A Carbamoyl Oxime-Based Highly Specific Fluorescent Chemodosimeter for Monitoring Labile Fe2+ in Food and Living Organisms.

Iron is an essential element in the composition of living organisms and plays a crucial role in a wide range of biological activities. The human body primarily obtains essential iron through the consumption of food. Therefore, it is vital for the health of human body to maintain iron homeostasis. The reducing character of the cellular microenvironment enables Fe2+ to occupy a dominant position within the cell. Hence, there is an urgent need for a simple and sensitive tool that can detect a large amount of Fe2+ in organisms. In this work, a highly specific fluorescent chemodosimeter NPCO ("NP" represents the naphthalimide fluorophore, and "CO" represents the carbamoyl oxime structure) for the detection of Fe2+ with excellent sensitivity (LOD = 82 nM) was constructed by incorporating a novel carbamoyl oxime structure as the recognition group. NPCO can be effectively employed for the detection of Fe2+ in food samples, living cells, and zebrafish. Furthermore, by using soybean sprouts as a model plant, the application of NPCO was expanded to detect Fe2+ in plants. Therefore, NPCO could be used as an excellent assay tool for detecting Fe2+ in organisms and is expected to be an important aid in exploring the mechanism of iron regulation.

Biothiols-activated near-infrared frequency up-conversion luminescence probe for early evaluation of drug-induced hepatotoxicity.

A novel biothiols-sensitive near-infrared (NIR) fluorescent probe RhDN based on a rhodamine skeleton was developed for early detection of drug-induced hepatotoxicity in living mice. RhDN can be used not only as a conventional large stokes shift fluorescent (FL) probe, but also as a kind of anti-Stokes frequency upconversion luminescence (FUCL) molecular probe, which represents a long wavelength excitation (808 nm) to short wavelength emission (760 nm), and response to Cys/Hcy/GSH with high sensitivity. Compared with traditional FL methods, the FUCL method exhibited a lower detection limit of Cys, Hcy, and GSH in 75.1 nM, 101.8 nM, and 84.9 nM, respectively. We exemplify RhDN for tracking endogenously biothiols distribution in living cells and further realize real-time in vivo bioimaging of biothiols activity in mice with dual-mode luminescence system. Moreover, RhDN has been successfully applied to visualize the detection of drug-induced hepatotoxicity in living mice. Overall, this report presents a unique approach to the development of large stokes shift NIR FUCL molecular probes for in vitro and in vivo biothiols biosensing.

Dual channel chemosensor for successive detection of environmentally toxic Pd2+ and CN- ions and its application to cancer cell imaging.

BACKGROUND: Detecting and neutralizing Pd2+ ions are a significant challenge due to their cytotoxicity, even at low concentrations. To address this issue, various chemosensors have been designed for advanced detection systems, offering simplicity and the potential to differentiate signals from different analytes. Nonetheless, these chemosensors often suffer from limited emission response and complex synthesis procedures. As a result, the tracking and quantification of residual palladium in biological systems and environments remain challenging tasks, with only a few chemosensing probes available for commercial use. RESULTS: In this paper, a straightforward approach for the selective detection of Pd2+ ions is proposed, which involves the design, synthesis, and utilization of a propargylated naphthalene-derived probe (E)-N'-((2-(prop-2-yn-1-yloxy)naphthalen-1-yl)methylene)benzohydrazide (NHP). The NHP probe exhibits sensitive dual-channel colorimetry and fluorescence Pd2+ detection over other tested metal ions. The detection process is performed through a catalytic depropargylation reaction, followed by an excited state intramolecular proton transfer (ESIPT) process, the detection limit is as low as 11.58 × 10-7 M under mild conditions. Interestingly, the resultant chemodosimeter adduct (E)-N'-((2-hydroxynaphthalen-1-yl)methylene)benzohydrazide (NHH) was employed for the consecutive detection of CN- ions, exhibiting an impressive detection limit of 31.79 × 10-8 M. Validation of both detection processes was achieved through 1H nuclear magnetic resonance and density functional theory calculations. For real-time applications of the NHP and NHH probes, smartphone-assisted detection, and intracellular detection of Pd2+ and CN- ions within HeLa cells were studied. SIGNIFICANCE: This research presents a novel naphthalene derivative for visually detecting environmentally toxic Pd2+ and CN- ions. The synthesized probe selectively binds to Pd2+, forming a chemodosimeter. It successfully detects CN- ions through colorimetry and fluorimetry, offering a low detection limit and quick response. Notably, it's the first naphthalene-based small molecule to serve as a dual probe for toxic analytes - palladium and cyanide. Moreover, it effectively detects Pd2+ and CN- intracellularly in cancer cells.

Multi-Spectroscopic and TD-DFT Studies on Chromogenic and Fluorogenic Detection of Cyanide in an Aqueous Solution.

Different spectroscopic techniques and Density Functional Theory (DFT)/Time-Dependent Density Functional Theory (TDDFT) calculations have been employed to investigate the dual channel CN- detection behaviour of the developed chemo-dosimeter (AK3). The CN- with AK3 reaction triggered a colour change from pale yellow to colourless and enhanced fluorescence. UV-Vis, fluorescence, 1H & 13C NMR and mass techniques coupled with theoretical calculations (Mulliken charges, dihedral angles) revealed that the CN- sensing process mechanism involves deprotonation of the N-H group followed by nucleophilic addition reaction. Detailed TD-DFT calculations showed that the relaxation of excited electrons from LUMO and to two different ground states is responsible for the weak/moderate fluorescence of AK3. Nucleophilic addition of CN- to the C-atom of the CH = CH bridge terminated the π-conjugation between donor and acceptor regions, reduced the coplanarity, decreased the ICT transition and consequently enhanced the fluorescence of the probe. The practical utility of the probe was demonstrated by detecting cyanide in food materials and determining CN- in environmental water samples.

Recent Development on Sensing Strategies for Small Molecules Detections.

Sensors play a critical role in the detection and monitoring of various substances present in our environment, providing us with valuable information about the world around us. Within the field of sensor development, one area that holds particular importance is the detection of small molecules. Small molecules encompass a wide range of organic or inorganic compounds with low molecular weight, typically below 900 Daltons including gases, volatile organic compounds, solvents, pesticides, drugs, biomarkers, toxins, and pollutants. The accurate and efficient detection of these small molecules has attracted significant interest from the scientific community due to its relevance in diverse fields such as environmental pollutants monitoring, medical diagnostics, industrial optimization, healthcare remedies, food safety, ecosystems, and aquatic and terrestrial life preservation. To meet the demand for precise and efficient monitoring of small molecules, this summary aims to provide an overview of recent advancements in sensing and quantification strategies for various organic small molecules including Hydrazine, Glucose, Morpholine, Ethanol amine, Nitrosamine, Oxygen, Nitro-aromatics, Phospholipids, Carbohydrates, Antibiotics, Pesticides, Drugs, Adenosine Triphosphate, Aromatic Amine, Glutathione, Hydrogen Peroxide, Acetone, Methyl Parathion, and Thiophenol. The focus is on understanding the receptor sensing mechanism, along with the electrical, optical, and electrochemical response. Additionally, the variations in UV-visible spectral properties of the ligands upon treatment with the receptor, fluorescence and absorption titration analysis for limit of detection (LOD) determination, and bioimaging analysis are discussed wherever applicable. It is anticipated that the information gathered from this literature survey will be helpful for the perusal of innovation regarding sensing strategies.

A Near-Infrared Fluorescent Probe for Recognition of Hypochlorite Anions Based on Dicyanoisophorone Skeleton.

A novel near-infrared (NIR) fluorescent probe (SWJT-9) was designed and synthesized for the detection of hypochlorite anion (ClO-) using a diaminomaleonitrile group as the recognition site. SWJT-9 had large Stokes shift (237 nm) and showed an excellent NIR fluorescence response to ClO- with the color change under the visible light. It showed a low detection limit (24.7 nM), high selectivity, and rapid detection (within 2 min) for ClO-. The new detection mechanism of SWJT-9 on ClO- was confirmed by 1H NMR, MS spectrum, and the density functional theory (DFT) calculations. In addition, the probe was successfully used to detect ClO- in HeLa cells.

Green synthesis of naphthyl derivative as an optical sensor for the detection of l-carnitine in food samples.

An economical and green approach to the synthesis of naphthyl derivative for detection of l-carnitine (3-hydroxy-4-N-trimethyl-aminobutyrate) is practically important. We developed a naphthyl derivative as a probe showing 'turn-on' response towards l-carnitine selectively at pH 7.2 through ICT mechanism with a good limit of detection (LOD) of 0.126 µM. Using Job's plot for determining the binding stoichiometry, it was found that probe could form a more stable complex (1:1) with carnitine. The binding constant (K) between probe and carnitine was calculated as 8 × 107  M-1 using the Benesi-Hildebrand plot. The binding interaction of the probe with l-carnitine was confirmed by nuclear magnetic resonance titrations, Fourier-transform infrared spectroscopy, photo physical studies and density functional theory calculations. Meanwhile, the probe can be used to quantitatively detect carnitine in food samples.

Vinyl substituted triphenylamine based turn-off fluorescent probe for selective and sensitive detection of mercury (II) in water and live cells.

Here, we report vinyl substituted triphenylamine (TPA-alk) fluorescent probe for the rapid and efficient detection of mercury ion (Hg2+) in water and biological environment. TPA-alk detects Hg2+ selectively over a wide range of competitive metal ions with a blue shift of 43 nm in the UV absorbance spectrum. The detection limit is found to be 0.146 µM (29.2 ppb) with high selectivity over a wide range of competitive metal ions. DFT study explains the blue shift in the UV-vis absorption band of the optical probe upon the addition of Hg2+. Cell viability assay illustrates that the probe is biocompatible and it has low cytotoxicity even at its higher concentration. Cell imaging studies demonstrate the efficiency of the TPA-alk probe for the micromolar detection of mercury (II) in live BMG1 cells.

An Anthracene and Indole-based Fluorescent Probe for the Detection of Chromium(III) Ions in Real Water Samples.

A novel fluorescent probe possessing anthracene with an indole unit was designed and synthesized to detect chromium(III) ions (Cr3+) with high sensitivity and selectivity. The probe was synthesized in one step by mixing two commercially available chemicals, 2-aminoanthracene and Indole-5-carboxaldehyde. The probe molecule (ANT-In) demonstrates distinct properties, for instance, "turn-on" fluorescence response, high sensitivity and selectivity in less than one minute, and low detection limit (0.2 µM) via hydrolysis of the C = N bond. Additionally, the probe ANT-In was successfully used to identify the presence of chromium(III) ions in real water samples.

Recent Advances in Chemodosimeters Designed for Amines.

The analysis of amines has long been a very important task in science, industry, and healthcare. To date, this task has been accomplished by using expensive and time-consuming methods. Colorimetric and fluorescent chemodosimeters enable the fast, accurate, and sensitive analysis of various species with inexpensive instruments or the naked eye. Accordingly, the studies on these probes have gained great momentum in the last 20 years. In this review, amine chemodosimeters developed in the last 10 years were investigated. The investigated chemodosimeters are metal-free structures based on small organic compounds. The strategies for the detection, differentiation, and quantification of amines were discussed by considering the reaction types.

Nucleophilic Approach to Cyanide Sensing by Chemosensors.

Cyanide anion has wide use in industrial areas; however, it has a high toxic effect on the environment as waste. Moreover, plant seeds contain cyanide that is often consumed by human beings. Therefore, many studies are carried out to determine cyanide. Especially, optical sensors showing colorimetric and fluorimetric changes have been of considerable interest due to their easy, cheap, and fast responses. This review discusses recent developments in the colorimetric and fluorimetric detection of cyanide by nucleophilic addition to different types of receptors via the chemodosimeter approach. The sensitivity and selectivity of the sensors have been reviewed for changes in absorption and fluorescence, naked-eye detection, real sample application, and detection limits when interacting with cyanide.

A cationic iridium(III) complex containing a thiosemicarbazide unit: Synthesis and application for turn-on chemiluminescent detection of Hg2.

A novel cationic iridium(III) complex [(ppy)2Ir(bPCPC)]PF6 (ppy: 2-phenylpyridine; bPCPC: 2-([2,2'-bipyridine]-4-carbonyl)-N-phenylhydrazinecarbothioamide) containing a thiosemicarbazide unit was designed and synthesized. The thiosemicarbazide unit was a sensitive functional group to Hg2+, when it reacted with Hg2+, it was desulphurized and thus led to the formation of 1,3,4-oxadiazole, [(ppy)2Ir(bPCPC)]PF6 resultantly was used as a "turn-on" chemodosimeter for luminescent detection of Hg2+ in DMF/PBS buffer solution at pH = 7-11. Except for Ag+, recognition capability of [(ppy)2Ir(bPCPC)]PF6 to Hg2+ was not interfered by other common metal ions (Co2+, Li+, Zn2+, Pb2+, K+, Al3+, Na+, Mn2+, Cu2+, Fe2+, Fe3+, Cr3+, Ba2+, Mg2+, Ni2+ and Ca2+). The detection limit was 1.83 × 10-9 mol∙L-1 (0.37 ppb), which indicated the complex was a highly sensitive chemiluminescent detection reagent of Hg2+.

Ratiometric fluorescence chemodosimeter for hydrazine in aqueous solution and gas phase based on Quinoline-Malononitrile.

The widespread use of Hydrazine (N2H4) in many areas of the chemical industry, brings potential risks to human health and environmental pollution. To detect N2H4 effectively, a simple ratio fluorescence probe (QMM), designed and synthesized through Vilsmeier reaction and Knoevenagel reaction, was prepared for the specific response of N2H4 based on the irreversible chemical reaction. The ratiometric fluorescence chemodosimeter displayed a response for hydrazine with high selectivity, sensitivity and anti-interference ability. The measured detection limit is 38.30 nm (0.122 ppb), which is far lower than the maximum allowable level of the U.S. Environmental Protection Agency (10 ppb). Moreover, test paper and TLC plates loading QMM had been made, which could be utilized to detect hydrazine both in aqueous solution samples and in gas phase samples. Thus QMM could serve as an easily manufactured, low-cost, efficient and portable solid-state optical probe to detect hydrazine in field measurements.

A Double-Site Chemodosimeter for Selective Fluorescence Detection of a Nerve Agent Mimic.

A novel two-site chemodosimeter (SWJT-4) based on fluorescein skeleton to detect diethyl chlorophosphate (DCP) was designed and synthesized. It is a turn-on fluorescent probe for DCP with good selectivity and obvious color change in aqueous solution. Interestingly, the two oxime groups of SWJT-4 as dual response sites initiated different reactions with DCP to form a cyano group and an isoxazole ring, respectively. The corresponding mechanism was confirmed by 1H NMR, MS and DFT calculation. Moreover, SWJT-4 could be used as a fluorescent test paper to detect DCP vapor.

A New Fluoride Chemodosimeter Based on 3-Ether-Substituted 1, 8-Naphthalimide Derivatives.

We developed a new chromogenic and fluorescent "off-on" 1, 8-naphthalimide-derivated chemosensor 1 based on an F--triggered desilylation reaction. It showed significant variations in UV/visible absorption (510 nm) and fluorescence emission wavelength (580 nm) for selective detection of fluorides in THF/H2O system (v/v, 50:50). Moreover, chemodosimeter 1-loaded test strips were successfully fabricated todetect fluorides efficiently.

Chromogenic chemodosimeter based on a silylated azo compound detects cyanide in water and cassava.

A novel silylated azo compound was synthesized and fully characterized. This compound was used in a chromogenic chemodosimeter approach for the highly selective detection of cyanide (CN-) in acetonitrile/water and in an aqueous micellar system. The anion breaks the Si-O bond, delivering a dye and causing a change in the color of the solution (from yellow to blue). The chemodosimeter was employed for the naked-eye and quantitative detection of CN- in tap water and cassava roots.

Azulene-A Bright Core for Sensing and Imaging.

Azulene is a hydrocarbon isomer of naphthalene known for its unusual colour and fluorescence properties. Through the harnessing of these properties, the literature has been enriched with a series of chemical sensors and dosimeters with distinct colorimetric and fluorescence responses. This review focuses specifically on the latter of these phenomena. The review is subdivided into two sections. Section one discusses turn-on fluorescent sensors employing azulene, for which the literature is dominated by examples of the unusual phenomenon of azulene protonation-dependent fluorescence. Section two focuses on fluorescent azulenes that have been used in the context of biological sensing and imaging. To aid the reader, the azulene skeleton is highlighted in blue in each compound.

Visualizing and Isolating Iron-Reducing Microorganisms at the Single-Cell Level.

Iron-reducing microorganisms (FeRM) play key roles in many natural and engineering processes. Visualizing and isolating FeRM from multispecies samples are essential to understand the in situ location and geochemical role of FeRM. Here, we visualized FeRM by a "turn-on" Fe2+-specific fluorescent chemodosimeter (FSFC) with high sensitivity, selectivity, and stability. This FSFC could selectively identify and locate active FeRM from either pure culture, coculture of different bacteria, or sediment-containing samples. Fluorescent intensity of the FSFC could be used as an indicator of Fe2+ concentration in bacterial cultures. By combining the use of the FSFC with that of a single-cell sorter, we obtained three FSFC-labeled cells from an enriched consortium, and all of them were subsequently shown to be capable of iron reduction; two unlabeled cells were shown to have no iron-reducing capability, further confirming the feasibility of the FSFC.IMPORTANCE Visualization and isolation of FeRM from samples containing multiple species are commonly needed by researchers from different disciplines, such as environmental microbiology, environmental sciences, and geochemistry. However, no available method has been reported. In this study, we provide a method to visualize FeRM and evaluate their activity even at the single-cell level. When this approach is combined with use of a single-cell sorter, FeRM can also be isolated from samples containing multiple species. This method can be used as a powerful tool to uncover the in situ or ex situ role of FeRM and their interactions with ambient microbes or chemicals.

A new bivalent fluorescent fusion protein for differential Cu(II) and Zn(II) ion detection in aqueous solution.

Simple and easy to engineer metal-sensing molecules that are capable of differentiating metal ions and producing metal-specific signals are highly desirable. Metal ions affect the thermal stability of proteins by increasing or decreasing their resistance to unfolding. This work illustrates a new strategy for designing bivalent fluorescent fusion proteins capable of differentiating metal ions in solution through their distinct effects on a protein's thermal stability. A new dual purpose metal sensor was developed consisting of biotin protein ligase (BirA) from B. pseudomallei (Bp) fused to green fluorescent protein (GFP). When coupled with differential scanning fluorimetry of GFP-tagged proteins (DSF-GTP) for signal-transduction detection, Bp BirA-GFP yields distinct protein unfolding signatures with Zn(II) and Cu(II) ions in aqueous solutions. The limit of detection of the system is ∼1 µM for both metal species. The system can be used in a variety of high-throughput assay formats including for the screening of metal-binding proteins and chelators. Bp BirA-GFP has also the additional benefit of being useful in Cu(II) ion field-testing applications through simple visual observation of a temperature-dependent loss of fluorescence. Bp BirA-GFP is the first example of a 2protein-based dual purpose Cu(II) and Zn(II) ion sensor compatible with two different yet complementary signal-transduction detection systems.

Application of Boroisoquinoline Fluorophores as Chemodosimeters for Fluoride Ion and Pd (0).

The development of novel chemodosimeters is currently a prosperous field in organic chemistry. Recently, a new family of fluorophores, the boroisoquinolines, were introduced with satisfying photophysical properties. As a continuation of this research, the application of boroisoquinolines is presented as chemodosimeters for fluoride anion and Pd (0). The new tools showed good selectivity for the detection of the analytes. Moreover, the mechanism of action was investigated experimentally.