Bottlebrush Block Copolymers Research Articles

Programmable Reconfiguration of Supramolecular Bottlebrush Block Copolymers: From Solution Self-Assembly to Co-Crystallization-Assistant Self-Assembly.

Achieving structural reconfiguration of supramolecular bottlebrush block copolymers toward topological engineering is of particular interest but challenging. Here, we address the creation of supramolecular architectures to discover how assembled topology influences the structured aggregates, combining hydrogen-bonded (H-bonded) bottlebrush block copolymers and electrostatic interaction induced polymer/inorganic eutectics. We first design H-bonding linear-brush block copolymer P(NBDAP-co-NBC)-b-P(NBPEO), bearing linear block P(NBDAP-co-NBC) (poly(norbornene-terminated diaminopyridine-co-norbornene-terminated hexane)) with pendant H-bonding DAP (diaminopyridine) motifs, and PEO (poly(ethylene oxide)) densely grafted P(NBPEO) brush block. Thanks to H-bonding association between DAP and thymine (Thy), incorporation of Thy-functionalized polystyrene (Thy-PS65) enables solution self-assembly and formation of H-bonded bottlebrush block copolymers, generating augmented nanospheres with increasing Thy-PS65 amount. Noteworthy that integration of inorganic cluster silicotungstic acid (STA) to P(NBC-co-NBDAP)-b-P(NBPEO), endows the formation of PEO/STA eutectic core. Therefore, co-crystallization-assistant self-assembly at the interfaces of polymeric, inorganic and supramolecular chemistry is realized, reflecting multi-stage morphology transformation from hexagonal platelets, needle-like, curved rod-like micelles, finally to end-to-end closed rings, by gradually increasing Thy-PS65 while fixing STA content. Interestingly, such solution self-assembly to co-crystallization-assistant self-assembly strategy not only endows unique nanostructure transition, also induce in-to-out reconfiguration of PS domains. These findings clearly provide unique methodology towards programmable fabrication of geometrical objects promising in smart materials.

Crystallization-Driven Controlled 2D Self-Assemblies via Aqueous RAFT Emulsion Polymerization.

Aqueous emulsion polymerization is a robust technique for preparing nanoparticles of block copolymers; however, it typically yields spherical nanoassemblies. The scale preparation of nanoassemblies with nonspherical high-order morphologies is a challenge, particularly 2D core-shell nanosheets. In this study, the polymerization-induced self-assembly (PISA) and crystallization-driven self-assembly (CDSA) are combined to demonstrate the preparation of 2D nanosheets and their aggregates via aqueous reversible addition-fragmentation chain transfer (RAFT) emulsion polymerization. First, the crucial crystallizable component for CDSA, hydroxyethyl methacrylate polycaprolactone (HPCL) macromonomer is synthesized by ring opening polymerization (ROP). Subsequently, the RAFT emulsion polymerization of HPCL is conducted to generate crystallizable nanomicelles by a grafting-through approach. This PISA process simultaneously prepared spherical latices and bottlebrush block copolymers comprising poly(N',N'-dimethylacrylamide)-block-poly(hydroxyethyl methacrylate polycaprolactone) (PDMA-b-PHPCL). The latexes are now served as seeds for inducing the formation of 2D hexagonal nanosheets, bundle-shaped and flower-like aggregation via the CDSA of PHPCL segments and unreacted HPCL during cooling. Electron microscope analysis trace the morphology evolution of these 2D nanoparticles and reveal that an appropriate crystallized component of PHPCL blocks play a pivotal role in forming a hierarchical structure. This work demonstrates significant potential for large-scale production of 2D nanoassemblies through RAFT emulsion polymerization.

Programmable Reconfiguration of Supramolecular Bottlebrush Block Copolymers: From Solution Self‐Assembly to Co‐Crystallization‐Assistant Self‐Assembly

Achieving structural reconfiguration of supramolecular bottlebrush block copolymers toward topological engineering is of particular interest but challenging. Here, we address the creation of supramolecular architectures to discover how assembled topology influences the structured aggregates, combining hydrogen‐bonded (H‐bonded) bottlebrush block copolymers and electrostatic interaction induced polymer/inorganic eutectics. We first design H‐bonding linear‐brush block copolymer P(NBDAP‐co‐NBC)‐b‐P(NBPEO), bearing linear block P(NBDAP‐co‐NBC) (poly(norbornene‐terminated diaminopyridine‐co‐norbornene‐terminated hexane)) with pendant H‐bonding DAP (diaminopyridine) motifs, and PEO (poly(ethylene oxide)) densely grafted P(NBPEO) brush block. Thanks to H‐bonding association between DAP and thymine (Thy), incorporation of Thy‐functionalized polystyrene (Thy‐PS) enables solution self‐assembly and formation of H‐bonded bottlebrush block copolymers, generating augmented nanospheres with increasing Thy‐PS amount. Noteworthy that integration of inorganic cluster silicotungstic acid (STA) to P(NBC‐co‐NBDAP)‐b‐P(NBPEO), endows the formation of PEO/STA eutectic core. Therefore, co‐crystallization‐assistant self‐assembly at the interfaces of polymeric, inorganic and supramolecular chemistry is realized, reflecting multi‐stage morphology transformation from hexagonal platelets, needle‐like, curved rod‐like micelles, finally to end‐to‐end closed rings, by gradually increasing Thy‐PS while fixing STA content. Interestingly, such solution self‐assembly to co‐crystallization‐assistant self‐assembly strategy not only endows unique nanostructure transition, also induce in‐to‐out switch of PS domains. These findings clearly provide unique methodology towards programmable fabrication of geometrical objects promising in smart materials.

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.

Modifying the Backbone Chemistry of PEG-Based Bottlebrush Block Copolymers for the Formation of Long-Circulating Nanoparticles.

Nanoparticle physicochemical properties have received great attention in optimizing the performance of nanoparticles for biomedical applications. For example, surface functionalization with small molecules or linear hydrophilic polymers is commonly used to tune the interaction of nanoparticles with proteins and cells. However, it is challenging to control the location of functional groups within the shell for conventional nanoparticles. Nanoparticle surfaces composed of shape-persistent bottlebrush polymers allow hierarchical control over the nanoparticle shell but the effect of the bottlebrush backbone on biological interactions is still unknown. The synthesis is reported of novel heterobifunctional poly(ethylene glycol) (PEG)-norbornene macromonomers modified with various small molecules to form bottlebrush polymers with different backbone chemistries. It is demonstrated that micellar nanoparticles composed of poly(lactic acid) (PLA)-PEG bottlebrush block copolymer (BBCP) with neutral and cationic backbone modifications exhibit significantly reduced cellular uptake compared to conventional unmodified BBCPs. Furthermore, the nanoparticles display long blood circulation half-lives of ≈22hours and enhanced tumor accumulation in mice. Overall, this work sheds light on the importance of the bottlebrush polymer backbone and provides a strategy to improve the performance of nanoparticles in biomedical applications.

Bottlebrush Block Copolymers at the Interface of Immiscible Liquids: Adsorption and Lateral Packing.

Amphiphilic bottlebrush block copolymers (BBCPs), having a hydrophilic bottlebrush polymer (BP) linked covalently to a hydrophobic BP, were found to segregate to liquid-liquid interfaces to minimize the free energy of the system. The key parameter influencing the outcome of the experiments is the ratio between the degree of polymerization of the backbone (NBB) and that of the side-chain brushes (NSC). Specifically, a spherical, star-like configuration results when NBB < NSC, while a cylindrical, bottlebrush-like shape is preferred when NBB > NSC. Dynamic interfacial tension (γ) and fluorescence recovery after photobleaching (FRAP) measurements show that the BBCP configuration influences the areal density and in-plane diffusion at the fluid interface. The characteristic relaxation times associated with BBCP adsorption (τA) and reorganization (τR) were determined by fitting time-dependent interfacial tension measurements to a sum of two exponential relaxation functions. Both τA and τR initially increased with NBB up to 92 repeat units, due to the larger hydrodynamic radius in solution and slower in-plane diffusivity, attributed to a shorter cross-sectional diameter of the side-chains near the block junction. This trend reversed at NBB = 190, with shorter τA and τR attributed to increased segregation strength and exposure of the bare water/toluene interface due to tilting and/or wiggling of the backbone chains, respectively. The adsorption energy barrier decreased with higher NBB, due to a reduced BBCP packing density at the fluid interface. This study provides fundamental insights into macromolecular assembly at fluid interfaces, as it pertains to unique bottlebrush block architectures.

Host-Guest Interaction Mediated Interfacial Co-Assembly of Cyclodextrin and Bottlebrush Surfactants for Precisely Tunable Photonic Supraballs.

Investigations of host-guest interactions at water-oil (w/o) interfaces are limited in single emulsion systems producing simple self-assembled objects with limited uses. Here, within hierarchically ordered water-in-oil-in-water (w/o/w) multiple emulsion droplets, interfacial self-assembly of (polynorbornene-graft-polystyrene)-block-(polynorbornene-graft-polyethylene glycol) (PNPS-b-PNPEG) bottlebrush block copolymers can be precisely controlled through host-guest interactions. α-Cyclodextrin (α-CD) in the aqueous phase can thread onto PEG side chains of the bottlebrush surfactants adsorbed at the w/o interface, leading to dehydration and collapsed chain conformation of the PEG block. Consequently, spherical curvature of the w/o internal droplets increases with the increased asymmetry of the bottlebrush molecules, producing photonic supraballs with precisely tailored structural parameters as well as photonic bandgaps. This work provides a simple but highly effective strategy for precise manipulation of complex emulsion systems applicable in a variety of applications, such as photonic pigments, cosmetic products, pesticides, artificial cells, etc.

Synthesis and self-assembly of bottlebrush block copolymer electrolytes for solid-state supercapacitors

All-solid-state supercapacitors have attracted increasing attention in recent decades owing to rapid advancements in safe, flexible, and wearable energy storage devices. This study demonstrates a bottlebrush block copolymer electrolyte consisting of poly(styrene-b-butadiene-b-styrene)-g-poly(ethylene glycol) behenyl ether methacrylate (SBS-g-PEGBEM) (simply SgP) for all-solid-state supercapacitors. Due to the adhesive nature and robust mechanical properties of SgP film, devices can be manufactured without the need for separators or packaging. The nonpolar SBS domains serve as scaffolds within the polymer matrix, while the polar PEGBEM domains offer interactive sites for polar ionic liquids (ILs). The synergy between precisely defined nanostructures and the subsequent well-dissociated ions enhances efficient ion transport through the ionic channels. As a result, the supercapacitor with SgP/IL electrolyte exhibits remarkable electrochemical performance. This includes a wide potential window of 2.4 V, an ionic conductivity of 2.4 mS cm−1, and maximum energy density and power density of 28.1 Wh kg−1 and 3080 W kg−1, respectively. The supercapacitor also demonstrates high cycle stability with 87.7 % capacitance retention after 5,000 cycles. The positive impact of the PEGBEM side chains is investigated via molecular dynamics simulations. Thus, this study presents a novel strategy for solid-state electrolytes, offering potential advancements in next-generation energy storage devices.

Photonic Pigments of Polystyrene-block-Polyvinylpyrrolidone Bottlebrush Block Copolymers via Sustainable Organized Spontaneous Emulsification.

Prior studies on photonic pigments of amphiphilic bottlebrush block copolymers (BBCPs) through an organized spontaneous emulsification (OSE) mechanism have been limited to using polyethylene glycol (PEG) as the hydrophilic side chains and toluene as the organic phase. Herein, a family of polystyrene-block-polyvinylpyrrolidone (PS-b-PVP) BBCPs are synthesized with PVP as the hydrophilic block. Biocompatible and sustainable anisole is employed for dissolving the obtained BBCPs followed by emulsification of the solutions in water. Subsequent evaporation of oil-in-water emulsion droplets triggers the OSE mechanism, producing thermodynamically stable water-in-oil-in-water (w/o/w) multiple emulsions with uniform and closely packed internal droplet arrays through the assembly of the BBCPs at the w/o interface. Upon solidification, the homogeneous porous structures are formed within the photonic microparticles that exhibit visible structural colors. The pore diameter is widely tunable (150∼314 nm) by changing the degree of polymerization of BBCP (69∼110), resulting in tunable colors across the whole visible spectrum. This work demonstrates useful knowledge that OSE can be generally used in the fabrication of ordered porous materials with tunable internal functional groups, not only for photonic applications, but also offers a potential platform for catalysis, sensing, separation, encapsulation, etc.

Mesoporous Single Atom-Cluster Fe-N/C Oxygen Evolution Electrocatalysts Synthesized with Bottlebrush Block Copolymer-Templated Rapid Thermal Annealing.

Current electrocatalysts for oxygen evolution reaction (OER) are either expensive (such as IrO2, RuO2) or/and exhibit high overpotential as well as sluggish kinetics. This article reports mesoporous earth-abundant iron (Fe)-nitrogen (N) doped carbon electrocatalysts with iron clusters and closely surrounding Fe-N4 active sites. Unique to this work is that the mechanically stable mesoporous carbon-matrix structure (79 nm in pore size) with well-dispersed nitrogen-coordinated Fe single atom-cluster is synthesized via rapid thermal annealing (RTA) within only minutes using a self-assembled bottlebrush block copolymer (BBCP) melamine-formaldehyde resin composite template. The resulting porous structure and domain size can be tuned with the degree of polymerization of the BBCP backbone, which increases the electrochemically active surface area and improves electron transfer and mass transport for an effective OER process. The optimized electrocatalyst shows a required potential of 1.48 V (versus RHE) to obtain the current density of 10 mA/cm2 in 1 M KOH aqueous electrolyte and a small Tafel slope of 55 mV/decade at a given overpotential of 250 mV, which is significantly lower than recently reported earth-abundant electrocatalysts. Importantly, the Fe single-atom nitrogen coordination environment facilitates the surface reconstruction into a highly active oxyhydroxide under OER conditions, as revealed by X-ray photoelectron spectroscopy and in situ Raman spectroscopy, while the atomic clusters boost the single atoms reactive sites to prevent demetalation during the OER process. Density functional theory (DFT) calculations support that the iron nitrogen environment and reconstructed oxyhydroxides are electrocatalytically active sites as the kinetics barrier is largely reduced. This work has opened a new avenue for simple, rapid synthesis of inexpensive, earth-abundant, tailorable, mechanically stable, mesoporous carbon-coordinated single-atom electrocatalysts that can be used for renewable energy production.

Direct-ink-write cross-linkable bottlebrush block copolymers for on-the-fly control of structural color

Additive manufacturing capable of controlling and dynamically modulating structures down to the nanoscopic scale remains challenging. By marrying additive manufacturing with self-assembly, we develop a UV (ultra-violet)-assisted direct ink write approach for on-the-fly modulation of structural color by programming the assembly kinetics through photo-cross-linking. We design a photo-cross-linkable bottlebrush block copolymer solution as a printing ink that exhibits vibrant structural color (i.e., photonic properties) due to the nanoscopic lamellar structures formed post extrusion. By dynamically modulating UV-light irradiance during printing, we can program the color of the printed material to access a broad spectrum of visible light with a single ink while also creating color gradients not previously possible. We unveil the mechanism of this approach using a combination of coarse-grained simulations, rheological measurements, and structural characterizations. Central to the assembly mechanism is the matching of the cross-linking timescale with the assembly timescale, which leads to kinetic trapping of the assembly process that evolves structural color from blue to red driven by solvent evaporation. This strategy of integrating cross-linking chemistry and out-of-equilibrium processing opens an avenue for spatiotemporal control of self-assembled nanostructures during additive manufacturing.

Hydrolysis-Induced Morphology Evolution of Linear and Bottlebrush Block Copolymers in Thin Films with Acid Vapor or Photoacid Generators

Hydrolysis-Induced Morphology Evolution of Linear and Bottlebrush Block Copolymers in Thin Films with Acid Vapor or Photoacid Generators

Self‐assembly and degradation of photolabile diblock bottlebrushes

AbstractAqueous self‐assembly of amphiphilic block copolymers form diverse nanostructured morphologies depending on block volume fraction and solvophilicity. Stimuli‐responsive motifs have been combined with self‐assembled micelles to afford spatiotemporal, on‐demand encapsulation and payload release. However, the role of modular polymer architecture (i.e., bottlebrushes) in stimuli‐responsive aqueous self‐assembly is not fully understood. The synthesis, aqueous self‐assembly, and photoirradiation of photolabile, amphiphilic bottlebrush block copolymers is presented herein. Specifically, the efficient photoscission of o‐nitrobenzene motifs at the junction of a poly(norbornene o‐nitrobenzene polystyrene)‐block‐poly(norbornene polyethylene glycol) diblock bottlebrush side chain and backbone cleaved away hydrophobic polystyrene side chains and artificially increased the volume fraction of poly(ethylene glycol) (fPEG). In doing so, self‐assembled micelles readily degrade to micelle‐to‐micelle and micelle‐to‐aggregate structures after photoirradiation. Finally, this bottlebrush micelle system is used to demonstrate the efficient encapsulation and stimuli‐responsive release of Nile Red that is monitored by fluorescence spectroscopy and dynamic light scattering. The contribution of this work expands the utility of amphiphilic bottlebrush systems as highly efficient and responsive, hierarchically assembled nanomaterials.

Nanoscale Surface Topography of Polyethylene Glycol-Coated Nanoparticles Composed of Bottlebrush Block Copolymers Prolongs Systemic Circulation and Enhances Tumor Uptake.

Improving the performance of nanocarriers remains a major challenge in the clinical translation of nanomedicine. Efforts to optimize nanoparticle formulations typically rely on tuning the surface density and thickness of stealthy polymer coatings, such as poly(ethylene glycol) (PEG). Here, we show that modulating the surface topography of PEGylated nanoparticles using bottlebrush block copolymers (BBCPs) significantly enhances circulation and tumor accumulation, providing an alternative strategy to improve nanoparticle coatings. Specifically, nanoparticles with rough surface topography achieve high tumor cell uptake in vivo due to superior tumor extravasation and distribution compared to conventional smooth-surfaced nanoparticles based on linear block copolymers. Furthermore, surface topography profoundly impacts the interaction with serum proteins, resulting in the adsorption of fundamentally different proteins onto the surface of rough-surfaced nanoparticles formed from BBCPs. We envision that controlling the nanoparticle surface topography of PEGylated nanoparticles will enable the design of improved nanocarriers in various biomedical applications.

Architectural control over morphologies of bottlebrush block copolymer superstructures

The morphology of superstructures formed by bottlebrush block copolymers in the melt can be tuned by changing the side chain length or/and their grafting density at constant volume fractions of the blocks. This feature enables fabrication of microphase separated bulk structures and mesoporous materials thereof with spherical or cylindrical domains (precursors of the mesopores), with high porosity unattainable for materials produced from conventional linear block copolymers. These paradigms are proven by DPD simulations that allow constructing morphological phase diagrams of the melt of block copolymers comprising one linear and one bottlebrush block and comparing the simulation results to the predictions of the mean field analytical theory. While the binodal lines separating the stability regions of spherical and cylindrical domains predicted by the theory perfectly match the simulation results, the simulation indicates appearance of a gyroid phase around the theoretical binodal separating the stability ranges of cylinders and lamellae. The results of our work provide guidelines for macromolecular design of novel composite and mesoporous materials with a wide spectrum of potential applications.

Topological structure-induced self-assembly of highly asymmetric PLLA-b-QPDMAEMA block copolymers in solution: Linear versus bottlebrush

During self-assembly process of block copolymers in solution, when the volume fraction of solvophobic blocks is too low, usually below 10%, the copolymers generally tend to dissolve, which has caused trouble. Herein, a bottlebrush block copolymer composed of poly(L-lactic acid) (PLLA) and quaternized poly(N,N-dimethylaminoethylmethacrylate) (QPDMAEMA), whose content of solvophobic block PLLA was below 2 wt%, was prepared. Owing to the rigidity derived from the advantages of topological structure of bottlebrush-like molecules, the interfacial curvature between two incompatible microphases is maintained, and this highly asymmetric copolymer unexpectedly spontaneously assembles into uniform spherical micelles with diameters of tens of nanometers. The morphology of aggregates was verified by dynamic light scattering, transmission electron microscopy and atomic force microscope. This study expands the understanding of traditional theory about copolymers self-assembly in solution, which helps to design, prepare, and apply polymer micelles with various structures from a broader perspective.

Recent advances in block copolymer self‐assembly: From the lowest to the highest

AbstractA perspective is presented on recent developments in block copolymers (BCPs), capable of forming sub‐10 nm nanostructures and bottlebrush block copolymers (BBCPs), capable of forming supra‐100 nm nanostructures. Over the last few decades, BCP research has emphasized pattern miniaturization for application in next‐generation lithography tools in the semiconductor industry. The first part focuses on the recent efforts that investigated high‐χ linear BCPs evolved from conventional poly(styrene‐b‐methyl methacrylate) (PS‐b‐PMMA) pairs. Recently, novel BCP structures capable of forming nanostructures with significant periodicities for controlling visible light have gained considerable attention. The second part reviews the literature on BBCPs that exhibit the potential to create supra‐100 nm nanostructures. Finally, the future aspect on BCP lithography is discussed.

Rapid Fabrication of Metal-Nitrogen Doped Ordered Large-Pore Mesoporous Carbons Using Bottle Brush Block Copolymer Templates for Highly Efficient Water Oxidation

We describe a simple and fast method to fabricate ordered mesoporous carbon materials for electrocatalyst applications. Over the past decades, mesoporous carbons have been widely applied for photonics, energy storage devices, separation technologies, and electrocatalyst applications.1 These materials can be inexpensively prepared and have good electrical conductivity and chemical and mechanical stability. Linear block copolymer templates or polystyrene beads are widely used to create porosity in carbon materials. However, the existing methods have limitations in accessing a wide range of pore dimensions and porosities. Recently bottlebrush block copolymer (BBCP) templates have drawn significant attention for producing ordered carbon materials with ordered pores with tunable diameters ranging from 15 to 100 nm, which facilitates ion diffusion and mass transport during the electrochemical processes while maintaining high surface area.2 BBCP-derived large-pore mesoporous carbons are potential candidates for electrocatalyst applications. While water splitting produces hydrogen gas, oxygen gas simultaneously evolves via an oxygen evolution reaction (OER) or water oxidation.3 In OER, oxygen-oxygen bond formation involves a complicated proton-coupled mechanism. For this reason, most OER electrocatalysts require a high overpotential to overcome the sluggish kinetic energy barrier to generate oxygen gas during water oxidation, which is often associated with high costs and poor availability.4 Hence, developing a low-cost, highly efficient OER catalyst is necessary to lower the overpotential.Herein, we demonstrate efficient metal-nitrogen-doped mesoporous carbon materials using a simple and fast rapid thermal annealing (RTA) process. BBCP/precursor self-assembly, carbonization and template removal using the RTA process (high heating rate up to 100 °C / sec) occurred within a few minutes. The resulting electrocatalysts were characterized by small-angle X-ray scattering (SAXS), X-ray photoelectron spectroscopy (XPS), and Raman spectroscopy. We used nickel foam as a support under basic conditions for electrochemical evaluation. The results showed ample catalytic active sites and an overpotential of <260 mV along with a low Tafel value of 55 mV/decade at a current density of 10 mA/cm2. Our findings can have significant implications for designing various metal-doped mesoporous carbon materials for energy and environmental applications, specifically metal-air batteries and CO2 reduction. References H.-F. Fei, W. Li, S. Nuguri, H.-J. Yu, B. M. Yavitt, W. Fan and J. J. Watkins, Chemistry of Materials, 32, 6055 (2020).H.-F. Fei, B. M. Yavitt, S. Nuguri, Y.-G. Yu and J. J. Watkins, Macromolecules, 54, 10943 (2021).D. Saha, V. Patel, P. R. Selvaganapathy and P. Kruse, Nanoscale Advances, 4, 125 (2022).H. Zhou, F. Yu, J. Sun, R. He, S. Chen, C.-W. Chu and Z. Ren, Proceedings of the National Academy of Sciences, 114, 5607 (2017).

Synthesis of Bottlebrush Polymers by Z-/E-Specific Living Ring-Opening Metathesis Polymerization, Exhibiting Different Thermal Properties.

Synthesis of bottlebrush polymers (BBPs) and block copolymers by Z-/E-specific living ring-opening metathesis polymerization (ROMP) of N-substituted-norbornene-2,3-dicarboximides containing long alkyl chains (n-octadecyl, n-tetradecyl, etc.) has been attained by the vanadium(V)-alkylidene catalysts V(CHSiMe3)(ArN)[OC(CF3)3](PMe3)2 [Ar = 2,6-Cl2C6H3 (1), C6F5 (2)] and V(CHSiMe3)(2,6-F2C6H3N)(OC6Cl5)(PMe3)2 (3). The ROMPs using 1 afforded the BBPs with exclusive Z selectivity (98 to >99% cis) even at high temperature (up to 80 °C) in the presence of PMe3, whereas the ROMPs using 3 gave the BBPs with high E selectivity (90% trans). These ROMPs proceeded in a living manner (even at 80 °C using 1), affording various (amphiphilic) block copolymers while maintaining high E/Z selectivity. The resultant Z- and E-selective BBPs especially prepared from N-(n-octadecyl)norbornene-2,3-dicarboximide possessed different melting temperatures due to different degrees of interpolymer alkyl side chain interaction (side chain crystallization).

Self-Assembly and In Situ Quaternization of Triblock Bottlebrush Block Copolymers via Organized Spontaneous Emulsification for Effective Loading of DNA.

Microspheres bearing large pores are useful in the capture and separation of biomolecules. However, pore size is typically poorly controlled, leading to disordered porous structures with limited performances. Herein, ordered porous spheres with a layer of cations on the internal surface of the nanopores are facilely fabricated in a single step for effective loading of DNA bearing negative charges. Triblock bottlebrush copolymers (BBCPs), (polynorbornene-g-polystyrene)-b-(polynorbornene-g-polyethylene oxide)-b-(polynorbornene-g-bromoethane) (PNPS-b-PNPEO-b-PNBr), are designed and synthesized for fabrication of the positively charged porous spheres through self-assembly and in situ quaternization during an organized spontaneous emulsification (OSE) process. Pore diameter as well as charge density increase with the increase of PNBr content, resulting in a significant increase of loading density from 4.79 to 22.5ngµg-1 within the spheres. This work provides a general strategy for efficient loading and encapsulation of DNA, which may be extended to a variety of different areas for different real applications.