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Polymeric ionic liquids (PILs) are an emerging class of materials that combine the attractive properties of ionic liquids with the sequence complexity and mechanical characteristics of macromolecules. While significant advances have occurred in the context of synthesis and characterization of such materials, comparatively less understanding exists on the mechanisms underlying ion transport in such materials. In this perspective article, the status of understanding in related systems of salt-doped polymer electrolytes, (non-ionic-liquid-based) single-ion polymer conductors and room temperature ionic liquids is briefly reviewed. Subsequently, some recent developments in the context of PILs are discussed to identify some open questions confronting the issue of ion transport in such materials.

We employ a combination of the single chain in mean field simulation approach with the solution of Poisson's equation to study the influence of charge heterogeneities on the structure of protein-polyelectrolyte complexes. By adopting a coarse-grained model of representing proteins as charged nanoparticles, we studied the influence of the pattern of charge heterogeneities, net charge, ratio of positive to negative charges on the patches, and the volume fraction of the particles on the structural and aggregation characteristics of proteins in polyelectrolyte solutions. Our results demonstrate that the pattern of charge heterogeneities can exert a significant influence on the resulting characteristics of the aggregates, in some cases leading to a transformation from polymer-bridged complexes into direct particle aggregates driven by the attraction between oppositely charged patches.

We report the results of atomistic molecular dynamics simulations on polymerized 1-butyl-3-vinylimidazolium-hexafluorophosphate ionic liquids, studying the influence of the polymer molecular weight on the ion mobilities and the mechanisms underlying ion transport, including ion-association dynamics, ion hopping, and ion–polymer coordinations. With an increase in polymer molecular weight, the diffusivity of the hexafluorophosphate (PF6−) counterion decreases and plateaus above seven repeat units. The diffusivity is seen to correlate well with the ion-association structural relaxation time for pure ionic liquids, but becomes more correlated with ion-association lifetimes for larger molecular weight polymers. By analyzing the diffusivity of ions based on coordination structure, we unearth a transport mechanism in which the PF6− moves by “climbing the ladder” while associated with four polymeric cations from two different polymers.

In this review article, we discuss some recent developments in the context of the use of block copolymers (BCP) as compatibilizers in ternary blend organic photovoltaic devices. At the outset, we review some of the salient experimental studies and highlight the successes achieved in using BCPs to improve the long-term stability of the donor–acceptor based devices. We suggest that the physico-electro-chemical properties of BCP compatibilizers may be targeted as a hitherto less-explored handle to modulate the morphology and device characteristics of such systems. In this regard, we propose that coarse-grained computer simulation tools, despite being limited in their ability to capture complex interaction features and crystallization phenomena, can serve as a guide to narrow and/or identify parametric regions where morphologies desirable for better exciton and charge transport can be achieved. Furthermore, we suggest that the output of the morphological predictions can be combined with coarse-grained device simulation approaches to identify the overall photovoltaic properties of the ternary blends containing such BCP compatibilizers. Together, such computational studies can serve to connect the molecular structure and electronic properties of the BCP to the overall device properties and, thereby, to enable a rational molecular design of BCP compatibilizers for organic photovoltaic devices.

In recent studies, we demonstrated that the addition of block copolymers to binary donor–acceptor blends represents an effective approach to target equilibrium, co-continuous morphologies of interpenetrating donors and acceptors. Here, we report a study of the impact of all-conjugated poly(thieno[3,4-b]-thiophene-co-benzodithiophene)-b-polynaphthalene diimide (PTB7-b-PNDI) block copolymer additives on the electronic properties and photovoltaic performance of bulk heterojunction organic photovoltaic active layers comprised of a PTB7 donor and a phenyl-C61-butyric acid methyl ester (PCBM61) acceptor. We find that small amounts of BCP additives lead to improved performance due to a large increase in the device open-circuit voltage (VOC), and the VOC is pinned to this higher value for higher BCP additive loadings. Such results contrast prior studies of ternary blend OPVs where either a continuous change in VOC or a value of VOC pinned to the lowest value is observed. We hypothesize and provide evidence in the form of device and morphology analyses that the impact of VOC is likely due to the formation of a parallel bulk heterojunction made up of isolated PCBM and PNDI acceptor domains separated by intermediate PTB7 donor domains. Altogether, this work demonstrates that all-conjugated block copolymers can be utilized as additives to both dictate morphology and modulate the electronic properties of the active layer.

Polymer nanocomposites are a class of materials that consist of a polymer matrix filled with inorganic/organic nanoscale additives that enhance the inherent macroscopic (mechanical, optical and electronic) properties of the polymer matrix. Over the past few decades such materials have received tremendous attention from experimentalists, theoreticians, and computational scientists. These studies have revealed that the macroscopic properties of polymer nanocomposites depend strongly on the (microscopic) morphology of the constituent nanoscale additives in the polymer matrix. As a consequence, intense research efforts have been directed to understand the relationships between interactions, morphology, and the phase behavior of polymer nanocomposites. Theory and simulations have proven to be useful tools in this regard due to their ability to link molecular level features of the polymer and nanoparticle additives to the resulting morphology within the composite. In this article we review recent theory and simulation studies, presenting briefly the methodological developments underlying PRISM theories, density functional theory, self-consistent field theory approaches, and atomistic and coarse-grained molecular simulations. We first discuss the studies on polymer nanocomposites with bare or un-functionalized nanoparticles as additives, followed by a review of recent work on composites containing polymer grafted or functionalized nanoparticles as additives. We conclude each section with a brief outlook on some potential future directions.

We develop and implement a new hybrid methodology combining self-consistent field theory (SCFT) and Monte Carlo simulations to study the complexation between negatively charged semiflexible linear polyelectrolyte (LPE) molecules and a positively charged dendrimer containing grafts of neutral polymers. We examine the influence of LPE stiffness, length of the dendrimer grafts, and solution pOH upon the characteristics of the resulting complexes. Our results indicate that increasing LPE stiffness reduces the dendrimer–LPE binding affinity and results in an overall higher net charge carried within the dendrimer molecule. When we varied the size of the grafts, the dendrimer–LPE binding strength was seen to decrease with increasing grafting chain length for the flexible LPE chains. In contrast, for stiff LPE chains, the binding strength was not seen to vary significantly with the grafting lengths. Overall, longer grafting lengths were seen to reduce the fraction of exposed LPE molecules, suggesting that grafted dendrimers may better shield nucleic acid material from serum nucleases. Lastly, we found that increasing the solution pOH was seen to enhance both the binding between the dendrimer and LPE molecules and the total positive charge carried by the complex.

We use computer simulations to study the phase separation behavior of amphiphilic linear gradient copolymer solution under poor solvent conditions. Using the bond fluctuation model and parallel tempering algorithm, we explore the influence of the gradient strength (the largest difference in the instantaneous composition along the copolymer) upon the phase separation characteristics. Under poor solvent conditions, the chains collapse to form micelle-like aggregates. We find that the critical temperature for this transition exhibits a linear dependence on the gradient strength of the copolymers. A systematic quantification of the cluster characteristics formed during the phase separation also reveals a strong dependence of aggregation numbers and the bridging statistics upon the gradient strength of the copolymers. Analysis of our results reveals that the critical parameter determining the thermodynamic behavior of gradient copolymers is in fact the average length of the hydrophobic sequences in the gradient copolymers. We demonstrate that the latter provides a useful measure to quantitatively predict the critical transition temperature of the gradient copolymer solution. We also present a few results from the framework of an annealed representation of the sequences of the gradient copolymer to demonstrate the limitations arising from such a model representation.

We examine the role of neutral dendrimer grafts upon the conformations and the drug complexation efficacy of weakly basic polyelectrolyte dendrimers by using a self-consistent field theory approach. Our results indicate that grafted chains modify the conformations of the dendrimers and lead to a swelling of the dendrimer, the degree of which increases with increasing chain length of the grafts. In turn, such conformational changes leads to a higher charge being carried by the dendrimer molecule. We compare the encapsulation efficacy of grafted and non-grafted dendrimers and find that for strong enough enthalpic and/or electrostatic interactions, the grafted dendrimers are capable of higher amounts of encapsulation than the non-grafted counterparts. By isolating the influences of electrostatic and enthalpic interactions, we clarify the physics behind the observed enhanced encapsulation.

We review some recent research developments in coarse-grained modeling based on mean-field approaches of the equilibrium dispersion and structure of polymer nanoparticle composites. We focus on three issues: (i) dispersion and phase behavior of particles in homopolymer matrices; (ii) dispersion in mixtures of homopolymers with grafted nanoparticles; (iii) self-assembly and organization of nanoparticles in block copolymer matrices. In each of these topics, we highlight that the dispersability and the resulting structure of the nanoparticle suspension may exhibit far more complexities than one may deduce using simple miscibility criterion involving the energetic interactions between the polymer matrix and the particle. In each case, we review our own research contributions accompanied by a brief discussion of related theoretical studies and some possible future directions.