Patterned Surface Derivatization Using Diels-Alder Photoclick Reaction
Patterned Surface Derivatization Using Diels-Alder Photoclick Reaction
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DOI：
10.1021/ja205652m
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发表时间：
2011-10-05
影响因子：
15
通讯作者：
Popik, Vladimir V.
中科院分区：
文献类型：
--
作者：
Arumugam, Selvanathan;Popik, Vladimir V.
证明了光化学诱导的杂diels - Alder反应在光导表面衍生化和图案化中的应用。用乙烯基醚基团功能化的玻片覆盖3-（羟甲基）-2-萘酚（NQMP）共轭底物的水溶液。随后通过遮光罩照射导致后一种功能在暴露区域有效地转化为活性的2-萘醌-3-甲基（oNQM）。oNQM对固定的乙烯醚分子进行了非常容易的diols - alder加成反应(k（D-A）近似为4 × 10(4) M(-1)s(-1))，从而在底物和表面之间形成了光化学稳定的共价键。未反应的oNQM基团迅速水化以再生NQMP。在乙烯基醚中加入光化学生成的oNQM的化学反应在水溶液中效果良好，在环境条件下进行速度快，并且不需要催化剂或其他试剂。这种光点击策略代表了一种不寻常的光模式：表面本身是光化学惰性的，而光反应成分存在于光溶液中。光点击试剂的活性形式在水溶液中的寿命短（在H2O中约为7ms），防止其从照射部位迁移，从而允许表面衍生化的空间控制。邻萘醌甲醚前体和乙烯醚在黑暗中都是稳定的，并且与其他衍生化技术如乙炔叠氮化反应是正交的。
The utility of photochemically induced hetero-Diels Alder reaction for the light-directed surface derivatization and patterning was demonstrated. Glass slides functionalized with vinyl ether moieties are covered with aqueous solution of substrates conjugated to 3-(hydroxymethyl)-2-naphthol (NQMP). Subsequent irradiation via shadow mask results in an efficient conversion of the latter functionality into reactive 2-napthoquinone-3-methide (oNQM) in the exposed areas. oNQM undergoes very facile hetero Diels-Alder addition (k(D-A) approximate to 4 x 10(4) M(-1)s(-1)) to immobilized vinyl ether molecules resulting in a photochemically stable covalent link between a substrate and a surface. Unreacted oNQM groups are rapidly hydrated to regenerate NQMP. The click chemistry based on the addition of photochemically generated oNQM to vinyl ether works well in aqueous solution, proceeds at high rate under ambient conditions, and does not require catalyst or additional reagents. This photoclick strategy represents an unusual paradigm in photopatterning: the surface itself is photochemically inert, while photoreactive component is present in the solution. The short lifetime (tau approximate to 7 ms in H2O) of the active form of a photoclick reagent in aqueous solution prevents its migration from the site of irradiation, thus allowing for the spatial control of surface derivatization. Both o-napthoquinone methide precursors and vinyl ethers are stable in dark and the reaction is orthogonal to other derivatization techniques, such as acetylene-azide click reaction.