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Chemisorption of microcystins to a thiol and amine functionalized organosilica
Separation and Purification Technology ( IF 8.6 ) Pub Date : 2018-01-04 , DOI: 10.1016/j.seppur.2018.01.004
Paul L. Edmiston , Kimberly A. Carter , Amy L. Graham , Emily J. Gleason

Microcystins are cyclic heptapeptide toxins produced by cyanobacteria that are frequently detected in surface waters during seasonal blooms. Chemisorption of microcystin through covalent bond formation to the acryloyl group common to all congeners was hypothesized to be a high affinity adsorption mechanism. Sol-gel derived organosilica materials were synthesized as sorbents that could potentially facilitate a Michael addition reaction between an immobilized thiol group on the adsorbent and the acryloyl group of microcystin. Amine groups were also added to the organosilica to catalyze the thiol addition reaction at neutral pH. Adsorption isotherms of microcystin-LR, -LA, and –RR were measured for sol–gel derived sorbents and compared to adsorption by wood-based powdered activated carbon, which has been demonstrated to be an effective adsorbent for microcystin. The amine/thiol containing organosilica demonstrated a broad specificity to remove all three congeners from water. Adsorption capacities for MC-LR from natural water were reduced compared to deionized water, especially for the thiol-amine organosilica media. Adsorption of Cu(II) ions by the amine/thiol organosilica was measured which indicated metal ions were bound, however, the degree of metal ion binding was insufficient to significantly decrease adsorption microcystin. Overall, the reaction of microcystin with a surface thiol appeared to be promoted by an initial physical adsorption event and thiol deprotonation by the amines to create a better nucleophile for the Michael addition reaction.



中文翻译:

微囊藻毒素对硫醇和胺官能化有机硅的化学吸附

微囊藻毒素是由蓝细菌产生的环状七肽毒素,经常在季节性开花期间在地表水中检测到。假设通过对所有同类物共有的丙烯酰基通过共价键形成对微囊藻毒素进行化学吸附是一种高亲和力的吸附机制。溶胶-凝胶衍生的有机二氧化硅材料被合成为吸附剂,可以潜在地促进吸附剂上固定的巯基与微囊藻毒素的丙烯酰基之间的迈克尔加成反应。还将胺基团添加至有机二氧化硅以在中性pH下催化硫醇加成反应。对微囊藻毒素-LR,-LA和-RR的吸附等温线对溶胶-凝胶衍生的吸附剂进行了测量,并将其与木质粉末状活性炭的吸附进行了比较,已被证明是有效的微囊藻毒素吸附剂。含有胺/硫醇的有机硅具有广泛的特异性,可以从水中去除所有三个同类物。与去离子水相比,天然水对MC-LR的吸附能力降低,尤其是硫醇胺有机硅介质的吸附能力。测量了胺/硫醇有机二氧化硅对Cu(II)离子的吸附,表明金属离子已结合,但是,金属离子的结合程度不足以显着减少微囊藻毒素的吸附。总的来说,微囊藻毒素与表面硫醇的反应似乎通过初始的物理吸附事件和胺的硫醇去质子化而促进,从而为迈克尔加成反应产生更好的亲核试剂。含有胺/硫醇的有机硅具有广泛的特异性,可以从水中去除所有三个同类物。与去离子水相比,天然水对MC-LR的吸附能力降低,尤其是硫醇胺有机硅介质的吸附能力。测量了胺/硫醇有机硅对铜离子的吸附,表明金属离子已结合,但是金属离子的结合程度不足以显着减少微囊藻毒素的吸附。总的来说,微囊藻毒素与表面硫醇的反应似乎通过初始的物理吸附事件和胺的硫醇去质子化而促进,从而为迈克尔加成反应产生更好的亲核试剂。含有胺/硫醇的有机硅具有广泛的特异性,可以从水中去除所有三个同类物。与去离子水相比,天然水对MC-LR的吸附能力降低,尤其是硫醇胺有机硅介质的吸附能力。测量了胺/硫醇有机二氧化硅对Cu(II)离子的吸附,表明金属离子已结合,但是,金属离子的结合程度不足以显着减少微囊藻毒素的吸附。总的来说,微囊藻毒素与表面硫醇的反应似乎通过初始的物理吸附事件和胺的硫醇去质子化而促进,从而为迈克尔加成反应产生更好的亲核试剂。特别是对于硫醇胺有机二氧化硅介质。测量了胺/硫醇有机二氧化硅对Cu(II)离子的吸附,表明金属离子已结合,但是,金属离子的结合程度不足以显着减少微囊藻毒素的吸附。总的来说,微囊藻毒素与表面硫醇的反应似乎通过初始的物理吸附事件和胺的硫醇去质子化而促进,从而为迈克尔加成反应产生更好的亲核试剂。特别是对于硫醇胺有机二氧化硅介质。测量了胺/硫醇有机二氧化硅对Cu(II)离子的吸附,表明金属离子已结合,但是,金属离子的结合程度不足以显着减少微囊藻毒素的吸附。总的来说,微囊藻毒素与表面硫醇的反应似乎通过初始的物理吸附事件和胺的硫醇去质子化而促进,从而为迈克尔加成反应产生更好的亲核试剂。

更新日期:2018-01-04
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