Chair of Environmental Chemistry and Bioanalytics, Faculty of Chemistry, Nicolaus Copernicus University in Toruń, 7 Gagarin Str., PL-87-100, Toruń Poland.
Chair of Organic Chemistry, Faculty of Chemistry, Nicolaus Copernicus University in Toruń, 7 Gagarin Str., PL-87-100, Toruń, Poland.
Talanta. 2021 Jan 1;221:121662. doi: 10.1016/j.talanta.2020.121662. Epub 2020 Sep 14.
Cross-linked poly(ionic liquid)s were successfully used for the first time in the preparation of oligonucleotide biological samples. The adsorbents were prepared by co-polymerization of imidazolium-based ionic liquids and divinylbenzene. Consequently, the following three adsorbents were prepared and comprehenzively characterized: poly(3-butyl-1-vinylimidazolium bromide-co-divinylbenzene), poly(3-hexyl-1-vinylimidazolium bromide-co-divinylbenzene) and poly(2-(1-vinylimidazoliumyl)acetate-co-divinylbenzene). Oligonucleotides were adsorbed onto the surface of these materials at low pH values. Preliminary studies of the desorption of the analytes included testing the influence of different types of salts, as well as their concentrations and pH, and organic solvents on the recovery. This allowed for determining the adsorbent and the desorption conditions for further optimization with the use of central composition design. The chosen adsorbent was poly(2-(1-vinylimidazoliumyl)acetate-co-divinylbenzene), and the optimal desorption conditions (5 mM ammonium acetate (pH = 9.5)/methanol (50/50, v/v)) gave a recovery of 99.7 ± 0.3%. The dispersive micro-solid-phase extraction procedure was successfully applied for the extraction of oligonucleotides with various modifications and lengths. Finally, the developed method was used to extract 2'-O-methyl oligonucleotide and its two synthetic metabolites from enriched human plasma without any pre-purification, yielding recoveries over 80%.
交联聚离子液体首次成功用于制备寡核苷酸生物样品。吸附剂通过基于咪唑鎓的离子液体和二乙烯基苯的共聚来制备。因此，制备并综合表征了以下三种吸附剂：聚（3-丁基-1-乙烯基咪唑溴化物-co-二乙烯基苯）、聚（3-己基-1-乙烯基咪唑溴化物-co-二乙烯基苯）和聚（2-（1-乙烯基咪唑基）乙酸酯-co-二乙烯基苯）。在低 pH 值下，寡核苷酸被吸附到这些材料的表面上。对分析物解吸的初步研究包括测试不同类型盐及其浓度和 pH 值以及有机溶剂对回收率的影响。这允许确定吸附剂和解吸条件，以便进一步使用中心组合设计进行优化。选择的吸附剂为聚（2-（1-乙烯基咪唑基）乙酸酯-co-二乙烯基苯），最佳解吸条件（5 mM 乙酸铵（pH = 9.5）/甲醇（50/50，v/v））可实现 99.7 ± 0.3%的回收率。分散微固相萃取程序成功应用于各种修饰和长度的寡核苷酸的提取。最后，该方法用于从未经过任何预纯化的富集人血浆中提取 2'-O-甲基寡核苷酸及其两种合成代谢物，回收率超过 80%。
