Modulating the Molecular Geometry and Solution Self-Assembly of Amphiphilic Polypeptoid Block Copolymers by Side Chain Branching Pattern.

Solution self-assembly of coil-crystalline diblock copolypeptoids has attracted increasing attention due to its capability to form hierarchical nanostructures with tailorable morphologies and functionalities. While the N-substituent (or side chain) structures are known to affect the crystallization of polypeptoids, their roles in dictating the hierarchical solution self-assembly of diblock copolypeptoids are not fully understood. Herein, we designed and synthesized two types of diblock copolypeptoids, i.e., poly(N-methylglycine)-b-poly(N-octylglycine) (PNMG-b-PNOG) and poly(N-methylglycine)-b-poly(N-2-ethyl-1-hexylglycine) (PNMG-b-PNEHG), to investigate the influence of N-substituent structure on the crystalline packing and hierarchical self-assembly of diblock copolypeptoids in methanol. With a linear aliphatic N-substituent, the PNOG blocks pack into a highly ordered crystalline structure with a board-like molecular geometry, resulting in the self-assembly of PNMG-b-PNOG molecules into a hierarchical microflower morphology composed of radially arranged nanoribbon subunits. By contrast, the PNEHG blocks bearing bulky branched aliphatic N-substituents are rod-like and prefer to stack into a columnar hexagonal liquid crystalline mesophase, which drives PNMG-b-PNEHG molecules to self-assemble into symmetrical hexagonal nanosheets in solution. A combination of time-dependent small/wide-angle X-ray scattering and microscopic imaging analysis further revealed the self-assembly mechanisms for the formation of these microflowers and hexagonal nanosheets. These results highlight the significant impact of the N-substituent architecture (i.e., linear versus branched) on the supramolecular self-assembly of diblock copolypeptoids in solution, which can serve as an effective strategy to tune the geometry and hierarchical structure of polypeptoid-based nanomaterials.

Local orientation of chains at crystal/amorphous interfaces buried in isotactic polypropylene thin films.

A better understanding of the aggregation states of polymer chains in thin films is of pivotal importance for developing thin film polymer devices in addition to its inherent scientific interest. Here we report the preferential orientation of the crystalline lamellae for isotactic polypropylene (iPP) in spin-coated films by grazing incidence of wide-angle X-ray diffraction in conjunction with sum frequency generation vibrational spectroscopy, which provides information on the local conformation of chains at crystal/amorphous interfaces buried in a thin film. The crystalline orientation of iPP, which formed cross-hatched lamellae induced by lamellar branching, altered from a mixture of edge-on and face-on mother lamellae to preferential face-on mother lamellae with decreasing thickness. The orientation of methyl groups at the crystal/amorphous interfaces in the interior region of the iPP films changed, accompanied by a change in the lamellar orientation.

Polypeptoid polymers: Synthesis, characterization, and properties.

Polypeptoids, a class of peptidomimetic polymers, have emerged at the forefront of macromolecular and supramolecular science and engineering as the technological relevance of these polymers continues to be demonstrated. The chemical and structural diversity of polypeptoids have enabled access to and adjustment of a variety of physicochemical and biological properties (eg, solubility, charge characteristics, chain conformation, HLB, thermal processability, degradability, cytotoxicity and immunogenicity). These attributes have made this synthetic polymer platform a potential candidate for various biomedical and biotechnological applications. This review will provide an overview of recent development in synthetic methods to access polypeptoid polymers with well-defined structures and highlight some of the fundamental physicochemical and biological properties of polypeptoids that are pertinent to the future development of functional materials based on polypeptoids.

Thermal Properties and Segmental Dynamics of Polymer Melt Chains Adsorbed on Solid Surfaces.

The glass transition of supported polystyrene (PS) and poly(2-vinylpyridine) (P2VP) thin films in the vicinity of the substrate interface was studied by using a nanoplasmonic sensing (NPS) method. This "nanocalorimetric" approach utilizes localized surface plasmon resonance from two-dimensional arrangements of sensor nanoparticles deposited on SiO2-coated glass substrates. The NPS results demonstrated the existence of a high glass transition temperature ( Tg,high) along with the bulk glass transition temperature ( Tg,bulk ≈ 100 °C for PS and P2VP) within the thin films: Tg,high ≈ 160 °C for PS and Tg,high ≈ 200 °C for P2VP. To understand the origin of the Tg,high, we also studied the thermal transitions of lone polymer chains strongly adsorbed onto the substrate surface using solvent rinsing. Interestingly, the NPS data indicated that the Tg,high is attributed to the adsorbed polymer chains. To provide a better understanding of the mechanism of the Tg,high, molecular dynamics simulations were performed on a PS film adsorbed on hydrophobic and hydrophilic substrates. The simulation results illuminated the presence of a higher density region closest to the substrate surface regardless of the magnitude of the polymer-solid interactions. We postulate that the highly packed chain conformation reduces the free volume at the substrate interface, resulting in the Tg,high. Moreover, the simulation results revealed that the deviation of the Tg,high from the bulk Tg,bulk becomes larger as the polymer-substrate interaction increases, which is in line with the experimental findings.

Structure-induced switching of interpolymer adhesion at a solid-polymer melt interface.

Here we report a link between the interfacial structure and adhesive property of homopolymer chains physically adsorbed (i.e., via physisorption) onto solids. Polyethylene oxide (PEO) was used as a model and two different chain conformations of the adsorbed polymer were created on silicon substrates via the well-established Guiselin's approach: "flattened chains" which lie flat on the solid and are densely packed, and "loosely adsorbed polymer chains" which form bridges jointing up nearby empty sites on the solid surface and cover the flattened chains. We investigated the adhesion properties of the two different adsorbed chains using a custom-built adhesion testing device. Bilayers of a thick PEO overlayer on top of the flattened chains or loosely adsorbed chains were subjected to the adhesion test. The results revealed that the flattened chains do not show any adhesion even with the chemically identical free polymer on top, while the loosely adsorbed chains exhibit adhesion. Neutron reflectivity experiments corroborated that the difference in the interfacial adhesion is not attributed to the interfacial brodening at the free polymer-adsorbed polymer interface. Instead, coarse-grained molecular dynamics simulation results suggest that the tail parts of the loosely adsorbed chains act as "connector molecules", bridging the free chains and substrate surface and improving the interfacial adhesion. These findings not only shed light on the structure-property relationship at the interface, but also provide a novel approach for developing sticking/anti-sticking technologies through precise control of the interfacial polymer nanostructures.

In situ electrochemical high-energy X-ray diffraction using a capillary working electrode cell geometry.

The ability to generate new electrochemically active materials for energy generation and storage with improved properties will likely be derived from an understanding of atomic-scale structure/function relationships during electrochemical events. Here, the design and implementation of a new capillary electrochemical cell designed specifically for in situ high-energy X-ray diffraction measurements is described. By increasing the amount of electrochemically active material in the X-ray path while implementing low-Z cell materials with anisotropic scattering profiles, an order of magnitude enhancement in diffracted X-ray signal over traditional cell geometries for multiple electrochemically active materials is demonstrated. This signal improvement is crucial for high-energy X-ray diffraction measurements and subsequent Fourier transformation into atomic pair distribution functions for atomic-scale structural analysis. As an example, clear structural changes in LiCoO2 under reductive and oxidative conditions using the capillary cell are demonstrated, which agree with prior studies. Accurate modeling of the LiCoO2 diffraction data using reverse Monte Carlo simulations further verifies accurate background subtraction and strong signal from the electrochemically active material, enabled by the capillary working electrode geometry.

Novel Effects of Compressed CO2 Molecules on Structural Ordering and Charge Transport in Conjugated Poly(3-hexylthiophene) Thin Films.

We report the effects of compressed CO2 molecules as a novel plasticization agent for poly(3-hexylthiophene) (P3HT)-conjugated polymer thin films. In situ neutron reflectivity experiments demonstrated the excess sorption of CO2 molecules in the P3HT thin films (about 40 nm in thickness) at low pressure (P = 8.2 MPa) under the isothermal condition of T = 36 °C, which is far below the polymer bulk melting point. The results proved that these CO2 molecules accelerated the crystallization process of the polymer on the basis of ex situ grazing incidence X-ray diffraction measurements after drying the films via rapid depressurization to atmospheric pressure: both the out-of-plane lamellar ordering of the backbone chains and the intraplane π-π stacking of the side chains were significantly improved, when compared with those in the control P3HT films subjected to conventional thermal annealing (at T = 170 °C). Electrical measurements elucidated that the CO2-annealed P3HT thin films exhibited enhanced charge carrier mobility along with decreased background charge carrier concentration and trap density compared with those in the thermally annealed counterpart. This is attributed to the CO2-induced increase in polymer chain mobility that can drive the detrapping of molecular oxygen and healing of conformational defects in the polymer thin film. Given the universality of the excess sorption of CO2 regardless of the type of polymers, the present findings suggest that CO2 annealing near the critical point can be useful as a robust processing strategy for improving the structural and electrical characteristics of other semiconducting conjugated polymers and related systems such as polymer:fullerene bulk heterojunction films.

Nanoscale adsorbed structures as a robust approach for tailoring polymer film stability.

The stability or wettability of thin polymer films on solids is of vital interest in traditional technologies as well as in new emerging nanotechnologies. We report here that nanoscale structures of polymer chains adsorbed onto a solid surface play a crucial role in the thermal stability of the film. In this study, polystyrene (PS) spin-cast films (20 nm in thickness) with eight different molecular weights prepared on silicon (Si) substrates were used as a model. When low molecular weight (Mw≤ 50 kDa) PS films were subjected to thermal annealing at temperatures far above the bulk glass transition temperature, dewetting occurred promptly, while high molecular weight (Mw≥ 123 kDa) PS films were stable for at least 6 weeks at 150 °C. We reveal a strong correlation between the film stability and the two different interfacial structures of the adsorbed polymer chains: their opposing wettability against chemically identical free polymer chains results in a wetting-dewetting transition at the adsorbed polymer-free polymer interface. This is a unique aspect of the stability of polymer thin films and may be generalizable to other polymer systems regardless of the magnitude of solid-polymer attractive interactions.

Melt crystallization/dewetting of ultrathin PEO films via carbon dioxide annealing: the effects of polymer adsorbed layers.

The effects of CO2 annealing on the melting and subsequent melt crystallization processes of spin-cast poly(ethylene oxide) (PEO) ultrathin films (20-100 nm in thickness) prepared on Si substrates were investigated. By using in situ neutron reflectivity, we found that all the PEO thin films show melting at a pressure as low as P = 2.9 MPa and at T = 48 °C which is below the bulk melting temperature (Tm). The films were then subjected to quick depressurization to atmospheric pressure, resulting in the non-equilibrium swollen state, and the melt crystallization (and/or dewetting) process was carried out in air via subsequent annealing at given temperatures below Tm. Detailed structural characterization using grazing incidence X-ray diffraction, atomic force microscopy, and polarized optical microscopy revealed two unique aspects of the CO2-treated PEO films: (i) a flat-on lamellar orientation, where the molecular chains stand normal to the film surface, is formed within the entire film regardless of the original film thickness and the annealing temperature; and (ii) the dewetting kinetics for the 20 nm thick film is much slower than that for the thicker films. The key to these phenomena is the formation of irreversibly adsorbed layers on the substrates during the CO2 annealing: the limited plasticization effect of CO2 at the polymer-substrate interface promotes polymer adsorption rather than melting. Here we explain the mechanisms of the melt crystallization and dewetting processes where the adsorbed layers play vital roles.

Functionalization of Carbon Nanotubes in Polystyrene and Properties of Their Composites: A Review.

The inherent π-π interfacial interaction between carbon nanotubes (CNTs) and polystyrene (PS) makes the CNT/PS composite a representative thermoplastic nanocomposite. However, the strong van der Waals force among CNTs poses challenges to achieving effective dispersion. This review provides an overview of various CNT functionalization methods for CNT/PS composites, encompassing covalent grafting with PS-related polymers and non-covalent modification. A focus in this section involves the pre-introduction surface modification of CNTs with PS or PS-related polymers, substantially enhancing both CNT dispersibility and interfacial compatibility within the PS matrix. Furthermore, a comprehensive summary of the mechanical, electrical, thermal, and electromagnetic shielding properties of CNT/PS nanocomposites is provided, offering an overall understanding of this material. The surface modification methods of CNTs reviewed in this paper can be extended to carbon material/aromatic polymer composites, assisting researchers in customizing the optimal surface modification methods for CNTs, maximizing their dispersibility, and fully unleashing the various properties of CNTs/polymer composites. Additionally, high-performance CNTs/PS composites prepared using appropriate CNT modification methods have potential applications in areas such as electronic devices, sensors, and energy storage and conversion.

Highly Aligned Graphene Aerogels for Multifunctional Composites.

Stemming from the unique in-plane honeycomb lattice structure and the sp2 hybridized carbon atoms bonded by exceptionally strong carbon-carbon bonds, graphene exhibits remarkable anisotropic electrical, mechanical, and thermal properties. To maximize the utilization of graphene's in-plane properties, pre-constructed and aligned structures, such as oriented aerogels, films, and fibers, have been designed. The unique combination of aligned structure, high surface area, excellent electrical conductivity, mechanical stability, thermal conductivity, and porous nature of highly aligned graphene aerogels allows for tailored and enhanced performance in specific directions, enabling advancements in diverse fields. This review provides a comprehensive overview of recent advances in highly aligned graphene aerogels and their composites. It highlights the fabrication methods of aligned graphene aerogels and the optimization of alignment which can be estimated both qualitatively and quantitatively. The oriented scaffolds endow graphene aerogels and their composites with anisotropic properties, showing enhanced electrical, mechanical, and thermal properties along the alignment at the sacrifice of the perpendicular direction. This review showcases remarkable properties and applications of aligned graphene aerogels and their composites, such as their suitability for electronics, environmental applications, thermal management, and energy storage. Challenges and potential opportunities are proposed to offer new insights into prospects of this material.

Suppressing Dielectric Loss in MXene/Polymer Nanocomposites through Interfacial Interactions.

Although numerous polymer-based composites exhibit excellent dielectric permittivity, their dielectric performance in various applications is severely hampered by high dielectric loss induced by interfacial space charging and a leakage current. Herein, we demonstrate that embedding molten salt etched MXene into a poly(vinylidene fluoride-trifluoroethylene-chlorofluoroethylene) (P(VDF-TrFE-CFE))/poly(methyl methacrylate) (PMMA) hybrid matrix induces strong interfacial interactions, forming a close-packed inner polymer layer and leading to significantly suppressed dielectric loss and markedly increased dielectric permittivity over a broad frequency range. The intensive molecular interaction caused by the dense electronegative functional terminations (-O and -Cl) in MXene results in restricted polymer chain movement and dense molecular arrangement, which reduce the transportation of the mobile charge carriers. Consequently, compared to the neat polymer, the dielectric constant of the composite with 2.8 wt % MXene filler increases from ∼52 to ∼180 and the dielectric loss remains at the same value (∼0.06) at 1 kHz. We demonstrate that the dielectric loss suppression is largely due to the formation of close-packed interfaces between the MXene and the polymer matrix.

Recent Experimental Advances in Characterizing the Self-Assembly and Phase Behavior of Polypeptoids.

Polypeptoids are a family of synthetic peptidomimetic polymers featuring N-substituted polyglycine backbones with large chemical and structural diversity. Their synthetic accessibility, tunable property/functionality, and biological relevance make polypeptoids a promising platform for molecular biomimicry and various biotechnological applications. To gain insight into the relationship between the chemical structure, self-assembly behavior, and physicochemical properties of polypeptoids, many efforts have been made using thermal analysis, microscopy, scattering, and spectroscopic techniques. In this review, we summarize recent experimental investigations that have focused on the hierarchical self-assembly and phase behavior of polypeptoids in bulk, thin film, and solution states, highlighting the use of advanced characterization tools such as in situ microscopy and scattering techniques. These methods enable researchers to unravel multiscale structural features and assembly processes of polypeptoids over a wide range of length and time scales, thereby providing new insights into the structure-property relationship of these protein-mimetic materials.

Understanding the thermomechanical behavior of graphene-reinforced conjugated polymer nanocomposites via coarse-grained modeling.

Graphene-reinforced conjugated polymer (CP) nanocomposites are attractive for flexible and electronic devices, but their mechanical properties have been less explored at a fundamental level. Here, we present a predictive multiscale modeling framework for graphene-reinforced poly(3-alkylthiophene) (P3AT) nanocomposites via atomistically informed coarse-grained molecular dynamics simulations to investigate temperature-dependent thermomechanical properties at a molecular level. Our results reveal reduced graphene dispersion with increasing graphene loading. Nanocomposites with shorter P3AT side chains, lower temperatures, and higher graphene content exhibit stronger mechanical responses, which correlates with polymer dynamics. The elastic modulus increases linearly with the graphene content, which slightly deviates from the "Halpin-Tsai" micromechanical model prediction. Local stiffness analysis shows that graphene possesses the highest stiffness, followed by the P3AT backbone and side chains. Deformation-induced stronger chain alignment of the P3AT backbone compared to graphene may further promote conductive behavior. Our findings provide insights into the dynamical heterogeneity of nanocomposites, paving the way for understanding and predicting their thermomechanical properties.

Revealed architectures of adsorbed polymer chains at solid-polymer melt interfaces.

We report the chain conformations of polymer molecules accommodated at the solid-polymer melt interfaces in equilibrium. Polystyrene "Guiselin" brushes (adsorbed layers) with different molecular weights were prepared on Si substrates and characterized by using x-ray and neutron reflectivity. The results are intriguing to show that the adsorbed layers are composed of the two different nanoarchitectures: flattened chains that constitute the inner higher density region of the adsorbed layers and loosely adsorbed polymer chains that form the outer bulklike density region. In addition, we found that the lone flattened chains, which are uncovered by the additional prolonged solvent leaching (∼120 days), are reversibly densified with increasing temperature up to 150 °C. By generalizing the chain conformations of bulks, we postulate that the change in probabilities of the local chain conformations (i.e., trans and gauche states) of polymer molecules is the origin of this densification process.

Polymer Nanocomposite Dielectrics: Understanding the Matrix/Particle Interface.

Polymer nanocomposite dielectrics possess exceptional electric properties that are absent in the pristine dielectric polymers. The matrix/particle interface in polymer nanocomposite dielectrics is suggested to play decisive roles on the bulk material performance. Herein, we present a critical overview of recent research advances and important insights in understanding the matrix/particle interfacial characteristics in polymer nanocomposite dielectrics. The primary experimental strategies and state-of-the-art characterization techniques for resolving the local property-structure correlation of the matrix/particle interface are dissected in depth, with a focus on the characterization capabilities of each strategy or technique that other approaches cannot compete with. Limitations to each of the experimental strategy are evaluated as well. In the last section of this Review, we summarize and compare the three experimental strategies from multiple aspects and point out their advantages and disadvantages, critical issues, and possible experimental schemes to be established. Finally, the authors' personal viewpoints regarding the challenges of the existing experimental strategies are presented, and potential directions for the interface study are proposed for future research.

Multiscale Crystalline Structure of Confined Polypeptoid Films: The Effect of Alkyl Side Chain Branching.

We report the effect of alkyl side chain branching on melt-recrystallization of nanoconfined polypeptoid films using poly(N-octyl glycine) (PNOG) and poly(N-2-ethyl-1-hexyl glycine) (PNEHG) as model systems. Upon cooling from the isotropic melt, confined PNOG molecules recrystallize into a near-perfect orthorhombic crystal structure with the board-like molecules stacked face-to-face in the substrate-parallel direction, resulting in long-range ordered wormlike lamellae that occupy the entire film. By contrast, rod-like PNEHG molecules bearing branched N-2-ethyl-1-hexyl side chains stack into a columnar hexagonal mesophase with their backbones oriented parallel to the substrates, forming micron-sized sheaf-like superstructures under confinement, exposing large areas of empty spaces in the film. These findings highlight the effect of alkyl side chain branching on the packing motif and multiscale crystalline structure of polypeptoids under a nanoconfined geometry.

Solution Self-Assembly of Coil-Crystalline Diblock Copolypeptoids Bearing Alkyl Side Chains.

Polypeptoids, a class of synthetic peptidomimetic polymers, have attracted increasing attention due to their potential for biotechnological applications, such as drug/gene delivery, sensing and molecular recognition. Recent investigations on the solution self-assembly of amphiphilic block copolypeptoids highlighted their capability to form a variety of nanostructures with tailorable morphologies and functionalities. Here, we review our recent findings on the solutions self-assembly of coil-crystalline diblock copolypeptoids bearing alkyl side chains. We highlight the solution self-assembly pathways of these polypeptoid block copolymers and show how molecular packing and crystallization of these building blocks affect the self-assembly behavior, resulting in one-dimensional (1D), two-dimensional (2D) and multidimensional hierarchical polymeric nanostructures in solution.

Ultrastable Glassy Polymer Films with an Ultradense Brush Morphology.

Glassy polymer films with extreme stability could enable major advancements in a range of fields that require the use of polymers in confined environments. Yet, from a materials design perspective, we now know that the glass transition temperature (Tg) and thermal expansion of polymer thin films can be dramatically different from those characteristics of the bulk, i.e., exhibiting confinement-induced diminished thermal stability. Here, we demonstrate that polymer brushes with an ultrahigh grafting density, i.e., an ultradense brush morphology, exhibit a significant enhancement in thermal stability, as manifested by an exceptionally high Tg and low expansivity. For instance, a 5 nm thick polystyrene brush film exhibits an ∼75 K increase in Tg and ∼90% reduction in expansivity compared to a spin-cast film of similar thickness. Our results establish how morphology can overcome confinement and interfacial effects in controlling thin-film material properties and how this can be achieved by the dense packing and molecular ordering in the amorphous state of ultradense brushes prepared by surface-initiated atom transfer radical polymerization in combination with a self-assembled monolayer of initiators.

Cyclic Topology Enhancing Structural Ordering and Stability of Comb-Shaped Polypeptoid Thin Films against Melt-Induced Dewetting.

We investigated the effect of cyclic chain topology on the molecular ordering and thermal stability of comb-shaped polypeptoid thin films on silicon (Si) substrates. Cyclic and linear poly(N-decylglycine) (PNDG) bearing long n-decyl side chains were synthesized by ring-opening polymerization of N-decylglycine-derived N-carboxyanhydrides. When the spin-coated thin films were subjected to thermal annealing at temperatures above the melting temperature (T > T m), the cyclic PNDG films exhibited significantly enhanced stability against melt-induced dewetting than the linear counterparts (l-PNDG). When recrystallized at temperatures below the crystallization temperature (T < T c), the homogeneous c-PNDG films exhibit enhanced crystalline ordering relative to the macroscopically dewetted l-PNDG films. Both cyclic and linear PNDG molecules adopt cis-amide conformations in the crystalline film, which transition into trans-amide conformations upon melting. A top-down solvent leaching treatment of both l/c-PNDG films revealed the formation of an irreversibly physisorbed monolayer with similar thickness (ca. 3 nm) on the Si substrate. The physisorbed monolayers are more disordered relative to the respective thicker crystalline films for both cyclic and linear PNDGs. Upon heating above T m, the adsorbed c-PNDG chains adopt trans-amide backbone conformation identical with the free c-PNDG molecules in the molten film. By contrast, the backbone conformations of l-PNDG chains in the adsorbed layers are notably different from those of the free chains in the molten film. We postulate that the conformational disparity between the chains in the physically adsorbed layers versus the free chains in the molten film is an important factor to account for the difference in the thermal stability of PNDG thin films. These findings highlight the use of cyclic chain topology to suppress the melt-induced dewetting in polymer thin films.