A Turn-On Fluorescence-Based Fibre Optic Sensor for the Detection of Mercury

The design, development, and evaluation of an optical fibre sensor for the detection of Hg2+ in aqueous media are discussed in detail in this paper. A novel fluorescent polymeric material for Hg2+ detection, based on a coumarin derivative (acting as the fluorophore) and an azathia crown ether moiety (acting as the mercury ion receptor), has been synthesized. The fluorophore was covalently immobilized onto the fibre surface by polymerisation using the ion imprinting technique and exhibited a significant increase in fluorescence intensity in response to Hg2+ via a photoinduced electron transfer (PET) mechanism. The sensor provided a response over a concentration range of 0–28 µM with an acceptable response rate of around 11 min and a recovery rate of around 30 min in a Tris-EDTA buffer solution. A detection limit of 0.15 µM was obtained with a possibility of improvement by changing the thickness of the polymer layer and using a more sensitive detector. High-quality performance is seen through a high selectivity for Hg2+ over other metal ions, excellent photo-stability and reversibility which was also demonstrated, making this type of sensor potentially well suited for in-situ monitoring of mercury in the environment

A critical review on the use of molecular imprinting for trace heavy metal and micropollutant detection

Molecular recognition has been described as the “ultimate” form of sensing and plays a fundamental role in biological processes. There is a move towards biomimetic recognition elements to overcome inherent problems of natural receptors such as limited stability, high-cost, and variation in response. In recent years, several alternatives have emerged which have found their first commercial applications. In this review, we focus on molecularly imprinted polymers (MIPs) since they present an attractive alternative due to recent breakthroughs in polymer science and nanotechnology. For example, innovative solid-phase synthesis methods can produce MIPs with sometimes greater affinities than natural receptors. Although industry and environmental agencies require sensors for continuous monitoring, the regulatory barrier for employing MIP-based sensors is still low for environmental applications. Despite this, there are currently no sensors in this area, which is likely due to low profitability and the need for new legislation to promote the development of MIP-based sensors for pollutant and heavy metal monitoring. The increased demand for point-of-use devices and home testing kits is driving an exponential growth in biosensor production, leading to an expected market value of over GPB 25 billion by 2023. A key requirement of point-of-use devices is portability, since the test must be conducted at “the time and place” to pinpoint sources of contamination in food and/or water samples. Therefore, this review will focus on MIP-based sensors for monitoring pollutants and heavy metals by critically evaluating relevant literature sources from 1993 to 2022

Fluorescent optical fibre chemosensor for the detection of mercury

This work aims to develop a stable, compact and portable fibre optic sensing system which is capable of real time detection of the mercury ion (II), Hg2+. A novel fluorescent polymeric material for Hg2+ detection, based on a coumarin derivative (acting as the fluorophore) and an azathia crown ether moiety (acting as the mercury ion receptor), has been designed and synthesized. The material was covalently attached to the distal end of an optical fibre and exhibited a significant increase in fluorescence intensity in response to Hg2+ in the μM concentration range via a photoinduced electron transfer (PET) mechanism. The sensor has also demonstrated a high selectivity for Hg2+ over other metal ions. A washing protocol was identified for sensor regeneration, allowing the probe to be re-used. The approach developed in this work can also be used for the preparation of sensors for other heavy metals

An ion imprinted polymer for the selective extraction of mercury (II) ions in aqueous media

This thesis presents the application of an imprinted mercury(lI) polymer that we synthesized by copolymerizing the functional and cross-linking monomers, N'-[3-(Trimethoxysilyl)propyl] diethylenetriamine (TPET) and tetraethylorthosilicate (TEOS) in the presence of mercury (II) ions as template. A bulk polymerization method following a double-imprinting procedure and employing hexadecyltrimethylammonium bromide (CTAB), as a second template to improve the efficiency of the polymer was employed in the synthesis. The imprinted polymer particles were characterized by Fourier transform infrared (FTIR) spectroscopy, scanning electron microscopy (SEM) and their average size determined by screen analysis using standard test sieves. The relative selective coefficients (k') of the imprinted polymer evaluated from selective binding studies between Hg ²⁺and Cu²⁺ or Hg²⁺ and Cd²⁺, were 10588 and 3147, respectively. These values indicated highly favored Hg²⁺ extractions over the two competing ions. Application of the polymer to various real water samples (tap, sea, river, pulverized coal solution, treated and untreated sewerage from the vicinity of Grahamstown in South Africa) showed high extraction efficiencies (EEs) of Hg²⁺ ions; (over 84% in all cases) as evaluated from the detected unextracted Hg²⁺ ions by inductively coupled plasma optical emission spectroscopy (ICP-OES). The limit of detection (LOD, 3ơ) of the method was evaluated to be 0.036 ng ml⁻¹ and generally the data (n=10) had percentage relative standard deviation (%RSD) of less than 4%. These findings indicate that the double-imprinted polymer has potential to be used as an efficient extraction material for the selective pre-concentration of mercury(lI) ions in aqueous environments.KMBT_363Adobe Acrobat 9.54 Paper Capture Plug-i

Molecular Imprinting of Peptides and Proteins

Molecular imprinting described as a method utilized to create artificial receptors and antibodies by construction of selective recognition sites in a synthetic polymer can be a promising tool for generating peptide and protein artificial specific recognition sites. These materials, as potential antibody substitutes, have attracted great interest and attention in different fields such as peptide and protein purification and separation, chemical/electrochemical/optical sensors/biosensors, chromatographic stationary phases, and enzyme mimics. This review has focused on fundamentals of molecularly imprinted polymers in terms of selection of molecular template, functional monomer, cross linker, and polymerization format. Furthermore, several applications of peptide/protein-imprinted materials are highlighted and challenges regarding the intrinsic properties of peptide/ protein imprinting have been emphasized.HighlightsHighlights the fundamentals of peptides and proteins molecular imprinting.Summarizes the essential elements and polymer formats of peptide/protein imprinted materials.Highlights the applications of peptide/protein imprinting.Highlights the challenges in peptide/protein imprinting

Recent developments in sensing devices based on polymeric systems

This review is focused on the analysis of recent developments in the application of polymers in the detection and quantification of target species. The work begins with a description of the polymers that are employed as sensory materials, covering molecularly imprinted polymers or MIPs, hybrid polymers, acrylic polymers, conductive polymers, polymers with chiral motifs and also the use of polymeric arrays. After the description of the sensory polymers, the different target species which can be detected using sensory polymeric devices, including metallic cations and anionic species, gases, explosives, radionuclides and bacteria or the recent biomedical and biological applications is described. Finally, the sensory devices fabricated using smart polymers, including, for example, sensory devices based on Quartz Crystal Microbalances or the use of micro and nanoporous materials as substrates for sensory polymeric coatings is listed and reviewed. The work also details the different detection mechanisms based on the type of response of the sensory polymers, such as electrical, piezoelectric or fluorescence. In brief, the review details a review of the research work published in the last 10 years in this quickly evolving field, with special emphasis in the biomedical and biological applications, which have emerged recently raising great attention. To conclude, some perspectives and future challenges that must be overcome by this research field in the next years is exposed.FEDER (Fondo Europeo de Desarrollo Regional) and the Spanish Agencia Estatal de Investigación (AEI) (MAT2017-84501-R

State-of-the-Art of (Bio)Chemical Sensor Developments in Analytical Spanish Groups

(Bio)chemical sensors are one of the most exciting fields in analytical chemistry today. The development of these analytical devices simplifies and miniaturizes the whole analytical process. Although the initial expectation of the massive incorporation of sensors in routine analytical work has been truncated to some extent, in many other cases analytical methods based on sensor technology have solved important analytical problems. Many research groups are working in this field world-wide, reporting interesting results so far. Modestly, Spanish researchers have contributed to these recent developments. In this review, we summarize the more representative achievements carried out for these groups. They cover a wide variety of sensors, including optical, electrochemical, piezoelectric or electro-mechanical devices, used for laboratory or field analyses. The capabilities to be used in different applied areas are also critically discussed

Recent Trends in Monitoring of European Water Framework Directive Priority Substances Using Micro-Sensors: A 2007–2009 Review

This review discusses from a critical perspective the development of new sensors for the measurement of priority pollutants targeted in the E.U. Water Framework Directive. Significant advances are reported in the paper and their advantages and limitations are also discussed. Future perspectives in this area are also pointed out in the conclusions. This review covers publications appeared since December 2006 (the publication date of the Swift report). Among priority substances, sensors for monitoring the four WFD metals represent 81% of published papers. None of analyzed publications present a micro-sensor totally validated in laboratory, ready for tests under real conditions in the field. The researches are mainly focused on the sensing part of the micro-sensors. Nevertheless, the main factor limiting micro-sensor applications in the environment is the ruggedness of the receptor towards environmental conditions. This point constitutes the first technological obstacle to be overcome for any long-term field tests

Molecularly imprinted polymer-based sensors for priority pollutants

Globally, there is growing concern about the health risks of water and air pollution. The U.S. Environmental Protection Agency (EPA) has developed a list of priority pollutants containing 129 different chemical compounds. All of these chemicals are of significant interest due to their serious health and safety issues. Permanent exposure to some concentrations of these chemicals can cause severe and irrecoverable health effects, which can be easily prevented by their early identification. Molecularly imprinted polymers (MIPs) offer great potential for selective adsorption of chemicals from water and air samples. These selective artificial bio(mimetic) receptors are promising candidates for modification of sensors, especially disposable sensors, due to their low-cost, long-term stability, ease of engineering, simplicity of production and their applicability for a wide range of targets. Herein, innovative strategies used to develop MIP-based sensors for EPA priority pollutants will be reviewed. © 2021 by the authors. Licensee MDPI, Basel, Switzerland