Article
Chemistry, Physical
Bohang Wu, Lin Liu, Lu Zhou, Jose Rodrigo Magana, Marco M. R. M. Hendrix, Jiahua Wang, Chendan Li, Peng Ding, Yiming Wang, Xuhong Guo, Ilja K. Voets, Martien A. Cohen Stuart, Junyou Wang
Summary: The study developed a supramolecular polymer based on BTA, which forms stable fibers in the presence of appropriate metal ions; experiments showed that the formation and structure of the fibers were very similar for various transition metal ions, enabling the introduction of different functionalities by choosing different metal ions.
JOURNAL OF COLLOID AND INTERFACE SCIENCE
(2022)
Article
Polymer Science
Oleksandr Zagorodko, Tetiana Melnyk, Olivier Rogier, Vicent J. Nebot, Maria J. Vicent
Summary: This study successfully induced the self-assembly of twisted one-dimensional higher-order nanofibers using modified water-soluble benzene-1,3,5-tricarboxamide-based di- and tripeptide derivatives, with morphology dependent on the nature, order, and quantity of amino acids. Additionally, pairwise interfiber interactions observed during fiber splitting events provided insights into the gradual distortion of C3 symmetry in higher-order fibers.
Article
Chemistry, Multidisciplinary
Shahzad Hafeez, Monize Caiado Decarli, Agustina Aldana, Mahsa Ebrahimi, Floor A. A. Ruiter, Hans Duimel, Clemens van Blitterswijk, Louis M. Pitet, Lorenzo Moroni, Matthew B. Baker
Summary: This article investigates a synthetic supramolecular/covalent strategy for creating a tough hydrogel with the hierarchical fibrous architecture of the extracellular matrix (ECM). The hydrogelator self-assembles to form a viscoelastic hydrogel and is reinforced by covalent intra- and interfiber cross-links, resulting in enhanced mechanical properties. The hydrogels exhibit high tensile strain and compressive strain, are shear-thinning, and can be 3D bioprinted. Additionally, the hydrogels enable the bioprinting and differentiation of human mesenchymal stromal cell (hMSC) spheroids into chondrogenic tissue.
ADVANCED MATERIALS
(2023)
Article
Chemistry, Multidisciplinary
Silvia Pujals, Lorenzo Albertazzi, Edgar Fuentes, Yeray Gabaldon, Mario Collado, Shikha Dhiman
Summary: Supramolecular assemblies have unique formulation possibilities and adaptive behavior, making them attractive in the field of drug delivery. However, their non-covalent nature poses challenges when facing in vivo conditions. This study investigates the stability-responsiveness tradeoff of three monomers and finds distinct regimes. Furthermore, the study reveals a disconnection between intrinsic supramolecular robustness and supramolecular stability in the biological environment, influenced by the disassembly pathway upon protein interaction.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Multidisciplinary
Nada Aljuaid, Jani Seitsonen, Janne Ruokolainen, Francesca Greco, Ian W. Hamley
Summary: This study found that analogues of benzene-1,3,5-tricarboxamide can self-assemble into micelles or nanotapes in aqueous solution, depending on the architecture of alkyl and PEG chains. The compounds exhibit selective cytotoxicity to breast cancer cells, showing strong stability in acidic tumor conditions and cell culture media.
Article
Materials Science, Multidisciplinary
Zhongxuan Li, Hongmei Qu, Yuanyuan Zhai, Liqiang Liu
Summary: Three supramolecular gelators with benzene 1,3,5-tricarboxamide (BTA) motif were synthesized and studied for their gelation behavior. Among them, 3a exhibited excellent gelation behavior in a variety of aromatic solvents, phase-selectively gelling aromatic solvents, removing toxic dyes, and gelling crude oil. These smart systems have the potential to be effectively used in water purification and oil spills remediation.
Article
Chemistry, Physical
M. Raynal, Y. Li, C. Troufflard, C. Przybylski, G. Gontard, T. Maistriaux, J. Ide, R. Lazzaroni, L. Bouteiller, P. Brocorens
Summary: The study investigates the self-assembly behavior of amino-ester benzene-1,3,5-tricarboxamide monomers and reveals that both ester and amide carbonyls are involved in the hydrogen bond network of the dimeric species formed. Various conformations coexist in solution with rapid interconversion between them, leading to a symmetric structure. This fluxional behavior likely originates from a larger range of energetically favorable conformations accessible through rotation of the side chains.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2021)
Article
Chemistry, Organic
Sandra M. C. Schoenmakers, Bart W. L. van den Bersselaar, Shikha Dhiman, Lu Su, Anja R. A. Palmans
Summary: By starting from commercially available 5-aminoisophthalic acid, this study successfully synthesized inverted amide BTAs (iBTAs), improving synthetic efficiency while maintaining fiber structure and dynamics. Incorporating iBTAs into conventional BTA-based supramolecular polymers solved solubility issues, forming fibers similar to BTA homopolymers.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2021)
Article
Nanoscience & Nanotechnology
Kuo Su, Peng Zhao, Yu Ren, Yi Zhang, Guang Yang, Yuqiong Huang, Yaqing Feng, Bao Zhang
Summary: Surface defects in perovskite films are a major obstacle to the efficiency and stability of perovskite solar cells due to nonradiative recombination. The use of Por-BTA as an interface material effectively passivates these defects, improving interface contact and charge transfer. PSC devices treated with Por-BTA show increased power conversion efficiency, improved stability, and enhanced performance, indicating a promising direction for the design of organic molecules in PSCs.
ACS APPLIED MATERIALS & INTERFACES
(2021)
Article
Chemistry, Multidisciplinary
Noriyuki Tsukahara, Jun Yoshinobu
Summary: We investigate the formation processes and structures of self-assembled layers of 1,3,5-tris(4-bromophenyl)benzene (TBB) molecules on Ag(111) and Si(111) (/3×/3)-Ag surfaces using STM measurements and DFT calculations. Our findings demonstrate that the interplay between intermolecular interaction and molecule-substrate interaction plays a crucial role in controlling the characteristic structures of the self-assembled layers on the surfaces.
Article
Materials Science, Biomaterials
Shahzad Hafeez, Fiona R. Passanha, Antonio J. Feliciano, Floor A. A. Ruiter, Afonso Malheiro, Rene P. M. Lafleur, Nicholas M. Matsumoto, Clemens van Blitterswijk, Lorenzo Moroni, Paul Wieringa, Vanessa L. S. LaPointe, Matthew B. Baker
Summary: This study demonstrates that modular mixing enables tunable fibrous hydrogels, providing a biomimetic environment for cell encapsulation and suitable for the formation and culture of spheroids in 3D.
BIOMATERIALS SCIENCE
(2022)
Article
Chemistry, Multidisciplinary
Shahzad Hafeez, Ana A. Aldana, Hans Duimel, Floor A. A. Ruiter, Monize Caiado Decarli, Vanessa Lapointe, Clemens van Blitterswijk, Lorenzo Moroni, Matthew B. Baker
Summary: Traditional synthetic covalent hydrogels lack the native tissue dynamics and hierarchical fibrous structure found in the extracellular matrix (ECM). Here, the molecular tuning of a supramolecular benzene-1,3,5-tricarboxamide (BTA) hydrogelator via simple modulation of hydrophobic substituents is reported. These hydrogels show high cell viability for chondrocytes and human mesenchymal stem cells, establishing their use in tissue engineering applications.
ADVANCED MATERIALS
(2023)
Article
Chemistry, Multidisciplinary
Celine Nieuwland, Siebe Lekanne Deprez, Claris de Vries, Celia Fonseca Guerra
Summary: Our quantum chemical analyses revealed that replacing O with the larger chalcogens S and Se in benzene-1,3,5-tricarboxamides (OBTAs) enhances intermolecular interactions and increases the stability of hydrogen-bonded supramolecular polymers due to improved geometry for self-assembly and enhanced covalent interactions. Additionally, the cooperativity in benzene-1,3,5-triamide (BTA) self-assembly is attributed to charge separation in the sigma-electronic system following the covalency in the hydrogen bonds.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Polymer Science
Radoslav Z. Pavlovic, Simon A. Egner, Liam C. Palmer, Samuel I. Stupp
Summary: The objective of this perspective is to highlight the impact of dynamic nature in supramolecular polymers based on noncovalent bonding among monomers. Peptide amphiphile supramolecular polymers are discussed, with a focus on recent results on their dynamic behavior and potential functions. The study is motivated by the unprecedented bioactivity in supramolecular polymers, aiming to find strategies for reversing paralysis caused by traumatic injuries or disease and exploring novel functions through chemical design and understanding of supramolecular motion.
JOURNAL OF POLYMER SCIENCE
(2023)
Article
Chemistry, Physical
Filip Perlitius, Anna Walczak, Miroslava Conkova, Grzegorz Markiewicz, Jack Harrowfield, Artur R. Stefankiewicz
Summary: This study investigates the non-covalent aggregation of four benzene-1,3,5-tricarboxamide (BTA) derivatives formed from glycine or L-valine esters in both solid-state and chloroform solution. The study reveals the significant role of the steric bulk of the C-terminus protecting group in supramolecular aggregation in the solid-state and highlights the essential influence of substituent steric bulk on the nature and stability of BTA aggregates in distinct phases.
JOURNAL OF MOLECULAR LIQUIDS
(2022)
Article
Multidisciplinary Sciences
Roderick P. Tas, Marco M. R. M. Hendrix, Ilja K. Voets
Summary: Antifreeze proteins (AFPs) have been found to bind ice and lower freezing temperatures, making them crucial for the survival of organisms in icy environments. However, there is still debate over the mechanisms through which they function. In this study, subzero nanoscopy was used to observe the dynamics of individual AFPs binding to ice crystals. The results provided experimental evidence for the adsorption-inhibition paradigm and highlighted the importance of reversible binding to ice in the overall model of AFP activity.
PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA
(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)
Editorial Material
Chemistry, Multidisciplinary
Jillian M. Buriak, Deji Akinwande, Natalie Artzi, C. Jeffrey Brinker, Cynthia Burrows, Warren C. W. Chan, Chunying Chen, Xiaodong Chen, Manish Chhowalla, Lifeng Chi, William Chueh, Cathleen M. Crudden, Dino Di Carlo, Sharon C. Glotzer, Mark C. Hersam, Dean Ho, Tony Y. Hu, Jiaxing Huang, Ali Javey, Prashant V. Kamat, Il-Doo Kim, Nicholas A. Kotov, T. Randall Lee, Young Hee Lee, Yan Li, Luis M. Liz-Marzan, Paul Mulvaney, Prineha Narang, Peter Nordlander, Rahmi Oklu, Wolfgang J. Parak, Andrey L. Rogach, Mathieu Salanne, Paolo Samori, Raymond E. Schaak, Kirk S. Schanze, Tsuyoshi Sekitani, Sara Skrabalak, Ajay K. Sood, Ilja K. Voets, Shu Wang, Shutao Wang, Andrew T. S. Wee, Jinhua Ye
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
Chemistry, Applied
Sanam Foroutanparsa, Mariska Bruls, C. Elizabeth P. Maljaars, Roderick P. Tas, Ilja K. Voets
Summary: The acid-induced destabilization of casein micelles leads to milk coagulation, which is important for yogurt formation. The resulting protein network is formed by the aggregation and reconfiguration of casein micelles, with the release of a portion of caseins. The organization and distribution of individual alpha s1- and beta-caseins within this complex network and their dependence on yogurt composition and processing are still unknown.
FOOD HYDROCOLLOIDS
(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, Multidisciplinary
Robbert J. de Haas, Jannick van Ossenbruggen, Jeffrey van der Hoeven, Roel J. Timmermans, Roderick P. Tas, Ilja K. Voets, Renko de Vries
Summary: Solid interfacing biomaterials are crucial for bionanotechnology and biosensing applications. Flat solenoidal proteins are suitable scaffolds for designing solid-binding proteins, and a variant called RiSiBP-6 has been developed through mutation and shown to bind strongly to silica surfaces. The fusion of sfGFP-RiSiBP-6 allows for the functional display of a monolayer of sfGFP cargo on silica surfaces, indicating the potential of flat solenoidal proteins as scaffolds for solid-binding protein design.
ADVANCED MATERIALS INTERFACES
(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, 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
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)