Crystal‐to‐Crystal Synthesis of Helically Ordered Polymers of Trehalose by Topochemical Polymerization

Hema, Kuntrapakam; Gonnade, Rajesh G.; Sureshan, Kana M.

doi:10.1002/ange.201914164

Angewandte Chemie

2020

DOI: 10.1002/ange.201914164

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Crystal‐to‐Crystal Synthesis of Helically Ordered Polymers of Trehalose by Topochemical Polymerization

Kuntrapakam Hema

Rajesh G. Gonnade

Kana M. Sureshan

Abstract: The synthesis of crystalline helical polymers of trehalose via topochemical azide–alkyne cycloaddition (TAAC) of a trehalose‐based monomer is presented. An unsymmetrical trehalose derivative having azide and alkyne crystallizes in two different forms having almost similar packing. Upon heating, both the crystals undergo TAAC reaction to form crystalline polymers. Powder X‐ray diffraction (PXRD) studies revealed that the monomers in both the crystals polymerize in a crystal‐to‐crystal fashion; circular dichrois… Show more

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Cited by 12 publications

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“…[23] We have been interested in the topochemical azide-alkyne cycloaddition (TAAC) reaction, the lattice-controlled cycloaddition reaction between proximally placed azide and alkyne groups giving triazole products in the crystals. [24] We have exploited this reaction for synthesizing several biopolymer-mimics wherein the small-biomoleculebased monomers are linked by triazolyl-linkages. [25] Along these lines, we planned to synthesize a novel pseudoprotein with Gly-Phe-Gly repeats using the dipeptide 1.…”

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β‐Sheet to Helical‐Sheet Evolution Induced by Topochemical Polymerization: Cross‐α‐Amyloid‐like Packing in a Pseudoprotein with Gly‐Phe‐Gly Repeats

Hema

Sureshan

2020

Angewandte Chemie

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Protein‐mimics are of great interest for their structure, stability, and properties. We are interested in the synthesis of protein‐mimics containing triazole linkages as peptide‐bond surrogate by topochemical azide‐alkyne cycloaddition (TAAC) polymerization of azide‐ and alkyne‐modified peptides. The rationally designed dipeptide N3‐CH2CO‐Phe‐NHCH2CCH (1) crystallized in a parallel β‐sheet arrangement and are head‐to‐tail aligned in a direction perpendicular to the β‐sheet‐direction. Upon heating, crystals of 1 underwent single‐crystal‐to‐single‐crystal polymerization forming a triazole‐linked pseudoprotein with Gly‐Phe‐Gly repeats. During TAAC polymerization, the pseudoprotein evolved as helical chains. These helical chains are laterally assembled by backbone hydrogen bonding in a direction perpendicular to the helical axis to form helical sheets. This interesting helical‐sheet orientation in the crystal resembles the cross‐α‐amyloids, where α‐helices are arranged laterally as sheets.

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confidence: 99%

β‐Sheet to Helical‐Sheet Evolution Induced by Topochemical Polymerization: Cross‐α‐Amyloid‐like Packing in a Pseudoprotein with Gly‐Phe‐Gly Repeats

Hema

Sureshan

2020

Angewandte Chemie

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Solid‐Phase Radical Polymerization of Halogen‐Bond‐Based Crystals and Applications to Pre‐Shaped Polymer Materials

Wang

Goto

2020

Angewandte Chemie

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Liquid vinyl monomers were converted into solid crystals via halogen bonding. They underwent solid‐phase radical polymerizations through heating at 40 °C or ultraviolet photo‐irradiation (365 nm). The X‐ray crystallography analysis showed the high degree of monomer alignment in the crystals. The polymerizations of the solid monomer crystals yielded polymers with high molecular weights and relatively low dispersities because of the high degree of the monomer alignment in the crystal. As a unique application of this system, the crystalized monomers were assembled to pre‐determined structures, followed by solid‐phase polymerization, to obtain a two‐layer polymer sheet and a three‐dimensional house‐shaped polymer material. The two‐layer sheet contained a unique asymmetric pore structure and exhibited a solvent‐responsive shape memory property and may find applications to asymmetric membranes and polymer actuators.

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Azide⋅⋅⋅Oxygen Interaction: A Crystal Engineering Tool for Conformational Locking

et al. 2021

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We have designed, synthesized, and crystallized 36 compounds, each containing an azide group and an oxygen atom separated by three bonds. Crystal structure analysis revealed that each of these molecules adopts a conformation in which the azide and oxygen groups orient syn to each other with a short O⋅⋅⋅Nβ contact. Geometry‐optimized structures [using M06‐2X/6–311G(d,p) level of theory] also showed the syn conformation in all 36 of these cases, suggesting that this is not merely a crystal packing effect. Quantum topological analysis using Bader's Atoms in Molecules (AIM) theory revealed bond paths and bond critical points (BCP) in these structures suggesting its nature and energetics to be similar to weak hydrogen bonding. The NCI‐RDG plot clearly revealed the attractive interaction consisting of electrostatic or dispersive components in all the 36 systems. NBO analysis suggested a weak orbital‐relaxation (charge‐transfer) contribution of energy for a few (sp2)O‐donor systems. Natural population analysis (NPA) and molecular electrostatic potential mapping (MESP) of these crystal structures further revealed the existence of favorable azide‐oxygen interaction. A CSD search indicated the frequent and consistent occurrence of this interaction and its role dictating the syn conformation of azide and oxygen in molecules where these groups are separated by 2–4 bonds.

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Crystal‐to‐Crystal Synthesis of Helically Ordered Polymers of Trehalose by Topochemical Polymerization

Cited by 12 publications

References 89 publications

β‐Sheet to Helical‐Sheet Evolution Induced by Topochemical Polymerization: Cross‐α‐Amyloid‐like Packing in a Pseudoprotein with Gly‐Phe‐Gly Repeats

β‐Sheet to Helical‐Sheet Evolution Induced by Topochemical Polymerization: Cross‐α‐Amyloid‐like Packing in a Pseudoprotein with Gly‐Phe‐Gly Repeats

Solid‐Phase Radical Polymerization of Halogen‐Bond‐Based Crystals and Applications to Pre‐Shaped Polymer Materials

Azide⋅⋅⋅Oxygen Interaction: A Crystal Engineering Tool for Conformational Locking

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