Liquid crystal-based sensors for the detection of heavy metals using surface-immobilized urease

In this study, a new method for the detection of heavy metals in aqueous phase was developed using liquid crystals (LCs). When UV-treated nematic LC, 4-cyano-4'-pentyl biphenyl (5CB) that was confined in the urease-modified gold grid was immersed in a urea solution, an optical response from bright to dark was observed under a polarized microscope, indicating that a planar-to-homeotropic orientational transition of the LC occurred at the aqueous/LC interface. Since urease hydrolyzes urea to produce ammonia, which would be ionized into ammonium and hydroxide ions, the main product of the photochemically degraded 5CB, 4-cyano-4'-biphenylcarboxylic acid (CBA), was deprotonated and self-assembled at the interface, inducing the orientational transition in the LC. Due to the high sensitivity and rapid response of this system, detection of heavy metal ions was further exploited. The divalent copper ion, which could effectively inhibit the activity of urease, was used as a model heavy metal ion. The optical appearance of the LC did not change when urea was in contact with the copper nitrate hydrate-blocked urease. After the copper-inhibited urease was reactivated by EDTA, a bright-to-dark shift in the optical signal was regenerated, indicating an orientational transition of the LC. This type of LC-based sensor shows high spatial resolution due to its optical characteristics and therefore could potentially be used to accurately monitor the presence of enzyme inhibitors such as heavy metal ions in real-time.     

Graphene-based nanocomposites as sensing elements for the electrochemical detection of pesticides: a review

Journal of Solid State Electrochemistry - Only about 3% of Earth’s water is freshwater out of which only 0.4% is accessible as surface water in the form of lakes, rivers and groundwater. When...     

Sensitive detection of heavy metals ions based on the calixarene derivatives-modified piezoelectric resonators: a review

Heavy-metal pollution is a foremost concern, as excessive heavy metals produce environmental contamination, and the accumulative effects of heavy metals pose a major hazard to human health. There is an urgent need for a fast, sensitive and effective method for detecting heavy metal cations in the environment. In recent years, using Quartz Crystal Microbalance (QCM) technique, significant progress was achieved in quantitative analysis by providing a new approach for determination of chemical content analysis. The objective aim of this review is to assess the research development of QCM applications in detection of heavy metal cations in natural water (or aqueous solution) and reflect the challenges and forthcoming point of view for QCM-based sensors for heavy-metal ions. A brief outline about the basic measurement methodologies and analytical techniques is given. To illustrate applications of the QCM techniques, the influence of the structural transformation resulting from polymer, macrocyclic ‘calixarenes’ and nanostructural coating on sensation will be discussed. Lastly, we summarise fields of applications and future forecast for the utilisation of functionalised QCM surface as a chemical sensor to study the interaction of heavy metal ions with calixarenes.     

Speciation analysis of heavy metals in natural waters: a review.

Metal speciation in natural waters is of increasing interest and importance because toxicity, bioavailability, environmental mobility, biogeochemical behavior, and potential risk in general are strongly dependent on the chemical species of metals. This paper provides an overview of the need for speciation of heavy metals in natural waters, the chemical and toxicological aspects of speciation, and the analytical procedures for separation and the different techniques for final determination that are used today. The trends and developments of speciation are also discussed. Finally, the case of chromium (Cr) was selected for a detailed presentation because the speciation of this metal has attracted a great deal of interest in view of the toxic properties of Cr(VI).     

Significance of nanomaterials in electrochemical sensors for nitrate detection: A review

Nanomaterial-enabled electrochemical sensors are designed as an economical, efficient, and user-friendly analytical tool for on-site and routine nitrate analysis over a wide range of environmental samples. The remarkable advances and tunable attributes of nanomaterials have greatly improved the analytical performance of electrochemical nitrate sensors. In this review, a comprehensive elucidation of the recent advances in nanomaterial-based electrochemical nitrate sensors is presented. The review firstly provides a general introduction, followed by typical electrochemical sensing methods. The next two sections detail various nanomaterials, including graphene derivatives, carbon nanotubes/fibers, metal/bimetal/metal oxide nanoparticles, and conducting polymers for modifying electrodes in enzymatic and non-enzymatic electrochemical nitrate sensors. Finally, the perspectives and current challenges in achieving real-world applications of nanomaterial-based electrochemical nitrate sensors are outlined.     

Recent advances in photoelectrochemical sensors for detection of ions in water

Over the last 50 years, the explosive adoption of modern agricultural practices has led to an enormous increase in the emission of non-biodegradable and highly biotoxic ions into the hydrosphere. Excess intake of such ions, even essential trace elements such as Cu²⁺ and F⁻, can have serious consequences on human health. Therefore, to ensure safe drinking water and regulate wastewater discharge, photoelectrochemical (PEC) online sensors were developed, with advantages such as low energy consumption, inherent miniaturization, simple instrumentation, and fast response. However, there is no publicly available systematic review of the recent advances in PEC ion sensors available in the literature since January 2017. Thus, this review covers the various strategies that have been used to enhance the sensitivity, selectivity, and limit of detection for PEC ion sensors. The photoelectrochemically active materials, conductive substrates, electronic transfer, and performance of various PEC sensors are discussed in detail and divided into sections based on the measurement principle and detected ion species. We conclude this review by highlighting the challenges and potential future avenues of research associated with the development of novel high-performance PEC sensors.     

Electrochemical sensing of heavy metals in biological media: A review

Trace metals are required in the body as they play a significant role in several biochemical processes. Moreover, certain heavy metals are beneficial at appropriate levels. Copper (Cu), for example, is essential for red blood cell formation, bone strength, and infant growth. Despite these fundamental roles, Cu can become toxic at high levels. Other heavy metals such as lead (Pb), cadmium (Cd), manganese (Mn), and mercury (Hg), have been identified to cause acute and chronic health complications. For these reasons, rapid, real-time quantification of such metals in biological media is of interest to improving human health outcomes. Electrochemical methods offer numerous advantages, such as portability, capability to be miniaturized, low cost, and ease-of-use. In this review, we examine recent developments in electrochemical sensing for the detection of heavy metals in biological media. To meet the requirements for inclusion in this review, the electrochemical sensor must have been evaluated in biological media (blood, serum, sweat, saliva, urine, brain tissue/cells). Several applications are explored to examine recent advancements in electrochemical sensing within these matrices. Addressing the challenges through materials, device, and system innovations, it is expected that electrochemical sensing of heavy metals in biological media will facilitate future diagnoses and treatments in healthcare.     

Nanomaterial-based electrochemical sensors and optical probes for detection and imaging of peroxynitrite: a review

Peroxynitrite (PON for short) is a powerful nitrating, nitrosating and oxidative agent for cellular constituents. In vivo, PON is formed through the diffusion-controlled reaction between superoxide radical (O₂ ^?- ) and nitric oxide (?NO). This critical review (with 67 refs.) covers the state of the art in nanomaterial-based (a) detection and imaging of PON inside cells and (b) monitoring of cellular events such as cellular oxidative burst by using optical or electrochemical methods. It starts with the formation, fate and pathophysiology of PON in vivo. The next part summarizes nanomaterial based electrochemical microsensors featuring nanofilms and nanostructured electrodes, nanospheres, 3D nanostructures and graphene-supported catalysts. A following chapter covers techniques based on optical nanoprobes, starting with nanomaterials used in optical detection of PON (including quantum dots, carbon dots, fluorescent organic polymer dots, rare earth nanocrystals including upconversion nanoparticles, iron oxide nanoparticles, gold nanoparticles, and fluorophore-modified nanoporous silicon). This is followed by subsections on strategies for optical detection of PON (including color changes, fluorescence quenching, activation and recovery), and on schemes for optimized spatial and temporal resolution, for improving sensitivity, selectivity, and (photo)stability. We then address critical issues related to biocompatibility, pharmacokinetics, give a number of representative practical applications and discuss challenges related to PON detection. The review concludes with a discussion of latest developments and future perspectives.

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Zinc oxide nanostructured platform for electrochemical detection of heavy metals

ZnO nanoparticles (ZnO-NP) were prepared by a facile precipitation technique using di-isopropyl amine as precipitating agent. The morpho-structure and porosity of the as-prepared nano-powder were investigated by FT-IR analysis, X-ray diffraction (XRD), scanning electron microscopy (SEM), and BET analysis. By drop-casting, a composite film was deposited to obtain ZnO-NP-Nafion/GCE modified electrode. The modified electrode was investigated by cyclic voltammetry, electrochemical impedance spectroscopy, and square wave anodic stripping voltammetry (SWASV) for the detection of Pb²⁺, Cd²⁺, Cu²⁺, and Fe³⁺, and it was successfully applied for the detection of Pb²⁺ and Cu²⁺ in real water samples.     

Design of a portable luminescence bio-tool for on-site analysis of heavy metals in water samples

ABSTRACT

In this work, we report an innovative tool for heavy metal screening in water samples. This new chemiluminescent set-up screens the light generated from luminol oxidation by horseradish peroxidase (HRP) in the presence of hydrogen peroxide (H₂O₂). The pollutant concentrations in real water samples were calculated by studying the effect of metal ions on chemiluminescence signal. Owing to its simplicity, portability and low cost, this approach presents a real alternative to classical optical methods. It is constructed with simple materials: a black box containing a cuvette and a micro-camera. When the enzymatic reaction takes place, the luminescence is captured by the camera placed in upright position. The image can be saved automatically in a computer for further analysis using a MATLAB interface. The RGB diagram is then established to determine the analyte concentrations in the tested samples. This method was successfully applied for the determination of mercury (Hg), lead (Pb) and cadmium (Cd) in lake and field water samples. In these experiments, three concentrations of each analytes were tested (5, 25 and 50 µg/L). We noted a good proportionality between the analyte concentration and the chemiluminescent detection intensity. Detection of binary and tertiary combinations of heavy metals has been also investigated. The developed biosensor showed low detection limits for the tested heavy metals: 1, 0.7 and 0.02 for Hg²⁺, Pb²⁺ and Cd²⁺, respectively. Finally, excellent recoveries ranging from 98% to 104% were obtained for the HRP-inhibition assay.     

Critical review of bio/nano sensors for arsenic detection

Detection of arsenic is a long-standing challenge in environmental analytical chemistry. In recent years, using biomolecules and nanomaterials for sensing arsenic has been growingly reported. In this article, this field is critically reviewed based on some recent fundamental understandings including interactions between arsenic and gold, thiol, and DNA aptamers. First, taking advantage of the adsorption of As(III) on noble metal surfaces such as silver and gold, sensors were developed based on surface enhanced Raman spectroscopy, electrochemistry and colorimetry. In addition, by functionalizing metal nanoparticles with thiol containing molecules, As(III) induced aggregation of the particles based on As(III)/thiol interactions. As(V) interacts with metal oxides strongly and competitive sensors were developed by displacing pre-adsorbed DNA oligonucleotides. A DNA aptamer was selected for As(III) and many sensors were reported based on this aptamer, although careful binding measurements indicated that the sequence has no affinity towards As(III). Overall, bio/nano systems are promising for the detection of arsenic. Future work on fundamental studies, searching for more specific arsenic binding materials and aptamers, incorporation of sensors into portable devices, and more systematic test of sensors in real samples could be interesting and useful research topics.     

Use of bioluminescent bacterial sensors as an alternative method for measuring heavy metals in soil extracts

The luminescence based bacterial sensor strains Pseudomonas fluorescens OS8 (pTPT11) for mercury detection and Pseudomonas fluorescens OS8 (pTPT31) for arsenite detection were used in testing their application in detecting heavy metals in soil extracts. Three different soil types (humus, mineral and clay) were spiked with 1, 100 or 500 μg g⁻¹ Hg²⁺ or As³⁺. Samples were taken 1, 14 and 30 days and extracted with water, ammonium acetate, hydrogen peroxide and nitric acid to represent water soluble, bioavailable, organic matter bound and residual fractions, respectively. The lowest mercury-concentration measured using biosensor (0.003 μg kg⁻¹) was considerably lower than by chemical method (0.05 μg kg⁻¹). The sensor strain with pTPT31 appeared to have a useful detection range similar to that of chemical methods. Concentration results with chemical and biosensor analysis were very similar in the case of mercury-spiked samples. Although some of the arsenite samples showed higher variation between methods, it is concluded that the bacteria can be used as an alternative traditional methods for different types of samples.     

Removal of heavy metals from wastewater using micellar enhanced ultrafiltration technique: a review

Application of Micellar enhanced ultrafiltration (MEUF) for the removal of different heavy metals has been reviewed. It is considered an economical alternative available to the conventional membrane separation process, because it reduces the requirement of higher pressure and high membrane costs. MEUF is a separation processes which uses surfactants and ultrafiltration membranes to remove multivalent ions from wastewater with high percent rejection using electrostatic attraction between metals and micelles.     

Metallothionein-cross-linked hydrogels for the selective removal of heavy metals from water

The diverse functional repertoire of proteins promises to yield new materials with unprecedented capabilities, so long as versatile chemical methods are available to integrate biomolecules with synthetic components. As a demonstration of this potential, we have used site-selective strategies to cross-link polymer chains using the N- and C-termini of a metallothionein derived from a pea plant. This arrangement directly relates the swelling volume of the polymer to the folded state of the protein. The material retains the protein's ability to remove heavy metal ions from contaminated water samples, and can be regenerated through the subsequent addition of inexpensive chelators. The change in hydrogel volume that occurs as metal ions are bound allows the detection of contaminants through simple visual inspection. The utility of this bulk property change is demonstrated in the construction of a low-cost device that can report heavy metal contamination with no external power requirements. Most importantly, the generality of the protein modification chemistry allows the immediate generation of new hybrid materials from a wide range of protein sequences.     

Zeolite-fiber integrated optical chemical sensors for detection of dissolved organics in water

MFI zeolite coated optical fiber sensors have been developed for in situ detection of dissolved organics in water. The sensors operate by monitoring the optical reflectivity changes caused by the selective adsorption of organic molecules, i.e., 2-propanol or pentanoic acid in this study, from aqueous solutions in the zeolitic pores. Reversible and monotonic sensor signals were observed in response to the variation of 2-propanol concentration in water with fast response. However, the sensor exhibited a much slower response to pentanoic acid than to 2-propanol. It was also found that substitution of Si by Al in the MFI framework increased the adsorption of pentanoic acid that resulted in enhanced sensor responses.     

Progress on sensors based on nanomaterials for rapid detection of heavy metal ions

The heavy metal ions,especially Cd~(2+),Pb~(2+) and Hg~(2+),show extremely hazard to the environment and human being.The measurement of heavy metal ions using sensors is catching more and more attention for its advantages of high sensitivity and selectivity,low-cost,convenience to handle and rapid detection.In recent years,nanomaterials such as gold nanoparticles(NPs),magnetic nanoparticles,graphene and nanocomposite materials are applied in sensors for improving sensitivity and selectivity,making the research on electrochemical(EC) sensors,spectrometric biosensors and colorimetric biosensors become a hot spot in the application to investigate heavy metal ions,in particular,Cd~(2+),Pb~(2+) and Hg~(2+).In this short review,the research of advanced detection of Cd~(2+),Pb~(2+) and Hg~(2+) and its progress based on nanomaterial sensors in recent years is reviewed.     

Adsorption of a few heavy metals on natural and modified kaolinite and montmorillonite: a review

The feasibility of using two important and common clay minerals, kaolinite and montmorillonite, as adsorbents for removal of toxic heavy metals has been reviewed. A good number of works have been reported where the modifications of these natural clays were done to carry the adsorption of metals from aqueous solutions. The modification was predominantly done by pillaring with various polyoxy cations of Zr4+, Al3+, Si4+, Ti4+, Fe3+, Cr3+or Ga3+, etc. Preparation of pillared clays with quaternary ammonium cations, namely, tetramethylammonium-, tetramethylphosphonium- and trimethyl-phenylammonium-, N'-didodecyl-N, N'-tetramethylethanediammonium, etc, are also common. Moreover, the acid treatment of clays often boosted their adsorption capacities. The adsorption of toxic metals, viz., As, Cd, Cr, Co, Cu, Fe, Pb, Mn, Ni, Zn, etc., have been studied predominantly. Montmorillonite and its modified forms have much higher metal adsorption capacity compared to that of kaolinite as well as modified-kaolinite.     

Heavy metals in lake water: a review on occurrence and analytical determination

Many lakes especially in Asia are source of livelihood for the surrounding communities. With increased urbanisation and industrialisation, however, these lakes are threatened with emerging environmental contaminants, including heavy metals. Some heavy metals are harmful to human health and the environment. This review aims to describe the different sampling, sample preparation and pretreatment, and instrumental methods of analysis for heavy metals in lake water. Filtration and acid digestion are common sample treatment methods used prior to analytical determination. Atomic absorption spectroscopy and inductively-coupled plasma – mass spectrometry (ICP-MS) are typical analytical techniques but nowadays ICP-MS is frequently used. This review also describes the sources and extent of heavy metals contamination in different lakes. Although some lakes still have natural levels of heavy metals in the water, many have elevated concentrations due to anthropogenic sources, such as vehicular, household, agricultural, industrial and mining activities.     

Carbon nanotube-based extraction and electrochemical detection of heavy metals

In this mini review, recent trends and challenges in developing carbon nanotube-based extraction and electrochemical detection of heavy metals in water are reviewed. Carbon nanotubes (CNT) have electrical, mechanical, chemical, and structural properties superior to those of conventional materials, for example graphite and activated carbon. CNT-based procedures are also more efficient than traditional techniques and methods, for example liquid?Cliquid extraction, atomic-absorption spectroscopy, flame photometry, and inductively coupled plasma, because they can enable rapid, sensitive, simple, and low-cost on-site detection. Different forms of CNT, including as-grown, oxidised, and functionalised CNT, can be well suited to metal adsorption. The measurement procedure relies on adsorbing the metal on the CNT surface after reasonable contact time, either by applying an electrical potential or under open-circuit conditions, and subsequent quantification. Different types of CNT-based electrode, including composite, paste, and binder-free, can be fabricated and used for metal detection. Application of CNT and their novel properties to the adsorption and detection of heavy metals is discussed in detail.