Detection Of Copper Ions Research Articles

A graphene quantum dots based dual-modal fluorometric and visualized detection of copper ions

A graphene quantum dots based dual-modal fluorometric and visualized detection of copper ions

High-Sensitivity Detection of Copper Ions in Water via Cellulose Nanomaterial Nano-Antennas and DFT studies

The widespread occurrence of copper in water presents serious health hazards, requiring improvement of a method to monitor and remove copper ions in the field. In this study, a fresh approach is introduced that incorporates Cellulose Nanomaterials (CNMs) with a unique rod-like structure, offering a large surface area that is perfect for adsorbing cupral, a Cu(II) ion probe. By using this arrangement, toxic copper can be rapidly and visibly detected. Without any special tools, it's easy to see the color change from off-white to brown. The copper nano-antenna (CNA) has an impressively high sensitivity, detecting as low as 2.5 × 10-7 M through image analysis and 4.3 × 10-8 M with spectrophotometric methods. The values fall significantly below the WHO drinking water guidelines of 2 ppm. The CNA's ability to detect at low thresholds and be easily regenerated makes it an effective tool for initial water testing. According to the findings, the CNA could be a promising solution for enhancing safety in drinking water by allowing real-time visualization of copper ions, with only 5 mg required for measurements. Computational analysis has been conducted to study the structural properties of copper and its copper complex (Cu(CNA)2). There is a significant-close agreement between the theoretical and experimental results. The developed CNA material was tested in various environmental and real samples for detecting Cu2+ ions, especially in water and whitening cream samples showing the material application for real-world applications.

Development of a two component system based biosensor with high sensitivity for the detection of copper ions

Recent advancements in bacterial two-component systems (TCS) have spurred research into TCS-based biosensors, notably for their signal amplification and broad input responsiveness. The CusRS system in Escherichia coli (E. coli), comprising cusS and cusR genes, is a copper-sensing module in E. coli. However, due to insufficient sensing performance, CusRS-based biosensors often cannot meet practical requirements. To address this issue, we made improvements and innovation from several aspects. CusR and CusS expression were adjusted to enhance the Cu(II) biosensor’s performance. A copy-number inducible plasmid was used for signal amplification, while removing copper detox genes cueO and cusCFBA improved sensitivity and lowered detection limits. Ultimately, in the optimized biosensor of Cu26, the fold-change (I/I0) increased from 1.5-fold to 18-fold at 1 μM, rising to 100-fold after optimizing the cell culture procedure. The biosensor’s high fluorescence enabled rapid, instrument-free detection and an improved analysis strategy reduced the detection limit to 0.01 μM, surpassing traditional methods.

Mandarin Peels-Derived Carbon Dots: A Multifaceted Fluorescent Probe for Cu(II) Detection in Tap and Drinking Water Samples.

Carbon dots (CDs) derived from mandarin peel biochar (MBC) at different pyrolysis temperatures (200, 400, 600, and 800 °C) have been synthesized and characterized. This high-value transformation of waste materials into fluorescent nanoprobes for environmental monitoring represents a step forward towards a circular economy. In this itinerary, CDs produced via one-pot hydrothermal synthesis were utilized for the detection of copper (II) ions. The study looked at the spectroscopic features of biochar-derived CDs. The selectivity of CDs obtained from biochar following carbonization at 400 °C (MBC400-CDs towards various heavy metal ions resulted in considerable fluorescence quenching with copper (II) ions, showcasing their potential as selective detectors. Transmission electron microscopic (TEM) analysis validated the MBC-CDs' consistent spherical shape, with a particle size of <3 nm. The Plackett-Burman Design (PBD) was used to study three elements that influence the F0/F ratio, with the best ratio obtained with a pH of 10, for 10 min, and an aqueous reaction medium. Cu (II) was detected over a dynamic range of 4.9-197.5 μM and limit of detection (LOD) of 0.01 μM. Validation testing proved the accuracy and precision for evaluating tap and mountain waters with great selectivity and no interference from coexisting metal ions.

An interesting aggregation induced red shifted emissive and ESIPT active hydroxycoumarin tagged symmetrical azine: Colorimetric and fluorescent turn on–off–on response towards Cu2+ and Cysteine, real sample analysis and logic gate application

We report a newly synthesized 7-diethylamino-4-hydroxycoumarin tagged symmetrical azine derivative (SHC), with an interesting color transformation from yellowish green to orange via aggregation induced red shifted emissive (117 nm) feature in THF-H2O mixture. Interestingly, the single crystal X-ray analysis of this molecule demonstrates that two hydroxycoumarin moieties were present in azine unit, among them one of the coumarin units was exist as enol form and another one transferred to keto form via ground state proton transfer reaction. The optical responses of the compound in different solvents exposed the observation of dual emissive bands which corresponds to the presence of ESIPT phenomenon in SHC molecule. Further, this characteristic was confirmed by absorption, emission, solid state structure and time resolved fluorescence decay measurements. Furthermore, the fluorophore, SHC was exploited as a colorimetric and turn on–off–on fluorescent probe for detection of Cu2+ ions and Cysteine (Cys). The 1:1 binding ratio of the probe with Cu2+ and Cys with SHC-Cu2+, was established via Job plot analysis, mass spectral technique and the DFT calculations. The probe, SHC was employed for the detection of copper ions in the environmental real water samples. Finally, the reversible fluorescent turn on–off–on character of the probe, SHC was established to construct the IMPLICATION logic gate application.

A systematic study of fluorescent coumarin sensors for the detection of aqueous copper ions and aqueous hydrogen sulphide

ABSTRACT The induced quenching in fluorescence upon addition of copper (Cu2+) ions and subsequent regain with aqueous hydrogen sulphide (HS−) was studied with a series of coumarin di(picolyl)amine-based compounds, with varying electron withdrawing/donating abilities. The coumarin analogue with an amino group at the 7-position was the most emissive, followed by the methoxy-variant with both the t-butyl- and difluoro-variants being weakly emissive. The amino-variant was also most responsive to quenching upon the addition of Cu2+ ions and was the most responsive to the subsequent addition of HS− ions. All compounds were shown to form predominately a 1:1 copper(II) complex, supported by mass spectral studies and X-ray crystallography. This investigation sheds light on the structural aspects of the copper-sensor interactions and subsequent copper sequestration, contributing to the understanding of their fluorescence properties and potential applications in sensing and imaging.

4-Diphenylaminobenzaldehyde-formulated isonicotinohydrazide for the rapid recognition of Cu2+ ions; Application of RGB tool, pharmaceutical samples, and DFT studies

High copper concentrations have been linked to several harmful illnesses in humans and negatively affect the kidneys and liver. The design and synthesis of simple and effective chemosensors for recognizing copper (Cu2+) ions are extremely significant. However, most of the colorimetric chemosensors have been developed using an intramolecular charge transfer binding mechanism based on donor-acceptor conjugation systems. This study aimed to fabricate a novel Schiff base colorimetric chemosensor, N'-(4-(diphenylamine) benzylidene) isonicotinohydrazide (DPBA-INH), with high sensitivity and selectivity towards copper ions in the semi-aqueous medium (DMSO: H2O, 7:3, v/v). The synthesized receptor DPBA-INH was distinguished using various spectroscopic methods, including NMR analysis, Fourier transform infrared spectroscopy, HRMS, and ultraviolet-visible (UV–vis) spectroscopy. When exposed to sunlight, the receptor DPBA-INH with Cu2+ ion complexation exhibited a color change from orange to pale yellow. A Job's plot and electrospray ionization mass spectra confirmed the presence of complexation at a stoichiometric binding proportion of the receptor to Cu2+ ions of 1:1. The receptor DPBA-INH interacts with Cu2+ ions in a 1:1 stoichiometric manner with a detection limit of 1.40 × 10−7 M. The experimental results were supported by a theoretical DFT study. Moreover, the receptor effectively measured Cu2+ ions in pharmaceutical samples and test strip analyses. Furthermore, the rapid colorimetric recognition of Cu2+ ions in a semi-aqueous medium was achieved using DPBA-INH, which was demonstrated to be an excellent receptor. Notably, DPBA-INH was employed to detect copper ions in real water samples.

Sensing at Your Fingertip: On-Glove Electrochemical Sensor for Copper Detection on Vine Leaves

Intensive use of copper-based pesticides in agriculture can impact human health and biodiversity: the accumulation of this metal in soil negatively affects crop yields. There is growing interest in developing new tools that are capable of monitoring copper occurrence in agricultural contexts through the use of quick and user-friendly approaches for non-specialists, e.g., farmers. This work focuses on the development of a glove-based electrochemical sensor, enhanced with gold nanoparticles, for the detection of copper ions on leaves. The developed device proved was capable of detecting copper ions contained in a copper-based pesticide commonly used in agriculture (Cupravit Bio Advanced). The on-glove analytical device was characterized using garden leaf as the model system and subsequently applied to on-site detection of copper ions on vine leaf treated with Cupravit Bio Advanced. The procedure was very facile: sampling was carried out by touching the leaf with the strip and the stripping-voltammetric measurement was performed by adding a few microliters of an acidic solution to the strip. The on-glove approach allowed evaluation of the level of copper-based pesticide used, avoiding complex and time-consuming tasks. Such operation opens up a wide range of possibilities for improving precision agriculture and sustainable development at the point-of-need for the use of non-specialists.

Dual-color fluorescent multi-component hybrid materials for copper ion detection, NADH regeneration and cell imaging

Gold nanoclusters (AuNCs) exhibit unique physical, chemical and photoelectric properties with various advantages. On the other hand, small organic fluorescent molecules show alternative specialized characteristics. To overcome their weaknesses and integrate strengths, we propose here a workable platform to fabricate protein-gold-dye multifunctional hybrid materials. Briefly, protein skeleton bovine serum albumin (BSA), AuNCs, and organic molecule dye Thioflavin T (ThT) are co-assembled mutually to form a dual-color fluorescent material BSA-AuNCs@ThT. This approach is simple, cost-effective, green and environmental friendly. To tackle their biological application, we coat BSA-AuNCs@ThT with cationic polyethyleneimine (PEI). The prepared BSA-AuNCs@ThT@PEI hybrid materials can be used to fluorescence imaging of microbial cells as well as HeLa cells. Due to the unique background of BSA-AuNCs@ThT@PEI, the hybrid materials work well in differentiate heavy metal ions such as Hg2+ and Cu2+ ions. Moreover, this system is also suitable to do the photocatalytic transformation and regeneration of coenzyme NADH. Therefore, we propose this platform to build new nano-dye hybrid materials for copper ion detection, NADH regeneration and cell imaging, or potentially other applications.

One-step preparation of orange-red Emitting carbon dots for visual detection of copper ions in the water environment

In this study, p-aminophenol and o-phenylenediamine were used as materials in a straightforward one-step hot solvent approach for generating a nitrogen-doped carbon dot. Fourier Transform Infrared Spectroscopy (FT-IR), Transmission Electron Microscopy (TEM), Scanning Electron Microscopy (SEM), X-ray Diffraction (XRD), and UV–Vis analysis were used to analyze the resultant CDs composites. Furthermore, fluorescence and absorption spectroscopy were used to assess the optical characteristics. Following the addition of Cu2+, CDs’ fluorescence was quenched statically, resulting in the formation of a non-fluorescent complex. Based on this, a highly selective fluorescent technique was developed with a detection limit of 2.71 μM and a relevant linear range of 10–100 μM for Cu2+. More convenient to carry and detect sodium alginate gel beads doped with carbon dots were prepared for visual detection of Cu2+. Using this method, Cu2+ ions from various environmental sources can be detected rapidly, cheaply, environmentally friendly, and selectively.

Ratiometric Fluorescent Probes for Copper Ion Detection and Cuproptosis Studies

Abstract: This study reviews the latest progress of ratiometric fluorescent probes of copper ions from 2022 till now. As a key trace element in biological systems, copper ions play an important role in a variety of biological processes. However, the abnormal change in copper ion concentration is closely related to a variety of diseases, so the development of highly sensitive and highly selective copper ion detection methods is of great significance for scientific research and clinical diagnosis. In this paper, we first introduced the classification of copper ion fluorescence probes, including molecular sensors based on five-membered azocycles, six-membered azocycles, imide groups (R2C=NR'), oxygen and nitrogen functional groups (such as ethers, aldehydes, ketones, esters, carboxylic acids and hydroxyl groups) and group ⅥA elements. Subsequently, the application of nanosensors in the detection of copper ions is further discussed, especially the nanosensors in which copper is used as a reactant, catalyst or alternative reaction. Finally, the current research status of copper ion fluorescence probes is summarized, and the future development direction is prospected in order to provide reference and inspiration for the design of new high-efficiency copper ion detection tools.

Cuproptosis in microsatellite stable colon cancer cells affects the cytotoxicity of CD8+T through the WNT signaling pathway

The microsatellite stable (MSS) colon cancer (CC) has long been considered resistant to immunotherapy. Cuproptosis, as a novel form of cell death, may interact with tumor immunity. This project focused on the impact of cuproptosis on the cytotoxicity of CD8+T in MSS CC, aiming to provide effective clues for improving the treatment strategy of MSS CC. The study developed an MSS CC cuproptosis model using 50 nM elesclomol and 1 μM CuCl2. Cuproptotic SW480 cells were directly co-cultured with CD8+ T cells. Cuproptosis levels were assessed via intracellular copper ion detection, Western blot, and confocal laser scanning microscopy. CCK-8, Hochest/PI staining, CFSE cell proliferation assay, LDH cytotoxicity detection, and ELISA were used to evaluate CD8+ T cell immune activity and cytotoxicity. Transcriptome sequencing and bioinformatics analysis identified regulated signals in cuproptotic SW480 cells. A rescue experiment utilized a WNT pathway activator (BML-284). PD-L1 expression in cells/membranes was analyzed using qRT-PCR, Western blot, and flow cytometry. NSG mice were immunoreconstituted, and the effects of cuproptosis on immune infiltration and cancer progression in MSS CC mice were assessed using ELISA and immunohistochemistry (IHC). Treatment with 50 nM elesclomol and 1 μM CuCl2 significantly increased cuproptosis in SW480 cells. Co-culture with CD8+ T cells enhanced their cytotoxicity. Sequencing revealed cuproptosis-mediated modulation of immune and inflammatory pathways, including WNT signaling. Rescue experiments showed downregulation of WNT signaling in cuproptotic SW480 cells. Indirectly, CD8+ T cell immune function was enhanced by reducing PD-L1 expression. In mice, cuproptosis resulted in increased infiltration of CD8+ T cells in tumor tissue, leading to delayed cancer progression compared to the control group. Cuproptosis in MSS CC cells enhances the cytotoxicity of CD8+ T cells, which may be achieved through downregulation of the WNT signaling pathway and decreased expression of PD-L1. In the future, drugs that can induce cuproptosis may be a promising approach to improve MSS CC immunotherapy.

Novel Schiff base decorated cyclotriphosphazene chemosensors for Fe and Cu ions detection

In this study, new 2-aminobenzothiazole derivative Schiff base decorated cyclotriphosphazene compounds (SBCTP 1 and 2), which are likely to have chemical sensor properties, were designed and synthesized successfully. The compounds were structurally characterized by mass analysis and NMR (1H, 13C and 31P) spectroscopies. Photophysical and chemosensory properties of SBCTP 1 and 2 against some analytes were examined by UV–vis and Fluorescence spectrophotometry. While a significant increase was observed in the UV–vis absorption signals observed at 350 nm with the addition of Fe3+ and Fe2+ ions and a new absorption band was observed at 290 nm with the addition of Cu2+. In addition, according to Job's plot obtained from UV–vis absorption titrations, the complex stoichiometries of SBCTP 1 and 2 with selective analytes were determined as 1:1 (L/M) and 1:2 (L/M), respectively. The selective interaction of donor atoms on SBCTP 1 and 2 with Cu2+, Fe2+ and Fe3+ ions give these compounds chemosensory properties. This study showed that the synthesized Schiff base decorated cyclotriphosphazene compounds (SBCTP 1 and 2) could be new chemosensors with high selective and immediate sensitivity for the detection of iron and copper ions.

Chalcone derived bis-organosilane and its magnetic nanoparticles: Unveiling precision in selective Cu(II) ion detection and elucidating biocompatibility

The escalating concern regarding the adverse effects of metal ion toxicity on both human health and environmental ecosystems necessitates the development of efficient detection methodologies. This study presents a focused investigation on the selective and sensitive detection of Cu(II) ions employing hybrid magnetic nanoparticles derived from chalcone-based bis-organosilane. These nanoparticles exhibit a notably low detection limit in the nano-scale range, rendering the sensor highly sensitive to Copper(II) ion detection while maintaining robust anti-interference capabilities, even in the presence of diverse metal ions. Real sample analysis confirms the sensor’s efficacy in detecting Cu(II) ions below WHO-prescribed levels. Computational analyses reveal molecular interactions and biological activities, including potent antibacterial and antioxidant properties, suggesting promising applications. Furthermore, the biological effectiveness of chalcone-derived bis-organosilane is investigated, unveiling notable antibacterial efficacy and also exhibiting potential as a scavenger of free radicals, indicating promising applications in both antibacterial and antioxidant domains.

Ionophore-based nanospheres enable selective and sensitive fluorescence detection of copper ions

A novel ionophore-based fluorescent nanosensor has been successfully fabricated for the sensitive and selective detection of Cu2+ ions. The nanosensor was constructed through self-assembly of amphiphilic block copolymers, incorporating elesclomol as a Cu2+ ionophore and long-chain dialkylcarbocyanines (DiD) as a fluorescent dye. This design exhibits an "ON/OFF" fluorescence response, where Cu2⁺ ions are selectively sequestered within the nanosensors, resulting in fluorescence quenching of DiD. This strategy enables rapid and highly selective Cu2⁺ sensing with remarkable fluorescence quenching efficiency (up to 93.5 %) and an exceptionally low detection limit of 28.6 nM. The linear detection range extends over two orders of magnitude (0.05–10 μM). Furthermore, the feasibility of this nanosensor for practical applications was confirmed through successful determination of Cu2+ in real water and beer samples, with excellent recovery rates. This nanosensor offers advantages of simplicity, rapidity, and cost-effectiveness, holding significant potential for sensitive and selective Cu2+ detection in various biological and environmental samples.

Improvement of fluorescence properties by surface modification of CdS-ZnS quantum dots by thiol compounds and its application as a sensitive fluorescence probe for copper ion detection.

The capped CdS-ZnS quantum dots (QDs) were synthesized with various thiol capping agents of glycolic acid (TGA), mercaptosuccinic acid (MSA), and L-cysteine (LCY) and used as fluorescence probe for determination of Cu (II) ions. The method of two-level three-factor full-factorial experiment design was used to achieve the best optical fluorescence emission. Results revealed that Cu (II) ions can effectively quench the emission of QDs, and the fluorescence intensity is linearly decreased with increasing Cu (II) ion concentration. The limit of detection for CdS-ZnS@ QDs capped with TGA, MSA, and LCY was obtained at 1.15 ×10-7, 1.32 ×10-7, and 2.19 ×10-7mol L-1, respectively, with linear dynamic range of 3.13 ×10-6 to 1.41 ×10-4mol L-1. Luminescence quantum yields of CdS-ZnS@LCY, CdS-ZnS@MSA, and CdS-ZnS@TGA were obtained at 4.17, 1.92, and 2.47, respectively. Results indicated that no significant quenching occurred in the presence of the other metal ions. The binding constant (Kb) of capped CdS-ZnS@ QDs with Cu2+ and the other metal ions was also investigated and discussed. The Kb value for Cu2+ was obtained considerably more than that the other ions. This work presents a new and sensitive method for determination of Cu2+ ion.

Eco-friendly sustainable fluorescent coal-based carbon dots as a highly selective probe for Cu2+detection

Carbon dots as fluorescent probes exhibit brilliant sensitivity and selectivity in copper ion detection, which greatly depends on their microstructure. Herein, a mild oxidation method was adopted to tailor the organic macromolecules of coal and its derivatives for preparing coal-based carbon dots. Such coal-based carbon dots comprise a carbonaceous center dominated by sp2 microcrystalline carbon, surface defects formed by sp3 amorphous carbon, and oxygen/nitrogen-containing functional groups. The coal-based humic acid-based carbon dots (HA-CDs) exhibit high dispersity (∼7.6 nm), high sp2 microcrystalline carbon (61.73 %), abundant carboxyl groups (2.09 %), hydroxy groups (8.93 %), and pyridinic nitrogen (1.06 %). Due to their unique microstructure, the HA-CDs in aqueous solutions exhibit prominent fluorescence stability under different pH conditions and show superior selectivity and sensitivity to Cu2+ even in the existence of other metal ions. Within the concentration range of 0–40 µmol/L, the fluorescence intensity of HA-CDs linearly correlates with the concentration of Cu2+. The limit of detection is 0.014 µmol/L, allowing for tracing the Cu2+ concentration in flowing water. This work affords a novel idea for the microstructure design of high-sensitivity carbon dots for Cu2+ detection in the water environment.

Nanocomposite-modified nanopores: A promising platform for selective detection of copper ions

This research introduces an innovative platform designed for the selective detection of copper (II) (Cu2+) ions, employing a singular nanopore embedded within a 12 μ m-thick polyethylene terephthalate (PET) membrane. The track-etched nanopore was subsequently modified with nanomaterials in an allylamine hydrochloride (PAH)-modified asymmetric nanopore through electrostatic interactions. The nanomaterials included copper oxide (CuO), graphene oxide (GO), and their composite (GO/CuO), were synthesized using wet chemistry, and their structures and optical properties were thoroughly investigated using x-ray diffraction and diffuse reflectance spectroscopy. In the distinctive feature of the platform, Cu2+ ions gain access to coordination sites across a broad surface covered by the immobilized nanomaterials, facilitating effective binding. The selective response of GO/CuO modified pores towards Cu2+ ions was notably observed through ion transportation (I –V) studies, surpassing the response of unmodified nanopores and those modified with CuO alone. This selective behavior was demonstrated in the presence of various monovalent and divalent competing ions. Quantitative assessment of I –V studies was conducted by evaluating the intrinsic rectification ratio of asymmetric nanopores, providing a robust measure of platform's efficacy. Furthermore, we identified the optimal pH for detecting Cu2+ ions as 7, enhancing the specificity and accuracy of our method.

Tetraphenylethylene tethered 1-(pyridine-2-yl)imidazo[1,5-a]pyridine: Synthesis, aggregation induced emission, copper(II) ion detection and imaging of latent fingerprint

The development of aggregation induced emissive probe with high sensitivity and selectivity for Cu2+ ions is a fascinating research in biomedical sciences. In this context, we have successfully synthesized an aggregation induced emissive probe for the selective detection of Cu2+ ions by incorporating a 1-(pyridine-2-yl)imidazo[1,5-a]pyridine arm in the tetraphenylethylene framework. The aggregates have been characterized using pivotal microscopic and photophysical measurements. The results exhibits that the aggregates have a spherical shape with an average size of 90 nm and a fluorescence quantum yield of ∼23 %. The aggregated fluorescent probe exhibited an excellent selectivity towards Cu2+ ions with a detection limit of 83 nM and presented a good efficacy over diverse environmental water samples. Furthermore, the quenching type is delineated as static due to complexation followed by deaggregation which was supported by dynamic light scattering and Tyndall effect experiments. In addition, the high solid state emissive property of the probe makes it a potential candidate for latent fingerprint analysis to gather level 2 and 3 information thereby playing a substantial role in forensic investigations.

Innovative indenone-derivative colorimetric fluorescent probe: A approach for copper ion detection in water.

Copper (Cu2+) is a metal chemical element closely related to human life and is widely used in many fields. However, with the discharge of copper wastewater, the water quality will be seriously affected, leading to excessive intake of Cu2+ and a variety of diseases. Hence, there is a pressing need for an effective detection method for Cu2+ in aqueous environments. Leveraging the remarkable attributes of GFP chromophores and indenone derivatives, we have created a novel colorimetric fluorescent probe P-Cu2+, tailored for efficient copper ion detection. The addition of Cu2+ causes the solution to visibly change from colorless to a pronounced yellow, enabling naked-eye detection and offering promise for real sample analysis.