Article
Chemistry, Multidisciplinary
Zongshang Li, Ke Xiao, Qingyun Wan, Rui Tang, Kam-Hung Low, Xiaodong Cui, Chi-Ming Che
Summary: The introduction of multiple kinetic aggregation states (Aggs) into the self-assembly pathway can increase the complexity and flexibility of the self-assemblies. This was achieved by using a series of chiral and achiral d(10) Au-I bis(N-heterocyclic carbene, NHC) complexes, where the achiral complex could undergo self-assembly with multiple kinetic Aggs. The chiral Au-I self-assemblies exhibited nonlinear optical response of second harmonic generation (SHG) and could function as optical waveguides with strong emission polarization, while these properties were absent in the achiral analogue.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Keigo Tashiro, Takuho Saito, Hironari Arima, Natsuki Suda, Balaraman Vedhanarayanan, Shiki Yagai
Summary: Chemists have constructed sophisticated artificial nanostructured systems through self-assembly, including scissor-shaped photochromic dyads that hierarchically self-assemble into discrete nanostructures with photoresponsive properties. These nanostructures, such as azobenzene dyads, can be dissociated and reorganized through the photoisomerization of azobenzene units, enabling controllable and adjustable structures.
Article
Chemistry, Multidisciplinary
Xiao-Qiao Xie, Yunfei Zhang, Yujia Liang, Mengke Wang, Yihan Cui, Jingjing Li, Chun-Sen Liu
Summary: By using boronic ester based dynamic covalent chemistry and coupling it with an internal pH feedback system, a new chemically fueled reaction network for non-equilibrium supramolecular chiral G-quadruplex hydrogels with programmable lifetimes has been developed. The system exhibits high transparency, conductivity, excellent injectability, and rapid self-healing properties.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Wei Zuo, Yu Tao, Zhipeng Luo, Anyang Li, Shanshan Wang, Xinrui Qiao, Fen Ma, Chuandong Jia
Summary: Inspired by the signal transduction function of organophosphates, bioactive organophosphates were used as chiral nodes to control the stereoselective assembly of hydrogen-bonded anionic cages. Antibiotics such as phosphonomycin and clindamycin phosphate, antiviral drug tenofovir, and natural product AMP were assembled with an achiral bis-monourea ligand to form quadruple or triple helicates with stereoselectivity. The stereoselectivity could be enhanced by lowering temperature or using stronger-binding cations as templates. Enantioselectivity was achieved when binding chiral quaternary ammonium cations with the chiral anionic cages as hosts.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Physical
Zhong-Liang Gong, Ti-Xiong Dan, Jiannian Yao, Yu-Wu Zhong
Summary: This study reported a pair of enantiomeric tridentate platinum-isocyanide complexes, achieving enhanced red phosphorescence and CPL through solution-state aggregation. The research provides insight into the mechanism of supramolecular chirality amplification.
Review
Biochemistry & Molecular Biology
Manuela Stefanelli, Gabriele Magna, Corrado Di Natale, Roberto Paolesse, Donato Monti
Summary: Conjugating the porphyrin ring with an amino acid via amide linkage allows for the creation of both amphiphilicity and chirality in the macrocycle. The use of proline residue is advantageous due to its conformational rigidity, which allows for efficient transfer and amplification of molecular chirality in aqueous environments. This article describes the evolution of studies conducted by the authors to achieve chiral systems from porphyrin-proline derivatives, both in solution and in the solid state. The discussion focuses on fundamental aspects that influence the resulting molecular architectures, including the nature of the appended group, the presence of coordinated metal ions, and the properties of the solvent. The fine-tuning of these parameters enables the creation of stereospecific structures with distinct chiroptical and morphological features. Solid films based on these chiral systems are also obtained and their recognition abilities in gaseous and liquid phases are discussed.
INTERNATIONAL JOURNAL OF MOLECULAR SCIENCES
(2022)
Article
Chemistry, Physical
Yuxia Zhang, Zhongxing Geng, Yu Zhang, Zhaoran Xu, Hang Li, Yixiang Cheng, Yiwu Quan
Summary: The study synthesized three achiral pyrene derivatives and found that only the chiral co-assembly could form regular and orderly helical nanofibers, emitting a strong deep blue circularly polarized luminescence signal.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2021)
Article
Chemistry, Multidisciplinary
Shuguo An, Aiyou Hao, Pengyao Xing
Summary: This study reports the first example of polyhedral oligosilsesquioxane (POSS) derivatives that can self-assemble into well-defined chiral nanoassemblies. These chiral nanoassemblies exhibit active chiroptical responses and can bind guest molecules through charge-transfer interactions, offering a new design protocol for functional chiral materials.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Longfei Yao, Kuo Fu, Xuejuan Wang, Menglu He, Wannian Zhang, Peng-Yu Liu, Yu-Peng He, Guofeng Liu
Summary: The study focuses on the dynamic supramolecular chirality inversion (SMCI), which deepens understanding of chiral transfer and amplification and aids in the development of chiral nanomaterials. The researchers successfully developed a hierarchical coassembly system based on mPAzPCC and various metal ions, achieving effective chirality transfer and temporal-controlled SMCI. The work provides insight into metal ion-mediated supramolecular asymmetric catalysis and bioinspired chiral sensing.
Article
Biotechnology & Applied Microbiology
Xuejiao Yang, Honglei Lu, Yinghua Tao, Hongyue Zhang, Huaimin Wang
Summary: This study reports a method to control the fiber alignment, chirality, and stiffness of aromatic peptide hydrogels through heterodimerization of enantiomeric mixtures. The relative ratio of L and D enantiomers can also regulate the adhesion and morphology of mammalian cells. This work provides a new strategy for controlling supramolecular chirality in materials science.
JOURNAL OF NANOBIOTECHNOLOGY
(2022)
Article
Chemistry, Multidisciplinary
Ikuya Matsumoto, Ryo Sekiya, Takeharu Haino
Summary: By decorating nanographenes with alkyl chains and controlling concentration, solvent polarity, temperature, and sonication, it is possible to achieve self-assembly and formation of stacked structures. Optical measurements and AFM images confirm the presence of stacked structures, while molecular mechanics calculations model the interactions within the aggregates. The nanographenes exhibit concentration-dependent morphologies, forming stacked structures at low concentrations and polymer-like network structures at higher concentrations on mica.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Bowen Shen, Chunyu Pan, Xiaopeng Feng, Jehan Kim, Mo Sun, Myongsoo Lee
Summary: Researchers report spontaneous chirality induction in a single layer 2D network structure formed from the self-assembly of tetrapod azobenzene molecules. The chirality induction occurs due to the slipping of multiple sublayers in a preferred direction, where the sublayer consists of different molecular arrangements in the in-plane a and b directions, breaking both the plane of symmetry and inversion symmetry. The protruded azobenzene units in the pore interior can be selectively isomerized upon UV irradiation, resulting in a reversible deformation of the chiral pores while maintaining the 2D frameworks. The chiral network can selectively trap one enantiomer from a racemic solution and release it upon UV irradiation.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Sylvain Sudan, Farzaneh Fadaei-Tirani, Rosario Scopelliti, Kristina E. Ebbert, Guido H. Clever, Kay Severin
Summary: Thirteen palladium-ligand assemblies with different structures and topologies were studied for their ability to bind lithium ions. It was found that the addition of LiBF4 caused a significant structural rearrangement in one case, converting a dinuclear [Pd2L4](4+) complex into a low-symmetry [Pd4L8](8+) assembly with two binding pockets for solvated LiBF4 ion pairs. This rearrangement was only induced by Li+, indicating highly specific host-guest interactions. Structural analysis revealed that the [Pd4L8](8+) receptor had a compact structure with multiple intramolecular interactions, similar to natural and synthetic foldamers.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Irene Regeni, Bin Chen, Marina Frank, Ananya Baksi, Julian J. Holstein, Guido H. Clever
Summary: This study introduces a strategy to incorporate four members of the classic coal-tar dye family into [Pd2L4] self-assemblies, investigating their performance in different ligands and color ranges, showing potential applications in chiroptical recognition, photo-redox catalysis, and optical materials. The results demonstrate different behaviors of the self-assemblies based on this new ligand class, such as chiral induction, binding modes distinction, and rearrangement to new structures.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Daniel Hugenbusch, Marc Lehr, Jan-Simon von Glasenapp, Anna J. McConnell, Rainer Herges
Summary: We report the photo-switching properties of two regioisomeric diazocine ligands. The self-assembly of these ligands with Co-II ions was studied, and reversible transformation between different ligand configurations and Co-II complexes was achieved through light-controlled switching.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
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
Chemistry, Applied
Anjana Sathyan, Linlin Deng, Tessa Loman, Anja R. A. Palmans
Summary: Bioorthogonal catalysis using transition-metal-based complexes (TMCs) shows promise for converting substrates to desired products in complex cellular media. Compartmentalization of the catalyst into tailor-made carrier materials, such as synthetic amphiphilic polymers, not only provides active catalysis but also allows for targeted delivery in therapeutic applications.
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
Polymer Science
Ramkrishna Sarkar, Soumabrata Majumdar, Sierd Kuil, Jorg Mallens, Joost J. B. van Der Tol, Rint P. Sijbesma, Johan P. A. Heuts, Anja R. A. Palmans
Summary: Dynamic covalent networks (DCNs) utilize chemical bonds that can break and reform to allow for network reconfiguration under appropriate processing conditions. The addition of the acylsemicarbazide (ASC) motif, capable of hydrogen bonding and dynamic bond exchange, has expanded the repertoire of dynamic covalent bonds. This study demonstrates that the sulfur congener, thioacylsemicarbazide (TASC), also functions as a dynamic covalent bond, albeit with a slower exchange rate than ASC. DCNs based on siloxane incorporating ASC, TASC, or both, exhibit tunable relaxation dynamics that decrease with a higher proportion of TASC motifs. The reduction in stress relaxation is accompanied by a decrease in network creep, and can be controlled by adjusting the ASC/TASC ratio. These networks can be easily processed and dissolved using compression molding and excess hydrazide treatment, respectively. The ability to manipulate network properties and creep in dynamic covalent polymeric networks through minor modifications in dynamic bond structure provides a versatile synthetic approach that can be applied within a wide temperature range.
JOURNAL OF POLYMER SCIENCE
(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)
Review
Chemistry, Multidisciplinary
Stefan Wijker, Anja R. A. Palmans
Summary: This article reviews different methods to fold synthetic polymers into structured, functional nanoparticles and compares their design principles to protein folding. The importance of structure for functional stability and diverse applications in complex media and cellular environments is emphasized. The similarities and differences between protein folding and synthetic polymer folding are highlighted in the formation of structured nanocompartments in water.
Article
Chemistry, Multidisciplinary
Anjana Sathyan, Tessa Loman, Linlin Deng, Anja R. A. Palmans
Summary: Rh-catalysed NH carbene insertion reactions were successfully introduced into living cells using amphiphilic polymeric nanoparticles. The hydrophobic dirhodium carboxylate catalysts were efficiently encapsulated in the nanoparticles, which promoted NH carbene insertions and cyclisation reactions. The best catalyst was exported to HeLa cells, resulting in the synthesis of fluorescent and cytotoxic compounds within a short time. This study expands the repertoire of bioorthogonal reactions and shows promising potential for biomedical applications.
Article
Chemistry, Multidisciplinary
Stefan Wijker, Rico Monnink, Luc Rijnders, Linlin Deng, Anja R. A. Palmans
Summary: Single-chain polymeric nanoparticles (SCPNs) containing solvatochromic pyrazoline adducts maintain conformational and operational stability in complex media and cellular compartments. The connectivity of the adduct plays a crucial role in modulating interactions with the surrounding media.
CHEMICAL COMMUNICATIONS
(2023)