An aggregation-induced emission-based ratiometric fluorescent chemosensor for Hg(II) and its application in Caenorhabditis elegans imaging.

A chromone-based ratiometric fluorescent probe L2 was developed for the selective detection of Hg(II) in a semi-aqueous solution based on aggregation-induced emission (AIE) and chelation-enhanced fluorescence (CHEF) effect. The probe L2 fluoresced significantly at 498 nm in its aggregated state, and when chelated with Hg(II), the soluble state fluoresced 1-fold higher. In addition, Job's plot reveals that the probe forms a 1:1 stoichiometry complex with Hg(II) with an association constant of 9.10 × 103M-1 estimated by the BH plot. The probe L2 detects Hg(II) down to 22.47 nM without interference from other interfering ions. The FTIR, ESI mass, and DFT-based computational studies investigated the binding mechanism of probe L2 with Hg(II). Taking advantage of its AIE characteristics, the probe L2 was successfully applied for bio-capability analysis in Caenorhabditis elegans (a nematode worm) imaging of Hg(II) in a living model.

Novel Discrete and Imprinted Fluoride-Selective Sensors: Bridging the Gap from DMSO to Aqueous Samples.

Fluoride in drinking water has beneficial or harmful health effects depending on its concentration. This highlights the need for new low-cost and portable sensors capable of in situ monitoring of F- ions. Unfortunately, achieving high levels of water compatibility and fluoride specificity remains a challenge. Here, four new urea-based discrete sensors are prepared and characterized. The sensors containing anthracenyl- (5) and 9H-fluorenyl- (7) signaling units exhibit intense luminescent emissions in dimethyl sulfoxide, the former being particularly sensitive and selective to fluoride. In water, 5 displays a superior sensitivity (871 M-1) and a detection limit (8 µm) below international guidelines, albeit with cross-sensitivity to H2PO4‾. To enhance the performance, 5 and 7 are embedded into a fluoride-imprinted polymeric matrix to give solid-state sensors (5P and 7P, respectively). 5P shows good sensitivity (360 M-1) and specificity in water. Besides, it has a low detection limit (35 µm) and a response linear range (118-6300 µm) encompassing the limit established by the Environmental Protection Agency (211 µm). Furthermore, 5P also displays good reusability and adequate recovery values in real-sample testing (102 ± 2%), constituting the first example of a low-cost anion-imprinted polymeric probe tailored for the selective sensing of fluoride in aqueous samples.

Self-Assembled and Polymerized Hierarchical Nanostructure Films of Cyanostilbene-Based Reactive AIEgens for Smart Chemosensors.

For the development of acid-responsive advanced fluorescent films with a 2D nanostructure, a pyridyl cyanostilbene-based AIEgen (PCRM) is newly synthesized. The synthesized PCRM exhibits aggregation-induced emission (AIE) and responds reversibly to acid and base stimuli. To fabricate the nanoporous polymer-stabilized film, PCRM and 4-(octyloxy)benzoic acid (8OB) are complexed in a 1:1 ratio through hydrogen bonding. The PCRM-8OB complex with a smectic mesophase is uniaxially oriented at first and photopolymerized with a crosslinker. By subsequently removing 8OB in an alkaline solution, nanopores are generated in the self-assembled and polymerized hierarchical 2D nanostructure film. The prepared nanoporous fluorescent films exhibit not only the reversible response to acid and base stimuli but also mechanical and chemical robustness. Since the nanoporous fluorescent films have different sensitivities to trifluoroacetic acid (TFA) depending on the molecular orientation in the film, advanced acid vapor sensors that can display the risk level according to the concentration of TFA are demonstrated. Reactive AIEgens-based hierarchical nanostructure films with nanopores fabricated by a subsequent process of self-assembly, polymerization, and etching can open a new door for the development of advanced chemosensors.

Differential Sensing Approach as a Pattern-based Discrimination for Biological Samples.

The differential sensing approach uses fingerprint patterning to distinguish uncharacterized biological samples. Inspired by natural sensory systems, an array of cross-reactive sensors generates unique response fingerprint depending on the samples. Until today, this array system has been developed using various materials, including the library of surface-charged nanoparticles and chemosensors. Many differential array systems have demonstrated accurate identification of bacterial species, viral subtypes, and cancer cells, as well as distinguishing disease states in blood or urine. This capability is particularly important for distinguishing between normal and abnormal states when specific marker molecules have not yet been identified, providing a powerful diagnostic tool. In this concept, we summarized representative outcomes of differential sensing applications for biological sample discrimination.

A GFP Inspired 8-Methoxyquinoline-Derived Fluorescent Molecular Sensor for the Detection of Zn2+ by Two-Photon Microscopy.

An effective, GFP-inspired fluorescent Zn2+ sensor is developed for two-photon microscopy and related biological application that features an 8-methoxyquinoline moiety. Excellent photophysical characteristics including a 37-fold fluorescence enhancement with excitation and emission maxima at 440 nm and 505 nm, respectively, as well as a high two-photon cross-section of 73 GM at 880 nm are reported. Based on the experimental data, the relationship between the structure and properties was elucidated and explained backed up by DFT calculations, particularly the observed PeT phenomenon for the turn-on process. Biological validation and detailed experimental and theoretical characterization of the free and the zinc-bound compounds are presented.

ZnO-Salen NPs Employed as Chemosensor for Detection of Al3+ and K+ in Aqueous Medium, Developing Human Cell Images.

ZnO nanoparticles (NPs) were prepared and characterized by different analytical methods and then they were used to decorate with N, N´-bis(salicylidene)ethylenediamine (salen) in order to perform as receptor for the metal ions in an aqueous medium. The results show that ZnO-salen selectively detects Al3+ ions in aqueous medium since the intensity of fluorescence has been enhanced significantly. However, the presence of K+ in the medium further intensified the fluorescence emission for the [ZnO-salen-Al3+] system. The above system has been applied to recognize Al3+ and K+ in cells by developing the cell images, for which, the fluorescence image is brightened if a human glioblastoma U251 cell contains [ZnO-salen-Al3+] + K+ ions, consisting of the fluorescence titration. The binding global constant for Al3+ and the subsequent recognition of K+ by ZnO-salen resulted in ß2(Al3+) = 6.61 × 103 and ß2(K+) = 3.71 × 103 with a detection limit of 36.51 µM for Al3+ and 17.39 µM for K+. In the cell toxicity analysis, the cell viability was over 85% for the ZnO-salen even in the concentration as high as 100 mM.

A Quick, Highly Selective and Sensitive Colorimetric and Fluorimetric Sensor for Cyanide Ion.

A newly developed diindolium moiety has been synthesized and structurally investigated by employing a number of spectroscopic methods like NMR and HRMS in order to serve as a cyanide sensor DI. The interaction between DI and the CN- ion causes a noticeable color shift from pink to colorless, making it easy to detect CN- ions with the naked eye. Besides, the sensor exhibited fluorescence color change from orange to light blue under UV lamp. Sensor DI has remarkable selectivity and sensitivity in distinguishing between CN- and a wide range of interfering anions. The sensing mechanism of sensor DI towards CN- ion involves the nucleophilic addition process of CN- to the electron deficient indolium moiety. The detection limit of cyanide ion by sensor DI is calculated to be 1.4 × 10- 7 M by UV-visible and 8.2 × 10- 8 M by fluorescence technique which are lower than the limit set by WHO. The application of sensor DI for cyanide ion is utilized by making test kit and by taking different sources of water to test the presence of cyanide ion.

Ultrasound-Assisted Synthesis of Chalcone: A Highly Sensitive and Selective Fluorescent Chemosensor for the Detection of Fe3+ in Aqueous Media.

The chalcone compound DHPO was synthesized through a chemical reaction between 1-(2-hydroxyphenyl)-ethanone and 3,4-dimethoxy benzaldehyde under ultrasound irradiation. The interaction between the DHPO compound and several metal ions was studied using fluorescence behavior, revealing that the chalcone function as a "turn on and turn off" switch fluorescent sensor, for selectively and sensitively detecting Fe3+ ions. The process of fluorescence quenching and complexation of DHPO with Fe3+ ion was further studied using methods such as Benesi-Hildebrand, Stern-Volmer plot, and job plot.

A 1,8-Naphthalimide-based Tripodal Fluorescent Chemosensor to Selectively Detect Copper Ions.

A 1,8-naphthalimide-based tripodal fluorescent ligand (L3) was synthesized through the copper (I) catalyzed Huisgen azide-alkyne cycloaddition reaction of 2-(2-azidoethyl)-6-morpholino-1 H-benzo[de]isoquinoline-1,3(2 H)-dione with triproparagylamine. Naphthalimide acts as the fluorophore while the triazole and amine nitrogens chelate the metal ion. L3 showed a selective fluorescence turn-off for Cu(II) over other metal ions in aqueous acetonitrile solution. A Job's plot, Benesi-Hildbrand plot and high-resolution mass spectrometry data confirm a 1:1 binding stoichiometry with a binding constant of 7.8 х105 M- 1 while addition of disodium EDTA demonstrates its reversibility. The structure and stability of the complex was supported by theoretical calculations. The limit of detection for Cu(II) was calculated to be 0.3 µM which is considerably lower than WHO recommended Cu(II) limit in drinking water.

Photophysical Investigation of One Pot Synthesized Novel Indenofluorene Derivative (BDP) as a Fluorescent Chemosensor for the Detection of Fe3+ Ion.

An Indane-1-one derivative 11-(1-benzyl-1H-indol-3-yl)-10,12-dihydrodiindeno[1,2-b:2',1'-e]-pyridine (BDP) has been synthesized by the reaction of Indan-1-one with 1-benzyl-1H-indole-3-carbaldehyde. FT-IR, 1H-NMR, 13N-NMR and Mass spectroscopic techniques has been used to confirmed the structure of BDP. The observed photophysical changes in BDP across various solvents were associated. The impact of various interactions on photophysical parameters, including Stokes shift, dipole moment, oscillator strength, and fluorescence quantum yields, has been assessed in relation to solvent polarity. Moreover, BDP demonstrates potential as a selective fluorescent chemosensor for detecting Fe3+ ion within a range of cations in an aqueous DMSO environment. A thorough investigation into the recognition mechanism of BDP towards Fe3+ ion has been conducted using Benesi-Hildebrand and Stern-Volmer, measurements. BDP forms a 2:1 complex with the Fe3+ ion, exhibiting fluorescent quenching behaviour.

Naphthalimide Based Optical Probe for the Detection of Hydrazine in Water and Their Application in Test Strips and Silica Supported Material.

A newly synthesized naphthalimide-based fluorophore probe NIA was used to detect hydrazine. This probe, based on the Gabriel mechanism exhibited a highly sensitive revealing of hydrazine in naked eyes colorimetric as well as fluorescent recognition against other amines in an aqueous solution in DMSO - HEPES buffer. When hydrazine hydrate was added to the probe NIA, the absorption was red shifted from 403 nm to 520 nm. The titration studies by adding hydrazine to show two apparent isosbestic points found at 358 and 450 nm, respectively. Further, investigation of emission spectra upon addition of hydrazine hydride the emission peak at 493 nm gradually decreased up to 2.4 equiv. and when increasing the hydrazine hydride concentration from 2.4 equiv. to 4.4 equiv., the fluorescence intensity increased at 530 nm. which is exhibiting a raised ratiometric emission intensity at 530 nm. Further investigation of the selectivity of probe NIA revealed colorimetric and fluorimetric responses to interferences with other test amines. 1H NMR and HR-mass proved the Gabriel mechanism bath for detecting hazardous hydrazine by probe NIA. This probe NIA allowed the rapid and ultrasensitive detection of hydrazine hydride with a low detection limit of 0.26 nM. In view of the outstanding properties, probe NIA has been effectively performed to detect hydrazine using various techniques, including a test kit, silica support, and actual environmental water samples.

Highly Sensitive and Selective Recognition of Zn2⁺ and Fe2⁺ Ions Using a Novel Thiophene-Derived Hydrazone Dual Fluorometric Sensor.

The selective detection of Zn2⁺ and Fe2⁺ ions is critical in environmental and biological studies. Schiff base chemosensors hold promise, but exploration of thiophene-derived variants remains limited. This work introduces a novel thiophene-derived Schiff base sensor (TBH), synthesized through the condensation reaction of thiophene-2-carboxaldehyde with benzil-bis-hydrazone, for the selective detection of Zn2⁺ and Fe2⁺ ions. TBH exhibits remarkable selectivity, with a significant 185-fold fluorescence enhancement for Zn2⁺ and complete quenching 99% for Fe2⁺, allowing for distinct detection of both ions. Notably, TBH demonstrates high binding affinity towards Zn2⁺ and Fe2⁺, even in the presence of competing cations, forming stable 1:1 complexes. This finding is supported by absorption and emission titration studies and FT-IR analysis as well. This easily synthesized, rapid and cost-effective sensor offers a promising approach for sensitive and differentiated dual detection of Zn2⁺ and Fe2⁺ in environmental and biological systems.

Colorimetric and Fluorometric N-Acylhydrazone-based Chemosensors for Detection of Single to Multiple Metal Ions: Design Strategies and Analytical Applications.

The development of optical sensors for metal ions has gained significant attention due to their broad applications in biology, the environment, and medicine. Colorimetric and fluorometric detection methods are particularly valued for their simplicity, cost-effectiveness, high detection limits, and analytical power. Among various chemical probes, the hydrazone functional group stands out for its extensive study and utility, owing to its ease of synthesis and adaptability. This review provides a comprehensive overview of N-acylhydrazone-based probes, serving as highly effective colorimetric and fluorometric chemosensors for a diverse range of metal ions. Probes are categorized into single-ion, dual-ion, and multi-ion chemosensors, each further classified based on the detected metal(s). Additionally, the review discusses detection modes, detection limits, association constants, and spectroscopic measurements.

Copper(II) Driven Fluorescence switch-on Detection of Ovalbumin and GSH Using a Pyridoxal 5'-phosphate Derived Tetradentate Schiff Base and its Applications.

The facile detection of glutathione (GSH) and ovalbumin (OVA) is of great importance in biological research. Herein, a tetradentate Schiff base N, N'-bis(pyridoxal-5-phosphate)-o-phenylenediamine (L) obtained by condensing two moles of pyridoxal 5'-phosphate (PLP) with one mole of 1,2-phenylenediamine was employed for the fluorescence switch-on detection of GSH and OVA. When excited at 389 nm, receptor L showed a weak emission at 454 nm in an aqueous medium. The addition of GSH to the solution of L caused a significant fluorescence enhancement at 454 nm. Amino acids (leucine, glycine, serine, tryptophan, homocysteine, alanine, methionine, arginine and proline) and albumins (bovine serum albumin and OVA) failed to alter the fluorescence profile of L. Receptor L can be applied to detect GSH down to 1.16 µM. However, the fluorescence emission of L was quenched upon the formation of the L-Cu2+ complex. The addition of GSH and OVA to the in-situ formed L-Cu2+ complex restored not only the fluorescence emission of L but also a noticeable fluorescence enhancement observed at 454 nm. The decomplexation of L-Cu2+, along with the interaction of L with GSH and OVA is expected to suppress the conformational flexibility of L that enhanced the fluorescent intensity at 454 nm. Using L-Cu2+ complex, the concentration of OVA and GSH can be detected down to 0.31 µM and 0.20 µM, respectively. Molecular docking and dynamics simulation were performed to analyze the binding mode, conformational flexibility and dynamic stability of the L-Cu2+-OVA complex. Finally, the analytical novelty of L-Cu2+ was examined by detecting GSH/OVA in real biological samples, such as human blood serum, urine, and egg white.

A Prompt Study on Recent Advances in the Development Of Colorimetric and Fluorescent Chemosensors for "Nanomolar Detection" of Biologically Important Analytes.

Fluorescent and colorimetric chemosensors for selective detection of various biologically important analytes have been widely applied in different areas such as biology, physiology, pharmacology, and environmental sciences. The research area based on fluorescent chemosensors has been in existence for about 150 years with the development of large number of fluorescent chemosensors for selective detection of cations as metal ions, anions, reactive species, neutral molecules and different gases etc. Despite the progress made in this field, several problems and challenges still exist. The most important part of sensing is limit of detection (LOD) which is the lowest concentration that can be measured (detected) with statistical significance by means of a given analytical procedure. Although there are so many reports available for detection of millimolar to micromolar range but the development of chemosensors for the detection of analytes in nanomolar range is still a challenging task. Therefore, in our current review we have focused the history and a general overview of the development in the research of fluorescent sensors for selective detection of various analytes at nanomolar level only. The basic principles involved in the design of chemosensors for specific analytes, binding mode, photophysical properties and various directions are also covered here. Summary of physiochemical properties, mechanistic view and type of different chemosensors has been demonstrated concisely in the tabular forms.

Spectroscopic Rationalization of Selective Colorimetric Chemosensing of Fe(lll) in Aqueous Medium by a New Mono-Substituted Dibenzodiaza-Crown Ether Macrocyclic Ligand Appended with Mono 2-Benzimidazole N-Pendant Side Arm.

Optical chemosensor L comprising of a new mono-N-substituted derivative of dibenzodiaza-crown ether macrocyclic ligand bearing a 2-benzimidazole (2Bim) side arm was synthesized, and characterized by FT-IR, elemental microanalyses, 1H NMR, and 13C NMR, UV-visible, fluorescence (FL) spectroscopy. The colorimetric chemosensing behavior of L toward the library metal ions was examined, wherein L represented a prompt and selective yellow-to-purple color change for Fe(III) cation in a 25µM solution with LOD as 0.23 µM in ethanol:water (9:1, v/v), even in the presence of the other library metal ions (LMI). Based on the 1H NMR, UV-visible, and FL observations the coordination sphere of Fe(III) was shared with two 2-benzoimidazole (2Bim) side arms which were also confirmed by the elemental microanalyses (in the solid state) and the Job plot method (in the solution) of the complex. Moreover, the above-mentioned color change was attributed to the presence of a strong charge transfer (LMCT) band for the Fe(III)/L interaction in the solution. Furthermore, the viscosity measurement in the presence of Fe(III) uncovered an increase at 0.5-1.0 ratios for Fe(III)/L, attributable to the formation of a self-assembly in the solution. A TLC paper strip was impregnated by L for selective detection of Fe(III), demonstrating a live color change for Fe(III) at 0-5 mM in the presence of LMI.

Chromene Carbohydrazide- Schiff Base as a Highly Selective Turn-Off Fluorescence Chemosensor for In3+ Ion and its Application.

A new 7-(diethylamino)-2-oxo-2 H-chromene-3-carbohydrazide design to synthesize a simple Schiff-base condition. The synthesized molecules' (probe L) photophysical properties were investigated in various solvent systems and solvent-poor-solvent assays. Probe L exhibits the absorbance band at 440 nm and the emission band at 488 nm in DMSO: H2O (7:3, v/v). Further, probe L shows selective turn-off emission recognition of In3+ ions in DMSO: H2O (7:3, pH = 7.4). By Job's plot and ESI mass analysis, probe L forms a 1:2 stoichiometry complex with an estimated association constant of 4.04 × 104 M- 2 with In3+ ions. Metal induces CHEQ (chelation-caused fluorescence quenching) to reduce the intensity of probe L's emission, and the estimated quenching constant was 4.52 × 104 M- 1. The limit of detection was found to be 5.93 nM; the time response of the sensor is instantaneous, and its reversible nature was confirmed using EDTA additions. Solid substrates (test strips) were designed and tested for fast, reliable, user-friendly, and real-time sensing of In3+ ions for on-site applications. The binding mechanism of probe L with In3+ ions was investigated using 1H NMR titration and DFT/TD-DFT studies.

Synthesis, Crystal Structure, DFT and Fluorescence Quenching Study of Novel syringe aldehyde-derived hydrazinyl-imidazole Based Schiff base Chemosensor.

In this study, we report a new syringe aldehyde-derived hydrazinyl-imidazole based fluorescent sensor (L) for sensitive detection of different inorganic quenchers (halide ions, bicarbonate ion, sulphide ion and transition metal ions). The chromophore (L) was obtained in good yield by the 1:1 condensation reaction of 2-hydrazino-4,5-dihydroimidazole hydrobromide and 4-hydroxy-3,5-dimethoxy benzaldehyde. L exhibited strong fluorescence in the visible region (around 380 nm) and its interaction with different quenchers was studied in details via fluorescence technique. For the halide ions series, its sensitivity is higher for NaF (Climit = 4 × 10- 4 M) than for NaCl while the fluorescence quenching occurred mainly through a dynamic process. Similar considerations were observed for HCO3- and S2- quencher too, when static and dynamic quenching take place simultaneously. Regarding transition metal ions, at a fixed ion concentration (4 × 10- 6 M), best performance was achieved for Cu2+ and Fe2+ (fluorescence intensity was reduced by 79% and 84.9% respectively), while for other metal ions, the sensor performance was evaluated and found to be very less (< 40%). Thus, minimum detection limits (10- 6 - 10- 5 M range) recommended the use of such derivatives as highly sensitive sensors capable to monitor delicate changes in varied environments.

Efficient Mercury Ion Detection in Water: CdTe/CdS/ZnS Quantum Dots as a Simple, Sensitive, and Rapid Fluorescence Sensor.

Mercury (Hg), a notorious heavy metal with detrimental impacts on human health and the environment, necessitates the development of precise measurement methods. This study introduces an expeditious and straightforward photochemical approach to synthesize thioglycolic acid (TGA)-stabilized CdTe/CdS/ZnS core/multi-shell quantum dots (QDs). The synthesized CdTe/CdS/ZnS QDs were comprehensively characterized using fluorescence spectroscopy, transmission electron microscopy (TEM), energy-dispersive X-ray spectroscopy (EDS), Field Emission Scanning Electron Microscopy (FESEM), and X-Ray diffraction (XRD). XRD and EDS results confirmed the successful formation of CdTe/CdS/ZnS structure. Also, FESEM and TEM results showed that CdTe/CdS/ZnS QDs were spherical. Results showed that synthesized Exhibiting vibrant green fluorescence and notable quenching in the presence of Hg2+ ions, these QDs emerge as promising candidates for fabricating a fluorescent sensor. The proposed sensor demonstrates notable sensitivity to Hg2+, featuring a detection limit of 16.32 nM and a linear range from 20 nM to 70 nM. The sensor's selectivity was confirmed by analyzing various anions and cations. Moreover, when tested with tap water, river water, and agricultural samples, the sensor exhibited reliable performance, validated by Inductively Coupled Plasma (ICP) analysis. Additionally, CdTe/CdS/ZnS QDs immobilized on micro pads proved effective for on-site water sample analysis, presenting a versatile solution for environmental monitoring.

Optical Chemosensor as a Sensitive and Selective Tool for the Detection of Thiocyanate Ions Via Cu2+ Induced Sensor and Its Practical Application.

In various fields, including analytical, environmental, and biochemistry, the detection of ions is significant. A simple probe, 3-(1-((4-aminophenyl)imino)ethyl)-4-hydroxy-6-methyl-2H-pyran-2-one (DPD), was designed for this study and used for the detection of Cu2+ ions in methanol, based on dehydroacetic acid and phenylenediamine moieties. Binding interactions studies were performed using UV-Vis measurements, which showed selective binding behaviour towards Cu2+ ions. The HRMS spectral data and Job's plot were used to check the stoichiometry ratio of 2:1 of a probe to Cu2+ ions. A detection limit of 1.38×10-7 M for Cu2+ ions was observed. Theoretical DFT calculations were used to determine the quantum parameters and the energy gap between frontier molecular orbitals. Interestingly, the DPD-Cu2+ complex acted as a probe for the detection of SCN- ions at a low LOD value, i.e., 1.97×10-7 M. A novel incidence of reversibility with SCN- ions was reported using the HRMS technique. Next, real water and blood samples were used, and the concentration of Cu2+ ions was calculated to further analyse the practical applicability of the probe. The DPD probe showed better selectivity and sensitivity than previously reported sensors, especially in complex matrices, where other sensors frequently experience interference and detection limit issues, indicating its potential as an advanced tool for ion detection in various applications.