Key Laboratory of Polyoxometalate and Reticular Material Chemistry of Ministry of Education, Key Laboratory of Nanobiosensing and Nanobioanalysis at Universities of Jilin Province, Department of Chemistry, Northeast Normal University, Changchun, 130024, China.
Key Laboratory of Polyoxometalate and Reticular Material Chemistry of Ministry of Education, Key Laboratory of Nanobiosensing and Nanobioanalysis at Universities of Jilin Province, Department of Chemistry, Northeast Normal University, Changchun, 130024, China.
Anal Chim Acta. 2022 May 29;1209:339876. doi: 10.1016/j.aca.2022.339876. Epub 2022 Apr 27.
Owing to the desirable structures, covalent organic frameworks (COFs) have emerged as promising porous crystalline materials in bioanalytical and biomedical science. However, the application of their merits for analysis of hydrophobic peptides in complicated bio-samples has not been well investigated, possibly due to challenges in developing materials with high-specific binding effect of target peptides and accurate controllable pore-size for high selectivity. In this study, we proposed the size-exclusive peptide enrichment with Azo-COF constructed from 1,3,6,8-tetrabromopyrene (TBPy) building block and p-azoaniline linking units. The as-synthesized sieve-like COFs show high surface area together with accessible nanometer pore size (∼2.5 nm). With these advantages, specific enrichment of hydrophobic peptides using Azo-COF can be achieved by simply packing them in a 100 μL Axygen pipette tip. A maximum capacity of 36 mg g for FGFGF was obtained, which is more than a magnitude order larger than those of hydrophilic peptides. Furthermore, this method was successfully applied in analysis of hydrophobic peptides in tryptic digest of proteins and real human serum samples, indicating that the proposed method is promising for high-selective peptides enrichment from complex biological samples, and is of great value for further application of the functional materials in bioanalysis.
由于具有理想的结构，共价有机骨架（COFs）作为一种有前途的多孔晶体材料，在生物分析和生物医学科学中已经崭露头角。然而，它们在分析复杂生物样品中疏水性肽的优点的应用尚未得到很好的研究，这可能是由于开发对目标肽具有高特异性结合作用和高选择性的准确可控孔径的材料存在挑战。在本研究中，我们提出了一种由 1,3,6,8-四溴芘（TBPy）构建块和 p-偶氮苯胺连接单元构建的具有尺寸排他性的偶氮 COF 用于肽的选择性富集。所合成的筛状 COFs 具有高比表面积和可及的纳米孔径（~2.5nm）。利用这些优势，通过简单地将它们填充在 100μL 的 Axygen 吸头中，就可以实现疏水性肽的特异性富集。对于 FGFGF，获得了 36mg/g 的最大容量，比亲水性肽大一个数量级以上。此外，该方法还成功地应用于蛋白质酶解物和真实人血清样品中疏水性肽的分析，表明该方法有望从复杂生物样品中高选择性地富集肽，并且对于功能材料在生物分析中的进一步应用具有重要价值。
