Bottlebrush Architecture Research Articles

Supersoft Polymer Melts in Binary Blends of Bottlebrush cis-1,4-Polyfarnesene and cis-1,4-Polyisoprene.

Binary blends of polyterpenes are employed comprising cis-1,4-polyfarnesene (PF) with a bottlebrush architecture, and linear cis-1,4-polyisoprene (PI) as model systems toward supersoft polymer melts. The bottlebrush PF results in a low plateau modulus ( Pa) that can further be reduced with the addition of PI. Depending on the fraction of short PI chains in the athermal and nearly isofrictional blends, plateau moduli in the range from 1 to 10kPa can be achieved. Tube dilation is very efficient in the present binary blends as compared to more common blends comprising long/short or linear/star chains of identical polymer structure.

Zwitterionic Poly-Carboxybetaine Polymers Restore Lubrication of Inflamed Articular Cartilage.

Osteoarthritis is a degenerative joint disease that is associated with decreased synovial fluid viscosity and increased cartilage friction. Though viscosupplements are available for decades, their clinical efficacy is limited and there is ample need for more effective joint lubricants. This study first evaluates the tribological and biochemical properties of bovine articular cartilage explants after stimulation with the inflammatory cytokine interleukin-1β. This model is then used to investigate the tribological potential of carboxybetaine (CBAA)-based zwitterionic polymers of linear and bottlebrush architecture. Due to their affinity for cartilage tissue, these polymers form a highly hydrated surface layer that decreases friction under high load in the boundary lubrication regime. For linear pCBAA, these benefits are retained over several weeks and the relaxation time of cartilage explants under compression is furthermore decreased, thereby potentially boosting the weeping lubrication mechanism. Bottlebrush bb-pCBAA shows smaller benefits under boundary lubrication but is more viscous than linear pCBAA, therefore providing better lubrication under low load in the fluid-film regime and enabling a longer residence time to bind to the cartilage surface. Showing how CBAA-based polymers restore the lost lubrication mechanisms during inflammation can inspire the next steps toward more effective joint lubricants in the future.

Selective electrochemical degradation of bottlebrush elastomers

AbstractWe introduce a simple synthetic strategy to selectively degrade bottlebrush networks derived from well‐defined poly(4‐methylcaprolactone) (P4MCL) bottlebrush polymers. Functionalization of the hydroxyl groups present at the terminal ends of P4MCL side chains with α‐lipoic acid resulted in bottlebrush polymers having a range of molecular weights (Mn = 45–2200 kg mol−1) and a tunable number of reactive dithiolane chain ends. These functionalized chain ends act as efficient crosslinkers due to radical ring‐opening of the dithiolane rings under UV light. The resulting redox‐active disulfide crosslinks enable mild electrochemical or chemical degradation of the SS crosslinks to regenerate the starting bottlebrush polymer. P4MCL side chains and the disulfides can be degraded simultaneously using harsher reducing conditions. This combination of bottlebrush architecture with facile disulfide crosslinking presents a versatile platform for preparing highly tunable elastomers that undergo controlled degradation under mild conditions.

Hybrid Bonding Bottlebrush Polymers Grafted from a Supramolecular Polymer Backbone.

Bottlebrush polymers, macromolecules consisting of dense polymer side chains grafted from a central polymer backbone, have unique properties resulting from this well-defined molecular architecture. With the advent of controlled radical polymerization techniques, access to these architectures has become more readily available. However, synthetic challenges remain, including the need for intermediate purification, the use of toxic solvents, and challenges with achieving long bottlebrush architectures due to backbone entanglements. Herein, we report hybrid bonding bottlebrush polymers (systems integrating covalent and noncovalent bonding of structural units) consisting of poly(sodium 4-styrenesulfonate) (p(NaSS)) brushes grafted from a peptide amphiphile (PA) supramolecular polymer backbone. This was achieved using photoinitiated electron/energy transfer-reversible addition-fragmentation chain transfer (PET-RAFT) polymerization in water. The structure of the hybrid bonding bottlebrush architecture was characterized using cryogenic transmission electron microscopy, and its properties were probed using rheological measurements. We observed that hybrid bonding bottlebrush polymers were able to organize into block architectures containing domains with high brush grafting density and others with no observable brushes. This finding is possibly a result of dynamic behavior unique to supramolecular polymer backbones, enabling molecular exchange or translational diffusion of monomers along the length of the assemblies. The hybrid bottlebrush polymers exhibited higher solution viscosity at moderate shear, protected supramolecular polymer backbones from disassembly at high shear, and supported self-healing capabilities, depending on grafting densities. Our results demonstrate an opportunity for novel properties in easily synthesized bottlebrush polymer architectures built with supramolecular polymers that might be useful in biomedical applications or for aqueous lubrication.

Diblock bottlebrush polymer in a non-polar medium: Self-assembly, surface forces, and superlubricity

Whilst bottlebrush polymers have been studied in aqueous media for their conjectured role in biolubrication, surface forces and friction mediated by bottlebrush polymers in non-polar media have not been previously reported. Here, small-angle neutron scattering (SANS) showed that a diblock bottlebrush copolymer (oligoethyleneglycol acrylate/ethylhexyl acrylate; OEGA/EHA) formed spherical core–shell aggregates in n-dodecane (a model oil) in the polymer concentration range 0.1–2.0 wt%, with a radius of gyration Rg ∼ 7 nm, comprising 40–65 polymer molecules per aggregate. The surface force apparatus (SFA) measurements revealed purely repulsive forces between surfaces bearing inhomogeneous polymer layers of thickness L ∼ 13–23 nm, attributed to adsorption of a mixture of polymer chains and surface-deformed micelles. Despite the surface inhomogeneity, the polymer layers could mediate effective lubrication, demonstrating superlubricity with the friction coefficient as low as µ ∼ 0.003. The analysis of velocity-dependence of friction using the Eyring model shed light on the mechanism of the frictional process. That is, the friction mediation was consistent with the presence of nanoscopic surface aggregates, with possible contributions from a gel-like network formed by the polymer chains on the surface. These unprecedented results, correlating self-assembled polymer micelle structure with the surface forces and friction the polymer layers mediate, highlight the potential of polymers with the diblock bottlebrush architecture widespread in biological living systems, in tailoring desired surface interactions in non-polar media.

Molecular brushes based on poly(amino acid)s: synthesis, structures, and applications

AbstractPolymer science is witnessing rapid advancements in the precision construction of synthetic macromolecules. Beyond the impressive advances in molecular brush, the integration of poly(amino acid)s into bottlebrush architectures leads to a novel class of materials known as molecular brushes based on poly(amino acid)s (MBPAs). These materials not only possess biorelated functions but also enable the incorporation of the diverse secondary structures found in poly(amino acid)s into the bulk polymers. Here we present a comprehensive and critical summary of three synthetic strategies and three different constructions for MBPAs. Furthermore, we highlight their potential in the development of advanced materials for a broad range of applications, encompassing antimicrobial activity, pharmaceutical delivery, and bioimaging.

Polymer architecture effect on rheology and segmental dynamics in poly (methyl methacrylate)-silica nanocomposite melts.

Architecturally different polymer chains lead to fundamentally different rheological responses and internal dynamics, which can be utilized to rationalize advanced thermoplastic nanocomposites with tunable mechanical behavior. In this work, three model poly (methyl methacrylate) (PMMA) polymers with linear, bottlebrush, and star architectures with the same total molar mass were investigated in their neat form, and nanocomposites with well-dispersed silica nanoparticles using rheology and broadband dielectric spectroscopy (BDS). The master curves of the dynamic moduli obtained by time-temperature superposition (TTS) over the entire range from the Rouse regime to the terminal flow and a sequence of significantly different relaxation modes were observed for the samples with linear and branch chains. While linear chains form an entangled polymer network, the branched bottlebrush, and star chains show a viscoelastic response with no sign of rubbery entanglement plateau and a weak arm relaxation regime between Rouse and terminal flow, akin to other branched polymers. Moreover, branched chains showed a higher fragility index (m = 3.46 for the bottlebrush and 5.36 for the star) compared to linear chains (m = 3.29) due to dynamical heterogeneities induced by arm relaxation. The addition of nanoparticles affects only the terminal relaxation regime, where the whole chain motion is hindered by the attractive nanoparticles. The dynamics of the polymer segment were investigated by performing broadband dielectric spectroscopy (BDS) at a frequency range from 10-2 Hz to 107 Hz. The results revealed more than 10 times slower segmental relaxation for the star homopolymers and a slowdown in the α-relaxation process for all three architectures in their composite form. The dynamical slowdown in the composites is temperature dependent and more pronounced at low temperatures (leading to approximately equal to 80 times slower dynamics for nanocomposite with bottlebrush PMMA at 150 °C) due to prolonged relaxation of the interfacial polymer compared to the matrix chains. The results from this study have practical applications in fields such as gas separation and polymeric electrolyte membranes, where simultaneous improvement of segmental mobility and mechanical moduli is highly desired.

Clickable Polyprolines from Azido-proline N-Carboxyanhydride.

Polyproline is a material of great interest in biomedicine due to its helical scaffold of structural importance in collagen and mucins and its ability to gel and to change conformations in response to temperature. Appending of function-modulating chemical groups to such a material is desirable to diversify potential applications. Here, we describe the synthesis of high-molecular-weight homo, block, and statistical polymers of azide-functionalized proline. The azide groups served as moieties for highly efficient click-grafting, as stabilizers of the polyproline PPII helix, and as modulators of thermoresponsiveness. Saccharides and ethylene glycol were utilized to explore small-molecule grafting, and glutamate polymers were utilized to form polyelectrolyte bottlebrush architectures. Secondary structure effects of both the azide and click modifications, as well as lower critical solution temperature behavior, were characterized. The polyazidoprolines and click products were well tolerated by live human cells and are expected to find use in diverse biomedical applications.

Self-Healable, Stretchable, and Super-Soft Bottlebrush Polyester Elastomers for Highly Sensitive Flexible Sensors

While much effort has been devoted to the creation of super-soft elastomers, there is a dearth of research aimed at self-healable and super-soft renewable elastomers. Herein, self-healing and super-soft renewable elastomers are developed based on bottlebrush architecture design and dynamic associative transesterification. The bottlebrush polymer precursors are generated by ring-opening metathesis polymerization (ROMP) of the norbornene-terminated macromonomer poly(ε-caprolactone-co-l-lactide) (PCLLA) (NB-PCLLA). After introducing alkyne groups onto the end of PCLLA side chains, the bottlebrush polymers are cross-linked to achieve elastomer networks via a UV-induced “click” thiol-yne reaction between the terminal alkyne groups and the dithiothreitol (DTT) additive. The resulting materials exhibit a shear modulus as low as 17 kPa, high stretchability with breaking strains as large as 315%, and a self-healing efficiency of 95.6% at an elevated temperature of 80 °C. Taking the super-softness advantage, flexible sensor devices are assembled based on the prepared elastomer, which are highly sensitive to deformation with a gauge factor of 0.347. This work demonstrates that high-performance biodegradable materials with unique properties that conventional linear polymers impossibly possess can be easily constructed by molecular architecture design using bottlebrush polymers as building blocks.

Structure and Phase Behavior of Bottlebrush Diblock Copolymer-Linear Homopolymer Ternary Blends

In this work, we systematically investigated the structure and phase behavior of ternary mixtures containing an AB bottlebrush diblock copolymer and A and B linear homopolymers, where A is polystyrene and B is poly(ethylene oxide), using a combination of small-angle X-ray scattering and cloud point measurements. We found that the overall phase behavior of such mixtures closely resembles the linear counterparts, with lamellae occurring in the copolymer-rich region, macrophase separation in the homopolymer-rich region, and a bicontinuous microemulsion in between. However, the increase in lamellar and microemulsion domain spacing with increasing homopolymer content is significantly weaker than that found with ternary mixtures containing linear diblock copolymers and depends on the relative size of the homopolymers and bottlebrush side chains. We attribute this behavior to an unconventional spatial distribution of the homopolymer within the bottlebrush architecture of the diblock copolymer. These ternary mixtures offer a promising platform for the design of cocontinuous materials with an expanded parameter space made possible by the application of bottlebrush polymers.

Novel epoxy-terminated macromonomers and their polymerization for synthesis of bottle-brush type amphiphilic block copolymers.

Architecture of polymers has vital implications for their physical properties and applications. In this study, synthesis of a series of novel epoxy-terminated macromonomers namely Ep-DEGMME, Ep-TEGMME, Ep-EGMEE, Ep-EGMBE, and Ep-EGMHE is reported. The synthesized macromonomers vary in number of ethylene oxide units and length of the alkyl group. These macromonomers are first homopolymerized by anionic ring-opening polymerization for synthesis of homopolymers of a molar mass range. Subsequently, these macromonomers with different lengths of two segments (alkyl group and ethylene oxide units) are copolymerized with other monomers for synthesis of bottle-brush type architectures. In the first case, di- and tri-block copolymers of Ep-EGMBE are synthesized while using MeO-PEG or PEG as a macroinitiator; the resulting block copolymers have hydrophilic handle and hydrophobic brush. On the same lines, block copolymers of Ep-TEGMME with ε-caprolactone have hydrophobic handle and hydrophilic brush. The synthesized block copolymers are comprehensively characterized by SEC and liquid chromatography at critical conditions. The analysis reveals the successful synthesis of block copolymers while providing information on relative total molar mass, and individual block lengths of the block copolymers, along with amount of unwanted homopolymers in the sample.

A fluffy all-siloxane bottlebrush architecture for liquid-like slippery surfaces

A transparent all-siloxane bottlebrush liquid-like surface is created by in situ sequential reactions. This unique non-linear architecture improves the grafting density and shows superior sliding performances compared to its linear counterparts.

Core-Shell Gyroid in ABC Bottlebrush Block Terpolymers.

Block polymer self-assembly provides a versatile platform for creating useful materials endowed with three-dimensional periodic network morphologies that support orthogonal physical properties such as high ionic conductivity and a high elastic modulus. However, coil configurations limit conventional linear block polymers to finite ordered network dimensions, which are further restricted by slow self-assembly kinetics at high molecular weights. A bottlebrush architecture can circumvent both shortcomings owing to extended backbone configurations due to side chain crowding and molecular dynamics substantially free of chain entanglements. However, until now, network morphologies have not been reported in AB bottlebrush block copolymers, notwithstanding favorable mean-field predictions. We explored the phase behavior by small-angle X-ray scattering of 133 poly(ethylene-alt-propylene)-b-polystyrene (PEP-PS) diblock and PEP-PS-PEO triblock bottlebrush copolymers prepared by ring-opening metathesis polymerization (ROMP) of norbornene-functionalized poly(ethylene-alt-propylene) (PEP), poly(styrene) (PS), and poly(ethylene oxide) (PEO) macromonomers with total backbone degrees of polymerization Nbb between 20 and 40. The PEP-PS diblocks exhibited only cylindrical and lamellar morphologies over the composition range of ca. 30-70%. However, addition of variable-length bottlebrush PEO blocks to diblocks containing 30-50% PS led to the formation of a substantial core-shell double gyroid (GYR) phase window containing 20 bottlebrush triblock specimens, which is the focus of this report. Encouragingly, the GYR unit cell dimensions increased as d ∼ Nbb0.92, portending the ability to access larger network dimensions than previously obtained with linear AB or ABC block polymers. This work highlights extraordinary opportunities associated with applying facile ROMP chemistry to multiblock bottlebrush polymers.

Versatile Light-Mediated Synthesis of Dry Ion-Conducting Dynamic Bottlebrush Networks with High Elasticity, Interfacial Adhesiveness, and Flame Retardancy

Dry ion-conducting elastomers possess superior reliability in soft ionotronic devices when compared to ion-conducting gels that suffer from liquid evaporation or leakage issues. Recent works have shown that bottlebrush architecture can effectively reduce structural relaxation time so that the bottlebrush polymers have concentrated charge carriers and high chain mobility that result in good ionic conductivity and mechanical flexibility. Here, we report a novel and versatile light-mediated strategy for synthesizing dry ion-conducting elastomers with dynamic bottlebrush network structures. The obtained dry ion-conducting dynamic bottlebrush networks (DICDBNs) are colorless and highly transparent and can be simply patterned. We systematically investigate the influence of the number and length of the side chains in the DICDBNs on the physicochemical properties of the resultant materials and find that the optimized DICDBNs have high room-temperature ionic conductivity (2.05 × 10–4 S cm–1), good elasticity (stretchability 923%, 83.3% toughness recovery after 100 uninterrupted strain cycles at a strain of 300%), outstanding healing ability (healing efficiency 90.5%), on-demand degradability, excellent interfacial adhesiveness, good flame retardancy, and strain and temperature dual sensitivity, making them promising candidates for multifunctional wearable ionotronics.

Antimicrobial Polymers of Linear and Bottlebrush Architecture: Probing the Membrane Interaction and Physicochemical Properties

Polymeric antimicrobial peptide mimics are a promising alternative for the future management of the daunting problems associated with antimicrobial resistance. However, the development of successful antimicrobial polymers (APs) requires careful control of factors such as amphiphilic balance, molecular weight, dispersity, sequence, and architecture. While most of the earlier developed APs focus on random linear copolymers, the development of APs with advanced architectures proves to be more potent. It is recently developed multivalent bottlebrush APs with improved antibacterial and hemocompatibility profiles, outperforming their linear counterparts. Understanding the rationale behind the outstanding biological activity of these newly developed antimicrobials is vital to further improving their performance. This work investigates the physicochemical properties governing the differences in activity between linear and bottlebrush architectures using various spectroscopic and microscopic techniques. Linear copolymers are more solvated, thermo-responsive, and possess facial amphiphilicity resulting in random aggregations when interacting with liposomes mimicking Escheria coli membranes. The bottlebrush copolymers adopt a more stable secondary conformation in aqueous solution in comparison to linear copolymers, conferring rapid and more specific binding mechanism to membranes. The advantageous physicochemical properties of the bottlebrush topology seem to be a determinant factor in the activity of these promising APs.

Mesoscale Modeling of Agglomeration of Molecular Bottlebrushes: Focus on Conformations and Clustering Criteria.

Using dissipative particle dynamics, we characterize dynamics of aggregation of molecular bottlebrushes in solvents of various qualities by tracking the number of clusters, the size of the largest cluster, and an average aggregation number. We focus on a low volume fraction of bottlebrushes in a range of solvents and probe three different cutoff criteria to identify bottlebrushes belonging to the same cluster. We demonstrate that the cutoff criteria which depend on both the coordination number and the length of the side chain allows one to correlate the agglomeration status with the structural characteristics of bottlebrushes in solvents of various qualities. We characterize conformational changes of the bottlebrush within the agglomerates with respect to those of an isolated bottlebrush in the same solvents. The characterization of bottlebrush conformations within the agglomerates is an important step in understanding the relationship between the bottlebrush architecture and material properties. An analysis of three distinct cutoff criteria to identify bottlebrushes belonging to the same cluster introduces a framework to identify both short-lived transient and long-lived agglomerates; the same approach could be further extended to characterize agglomerates of various macromolecules with complex architectures beyond the specific bottlebrush architecture considered herein.

Synthesis and Micellization of Bottlebrush Poloxamers.

Bottlebrush polymers are characterized by an expansive parameter space, including graft length and spacing along the backbone, and these features impact various structural and physical properties such as molecular diffusion and bulk viscosity. In this work, we report a synthetic strategy for making grafted block polymers with poly(propylene oxide) and poly(ethylene oxide) side chains, bottlebrush analogues of poloxamers. Combined anionic and sequential ring-opening metathesis polymerization yielded low dispersity polymers, at full conversion of the macromonomers, with control over graft length, graft end-groups, and overall molecular weight. A set of bottlebrush poloxamers (BBPs), with identical graft lengths and composition, was synthesized over a range of molecular weights. Dynamic light scattering and transmission electron microscopy were used to characterize micelle formation in aqueous buffer. The critical micelle concentration scales exponentially with overall molecular weight for both linear and bottlebrush poloxamers; however, the bottlebrush architecture shifts micelle formation to a much higher concentration at a comparable molecular weight. Consequently, BBPs can exist in solution as unimers at significantly higher molecular weights and concentrations than the linear analogues.

Regulating Tissue-Mimetic Mechanical Properties of Bottlebrush Elastomers by Magnetic Field.

We report on a new class of magnetoactive elastomers (MAEs) based on bottlebrush polymer networks filled with carbonyl iron microparticles. By synergistically combining solvent-free, yet supersoft polymer matrices, with magnetic microparticles, we enable the design of composites that not only mimic the mechanical behavior of various biological tissues but also permit contactless regulation of this behavior by external magnetic fields. While the bottlebrush architecture allows to finely tune the matrix elastic modulus and strain-stiffening, the magnetically aligned microparticles generate a 3-order increase in shear modulus accompanied by a switch from a viscoelastic to elastic regime as evidenced by a ca. 10-fold drop of the damping factor. The developed method for MAE preparation through solvent-free coinjection of bottlebrush melts and magnetic particles provides additional advantages such as injection molding of various shapes and uniform particle distribution within MAE composites. The synergistic combination of bottlebrush network architecture and magnetically responsive microparticles empowers new opportunities in the design of actuators and active vibration insulation systems.

Single-Chain Conformation of Poly(α-olefins) in Dilute Solutions at the Crossover between Linear and Bottlebrush Architectures

Single-Chain Conformation of Poly(α-olefins) in Dilute Solutions at the Crossover between Linear and Bottlebrush Architectures

Chain Exchange Kinetics of Bottlebrush Block Copolymer Micelles

Chain exchange kinetics of the bottlebrush core micelles formed by poly(5-perfluorooctyl-2-norbornene-block-N-cyclohexyl-exo-norbornene-5,6-dicarboxyimide) (PF-b-PC) block copolymer in tetrahydrofuran (THF), selective for PC blocks, were investigated by time-resolved small-angle neutron scattering (TR-SANS). The bottlebrush PF core blocks are densely tethered with rigid fluoroalkyl side chains. Despite the unfavorable interaction between the PF cores and the medium, TR-SANS revealed that the chain exchange between the bottlebrush core micelles occurs within a measurable timescale (∼1 h) at 40 °C. The measured exchange kinetics were successfully described by the model based on the thermodynamic barrier for the core block extraction and the solvent plasticizing effect associated with partial swelling of the PF cores. This chain exchange rate is also partly attributed to the bottlebrush architecture of PF blocks, as supported by lower melt viscosities of PF homopolymers than those of the analogous fluorine-containing linear polymers. These results are discussed in terms of current understanding of molecular exchange between block copolymer micelles, and particular attention is paid to the issue of polymer architecture, given the bottlebrush type of the core block.