Article
Materials Science, Multidisciplinary
Eigo Shimaoka, Masaki Kunihiro, Masahiro Funahashi
Summary: Oligo(p-phenylenevinylene)-based chiral nematic liquid crystals were synthesized and showed tunable reflection band for circularly polarized fluorescence. The glassy chiral nematic films exhibited left-handed circularly polarized light at room temperature.
ACS APPLIED POLYMER MATERIALS
(2022)
Article
Chemistry, Multidisciplinary
Mingfang Ma, Bo Wang, Aiyou Hao, Pengyao Xing
Summary: This study presents a co-assembly strategy to introduce hydrophilic chiral amines into OPV-appended carboxylic acids, resulting in the formation of chiral assemblies with tunable optical activity. The participation of chiral amines alters the aromatic stacking, enhances the luminescence of the OPV compounds, and facilitates the emergence of Cotton effects and circularly polarized luminescence. This work demonstrates the potential of OPV luminophores in chiroptical applications.
Article
Nanoscience & Nanotechnology
Florian Malotke, Tobias Thiele, Jochen S. Gutmann, Michael Giese
Summary: A modular tool box for photoresponsive cholesteric liquid crystals based on hydrogen-bonded assemblies is developed, allowing tunable structural coloration. The blue shift in cholesteric liquid-crystalline thin films is attributed to the photoinduced destruction of smectic clusters, resulting in a contraction of the helical structure. Furthermore, the use of a stereolithography 3D printer enables the direct transfer of digital information into a multicolor photonic pattern.
ACS APPLIED MATERIALS & INTERFACES
(2023)
Article
Chemistry, Multidisciplinary
Yuelin Zhong, Wenbo Dong, Shijie Ren, Longyu Li
Summary: This paper designs and synthesizes two Kagome topological COFs for enhancing photocatalytic hydrogen evolution through a two in one strategy. COF-954 shows high hydrogen production rates both under visible light and UV-vis light irradiation, and performs well in natural seawater.
ADVANCED MATERIALS
(2023)
Article
Polymer Science
Zhiqin Wang, Chen Ma, Xiaoyu Huang, Guolin Lu, Mitchell A. Winnik, Chun Feng
Summary: The introduction of metal ions in the self-seeding process of copolymer micelles significantly increases the resistance of seed micelles to dissolution, explained by the formation of noncovalent cross-linking within the P2VP layer.
Article
Chemistry, Multidisciplinary
Wenbo Dong, Zhiying Qin, Kuixing Wang, Yueyuan Xiao, Xiangyang Liu, Shijie Ren, Longyu Li
Summary: This study investigates the effect of imine-bond orientation on the photocatalytic properties of covalent organic frameworks (COFs). Two novel COFs with different imine-bond orientations are synthesized and compared. The results show that the orientation of the imine bonds greatly affects the photoelectric properties of COFs. Protonation of COFs using ascorbic acid can further enhance the photocatalytic performance by altering the direction of electron transfer.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Nan Dai, Hao Zhao, Wen Yu, Fengting Lv, Libing Liu, Shu Wang
Summary: The study presents a facile intracellular catalysis system for enhancing the production of bio-based material in microorganisms by covalently linking synthetic metal catalyst. The synthetic metal catalyst demonstrated resistance to toxic biomolecules and enhanced biosynthesis in complicated biological systems. This work suggests the potential of using synthetic metal catalysts for regulating microbial biosynthesis intracellularly.
SCIENCE CHINA-CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Taito Hashimoto, Ryusei Oketani, Masaki Nobuoka, Shu Seki, Ichiro Hisaki
Summary: Non-stoichiometric mixed frameworks composed of tetrakis(4-carboxyphenyl)hexahydropyrene and pyrene derivatives have been synthesized via co-crystallization and were characterized by X-ray crystallography. The composition ratio of the mixed frameworks was determined, indicating that they can be formed over a wide range of ratios. Microscopic Raman spectroscopy revealed a non-uniform distribution of components within the single crystal.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Organic
Hui Wang, Hongchi Zhao, Shuang Chen, Libin Bai, Zhiyi Su, Yonggang Wu
Summary: Symmetric ladder-type oligo(p-aniline)s and poly(p-aniline)s were successfully synthesized by an intramolecular ring closure in a highly efficient SNAr reaction from oligo(p-phenylene)s and poly(p-phenylene)s with fluorine (F) and secondary amine (NH) groups. Unlike Cadogan ring closure, the newly designed cyclization reaction will not produce a mixture of symmetric and nonsymmetric structures. Moreover, the introduction of the F atom does not hinder Suzuki polymerization, indicating the possibility of preparing regular oligomers and polymers with a nitrogen bridge.
Article
Thermodynamics
Mustafa Okumus, Sinan Dindar
Summary: A novel hydrogen-bonded liquid crystalline binary complex system was synthesized from 4-(octyloxy)benzoic acid and n-aminobenzoic acid. The thermal properties and mesogenic phase textures were investigated using DSC and POM experiments, showing a phase sequence of Cr <-> SmA <-> SmC <-> N <-> I. The most stable phase was found to be SmC, and the optical tilt angle increased for the complexes. FTIR and XRD results confirmed the presence of hydrogen bonds and monoclinic molecular ordering in the synthesized complexes.
JOURNAL OF THERMAL ANALYSIS AND CALORIMETRY
(2023)
Article
Chemistry, Physical
Mohamed Alaasar, Jaques-Christopher Schmidt, Xiaoqian Cai, Feng Liu, Carsten Tschierske
Summary: This study reports two new series of supramolecular photosensitive polycatenar mesogens formed by hydrogen bonding, showing different liquid crystal phases depending on the position of the fluorine atom. Core fluorination is identified as a powerful tool for controlling spontaneous helical self-assembly in supramolecular liquid and liquid crystalline materials.
JOURNAL OF MOLECULAR LIQUIDS
(2021)
Article
Chemistry, Physical
Huangsheng Yang, Jiahui Fu, Wei Huang, Tong Wu, Siming Huang, Guosheng Chen, Gangfeng Ouyang
Summary: Biomimetic engineering presents a new self-propelled hydrogen-bonded enzymatic framework. This framework is achieved through a biomimetic bottom-up strategy and consists of a metal-free, mesoporous, and photoactive hydrogen-bonded organic framework grown around catalase. The resulting framework enables self-propelled motion through the generation of biocatalytic bubbles.
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, Multidisciplinary
Hongshuang Guo, Tero-Petri Ruoko, Hao Zeng, Arri Priimagi
Summary: This study combines irreversible shape memory effect and reversible actuation of liquid crystal elastomers (LCEs) to design LCEs that can be programmed into multiple temporary shapes while maintaining reversible deformability. LCEs are crosslinked via dynamic hydrogen bonds to achieve shape programming via shape memory effect, and mild thermal or photothermal stimulation for reversible actuation. The study demonstrates concept validation robotic applications such as adjustable grippers for different-sized objects and shape-morphing crawling robots for constrained spaces.
ADVANCED FUNCTIONAL MATERIALS
(2023)
Article
Biochemistry & Molecular Biology
Mengke Hu, Chenxi Wu, Shufan Feng, Jianli Hua
Summary: This study presents the synthesis of a high crystalline perylene-based hydrogen-bonded organic framework (HOF) for photocatalytic hydrogen peroxide (H2O2) production. Compared to the amorphous analog sample, the organic framework showed higher photocatalytic activity and quantum yield, attributed to the promotion of photocarrier separation and transfer due to its high crystallinity.
Article
Chemistry, Multidisciplinary
Enquan Jin, Shuai Fu, Hiroki Hanayama, Matthew A. Addicoat, Wenxin Wei, Qiang Chen, Robert Graf, Katharina Landfester, Mischa Bonn, Kai A. Zhang, Hai Wang, Klaus Mullen, Akimitsu Narita
Summary: Synthesis of covalent organic frameworks with desirable organic units leads to advanced materials with unique functionalities, with sp(2)-carbon-conjugated COFs providing a platform to build highly stable and crystalline porous polymers. A 2D olefin-linked COF using nanographene, dibenzo[hi,st]ovalene (DBOV), as a building block was prepared, showing ABC-stacked lattices, enhanced stability, and high charge-carrier mobility.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Multidisciplinary Sciences
Elisabeth Weyandt, Luigi Leanza, Riccardo Capelli, Giovanni M. Pavan, Ghislaine Vantomme, E. W. Meijer
Summary: This study demonstrates the modulation of aggregate morphology in a zinc porphyrin-based supramolecular system through the judicious use of a manganese porphyrin monomer. The chirality of the monomer can influence the supramolecular behavior.
NATURE COMMUNICATIONS
(2022)
Article
Chemistry, Multidisciplinary
Brigitte A. G. Lamers, Martin H. C. van Son, Freek de Graaf, Bart W. L. van den Bersselaar, Bas F. M. de Waal, Kazuki Komatsu, Hiroshi Sato, Takuzo Aida, Jose Augusto Berrocal, Anja R. A. Palmans, Ghislaine Vantomme, Stefan C. J. Meskers, E. W. Meijer
Summary: The assembly of highly ordered nanomaterials through charge transfer interactions is achieved in this study, where pyrene and naphthalenediimide functionalized oligodimethylsiloxanes are synthesized and co-assembled in bulk. By tuning the donor-acceptor interactions through connecting pyrene and NDI to the same oligomer or to two separate oligomers, different types of donor-acceptor molecules are obtained. The discreet length of the oligodimethylsiloxane units plays a crucial role in the formation of liquid crystalline materials and CT dimers.
MATERIALS HORIZONS
(2022)
Article
Polymer Science
Sandra M. C. Schoenmakers, A. J. H. Spiering, Svenja Herziger, Christoph Boettcher, Rainer Haag, Anja R. A. Palmans, E. W. Meijer
Summary: This study investigates the changes in properties of a supramolecular polymer containing chiral monomers over time. It was found that the helical preference increases, helical pitch decreases, and monomer exchange dynamics weaken as time progresses.
Article
Polymer Science
Brigitte A. G. Lamers, Brett P. P. Fors, E. W. Meijer
Summary: The effect of blending oligomers of different lengths of discrete hydrazone end-functionalized oligo(dimethylsiloxanes) on morphological order was studied. A distinct boundary exists between good and poor morphological order at a certain dispersity.
JOURNAL OF POLYMER SCIENCE
(2023)
Article
Chemistry, Multidisciplinary
Joost J. B. van der Tol, Tom A. P. Engels, Ruth Cardinaels, Ghislaine Vantomme, E. W. Meijer, Fabian Eisenreich
Summary: Reported a method for light-controlled liquid-to-solid transition of polysiloxanes, which forms strong supramolecular cross-links through photoisomerization. This method allows for tailoring the mechanical properties of polymers without the use of plasticizers or hardeners.
ADVANCED FUNCTIONAL MATERIALS
(2023)
Article
Chemistry, Multidisciplinary
Martin H. C. van Son, Anton M. Berghuis, Bas F. M. de Waal, Felix A. Wenzel, Klaus Kreger, Hans-Werner Schmidt, Jaime Gomez Rivas, Ghislaine Vantomme, E. W. Meijer
Summary: In this study, functionalization of C-3-symmetric carbonyl-bridged triarylamine trisamide (CBT) with oligodimethylsiloxane (oDMS) side chains was shown to lead to fully covered surfaces with aligned domains, enabling long-range exciton transport.
ADVANCED MATERIALS
(2023)
Article
Mechanics
Emmanouil Vereroudakis, Nathan Van Zee, E. W. Meijer, Dimitris Vlassopoulos
Summary: We investigated the behavior of a supramolecular polymer under repeated shear-startup runs. This test, proposed 50 years ago, is used to measure disentanglement kinetics in linear polymers. The recovery time was found to mainly reflect chain reorientation, but for the supramolecular polymer in this study, it was rate independent. This difference is attributed to the different mechanism of stress relaxation involving bond breaking/recombination and reptation processes. The repeated shear-startup protocol can serve as an indicator of polymer signatures and a tool to evaluate stress relaxation models.
JOURNAL OF NON-NEWTONIAN FLUID MECHANICS
(2023)
Article
Chemistry, Multidisciplinary
Stef A. H. Jansen, Elisabeth Weyandt, Tsubasa Aoki, Takayoshi Akiyama, Yoshimitsu Itoh, Ghislaine Vantomme, Takuzo Aida, E. W. Meijer
Summary: Complexity in supramolecular polymer systems is caused by interactions between different components, including solvent molecules. This study reveals that both thermally bisignate and dilution-induced assembly phenomena in multicomponent systems are driven by the same underlying interaction mechanism. By investigating the interaction between amide-decorated supramolecular polymers and aliphatic alcohols, the temperature-dependency and dominance of the interaction at high monomer concentrations were unveiled. These insights allow for the control and manipulation of supramolecular polymer systems, opening the door to building complex and functional structures.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Yingluo Zhao, Hiroko Kawano, Hiroshi Yamagishi, Saya Otake, Yoshimitsu Itoh, Hubiao Huang, E. W. Meijer, Takuzo Aida
Summary: In this article, we report the complex pathway complexity in thesupramolecular polymerization of a chiral monomer, which exhibits an anomalous chiroptical feature. Through AgBF4-mediated supramolecular polymerization, we developed a planar-chiral ferrocene-cored tetratopic pyridyl monomer FcL, leading to the formation of nanotubes composed of metal-organic nanorings (FcNTs). The formation of homochiral nanorings (FcNRs) was observed even from racemic FcL, suggesting the existence of two competing pathways for producing FcNRs in the polymerization process.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Freek V. de Graaf, Stef A. H. Jansen, Tobias Schnitzer, E. W. Meijer, Ghislaine Vantomme
Summary: Amplification of asymmetry in complex molecular systems is achieved by controlling the helicity of supramolecular assemblies through non-stereoselective methylation reactions. Methylating chiral glutamic acid side chains in benzene-1,3,5-tricarboxamide (BTA) derivatives modulates the assembly properties. The introduction of methyl ester-BTAs as reacted comonomers induces a stronger bias in the screw-sense of helical fibers predominantly composed of stacked achiral alkyl-BTA monomers, leading to asymmetry amplification.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Physical
Laura Rijns, Joris W. Peeters, Simone I. S. Hendrikse, Marle E. J. Vleugels, Xianwen Lou, Henk M. Janssen, E. W. Meijer, Patricia Y. W. Dankers
Summary: This research reveals the importance of molecular dynamics and gel dynamics in cellular spreading. Epithelial cells are insensitive to gel dynamics, while fibroblasts are sensitive to the gel dynamics in soft gels and dependence on gel stiffness.
CHEMISTRY OF MATERIALS
(2023)
Article
Chemistry, Multidisciplinary
Stef A. H. Jansen, Hao Su, Tobias Schnitzer, Ghislaine Vantomme, E. W. Meijer
Summary: In this study, the temperature-dependent microstructure of copolymers of triazine- and benzene-derivatives was investigated. It was found that the interplay between these two monomers determines the helicity of the copolymers, similar to the mixed majority-rules phenomenon.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Multidisciplinary
Joost J. B. van der Tol, Ghislaine Vantomme, E. W. Meijer
Summary: In this study, the compatibility between solvents and supramolecular polymers was systematically investigated using Hansen solubility parameters (δ (D), δ (H), and δ (P)). A dual-sphere model was applied to describe the solubility space of the monomeric state and supramolecular polymer state. Further studies revealed the formation of higher-order aggregated structures due to subtle differences in solvent polarity. The model was also applied to structurally different monomers, demonstrating its generality and the importance of supramolecular monomer design.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Virgil Percec, Ning Huang, Qi Xiao, Benjamin E. Partridge, Dipankar Sahoo, Mohammad R. Imam, Mihai Peterca, Robert Graf, Hans-Wolfgang Spiess, Xiangbing Zeng, Goran Ungar
Summary: Programming complex living and soft matter through primary structure and self-organization is key in designing functions in biological and synthetic nanoscience. Memory effects, such as supramolecular orientational memory (SOM), have been utilized in creating commercial technologies and engineering complex nanoscale soft matter. The discovery of SOM in a non-cubic Frank-Kasper phase suggests the potential expansion of this methodology to other periodic and quasiperiodic nanoarrays in soft and living complex matter.