Bottlebrush Polymers Research Articles

Versatile Light‐Mediated Synthesis of Degradable Bottlebrush Polymers Using α‐Lipoic Acid

AbstractBottlebrush polymers have a variety of useful properties including a high entanglement molecular weight, low Young's modulus, and rapid kinetics for self‐assembly. However, the translation of bottlebrushes to real‐world applications is limited by complex, multi‐step synthetic pathways and polymerization reactions that rely on air‐sensitive catalysts. Additionally, most bottlebrushes are non‐degradable. Herein, we report an inexpensive, versatile, and simple approach to synthesize degradable bottlebrush polymers under mild reaction conditions. Our approach relies on the “grafting‐through” polymerization of α‐lipoic acid (LA)‐functionalized macromonomers. These macromonomers can be polymerized under mild, catalyst‐free conditions, and due to reversibility of the disulfide bond in LA, the resulting bottlebrush polymers can be depolymerized by cleaving disulfide backbone bonds. Bottlebrushes with various side‐chain chemistries can be prepared through the atom transfer radical polymerization (ATRP) of LA‐functionalized macromonomers, and the backbone length is governed by the macromonomer molecular weight and solvent polarity. We also demonstrate that LA‐functionalized macromonomers can be copolymerized with acrylates to form degradable bottlebrush networks. This work demonstrates the preparation of degradable bottlebrush polymers with a variety of side‐chain chemistries and provides insight into the light‐mediated grafting‐through polymerization of dithiolane‐functionalized macromonomers.

Helical Star-Shaped Bottlebrush Polymers: From Controlled Synthesis to Tunable Photoluminescence and Circularly Polarized Luminescence.

The controlled synthesis of star-shaped bottlebrush polymers with tunable topologies is a challenge. However, such materials may exhibit distinct photoluminescence properties. Bottlebrush polymers have polymerization-induced emission (PIE) properties due to their aggregated side chains, and aggregation-induced emission (AIE) is also a unique luminescent property. In this work, we prepared a variety of highly active alkyne Pd catalysts and polymerized poly(L/D-lactic acid) macromonomers containing polymerizable phenylisocyanide groups as end groups to obtain a variety of topologically structured bottlebrush polymers with controllable molecular weights and narrow molecular weight distributions. Bottlebrush polymers with tetraphenyl ethylene (TPE) units as the core exhibit tunable photoluminescence and circularly polarized luminescence properties. We propose that such properties are due to the unique AIE characteristics of the TPE unit combined with the PIE characteristics of the bottlebrush polymer.

From Fully Stretched to Collapsed Chains: Bottlebrush Polymer Grafted Particles

From Fully Stretched to Collapsed Chains: Bottlebrush Polymer Grafted Particles

Degradable polyolefins prepared by integration of disulfides into metathesis polymerizations with 3,6-dihydro-1,2-dithiine.

Disulfide-containing polyolefins were synthesized by ring-opening metathesis polymerization (ROMP) of the 6-membered disulfide-containing cyclic olefin, 3,6-dihydro-1,2-dithiine, which was prepared by ring-closing metathesis of diallyl disulfide. This approach facilitated the production of disulfide-containing unsaturated polyolefins as copolymers with disulfide monomer units embedded within a poly(cyclooctene) or poly(norbornene) framework. The incorporation of disulfides into the polymer backbone imparts redox responsiveness and enables polymer degradation via chemical reduction or thiol-disulfide exchange. This ROMP copolymerization strategy yielded both linear polyolefins, as well as bottlebrush polymers, with degradable segments, thereby broadening the scope of responsive polymer architectures synthesized by ROMP.

Organization of A2‐Type Active Composite Nanorods

AbstractNanorods as building blocks are promising to construct functional superstructures. A paramagnetic Fe3O4‐based composite nanorod is large‐scale synthesized from the poly(2‐vinylpyridine) (P2VP) side chain grafted polymer bottlebrush by electrostatics‐mediated intramolecular crosslinking via metallic coordination. Ultrasonication‐assisted fracturing of the composite nanorod derives the corresponding A2‐type composite nanorods whose two ends are active with the metallic coordinated P2VP exposed. The active ends are prone to connection upon feeding ligands (acidic or alkaline) or metallic ions to trigger the organization of the A2‐type nanorods toward functional superstructures. Their microstructure is tunable from linear nanowires to branches, which is dependent on the valent state of the assistant chemicals. The report method is easily extended to derive a family of A2‐type active nanorods with varied compositions and functions which are capable to organize functional nanomaterials with tunable microstructure.

Bottlebrush Midblocks Promote Colloidal Bridging of Telechelic Polymers.

Telechelic polymers are effective rheological modifiers that bridge between associative constituents to form elastic networks. The performance of linear telechelic chains, however, is controlled by entropic forces and thus suffers from an upper limit on bridge formation. This work overcomes this limitation by utilizing telechelic triblock copolymers containing bottlebrush midblocks. By comparing the rheological properties of emulsions linked by telechelic bottlebrush polymers to those containing linear chains, we determined that telechelic polymers with bottlebrush midblocks form elastic networks more efficiently. These enhanced rheological properties arise from the high stiffness of the bottlebrush midblocks, which offsets the entropic stretching penalty for bridge formation, enabling them to more readily form networks. This molecular-level control over polymer conformation in complex fluids opens avenues for designing highly elastic networks with minimal polymeric additives.

Co-deposition of tannic acid and bottle-brush polymer to construct stable antifouling surface via hydrogen-bonding

The convenient preparation and excellent stability are two specific demands for antifouling surfaces. We designed a hydrogen-bonded network composed of tannic acid (TA) and bottle-brush polymer (BBP) to form an antifouling coating on diverse substrates. The BBP contained polyurethane backbone and polyethylene glycol (PEG) side chains which provided abundant hydrogen bond acceptors. Molecular dynamics (MD) simulation, 2D-IR and 1H NMR spectra confirmed that TA could interact with both the backbone and side chains of BBP. Owing to the strong affinity of TA to substrates and the hierarchical structure of bottle-brush polymer, TA/BBP coating possessed more intricate non-covalent network than TA/linear polymer coating and was more stable at physiologic pH. The excellent antifouling properties against serum albumin, red blood cells, fibroblasts and bacteria were demonstrated using different techniques. This work provided a strategy to prepare a stable antifouling coating relying solely on the hydrogen-bonded network of TA and BBP. Additionally, TA/BBP coating could be completely detached by strongly basic solution due to the dissociation of TA, which provided a possibility of cleaning and recycling substrates if necessary.

Effect of Grafting Density on the Crystallization Behavior of Molecular Bottlebrushes.

A unique case of sterically constrained crystallization arises in bottlebrush polymers bearing semicrystalline side chains. Bottlebrushes with grafted side chains can form crystalline structures governed by the complex interplay between side chain packing and backbone confinement. The confinement effect can be readily tuned by varying the side chain grafting density, thus affording control over the crystallization behavior of these systems. In this work, the grafting density effect on the crystallization behavior of molecular bottlebrushes comprising poly(ethylene oxide) (PEO) side chains grafted to a methacrylate backbone was systematically studied. Thermal analysis using differential scanning calorimetry showed that the bottlebrush polymers displayed suppressed crystallization temperatures, lower melting temperatures, and reduced crystallinities compared to linear homopolymer PEO. The crystalline morphology was investigated using polarized light, atomic force, and scanning electron microscopy. Isothermal crystallization experiments revealed a nonmonotonous dependence of the nucleation density on the side chain grafting density. The grafting density effect was also investigated using self-seeding experiments, revealing an increased clearing temperature and memory retention at higher grafting densities. This work highlights how grafting density influences the crystallization behavior of semicrystalline bottlebrushes, providing information for the processing and application of these unique polymers.

Versatile Light-Mediated Synthesis of Degradable Bottlebrush Polymers Using α-Lipoic Acid.

Bottlebrush polymers have a variety of useful properties including a high entanglement molecular weight, low Young's modulus, and rapid kinetics for self-assembly. However, the translation of bottlebrushes to real-world applications is limited by complex, multi-step synthetic pathways and polymerization reactions that rely on air-sensitive catalysts. Additionally, most bottlebrushes are non-degradable. Herein, we report an inexpensive, versatile, and simple approach to synthesize degradable bottlebrush polymers under mild reaction conditions. Our approach relies on the "grafting-through" polymerization of α-lipoic acid (LA)-functionalized macromonomers. These macromonomers can be polymerized under mild, catalyst-free conditions, and due to reversibility of the disulfide bond in LA, the resulting bottlebrush polymers can be depolymerized by cleaving disulfide backbone bonds. Bottlebrushes with various side-chain chemistries can be prepared through the atom transfer radical polymerization (ATRP) of LA-functionalized macromonomers, and the backbone length is governed by the macromonomer molecular weight and solvent polarity. We also demonstrate that LA-functionalized macromonomers can be copolymerized with acrylates to form degradable bottlebrush networks. This work demonstrates the preparation of degradable bottlebrush polymers with a variety of side-chain chemistries and provides insight into the light-mediated grafting-through polymerization of dithiolane-functionalized macromonomers.

Chemical Botany: Bottlebrush Polymers in Materials Science

Molecular architectures known as bottlebrush polymers provide unique opportunities to tune the structure and properties of soft materials with applications ranging from rubbers to thin films and composites. This review addresses recent developments and future opportunities in the field with an emphasis on materials science enabled by contemporary bottlebrush chemistry.

Beyond Traditional Stimuli: Exploring Salt-Responsive Bottlebrush Polymers-Trends, Applications, and Perspectives.

Bottlebrush polymers represent an important class of high-density side-chain-grafted polymers traditionally with high molecular weights, in which one or more polymeric side chains are tethered to each repeating unit of a linear polymer backbone, such that these macromolecules look like "bottlebrushes". The arrangement of molecular brushes is determined by side chains located at a distance considerably smaller than their unperturbed dimensions, leading to substantial monomer congestion and entropically unfavorable extension of both the backbone and the side chains. Traditionally, the conformation and physical properties of polymers are influenced by external stimuli such as solvent, temperature, pH, and light. However, a unique stimulus, salt, has recently gained attention as a means to induce shape changes in these molecular brushes. While the stimulus has been less researched to date, we see that these systems, when stimulated with salts, have the potential to be used in various engineering applications. This potential stems from the unique properties and behaviors these systems show when exposed to different salts, which could lead to new solutions and improvements in engineering processes, thus serving as the primary motivation for this narrative, as we aim to explore and highlight the various ways these systems can be utilized and the benefits they could bring to the field of engineering. This Review aims to introduce the concept of stimuli-responsive bottlebrush polymers, explore the evolutionary trajectory, delve into current trends in salt-responsive bottlebrush polymers, and elucidate how these polymers are addressing a variety of engineering challenges.

Artificial Channels Based on Bottlebrush Polymers: Enhanced Ion Transport Through Polymer Topology Control.

Synthetic structures mimicking the transport function of natural ion channel proteins have a wide range of applications, including therapeutic treatments, separation membranes, sensing, and biotechnologies. However, the development of polymer-based artificial channels has been hampered due to the limitation on available models. In this study, we demonstrate the great potential of bottlebrush polymers as accessible and versatile molecular scaffolds for developing efficient artificial ion channels. Adopting the bottlebrush configuration enhanced ion transport activity of the channels compared to their linear analogs. Matching the structure of lipid bilayers, the bottlebrush channel with a hydrophilic-hydrophobic-hydrophilic triblock architecture exhibited the highest activity among the series. Functionalized with urea groups, these channels displayed high anion selectivity. Additionally, we illustrated that the transport properties could be fine-tuned by modifying the chemistry of ion binding sites. This work not only highlights the importance of polymer topology control in channel design, but also reveals the great potential for further developing bottlebrush channels with customized features and diverse functionalities.

Artificial Channels Based on Bottlebrush Polymers: Enhanced Ion Transport Through Polymer Topology Control

AbstractSynthetic structures mimicking the transport function of natural ion channel proteins have a wide range of applications, including therapeutic treatments, separation membranes, sensing, and biotechnologies. However, the development of polymer‐based artificial channels has been hampered due to the limitation on available models. In this study, we demonstrate the great potential of bottlebrush polymers as accessible and versatile molecular scaffolds for developing efficient artificial ion channels. Adopting the bottlebrush configuration enhanced ion transport activity of the channels compared to their linear analogs. Matching the structure of lipid bilayers, the bottlebrush channel with a hydrophilic‐hydrophobic‐hydrophilic triblock architecture exhibited the highest activity among the series. Functionalized with urea groups, these channels displayed high anion selectivity. Additionally, we illustrated that the transport properties could be fine‐tuned by modifying the chemistry of ion binding sites. This work not only highlights the importance of polymer topology control in channel design, but also reveals the great potential for further developing bottlebrush channels with customized features and diverse functionalities.

Bottlebrush Polymers for Articular Joint Lubrication: Influence of Anchoring Group Chemistry on Lubrication Properties.

The role of carboxylic, aldehyde, or epoxide groups incorporated into bottlebrush macromolecules as anchoring blocks (or cartilage-binding blocks) is investigated by measuring their lubricating properties and cartilage-binding effectiveness. Mica modified with amine groups is used to mimic the cartilage surface, while bottlebrush polymers functionalized with carboxylic, aldehyde, or epoxide groups played the role of the lubricant interacting with the cartilage surface. We demonstrate that bottlebrushes with anchoring blocks effectively reduce the friction coefficient on modified surfaces by 75-95% compared to unmodified mica. The most efficient polymer appears to be the one with epoxide groups, which can react spontaneously with amines at room temperature. In this case, the value of the friction coefficient is the lowest and equals 0.009 ± 0.001, representing a 95% reduction compared to measurements on nonmodified mica. These results show that the presence of the functional groups within the anchoring blocks has a significant influence on interactions between the bottlebrush polymer and cartilage surface. All synthesized bottlebrush polymers are also used in the preliminary lubrication tests carried out on animal cartilage surfaces. The developed materials are very promising for future in vivo studies to be used in osteoarthritis treatment.

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.

Synthesis and self-assembly of high grafting density core-shell bottlebrush polymer with amphiphilic side chain

Self-assembly of bottlebrush polymers are widely studied in photonic bandgap materials, biomedical materials and nanomaterial with different structures. In this work, high grafting density bottlebrush polymer with amphiphilic QPDMA[FeCl4]-b-PS side chains grafting on every carbon atom of the backbone are prepared via grafting from approach. The para-isocyanobenzoate monomer modified with chain transfer agent (CTA) is designed and synthesized to prepared polymer backbones with CTA grafting on each atoms. The core-shell bottlebrush block copolymer is prepared by sequential reversible addition-fragmentation chain transfer polymerization of dimethylaminoethyl methacrylate and styrene. The inner core follows quaternization and ion exchange to form water soluble QPDMA[FeCl4] magnetic block. The resulting core-shell bottlebrush magnetic polymer (PCN-g-[QPDMA[FeCl4]-b-PS]) self-assembles into nanowires with magnetic QPDMA[FeCl4] as core and PS as corona in the shell selected solvent dichloromethane, the length of nanowires increases with self-assembly time. While it self-assembles into nanoparticle clusters in core selected aqueous solution. And, the thermal and magnetic properties are affected by the self-assembly morphology. Especially, the as prepared PCN-g-[QPDMA[FeCl4]-b-PS] and the nanoparticles cluster self-assembly are paramagnetic, but the nanowire self-assembly is superparamagnetic.

Efficient synthesis of bottle-brush polymers enabled by selective photoactivation strategy in NIR-induced PET-RAFT polymerization

Efficient synthesis of bottle-brush polymers enabled by selective photoactivation strategy in NIR-induced PET-RAFT polymerization

Elastomers based on polynorbornene with polar polysiloxane brushes for soft transducer applications

Elastomers based on cross‐linked bottlebrush polymers combine an extreme softness at low strains with a strain‐stiffening effect, which makes them attractive as active components in dielectric elastomer actuators (DEA). Their main disadvantage concerns the small relative permittivity, which lies in the range of 3.5, requiring relatively high driving voltage in actuators. We synthesized a bottlebrush polymeric elastomer with polar brushes, which exhibit an enhanced dielectric permittivity of 4.4. Anionic ring‐opening polymerization of a polar cyclosiloxane afforded telechelic polar brushes, while ring‐opening polymerization of a norbornene macromonomer gave a bottlebrush polymer which was cross‐linked to elastomers by a thiol‐ene reaction. Elastomers with a small elastic modulus below 100 kPa, strain at break exceeding 100%, attractive elasticity, and small mechanical loss factors (tanδ) were achieved. Temperature‐dependent impedance measurements revealed a transition temperature of ‐95 °C and an interfacial polarization. The multigram scale synthesis demonstrates the potential for scaling up, which opens the door to broader applications of these materials beyond actuators, such as capacitive sensors, batteries, and electroluminescent devices. Notably, these devices operate at extremely low voltages where the dielectric breakdown does not limit their functionality, but still, the softness and the increased dielectric permittivity are a plus.

Layer‐by‐Layer Deposition of a Polycationic Bottlebrush Polymer with Hyaluronic Acid Reveals Unusual Assembly Mechanism and Selective Effect on Cell Adhesion and Fate

AbstractThis study provides a detailed molecular mechanism of the layer‐by‐layer (LbL) film formation process involving BB polymers. The roles of adsorbed and non‐adsorbed chain segments during the layer buildup are revealed by employing surface force apparatus (SFA) and atomic force microscopy (AFM) to probe critical aspects such as surface coverage, polymer conformation at the surface, adhesive properties, and morphology after each layer deposition. The results show that the thickness, nanomechanical properties, and surface chemistry of the nanofilms are significantly influenced by the number of layers. All these cues have an important impact on cell behavior when employed as coatings for culture substrates. The evidence is shown that cells respond very differently to these cues and exhibit behavior that goes from superproliferation down to accelerated death.

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.