Article
Chemistry, Multidisciplinary
Jincai Li, Joseph J. Richardson, Hirotaka Ejima
Summary: This article reports the first synthesis of dithiocatechol-pendant polymers using a novel protection-deprotection strategy. The resulting polymers are soluble in common organic solvents and can be fully characterized by standard spectroscopic methods. The study also demonstrates the possibility of using reversible addition-fragmentation chain-transfer polymerization to synthesize dithiocatechol-pendant polymers.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Multidisciplinary
Cijil Raju, Kozhukunnon Mridula, Nikitha Srinivasan, Sooraj Kunnikuruvan, Kana M. Sureshan
Summary: We describe the topochemical syntheses of three polyarylopeptides containing a triazolylphenyl group integrated into the peptide backbone. Three different monomers with azide and arylacetylene end-groups were synthesized from glycine, L-alanine, and L-valine. Crystal structures of two of the monomers were determined by single-crystal X-ray diffractometry, revealing their steric constraints and molecular arrangements. Upon heating, the monomer molecules undergo significant motion within the crystal lattice, allowing for a transient reactive orientation and the formation of triazole-linked polyarylopeptides with different linkages.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Berengere Aubry, Remi Canterel, Muriel Lansalot, Elodie Bourgeat-Lami, Aissam Airoudj, Bernadette Graff, Celine Dietlin, Fabrice Morlet-Savary, Jan Blahut, Ladislav Benda, Guido Pintacuda, Emmanuel Lacote, Jacques Lalevee
Summary: The utilization of N-heterocyclic carbene-borane complexes in a borane-(meth)acrylate click reaction has shown promising results in developing polymers with improved properties for 3D printing fuels. The increased network density and faster polymerization kinetics due to the higher bond number of boranes relative to thiols contribute to enhanced mechanical properties and reduced solvent swelling in the materials. Solid-state NMR, DMA, and AFM techniques confirm the significant role of boron centers in influencing the network properties of the materials.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Biochemistry & Molecular Biology
Jonas Becker, Roberto Terracciano, Gokhan Yilmaz, Richard Napier, C. Remzi Becer
Summary: Glycopolymers have potential for biomedical applications by exploiting interactions between carbohydrates and lectins. They can be used for targeted drug delivery to specific cells through their specific recognition capabilities. However, a challenge in glycopolymers research is the specificity of recognition to receptors binding to the same sugar unit. In this study, a method for producing glycopolymers with a defined tacticity based on click chemistry was presented.
Article
Chemistry, Multidisciplinary
Kubra Kalayci, Hendrik Frisch, Christopher Barner-Kowollik, Vinh X. Truong
Summary: We introduce a visible light-induced Staudinger-Bertozzi ligation by combining a photolabile coumarin derivative with a triphenylphosphine moiety. Our study reveals that the uncaging process and Staudinger reaction can be triggered by green light (λ < 550 nm). We demonstrate the applicability of our approach in materials science through endgroup modification of water soluble poly(ethylene glycol) and green light-induced patterning of a solid substrate.
CHEMICAL COMMUNICATIONS
(2022)
Article
Polymer Science
Jinkang Dou, Minghui Xu, Bojun Tan, Hongchang Mo, Xianming Lu, Bozhou Wang, Ning Liu
Summary: Nitrile N-oxide-based click ligation is a promising technique for polymer crosslinking due to its catalyst-free and byproduct-free reactions. In this study, methyl groups were introduced to enhance the stability and reactivity of phenyl nitrile N-oxides. Novel aromatic nitrile N-oxides were synthesized and used as efficient reagents for catalyst-free crosslinking of natural rubber, resulting in elastomers with good mechanical properties.
Article
Chemistry, Applied
Stefano Torresi, Tamara Calvo-Correas, Senda Basasoro, Olatz Guaresti, Ana Alonso-Varona, Nagore Gabilondo, Arantxa Eceiza
Summary: A new biobased polyurethane formulation containing furan was synthesized and functionalized via Diels-Alder and retro Diels-Alder reactions, showing potential for versatile applications. The polymer, with high renewable content and spinnability, exhibits good biocompatibility and can be used in biomedical tissue engineering.
REACTIVE & FUNCTIONAL POLYMERS
(2022)
Article
Chemistry, Applied
Stefano Torresi, Tamara Calvo-Correas, Senda Basasoro, Olatz Guaresti, Ana Alonso-Varona, Nagore Gabilondo, Arantxa Eceiza
Summary: A biobased polyurethane formulation containing furan was synthesized and functionalized via reaction. The formulation was processed into nanofiber membranes using electrospinning. The polymer has the advantages of being catalyst-free, having high renewable content, and being easily producible. The membranes are highly hydrophobic, allowing for functionalization reactions in water with minimal impact on membrane integrity. The material also exhibits good biocompatibility, making it suitable for biomedical tissue applications.
REACTIVE & FUNCTIONAL POLYMERS
(2022)
Article
Chemistry, Multidisciplinary
Leona L. Rodrigues, Aaron S. Micallef, Michael C. Pfrunder, Vinh X. Truong, John C. McMurtrie, Tim R. Dargaville, Anja S. Goldmann, Florian Feist, Christopher Barner-Kowollik
Summary: A highly efficient ligation system based on visible light-induced rearrangement was introduced, generating a thiophenol for rapid thiol-Michael additions without the need for additives. The self-catalyzed ligation through pyridine mediated deprotonation of the photochemically generated thiophenol was described, leading to additive-free thiol-Michael reactions. The study explored various reaction conditions, solvents, and substrates, showcasing excellent end group fidelity in polymer modification.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Multidisciplinary
Teruhiko Matsubara, Kenjiro Takemura
Summary: By using alternative process designs without plastics for chemical and biological reactions, researchers can achieve a more sustainable and risk-free reaction process, benefiting future generations.
Review
Polymer Science
Yi Shi, Wangmeng Hou, Zheqi Li, Yongming Chen
Summary: Molecular bottlebrush (MBB) is an important type of unimolecular nanomaterial, and the chemical and physical properties of MBBs can be significantly affected by the topological structure of backbones and side chains. In recent years, researchers have successfully synthesized polymers with diverse architectures using MBB as building blocks. This mini-review briefly summarizes the recent progress on the tailor of well-defined MBBs with diverse architectures using a grafting-onto strategy combined with controlled polymerization technique.
MACROMOLECULAR RAPID COMMUNICATIONS
(2023)
Article
Chemistry, Multidisciplinary
Suhua Li, Gencheng Li, Bing Gao, Sidharam P. Pujari, Xiaoyan Chen, Hyunseok Kim, Feng Zhou, Liana M. Klivansky, Yi Liu, Hafedh Driss, Dong-Dong Liang, Jianmei Lu, Peng Wu, Han Zuilhof, John Moses, K. Barry Sharpless
Summary: SuFEx is a type of click chemistry that allows covalent linking of modular units through sulfur(vi) connective hubs, leading to the synthesis of structurally diverse copolymers with high efficiency and stable bonds. SuFEx click chemistry offers the potential for post-polymerization modification, enabling the synthesis of materials with control over composition and conformation, making it a powerful tool in polymer chemistry.
Article
Chemistry, Multidisciplinary
Wen Shang, Roxana F. Schlam, Magali B. Hickey, Jingye Zhou, Kraig A. Wheeler, Graciela C. Diaz de Delgado, Chun-Hsing Chen, Barry B. Snider, Bruce M. Foxman
Summary: Gamma-irradiation or heating treatment of sodium trans-2-butenoate can convert it into 1-hexene-3,4-dicarboxylate, but the mechanisms for the formation of the product differ between the two methods. Furthermore, gamma-irradiation can also induce a specific trimerization reaction of sodium trans-2-butenoate.
CRYSTAL GROWTH & DESIGN
(2021)
Article
Polymer Science
Bercis Pektas, Gokhan Sagdic, Ozgun Daglar, Serter Luleburgaz, Ufuk Saim Gunay, Gurkan Hizal, Umit Tunca, Hakan Durmaz
Summary: In this study, a polythioether with double clickable alkyne groups was prepared using a rapid polymerization method and combined with CuAAC click reaction to construct new topological polymers. The synthesis and post-polymerization modification processes were shown to be rapid and efficient.
Article
Multidisciplinary Sciences
Qiaochu Jiang, Wenjun Zhan, Xiaoyang Liu, Lin Bai, Manli Wang, Ying Xu, Gaolin Liang
Summary: The authors present an assembly-driven, regioselective metal-free azide-alkyne cycloaddition reaction with potential applications in biomedical contexts. In the absence of metal ions, supramolecular self-assembly in an aqueous solution is used to achieve excellent regioselectivity in the reaction, paving the way for more metal-free reactions in chemical biology.
NATURE COMMUNICATIONS
(2023)
Article
Chemistry, Multidisciplinary
Markus Bursch, Lukas Kunze, Amol M. Vibhute, Andreas Hansen, Kana M. Sureshan, Peter G. Jones, Stefan Grimme, Daniel B. Werz
Summary: Noncovalent interactions between azides and oxygen-containing moieties were investigated through computational study. Six new organic compounds with close intramolecular azide-oxygen contacts were synthesized, and a set of 44 high-quality gas-phase computational model systems were examined using different quantum mechanical methods. The nature of the noncovalent interaction, especially the roles of electrostatic and London dispersion interactions, were discussed, with London dispersion identified as a dominant factor.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Multidisciplinary
Rishika Rai, Kana M. Sureshan
Summary: The designed heterochiral dipeptide monomer underwent topochemical azide-alkyne cycloaddition (TAAC) polymerization to form two different polymorphs: PI with parallel beta-sheet packing and PII with antiparallel beta-sheet packing. PI reacted spontaneously at room temperature while PII remained intact even after complete reaction. The resulting aerogels from these polymorphs also underwent spontaneous TAAC reaction to yield a pseudoprotein with alternate D- and L-amino acids.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Arthi Ravi, Syed Zahid Hassan, Subhrajyoti Bhandary, Kana M. Sureshan
Summary: In this study, a rigid inositol-derived monomer functionalized with azide and alkyne was used for regiospecific and quantitative topochemical azide-alkyne cycloaddition (TAAC) polymerization in crystalline polymorphs. The study highlights the caution of overreliance on topochemical postulates for predicting reactivity at high temperatures.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
[Anonymous]
Summary: The research article discusses a topochemical reaction that results in the formation of polymorphs of triazolyl-linked polyinositol.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Subhrajyoti Bhandary, Atchutarao Pathigoolla, Mithun C. Madhusudhanan, Kana M. Sureshan
Summary: A new class of attractive intermolecular interaction between azide and ethynyl structural entities in a wide range of molecular crystals is reported. The supramolecular features of the azide-alkyne interaction were mapped by various crystallographic and quantum chemical approaches. The strength of the interaction is primarily guided by dispersion forces with an influencing contribution from electrostatics.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Green & Sustainable Science & Technology
Cijil Raju, Liby Ann Mathew, Kana M. Sureshan
Summary: A core-shell sorbent using natural fibers has been developed for efficient marine oil spill recovery, providing a simple method for oil absorption and recovery.
ADVANCED SUSTAINABLE SYSTEMS
(2022)
Article
Chemistry, Multidisciplinary
Cijil Raju, Sooraj Kunnikuruvan, Kana M. Sureshan
Summary: This study presents a new synthetic strategy for the cycloaddition reaction between non-polarized internal alkynes and azides to yield trisubstituted triazoles. By designing a cyclitol-derived monomer with azide and internal alkyne groups, the reactive orientation necessary for topochemical reaction was achieved through the crystal packing of the monomer molecules. Upon heating, the monomer underwent topochemical polymerization to form a trisubstituted-1,2,3-triazole-linked-polycyclitol.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Kuntrapakam Hema, Cijil Raju, Subhrajyoti Bhandary, Kana M. Sureshan
Summary: The regiochemistry of topochemical reactions is determined by the crystal structure, and precise crystal engineering is required for biasing the regiochemistry. By designing and synthesizing crystals, as well as controlling the reaction conditions, targeted polymers can be selectively obtained.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Multidisciplinary Sciences
Ravichandran Khazeber, Kana M. Sureshan
Summary: This study reports a helical peptide-polymer synthesized via TEAC polymerization. The polymer forms beta-sheets and supramolecular helices in the solid state. Structural analysis of the crystal lattice reveals that the adjacent molecules are preorganized for TEAC reaction. Single-crystal X-ray diffraction studies show that the polymer can be synthesized in a single-crystal-to-single-crystal fashion and undergoes reaction upon heating.
PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA
(2022)
Article
Chemistry, Multidisciplinary
Cijil Raju, Gunjan R. Ramteke, K. V. Jovan Jose, Kana M. Sureshan
Summary: A topochemical polymerization governed by a topotactic polymorphic transition is described. Crystallized form of monomer with azide and an internal alkyne did not react due to the specific arrangement of molecules. However, upon heating, a polymorphic transition occurred, resulting in a reactive form capable of undergoing topochemical reaction to form a polymer. This study highlights the unpredictability of topochemical reactivity based solely on crystal structure.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Arthi Ravi, Syed Zahid Hassan, Atchutarao Pathigoolla, Anu Lal, Babu Varghese, Kana M. Sureshan
Summary: We synthesized a designed monomer with azide and alkyne units that mimic alpha-D-galactose for topochemical azidealkyne cycloaddition polymerization. The resulting cross-linkable galactan-mimic showed improved properties, such as increased porosity, particle size, and thermal stability, when covalently cross-linked using bis-dioxaborolane as the dynamic covalent cross-linker. Our findings demonstrate that topochemical polymerization can be used to create polymers with enhanced properties from naturally available feedstock materials.
ACS SUSTAINABLE CHEMISTRY & ENGINEERING
(2023)
Article
Chemistry, Multidisciplinary
Rishika Rai, Ravichandran Khazeber, Kana M. Sureshan
Summary: A covalent helical polymer was synthesized by biomimicry, which exhibited high strength and load-bearing capacity in its single crystals, making it suitable for various technological applications.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Cijil Raju, Kozhukunnon Mridula, Nikitha Srinivasan, Sooraj Kunnikuruvan, Kana M. Sureshan
Summary: We describe the topochemical syntheses of three polyarylopeptides containing a triazolylphenyl group integrated into the peptide backbone. Three different monomers with azide and arylacetylene end-groups were synthesized from glycine, L-alanine, and L-valine. Crystal structures of two of the monomers were determined by single-crystal X-ray diffractometry, revealing their steric constraints and molecular arrangements. Upon heating, the monomer molecules undergo significant motion within the crystal lattice, allowing for a transient reactive orientation and the formation of triazole-linked polyarylopeptides with different linkages.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Javed R. Pathan, Subhrajyoti Bhandary, Kana M. Sureshan
Summary: We designed and synthesized a malonamide-derived monomer with azide and alkyne units for topochemical polymerization to produce nylon (n,3). Two polymorphs M1 and M2 were obtained upon crystallization of this monomer. The polymorphs exhibited suitable crystal packings for topochemical azide-alkyne cycloaddition polymerization. Depending on the polymorph, heating resulted in the regiospecific formation of either 1,4-disubstituted-1,2,3-triazolyl-linked polymer (M1) or 1,5-disubstituted-1,2,3-triazolyl-linked polymer (M2). These single-crystal-to-single-crystal polymerizations allowed for atomic resolution structure analysis using single-crystal X-ray diffraction. This is the first reported instance of synthesizing two chemically distinct polymers from a single monomer.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Vignesh Athiyarath, Liby Ann Mathew, Yakai Zhao, Ravichandran Khazeber, Upadrasta Ramamurty, Kana M. Sureshan
Summary: By packing a polymer in different ways, polymorphs with different properties can be obtained. In this study, we designed an Aib-rich monomer that crystallizes as two polymorphs and one hydrate. Upon heating, both polymorphs undergo topochemical polymerization. Polymorph I undergoes single-crystal-to-single-crystal polymerization and exhibits a screw-sense reversing helical structure, while polymorph II becomes amorphous. Different polymorphs and polymers show different mechanical properties according to their crystal packing. This study demonstrates the future potential of polymorphism and topochemistry in obtaining polymer polymorphs.
