Structure and sorption properties of multifunctional acrylic polymers designed for solid phase microextraction fibers
Introduction
Solid-phase microextraction (SPME) is an efficient, solvent-free sample preparation method that integrates sampling, isolation and concentration into one step [1]. Further developments of these technique greatly depends on breakthroughs in the area of new coating materials [2,3]. The preparation of home-made SPME fiber is expected to be simple, and core rod should be sufficiently robust for its use. Robustness it is determined by the thermal and mechanical stability and by the binding method of the coating material immobilized on the supporting core. Other properties of home-made fibers, such as corrosion resistance and selectivity, depend mainly on coating materials’ properties.
Many materials, ranging from widely used miscellaneous carbonaceous materials to versatile polymers, have been applied in home-made SPME coatings [[4], [5], [6], [7], [8]]. Among them polymers have long been used as sorbents. Therefore, in this paper, a novel photopolymerization-based preparation methodology for a SPME fiber coating material was proposed. In this methodology the coating material was prepared with use of monomer mixtures based on multifunctional polymers produced by photopolymerization by VIS or UV light [[9], [10], [11]] with a tapered optical fibre as the supporting core [12]. Some technical parameters of fabrication process, including time and optical power of polymerization, were subjected to multivariate optimization while taking into account uniformity, porosity, thickness and adhesion of the coating to the supporting core, as well. The SPME fibers will be fabricated in the next stage of research that could be coupled with gas chromatography for the extraction and determination of organosulfur and organophosphorus simulants of chemical warfare agents (CWAs).
However, information about selected physicochemical properties of synthesized polymers is necessary before their application. Studies on the reactions and changes of polymers depend on modification in functional groups and changes in the interactions between functional groups, which are accompanied by morphological transformations that have to be carried out. Therefore, analytical methods such as structural X-ray analysis, NMR or infrared spectroscopy were used to determine the chain structure and the aggregation structure of the selected polymer [13]. The promising sorption properties of certain acrylates demonstrated during the analysis of selected CWA related compounds [14,15] became an inspiration for the present research.
The purpose of the current research described in this article was the synthesis of several different polymers and a preliminary testing whether they will adsorb chemical compounds similar in structure to chemical warfare agents.
Section snippets
Materials and reagents
As monomers, initiators and co-initiators the following compounds were used: DTMPTA—ditrimethylol propane tetraacrylate, TMPTA—trimethylolpropane triacrylate, TCDMA—tricyclo (5.2.1.0) decanedimethanol diacrylate,EosinY—2′,4′,5′,7′-tetrabromofluorescein disodium salt, DMPAP—2,2-dimethoxy-2-phenylacetophenoneand MDEA—methyl diethanolamine, respectively. All were purchased from Aldrich and used as received without further purification. To support the sorption, OH–TSO—hydroxyl-terminated silicone
Testing of sorption properties of obtained polymers
The new polymer materials described in this paper were pre-tested for the sorption of simulated CWAs, such as 1,4-thioxane and trimethyl phosphate (TMP). The procedure for testing of sorption properties was based on literature data [28,29]. The experiment was conducted as follows. A small dish with a capacity of about 1 mL was placed in a vial with a capacity of 21.5 mL. Then, 10 mg of the sorbent (fabricated polymers or active carbon) was placed in the dish, and the variable quantity (in μL)
Results and discussion
Fig. 10 show the experimental results of the above-described chromatographic tests of the comparisons of the sorption properties of all tested polymers as a function of the amount of thioxane. Among polymers made using UV and VIS light, TCDMA had the best sorption properties in both cases. For these materials, the peak areas increased slowly, which suggests a higher level of absorbed thioxane. Additionally, the changes of these parameters for VIS light-polymerized TCDMA had a linear-like
Conclusions
Preliminary studies have shown that acrylic polymers adsorb both organosulfur and organophosphorus compounds efficiently. The best sorption properties were demonstrated by the newly developed sorbent TCDMA photopolymerized by VIS laser (TCDMA_532), which adsorbed TMP (one of the organophosphorus compounds) much better than activated carbon. Meanwhile, 1,4-thioxane was adsorbed using the same sorbent only slightly better than by activated carbon. However, its thermal properties need improvement
CRediT authorship contribution statement
Iwona Jakubowska: Conceptualization, Methodology, Validation, Investigation, Writing - original draft, Writing - review & editing. Stanisław Popiel: Conceptualization, Methodology, Writing - original draft, Investigation, Validation, Writing - review & editing, Funding acquisition. Mateusz Szala: Methodology, Investigation, Writing - original draft, Writing - review & editing. Michał Czerwiński: Investigation, Writing - original draft, Writing - review & editing. Maciej Chrunik: Investigation,
Declaration of competing interest
The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.
Acknowledgment
This work was supported by the Ministry of National Defence through the research grants GBMON/13-995/2018/WAT and GBMON/13-994/2018/WAT.
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