Design of a thermally controlled sequence of triazolinedione-based click and transclick reactions

Houck, Hannes A.; Bruycker, Kevin De; Billiet, Stijn; Dhanis, Bastiaan; Goossens, Hannelore; Çatak, Şaron; Speybroeck, Véronique Van; Winne, Johan M.; Prez, Filip Du

doi:10.1039/c7sc00119c

Cited by 51 publications

(58 citation statements)

References 30 publications

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“…Furthermore, we used the efficient, recently revisited "click chemistry" of 1,2,4-triazoline-3,5-diones (TAD) 17,18 to modify the double bonds along the PPE backbone to further adjust the material properties. This TADene chemistry can not only be applied as a reliable and convenient post-modification reaction of unsaturated polymers but will also introduce additional nitrogen atoms into the PPEs, which is expected to have a positive influence on their flame retardant performance.…”

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confidence: 99%

Triazolinedione-“clicked” poly(phosphoester)s: systematic adjustment of thermal properties

et al. 2017

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The thermal properties of halogen-free flame retardant poly(phosphoester)s from acyclic diene metathesis polycondensation have been optimized by a systematic post-modification using 1,2,4-triazoline-3,5-dione derivatives. The straightforward modification not only increased their glass transition temperatures significantly but also improved the thermal stability with respect to their char yields.Poly( phosphoester)s (PPEs) can be prepared via both ringopening polymerization and polycondensation.1,2 We recently applied ADMET polycondensation to prepare a variety of PPEs. [3][4][5][6] Currently, PPEs are studied in biomedical applications for their biocompatibility, 7 biodegradability and adjus- show higher resistance to leaching and migration, compared to low molecular weight additives. 9 Indeed, phosphorus is an efficient char promoter forming an accumulated protective layer on the materials surface, which limits the release of fuel to the flame. 10,11 Additionally, PPEs typically show low toxicity or almost smoke-free burning. 12,13 Recently, the combination of phosphorus-containing flame retardants with nitrogen compounds has attracted much attention. The combination of both elements physically and chemically can dramatically improve the action of the phosphorus species in the condensed phase upon combustion. 14,15 Nitrogen compounds are believed to act by the release of inert gases or by the promotion of char formation as a result of a condensation reaction.Besides phosphorus and nitrogen, the introduction of aromatic structures is also often mentioned to promote the charring. 16As a systematic study on the thermal properties and char yield, with structural variation of the main-and side chains of PPEs, is missing in the current literature, the main goal of this research was the preparation of modified PPEs via ADMET polycondensation, as a result of the variation of both the backbone and side chains. Furthermore, we used the efficient, recently revisited "click chemistry" of 1,2,4-triazoline-3,5-diones (TAD) 17,18 to modify the double bonds along the PPE backbone to further adjust the material properties. This TADene chemistry can not only be applied as a reliable and convenient post-modification reaction of unsaturated polymers but will also introduce additional nitrogen atoms into the PPEs, which is expected to have a positive influence on their flame retardant performance. TADs are one of the most reactive (di)enophiles and show quantitative conversions at room temperature with isolated alkenes or conjugated dienes, respectively in an Alder-ene or Diels-Alder reaction. TAD has recently been applied in a wide range of applications, such as self-healing, 19 surface chemistry, 20-22 and post-modification of unsaturated ADMET polymers. 23This is the first report on the post-modification of PPEs via their internal double bonds for tuning their thermal properties. Supposing that TAD-modification can increase the glass transition temperature (T g ), this would undoubtedly broaden the range of applications for PPEs...

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Triazolinedione-“clicked” poly(phosphoester)s: systematic adjustment of thermal properties

et al. 2017

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“…In order to fabricate amphiphilic peptide/peptoid‐coated silica particles, the ring‐opening copolymerization of equivalent masses of l ‐tryptophan NCA (W‐NCA) and d / l ‐phenylalanine NCA (F‐NCA) (1:1.2 molar equivalents respectively) was carried out to generate the hydrophobic poly(peptide) core, while chain extension via the ROP of sarcosine NCA (sar‐NCA) was employed to yield the hydrophilic poly(peptoid) corona. In addition to its hydrophobic nature, tryptophan was selected owing to its indole side group which is known to undergo catalyst‐free, reversible indole‐ene “click” reactions with triazolinediones . Conversely, d / l ‐phenylalanine was employed as a non‐reactive co‐monomer “spacer,” with the purpose of reducing potential intra‐molecular crosslinking between tryptophan residues.…”

Section: Resultsmentioning

confidence: 98%

Synthesis of Novel bis‐Triazolinedione Crosslinked Amphiphilic Polypept(o)ide Nanostructures

Brannigan

Kimmins

Bobbi

et al. 2019

Macro Chemistry & Physics

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Owing to their wide range of inherent functionality, hydrolytic stability, biodegradability, and low toxicity, polypeptide‐based materials have been increasingly exploited for controlled drug release applications. More recently, the incorporation of poly(α‐peptoid)s such as poly(sarcosine) into polypeptide‐based materials has been investigated owing to their potential as naturally derived “stealth polymers.” Here the synthesis of novel amphiphilic polypept(o)ide nanoparticles is described utilizing silica templates as a macroinitiator for the ring‐opening copolymerization of l‐tryptophan and d/l‐phenylalanine NCAs and subsequent chain extension with sarcosine NCA. These particles are subsequently crosslinked utilizing the TAD‐indole “click” chemistry and the silica templates are eroded via treatment with HF yielding core crosslinked amphiphilic polypept(o)ide nanostructures. This synthetic strategy offers a unique platform to yield naturally‐derived degradable core‐crosslinked nanostructures, which may have the potential to be utilized in the future as delivery vehicles for hydrophobic small molecules.

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“…Moreover, an observed activation energy E a,obs = 116.1 ± 8.5 kJ mol −1 could be derived from the kinetic study (Table S1, Supporting Information), which is in accordance with the values of previous studies on simple low molecular weight TAD‐indole systems (see Supporting Information for details). [ 32,33 ]…”

Section: Resultsmentioning

confidence: 99%

“…Specifically, we aimed to synthesize macromolecules bearing a numeric code by using the thermoreversible reaction of 1,2,4‐triazoline‐3,5‐dione (TAD) coupling reagents with indole substrates. [ 32–34 ] This was used in combination with the Passerini three‐component reaction (P‐3CR), which is the one‐pot reaction between a carboxylic acid, aldehyde or ketone, and isocyanide ( Figure ). [ 35 ] In contrast to the thermal unzipping of sequences that requires high degradation temperatures, [ 23 ] the bond scission profile of TAD‐indole linkages is accessible at a much milder temperature range (i.e., 60–150 °C).…”

Section: Introductionmentioning

confidence: 99%

From Sequence‐Defined Macromolecules to Macromolecular Pin Codes

et al. 2020

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Dynamic sequence‐defined oligomers carrying a chemically written pin code are obtained through a strategy combining multicomponent reactions with the thermoreversible addition of 1,2,4‐triazoline‐3,5‐diones (TADs) to indole substrates. The precision oligomers are specifically designed to be encrypted upon heating as a result of the random reshuffling of the TAD‐indole covalent bonds within the backbone, thereby resulting in the scrambling of the encoded information. The encrypted pin code can eventually be decrypted following a second heating step that enables the macromolecular pin code to be deciphered using 1D electrospray ionization‐mass spectrometry (ESI‐MS). The herein introduced concept of encryption/decryption represents a key advancement compared with current strategies that typically use uncontrolled degradation to erase and tandem mass spectrometry (MS/MS) to analyze, decipher, and read‐out chemically encrypted information. Additionally, the synthesized macromolecules are coated onto a high‐value polymer material, which demonstrates their potential application as coded product tags for anti‐counterfeiting purposes.

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Design of a thermally controlled sequence of triazolinedione-based click and transclick reactions

Abstract: An unprecedented relay of triazolinedione-based transclick reactions between three different substrates has been demonstrated both on small molecule and macromolecular level.

Cited by 51 publications

References 30 publications

Triazolinedione-“clicked” poly(phosphoester)s: systematic adjustment of thermal properties

Triazolinedione-“clicked” poly(phosphoester)s: systematic adjustment of thermal properties

Synthesis of Novel bis‐Triazolinedione Crosslinked Amphiphilic Polypept(o)ide Nanostructures

From Sequence‐Defined Macromolecules to Macromolecular Pin Codes

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