Secondary Structure Tuning of a Pseudoprotein Between β‐Meander and α‐Helical Forms in the Solid‐State

Sureshan, Kana M.; Athiyarath, Vignesh; Madhusudhanan, Mithun C.; Kunnikuruvan, Sooraj

doi:10.1002/anie.202113129

Cited by 16 publications

(6 citation statements)

References 109 publications

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“…Topochemical azide–alkyne cycloaddition (TAAC) polymerization has emerged as a reliable method to synthesize crystalline polymers of peptides, − carbohydrates, − polyols, , and nucleic acids. , When molecules of a monomer are head-to-tail organized in its crystal with the proximal placement of its reacting groups, viz ., azide and alkyne, it can undergo TAAC polymerization to yield a triazole-linked polymer . Depending on the relative orientation of the azide and alkyne units in the crystal lattice, the triazole linkage can be through its 1,4- or 1,5-position. , In order to demonstrate the generality and versatility of TAAC polymerization, we envisioned adopting this methodology for the synthesis of nylons.…”

Section: Results and Discussionmentioning

confidence: 99%

Two Structurally Different Polymers from a Single Monomer

Pathan,

Bhandary,

Sureshan

2023

J. Am. Chem. Soc.

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We designed and synthesized a malonamide-derived monomer, containing azide and alkyne units, for topochemical polymerization to yield nylon (n,3). This monomer on crystallization gave two concomitant polymorphs M1 and M2. Both the polymorphs show crystal packings that are suitable for topochemical azide–alkyne cycloaddition polymerization. On heating, polymorph M1 reacts regiospecifically to give 1,4-disubstituted-1,2,3-triazolyl-linked polymer, whereas polymorph M2 yields 1,5-disubstituted-1,2,3-triazolyl-linked polymer regiospecifically. In the case of polymorph M1, polymerization proceeds perpendicular to the hydrogen bonding direction, whereas in M2, the reaction occurs along the hydrogen bonding direction. This results in the two structurally different polymers having distinct topologies. These single-crystal-to-single-crystal polymerizations allowed us to study their structure at atomic resolution by single-crystal X-ray diffraction. This is the first report on the topochemical synthesis of two structurally isomeric polymers from a single monomer.

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Section: Results and Discussionmentioning

confidence: 99%

Two Structurally Different Polymers from a Single Monomer

Pathan,

Bhandary,

Sureshan

2023

J. Am. Chem. Soc.

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“…Topochemical reactions, the solid-state reactions driven by the proximal arrangement of reacting groups in the crystal lattice, are attractive because of their green (solvent-free, catalyst-free) conditions, non-requirement of purification, high yield, regio-/stereospecificity, and formation of unique products that are not conceivable via solution-phase chemistry. , Topochemical reactions have paved the way not only for the synthesis of interesting small molecules − but also for the synthesis of several polymers. − However, the main bottleneck toward a successful topochemical polymerization is the pre-organization of monomers in the crystal lattice with the reactive units aligned suitably for the polymerization reaction. In order to meet such requirements, a careful molecular design is necessary.…”

Section: Resultsmentioning

confidence: 99%

Regiospecific Synthesis of a Reprocessable Galactan-Mimic via Topochemical Polymerization

Ravi

Hassan

Pathigoolla

et al. 2023

ACS Sustainable Chem. Eng.

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We synthesized a designed monomer with azide and alkyne units that mimic α-D-galactose for topochemical azidealkyne cycloaddition polymerization to produce a cross-linkable galactan-mimic. The monomer molecules pre-organize in the crystals in a linear head-to-tail fashion, with the reactive units properly aligned for topochemical reaction. When the monomer crystals are heated, they undergo regiospecific topochemical azide-alkyne cycloaddition polymerization, resulting in a galactan-mimic with two vicinal diol units per repeating unit. We covalently cross-linked this galactan-mimic using bis-dioxaborolane as the dynamic covalent cross-linker. When compared to the parent galactan-mimic, the mesoporous cross-linked polymer had a sevenfold increase in porosity, a 200-fold increase in particle size, and higher thermal stability. We demonstrated that by varying the temperature, the extent of cross-linking and thus particle size can be reversibly tuned. Our findings show that topochemical polymerization can be used to create polymers with improved properties from monomers derived from naturally available feedstock materials.

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“…The topochemical azide–alkyne cycloaddition (TAAC) reaction has emerged as a reliable method for the synthesis of triazole‐linked polymers from monomers decorated with azide and alkyne groups [4h,l, 5] . If monomer molecules align head‐to‐tail in the crystal lattice, with proximally placed azide and alkyne units, they undergo a lattice‐controlled azide–alkyne cycloaddition reaction yielding crystalline polymers.…”

Section: Resultsmentioning

confidence: 99%

Topochemical Postulates: Are They Relevant for Topochemical Reactions Occurring at Elevated Temperatures?

et al. 2022

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A rigid inositol‐derived monomer functionalized with azide and alkyne as the complementary reactive groups (CRGs) crystallized as three distinct polymorphs I–III. Despite the unsuitable orientation of CRGs in the crystals for complete polymerization, all the three polymorphs underwent regiospecific and quantitative topochemical azide–alkyne cycloaddition (TAAC) polymerization upon heating to yield three different polymorphs of 1,2,3‐triazol‐1,4‐diyl‐linked‐poly‐neo‐inositol. The molecules in these polymorphs exploit the weak intermolecular interactions, free space in the crystal lattice, and heat energy for their large and cooperative molecular motion to attain a transient reactive orientation, ultimately leading to the regiospecific TAAC reaction yielding distinct crystalline polymers. This study cautions that the overreliance on topochemical postulates for the prediction of topochemical reactivity at high temperatures could be misleading.

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Secondary Structure Tuning of a Pseudoprotein Between β‐Meander and α‐Helical Forms in the Solid‐State

Cited by 16 publications

References 109 publications

Two Structurally Different Polymers from a Single Monomer

Two Structurally Different Polymers from a Single Monomer

Regiospecific Synthesis of a Reprocessable Galactan-Mimic via Topochemical Polymerization

Topochemical Postulates: Are They Relevant for Topochemical Reactions Occurring at Elevated Temperatures?

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