Advanced Materials as Adsorbents in Microextractions for the Determination of Contaminants: A Mini Review

The widespread presence of contaminants in water demands reliable and practical analytical methods to monitor them. However, before their determination, a sample pretreatment step is necessary. This has conventionally been performed using liquid-liquid extraction (LLE) or solid-phase extraction (SPE). Advances in material sciences have since been capitalized on, with new adsorbents used in conjunction with new sample pretreatment techniques based on microextractions. In this mini-review, we showcase some of our previously reported work that demonstrates how advanced materials such as graphene, molecularly imprinted polymers (MIPs), and polymeric cyclodextrins can be used as adsorbents for the determination of contaminants such as bisphenol A, steroids, sulfonamide antibiotics, and antimicrobial agents. These adsorbents formed an important component in the micro-solid phase extraction that was used for the pretreatment of the sample. A brief introduction to the adsorbents studied and evolution of extractions is provided. The distinctive features of the analytical methods used in the real sample analysis of the stated contaminants are highlighted.

Advanced materials; Analytical determination; Contaminants; Sample pretreatment

The presence of environmental pollutants such as herbicides, pharmaceutical waste, heavy metals (Kusumaningsih et al., 2012), and dyes (Mamat et al., 2018; Anuar et al., 2019) at trace levels has been the cause of much concern among the public and authorities. This has provided motivation for researchers to explore new materials that can be used for their removal. In analytical determination protocols, the use of these materials as adsorbents in sample preparation techniques has been keenly studied. Sample preparation is an important step in selectively isolating the analyte of interest from the sample before the analytical determination (normally using chromatographic methods). It also helps to preconcentrate the analytes, which is important in trace determinations. To achieve these objectives, extraction of the targeted analyte can be conducted using extractions (see section 3), and extractions using solid adsorbents have been  viewed as the way forward. The prime objective is to introduce new materials that are more selective and easily prepared, which can improve on the conventional methods. Advanced materials have been used in numerous applications such as the determination of parabens (Fumes & Lanças, 2016), sulfonamides (Rozaini et al., 2019), bisphenol A (Rozaini et al., 2017), triclosan (Alshishani et al., 2019), and endogenous steroids (Manaf et al., 2018) in both environmental waters and human urine. Another important objective is to reduce the consumption of organic solvents, which are used in large amounts in conventional liquid-liquid extraction (LLE). In this report, the use of graphene, molecularly imprinted polymers (MIPs), and polymers containing immobilized cyclodextrin (CD) are provided as examples of how these advanced materials can be used as adsorbents in sample microextractions before their analytical determination.

Advanced materials, due to their unique properties, have proven to be useful in numerous applications. We demonstrated how MIP, graphene, and CD were used as adsorbents for the microextraction of model antimicrobials, steroids, and veterinary drugs. The analytical techniques that resulted from these innovations were simple, effective, conserve solvents and materials, which support the green analytical chemistry initiatives.

The authors acknowledge the support received from the Ministry of Education Malaysia (Fundamental Research Grant Scheme – 015MA0-017), Universiti Teknologi PETRONAS (Yayasan Universiti Teknologi PETRONAS Research Grant Scheme – 015LC0-071), and Universitas Islam Riau (UIR matching grant-015ME0-038).

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