González-Hernández Providencia, Gutiérrez-Serpa Adrián, Lago Ana B, Estévez Laura, Ayala Juan H, Pino Verónica, Pasán Jorge
Laboratorio de Materiales para Análisis Químico (MAT4LL), Departamento de Química, Unidad Departamental de Química Analítica, Universidad de La Laguna (ULL), La Laguna, Tenerife 38206, Spain.
Unidad de Investigación de Bioanalítica y Medioambiente, Instituto Universitario de Enfermedades Tropicales y Salud Pública, Universidad de La Laguna (ULL), La Laguna, Tenerife 38206, Spain.
ACS Appl Mater Interfaces. 2021 Sep 29;13(38):45639-45650. doi: 10.1021/acsami.1c14416. Epub 2021 Sep 21.
Metal-organic frameworks (MOFs) are attractive materials used as sorbents in analytical microextraction applications for contaminants of emerging concern (CECs) from environmental liquid matrices. The demanding specs for a sorbent in the analytical application can be comprehensively studied by considering the interactions of the target analytes with the frameworks by the use of single-crystal X-ray diffraction, computational analysis, and adsorption studies, including the kinetic ones. The current study intends a better understanding of the interactions of target CECs (particularly, propylparaben (PPB) as a model) and three Zn-based layered pillared MOFs: [Zn(tz)(bdc)] (Htz = 1,2,4-triazole and Hbdc = 1,4-benzenedicarboxylic acid) and their amino derivatives [Zn(NH-tz)(bdc)] and [Zn(tz)(NH-bdc)] (NH-Htz = 3-amino-1,2,4-triazole and NH-Hbdc = 2-amino-1,4-benzenedicarboxylic acid). The crystal structures of the two solvate compounds ( (dma = dimethylacetamide) and ) were solved by single-crystal X-ray diffraction to determine the points of interaction between the framework and the guest molecules. They also served as a starting point for the computational modeling of the compound, showing that up to two PPB molecules can be hosted in one of the pores, while only one can be trapped in the second pore type, leading to a maximum theoretical capacity of 291.9 mg g. This value is close to the value obtained by the adsorption isotherm experiment for (283 mg g). This value is, by far, higher than those previously reported for other materials for the removal of PPB from water, and also higher than the experimental values obtained for (54 mg g) and (153 mg g). The kinetics of adsorption is not very fast, with uptake of about 40% in 3 h, although a 70% release in methanol is achieved in 1 h. In addition, a further comparison of performance in analytical microextraction (requiring only 10 mg of ) was carried out together with chromatographic analysis to support all insights attained, with the method being able to monitor CECs as low as μg L levels in complex environmental water samples, thus performing successfully for water monitoring even in multicomponent scenarios.
金属有机框架材料（MOFs）是一种有吸引力的材料，在分析微萃取应用中用作吸附剂，用于从环境液体基质中萃取新出现的关注污染物（CECs）。通过使用单晶X射线衍射、计算分析和吸附研究（包括动力学研究）来考虑目标分析物与框架之间的相互作用，可以全面研究分析应用中对吸附剂的严格要求。本研究旨在更好地理解目标CECs（特别是以对羟基苯甲酸丙酯（PPB）为模型）与三种锌基层柱状MOFs的相互作用：[Zn(tz)(bdc)]（Htz = 1,2,4-三唑，Hbdc = 1,4-苯二甲酸）及其氨基衍生物[Zn(NH-tz)(bdc)]和[Zn(tz)(NH-bdc)]（NH-Htz = 3-氨基-1,2,4-三唑，NH-Hbdc = 2-氨基-1,4-苯二甲酸）。通过单晶X射线衍射解析了两种溶剂化物（（dma = 二甲基乙酰胺）和）的晶体结构，以确定框架与客体分子之间的相互作用点。它们还作为化合物计算建模的起点，表明在其中一个孔中最多可容纳两个PPB分子，而在第二种孔类型中只能捕获一个，导致最大理论容量为291.9 mg g。该值接近通过吸附等温线实验获得的（283 mg g）的值。到目前为止，该值高于先前报道的用于从水中去除PPB的其他材料的值，也高于（54 mg g）和（153 mg g）获得的实验值。吸附动力学不是很快，3小时内摄取约40%，尽管在1小时内甲醇中的释放率达到70%。此外，与色谱分析一起对分析微萃取（仅需10 mg）的性能进行了进一步比较，以支持所获得的所有见解，该方法能够监测复杂环境水样中低至μg L水平的CECs，因此即使在多组分情况下也能成功用于水监测。
