickable entities. In this study, the direct generation of a hyperbranched polyether (HBPE) having decyl units at the periphery and a pendant allyl group on every repeat unit of the polymer backbone is described; the allyl groups serve as a reactive handle for postpolymerization modifications and permits the generation of a variety of internally functionalized HBPEs. In this design, the AB(2) monomer carries two decylbenzyl ether units (B-functionality), an aliphatic OH (A-functionality) and a pendant allyl group within the spacer segment; polymerization of the monomer readily occurs at 150 degrees C via melt transetherification process by continuous removal of 1-decanol under reduced pressure. The resulting HBPE has a hydrophobic periphery due to the presence of numerous decyl chains, while the allyl groups that remain unaffected during the melt polymerization provides an opportunity to install a variety of functional groups within the interior; thiol-ene click reaction with two different thiols, namely 3-mercaptopropionic acid and mercaptosuccinic acid, generated interesting amphiphilic structures. Preliminary field emission scanning electron microscope (FESEM) and Atomic Force Microscopy (AFM) imaging studies reveal the formation of fairly uniform spherical aggregates in water with sizes ranging from 200 to 400 nm; this suggests that these amphiphilic HBPs is able to reconfigure to generate jellyfish-like conformations that subsequently aggregate in an alkaline medium. The internal allyl functional groups were also used to generate intramolecularly core-crosslinked HBPEs, by the use of dithiol crosslinkers; gel permeation chromatography traces provided clear evidence for reduction in the size after crosslinking. In summary, we have developed a simple route to prepare core-clickable HBPEs and have demonstrated the quantitative reaction of the allyl groups present within the interior of the polymers; such HB polymeric systems that carry numerous functional groups within the core could have interesting applications in analyte sequestration and possibly sensing, especially from organic media. (c) 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 4125-4135

Impedance spectroscopy of novel hybrid composite films of polyvinylbutyral (PVB)/functionalized mesoporous silica

Polyvinyl butyral/functionalized mesoporous silica hybrid composite films have been fabricated by solution casting technique with various weight percentages of functionalized silica. A polyol (tripentaerythritol-electron rich component), which acts as an electron donor to the polymer backbone, was added to enhance the conductivity. The prepared composites were characterized by Fourier transformed infrared spectroscopy and the morphology was evaluated by scanning electron microscopy. Dielectric properties of these freestanding composites were studied using the two-probe method. The dielectric constant and impedance value decreased with the increase in applied frequency as well as with the increase in functionalized silica content in the polyvinyl butyral matrix. An increase in conductivity of the PVB/functionalized silica composites was also observed. (C) 2013 Elsevier Ltd. All rights reserved.

Polyanhydrides of Castor Oil-Sebacic Acid for Controlled Release Applications

A family of high molecular weight castor oil (CO)-based biodegradable polyanhydrides was synthesized by a catalyst-free melt-condensation reaction between prepolymers of CO and sebacic acid (SA). The structure of the polymers was characterized by H-1 NMR and Fourier transform infrared spectroscopy, which indicated the formation of the anhydride bond along the polymer backbone. Thermal analysis and X-ray diffraction confirmed the semicrystalline nature of the polymers. Incorporation of SA enhanced the crystallinity of the polymer. The hydrophobic nature of these polymers was revealed by contact angle goniometry. Water wettability decreased with increase in SA content. Compressive tests demonstrated a sharp increase in strength and decrease in ductility with increasing SA content. In vitro hydrolytic degradation studies indicated surface-eroding behavior. The degradation rate decreased with an increase of SA content in the polymers because of increased crystallinity. The release studies of both hydrophobic and hydrophilic dyes followed zero-order kinetics. In vitro cell studies to assess the cytotoxicity of the polymer confirmed minimal toxicity of the degradation products. Thus, a family of CO-SA polyanhydrides have been synthesized and characterized for controlled release applications where the physical, mechanical, and degradation kinetics can be modulated by varying the weight fraction of the prepolymers.

Correlation between Optical Properties and Nanomorphology of Fluoranthene-Based Conjugated Copolymer

Nanoparticles of conjugated polymers are receiving attention due to their interesting optical properties. Here we report nanoparticles of fluoranthene-based conjugated copolymer prepared by the Suzuki coupling reaction. The copolymer forms nanoparticles by the spontaneous self-assembly after evaporation of organic solvent. The mean diameter of the nanoparticles can be manipulated by varying solvent composition. We investigated the parameters that govern the nanostructured morphology of polymer by systematic variation of good and poor solvent. The UV vis and time-resolved fluorescence spectroscopy measurement reveal the use of poor solvent in the organization of nanostructures. Furthermore, transmission electron microscopy highlights the importance of rigidity of the polymer backbone in morphological development.

Controlled release kinetics of p-aminosalicylic acid from biodegradable crosslinked polyesters for enhanced anti-mycobacterial activity

Unlike conventional polymeric drug delivery systems, where drugs are entrapped in polymers, this study focuses on the incorporation of the drug into the polymer backbone to achieve higher loading and sustained release. Crosslinked, biodegradable, xylitol based polyesters have been synthesized in this study. The bioactive drug moiety, p-aminosalicylic acid (PAS), was incorporated in xylitol based polyesters to impart its anti-mycobacterial activity. To understand the influence of the monomer chemistry on the incorporation of PAS and its subsequent release from the polymer, different diacids have been used. Controlled release profiles of the drug from these polyesters were studied under normal physiological conditions. The degradation of the polyesters varied from 48% to 76% and the release of PAS ranged from 54% to 65% of its initial loading in 7 days. A new model was developed to explain the release kinetics of PAS from the polymer that accounted for the polymer degradation and drug concentration. The thermal, mechanical, drug release and cytocompatibility properties of the polymers indicate their suitability in biomedical applications. The released products from these polymers were observed to be pharmacologically active against Mycobacteria. The high drug loading and sustained release also ensured enhanced efficacy. These polymers form biocompatible, biodegradable polyesters where the sustained release of PAS may be tailored for potential treatment of mycobacterial infections. Statement of significance In the present work, we report on novel polyesters with p-aminosalicylic acid (PAS) incorporated in the polymer backbone. The current work aims to achieve controlled release of PAS and ensures the delivered PAS is stable and pharmacologically active. The novelty of this work primarily involves the synthetic chemistry of polymerization and detailed analysis and efficacy of active PAS delivery. A new kinetic model has been developed to explain the PAS release profiles. These polymers are biodegradable, cytocompatible and anti-mycobacterial in nature. (C) 2015 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

pi-conjugation and conformation in a semiconducting polymer: small angle x-ray scattering study

Small angle x-ray scattering (SAXS) in a poly[2-methoxy-5-(2'-ethyl-hexyloxy)-1,4-phenylene vinylene] (MEH-PPV) solution has shown the important role of pi-electron conjugation in controlling the chain conformation and assembly. By increasing the extent of conjugation from 30 to 100%, the persistence length (l(p)) increases from 20 to 66 angstrom. Moreover, a pronounced second peak in the pair distribution function has been observed in a fully conjugated chain, at larger length scales. This feature indicates that the chain segments tend to self-assemble as the conjugation along the chain increases. Xylene enhances the rigidity of the PPV backbone to yield extended structures, while tetrahydrofuran solvates the side groups to form compact coils in which the lp is much shorter.

Increasing ionic conductivity and mechanical strength of a plastic electrolyte by inclusion of a polymer

in this contribution we present a soft matter solid electrolyte which was obtained by inclusion of a polymer (polyacrylonitrile, PAN) in LiClO4/LiTFSI-succinonitrile (SN), a semi-solid organic plastic electrolyte. Addition of the polymer resulted in considerable enhancement in ionic conductivity as well as mechanical strength of LiX-SN (X=ClO4, TFSI) plastic electrolyte. Ionic conductivity of 92.5%-[1 M LiClO4-SN]:7.5%-PAN (PAN amount as per SN weight) composite at 25 degrees C recorded a remarkably high value of 7 x 10(-3) Omega(-1) cm(-1), higher by few tens of order in magnitude compared to 1 M LiClO4-SN. Composite conductivity at sub-ambient temperature is also quite high. At -20 degrees C, the ionic conductivity of (100 -x)%-[1 M LiClO4-SN]:x%-PAN composites are in the range 3 x 10(-5)-4.5 x 10(-4) Omega(-1) cm(-1), approximately one to two orders of magnitude higher with respect to 1 M LiClO4-SN electrolyte conductivity. Addition of PAN resulted in an increase of the Young's modulus (Y) from Y -> 0 for LiClO4-SN to a maximum of 0.4MPa for the composites. Microstructural studies based on X-ray diffraction, differential scanning calorimetry and Fourier transform infrared spectroscopy suggest that enhancement in composite ionic conductivity is a combined effect of decrease in crystallinity and enhanced trans conformer concentration. (c) 2008 Elsevier Ltd. All rights reserved.

Rheology of particle-loaded semi-dilute polymer solutions

We present measurements of the rheology of suspensions of rigid spheres in a semi-dilute polymer solution from experiments of steady and oscillatory shear. For a given value of the shear rate gamma, addition of particles enhances the viscosity and the first normal stress difference but decreases the magnitude of the second normal stress difference. The viscosity eta exhibits a power law variation in gamma for a range of gamma that grows with phi. The first normal stress N-1 is positive and its value grows with phi; it exhibits a clear power law variation for the entire range of gamma that was studied. The second normal stress difference N-2 is negative for the pure polymer solution and much smaller in magnitude than N-1; on addition of particles, its magnitude further decreases, and it appears to change sign at large phi. The behavior of N-1 and N-2 is at odds with the findings of recent studies on particle-loaded dilute polymer solutions and polymer melts. The small-amplitude oscillatory shear experiments show the linear viscoelastic properties, G(') and G('), increasing with phi at a given value of the angular frequency omega. The dynamic viscosity of the suspension differs substantially from its steady shear viscosity, and the difference increases as gamma, omega -> 0.

Complex dynamics in polymer nanocomposites

Polymer nanocomposites offer the potential to create a new type of hybrid material with unique thermal, optical, or electrical properties. Understanding their structure, phase behavior, and dynamics is crucial for realizing such potentials. In this work we provide an experimental insight into the dynamics of such composites in terms of the temperature, wave vector, and volume fraction of nanoparticles, using multispeckle synchrotron x-ray photon correlation spectroscopy measurements on gold nanoparticles embedded in polymethylmethacrylate. Detailed analysis of the intermediate scattering functions reveals possible existence of an intrinsic length scale for dynamic heterogeneity in polymer nanocomposites similar to that seen in other soft materials like colloidal gels and glasses.

Nano-indentation studies on polymer matrix composites reinforced by few-layer graphene

The mechanical properties of polyvinyl alcohol (PVA) and poly(methyl methacrylate) (PMMA)-matrix composites reinforced by functionalized few-layer graphene (FG) have been evaluated using the nano-indentation technique. A significant increase in both the elastic modulus and hardness is observed with the addition of 0.6 wt% of graphene. The crystallinity of PVA also increases with the addition of FG. This and the good mechanical interaction between the polymer and the FG, which provides better load transfer between the matrix and the fiber, are suggested to be responsible for the observed improvement in mechanical properties of the polymers.