液相色谱-质谱/质谱法测定牙用树脂水中双酚a的释放谱

B. P. D. Silva, Gabriel Rübensam, Claudiela Wachholz Saafeld, J. Weber
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引用次数: 0

摘要

牙科树脂由于其更有利的物理、化学和生物特性而被设计用来取代汞合金修复体。然而,根据其组成、聚合效率和聚合物基质的降解,双酚a可以存在,并因此从这种材料释放到人体中。据报道,添加剂的残留物和聚合物反应的少数副产物,如双酚a,可以通过聚合物水化、水-聚合物扩散、残留物溶解以及溶解残留物在水中与聚合物之间的平衡,从塑料中释放到水介质中。随着时间的推移,这可能会导致聚合物材料的外层几乎不含双酚a。然而,在口腔清洁过程中,新形成的一层可以通过刷牙去除,就像刷牙一样,将含有双酚a的新层暴露在水介质中。由于这种化合物的毒性作用,越来越多标有不含双酚a的塑料被引入牙科市场,包括牙齿涂层、牙科密封剂和树脂。然而,更具体的分析化学研究表明,在标记为不含双酚a的牙科树脂中发现了微量双酚a,并指出需要更灵敏和准确的检测方法,以帮助制造商评估其产品中是否存在本底污染物,并避免假阴性结果。在这种情况下,液相色谱-串联质谱法被认为是确认双酚a的最合适的方法之一,即使在低浓度,在高复杂的基质中,由于其高选择灵敏度。在目前的工作中,我们开发了一种灵敏、可靠、高效的方法,通过LC-MS/MS在巴西牙科市场购买的牙科树脂样品中追踪双酚a的释放谱。对5种不同品牌的树脂复合材料进行了8天的分析,其中4种树脂复合材料的双酚a含量从3.4 pg/mm2到10.1 ng/mm2不等。标记为不含双酚a的品牌释放的双酚a浓度为1.1 ng/mm2。然而,一个样本仅在3天内达到BPA释放最大值,一个在4天内达到最大值,两个样本在评估的窗口时间内几乎没有达到BPA释放到水中的最大值。LC-MS/MS方法的检测限和定量限分别为40 pg/mm2和100 pg/mm2,可以定量标记为不含BPA的复合材料中释放的BPA。为了进一步分析,我们将使用刷牙模拟器对树脂复合材料中BPA释放到水中的情况进行更全面的研究,以确定所获得的情况是否可能具有临床意义。
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RELEASE PROFILE OF BISPHENOL-A FROM DENTAL RESINS IN WATER ASSESSED BY LC-MS/MS
Dental resins have been designed to replace amalgam restorations due to their more favorable physical, chemical, and biological properties. However, depending on its composition, the efficiency of its polymerization, and the degradation of the polymer matrix, Bisphenol-A can be present and therefore released from this material to the human body. It has been reported that residues of additives and minority by-products of polymer reactions, such as Bisphenol-A, can be released from plastics into aqueous media through polymer hydration, water-polymer diffusion, residue dissolution, and equilibrium between dissolved residues in water and polymer. Over time, this could lead to a polymer material with an external layer practically free of Bisphenol-A. However, the newly formed layer could be removed by brushing during oral cleaning, similar to toothbrushing, exposing the new layer containing Bisphenol-A to the aqueous media. Due to the toxic effects of this compound, an increasing number of plastics labeled as BPA-free have been introduced to the dental market, including tooth coating, dental sealants, and resins. Nevertheless, more specific studies on analytical chemistry have revealed a trace of Bisphenol-A in dental resins labeled as BPA-free and pointed out the need for even more sensitive and accurate detection methods to help manufacturers evaluate the presence of background contaminations in their products and to avoid false-negative results. In this way, liquid chromatography-tandem mass spectrometry has been considered one of the most suitable methods for confirming Bisphenol-A even at low concentrations, in high complex matrices, due to its high select sensitivity. In the present work, we developed a sensitive, reliable, and efficient approach to trace the release profile of Bisphenol-A by LC-MS/MS in dental resin samples purchased in the Brazilian dental market. With the analysis of five different brands of resin composites performed in eight days of exposition to water, four of them released Bisphenol-A from 3.4 pg/mm2 to 10.1 ng/mm2. The brand labeled as BPA-free released BPA at concentrations of 1.1 ng/mm2. However, one sample reached the maximum of released BPA in only 3 days, one in 4 days, and two virtually did not reach a maximum of BPA released into the water in the window time assessed. Limits of detection and quantification of the LC-MS/MS method were 40 pg/mm2 and 100 pg/mm2, respectively, and allowed the quantification of BPA released from a composite labeled as BPA-free. For future analysis, we will conduct a more comprehensive study on the release profile of BPA from resin composites into the water using a tooth brushing simulator to determine if the obtained profiles might have clinical implications.
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