CAS Key Laboratory of Chemistry of Northwestern Plant Resources and Key Laboratory for Natural Medicine of Gansu Province, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou 730000, P. R. China.
ACS Appl Mater Interfaces. 2023 Sep 13;15(36):42981-42991. doi: 10.1021/acsami.3c08703. Epub 2023 Aug 29.
Porous organic polymers (POPs) based on calix[4]arene with a hydrophobic π-rich cavity and host-guest recognition properties exhibit a wide application range of molecular extraction and separation. However, it is still a challenge to improve the extraction and separation selectivity by exploring and seeking appropriate building blocks for the functionalization and pore size adjustment of calix[4]arene. Herein, an azophenyl calix[4]arene porous organic polymer (AC-POP) was proposed. By introducing an electron-rich cavity and adjusting the pore sizes of calix[4]arene, the AC-POP showed high selectivity extraction performance in triphenylmethane (TPM) dyes. The extraction mechanism was explored by adsorption thermodynamics study, density functional theory (DFT) calculation, and reduced density gradient (RDG) and electrostatic potential (ESP) analyses, which suggested that the selectivity adsorption of TPM dyes based on AC-POP was mainly the result of entropy driven by the hydrophobic effect. In addition, the noncovalent interactions including π-π stacking, van der Waals force, and electrostatic interaction were also important factors affecting the adsorption capacity of TPM dyes. Under optimal extraction conditions, the AC-POP possessed a maximum extraction amount of 95.3 mg·g for Rhodamine B (RB), high enrichment factor of about 100, and excellent reusability more than 10 times. Then, an analytical method of TPM dyes with AC-POP as a solid-phase extractant combined with high-performance liquid chromatography-ultraviolet (HPLC-UV) was established, which displayed excellent sensitivity with the limits of detection (LODs) and limits of quantitation (LOQs) in the ranges of 0.004-0.35 and 0.016-1.16, respectively. The mean recoveries for TPM dyes ranged from 85.0 to 109.4% with an RSD of 0.48-9.45%. The proposed method was successfully applied to the analysis of the five TPM dyes in seafood matrix samples.
基于杯[4]芳烃的多孔有机聚合物（POPs）具有疏水的富π空腔和主客体识别特性，在分子萃取和分离方面具有广泛的应用范围。然而，通过探索和寻求合适的构建块来实现杯[4]芳烃的功能化和孔径调整，以提高萃取和分离选择性仍然是一个挑战。在此，提出了一种偶氮苯杯[4]芳烃多孔有机聚合物（AC-POP）。通过引入富电子空腔并调整杯[4]芳烃的孔径，AC-POP 在三苯基甲烷（TPM）染料的高选择性萃取性能。通过吸附热力学研究、密度泛函理论（DFT）计算以及缩减密度梯度（RDG）和静电势（ESP）分析，探讨了萃取机制，这表明基于 AC-POP 的 TPM 染料的选择性吸附主要是疏水作用驱动的熵的结果。此外，包括π-π堆积、范德华力和静电相互作用在内的非共价相互作用也是影响 TPM 染料吸附量的重要因素。在最佳萃取条件下，AC-POP 对罗丹明 B（RB）的最大萃取量为 95.3 mg·g，富集因子约为 100，可重复使用 10 次以上。然后，建立了一种以 AC-POP 为固相萃取剂结合高效液相色谱-紫外（HPLC-UV）的 TPM 染料分析方法，该方法具有优异的灵敏度，检测限（LOD）和定量限（LOQ）分别在 0.004-0.35 和 0.016-1.16 范围内。TPM 染料的平均回收率在 85.0%至 109.4%之间，相对标准偏差（RSD）为 0.48%-9.45%。该方法成功应用于海鲜基质样品中五种 TPM 染料的分析。
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