o-phenylenediamine Derived Fluorescent Carbon Quantum dots for Detection of Hg(II) in Environmental Water.

With the expansion of human activities, the consequent influx of mercury (Hg) into the food chain and the environment is seriously threatening human life. Herein, nitrogen and sulfur co-doped fluorescent carbon quantum dots (yCQDs) were prepared via a hydrothermal method using o-phenylenediamine (OPD) and taurine as precursors. The morphological characteristics as well as spectral features of yCQDs indicated that the photoluminescence mechanism should be the molecular state fluorophores of 2, 3-diaminophenothiazine (oxOPD), which is the oxide of OPD. The as-synthesized yCQDs exhibited sensitive recognition of Hg2+. According to the investigation in combination of UV-Vis absorption spectra, time-resolved fluorescence spectra and quantum chemical calculations, the abundant functional groups on the surface of yCQDs allowed Hg2+ to bind with yCQDs through various interactions, and the formed complexes significantly inhibited the absorption of excitation light, resulting in the static fluorescence quenching of yCQDs. The proposed yCQDs was utilized for Hg2+ sensing with the limit of detection calculated to be 4.50 × 10- 8 M. Furthermore, the recognition ability of yCQDs for Hg2+ was estimated in tap water, lake water and bottled water, and the results indicated that yCQDs have potential applications in monitoring Hg2+.

Nitrogen and Sulfur co-doped Carbon dots as an "on-off-on" Fluorescent Sensor for the Detection of Hg2+ and Ampicillin.

Herein, a fluorescent "on-off-on" nanosensor based on N,S-CDs was developed for highly precise and sensitive recognition of Hg2+ and ampicillin (AMP). Nitrogen and sulfur co-doped carbon dots with blue fluorescence were synthesized by one-pot hydrothermal method using ammonium citrate and DL-methionine as precursors. N,S-CDs exhibited a surface abundant in -OH, -COOH, and -NH2 groups, aiding in creating non-fluorescent ground state complexes when combined with Hg2+, leading to the suppression of N,S-CDs' fluorescence. Subsequent to additional AMP application, the mixed system's fluorescence was restored. Based on this N,S-CDs sensing system, the thresholds for detection for AMP and Hg2+ were discovered to be 0.121 µM and 0.493 µM, respectively. Furthermore, this methodology proved effective in identifying AMP in real samples of tap and lake water, yielding satisfactory results. Consequently, in the area of bioanalysis in intricate environmental sample work, the sensing system showed tremendous promise.

A Simple Method for Synthesizing Nitrogen-Doped Carbon Quantum Dots for Fluorescent "Turn off" Mercury (II) Ion Sensing.

Here, straightforward and environmentally friendly fluorescent nitrogen doped carbon quantum dots (N-CQDs) with a high blue fluorescence emission at 455 nm are used for ultrasensitive Hg2+ ion detection. Folic acid and urea are used as carbon sources in the carbonization process. Two broad absorption bands at around 280 and 370 nm from UV-Vis spectrum and characteristic absorption peaks from infrared spectrum confirms the successful synthesis of the N-CQDs. Energy dispersive X-Ray analysis confirmed the elemental composition of the N-CQDs. Transmission electron microscopy showed the homogeneous globular morphology of the N-CQDs with an average particle size of 65 nm. Zeta potential measurement established the stability and surface charge of N-CQDs. Dynamic light scattering measurement showed the average size of N-CQDs. With the addition of Hg2+ ion to N-CQDs, the blue fluorescence emission is quenched. Moreover, the N-CQDs can be applied to real water sample such as pond water, river water, and tap water. The detection limit is approximately calculated to be 12 nM and linear range is 0-30 parts per billion.

Investigation of the Application and Mechanism of Nitrogen and Phosphorus Co-doped Carbon Dots for Mercury Ion Detection.

In this paper, we obtained nitrogen and phosphorus co-doped carbon dots through a hydrothermal method using o-phenylenediamine and citric acid in a 40% phosphoric acid environment. The carbon dots emitted fluorescence at 476 nm under excitation at 408 nm and exhibited good selectivity and high sensitivity towards mercury ions. These carbon dots showed excellent dispersibility in water and maintained stable fluorescence even in high concentration salt environments. The interaction between mercury ions and functional groups on the carbon dots surface through electrostatic interaction resulted in static quenching. Simultaneously, by detecting the lifetime and transient absorption spectra of the carbon dots, we observed that the coordination of mercury ions with the carbon dots broadened the band structure of the carbon dots, and the existing photoinduced electron transfer process increased the non-radiative transition channel. The combined effect of dynamic quenching and static quenching significantly reduced the fluorescence intensity of the carbon dots at 476 nm. The carbon dots exhibited linear detection of mercury ions in the range of 0.01-1 µM, with a detection limit as low as 0.0245 µM. In terms of practical water environmental detection applications, these carbon dots were able to effectively detect mercury ions in tap water and lake water, demonstrating their broad application prospects in the field of environmental metal analysis.

Synthesis of a water-stable CsPbBr3 perovskite for selective detection of mercury ion in water.

By using the method of low-temperature crystallization, CsPbBr3 perovskite nanocrystals (PNCs) coated with trifluoroacetyl lysine (Tfa-Lys) and oleamine (Olam) were synthesized in aqueous solution. The structure of the CsPbBr3 PNCs was characterized by many methods, such as ultraviolet (UV)-visible absorption spectrophotometer, fluorescence spectrophotometer, transmission electron microscopy (TEM), and X-ray diffraction (XRD) pattern. The fluorescence emission of the CsPbBr3 PNCs is stable in water for about 1 day at room temperature. It was also found that the fluorescence of the PNCs could be obviously and selectively quenched after the addition of mercury ion (Hg2+ ), allowing a visual detection of Hg2+ by the naked eye under UV light illumination. The fluorescence quenching rate (I0 /I) has a good linear relationship with the addition of Hg2+ in the concentration range 0.075 to 1.5 mg/L, with a correlation coefficient (R2 ) of 0.997, and limit of detection of 0.046 mg/L. The fluorescence quenching mechanism of the PNCs was determined by the fluorescence lifetime and X-ray photoelectron spectroscopy (XPS) of the PNCs. Overall, the synthesis method for CsPbBr3 PNCs is simple and rapid, and the as-prepared PNCs are stable in water that could be conveniently used for selective detection of Hg2+ in the water environment.

Shedding Light on Heavy Metal Contamination: Fluorescein-Based Chemosensor for Selective Detection of Hg2+ in Water.

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.

An Electrochemical Sensor Based on a Porous Biochar/Cuprous Oxide (BC/Cu2O) Composite for the Determination of Hg(II).

Mercuric ion (Hg2+) in aqueous media is extremely toxic to the environment and organisms. Therefore, the ultra-trace electrochemical determination of Hg2+ in the environment is of critical importance. In this work, a new electrochemical Hg2+ sensing platform based on porous activated carbon (BC/Cu2O) modified with cuprous oxide was developed using a simple impregnation pyrolysis method. Differential pulse anodic stripping voltammetry (DPASV) was used to investigate the sensing capability of the BC/Cu2O electrode towards Hg2+. Due to the excellent conductivity and large specific surface area of BC, and the excellent catalytic activity of Cu2O nanoparticles, the prepared BC/Cu2O electrode exhibited excellent electrochemical activity. The high sensitivity of the proposed system resulted in a low detection limit of 0.3 ng·L-1 and a wide linear response in the ranges from 1.0 ng·L-1 to 1.0 mg·L-1. In addition, this sensor was found to have good accuracy, acceptable precision, and reproducibility. All of these results show that the BC/Cu2O composite is a promising material for Hg2+ electrochemical detection.

A Benzothidiazole-Based Reversible Fluorescent Probe with Excellent Performances in Selectively and Sensitively Sensing of Hg2+ in Water.

The development of mercury ion selective fluorescent probe is significant because it is one of toxic heavy metals and poses great risks and hazards to human health. Herein, we develop a mercury ion-selective fluorescent probe, namely IB, based on imidazole decorated benzothiadiazole that obtained by a facile palladium catalytic C-N coupling reaction. IB exhibits high selectivity and sensitivity towards mercury ion in water with nearly 32-fold fluorescent enhancement. The detection limit is calculated to be 0.93 nmol/L. In addition, the sensing of mercury ion can be conducted in a wide pH scope ranging from 4.0 to 10.0. Subsequently, the mercury ion elicits fluorescence of IB solution can be quenched by the addition of cyanide anions, showing "off-on-off" fluorescence transformation with at least 5 cycles, demonstrating the reversible sensing ability of IB. Furthermore, an INHIBIT logical detector has been developed using mercury ion and cyanide anions as inputs and fluorescence of IB as output. Significantly, IB can be utilized for mercury ion detection in real water sample.

Carbon dots-modified paper-based chemiluminescence device for rapid determination of mercury (II) in cosmetics.

Here, a simple and portable paper-based analytical device (PAD) based on the inherent capability of carbon quantum dots (CQDs) to serve as a great emitter for the bis(2,4,6-trichlorophenyl)oxalate (TCPO)-hydrogen peroxide (H2O2) chemiluminescence (CL) reaction is introduced for the detection of harmful mercury ions (Hg2+ ). The energy is transferred from the unstable reaction intermediate (1,2-dioxetanedione) to CQDs, as acceptors, and an intensive orange-red CL emission is generated at ~600 nm, which is equal to the fluorescence emission wavelength of CQDs. The analytical applicability of this system was examined for the determination of Hg2+ . It was observed that Hg2+ could significantly quench the produced emission, which can be attributed to the formation of a stable and nonluminescent Hg2+ -CQDs complex. Accordingly, a simple and rapid PAD was established for monitoring Hg2+ , with a limit of detection of 0.04 µg ml-1 . No interfering effect on the signal was found from other examined cations, indicating the acceptable specificity of the method. The designed assay was appropriately utilized to detect Hg2+ ions in cosmetic samples with high efficiency. It was characterized by its low cost, ease of use, and was facile but accurate and high selective for the detection of Hg2+ ions. In addition, the portability of this probe makes it suitable for on-site screening purposes.

A novel near-infrared fluorescence probe for detecting and imaging Hg2+ in living cells.

Fluorescence imaging, as one of the important means of biological lesion analysis, is widely used in medical analysis. To improve detection specificity, near-infrared emission fluorescent probes have been developed. Sensitive and selective near-infrared (NIR) fluorescent probes for Hg2+ , which is a heavy metal ion harmful to human health, are urgently needed to investigate the physiological toxicity of Hg2+ . The NIR fluorophore based on the traditional structure of rhodamine was prepared by introducing anthocyanin functional groups, and a rhodamine spiro ring structure was constructed to recognize Hg2+ (CCS-Hg). The probe CCS-Hg demonstrated good selectivity and high detection sensitivity for Hg2+ and the most likely mechanism was verified through theoretical calculations. We applied the probe CCS-Hg in the examination of Hg2+ distribution in living cells by NIR fluorescence imaging. This work provides a promising molecular tool for studying the toxicological effects of mercury ions in cell.

Dual-target electrochemical DNA sensor for detection of Pb2+ and Hg2+ simultaneously by exonuclease I-assisted recycling signal amplification.

With the development of exonuclease, the exonuclease has been used to construct a variety of aptasensor and to realize the signal amplification. Among them, based on silver nanoparticles (Ag NPs) and exonuclease I (Exo I)-assisted cycle signal amplification strategy, we designed a novel high-sensitivity dual-target electrochemical biosensor to detect Pb2+ or Hg2+ in water. In the presence of Hg2+, the Hg2+ was fixed to the aptamer chain by thymine-Hg2+-thymine (T-Hg2+-T), resulting in the decrease of signal. When Pb2+ was present, DNA single strand S2 dissociated and was bound to Pb2+, which automatically triggered Exo I to selectively cut the single chain from the recognition site to achieve the cyclic amplification of the electrochemical signal. The interaction between aptamer and Exo I was investigated by gel electrophoresis. Under the optimum conditions in the scan range -0.20 to 0.60 V, the biosensor had high sensitivity with a linear range of 100 pg/L to 10.0 mg/L, Pb2+ or Hg2+, and the detection limits were 17.0 pg/L (R2 = 0.993) and 12.0 pg/L (R2 = 0.993), respectively. The relative standard deviation (RSD) of the sensor was 0.5-2.6%, and the recovery of spiked standard solutions was between 98.3 and 110%. The cycle amplification strategy supported by this enzyme has promising applications in detection of the two metal ions in various fields.

Highly sensitive detection of Hg2+ employing SPR sensor modified with chitosan/poly (vinyl alcohol)/SnO2 film.

Water contamination by mercury ions (Hg2+) causes irreversible and serious effect on the ambient environment, ecological systems, and human health, necessitating further improvement of Hg2+ monitoring at low concentrations. Here, we proposed a novel surface plasmon resonance (SPR) sensor for Hg2+ detection with desirable advantages of high sensitivity, simple operation, label-free, and low cost, in which the chitosan/poly (vinyl alcohol)/SnO2 composite film was modified on sensing surface as the active layer for sensitivity enhancement. Benefiting from the relatively high refractive index of SnO2 nanoparticles, the evanescent field generated at the metal-solution interface can be significantly enhanced, which results in a 5 times improvement of sensitivity. Through appropriate optimization in the aspects of componential constitutions, the sensor exhibits excellent sensitivity of 25.713 nm/µg/L and ultra-low calculated detection limit of 6.61 ng/L(32.95 pM). Such detection limit is strikingly lower than the limitation (10 nM) in drinking water set by the US Environmental Protection Agency. In addition, the as-prepared sensor presents relatively high selectivity for Hg2+, attributing to plenty of binding sites for specific adsorption produced by functionalized chitosan/poly (vinyl alcohol) composites, which have been furtherly verified by characterization of FTIR and XPS spectra. The proposed sensor also exhibits great repeatability and good time stability for 15 days. This work provides a promising strategy for developing high-performance SPR sensor for Hg2+ detection and a prospective application in environmental monitoring.

Colorimetric Chemosensor for Hg2+ Based on Nuclear Fast Red and a Cationic Polyelectrolyte in Aqueous Solution.

We have developed a colorimetric chemosensor based on an anionic organic dye, commercially available nuclear fast red (NFR) and a cationic polyelectrolyte, poly(diallyldimethylammonium chloride) (PDADMAC) for detection of Hg2+ in aqueous solution at physiological conditions. Upon addition of Hg2+, a bathchromic shift in the absorption was observed concomitantly with color change from pink to reddish violet which was easily detectable by the naked eye, while such a change was not observed for NFR alone, indicating that PDADMAC played an important role in detecting Hg2+. This investigation can propose the simple and valuable construction method for a novel chemosensor by mixture of a water-soluble organic dye and an oppositely charged polyelectrolyte.

Ratiometric assay of mercury ion based on nitrogen-doped carbon dots with two different optical signals: second-order scattering and fluorescence.

Ratiometric assays, which can effectively surmount external interference, have attracted extensive research interests. Herein, a novel ratiometric sensing platform for Hg2+ is designed based on nitrogen-doped carbon dots (N-CDs) with two different optical signals. Under a single excitation, N-CDs have two emission peaks around 668 nm and 412 nm, which are second-order scattering and fluorescence, respectively. Upon the addition of Hg2+, the weak scattering emission at 668 nm can be increased apparently, while the strong fluorescence intensity at 412 nm is weakened. Moreover, the ratio of scattering intensity to fluorescence intensity is linearly dependent on Hg2+ concentration (0.1-10 µM and 10-30 µM, respectively), and the detection limit is 66 nM. In addition, the ratiometric sensing mechanism is investigated in detail, which is due to the combined effect of aggregation-induced fluorescence quenching and scattering enhancement. Furthermore, the developed sensing approach holds a promising application for Hg2+ detection in actual samples. Graphical abstract.

A triazole-based fluorescence probe for detecting Hg2+ ions and its biological application.

A new compound, ethyl 5-phenyl-2-(p-tolyl)-2H-1,2,3-triazole-4-carboxylate was successfully introduced and synthesized as a novel rhodamine B derivative named REPPC, and characterized by 1 H nuclear magnetic resonance (NMR), 13 C NMR, and high resolution mass spectrometry (HRMS). It showed an obvious fluorescence and UV-visible light absorption enhancement towards Hg2+ ion without interference from common metal ions in N,N-dimethylformamide-H2 O (pH 7.4). The spirolactam ring moiety of rhodamine in REPPC was converted to the open-ring form generating a 1:1 complex with the intervention of a mercury ion, verified by electrospray ionization-mass spectroscopy testing and density functional theory calculation. REPPC was used to visualize the level of mercury ions in living HeLa cells with encouraging results.

Dual-emissive carbon dots for dual-channel ratiometric fluorometric determination of pH and mercury ion and intracellular imaging.

Dual-emissive carbon dots (CDs) were fabricated for dual-channel ratiometric fluorometric determination of pH and mercury ion (Hg2+) and intracellular imaging. Dual-emissive CDs were synthesized by one-pot solvothermal treatment of cabbage. The CDs exhibited two distinctive fluorescence emissions at 500 and 678 nm under single excitation at 410 nm. The green emission (500 nm) had reversible linear response to pH (7.0-12.0) due to deprotonation and protonation of surface functional groups and their non-covalent interactions. On the other hand, the red emission (678 nm) had efficient and selective fluorescence response to Hg2+ by formation of non-emission complex between CDs and Hg2+. The limit of detection (LOD) and limit of quantification (LOQ) for Hg2+ were 6.25 and 20.63 nM, respectively. The CDs have been successfully applied for label-free ratiometric fluorometric determination of pH and Hg2+ in fish and human serum samples with good recoveries (92.0-108.3%). In addition, the CDs had excellent photostability, low cytotoxicity, and good biocompatibility for intracellular imaging. All in all, the system was multi-functional in determination, high in sensitivity, and excellent in selectivity, which demonstrated wide and promising applicability for biosensing and bioimaging in the future. Graphical abstract Schematic presentation of dual-emission carbon dots (CDs) synthesized by solvothermal treatment of cabbage for dual-channel determination of pH and Hg2+.

Changing the Blood Test: Accurate Determination of Mercury(II) in One Microliter of Blood Using Oriented ZnO Nanobelt Array Film Solution-Gated Transistor Chips.

The measurement of ultralow concentrations of heavy metal ions (HMIs) in blood is challenging. A new strategy for the determination of mercury ions (Hg2+ ) based on an oriented ZnO nanobelt (ZnO-NB) film solution-gated field-effect transistor (FET) chip is adopted. The FET chips are fabricated with ZnO-NB film channels with different orientations utilizing the Langmuir-Blodgett (L-B) assembly technique. The combined simulation and I-V behavior results show that the nanodevice with ZnO-NBs parallel to the channel has exceptional performance. The sensing capability of the oriented ZnO-NB film FET chips corresponds to an ultralow minimum detectable level (MDL) of 100 × 10-12 m in deionized water due to the change in the electrical double layer (EDL) arising from the synergism of the field-induced effect and the specific binding of Hg2+ to the thiol groups (-SH) on the film surface. Moreover, the prepared FET chips present excellent selectivity toward Hg2+ , excellent repeatability, and a rapid response time (less than 1 s) for various Hg2+ concentrations. The sensing performance corresponds to a low MDL of 10 × 10-9 m in real samples of a drop of blood.

Pt NPs catalyzed chemiluminescence method for Hg2+ detection based on a flow injection system.

Establishing a simple and accurate method for Hg2+ detection is of great importance for the environment and human health. In this work, platinum nanoparticles (Pt NPs) with different capped agents and morphologies were synthesized. It was found that Pt NPs exhibited peroxidase-like activity that can catalyze the chemiluminescence (CL) of the luminol system without H2 O2 . The most intensive CL signals were obtained by using PVP-capped Pt NPs as catalysis. Based on the fact that Hg2+ could further enhance the CL intensity in the Pt NPs-luminol CL system, a Pt NPs-catalyzed CL method based on a flow injection system is developed for the sensitive analysis of Hg2+ . When the concentration of Hg2+ in the system increases, the CL intensity would together increase, thereby achieving sensitive Hg2+ detection. The limit of detection (LOD) was calculated to be 8.6 nM. This developed method provides a simple and rapid approach for the sensitive detection of Hg2+ and shows great promise for applications in other complex systems.

Colorimetric and turn-on Fluorescence Chemosensor for Hg2+ Ion Detection in Aqueous Media.

A new rhodamine 6G based fluorescent and colorimetric chemosensor, containing N-methyl imidazole nucleus, for the selective detection of Hg2+ ion was designed and synthesized. The results of UV-Vis and fluorescence spectral study indicated that the receptor is selective and sensitive towards Hg2+ with no noticeable interference with other competitive metal ions. The addition of Hg2+ to the receptor induced a rapid color change to pink from colorless and the turn-on fluorescence response toward Hg2+ among different cations was studied. The stoichiometric ratio of 1:1 between the receptor and Hg2+ was supported by Job's plot. The color change and turn-on fluorescence response upon addition of Hg2+ ion was ascribed by the spirolactam ring-opening mechanism. The probable mode of binding between the receptor and Hg2+ was confirmed by 1H NMR and Mass spectral study. For the practical application, its electrospun nanofiber test strips successfully applied to recognize Hg2+ ion in aqueous media. Graphical Abstract Schematic representation of Hg2+ detection by rhodamine based sensor.

Development of a paper-based method to detect Hg2+ in waste water using iturin from Bacillus subtilis.

Colorimetric, fluorescence, and paper-based method were developed to measure the Hg2+ level in water using iturin A, a lipopeptide produced by Bacillus subtilis. Firstly, iturin was used to synthesize highly stable and uniformly sized silver nanoparticles (AgNPs). Secondly, the iturin-AgNPs were found to be highly selective and sensitive to Hg2+. The absorbance of the reaction system showed a good linear correlation with the Hg2+ concentration from 0.5 to 5 mg/L at 450 nm in the UV-Vis spectroscopy detection with the limit of detection (LOD) of 0.5 mg/L. When the reaction system was detected by fluorescence measurement, a good linear relationship was found between the fluorescence intensity and Hg2+ concentration from 0.05 to 0.5 mg/ at 415 nm with the LOD of 0.05 mg/L. Lastly, a paper-based detection method was developed. The developed method was successfully used to detect Hg2+ in contaminated polluted waters and showed acceptable results in terms of sensitivity, selectivity and stability. The paper-based method could distinguish Hg2+ at levels higher than 0.05 mg/L, thereby meeting the guidelines of the effluent quality standard for industries (0.05 mg/L). In summary, this method can be used daily by various industries to monitor the Hg2+ level in effluent water.