Article
Polymer Science
Minjoon Baek, Hanseok Kim, Jaeman J. Shin
Summary: Hierarchically structured polymeric colloids were rapidly produced by confined self-assembly of bottlebrush random copolymers in evaporative emulsion droplets. The internal structures of the particles developed instantaneously during the early stage of solvent evaporation due to the confinement effect and fast-assembling polymer architecture. Different particle morphologies were achieved by adjusting the volume fraction of copolymers.
Article
Polymer Science
Xi Chen, Zhangyan Chen, Li Ma
Summary: A general approach is proposed to synthesize large-scale multi-stimuli-responsive bottlebrush-colloid Janus nanoparticles (JNPs) by tuning the composition of a single-chain nanoparticle (SCNP). The starting SCNP is achieved by electrostatic-mediated intramolecular crosslinking and synchronous incorporation of metallic species. The inorganic/organic compositions of the crosslinked colloid can be broadly tuned by using different metallic precursors and free radical initiators. Additionally, various polymer brushes can be grafted onto the PVBC tail through atom-transfer radical polymerization (ATRP).
Article
Polymer Science
Gaohuai Mei, Yinan Zheng, Yeran Fu, Meng Huo
Summary: RAFT-mediated polymerization-induced self-assembly (PISA) was used to evaluate the self-assembly behavior of amphiphilic random bottlebrush copolymers (BBCPs). The PISA of these BBCPs resulted in the formation of spherical micelles, whose hydrodynamic size increased with the growth of the hydrophobic side-chains. The size of the micellar core was correlated with the chain length of the hydrophobic side-chains, revealing an increased segregation strength between the hydrophilic and hydrophobic chains with the backbone length of the BBCPs.
Article
Polymer Science
Zhen Dong, Wenjun Huang, Xiaoqing Liu, Feng Yu, Chuanjiang Long, Sitong Feng, Lang Luo, Zhong-Ren Chen
Summary: A poly(norbornene-graft-styrene) (PNB-g-PS) supported mono(phenoxy-imine) metal complex was developed for ethylene polymerization. The catalysts showed improved catalytic activities, with the highest activities of 369 and 461 kg PE mol(-1) h(-1) for Ti and Zr catalysts with cumyl group ligands. The obtained polyethylenes have high crystallinities and tunable molecular weights, while bimodal polyethylenes were successfully prepared by combining two different phenoxy-imine ligands in one pot.
Article
Polymer Science
Qingliang Song, Qingshu Dong, Ruiqi Liang, Yazhen Xue, Mingjiang Zhong, Weihua Li
Summary: We have used dissipative particle dynamics simulations to investigate the self-assembly of ABC-type bottlebrush copolymers (BBCPs). We have observed various hierarchical structures formed through phase separation between A and B/C-blocks and between B and C-blocks. The stable parameter regions of the ABC-type BBCPs are larger than those of ABC star copolymers, and some novel hierarchical structures can be formed. The rigidity of the backbone significantly affects the formation of the hierarchical structure in ABC-type BBCPs, favoring the normal arrangement of B-substructures to A-superstructures.
Article
Polymer Science
Shifeng Nian, Zhouhao Fan, Guillaume Freychet, Mikhail Zhernenkov, Stefanie Redemann, Li-Heng Cai
Summary: Research on architecturally semiflexible BCPs reveals that the traditional understanding of domain size limitations does not apply in this case. Experimental findings suggest previously unrecognized mechanisms for the self-assembly of complex BCPs, expanding our knowledge in this field.
Article
Polymer Science
Sunting Xuan, Xi Jiang, Nitash P. Balsara, Ronald N. Zuckermann
Summary: The research shows that through utilizing complementary molecular shapes, selective assembly between sequence-defined peptoids can be achieved. Peptoids with different overall molecular shapes were able to form crystalline nanosheets with the same lattice structure in aqueous solution.
Article
Polymer Science
Irina K. Goncharova, Rinat S. Tukhvatshin, Dmitry N. Kholodkov, Roman A. Novikov, Vitaliy I. Solodilov, Ashot V. Arzumanyan
Summary: A methodology for synthesizing a wide range of all-siloxane polymers is suggested, which are heat and frost-resistant. The physical properties of the products are not only determined by the macromolecular structure, but also by the type of peripheral substituents, leading to significant differences in viscosity.
MACROMOLECULAR RAPID COMMUNICATIONS
(2021)
Article
Polymer Science
Mingqiu Hu, Xindi Li, Javid Rzayev, Thomas P. Russell
Summary: This study synthesized densely grafted bottlebrush statistical copolymers (BSCPs) and bottlebrush block copolymers (BBCPs) by hydrolyzing PSM chains to PGM chains to increase the segmental interaction parameter chi. The self-assembly of BBCPs was found to be slower after hydrolysis, but by utilizing the pre-existing ordered lamellar morphology, high-chi BBCPs with long-range order were successfully achieved. Analysis of Porod scattering invariant showed deviations in the density of each phase for high-chi BBCPs due to the restrictions placed on the configuration of the brushes.
Article
Polymer Science
Joseph F. Hassler, Nicholas J. Van Zee, Adelyn A. Crabtree, Frank S. Bates, Benjamin J. Hackel, Timothy P. Lodge
Summary: This work presents a synthetic strategy for making grafted block polymers with poly(propylene oxide) and poly(ethylene oxide) side chains, known as bottlebrush analogues of poloxamers. The bottlebrush architecture results in higher critical micelle concentration compared to linear analogues, allowing the polymers to exist as unimers at higher molecular weights and concentrations in solution.
Article
Polymer Science
Dongwoo Kim, Juhyuk Do, Kyungho Kim, Yeonji Kim, Hana Lee, Bongkuk Seo, Wonjoo Lee, Heung Bae Jeon, Hong Y. Cho, Hyun-jong Paik
Summary: In this study, a vinyl-containing macroinimer was prepared in situ using sulfoxide chemistry, allowing for the one-pot synthesis of hyperbranched polymers with a tunable distance between branch points. This innovative strategy of utilizing sulfoxide-modified ATRP initiators shows great potential in the synthesis of advanced polymers.
Article
Polymer Science
Wei Wen, Aihua Chen
Summary: By intrachain photo-cross-linking of azobenzene-containing amphiphilic linear block copolymer precursors, photoresponsive liquid crystalline SCJNPs were constructed and their self-assembly behavior in solution was investigated. Non-spherical assemblies were obtained, including lamellae and tubes, under the effect of the liquid crystal driving force. Additionally, photoinduced morphological transformations were observed for assemblies with different azobenzene contents.
Article
Polymer Science
Xi Chen, Dong-Po Song, Yuesheng Li
Summary: This research demonstrates the stabilization of ordered water-in-oil-in-water multiple emulsions and the formation of ordered porous microparticles upon solidification through binary blends of different amphiphilic bottle-brush block copolymers (BBCPs) with varying molecular weights. By adjusting the relative ratio of the two different BBCPs, the spherical curvature of internal droplets can be controlled, resulting in precisely tunable colors in the visible spectrum.
Review
Nanoscience & Nanotechnology
Liam R. MacFarlane, Huda Shaikh, J. Diego Garcia-Hernandez, Marcus Vespa, Tomoya Fukui, Ian Manners
Summary: pi-Conjugated polymers exhibit diverse electronic and optical properties. This review discusses the preparation of self-assembled nanoparticles from these polymers and their applications in optoelectronics, biomedical imaging and therapy, photocatalysis, and sensing. The development of pi-conjugated polymers has opened up new possibilities for functional organic materials similar to inorganic semiconductors, with nanoparticles based on these polymers showing promise in various emerging applications.
NATURE REVIEWS MATERIALS
(2021)
Article
Polymer Science
Hua-Feng Fei, Benjamin M. Yavitt, Sravya Nuguri, Yong-Guen Yu, James J. Watkins
Summary: The synthesis of a bottlebrush statistical copolymer (BSCP) architecture and its role in directing molecular packing in the bulk state is reported in this study. The BSCP was prepared via one-pot ring-opening metathesis polymerization of norbornene-capped macromonomers with similar reactivities, leading to a near-random compositional profile of polystyrene (PS) and poly(dimethyl siloxane) (PDMS) side chains along the backbone. The self-assembly of BSCP yielded oriented lamellar morphologies over large areas after thermal annealing without external guiding, providing potential applications in directed self-assembly of device architectures.
Article
Chemistry, Multidisciplinary
Runze Liu, Zehao Sun, Hejin Huang, Jeremiah A. Johnson, Alfredo Alexander-Katz, Caroline A. Ross
Summary: Diblock Janus-type A-branch-B bottlebrush copolymers (di-JBBCPs) consist of a backbone with alternating A and B side chains, allowing for microphase separation perpendicular to the backbone. The self-assembly of di-JBBCPs was theoretically investigated using a reparametrized dissipative particle dynamics (DPD) model, and the results were compared with experimental data. The model showed good correspondence with the experimentally observed cylinder, gyroid, and lamellar morphologies, and predicted additional spherical phases, indicating the diversity of morphologies achievable with complex BCP molecular architectures.
Article
Nanoscience & Nanotechnology
Zehao Sun, Runze Liu, Tingyu Su, Hejin Huang, Ken Kawamoto, Ruiqi Liang, Bin Liu, Mingjiang Zhong, Alfredo Alexander-Katz, Caroline A. Ross, Jeremiah A. Johnson
Summary: A simple method to generate three-dimensional layered mesh structures through intrinsic molecular confinement self-assembly is reported. The method extends the capabilities of block copolymer nanofabrication.
NATURE NANOTECHNOLOGY
(2023)
Article
Chemistry, Multidisciplinary
Keith E. L. Husted, Abraham Herzog-Arbeitman, Denise Kleinschmidt, Wenxu Zhang, Zehao Sun, Alyssa J. Fielitz, An N. Le, Mingjiang Zhong, Jeremiah A. Johnson
Summary: Graft copolymers provide a versatile platform for designing self-assembling materials, but controlling their thermomechanical and morphological properties has been challenging. In this study, a strategy for controlling these properties by varying pendant groups was discovered. This strategy allows for the design of a wide range of materials with different properties. The study also simplifies graft copolymer synthesis and provides access to a diverse family of silicone-based materials.
ACS CENTRAL SCIENCE
(2023)
Article
Chemistry, Multidisciplinary
Gabriel Bradford, Jeffrey Lopez, Jurgis Ruza, Michael A. Stolberg, Richard Osterude, Jeremiah A. Johnson, Rafael Gomez-Bombarelli, Yang Shao-Horn
Summary: Solid polymer electrolytes (SPEs) have the potential to improve lithium-ion batteries by enhancing safety and enabling higher energy densities. A chemistry-informed machine learning model was developed to predict ionic conductivity of SPEs, using data from hundreds of experimental publications. The model encodes the Arrhenius equation into the readout layer of a neural network and has improved accuracy in predicting ionic conductivity.
ACS CENTRAL SCIENCE
(2023)
Article
Chemistry, Physical
Matthew A. Pearson, Sachin Bhagchandani, Mircea Dinca, Jeremiah A. Johnson
Summary: A strategy of mixing multivalent polymer ligands with MOF-forming linkers and free linkers is investigated to alter the degree of polymer incorporation in polyMOFs and tune their properties, resulting in polyMOFs with superior N-2 and CO2 uptake. The mixed ligand approach is further extended to create multivariate (MTV)-polyMOFs without the addition of small molecule components.
MOLECULAR SYSTEMS DESIGN & ENGINEERING
(2023)
Article
Chemistry, Multidisciplinary
Herbert Wakefield, Ilia Kevlishvili, Kelsie E. Wentz, Yunxin Yao, Tatiana B. Kouznetsova, Sophia J. Melvin, Em G. Ambrosius, Abraham Herzog-Arbeitman, Maxime A. Siegler, Jeremiah A. Johnson, Stephen L. Craig, Heather J. Kulik, Rebekka S. Klausen
Summary: The cis- and trans-isomers of a silacycloheptene were selectively synthesized using a silyl dianion, providing a novel method for studying strained cycloalkenes. Quantum chemical calculations and crystallographic signatures confirmed that the trans-isomer is more strained than the cis isomer. The trans-isomer also exhibited unique reactivity in ring-opening metathesis polymerization (ROMP) and showed increased molecular compliance compared to carbon-based analogues.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Polymer Science
Haley K. Beech, Jeremiah A. Johnson, Bradley D. Olsen
Summary: Small angle neutron scattering was used to measure the single chain radii of gyration of end-linked polymer gels before and after cross-linking. The prestrain, which is the ratio of the average chain size in a cross-linked network to that of a free chain in solution, increased as gel synthesis concentration decreased near the overlap concentration. Dilute gels with higher loop fractions were found to be spatially homogeneous. The results provide a reference for network theories that rely on prestrain for the calculation of mechanical properties.
Article
Chemistry, Multidisciplinary
Junwoo Lee, Hyunwoo Bark, Yazhen Xue, Pooi See Lee, Mingjiang Zhong
Summary: In this study, a solution to the challenge of developing deformable organic conductors with good mechanical performance and charge mobility was presented. The researchers used size-selective ionic crosslinking to improve the softness and toughness of the composite materials, while ensuring excellent mixed ionic-electronic conductivity. The added ions also promoted charge carrier accumulation for stretchable thermoelectric generators with enhanced stability against humidity.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Alayna M. Johnson, Jeremiah A. Johnson
Summary: Bifunctional silyl ether (BSE)-containing high-density polyethylene (HDPE)-like materials have been synthesized under mild polymerization and hydrogenation conditions. Both the concentration of BSEs in the polymer chain and the silicon steric bulk can be tuned to yield materials with HDPE-like thermomechanical properties. The materials undergo two distinct deconstruction pathways and can be recycled without compromising their mechanical strength.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Michael A. Stolberg, Benjamin A. Paren, Pablo A. Leon, Christopher M. Brown, Gavin Winter, Kiarash Gordiz, Alberto Concellon, Rafael Gomez-Bombarelli, Yang Shao-Horn, Jeremiah A. Johnson
Summary: Solid polymer electrolytes have the potential to enable safer and more energy-dense batteries. This study investigates the impact of anion dissociation energy on ion conduction in solid polymer electrolytes. The researchers developed ionenes with various cations and found that the addition of a cation-coordinating solvent greatly enhanced ionic conductivity without disrupting the lamellar structure. This work demonstrates that molecular design can facilitate significant improvements in ion conduction in solid polymer electrolytes.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Polymer Science
Tetsu Ouchi, Wencong Wang, Brooke E. E. Silverstein, Jeremiah A. A. Johnson, Stephen L. L. Craig
Summary: The influence of strand length on deformation and tension in a polymer network was studied using mechanophore force probes. It was found that the critical strain at which measurable mechanochromism is observed is correlated with the strain hardening of the matrix, but independent of the molecular length of the probes. The rate of decoloration during relaxation of the network was found to depend on the relaxing strain, indicating the effect of residual tension on the reversion reaction.
Article
Chemistry, Multidisciplinary
Keith E. L. Husted, Abraham Herzog-Arbeitman, Denise Kleinschmidt, Wenxu Zhang, Zehao Sun, Alyssa J. Fielitz, An N. Le, Mingjiang Zhong, Jeremiah A. Johnson
Summary: Based on experimental results from a library of 92 polynorbornene-graft-polydimethylsiloxane (PDMS) copolymers, a versatile backbone-pendant sequence-control strategy is discovered, which provides a simple method for precisely controlling the thermomechanical and morphological properties of graft copolymers. Small structural variations of pendant groups in small-molecule comonomers have significant impacts on various properties of silicone-based graft copolymers, resulting in a wide range of designable materials properties. This study reveals a new pendant-group-mediated self-assembly strategy that simplifies graft copolymer synthesis and enables the development of a diverse family of silicone-based materials with tailored performance specifications.
ACS CENTRAL SCIENCE
(2023)
Article
Chemistry, Organic
Landon J. Kilgallon, Yang Shao-Horn, Jeremiah A. Johnson
Summary: A simple and scalable method for synthesizing DMTMSA and other trifluoromethanesulfonamide solvents is described. No specialized glassware is needed, and water is used as the solvent with an ice bath for cooling. The optimized process is highly efficient and reduces waste.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
