Search Results (53)

Rationally designing and synthesizing chemosensors capable of simultaneously detecting both anions and cations via water content modulation is challenging. In this study, we synthesized and characterized a novel triazine calixarene derivative-based iodide and copper ion-selective fluorescent “turn-off” sensor. This dual-channeled fluorescent probe is able to recognize Cu²⁺ and I⁻ ions simultaneously in aqueous systems. The fluorescent sensor s4 was synthesized by displacement reaction of acridine with 1, 3-bis (dichloro-mono-triazinoxy) benzene in acetonitrile. Mass spectrometry (MS), UV-vis, and fluorescence spectra were acquired to characterize the fluorescence response of s4 to different cations and anions, while infrared (IR) spectroscopy and isothermal titration calorimetry (ITC) were employed to study the underlying selectivity mechanism of s4 to Cu²⁺ and I⁻. In detail, s4 displayed extremely high sensitivity to Cu²⁺ with over 80% fluorescence decrement caused by the paramagnetic nature of Cu²⁺ in the aqueous media. The reversible fluorescence response to Cu²⁺ and the responses to Cu²⁺ in the solution of other potential interferent cations, such as Li⁺, Na⁺, K⁺, Ca²⁺, Cd²⁺, Zn²⁺, Sr²⁺, Ni²⁺, Co²⁺ were also investigated. Probe s4 also exhibited very good fluorescence selectivity to iodide ions under various anion (F⁻, Cl⁻, Br⁻, NO₃⁻, HSO₄⁻, ClO₄⁻, PF₆⁻, AcO⁻, H₂PO₄⁻) interferences. In addition to the fluorescent response to I⁻, s4 showed a highly selective naked-eye-detectable color change from colorless to yellow with the other tested anions. Full article

A primary challenge in the further development of anion sensors in real water samples of environmental concern is the need for highly water-soluble compounds that are able to detect low concentrations of analytes. Small-molecule sensors can mitigate solubility constraints and highly aromatic or conjugated systems may provide a new way to recognize target analytes with high sensitivity and/or selectivity. Organic aggregates that have the ability to form large frameworks can exhibit aggregated-induced emissions to detect target analytes, and their coagulation can provide enhanced detection via colorimetric or fluorescent measurements. This review aims to draw attention to the emerging area of small-molecule organic chemosensors that utilize aggregation to detect environmentally detrimental anions in an aqueous solution. A number of mechanisms of interaction for anion recognition are recognized and discussed here, including electrostatic interactions, covalent bond formation, hydrophobic interactions, and even complexation. Full article

2-(2′-aminophenyl)benzothiazole is a readily tunable fluorescent core with widespread applications in coordination chemistry, sensing, light-emitting processes, medicinal chemistry, and catalysis. This review provides an overview of the synthetic methodologies to access 2-(2′-aminophenyl)benzothiazole and its organic derivatives, including various phosphorous and silane pincer ligands. The luminescent properties will be discussed, with a special focus on ESIPT and AIE processes. The coordination of transition metals and lanthanides is presented, as well as their influence on biological and light-emitting properties. 2-(2′-aminophenyl)benzothiazole derivatives have also been employed as sensors for a range of cations and anions due to their various binding modes, as well as for bioimaging purposes. Recently, the first application in photocatalysis has emerged, showing one of the many openings for these organic building blocks in the future. Full article

Fluorescent materials for sensing have gained attention for the visual detection of different substances as metals and pesticides for environmental monitoring. This work presents fluorescent nanocomposites in solution, film, and paper obtained without capping and stabilizing agents, coming from quantum dots of cadmium sulfide (CdS QDs) and anionic–cationic polymer matrices. Fluorescent films were formed by casting and fluorescent paper by impregnation from the solutions. The optical properties of CdS QDs in solution showed absorption between 418 and 430 nm and a maximum emission at 460 nm. TEM analysis evidenced particle size between 3 and 6 nm and diffraction patterns characteristic of CdS nanocrystals. Infrared spectra evidenced changes in the wavenumber in the fluorescent films. The band gap values (2.95–2.82 eV) suggested an application for visible transmitting film. Fluorescent solutions by UV-vis and fluorescence evidenced a chemical interaction with glyphosate standard between 1 and 100 µg/mL concentrations. The analysis of red, green, and blue color codes (RGB) evidenced a color response of the fluorescent paper at 10 and 100 µg/mL, but the fluorescent films did not show change. Nanocomposites of chitosan and pectin, in solution and on paper, exhibited a behavior “turn-on” sensor, while carboxymethylcellulose had a “turn-off” sensor. This methodology presents three fluorescent materials with potential applications in visual sensing. Full article

A Dy(III) coordination polymer (CP), [Dy(spasds)(H₂O)₂]_n (1) (Na₂Hspasds = 5-(4-sulfophenylazo)salicylic disodium salt), has been synthesized using a hydrothermal method and characterized. 1 features a 2D layered structure, where the spasda³⁻ anions act as pentadentate ligands, adopting carboxylate, sulfonate and phenolate groups to bridge with four Dy centers in η₃-μ¹: μ², η₂-μ¹: μ¹, and monodentate coordination modes, respectively. It possesses a unique (4,4)-connected net with a Schläfli symbol of {4⁴·6²}{4}₂. The luminescence study revealed that 1 exhibited a broad fluorescent emission band at 392 nm. Moreover, the visual blue color has been confirmed by the CIE plot. 1 can serve as a dual-functional luminescent sensor toward Fe³⁺ and MnO₄⁻ through the luminescence quenching effect, with limits of detection (LODs) of 9.30 × 10⁻⁷ and 1.19 × 10⁻⁶ M, respectively. The LODs are relatively low in comparison with those of the reported CP-based sensors for Fe³⁺ and MnO₄⁻. In addition, 1 also has high selectivity and remarkable anti-interference ability, as well as good recyclability for at least five cycles. Furthermore, the potential application of the sensor for the detection of Fe³⁺ and MnO₄⁻ was studied through simulated wastewater samples with different concentrations. The possible sensing mechanisms were investigated using Ultraviolet-Visible (UV-Vis) absorption spectroscopy and density functional theory (DFT) calculations. The results revealed that the luminescence turn-off effects toward Fe³⁺ and MnO₄⁻ were caused by competitive absorption and photoinduced electron transfer (PET), and competitive absorption and inner filter effect (IFE), respectively. Full article

BTDs (2,1,3-benzothiadiazoles) are fluorescent heterocycles widely used in different applications, including biomarkers, sensing optical devices, OLEDs, organic transistors, and solar cells. This review mainly focuses on the current progress in the design of compounds derived from the BTD core, aiming for their use as chromogenic and/or fluorogenic devices for detecting anionic, cationic, and neutral analytes. Reactions and synthetic strategies that show the synthetic versatility of BTDs are initially presented, to provide a better understanding regarding the assembly of optical detection systems. The photophysical mechanisms of the detection are also described. A discussion is also presented on the target analytes for which the optical detection devices based on BTD were planned. The examples discussed here will offer the sensors community perspectives for developing new optical detection devices based on BTD for different types of analytes of importance for the most diverse areas of knowledge. Full article

The solvothermal synthesis of LnCl₃^.nH₂O with terephthalic acid (benzene-1,4-dicarboxylic acid, H₂BDC) produced metal–organic frameworks (LnBDC), [Ln₂(BDC)₃(H₂O)₄]_∞, where Ln = Sm, Eu, Tb, and Dy. The materials obtained were characterized by a number of physico-chemical techniques. The influence of the ionic radius of the lanthanides on the microstructural characteristics of the Ln-MOFs was evaluated by performing Rietveld refinement. The MOFs obtained were tested as fluorescent sensors for numerous cations and anions in water. The highly luminescent EuBDC and TbBDC demonstrated multi-responsive luminescence sensing functions to detect Ag(I), Fe(III), Cr(III), and Cr(VI), which are essential for their environmental applications. By applying the non-linear Stern–Volmer equation, the fluorescent quenching mechanism was determined. The stability of the obtained materials in water in a wide pH range (acidity pH = 4 and alkalinity pH = 9 solutions) was confirmed. Full article

Hydrazine, a highly toxic compound, demands sensitive and selective detection methods. Building upon our previous studies with pre-coumarin OFF–ON sensors for fluoride anions, we extended our strategy to hydrazine sensing by adapting phenol protecting groups (propionate, levulinate, and γ-bromobutanoate) to our pre-coumarin scaffold. These probes reacted with hydrazine, yielding a fluorescent signal with low micromolar limits of detection. Mechanistic studies revealed that hydrazine deprotection may be outperformed by a retro-Knoevenagel reaction, where hydrazine acts as a nucleophile and a base yielding a fluorescent diimide compound (6,6′-((1E,1′E)-hydrazine-1,2diylidenebis(methaneylylidene))bis(3(diethylamino)phenol, 7). Additionally, our pre-coumarins unexpectedly reacted with primary amines, generating a fluorescent signal corresponding to phenol deprotection followed by cyclization and coumarin formation. The potential of compound 3 as a theranostic Turn-On coumarin precursor was also explored. We propose that its reaction with ALDOA produced a γ-lactam, blocking the catalytic nucleophilic amine in the enzyme’s binding site. The cleavage of the ester group in compound 3 induced the formation of fluorescent coumarin 4. This fluorescent signal was proportional to ALDOA concentration, demonstrating the potential of compound 3 for future theranostic studies in vivo. Full article

Electrospray ionization mass spectrometry (ESI-MS) analysis is frequently associated with noncovalent adduct formation, both in positive and negative modes. Anion binding and sensing by mass spectrometry, notably more challenging compared to cation binding, will have major research potential with the development of appropriate sensors. Here, we demonstrated identification of stable bisquaternary dication adducts with trifluoroacetate (TFA⁻), Cl⁻ and HSO₄⁻ in positive-mode ESI-MS analysis. The observed adducts were stable in MS/MS mode, leading to the formation of characteristic fragment ions containing a covalently bound anion, which requires bond reorganization. This phenomenon was confirmed by computational methods. Furthermore, given that anion detection and anion sensor chemistry have gained significant prominence in chemistry, we conducted an analysis of the fluorescent properties of bisquaternary ammonium compound as a potential anion sensor. Full article

Quantum dots (QDs) have captured the attention of the scientific community due to their unique optical and electronic properties, leading to extensive research for different applications. They have also been employed as sensors for ionic species owing to their sensing properties. Detecting anionic species in an aqueous medium is a challenge because the polar nature of water weakens the interactions between sensors and ions. The anions bicarbonate (HCO₃⁻), carbonate (CO₃²⁻), sulfate (SO₄²⁻), and bisulfate (HSO₄⁻) play a crucial role in various physiological, environmental, and industrial processes, influencing the regulation of biological fluids, ocean acidification, and corrosion processes. Therefore, it is necessary to develop approaches capable of detecting these anions with high sensitivity. This study utilized CdTe QDs stabilized with cysteamine (CdTe-CYA) as a fluorescent sensor for these anions. The QDs exhibited favorable optical properties and high photostability. The results revealed a gradual increase in the QDs’ emission intensity with successive anion additions, indicating the sensitivity of CdTe-CYA to the anions. The sensor also exhibited selectivity toward the target ions, with good limits of detection (LODs) and quantification (LOQs). Thus, CdTe-CYA QDs show potential as fluorescent sensors for monitoring the target anions in water sources. Full article

Fluorescent film sensors are ideal for the real-time outdoor detection of heavy metal ions of Fe³⁺, but they are limited because of their low sensitivity and long response time due to their special structure. In this work, we constructed a fluorescent hydrogel for the specific detection of Fe³⁺, utilizing poly(9-fluorenecarboxylic acid) (PFCA) as the sensing moiety and sodium alginate (SA) as the cross-linking substrate, which exhibited a rapid and selective recognition of Fe³⁺ among a panel of 16 anions and 21 cations. It can sense Fe³⁺ at 0.1 nM immediately owing to the porous network structure of the PFCA-SA film that provided enhanced ion transport channels and active sites, and the “molecular line effect” of polymer PFCA. Moreover, we successfully applied this platform to detect Fe³⁺ in four different vegetable samples. This work provides an innovative and effective strategy for fabricating green and sustainable fluorescent sensors. Full article

GABA, the primary inhibitory neurotransmitter, stimulates GABAA receptors (GABAARs) to increase the chloride conductance of the cytosolic membrane. The driving forces for membrane chloride currents are determined by the local differences between intracellular and extracellular chloride concentrations (Cli and Clo, respectively). While several strategies exist for the measurement of Cli, the field lacks tools for non-invasive measurement of Clo. We present the design and development of a fluorescent lifetime imaging (FLIM)-compatible small molecule, N(4-aminobutyl)phenanthridiunium (ABP) with the brightness, spectral features, sensitivity to chloride, and selectivity versus other anions to serve as a useful probe of Clo. ABP can be conjugated to dextran to ensure extracellular compartmentalization, and a second chloride-insensitive counter-label can be added for ratiometric imaging. We validate the utility of this novel sensor series in two sensor concentration-independent modes: FLIM or ratiometric intensity-based imaging. Full article

In the past decades, porous coordination polymers (PCPs) based fluorescent (FL) sensors have received intense attention due to their promising applications. In this work, a soluble Zn-PCP is presented as a sensitive probe towards explosive molecules, chromate, and dichromate ions. In former reports, PCP sensors were usually ground into fine powders and then dispersed in solvents to form FL emulsion for sensing applications. However, their insoluble characters would cause the sensing accuracy which is prone to interference from environmental effects. While in this work, the as-made PCP could be directly soluble in organic solvents to form a clear solution with bright blue emission, representing the first soluble PCP based fluorescence sensor to probe explosive molecules under a homogeneous environment. Moreover, the FL PCP solution also shows sensitive detection behaviors towards the toxic anions of CrO₄²⁻ and Cr₂O₇²⁻, which exhibit a good linear relationship between the fluorescence intensity of Zn-PCP and the concentrations of both analytes. This work provides a reference for designing task-specific PCP sensors utilized under a homogeneous environment. Full article

Conjugated polymers (CPs) are an intriguing material with which to build fluorescent Cr₂O₇²⁻ sensors with excellent sensitivity, but they often lack specific recognition groups. In this study, several typical amino acids with N and O atom-identifying groups were incorporated into fluorene, and then six polyfluorene derivatives were synthesized using electrochemical polymerization. Compared to other cations and anions, all of these amino acid-functionalized polyfluorenes have good selectivity towards Cr₂O₇²⁻ and enable ultra-trace responses with detection thresholds at pM or even fM level. Full article

The peculiarities of the optical properties of 2-aryl-1,2,3-triazole acids and their sodium salts were investigated in different solvents (1,4-dioxane, dimethyl sulfoxide DMSO, methanol MeOH) and in mixtures with water. The results were discussed in terms of the molecular structure formed by inter- and intramolecular noncovalent interactions (NCIs) and their ability to ionize in anions. Theoretical calculations using the Time-Dependent Density Functional Theory (TDDFT) were carried out in different solvents to support the results. In polar and nonpolar solvents (DMSO, 1,4-dioxane), fluorescence was provided by strong neutral associates. Protic MeOH can weaken the acid molecules’ association, forming other fluorescent species. The fluorescent species in water exhibited similar optical characteristics to those of triazole salts; therefore, their anionic character can be assumed. Experimental ¹H and ¹³C-NMR spectra were compared to their corresponding calculated spectra using the Gauge-Independent Atomic Orbital (GIAO) method and several relationships were established. All these findings showed that the obtained photophysical properties of the 2-aryl-1,2,3-triazole acids noticeably depend on the environment and, therefore, are good candidates as sensors for the identification of analytes with labile protons. Full article