Abstract：
Enrichment and quantification of sugar phosphates (SPx) in biological samples were of great significance in biological medicine. In this work, a series of zirconium-based metal-organic frameworks (MOFs) with different degrees of defects, namely, HP-UiO-66-NH2-X, were synthesized using acetic acid as a modulator and were utilized as high-capacity adsorbents for the adsorption of SPx in biological samples. The results indicated that the addition of acetic acid altered the morphology of HP-UiO-66-NH2-X, with corresponding changes in pore size (3.99-9.28 nm) and specific surface area (894.44-1142.50 m2·g-1). HP-UiO-66-NH2-10 showed the outstanding performance by achieving complete adsorption of all four SPx using only 80 μg of the adsorbent. The excellent adsorption efficiency of HP-UiO-66-NH2-10 was also obtained with a wide pH range and short adsorption time (10 min). Adsorption experiments demonstrated that the adsorption process involved chemical adsorption and multilayer adsorption. By utilizing X-ray photoelectron spectroscopy and density functional theory to explain the adsorption mechanism, it was found that various interactions (including coordination, hydrogen bonding, and electrostatic interactions) collectively contributed to the exceptional adsorption capability of HP-UiO-66-NH2-10. Those results indicated that the defect strategy not only increased the specific surface area and pore size, providing additional adsorption sites, but also reduced the adsorption energy between HP-UiO-66-NH2-10 and SPx. Moreover, HP-UiO-66-NH2-10 showed a low limit of detection (0.001-0.01 ng·mL-1), high precision (<13.77%), and accuracy (80.10-111.83%) in serum, liver, and cells, good stability, high selectivity (SPx/glucose, 1:100 molar ratio), and high adsorption capacity (292 mg·g-1 for SPx). The practical detection of SPx from human serum was also verified, prefiguring the great potentials of defective zirconium-based MOFs for the enrichment and detection of SPx in the biological medicine.
摘要：
生物样品中糖磷酸盐（SPx）的富集和定量在生物医学中具有重要意义。在这项工作中,一系列具有不同程度缺陷的锆基金属有机骨架(MOFs),即,HP-UiO-66-NH2-X,使用乙酸作为调节剂合成，并用作吸附生物样品中SPx的高容量吸附剂。结果表明，乙酸的加入改变了HP-UiO-66-NH2-X的形态，孔径（3.99-9.28nm）和比表面积（894.44-1142.50m2·g-1）相应变化。HP-UiO-66-NH2-10仅使用80μg吸附剂即可实现所有四种SPx的完全吸附，从而显示出出色的性能。在较宽的pH范围和较短的吸附时间（10min）下，还获得了HP-UiO-66-NH2-10的优异吸附效率。吸附实验表明，吸附过程涉及化学吸附和多层吸附。利用X射线光电子能谱和密度泛函理论解释吸附机理,发现各种相互作用(包括协调，氢键,和静电相互作用）共同促进了HP-UiO-66-NH2-10的出色吸附能力。这些结果表明，缺陷策略不仅增加了比表面积和孔径，提供额外的吸附位点，但也降低了HP-UiO-66-NH2-10和SPx之间的吸附能。此外，HP-UiO-66-NH2-10检测限低(0.001-0.01ng·mL-1),高精度（<13.77%），和准确性（80.10-111.83%）的血清，肝脏,和细胞,稳定性好,高选择性(SPx/葡萄糖，1:100摩尔比)，和高吸附容量(对SPx为292mg·g-1)。人血清中SPx的实际检测也得到了验证，预示着有缺陷的锆基MOFs在生物医学中富集和检测SPx的巨大潜力。
