Search Results (34)

Efforts to quantify iron ion concentrations across fields such as environmental, chemical, health, and food sciences have intensified over the past decade, which drives advancements in analytical methods, particularly electrochemical sensors known for their simplicity, portability, and reliability. The development of electrochemical methods using non-mercury electrodes is increasing as alternatives to environmentally unsafe mercury-based electrodes. However, detecting iron species such as Fe(II) and Fe(III) remains challenging due to their distinct chemical properties, continuous oxidation-state interconversion, presence of interfering species, and complex behavior in diverse environments and matrixes. Selective trace detection demands careful optimization of electrochemical methods, including proper electrode materials selection, electrode surface modifications, operating conditions, and sample pretreatments. This review critically evaluates advancements over the past decade in mercury-free electrode materials and surface modification strategies for iron detection. Strategies include incorporating a variety of nanomaterials, composites, conducting polymers, membranes, and iron-selective ligands to improve sensitivity, selectivity, and performance. Despite advancements, achieving ultra-low detection limits in real-world samples with minimal interference remains challenging and emphasizes the need for enhanced sample pretreatment. This review identifies challenges, knowledge gaps, and future directions and paves the way for advanced iron electrochemical sensors for environmental monitoring, health diagnostics, and analytical precision. Full article

Mercury, a toxic heavy metal produced through both natural and anthropogenic processes, is found in all of Earth’s major systems. Mercury’s bioaccumulation characteristics in the human body have a significant impact on the liver, kidneys, brain, and muscles. In order to detect Hg²⁺ ions, a highly sensitive and specific fluorescent biosensor has been developed using a novel, modified seven amino acid peptide, FY7. The tyrosine ring in the FY7 peptide sequence forms a 2:1 complex with Hg²⁺ ions that are present in the water-based sample. As a result, the peptide’s fluorescence emission decreases with higher concentrations of Hg²⁺. The FY7 peptide’s performance was tested in the presence of Hg²⁺ ions and other metal ions, revealing its sensitivity and stability despite high concentrations. Conformational changes to the FY7 structure were confirmed by FTIR studies. Simultaneously, we designed a miniaturized setup to support an in-house-developed micro-volume capillary container for volume fluorometry measurements. We compared and verified the results from the micro-volume system with those from the commercial setup. The micro-volume capillary system accommodated only 2.9 µL of sample volume, allowing for rapid, sensitive, and selective detection of toxic mercury (II) ions as low as 0.02 µM. Full article

The removal and detection of highly toxic mercury(II) ions (Hg²⁺) in water used daily is essential for human health and monitoring environmental pollution. Efficient porous organic polymers (POPs) can provide a strong adsorption capacity toward heavy metal ions, although the complex synthetic process and inconvenient phase separation steps limit their application. Hence, a combination of POPs and magnetic nanomaterials was proposed and a new magnetic porous organic polymer adsorbent was fabricated by a green and mild redox reaction in the aqueous phase with trithiocyanuric acid (TA) and its sodium salts acting as reductive monomers and iodine acting as an oxidant. In the preparation steps, no additional harmful organic solvent is required and the byproducts of sodium iodine are generally considered to be non-toxic. The resulting magnetic poly(trithiocyanuric acid) polymers (MPTAPs) are highly porous, have large surface areas, are rich in sulfhydryl groups and show easy magnetic separation ability. The experimental results show that MPTAPs exhibit good adsorption affinity toward Hg²⁺ with high selectivity, rapid adsorption kinetics (10 min), a large adsorption capacity (211 mg g⁻¹) and wide adsorption applicability under various pH environments (pH 2~8). Additionally, MPTAPs can be reused for up to 10 cycles, and the magnetic separation step of MPTAPs is fast and convenient, reducing energy consumption compared to centrifugation and filtration steps required for non-magnetic adsorbents. These results demonstrate the promising capability of MPTAPs as superior adsorbents for effective adsorption and separation of Hg²⁺. Based on this, the prepared MPTAPs were adopted as magnetic solid-phase extraction (MSPE) materials for isolation of trace Hg²⁺ from aqueous samples. Under optimized conditions, the extraction and quantification of trace Hg²⁺ in water samples were accomplished using inductively coupled plasma mass spectrometry (ICP-MS) detection after MSPE procedures. The proposed MPTAPs-based MSPE-ICP-MS method is efficient, rapid, sensitive and selective for the determination of trace Hg²⁺, and was successfully employed for the accurate analysis of trace Hg²⁺ in tap water, wastewater, lake water and river water samples. Full article

This article discusses the design and analysis of a new chemical chemosensor for detecting mercury(II) ions. The chemosensor is a hydrazone made from 4-methylthiazole-5-carbaldehyde and fluorescein hydrazide. The structure of the chemosensor was confirmed using various methods, including nuclear magnetic resonance spectroscopy, infrared spectroscopy with Fourier transformation, mass spectroscopy, and quantum chemical calculations. The sensor’s ability in the highly selective and sensitive discovery of Hg²⁺ ions in water was demonstrated. The detection limit for mercury(II) ions was determined to be 0.23 µM. The new chemosensor was also used to detect Hg²⁺ ions in real samples and living cells using fluorescence spectroscopy. Chemosensor 1 and its complex with Hg²⁺ demonstrate a significant tendency to enter and accumulate in cells even at very low concentrations. Full article

In this work, the development of a novel method for the detection of mercury (II) ions in wastewater using a mercury ion-imprinted polymer (IIP) combined with a quartz crystal microbalance (QCM) is described. The IIP was successfully synthesized via the polymerization of a of a novel fluorescein- and 2-aminophenol-functionalized methacrylic acid monomer, which was noted to have high binding affinity to mercury (II) ions. This polymer was subsequently coated on a QCM chip to create an IIP-QCM sensor. This sensor was established to have high selectivity and good sensitivity to mercury (II) ions, and had a limit of detection (LOD) of 14.17 ppb, a limit of quantification (LOQ) of 42.94 ppb, a signal-to-noise ratio (S/N) of 4.29, good repeatability, and a working range of 42.94 ppb to 2 ppm. The sensor was also able to analyze tap water and wastewater samples. The IIP-QCM is, therefore, promising as a highly selective, cost-effective, and rapid mercury ion sensor for applications involving the detection of mercury in wastewater. Full article

Three novel dibenzo-18-crown-6 aldimines were successfully synthesised and structurally characterised via various spectroscopic methods (¹H,¹³H NMR, FT-IR) and their solution phase lead binding behaviours probed via absorption spectroscopy, the results are supported by Density Functional Theoretical (DFT) modelling. These methods revealed that the asymmetric nature of these compounds is such that at equilibrium the ether cavity adopts an open configuration where the constituent oxygen atoms exhibit a highly negative electrostatic potential; hence, they spontaneously (ΔG~−58 kJ mol⁻¹) interact/bind aqueous lead ions to form stable 2:1 metal–ligand complexes. As indicated by cyclic and square voltammetry studies, all compounds are redox active and polymerise relatively easily onto a platinum surface to form a multi-layered lead Ion-selective Membrane (ISM), the structure of which is confirmed by Scanning Electron Microscopy (SEM) and Electrochemical Impedance Spectroscopy (EIS). These novel Ion-selective Electrodes (ISEs), as characterised by Differential Pulse Anodic Stripping Voltammetry (D PASV), allow selective electrochemical detection and quantification of lead at concentrations as low as 10 ppm, over a range of 15–60 ppm, with only minimal interference from mercury(II) and aluminium(III) ions at a 1:1 analyte-interferent ratio. Full article

The toxicity of arsenic and mercury is highly dependent on their unique chemical forms, mobility, bioavailability, and biological roles. This places a strong demand on specific metal species analysis rather than total quantification. Graphene oxide (GO) is an excellent adsorbent for the extraction of metal ions; however, the functional moieties on the GO surface are not metal ion-specific. In this work, we chemically introduced thioglycolic acid to improve metal ion selectivity after the dual oxidation of graphite to generate graphene oxide (GO) nanosheets. The prepared adsorbent was characterized by various spectroscopic and microscopic techniques. A solid phase extraction method was developed after careful analysis and optimization of the prepared sorbent. The method shows a fairly good quantification limit of 0.20 µg L⁻¹ for As(III) and Hg(II) ions. From diverse water samples, the proposed sorbent preferentially removes As(III) and Hg(II) ions (tap water and groundwater). The remarkable wettability and analyte accessibility that the surface-bonded thiol functionality of GO sheets offers is an exciting feature. In a lesser amount of time, the GO−SH nanosorbent exhibits good extraction of traces of As(III) and Hg(II). The developed method exhibits good reliability and precision in terms of accuracy and relative standard deviation (RSD 3.8%; N = 5) and has low detection limits (0.04 µg L⁻¹). Real samples that had been spiked to a predefined level were analyzed in order to validate the established procedure. Full article

We developed a new optical sensor for tracing Hg(II) ions. The detection affinity examines within a concentration range of 0–4.0 µM Hg(II). The sensor film is based on Methyl 2-hydroxy-3-(((2S,2’R,3a’S,5R)-2-isopropyl-5,5’-dimethyl-4’-oxotetrahydro-2’H-spiro[cy-clohexane-1,6’-im-idazo[1,5-b]isoxazol]-2’-yl)methyl)-5-methylbenzoate (IXZD). The novel synthesized compound could be utilized as an optical turn-on chemosensor for pH. The emission intensity is highly enhanced for the deprotonated form concerning the protonated form. IXZD probe has a characteristic fluorescence peak at 481 nm under excitation of 351 nm with large Stocks shift of approximately 130 nm. In addition, the binding process of IXZD:Hg(II) presents a 1:1 molar ratio which is proved by the large quench of the 481 nm emission peak of IXZD and the growth of a new emission peak at 399 nm (blue shift). The binding configurations with one Hg(II) cation and its electronic characteristics were investigated by applying the Density Functional Theory (DFT) and the time-dependent DFT (TDDFT) calculations. Density functional theory (DFT) and the time-dependent DFT (TDDFT) theoretical results were provided to examine Hg(II)-IXZD structures and their electronic properties in solution. The developed chemical sensor was offered based on the intramolecular charge transfer (ICT) mechanism. The sensor film has a significantly low limit of detection (LOD) for Hg(II) of 0.025 μM in pH 7.4, with a relative standard deviation RSD_r (1%, n = 3). Lastly, the IXZD shows effective binding affinity to mercury ions, and the binding constant K_b was estimated to be 5.80 × 10⁵ M⁻¹. Hence, this developed optical sensor film has a significant efficiency for tracing mercury ions based on IXZD molecule-doped sensor film. Full article

Dyad compound NI-SP bearing 1,8-naphthalimide (NI) and styrylpyridine (SP) photoactive units, in which the N-phenylazadithia-15-crown-5 ether receptor is linked with the energy donor naphthalimide chromophore, has been evaluated as a ratiometric fluorescent chemosensor for mercury (II) ions in living cells. In an aqueous solution, NI-SP selectively responds to the presence of Hg²⁺ via the enhancement in the emission intensity of NI due to the inhibition of the photoinduced electron transfer from the receptor to the NI fragment. At the same time, the long wavelength fluorescence band of SP, arising as a result of resonance energy transfer from the excited NI unit, appears to be virtually unchanged upon Hg²⁺ binding. This allows self-calibration of the optical response. The observed spectral behavior is consistent with the formation of the (NI-SP)·Hg²⁺ complex (dissociation constant 0.13 ± 0.04 µM). Bio-imaging studies showed that the ratio of fluorescence intensity in the 440–510 nm spectral region to that in the 590–650 nm region increases from 1.1 to 2.8 when cells are exposed to an increasing concentration of mercury (II) ions, thus enabling the detection of intracellular Hg²⁺ ions and their quantitative analysis in the 0.04–1.65 μM concentration range. Full article

Carbon dots (CDs) show great potential in bioimaging and biosensing because of their good biocompatibility and excellent optical properties. However, CDs with intense red emissions for sensitive and selective detection are rarely reported. Herein, we prepared the red-emissive carbon dots (RCDs) through a facile hydrothermal method using tetra (4-carboxyphenyl) porphyrin (TCPP) and thiourea as starting materials. The obtained RCDs were characterized by TEM, XRD, and XPS. RCDs exhibited high water solubility and strong red emission (λ_em = 650 nm), with the fluorescence quantum yield as high as 26.7%, which was greatly higher than that of TCPP. Moreover, the as-prepared RCDs could be acted as a highly selective and sensitive probe for the detection of Hg²⁺ and glutathione (GSH) through the fluorometric titration method. The detection limits of Hg²⁺ and GSH were calculated to be 1.73 and 1.6 nM, respectively. The cellular experiments demonstrated the good biocompatibility of RCDs and their feasibility in bioimaging. Thus, this work provided a simple strategy to design and synthesize the highly red-emissive carbon dots, which showed promising application in biological and environmental assays. Full article

Biosensors for mercury (II) (Hg²⁺) with high sensitivity are urgently required for food safety, ecosystem protection and disease prevention. In this study, a simple and fast detection method of Hg²⁺ based on the molecular beacon aptamer was established, according to the principle that Hg²⁺ could change the structure of the molecular beacon aptamer, resulting in the changed fluorescence intensity. All of the detection conditions were optimized. It was found that an optimal molecular beacon aptamer MB3 showed the optimal response signal in the optimized reaction environment, which was 0.08 μmol/L MB3, 50 mmol/L tris buffer (40 mmol/L NaCl, 10 mmol/L MgCl₂, pH 8.1), and a 10 min reaction. Under the optimal detection conditions, the molecular beacon aptamer sensor showed a linear response to Hg²⁺ concentration within a range from 0.4 to 10 μmol/L and with a detection limit of 0.2254 μmol/L and a precision of 4.9%. The recovery rates of Hg²⁺ in water samples ranged from 95.00% to 99.25%. The method was convenient and rapid, which could realize the rapid detection of mercury ions in water samples. Full article

Heavy metal contaminants have serious consequences for the environment and human health. Consequently, effective methods for detecting their presence, particularly in water and food, are urgently required. Accordingly, the present study proposes a sensor capable of detecting mercury Hg(II) and lead Pb(II) ions simultaneously, using graphene oxide (GO) as a quenching agent and an aptamer solution as a reagent. In the proposed device, the aptamer sequences are labeled by FAM and HEX fluorescent dyes, respectively, and are mixed well with 500 ppm GO solution before injection into one inlet of the microchannel, and the heavy metal sample solution is injected into another inlet. The presence of Hg(II) and Pb(II) ions is then detected by measuring the change in the fluorescence intensity of the GO/aptamer suspension as the aptamer molecules undergo fluorescence resonance energy transfer (FRET). The selectivity of these two ions is also shown to be clear among other mixed heavy metal ions. The experimental results show that the aptamer sensors have a linear range of 10~250 nM (i.e., 2.0~50 ppb) for Hg(II) ions and 10~100 nM (i.e., 2.1~20.7 ppb) for Pb(II) ions. Furthermore, the limit of detection is around 0.70 ppb and 0.53 ppb for Hg(II) and Pb(II), respectively, which is lower than the maximum limits of 6 ppb and 10 ppb prescribed by the World Health Organization (WHO) for Hg(II) and Pb(II) in drinking water, respectively. Full article

The harmful impact of mercury on biological systems is of great concern. Regardless of the efforts made by the regulating agencies, a decrease in Hg²⁺ concentration has not been realized, and hence mercury accumulation in the environment remains of utmost concern. Designing novel and efficient probes for recognition and detection of toxic metals in environmental samples has been of primary importance. Among the available techniques, probe designs involving the study of spectral properties has been preferred because of its obvious ease of instrumentation. Furthermore, occurrence of significant changes in the visible portion of electronic spectra enables detection by the naked eye, thereby endorsing the preference for development of probes with off-on binary responses to aid in the in-field sample analysis. The prominence is further streamlined to the use of fluorescence to help characterize on-response the cellular detection of Hg²⁺ with ease. In order to overcome the problem of developing efficient probes or sensors bearing fluorescence on-response mechanism that can work effectively in physiological conditions, various methodologies, such as chemo-dosimetric reaction mechanisms for the designing of new luminescent ligands, are being adopted. Additionally, modified charge transfer processes are also being considered for optical detection of the mercury (II) ion. In this review, all such possible techniques have been discussed in detail. Full article

The widely spread use of the hanging mercury drop electrode (HMDE) for multi-ion analysis is primarily ascribed to the following reasons: (i) excellent reproducibility owing to the easy renewal of the electrode surface avoiding any hysteresis effect (i.e., a new identical drop is generated for each measurement to be accomplished); (ii) a wide cathodic potential window originating from the passive hydrogen evolution and solvent electrolysis; (iii) the ability to form amalgams with many redox-active metal ions; and (iv) the achievement of (sub)nanomolar limits of detection. On the other hand, the main controversy of the HMDE usage is the high toxicity level of mercury, which has motivated the scientific community to question whether the HMDE deserves to continue being used despite its unique capability for multi-metal detection. In this work, the simultaneous determination of Zn²⁺, Cd²⁺, Pb²⁺, and Cu²⁺ using the HMDE is investigated as a model system to evaluate the main features of the technique. The analytical benefits of the HMDE in terms of linear range of response, reproducibility, limit of detection, proximity to ideal redox behavior of metal ions and analysis time are herein demonstrated and compared to other electrodes proposed in the literature as less-toxic alternatives to the HMDE. The results have revealed that the HMDE is largely superior to other reported methods in several aspects and, moreover, it displays excellent accuracy when simultaneously analyzing Zn²⁺, Cd²⁺, Pb²⁺, and Cu²⁺ in such a complex matrix as digested soils. Yet, more efforts are required towards the definitive replacement of the HMDE in the electroanalysis field, despite the elegant approaches already reported in the literature. Full article

A variety of chemical sensing materials and procedures for conveniently detecting mercuric ion (II) (Hg²⁺) have been extensively explored. The detection challenges for accomplishing a simple, fast, and low investment procedure at the ultrasensitive level are ongoing. Herein we report a quadrillionth level for detecting Hg²⁺ by the surface-enhanced Raman scattering (SERS) technique. There is an interaction of silver nanoparticles decorated on a zinc-oxide tetrapod structure and coated on FTO glass (Ag@ZnO-FTO) with an organic ligand. 4,4′-Dipyridyl (DPy) performed as being chemisorbed by Ag nanoparticles interacting with a pyridine ring to produce plasmonic hot spots for SERS. The morphology of the surface and porous structure of the tetrapod becomes the powerful platform for enhanced SERS performance of DPy detection. In the absence of the augmentative electrolyte, the enhancement factor for DPy is more than 10⁷. The inhibiting of the aggregation between Ag and DPy was present following the appearance of Hg²⁺, demonstrated by the quenching of the SERS signal from the DPy molecules. The capability to reproduce and the selectivity of the sensing by DPy were both demonstrated. In addition, the applications for detecting Hg²⁺ in natural water and beverages were successfully detected. These results demonstrated the SERS sensors had the potential for detecting Hg²⁺ in practical use. Full article