背景:分析化学的当前趋势高度关注于引入对目标分析物具有高选择性的新提取材料,高提取能力以及可持续的特点。在这种情况下,引入能够对外部刺激做出反应的智能材料是该领域一种有希望的方法。然而,关于这种刺激响应性聚合物的发展的研究基本上集中在它们的合成和性质的控制上,几乎没有利用这些特性来产生聚合物,一旦它们的提取功能完成,它们可以降解成碎片,毒性很小或可以忽略不计,或甚至进入其组成单体的有效回收。
结果:评估了基于使用四嗪作为连接体的可降解和可回收的动态共价聚合物作为吸附剂的适用性,用于提取一组37种持久性有机污染物,包括10种多环芳烃,11种有机氯农药,14多氯联苯,和2种抗菌剂,从水样。开发了一种用于选择性提取目标分析物的微分散固相萃取程序,而他们的分离,决心,并通过气相色谱与质谱联用实现定量。对海水和废水的优化程序进行了验证,几乎所有分析物的平均相对回收率在72%至112%之间。具有令人满意的相对标准偏差值(<18%)。提取后,聚合物可以通过添加氨基酸L-酪氨酸降解,是可能的初始功能单体的定量回收。
结论:基于四嗪环的化学多功能性的响应性聚合物被用作样品制备中的吸附剂,提供了优异的结果,表现出良好的物理化学性质和使用后降解的能力。这种聚合物构成了一种有趣的替代品,可以通过单体的回收来减少化学废物,有助于发展更可持续的分析方法。
BACKGROUND: 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.
RESULTS: 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.
CONCLUSIONS: 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.