Ciarlantini Clarissa, Romano Susanna, Amici Gian Marco, Lacolla Elisabetta, Francolini Iolanda, Girelli Anna Maria, Martinelli Andrea, Piozzi Antonella
Department of Chemistry, Sapienza University of Rome, P. le Aldo Moro 5, 00185 Rome, Italy.
Department of Industrial, Electronic and Mechanical Engineering Roma Tre University, Via Vito Volterra 62, 00146 Rome, Italy.
Int J Mol Sci. 2025 Aug 8;26(16):7686. doi: 10.3390/ijms26167686.
Tetrabromobisphenol A (TBBPA) is a flame retardant widely added to polymer products. Successful isolation of target analytes from complex natural matrices relies on extraction materials that can selectively interact with the analytes. In this context, the use of magnetic nanostructured adsorbents, such as magnetic molecularly imprinted polymer systems (MMIPs), can play a key role in both selective matrix-analyte interactions and separation processes. Here, to achieve different TBBPA loadings, FeO nanoparticles (NPs) were coated with chitosan (CS) or (3-aminopropyl) triethoxysilane (APTES). Moreover, to further promote template-NP interactions and modulate the polymeric shell thickness of MMIPs, 3,4-dihydroxyhydrocinnamic acid (HC) was covalently bonded in different amounts to APTES-functionalized MNPs. Thermal, SEM, and elemental analyses showed a different coating degree of the nanocomposites (FeO@CS-MIP size d = 77 nm and FeO@APTES-MIP d = 20 nm). In addition, it was confirmed that the adsorption mechanism of TBBPA on FeO@APTES-HCX-MIPs was due to specific interactions between the systems and the analyte, unlike non-imprinted analogs (MNIPs). Among the developed systems, the Fe3O4@APTES-HC0.7-MIP sample showed the best extraction efficiency (85%) associated with good discharge efficiency (70%). Furthermore, this nanocomposite displayed high selectivity towards TBBPA (ε > 1) and good extraction efficiency in three consecutive cycles (67%), demonstrating great potential in the environmental field.
四溴双酚A（TBBPA）是一种广泛添加到聚合物产品中的阻燃剂。从复杂的天然基质中成功分离目标分析物依赖于能够与分析物选择性相互作用的萃取材料。在这种情况下，磁性纳米结构吸附剂的使用，如磁性分子印迹聚合物系统（MMIPs），在选择性基质-分析物相互作用和分离过程中都可以发挥关键作用。在此，为了实现不同的TBBPA负载量，用壳聚糖（CS）或（3-氨丙基）三乙氧基硅烷（APTES）包覆FeO纳米颗粒（NPs）。此外，为了进一步促进模板-纳米颗粒相互作用并调节MMIPs的聚合物壳层厚度，将不同量的3,4-二羟基氢化肉桂酸（HC）共价键合到APTES功能化的MNPs上。热分析、扫描电子显微镜和元素分析表明纳米复合材料具有不同的包覆程度（FeO@CS-MIP尺寸d = 77 nm，FeO@APTES-MIP d = 20 nm）。此外，已证实TBBPA在FeO@APTES-HCX-MIPs上的吸附机制是由于该系统与分析物之间的特异性相互作用，这与非印迹类似物（MNIPs）不同。在开发的系统中，Fe3O4@APTES-HC0.7-MIP样品显示出最佳的萃取效率（85%）以及良好的排放效率（70%）。此外，这种纳米复合材料对TBBPA表现出高选择性（ε > 1），并且在三个连续循环中具有良好的萃取效率（67%），在环境领域显示出巨大潜力。
