Modular modification of xylan with UV-initiated thiol-ene reaction

Leena Nurmi (Corresponding Author), Reeta Salminen, Harri Setälä

    Research output: Contribution to journalArticleScientificpeer-review

    2 Citations (Scopus)

    Abstract

    Birch xylan was functionalized with various thiols through UV initiated radical thiol-ene reaction under mild conditions. Xylan was allylated through etherification with allyl glycidyl ether under alkaline conditions. The allylated xylan was then reacted with thiols containing varying functional groups: trimethylbenzyl mercaptan, dodecanethiol, thioglycolic acid, l-cysteine and cysteamine hydrochloride. The reactions were conducted under homogeneous conditions at room temperature, either in water (hydrophilic thiols) or in DMF (hydrophobic thiols). The effect of reaction parameters to the functionalization efficiency was studied, including, for example, thiol excess, thiol character, initiator amount and reaction mixture concentration. The reactions were fast and 100% conversion of allyl groups was reached in most cases, sometimes already within 10 min. Water as solvent resulted generally in faster reactions when compared to DMF, and it was possible to conduct the aqueous reaction even without added UV initiator. It was also possible to incorporate two functionalities simultaneously during one reaction into the xylan structure.
    Original languageEnglish
    Pages (from-to)63-69
    JournalCarbohydrate Research
    Volume404
    DOIs
    Publication statusPublished - 2015
    MoE publication typeA1 Journal article-refereed

    Fingerprint

    Xylans
    Sulfhydryl Compounds
    Cysteamine
    Betula
    Water
    Functional groups
    Cysteine
    Temperature

    Keywords

    • xylan
    • chemical functionalization
    • thiol-ene chemistry

    Cite this

    @article{1212f42b823f406193819919cc22c08f,
    title = "Modular modification of xylan with UV-initiated thiol-ene reaction",
    abstract = "Birch xylan was functionalized with various thiols through UV initiated radical thiol-ene reaction under mild conditions. Xylan was allylated through etherification with allyl glycidyl ether under alkaline conditions. The allylated xylan was then reacted with thiols containing varying functional groups: trimethylbenzyl mercaptan, dodecanethiol, thioglycolic acid, l-cysteine and cysteamine hydrochloride. The reactions were conducted under homogeneous conditions at room temperature, either in water (hydrophilic thiols) or in DMF (hydrophobic thiols). The effect of reaction parameters to the functionalization efficiency was studied, including, for example, thiol excess, thiol character, initiator amount and reaction mixture concentration. The reactions were fast and 100{\%} conversion of allyl groups was reached in most cases, sometimes already within 10 min. Water as solvent resulted generally in faster reactions when compared to DMF, and it was possible to conduct the aqueous reaction even without added UV initiator. It was also possible to incorporate two functionalities simultaneously during one reaction into the xylan structure.",
    keywords = "xylan, chemical functionalization, thiol-ene chemistry",
    author = "Leena Nurmi and Reeta Salminen and Harri Set{\"a}l{\"a}",
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    doi = "10.1016/j.carres.2014.11.009",
    language = "English",
    volume = "404",
    pages = "63--69",
    journal = "Carbohydrate Research",
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    }

    Modular modification of xylan with UV-initiated thiol-ene reaction. / Nurmi, Leena (Corresponding Author); Salminen, Reeta; Setälä, Harri.

    In: Carbohydrate Research, Vol. 404, 2015, p. 63-69.

    Research output: Contribution to journalArticleScientificpeer-review

    TY - JOUR

    T1 - Modular modification of xylan with UV-initiated thiol-ene reaction

    AU - Nurmi, Leena

    AU - Salminen, Reeta

    AU - Setälä, Harri

    PY - 2015

    Y1 - 2015

    N2 - Birch xylan was functionalized with various thiols through UV initiated radical thiol-ene reaction under mild conditions. Xylan was allylated through etherification with allyl glycidyl ether under alkaline conditions. The allylated xylan was then reacted with thiols containing varying functional groups: trimethylbenzyl mercaptan, dodecanethiol, thioglycolic acid, l-cysteine and cysteamine hydrochloride. The reactions were conducted under homogeneous conditions at room temperature, either in water (hydrophilic thiols) or in DMF (hydrophobic thiols). The effect of reaction parameters to the functionalization efficiency was studied, including, for example, thiol excess, thiol character, initiator amount and reaction mixture concentration. The reactions were fast and 100% conversion of allyl groups was reached in most cases, sometimes already within 10 min. Water as solvent resulted generally in faster reactions when compared to DMF, and it was possible to conduct the aqueous reaction even without added UV initiator. It was also possible to incorporate two functionalities simultaneously during one reaction into the xylan structure.

    AB - Birch xylan was functionalized with various thiols through UV initiated radical thiol-ene reaction under mild conditions. Xylan was allylated through etherification with allyl glycidyl ether under alkaline conditions. The allylated xylan was then reacted with thiols containing varying functional groups: trimethylbenzyl mercaptan, dodecanethiol, thioglycolic acid, l-cysteine and cysteamine hydrochloride. The reactions were conducted under homogeneous conditions at room temperature, either in water (hydrophilic thiols) or in DMF (hydrophobic thiols). The effect of reaction parameters to the functionalization efficiency was studied, including, for example, thiol excess, thiol character, initiator amount and reaction mixture concentration. The reactions were fast and 100% conversion of allyl groups was reached in most cases, sometimes already within 10 min. Water as solvent resulted generally in faster reactions when compared to DMF, and it was possible to conduct the aqueous reaction even without added UV initiator. It was also possible to incorporate two functionalities simultaneously during one reaction into the xylan structure.

    KW - xylan

    KW - chemical functionalization

    KW - thiol-ene chemistry

    U2 - 10.1016/j.carres.2014.11.009

    DO - 10.1016/j.carres.2014.11.009

    M3 - Article

    VL - 404

    SP - 63

    EP - 69

    JO - Carbohydrate Research

    JF - Carbohydrate Research

    SN - 0008-6215

    ER -