Article
Chemistry, Physical
Zhiqiang Zhao, Zheng Bian, Yu Chen, Chuanqing Kang, Lianxun Gao, Guangshan Zhu
Summary: The study shows that chiral oligomers can self-assemble into vesicle-like particles in hydrophobic or hydrophilic solvent systems independently of molecular design and chemical environments. The vesicular membranes are likely stabilized by pi-pi stacking interactions between foldamer backbones and collective van der Waals interactions between side chains, as supported by TEM, UV, CD and PXRD data.
Article
Chemistry, Physical
Matthias Brosz, Nicholas Michelarakis, Uwe H. F. Bunz, Camilo Aponte-Santamaria, Frauke Graeter
Summary: Poly(para-phenylene ethynylene)s (PPEs) are a class of conjugated and semi-flexible polymers with a wide range of technological applications. In this study, a coarse-grained model for PPEs was developed using the Martini 3 force field to study large-scale assemblies computationally. The model successfully reproduced key structural and thermodynamic properties of single PPE chains and mixtures. It was found that chain entanglement increased with PPE chain length, while nematic ordering decreased. The Martini 3 PPE model allows for investigation of the structural organization of PPE bulk systems at large spatio-temporal scales and is predicted to be applicable for studying out-of-equilibrium behavior under mechanical force.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2022)
Article
Chemistry, Multidisciplinary
Cheng-Yan Wu, Shilong Su, Xi Zhang, Rui Liu, Bing Gong, Zhong-Lin Lu
Summary: This study presents a strategy for creating molecular nanotubes with defined lengths by tethering macrocyclic units and oligomer chains. The resulting tubular assemblies can form potassium and proton channels with relatively long open durations, indicating enhanced thermodynamic stability by reducing the number of molecular components. The findings demonstrate the feasibility and reliability of covalently tethering shape-persistent macrocyclic units for building molecular nanotubes.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Physical
Martijn Peters, Derese Desta, Senne Seneca, Gunter Reekmans, Peter Adriaensens, Jean-Paul Noben, Niels Hellings, Tanja Junkers, Anitha Ethirajan
Summary: Conjugated polymer nanoparticles (CNPs) are highly valued in bioimaging for their optical properties and biocompatibility, but face issues with unspecific protein adsorption. Research shows that PEGylation can modulate the uptake of CNPs by brain cells without affecting their optical properties, highlighting their potential as excellent bioimaging tools.
JOURNAL OF COLLOID AND INTERFACE SCIENCE
(2021)
Article
Polymer Science
Qinyong Song, Jiangtao Yue, Yingshi Zhao, Jiatao Zhu, Yuebin Lin, Qiuyang Zhang, Changjiang Pan, Sen Liu, Zhongmei Yang, Li Quan, Yiqing Wang
Summary: A highly photostable nanoprobe based on conjugated polymer, poly(para-phenylene ethynylene), has been developed. The tumor targeting ligands folate modification allows for easy and selective cellular uptake of these nanoprobes. By grafting extended polyester side chains, the interchain energy transfer between conjugated polymer backbones is minimized, leading to an increase in quantum yield.
Article
Polymer Science
Thomas Kerr-Phillips, Mona Damavandi, Lisa Pilkington, Kathryn A. Whitehead, Jadranka Travas-Sejdic, David Barker
Summary: The conformation of a fluorescent polymer is crucial in determining its fluorescent properties. This study investigated the effect of grafted polymeric side chains on the photoluminescent properties of poly(para-phenylene vinylene) (PPV) and poly(para-phenylene ethynylene) (PPE). Ionic grafts were found to decrease the quantum yield, contrary to expectations, while uncharged side chain grafts significantly increased the quantum yield. These results highlight the importance of molecular conformation in the photoluminescent properties of fluorescent polymers.
Article
Chemistry, Physical
Yusuke Hattori, Wakana Matsuda, Shu Seki
Summary: In this study, the investigation of conjugated oligomers with distinct chain lengths revealed a unique solid-solid transition only in the pentamer, resulting in uniaxial expansion in the condensed phase. Time-resolved microwave conductivity measurements highlighted the interplay between thermal activation of charge carriers and uniaxial expansion reducing electronic coupling in pi-stacking of adjacent molecules.
CHEMICAL PHYSICS LETTERS
(2022)
Article
Chemistry, Physical
Yajing Yang, Silvano R. Valandro, Zhiliang Li, Soojin Kim, Kirk S. Schanze
Summary: This paper investigates a series of phenylene ethynylene oligomers end-substituted with a 1,8-naphthalene imide acceptor. The photophysical properties of the oligomers are compared to unsubstituted counterparts, showing that the NI-substituted oligomers exhibit a lowest charge transfer excited state.
JOURNAL OF PHYSICAL CHEMISTRY A
(2021)
Article
Polymer Science
Naofumi Naga, Shingo Okado, Yui Ohara, Keiichi Noguchi
Summary: Poly(p-phenylene alkylene)s were successfully synthesized through Kumada coupling reaction, showing moderate yields and various properties depending on the choice of alpha,omega-dibromoalkane. X-ray diffraction and FT-IR analyses revealed differences in crystal structures among the polymers. Poly(p-phenylene co-alkylenes)s were newly prepared with lower melting temperatures compared to corresponding poly(p-phenylene alkylene)s. The WAXD profiles of the co-alkylene polymers demonstrated a mix of characteristics from the individual alkylene polymers, influenced by the feed ratios of the alpha,omega-dibromoalkanes.
JOURNAL OF POLYMER RESEARCH
(2022)
Article
Nanoscience & Nanotechnology
Han Sun, Samantha S. Yee, Habtom B. Gobeze, Ru He, Daniel Martinez, April L. Risinger, Kirk S. Schanze
Summary: We report a water-soluble polymer that can be used for photoactivated chemotherapy. The polymer undergoes electron transfer upon light activation, resulting in the release of an anticancer drug and cytotoxicity towards cancer cells.
ACS APPLIED MATERIALS & INTERFACES
(2022)
Article
Chemistry, Applied
Hongbin Li, Tengfei Li, Wenying Shi, Yin Tian, Jie Liu, Xiaohong Qin
Summary: By embedding PPTA/PSF microparticles into the PA composite layer of PSF hollow fiber membrane, the dye adsorption properties of the membrane were improved. The PPTA-embedded HFC membrane showed enhanced surface roughness, hydrophilicity, and electronegativity, resulting in increased dye adsorption capacity. These prepared PPTA-embedded hollow fiber composite membranes could potentially be used for treating textile dyeing wastewater.
REACTIVE & FUNCTIONAL POLYMERS
(2022)
Article
Materials Science, Composites
Shanju Zhang, Uwe H. F. Bunz, David G. Bucknall
Summary: This study reports the fabrication of chromatic conductive nanocomposites of PPEs and SWNTs via solution mixing, showcasing the dispersing capability of PPEs towards high concentrations of SWNTs in organic solvents. The nanocomposite solutions exhibit new absorption peaks and fluorescence quenching, while the solid films obtained through vacuum filtration display high strength, modulus, and conductivity.
JOURNAL OF COMPOSITES SCIENCE
(2021)
Article
Polymer Science
Khaled Belal, Francois Stoffelbach, Dominique Hourdet, Alba Marcellan, Joel Lyskawa, Lieselot de Smet, Aurelien Vebr, Jonathan Potier, Graeme Cooke, Richard Hoogenboom, Patrice Woisel
Summary: The swelling properties of hydrogels can be controlled by using supramolecular host-guest complexation, allowing for fine-tuning of the swelling behavior based on the composition of the hydrogel and the stoichiometry of binding events. Different counterions on the tetracationic macrocyclic host can further tune the swelling behavior in line with Pearson's absolute hardness scale. The theoretical model successfully describes the swelling behavior of these supramolecular hydrogels, taking into account the hydrophobic association of the naphthalene groups and their screening by host-guest complexation.
Article
Polymer Science
Yurachat Janpatompong, Kamil Suwada, Michael L. Turner, Guillaume De Bo
Summary: Understanding the stability of conjugated polymers towards mechanical stimuli is crucial for optimizing their use in electronic and optoelectronic devices. Mechanochemistry is a field that aims to control mechanical forces for chemical changes, and it can also be used to study the stability of conjugated polymers. Ultrasonication is a technique that can be used to test the mechanical integrity of phenylenevinylene block copolymers and demonstrate their stability to mechanical forces, making them suitable for flexible organic electronics.
Article
Polymer Science
Hyejin Kim, Byungjin Koo
Summary: Fluorescent conjugated polymers were reported to exhibit fluorescence quenching upon addition of Fe (III) ions, with alkyl functional PPE showing higher sensitivity than expected compared to triethylene glycol functional PPE. The polymer sensors displayed selectivity towards Fe3+ over other ions, and the quenching was determined to be static. A PPE-containing, fluorescent PDMS pad was developed for potential future applications in wearable sensor technology, demonstrating a dark stain when Fe solution was dropped on it.
MACROMOLECULAR RESEARCH
(2021)
Article
Nanoscience & Nanotechnology
Tatsuya Muramatsu, Shohei Shimizu, Jessica M. Clough, Christoph Weder, Yoshimitsu Sagara
Summary: This study presents a new approach to design mechanoresponsive reporter molecules based on rotaxanes. The fluorescence resonance energy transfer (FRET) between a donor and an acceptor is mechanically controlled in this system. Stretchable hydrogels containing the mechanophore showed a higher switching contrast in fluorescence compared to dry films due to increased molecular mobility and hydrophobic effects.
ACS APPLIED MATERIALS & INTERFACES
(2023)
Article
Chemistry, Multidisciplinary
Adarsh Suresh, Stuart J. Rowan, Chong Liu
Summary: Manufacturing low-density-high-strength carbon foams can benefit various industries. This study presents a method to create macroscale carbon foams with exceptional dimensional stability by pyrolysis of template-coating pairs. The resulting carbon foams exhibit remarkable dimensional stability and high specific strengths.
ADVANCED MATERIALS
(2023)
Article
Chemistry, Multidisciplinary
Youwei Ma, Xuesong Jiang, Jie Yin, Christoph Weder, Jose Augusto Berrocal, Zixing Shi
Summary: Chemical upcycling of polymers has become an emerging strategy to convert post-consumer waste into valuable chemicals and materials. However, due to the high stability of the chemical bonds in many polymers, their chemical modification is often challenging. In this study, a versatile approach for the upcycling of linear and cross-linked polyureas was developed using acetylacetone. The resulting compounds can be reacted with aromatic isocyanates to form highly dynamic aminoketoenamide bonds, enabling the preparation of healable and reprocessable poly(aminoketoenamide) networks through thermal treatment without any catalyst.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Review
Chemistry, Multidisciplinary
Micael G. Gouveia, Justus P. Wesseler, Jobbe Ramaekers, Christoph Weder, Philip B. V. Scholten, Nico Bruns
Summary: Protein-based therapeutics are a rapidly growing family of drugs that offer an attractive alternative to traditional therapeutic approaches. However, the use of protective carriers, such as lipid-based structures, is sometimes necessary due to the sensitivity of proteins to denaturation. Despite the advantages of polymersome-based targeted drug-delivery systems over lipid-based structures, the translation of polymersome formulations into approved pharmaceuticals has been slow. This review article highlights key obstacles in the development of polymersomes as protein nanocarriers and suggests areas for further exploration to advance their clinical translation.
CHEMICAL SOCIETY REVIEWS
(2023)
Editorial Material
Polymer Science
Stuart J. Rowan
Article
Chemistry, Multidisciplinary
Livius F. F. Muff, Austin S. S. Mills, Shane Riddle, Veronique Buclin, Anita Roulin, Hillel J. J. Chiel, Roger D. D. Quinn, Christoph Weder, Kathryn A. A. Daltorio
Summary: A mechanically compliant worm-like robot with a fully modular body based on soft polymers is reported. The robot consists of strategically assembled, electrothermally activated polymer bilayer actuators, enabling it to move through repeatable peristaltic locomotion on slippery or sticky surfaces and be oriented in any direction. The soft body allows the robot to wriggle through openings and tunnels much smaller than its cross-section.
ADVANCED MATERIALS
(2023)
Article
Chemistry, Multidisciplinary
Alex E. Crolais, Neil D. Dolinski, Nicholas R. Boynton, Julia M. Radhakrishnan, Scott A. Snyder, Stuart J. Rowan
Summary: A new series of catalyst-free, room-temperature dynamic thia-Michael acceptors bearing an isoxazolone motif were developed and utilized to access both dynamic covalent networks and linear polymers. By leveraging the generation of aromaticity upon thiol addition and tuning the electronic-withdrawing/donating nature of the acceptor at two different sites, a wide range of equilibrium constants were obtained. Integration into a ditopic isoxazolone-based Michael acceptor allowed access to both bulk dynamic networks and linear polymers with tailored thermomechanical properties.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Laura F. Hart, William R. Lenart, Jerald E. Hertzog, Jongwon Oh, Wilson R. Turner, Joseph M. Dennis, Stuart J. Rowan
Summary: Crosslinking in polymer networks leads to brittle materials, but using mobile crosslinks in mechanically interlocked polymers (MIPs) can result in tougher networks. This study explores the use of a metal ion-templated doubly threaded pseudo[3]-rotaxane (P3R) crosslinker to create slide-ring polycatenane networks (SR-PCNs) that combine the mobility features of SRNs and PCNs. Varying the ratio of P3R and covalent crosslinker allowed the researchers to create SR-PCNs with different amounts of interlocked crosslinking units. The mechanical properties of the networks were studied, showing that the metal ions fix the rings in the network and that the removal of the metal ions leads to increased relaxation and poroelastic draining.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Polymer Science
Hongbo Feng, Chang-Geun Chae, Christopher Eom, Gordon S. W. Craig, Stuart J. Rowan, Paul F. Nealey
Summary: Modification of a block copolymer using click chemistry has been shown to effectively control the properties of the copolymer. This study focuses on the modification of a glycidyl methacrylate block with amine-epoxy click chemistry to generate a series of block-random copolymers. The dependence of the effective interaction parameter and surface energy difference on the ratio of the more polar amine is determined, and a lamellae-forming copolymer with sub-10 nm features and zero surface energy difference is demonstrated. Different morphologies can be achieved by adjusting the ratio of the polar amine using this method.
Article
Chemistry, Multidisciplinary
Chuqiao Chen, Michael van der Naald, Abhinendra Singh, Neil D. Dolinski, Grayson L. Jackson, Heinrich M. Jaeger, Stuart J. Rowan, Juan J. de Pablo
Summary: Suspensions of polymeric nano-and microparticles are fascinating stress-responsive material systems that display a diverse range of flow properties under shear. This study focuses on suspensions of micrometer-sized polymeric particles with accessible glass transition temperatures (Tg) and demonstrates that a dramatic and nonmonotonic change in shear thickening occurs as the suspensions transition through the particles' Tg. This strategy enables the in situ tuning of the system's ability to shear jam by varying the temperature relative to Tg and lays the groundwork for other types of stimuli-responsive jamming systems through polymer chemistry.
ACS CENTRAL SCIENCE
(2023)
Article
Chemistry, Multidisciplinary
Derek J. Kiebala, Robert Style, Dimitri Vanhecke, Celine Calvino, Christoph Weder, Stephen Schrettl
Summary: Blending polymers with telechelic macromolecules that have excimer-forming chromophores as end-groups creates materials with sensitive and reversible mechanochromic response to strain. Confocal microscopy reveals phase-separated inclusions of the additive in various host polymers. The mechanochromism of the blends arises from the distortion of the inclusions, which deform homogeneously and reversibly in response to macroscopic strain, regardless of the additive content and matrix composition. These findings demonstrate the potential of using telechelic macromolecules as universal additives for the fabrication of mechanochromic materials.
ADVANCED FUNCTIONAL MATERIALS
(2023)
Article
Engineering, Environmental
Livius F. Muff, Sandor Balog, Jozef Adamcik, Christoph Weder, Roman Lehner
Summary: Research on polymer nanoparticles in the environment and their impact on animal and human health is growing. This study presents a method to prepare well-defined nanoparticles with tailored characteristics, allowing for their detection in complex environments and mimicking environmentally relevant morphologies.
ENVIRONMENTAL SCIENCE & TECHNOLOGY
(2023)
Article
Chemistry, Multidisciplinary
Hongbo Feng, Benjamin Kash, Soonmin Yim, Kushal Bagchi, Gordon S. W. Craig, Wen Chen, Stuart J. Rowan, Paul F. Nealey
Summary: By synthesizing block copolymers and random copolymers with specific composition ratios, two distinct wetting behaviors were demonstrated and explained.
Article
Chemistry, Multidisciplinary
Marissa M. Tranquilli, Benjamin W. Rawe, Guancen Liu, Stuart J. Rowan
Summary: The main-chain poly[n]catenane, resembling a macroscopic chain-link structure, was synthesized using a metallosupramolecular polymer (MSP) template. Closure of the thread components resulted in a mixture of cyclic, linear, and branched poly[n]catenanes. The study investigated the effect of the thread-like monomer structure on the poly[n]catenane synthesis and demonstrated the selective synthesis of branched poly[n]catenanes by tailoring the monomer structure.
Article
Automation & Control Systems
Livius F. Muff, Christoph Weder
Summary: This study develops segmented polyurethanes with crystallizable polyethylene glycol (PEG) soft segments and hard segments formed by the reaction of 1,6-hexane diisocyanate and 1,4-butanediol (BDO). By varying the molecular weight of the PEG segments and the hard-segment content, the thermal expansion of these materials is correlated with their crystallinity, resulting in high deflection and low switching temperatures.
ADVANCED INTELLIGENT SYSTEMS
(2023)
