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      Expanding the Applicability of Poly(Ionic Liquids) in Solid Phase Microextraction: Pyrrolidinium Coatings

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          Abstract

          Crosslinked pyrrolidinium-based poly(ionic liquids) (Pyrr-PILs) were synthesized through a fast, simple, and solventless photopolymerization scheme, and tested as solid phase microextraction (SPME) sorbents. A series of Pyrr-PILs bearing three different alkyl side chain lengths with two, eight, and fourteen carbons was prepared, characterized, and homogeneously coated on a steel wire by using a very simple procedure. The resulting coatings showed a high thermal stability, with decomposition temperatures above 350 °C, excellent film stability, and lifetime of over 100 injections. The performance of these PIL-based SPME fibers was evaluated using a mixture of eleven organic compounds with different molar volumes and chemical functionalities (alcohols, ketones, and monoterpenes). The Pyrr-PIL fibers were obtained as dense film coatings, with 67 μm thickness, with an overall sorption increase of 90% and 55% as compared to commercial fibers of Polyacrylate (85 μm) (PA85) and Polydimethylsiloxane (7 μm) (PDMS7) coatings, respectively. A urine sample doped with the sample mixture was used to study the matrix effect and establish relative recoveries, which ranged from 60.2% to 104.1%.

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          Aqueous biphasic systems: a boost brought about by using ionic liquids.

          During the past decade, ionic-liquid-based Aqueous Biphasic Systems (ABS) have been the focus of a significant amount of research. Based on a compilation and analysis of the data hitherto reported, this critical review provides a judicious assessment of the available literature on the subject. We evaluate the quality of the data and establish the main drawbacks found in the literature. We discuss the main issues which govern the phase behaviour of ionic-liquid-based ABS, and we highlight future challenges to the field. In particular, the effect of the ionic liquid structure and the various types of salting-out agents (inorganic or organic salts, amino acids and carbohydrates) on the phase equilibria of ABS is discussed, as well as the influence of secondary parameters such as temperature and pH. More recent approaches using ionic liquids as additives or as replacements for common salts in polymer-based ABS are also presented and discussed to emphasize the expanding number of aqueous two-phase systems that can actually be obtained. Finally, we address two of the main applications of ionic liquid-based ABS: extraction of biomolecules and other added-value compounds, and their use as alternative approaches for removing and recovering ionic liquids from aqueous media.
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            Transport phenomena through polymeric systems

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              Evolution of solid-phase microextraction technology.

              The main objective of this contribution is to describe the development of the concepts, techniques and devices associated with solid-phase microextraction, as a response to the evolution of understanding of the fundamental principles behind this technique. The discussion begins with an historical perspective on the very early work conduced almost a decade ago. As new fundamental understanding about the functioning of the technology developed, new ways of constructing and using the SPME devices evolved.
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                Author and article information

                Journal
                Materials (Basel)
                Materials (Basel)
                materials
                Materials
                MDPI
                1996-1944
                18 September 2017
                September 2017
                : 10
                : 9
                : 1094
                Affiliations
                [1 ]Instituto de Tecnologia Química e Biológica António Xavier, Universidade Nova de Lisboa, Av. Da República, 2780-157 Oeiras, Portugal; davidpatinha@ 123456itqb.unl.pt (D.J.S.P.); liliana.tome@ 123456itqb.unl.pt (L.C.T.)
                [2 ]CICECO—Aveiro Institute of Materials and Department of Chemistry, University of Aveiro, 3810-193 Aveiro, Portugal
                [3 ]POLYMAT, University of the Basque Country UPV/EHU, Joxe Mari Korta Center, Avda. Tolosa 72, 20018 Donostia-San Sebastian, Spain; isik.mehmet@ 123456ehu.eus (M.I.); david.mecerreyes@ 123456ehu.es (D.M.)
                [4 ]IKERBASQUE, Basque Foundation for Science, E-48011 Bilbao, Spain
                [5 ]Centro de Química Estrutural, Instituto Superior Técnico, Universidade de Lisboa, Avenida Rovisco Pais, 1049-001 Lisboa, Portugal
                Author notes
                [* ]Correspondence: armsil@ 123456ua.pt (A.J.D.S.); isabel.marrucho@ 123456tecnico.ulisboa.pt (I.M.M.); Tel.: +351-23-437-0711 (A.J.D.S.); +351-21-446-9724 (I.M.M.); Fax: +351-21-441-1277 (I.M.M.)
                Author information
                https://orcid.org/0000-0002-9827-627X
                https://orcid.org/0000-0002-0258-2206
                https://orcid.org/0000-0001-5403-8416
                Article
                materials-10-01094
                10.3390/ma10091094
                5615748
                28927003
                10e1c7b4-86de-494d-995f-aa5cf4058ab5
                © 2017 by the authors.

                Licensee MDPI, Basel, Switzerland. This article is an open access article distributed under the terms and conditions of the Creative Commons Attribution (CC BY) license ( http://creativecommons.org/licenses/by/4.0/).

                History
                : 07 August 2017
                : 14 September 2017
                Categories
                Article

                solid phase microextraction,poly(ionic liquids),uv-photopolymerization,gas chromatography,steel coatings,fibers

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