Bottlebrush Block Copolymers Research Articles

Enhancing ionic conductivity in tablet–bottlebrush block copolymer electrolytes with well-aligned nanostructures via solvent vapor annealing

Solvent vapor annealing was employed to obtain tablet–bottlebrush block copolymer electrolytes (BCPEs) with well-aligned lamellar nanostructures stable at high temperatures above 200 °C. The alignment greatly enhances the ionic conductivity of the BCPE, with value reaching 2.19 mS cm−1 at 200 °C.

Large-Pore Ordered Mesoporous Turbostratic Carbon Films Prepared Using Rapid Thermal Annealing for High-Performance Micro-pseudocapacitors.

Carbonization by rapid thermal annealing (RTA) of precursor films structured by a brush block copolymer-mediated self-assembly enabled the preparation of large-pore (40 nm) ordered mesoporous carbon (MPC)-based micro-supercapacitors within minutes. The large pore size of the fabricated films facilitates both rapid electrolyte diffusion for carbon-based electric double-layer capacitors and conformal deposition of V2O5 without pore blockage for pseudocapacitors. The pores were templated using bottlebrush block copolymers (BBCPs) via cooperative assembly of phenol-formaldehyde resin to produce microphase-segregated carbon precursor films on a variety of substrates. Ultrafast RTA processing (∼50 °C/s) at elevated temperatures (up to 1000 °C) then generated stable, conductive, turbostratic MPC films, resolving a significant bottleneck in rapid fabrication. MPC prepared on stainless steel at 900 °C demonstrated exceptionally high areal and volumetric capacitances of 6.3 mF/cm2 and 126 F/cm3 (at 0.8 mA/cm2 using 6 M KOH as the electrolyte), respectively, and 91% capacitance retention after 10,000 galvanostatic charge/discharge cycles. Post-RTA conformal V2O5 deposition yielded pseudocapacitors with 10-fold increase in energy density (20 μW h cm-2 μm-1) without adversely affecting the high power density (450 μW cm-2 μm-1). The use of RTA coupled with BBCP templating opens avenues for scalable, rapid fabrication of high-performance carbon-based micro-pseudocapacitors.

Janus Photonic Microspheres with Bridged Lamellar Structures via Droplet-Confined Block Copolymer Co-Assembly.

Artificial self-assembly systems typically exhibit limited capability in creating nature-inspired complex materials with advanced functionalities. Here, an effective co-assembly strategy is demonstrated for the facile creation of complex photonic structures with intriguing light reflections. Two different lipophilic and amphiphilic bottlebrush block copolymers (BCPs) are placed within shrinking droplets to enable a cooperative working mechanism of microphase segregation and organized spontaneous emulsification, respectively. Layer assemblies of the lipophilic BCP and uniform water nanodroplets stabilized by the bottlebrush surfactant are both generated, and co-assembled into a bridged lamellar structure with the alternating arrangement of layers and closely packed nanodroplet arrays. Janus microspheres with diverse dual optical characteristics are successfully fabricated, and reflected wavelengths of light are highly tunable simply by changing the formulation or molecular weight of BCP.

Janus Photonic Microspheres with Bridged Lamellar Structures via Droplet‐Confined Block Copolymer Co‐Assembly

AbstractArtificial self‐assembly systems typically exhibit limited capability in creating nature‐inspired complex materials with advanced functionalities. Here, an effective co‐assembly strategy is demonstrated for the facile creation of complex photonic structures with intriguing light reflections. Two different lipophilic and amphiphilic bottlebrush block copolymers (BCPs) are placed within shrinking droplets to enable a cooperative working mechanism of microphase segregation and organized spontaneous emulsification, respectively. Layer assemblies of the lipophilic BCP and uniform water nanodroplets stabilized by the bottlebrush surfactant are both generated, and co‐assembled into a bridged lamellar structure with the alternating arrangement of layers and closely packed nanodroplet arrays. Janus microspheres with diverse dual optical characteristics are successfully fabricated, and reflected wavelengths of light are highly tunable simply by changing the formulation or molecular weight of BCP.

Surface Topography of Polyethylene Glycol Shell Nanoparticles Formed from Bottlebrush Block Copolymers Controls Interactions with Proteins and Cells.

Although poly(ethylene glycol) (PEG) is commonly used in nanoparticle design, the impact of surface topography on nanoparticle performance in biomedical applications has received little attention, despite showing significant promise in the study of inorganic nanoparticles. Control of the surface topography of polymeric nanoparticles is a formidable challenge due to the limited conformational control of linear polymers that form the nanoparticle surface. In this work, we establish a straightforward method to precisely tailor the surface topography of PEGylated polymeric nanoparticles based on tuning the architecture of shape-persistent amphiphilic bottlebrush block copolymer (BBCP) building blocks. We demonstrate that nanoparticle formation and surface topography can be controlled by systematically changing the structural parameters of BBCP architecture. Furthermore, we reveal that the surface topography of PEGylated nanoparticles significantly affects their performance. In particular, the adsorption of a model protein and the uptake into HeLa cells were closely correlated to surface roughness and BBCP terminal PEG block brush width. Overall, our work elucidates the importance of surface topography in nanoparticle research as well as provides an approach to improve the performance of PEGylated nanoparticles.

Enhancement of Red Thermally Assisted Fluorescence in Bottlebrush Block Copolymers

The morphology of a material used in organic electronics can be equally as important as the functional properties of its components. This is particularly true of polymers, which may be hierarchical...

Assembly of Bottlebrush Block Copolymers and Nanoparticles in Ultrathin Films: Effect of Substrate–Copolymer Interaction on the Nanocomposite Morphology

Assembly of Bottlebrush Block Copolymers and Nanoparticles in Ultrathin Films: Effect of Substrate–Copolymer Interaction on the Nanocomposite Morphology

Yielding Behavior of Bottlebrush and Linear Block Copolymers

Block copolymers can exhibit a pronounced yield stress, but the impact of molecular architecture, chemistry, and self-assembly on macroscopic rheology remains poorly understood. Here, we study the linear-viscoelastic and yield-stress fluid behavior of two architectures—bottlebrush copolymers (with statistical or blocky sequences) and linear diblocks—that self-assemble into body-centered cubic (BCC) spheres and hexagonally close-packed cylinders (HEX). The dynamic properties of these polymers were probed by oscillatory frequency and amplitude sweeps at temperatures well below the order–disorder transition (TODT) to furnish insights into the yielding transition. All BCC-forming polymers have a similar signature of yielding: smaller yield strains (γy,BCC ≈ 0.053 < γy,HEX ≈ 0.18), sharper solid–liquid transitions, and better reversibility than HEX. Statistical bottlebrushes show the most frequency-independent structural modulus (G0) and no signs of defect relaxation. A simple power-law relationship captures the dependence of the normalized structural modulus (G0/RT) on the inter-micelle distance (d) across different architectures and morphologies [G0/(RT) = 1.31 × 104 (nm2.6 mol/m3) d–2.6]. These studies establish quantitative structure–property relationships that are relevant in contemporary applications, for example, extrusion-based 3D printing.

Supersoft Elastic Bottlebrush Microspheres with Stimuli-Responsive Color-Changing Properties in Brine.

Solvent-free supersoft elastomer is highly desirable for building photonic structures with significant stimuli-responsive color changes. We report supersoft elastic porous microspheres with vivid structural colors obtained via self-assembly of amphiphilic bottlebrush block copolymers at the water/oil interface templated by ordered water-in-oil-in-water double emulsions. The porous structure is composed of cross-linked bottlebrush polydimethylsiloxane (PDMS) as the supersoft elastic skeleton and bottlebrush poly(ethylene oxide) (PEO) as the internal responsive layer. The obtained microspheres show large reversible volume changes through well-controlled dehydration or hydration of PEO in response to salt ions in an aqueous environment. As a result, full-spectrum colors are obtained dependent on different salt concentrations. In-situ observation of color reflection of a microsphere indicates a gradual structural transition from the outside to the inside corresponding to migration of water molecules and salt ions. Moreover, rod-like bottlebrush PEO exhibits an anion-induced salting-out behavior different from that of random coil polymers. The significantly responsive behaviors of bottlebrush block copolymer (BBCP) assemblies in the presence of salt ions primarily rely on the supersoft elastic skeleton of the porous structure, providing a facile route to the creation of stimuli-responsive photonic materials by low-cost self-assembly methods.

Rapid Responsive Mechanochromic Photonic Pigments with Alternating Glassy-Rubbery Concentric Lamellar Nanostructures.

Photonic pigment particles prepared via self-assembly have been suffering from their poor mechanical performances; i.e., they can easily be damaged and lose structural color under a compression force. This greatly limits their uses as mechanochromic pigments. Here, a nanoscale concentric lamellar structure of alternating glassy-rubbery microdomains is successfully created within photonic microparticles through a confined self-assembly and photo-cross-linking strategy. The glassy domain is composed of polystyrene, and cross-linked bottlebrush polydimethylsiloxane served as the supersoft elastic domain. The obtained photonic structure not only shows large deformation and visible color changes under a loaded compression force but also rapidly recovers to its original state in less than 1 s (∼0.16 s) upon unloading. Continuously loading-unloading micro compression test indicates that no obvious damage can be identified after 250 cycles, indicating the high durability of the pigments against deformation. These pigments with different reflected colors are simply obtained using bottlebrush block copolymer formulations with tunable weight percentages of polymer additives. The mechanical robust photonic pigments may be useful in many important applications.

Self-Assembly of Bottlebrush Block Copolymers in Selective Solvent: Micellar Structures.

Block copolymers comprising chemically different bottlebrush blocks can self-assemble in selective solvents giving rise to micellar-like solution nanostructures. The self-consistent field theoretical approach is used for predicting relation between architectural parameters of both bottlebrush blocks (polymerization degrees of the main and side chains, density of grafting of the side chains to the backbone) and structural properties of micelles as well as critical micelle concentration (CMC). As predicted by the theory, replacement of linear blocks by bottlebrush ones with the same degrees of polymerization results in a decrease in the micellar core size (in aggregation number) and extension of the corona, whereas the CMC increases. These theoretical findings are in good agreement with results of computer simulations.

Implicit Side-Chain Model and Experimental Characterization of Bottlebrush Block Copolymer Solution Assembly

Bottlebrush polymers are a class of macromolecules with linear backbones and densely grafted side chains, possessing unique physical properties due to strong steric interactions between the side ch...

Discovery and Insights into Organized Spontaneous Emulsification via Interfacial Self-Assembly of Amphiphilic Bottlebrush Block Copolymers

Since the first discovery of spontaneous emulsification, the process has remained uncontrollable for centuries leading to unstable emulsion droplets with limited uses. Herein, by in situ observatio...

PolyChemPrint: A hardware and software framework for benchtop additive manufacturing of functional polymeric materials

AbstractAdditive manufacturing (AM, 3D Printing) of hierarchical polymer structures for a targeted function represents a grand challenge in the field of polymer science and engineering. Because advanced functional materials often do not possess suitable mechanical and rheological properties for conventional fused deposition modeling, a key challenge that researchers face is in integrating custom deposition tool heads that enable printing of non‐filamentary materials while preserving synchrony with the motion axes. In this article, we demonstrate a highly versatile hardware and software platform for melt and solution‐phase benchtop AM and highlight patterning and post‐deposition processing of a series of non‐filament forming functional polymers, including PS‐b‐PLA bottlebrush block copolymers, semiconducting polymer DPP2T‐TT, conducting polymer PEDOT:PSS [poly(3,4‐ethylenedioxythiophene)‐poly(styrenesulfonate)], and an SiO2‐PE nanoporous polymer matrix composite. We present a free and open‐source Python module, PolyChemPrint, which serves as a research‐optimized AM control software. The cross‐platform (Windows/Linux) software is designed to be extremely flexible in terms the hardware that can be connected and a detailed user manual and developer guide are provided for use by researchers without extensive computer programming experience. Finally, we provide extensive details of the hardware used for operation of low‐ and high‐pressure pneumatic extruders and a laser module as rapidly interchangeable tool heads.

Precise Synthesis and Thin Film Self-Assembly of PLLA-b-PS Bottlebrush Block Copolymers.

The ability of bottlebrush block copolymers (BBCPs) to self-assemble into ordered large periodic structures could greatly expand the scope of photonic and membrane technologies. In this paper, we describe a two-step synthesis of poly(l-lactide)-b-polystyrene (PLLA-b-PS) BBCPs and their rapid thin-film self-assembly. PLLA chains were grown from exo-5-norbornene-2-methanol via ring-opening polymerization (ROP) of l-lactide to produce norbornene-terminated PLLA. Norbonene-terminated PS was prepared using anionic polymerization followed by a termination reaction with exo-5-norbornene-2-carbonyl chloride. PLLA-b-PS BBCPs were prepared from these two norbornenyl macromonomers by a one-pot sequential ring opening metathesis polymerization (ROMP). PLLA-b-PS BBCPs thin-films exhibited cylindrical and lamellar morphologies depending on the relative block volume fractions, with domain sizes of 46–58 nm and periodicities of 70–102 nm. Additionally, nanoporous templates were produced by the selective etching of PLLA blocks from ordered structures. The findings described in this work provide further insight into the controlled synthesis of BBCPs leading to various possible morphologies for applications requiring large periodicities. Moreover, the rapid thin film patterning strategy demonstrated (>5 min) highlights the advantages of using PLLA-b-PS BBCP materials beyond their linear BCP analogues in terms of both dimensions achievable and reduced processing time.

Self-Assembled Photonic Microsensors with Strong Aggregation-Induced Emission for Ultra-Trace Quantitative Detection.

Ultratrace quantitative detection based on fluorescence is highly desirable for many important applications such as environmental monitoring or disease diagnosis, which however has remained a great challenge because of limited and irregular fluorescence responses to analytes at ultralow concentrations. Herein the problem is circumvented via local enrichment and detection of analytes within a microsensor, that is, photonic porous microspheres grafted with aggregation-induced emission gens (AIEgens). The obtained microspheres exhibit dual structural and molecular functions, namely, bright structural colors and strong fluorescence. Large fluorescence quenching induced by nitrophenol compounds in an aqueous environment is observed at ultralow concentrations (10-12-10-8 mol/L), enabling quantitative detection at a ppb level (ng/L). This is achieved within a porous structure with good connectivity between the nanopores to improve analyte diffusion, an internal layer of poly(ethylene oxide) (PEO) for analyte enrichment via hydrogen bonding, and homogeneous distribution of AIEgens within the PEO layer for enhanced fluorescence quenching. The fluorescent porous microspheres can be readily obtained in a single step templated by well-ordered water-in-oil-in-water double emulsion droplets with AIE amphiphilic bottlebrush block copolymers as the effective stabilizer.

Bottlebrush Block Copolymer Assembly in Ultraconfined Films: Effect of Substrate Selectivity

Ultraconfined block copolymer films present nonbulk structures that are highly sensitive to film thickness and are strongly influenced by the wetting properties of the substrate. Here, we describe ...

Oxidation Control of Bottlebrush Molecular Conformation for Producing Libraries of Photonic Structures

AbstractSelf‐assembly is important for creating photonic structures and structural color is typically tunable by varying the size of building blocks, which are themselves obtained after time‐consuming chemical syntheses. The molecular conformation of bottlebrush block copolymers (BBCPs) in solution can be manipulated to create libraries of photonic structures. Amphiphilic BBCPs bearing oxidation‐responsive ferrocene groups on the hydrophilic block are used to fabricate porous particles via evaporation‐induced self‐assembly of water‐in‐oil‐in‐water (W/O/W) double emulsions stabilized by the BBCP surfactant. In situ oxidation of the ferrocene groups by hydrogen peroxide at the W/O interface leads to enhanced hydrophilicity, more hydration, and chain extension of the hydrophilic block. Consequently, larger internal water droplets are spontaneously formed, yielding larger pores within the microparticles. The pore diameter is readily tunable from 144 to 301 nm with a single BBCP, thereby generating full‐spectrum structural colors. This work provides a straightforward method for fabrication of libraries of photonic pigments in an easy and scalable manner.

Oxidation Control of Bottlebrush Molecular Conformation for Producing Libraries of Photonic Structures.

Self-assembly is important for creating photonic structures and structural color is typically tunable by varying the size of building blocks, which are themselves obtained after time-consuming chemical syntheses. The molecular conformation of bottlebrush block copolymers (BBCPs) in solution can be manipulated to create libraries of photonic structures. Amphiphilic BBCPs bearing oxidation-responsive ferrocene groups on the hydrophilic block are used to fabricate porous particles via evaporation-induced self-assembly of water-in-oil-in-water (W/O/W) double emulsions stabilized by the BBCP surfactant. In situ oxidation of the ferrocene groups by hydrogen peroxide at the W/O interface leads to enhanced hydrophilicity, more hydration, and chain extension of the hydrophilic block. Consequently, larger internal water droplets are spontaneously formed, yielding larger pores within the microparticles. The pore diameter is readily tunable from 144 to 301 nm with a single BBCP, thereby generating full-spectrum structural colors. This work provides a straightforward method for fabrication of libraries of photonic pigments in an easy and scalable manner.

Confinement and Processing Can Alter the Morphology and Periodicity of Bottlebrush Block Copolymers in Thin Films.

Bottlebrush block copolymers (BBCPs) are intriguing architectural variations on linear BCPs with highly tunable structure. Confinement can have a significant impact on polymer assembly, giving rise to changes in morphology, assembly kinetics, and properties like the glass transition. Given that confinement leads to significant changes in the persistence length of bottlebrush homopolymers, it is reasonable to expect that BBCPs will see significant changes in their structure and periodicity relative to the bulk morphology. Understanding how confinement influences assembly will be important for designing BBCPs for thin film applications including membranes, integrated photonic structures, and potentially BCP lithography. In order to study the effects of confinement on BBCP conformation and morphology, a blade coating was used to prepare films with continuous variation in film thickness. Unlike thin films of linear BCPs, islands/holes were not observed, and instead mixtures of parallel and perpendicular morphologies emerge after annealing. The lamellar periodicity (L0) of the morphologies is found to be thickness dependent, increasing L0 with decreasing film thickness for blade coated films. Films coated out of tetrahydrofuran (THF) resulted in a single well-defined lamellar periodicity, verified through atomic force microscopy (AFM) and grazing incidence small-angle X-ray scattering (GISAXS), which increases dramatically from the bulk value (30.6 nm) and continues to increase as the film thickness decreases. The largest observed L0 was 65.5 nm, and this closely approaches the estimated upper limit of 67 nm corresponding to a fully extended backbone in a bilayer arrangement. Films coated out of propylene glycol methyl ether acetate (PGMEA) resulted in a mixture of perpendicular lamellae and a smaller, likely cylindrical morphology. The lamellar portion of the film shows the same thickness dependence as the lamellae observed in the THF coated films. The scaling of the lamellar L0 with respect to film thickness follows predictions for confined semiflexible polymers with weak excluded volume interactions and can be related to models for confinement of DNA. Spin coated films shows the same reduction in periodicity, although at very different film thicknesses. This result suggests that the material has shallow free-energy barriers to transitioning between different L0 and morphologies, a property that could be taken advantage of for patterning diverse structures with a single material.