Article
Polymer Science
Yuji Higaki, Takumi Masuda, Mai Nakamura, Masaya Takahashi
Summary: The cononsolvency-induced solvent composition-specific self-assembly of a double hydrophilic diblock copolymer was studied. The copolymer dissolved in water and ethanol but aggregated in mixtures with a specific ethanol volume fraction range due to the cononsolvency of one of its components. The copolymer produced well-ordered mesoscopic lattice structures in water-ethanol mixed solvents, and the morphology depended on the ethanol fraction and polymer concentration.
Article
Chemistry, Physical
Ryan P. Collanton, Christopher J. Ellison, Kevin D. Dorfman
Summary: Block copolymers have been studied for their role in interface thermodynamics at homopolymer interfaces. The research finds that interface thermodynamics are more sensitive to block degree of polymerization than to the number of blocks. In addition, a strong correlation is identified between the spatial uniformity of block junctions on the interface and the reduction of interfacial tension.
JOURNAL OF CHEMICAL PHYSICS
(2023)
Article
Chemistry, Multidisciplinary
Suna Azhdari, Yorick Post, Manuel Tromer, Deniz Coban, Giada Quintieri, Andre H. Groschel
Summary: The synthesis and properties of Janus nanoparticles with different shapes, such as spherical, cylindrical, and disk-like, are well understood. However, the synthesis of nanorings and bowl-shaped Janus nanoparticles is currently limited, preventing a thorough investigation of their properties. In this study, we successfully synthesized bowl-shaped Janus nanoparticles without any side products and controlled their size and shape by adjusting the amount of blended homopolymer. The use of Shirasu Porous Glass (SPG) membranes further allowed for control of the particle diameter. The findings of this study provide important insights for understanding the properties and potential applications of Janus nanoparticles.
Article
Chemistry, Multidisciplinary
Namkyu Yun, Cheol Kang, Sanghee Yang, Soon-Hyeok Hwang, Jun-Mo Park, Tae-Lim Choi
Summary: Size-tunable and uniform semiconducting 2D nanorectangles were achieved through living crystallization-driven self-assembly of a fully conjugated polyenyne homopolymer prepared by cascade metathesis and metallotropy polymerization. The resulting nanorectangles had precisely tuned sizes from 0.1 to 3.0 μm2, narrow dispersity mostly less than 1.1, and low aspect ratios less than 3.1.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Congcong Yin, Ming Liu, Zhe Zhang, Mingjie Wei, Xiansong Shi, Yatao Zhang, Jingtao Wang, Yong Wang
Summary: This study demonstrates a strategy of solvent vapor annealing to reorient the pore channels of covalent organic frameworks (COFs) from anisotropic orientation to perpendicular alignment. The COF thin films with flexible N-H bonds enable molecular rearrangement. A solvent with low relative permittivity and a conjugated structure is used to easily penetrate the COF interlayers. The solvent vapor weakens the pi-pi interaction and allows the COF monolayers to dissociate, leading to the reorientation of COF pore channels and improved separation precision.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Polymer Science
Xian Kong, Jian Qin
Summary: Microphase separation is a bottom-up strategy for fabricating nanostructures in polymeric systems. Usually, block copolymers or polyelectrolytes are used for microphase separation. However, recent research shows that neutral homopolymer blends can also undergo microphase separation with the addition of a small amount of salt and sufficient dielectric contrast. This discovery suggests a cost-effective and easy alternative for producing microphase separation, which could be useful in advanced material design and preparation.
Article
Polymer Science
Tianhang Zhou, Jurek Schneider, Zhenghao Wu, Florian Mueller-Plathe
Summary: Our study reveals that in strongly incompatible systems, regular multiblock copolymers show better compatibilization performance compared to symmetric diblock copolymers at the same areal concentration. Additionally, for unsymmetric diblock copolymers in strongly incompatible systems, the length of the shortest block is a more important determinant for the compatibilization efficiency than the ratio of block lengths.
Article
Chemistry, Multidisciplinary
Han Yi, Yuesheng Li, Dong-Po Song
Summary: The organized spontaneous emulsification (OSE) produces ordered water-in-oil-in-water (W/O/W) multiple emulsion droplets stabilized by bottlebrush block copolymer (BBCP) surfactants, templating ordered porous particles with visible structural colors. The use of homopolymer polystyrenes (hPS) to swell the PS domain effectively increases the W/O interfacial curvature of the internal droplets, allowing for tunable pore diameter and photonic bandgaps in the visible spectrum.
CHINESE JOURNAL OF CHEMISTRY
(2023)
Article
Multidisciplinary Sciences
Sanghee Yang, Sung-Yun Kang, Tae-Lim Choi
Summary: The authors have successfully controlled the length of 2D sheets of conjugated polymers by blending, heating, and seeded-growth strategies, providing a new method for preparing semi-conducting two-dimensional polymer nanoobjects.
NATURE COMMUNICATIONS
(2021)
Article
Chemistry, Physical
Saul J. Hunter, Mahmoud H. Abu Elella, Edwin C. Johnson, Laura Taramova, Emma E. Brotherton, Steven P. Armes, Vitaliy V. Khutoryanskiy, Mark J. Smallridge
Summary: Spherical aldehyde-functionalized nanoparticles were prepared through aqueous emulsion polymerization, and when combined with oil droplets, formed nanoemulsions. The aldehyde-functionalized nanoparticles showed stronger adhesion to sheep nasal mucosal tissue due to the formation of imine bonds.
JOURNAL OF COLLOID AND INTERFACE SCIENCE
(2023)
Article
Polymer Science
Bo Zhang, Shuyi Xie, Timothy P. Lodge, Frank S. Bates
Summary: The use of asymmetric diblock copolymers in ternary polymer blends significantly impacts the ordered phase regime, but has a marginal effect on the region displaying macroscopic phase separation. This study also provides useful guidance for tuning the interfacial curvature, a crucial factor in the formation of bicontinuous microemulsions.
Article
Polymer Science
Kyle D. Mehringer, Brad J. Davis, Lisa K. Kemp, Guorong Ma, Samuel B. Hunt, Robson F. Storey, Xiaodan Gu, Travis L. Thornell, Dane N. Wedgeworth, Yoan C. Simon, Sarah E. Morgan
Summary: Incorporating dynamic covalent bonds into block copolymers provides useful molecular level information during mechanical testing. The inclusion of these units has little effect on the morphology of the polymer.
MACROMOLECULAR RAPID COMMUNICATIONS
(2022)
Article
Chemistry, Multidisciplinary
Yao-Yao Zhang, Guan-Wen Yang, Rui Xie, Xiao-Feng Zhu, Guang-Peng Wu
Summary: This study reports a simple method to synthesize well-defined polyether-block-polycarbonate copolymers through switchable catalysis from mixtures of epoxides. This approach has a broad substrate scope and allows for the controlled construction of oxygen-rich polymers.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Polymer Science
Min Su, Yu-Jing Sheng, Yu-Jiao Chen, Tao Li, Quan-Xi Shi, Hang Xiao, Meng-Qin Pu, Hongli Bao, Wen-Ming Wan
Summary: A versatile living polymerization method is reported, which allows the precise synthesis of narrow distributed polystyrenes through the introduction of a well-established all-in-one covalent-anionic-radical Barbier strategy, using a wide variety of organohalides as initiators under mild conditions.
Article
Polymer Science
Joanna Smenda, Karol Wolski, Kamila Chajec, Szczepan Zapotoczny
Summary: The synthesis of surface-grafted polymers with varied functionality is crucial for the fabrication of advanced devices like nano (micro) sensors or nanoelectronic devices. The development of economical and eco-friendly synthetic strategies, such as metal-free surface-initiated ATRP, is important for scaling up the production of such polymer brushes. This approach allows the synthesis of complex polymer structures with versatility and simplicity, making it accessible even for non-experts and ready for large-scale production.
Article
Chemistry, Multidisciplinary
Hang Zhang, Charles E. Diesendruck
Summary: In this study, the influence of helical structures on covalent mechanochemistry was investigated by preparing polymer chains with different helicities. The results revealed that chains with higher helicity have faster mechanochemistry rates, indicating that helix-induced chain rigidity improves the efficiency of mechanical energy transduction.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Kanika Aggarwal, Saja Bsoul, John C. Douglin, Songlin Li, Dario R. Dekel, Charles E. Diesendruck
Summary: Metallopolymers, with metal centers assuming ion transport function, show exceptional alkaline stability in AEMFCs, surpassing current quaternary ammonium cations, and provide a scientific base for further advancements in the field.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Electrochemistry
Zi-Ye Xiao, Charles E. Diesendruck, Viatcheslav Freger, Dario R. Dekel
Summary: In this study, ultra-thin polymer films with significant anion conductance were successfully prepared by electropolymerizing homopolymer and copolymer from vinylbenzyltrimethylammonium chloride and divinylbenzene using cyclic voltammetry. The morphologies and film properties of the electropolymerized polymers were analyzed, and high anion conductance of up to 2 mS was observed in the films. This technique shows potential for the development of anion-conducting electrodes for advanced electrochemical devices.
JOURNAL OF THE ELECTROCHEMICAL SOCIETY
(2022)
Article
Chemistry, Inorganic & Nuclear
Kanika Aggarwal, Songlin Li, Elisa Ivry, Dario R. Dekel, Charles E. Diesendruck
Summary: Metallopolymers have potential as anion exchange membranes (AEMs) in fuel cells and water electrolysis applications. By synthesizing metallopolymers and studying the electronic effects of ligands, the relationship between metal-ligand pairs and AEM properties can be understood. Optimizing the design of complexes with correct electronic parameters can advance the development of practical AEMs for alkaline fuel cells and water electrolyzers.
Article
Multidisciplinary Sciences
Deb Kumar Bhowmick, Tapan Kumar Das, Kakali Santra, Amit Kumar Mondal, Francesco Tassinari, Rony Schwarz, Charles E. Diesendruck, Ron Naaman
Summary: We describe the spin polarization-induced chirogenic electropolymerization of achiral 2-vinylpyridine, which forms a layer of enantioenhanced isotactic polymer on the electrode. The chirality of the polymer film formed on the electrode was confirmed by measuring its electron spin polarization properties as a function of its thickness. Two methods were used: spin polarization measurement by magnetic contact atomic force microscopy and assessment of magnetoresistance in a sandwich-like four-point contact structure. High spin-selective electron transmission was observed, even for a layer thickness of 120 nm. The change in circular dichroism signal correlated with the change in spin polarization as a function of thickness, and the spin-filtering efficiency increased with temperature.
Article
Chemistry, Physical
Sapir Willdorf-Cohen, Alexander Kaushansky, Dario R. Dekel, Charles E. Diesendruck
Summary: Solvent molecules have a significant impact on chemical reactions, especially when they interact with reactants or catalysts. This study demonstrates that microsolvation of water can change the chemoselectivity of hydroxide ions by affecting their basicity and nucleophilicity differently.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2022)
Article
Multidisciplinary Sciences
Alexander D. Snyder, Zachary J. Phillips, Jack S. Turicek, Charles E. Diesendruck, Kalyana B. Nakshatrala, Jason F. Patrick
Summary: Synthetic materials with self-repair capabilities similar to biological systems are crucial for meeting the infrastructural demands of the 21st century. In this study, the authors developed fiber-reinforced composites that can rapidly and repeatedly self-heal in situ while maintaining structural integrity. This finding overcomes existing obstacles in achieving mechanical self-recovery and has the potential to extend the lifespan and widespread use of bioinspired structural materials.
NATURE COMMUNICATIONS
(2022)
Article
Chemistry, Multidisciplinary
Hang Zhang, Charles E. Diesendruck
Summary: This study found that mechanochemical reactions in block copolymers (BCPs) may have unexpected consequences when subjected to mechanical stress. The activation of mechanophores is accelerated even when they are located at the chain ends, indicating a significant mechanochemical response throughout the polymer chain, even in regions far from the center.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Materials Science, Multidisciplinary
Iris Agami, Nansi Gjineci, Songlin Li, Simcha Srebnik, Dario R. Dekel, Charles E. Diesendruck
Summary: In recent years, the development of anion-exchange membranes (AEMs) for anion-exchange membrane fuel cell (AEMFC) applications has been rapidly growing due to their numerous advantages over mainstream proton-exchange membrane fuel cells. However, a major challenge in the development of practical AEMs is the low chemical stability of the AEM quaternary ammonium (QA) functional groups in the strongly alkaline and dry environment during AEMFC operation. This study investigates the impact of polymer chain folding on the chemical stability of the QA groups and finds that folded chains exhibit significantly improved stability compared to linear chains, providing a simple method for preparing chemically stable AEMs with different QA groups and polymer backbones.
ACS APPLIED POLYMER MATERIALS
(2022)
News Item
Chemistry, Multidisciplinary
Charles E. Diesendruck
Summary: Scientists have long studied how polymers break in solutions, but understanding how chains stretch to the point of breaking covalent bonds has proven to be challenging. However, a recent set of experiments strongly support a dynamic model suggesting that chains uncoil from the ends to the middle while simultaneously relaxing.
Article
Engineering, Environmental
Zohar Sahray, Amit N. Shocron, Rana Uwayid, Charles E. Diesendruck, Matthew E. Suss
Summary: Capacitive deionization (CDI) is an emerging technology used for brackish water desalination and ion selective separations. A one-dimensional transient CDI model was used to study the mechanisms enabling monovalent-selective separations. It was discovered that an asymmetric CDI cell with a chemically functionalized cathode induces electric charges in the pristine anode, leading to monovalent cation selectivity. The study also uncovered a novel operational regime called capacitive ion exchange for resin-less exchange of monovalent cations for divalent cations.
Article
Chemistry, Multidisciplinary
Hang Zhang, Alan Z. Zoubi, Meredith N. Silberstein, Charles E. Diesendruck
Summary: Mechanochemistry can cause the degradation of covalent macromolecules, including block copolymers. By preparing polymers with different ratios of butyl acrylate and methyl methacrylate and subjecting them to ultrasonication, it was found that the mechanochemistry rate constant of all BCPs was similar to that of the methacrylate homopolymer, regardless of the amount of the methacrylate monomer. Size-exclusion chromatography revealed the presence of a secondary selective scission site at the covalent connection between the two blocks. Molecular dynamics modeling showed that dynamic phase separation of the blocks induced an unusual distribution of applied forces, leading to force focusing at the interface.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Polymer Science
Sally Nijem, Ying Song, Rony Schwarz, Charles E. Diesendruck
Summary: Mechanophores are useful tools for studying and detecting mechanical stress, but their optical signals are limited. Gas-releasing mechanophores provide a chemical signal that can be easily detected, although the exact location of the damage is lost. This study presents a flex-activated CO-releasing mechanophore incorporated into a PMMA network, which releases CO in large amounts and can be detected even with a commercial CO-detector.
Article
Engineering, Environmental
Rana Uwayid, Charles E. Diesendruck, Matthew E. Suss
Summary: This study compares the performance differences between weak-acid and strong-acid functionalized cathodes in CDI cells, and provides insights for the selection of surface functionalization.
ENVIRONMENTAL SCIENCE-WATER RESEARCH & TECHNOLOGY
(2022)
Article
Chemistry, Physical
Sapir Willdorf-Cohen, Alexander Kaushansky, Dario R. Dekel, Charles E. Diesendruck
Summary: This study discusses the impact of solvent molecules on chemical reactions, particularly through the electronic interactions in ion microsolvation. Using the reaction between hydroxide and quaternary ammonium salts as an example, it demonstrates how water microsolvation can alter the chemical selectivity of hydroxide. The reactivity of hydroxide as a base is more affected by water microsolvation than its reactivity as a nucleophile.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2022)
