Current trends in Analytical Chemistry are highly focused on the introduction of new extraction materials with a high selectivity towards the target analytes, high extraction capacity as well as sustainable characteristics. In this context, the introduction of smart materials able to respond to an external stimulus constitutes a promising approach in the field. However, investigations regarding the development of such stimuli-responsive polymers have been basically centered on their synthesis and the control of their properties, and hardly on exploiting such properties to generate polymers that, once their extraction function is fulfilled, they can be degraded into fragments with little or negligible toxicity, or even into their constituent monomers for an efficient recycling. The applicability of a degradable and recyclable dynamic covalent polymer based on the use of tetrazine as a linker was assessed as sorbent for the extraction of a group of 37 persistent organic pollutants, including 10 polycyclic aromatic hydrocarbons, 11 organochlorine pesticides, 14 polychlorinated biphenyls, and 2 antibacterial agents, from water samples. A microdispersive solid-phase extraction procedure was developed for the selective extraction of the target analytes, while their separation, determination, and quantification were achieved by gas chromatography coupled to mass spectrometry. The optimized procedure was validated for seawater and wastewater obtaining mean relative recovery values between 72 and 112 % for almost all the analytes, with satisfactory relative standard deviation values (<18 %). After extraction, the polymer could be degraded by adding the amino acid L-tyrosine, being possible a quantitative recovery of the initial functional monomer. A responsive polymer based on the chemical versatility of the tetrazine ring was used as sorbent in sample preparation providing excellent results, showing good physicochemical properties and the ability to be degraded after use. This polymer constitutes an interesting alternative to reduce chemical waste through the recycling of monomers, contributing to the development of more sustainable analytical methodologies.

中文翻译：

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四嗪基动态共价聚合物作为样品制备中的可降解提取材料


当前分析化学的趋势高度集中于引入对目标分析物具有高选择性、高萃取能力以及可持续特性的新型萃取材料。在这种背景下，引入能够响应外部刺激的智能材料是该领域一种有前途的方法。然而，有关此类刺激响应聚合物开发的研究基本上集中在它们的合成及其性能的控制上，而很少利用这些性能来生成一旦实现其提取功能就可以降解成碎片的聚合物。毒性很小或可以忽略不计，甚至可以转化为组成单体以进行有效回收。评估了基于使用四嗪作为连接剂的可降解和可回收动态共价聚合物作为吸附剂萃取 37 种持久性有机污染物的适用性，其中包括 10 种多环芳烃、11 种有机氯农药、14 种多氯联苯和2 抗菌剂，来自水样。开发了一种微分散固相萃取程序，用于选择性萃取目标分析物，同时通过气相色谱法与质谱联用来实现它们的分离、测定和定量。优化的程序针对海水和废水进行了验证，几乎所有分析物的平均相对回收率在 72% 至 112% 之间，且具有令人满意的相对标准偏差值 (<18%)。提取后，可以通过添加氨基酸L-酪氨酸来降解聚合物，从而可以定量回收初始功能单体。 基于四嗪环化学多功能性的响应聚合物在样品制备中用作吸附剂，提供了优异的结果，显示出良好的物理化学性质和使用后降解的能力。这种聚合物是一种有趣的替代品，可以通过单体回收来减少化学废物，从而有助于开发更可持续的分析方法。