A Fluorescent and Colorimetric Chemosensor Detecting Pd2+ Based on Chalcone Structure with Triphenylamine.

A fluorometric and colorimetric chemosensor DiPP ((E)-3-(4-(diphenylamino)phenyl)-1-(pyridin-2-yl)prop-2-en-1-one) based on chalcone structure with a triphenylamine group was synthesized. Sensor DiPP detected Pd2+ with fluorescence turn-off and via colorimetry variation of yellow to purple. The binding ratio of DiPP to Pd2+ turned out to be 1 : 1. Detection limits for Pd2+ by DiPP were analyzed to be 0.67 µM and 0.80 µM through the fluorescent and colorimetric methods. Additionally, the fluorescent and colorimetric test strips were applied for probing Pd2+ and displayed that DiPP could obviously discriminate Pd2+ from other metals. The binding feature of DiPP to Pd2+ was presented by ESI-mass, Job plot, NMR titration, ESI-mass, and DFT calculations.

A colorimetric/ratiometric chemosensor based on an aggregation-induced emission strategy for tracing hypochlorite in vitro and in vivo.

Excessive levels of hypochlorite (ClO-) negatively affect environmental and biological systems. Thus, it is essential to develop sensors that can identify ClO- in various systems such as the environment and living organisms. In this study, we report the development and evaluation of a novel aggregation-induced emission (AIE) strategy-based colorimetric and ratiometric fluorescent chemosensor 2,2'-(((1E,1'E)-[2,2'-bithiophene]- 5,5'-diylbis(methanylylidene))bis(hydrazin-1-yl-2-ylidene))bis(N,N,N-trimethyl-2-oxoethan-1-aminium) chloride (BMH-2∙Cl) for detecting ClO-. BMH-2∙Cl enabled highly selective ClO- detection through a color change from yellow to colorless and a fluorescence color change from turquoise to blue in a perfect aqueous solution. BMH-2∙Cl exhibited low limits of detection (2.4 ×10-6 M for colorimetry and 2.9 ×10-7 M for ratiometric fluorescence) for detecting ClO- with a rapid response within 5 s. The detection mechanism for ClO- and an AIE property change of BMH-2∙Cl were demonstrated by 1H NMR titration, ESI-MS, variation of water fraction (fw) and theoretical calculations. In particular, we confirmed not only the practicality of BMH-2∙Cl by using test strips, but also demonstrated the potential for efficient ClO- detection in biological and environmental systems such as real water samples, living zebrafish and bean sprouts.

Colorimetric Chemosensor for Cu2+ and Fe3+ Based on a meso-Triphenylamine-BODIPY Derivative.

Optical chemosensors are a practical tool for the detection and quantification of important analytes in biological and environmental fields, such as Cu2+ and Fe3+. To the best of our knowledge, a BODIPY derivative capable of detecting Cu2+ and Fe3+ simultaneously through a colorimetric response has not yet been described in the literature. In this work, a meso-triphenylamine-BODIPY derivative is reported for the highly selective detection of Cu2+ and Fe3+. In the preliminary chemosensing study, this compound showed a significant color change from yellow to blue-green in the presence of Cu2+ and Fe3+. With only one equivalent of cation, a change in the absorption band of the compound and the appearance of a new band around 700 nm were observed. Furthermore, only 10 equivalents of Cu2+/Fe3+ were needed to reach the absorption plateau in the UV-visible titrations. Compound 1 showed excellent sensitivity toward Cu2+ and Fe3+ detection, with LODs of 0.63 µM and 1.06 µM, respectively. The binding constant calculation indicated a strong complexation between compound 1 and Cu2+/Fe3+ ions. The 1H and 19F NMR titrations showed that an increasing concentration of cations induced a broadening and shifting of the aromatic region peaks, as well as the disappearance of the original fluorine peaks of the BODIPY core, which suggests that the ligand-metal (1:2) interaction may occur through the triphenylamino group and the BODIPY core.

Dabcyl as a Naked Eye Colorimetric Chemosensor for Palladium Detection in Aqueous Medium.

Industrial activity has raised significant concerns regarding the widespread pollution caused by metal ions, contaminating ecosystems and causing adverse effects on human health. Therefore, the development of sensors for selective and sensitive detection of these analytes is extremely important. In this regard, an azo dye, Dabcyl 2, was synthesised and investigated for sensing metal ions with environmental and industrial relevance. The cation binding character of 2 was evaluated by colour changes as seen by the naked eye, UV-Vis and 1H NMR titrations in aqueous mixtures of SDS (0.02 M, pH 6) solution with acetonitrile (99:1, v/v). Out of the several cations tested, chemosensor 2 had a selective response for Pd2+, Sn2+ and Fe3+, showing a remarkable colour change visible to the naked eye and large bathochromic shifts in the UV-Vis spectrum of 2. This compound was very sensitive for Pd2+, Sn2+ and Fe3+, with a detection limit as low as 5.4 × 10-8 M, 1.3 × 10-7 M and 5.2 × 10-8 M, respectively. Moreover, comparative studies revealed that chemosensor 2 had high selectivity towards Pd2+ even in the presence of other metal ions in SDS aqueous mixtures.

A novel design of multiple ligands for ultrasensitive colorimetric chemosensor of glutathione in plasma sample.

In this study, we developed a novel colorimetric chemosensor for selective and sensitive recognition of Glutathione (GSH) using a simple binary mixture of commercially accessible and inexpensive metal receptors with names, Bromo Pyrogallol Red (BPR) and Xylenol Orange (XO). This procedure is based on the synergistic coordination of BPR and XO with cerium ion (Ce3+) for the recognition of GSH over other available competitive amino acids (AAs) especially thiol species in aqueous media. Generally, cysteine (Cys) and homocysteine (hCys) can seriously interfere with the detection of GSH among common biological species because they possess similar chemical behavior. Using all the information from 1HNMR and FT-IR studies, the proposed interaction is presented in which GSH acts as a tri-dentate ligand with three N donor atoms in conjunction with BPR and XO as mono and bi-dentate ligands respectively. This approach opens a path for selective detection of other AAs by argumentatively selecting the ensemble of mixed organic ligands from commercially available reagents, thereby eliminating the need for developing synthetic receptors, sample preparation, organic solvent mixtures, and expensive equipment. Evaluating the feasibility of the existing method was led to the determination of GSH in human plasma samples.

A New Reversible Colorimetric Chemosensor Based on Julolidine Moiety for Detecting F.

We synthesized an original reversible colorimetric chemosensor PDJ ((E)-9-((2-(6-chloropyridazin-3-yl)hydrazono)methyl)-2,3,6,7-tetrahydro-1H,5H-pyrido[3,2,1-ij]quinolin-8-ol) for the detection of F-. PDJ displayed a selective colorimetric detection to F- with a variation of color from colorless to yellow. Limit of detection of PDJ for F- was calculated as 12.1 µM. The binding mode of PDJ and F- turned out to be a 1:1 ratio using Job plot. Sensing process of F- by PDJ was demonstrated by 1H NMR titration and DFT calculation studies that suggested hydrogen bond interactions followed by deprotonation. Moreover, the practicality of PDJ was demonstrated via a reversible test with TFA (trifluoroacetic acid).

A dual-channel 'turn-on' fluorescent chemosensor for high selectivity and sensitivity detection of CN¯ based on a coumarin-Schiff base derivative in an aqueous system.

Novel strategies still need to be proposed that can be used to identify and detect toxic environmental pollutants. In this paper, two channels of colorimetry and fluorescence 'turn-on' fluorescent probe 1 (7-hydroxy-8-[(2-hydroxy-phenylimino)- methyl]-4-methylbenzopyran-2-one) for the simple yet highly selective detection of CN¯ have been successfully designed and synthesized. Crystal features of probe 1 were defined using X-ray single crystal diffractometry. Probe 1 showed a strongly colorimetric and fluorescence response to CN¯ that induced obvious naked-eye colour changes in aqueous solution (DMSO/H2 O, 3:1 v:v). In addition, probe 1 for CN¯ detection displayed low detection limits of 3.91 × 10-8 M, which were significantly lower than the 1.9 × 10-6 M maximum level specified by the World Health Organization (WHO) for potable water. The sensing mechanism for probe 1 was attributed to the deprotonation process as shown by 1 H NMR titration. Moreover, based on the visible colorimetry and fluorescence change for probe 1 to CN¯, measurement was performed for simulated water samples containing CN¯. This study provides a broad prospect for solving other pollution problems and promoting the design of new fluorescent materials.

Dye/metal ion-based chemosensing ensemble towards l-histidine and l-lysine determination in water via different optical responses.

In this study, a novel simple type of label-free, ultra-sensitive, and highly selective UV-Vis absorption and naked-eye detection of histidine (His) and lysine (Lys) using a dye/metal ion ensemble is developed. The outcoming high sensitivity and selectivity for histidine and lysine were attained by changing the metal ions. The indicator is released due to its displacement from the murexide (Mure)/Cu2+ complex by histidine and the change in absorbance may be due to the further complexation of lysine with the additional coordination sites present in the zinc atom of Mure/Zn2+ complex. The label-free chemosensor provided sensitive and selective detection of l-histidine and l-lysine with detection limits of 9.1 and 9.4 nmol L-1, respectively. The protocol especially offers high selectivity for the determination of His and Lys among amino acids found in human urine samples. Furthermore, INHIBIT and NAND molecular logic gates were obtained using chemical inputs and UV-Vis absorbance signal output.

Detection of Copper(II) in Water by Methylene Blue Derivatives.

Two novel phenothiazin-5-ium derivatives bearing cyclam moieties (3 a+ and 3 b+ ) were synthesized and investigated as Cu2+ sensors. Both ligands show intense spectral changes in the presence of Cu2+ in aqueous solutions. The high molar extinction coefficient of the chromophore allows both naked eye detection and spectrophotometric quantitative determination of the cation at a micromolar-concentration scale. 3 a+ was found to outperform 3 b+ , showing negligible spectral changes in the presence of excesses of other metal cations.

Colorimetric Chemosensor and Turn on Fluorescence Probe for pH Monitoring Based on Xanthene Dye Derivatives and its Bioimaging of Living Escherichia coli Bacteria.

A new turn on fluorescence probe based on 3',6'-dihydroxy-6-methyl-2-((pyridin-2-ylmethylene)amino)-4-(p-tolyl)spiro[benzo[f]isoindole-1,9'-xanthen]-3(2H)-one (BFFPH) derived from benzo[f]fluorescein was prepared. Full characterization of the prepared probe using spectroscopic analysis was described such as IR, NMR and MS spectra. The sensitivity of BFFPH for monitoring of pH change in alkaline medium was studied. BFFPH exhibited a high sensitivity to alkaline pH by two pKa values at 8.82 and 10.66 in UV/vis spectroscopy titration. The pH monitoring was studied in broad range of pH values (2.5-12.2) at two pKa values at 8.72 and 10.73 by recording the effect of pH on the fluorescence intensity of BFFPH. The acid-base reversibility character of the probe was investigated as well as the effect of the pH change on the fluorescence quantum yield. The application of the prepared BFFPH probe for detection of living Escherichia coli (E. coli) bacteria using confocal fluorescence microscope was investigated.

A Rhodamine Derivative Based Chemosensor with High Selectivity and Quick Respond to Cr3+ in Aqueous Solution.

In this paper, a new kind of colorimetric chemsensor aiming at detecting Cr3+ has been synthesized, and it is based on the "Off-On" effect of a rhodamine derivative. Comparing with other metal irons (Na+, K+, Ni2+, Hg2+, Fe3+, Mn2+, Co2+, Cd2+, Cu2+, Pb2+, Zn2+, Mg2+, Ba2+, Ag+, Fe2+, Ce3+), the chemsensor has a quick and accurate response to Cr3+ in H2O-EtOH solution (4/1, v/v). There is an obvious change in color, from colorless to bright pink when Cr3+ is detected. According to the fitting curve based on Benesi-Hildebrand equation and working curve of absorption strength in UV-vis spectrum, the binding pattern of Cr3+ and the rhodamine derivative follows a 1:1 stoichiometry. The chemsensor shows great potential in monitoring Cr3+ in the aqueous medium with high efficiency, which is supposed to complete the recognition in the minimum as 5.2 × 10-7 mol/L within 5 min.

Development of a New Colorimetric Chemosensor for Selective Determination of Urinary and Vegetable Oxalate Concentration Through an Indicator Displacement Assay (IDA) in Aqueous Media.

The paper proposes a method that exhibits operational simplicity for the indirect spectrophotometric determination of oxalate ion. We developed Reactive Blue 4 (RB4) as a sensor by complexation with copper ion as a simple, inexpensive yet selective colorimetric chemosensing ensemble for the recognition of oxalate over other available competitive analytes via indicator displacement assay (IDA) in both solution (aqueous medium) and solid state (paper-based experiment). The addition of oxalate to RB4-Cu2+ complex changed the colour from sky blue to dark blue due to the regeneration of RB4 by the chelation of oxalate as the competitive analyte with Cu2+. The absorbance band increase is linear with oxalate concentration from 1.76 to 49.4 µmol/L with a detection limit of 0.62 µmol/L. This measurement mode did not show any influence of interferences (available anions and ascorbic acid). This approach eliminated the need for the separation stages, enzymatic multiple-step reactions, sample preparation, organic solvent mixture, chemical modifications and equipment developed to a high degree of complexity. The oxalate determination gave results in different real samples such as urine, mushroom and spinach, which demonstrated the applicability of the existing method. Furthermore, this colorimetric system can serve as IMPLICATION molecular logic gate using Cu2+ and oxalate (C2O4 2-) as inputs and UV-Vis absorbance signal as the output with potential monitoring applications.

Synthesis and crystal structure of a highly selective colorimetric and fluorometric sensor for hydrogen sulfide.

A novel Cu(II) complex chemosensor for hydrogen sulfide with azo as the colorimetric group has been synthesized. The complex and ligand crystals were obtained and the molecular structures were characterized by X-ray diffraction and Electrospray ionization High resolution mass spectrometer (ESI-HRMS). The photophysical and recognition properties were examined. The complex can recognize S2- , with an obvious color change from yellow to red based on a copper ion complex displacement mechanism. By contrast, no obvious changes were observed in the presence of other anions (AcO- , H2 PO4- , F- , Cl- , Br- and I- ). We present a simple, easily prepared, yet efficient, inorganic reaction-based sensor for the detection of S2- . The complex should have many chemical and analytical applications in the sensing of hydrogen sulfide.

A Fluorescent Sensor for Al(III) and Colorimetric Sensor for Fe(III) and Fe(II) Based on a Novel 8-Hydroxyquinoline Derivative.

A novel 8-hydroxyquinoline-based fluorescent and colorimetric chemosensor was designed, synthesized and fully characterized. The sensor showed high selectivity and sensitivity toward Al(3+) over other tested cations in EtOH/H2O (1:99, v/v) medium. The increase in fluorescence intensity was linearly proportional to the concentration of Al(3+) with a detection limit of 7.38 × 10(-6) M. Moreover, the sensor exhibited an obvious color change from yellow to black in the presence of Fe(2+) and Fe(3+) in EtOH/THF (99:1, v/v) solution. The absorbance changes showed a linear response to iron ions with the detection limits of 4.24 × 10(-7) M and 5.60 × 10(-7) M for Fe(2+) and Fe(3+), respectively. Thus, this chemosensor provides a novel approach for selectively recognition of Al(3+), Fe(3+) and Fe(2+) among environmentally relevant metal ions.

A water-soluble colorimetric chemosensor for sequential probing of Cu2+ and S2- and its practical applications to test strips, reversible test, and water samples.

A water-soluble colorimetric chemosensor NHOP ((E)-1-(2-(2-(2-hydroxy-5-nitrobenzylidene)hydrazineyl)-2-oxoethyl)pyridin-1-ium) chloride) was developed for the sequential probing of Cu2+ and S2-. NHOP underwent a color change from pale yellow to colorless in the presence of Cu2+ in pure water. The binding ratio between NHOP and Cu2+ was confirmed to be 1:1 by the Job plot and ESI-MS (electrospray ionization mass spectrometry). The detection limit of NHOP for Cu2+ was calculated as 0.15 µM, which was far below the EPA (Environmental Protection Agency) standard (20 µM). The NHOP-coated test strip was able to easily monitor Cu2+ in real-time. Meanwhile, the NHOP-Cu2+ complex reverted from colorless to pale yellow in the presence of S2- through the demetallation. The stoichiometric ratio between NHOP-Cu2+ and S2- was determined to be 1:1 by analyzing the Job plot and ESI-MS. The detection limit of NHOP-Cu2+ for S2- was calculated as 0.29 µM, which was very below the WHO (World Health Organization) guideline (14.7 µM). NHOP successfully achieved the quantification for Cu2+ and S2- in water samples. NHOP could work as a sequential probe for Cu2+ and S2- at the biological pH range (7.0-8.4). Moreover, NHOP could successively probe Cu2+ and S2- at least three cycles because of its reversible property. The detection mechanisms of NHOP for Cu2+ and NHOP-Cu2+ for S2- were demonstrated with Job plot, ESI-MS, and DFT (density functional theory) calculations. Therefore, NHOP could work as an efficient sequential probe for Cu2+ and S2- in environmental systems.

Colorimetric and fluorometric bimodal amine chemosensor based on deprotonation-induced intramolecular charge transfer: Application to food spoilage detection.

Amine derivatives are signature organic compounds generated from rotten protein food. Thus, sensitive detection of the presence of amines in protein foods can be a critical technique for monitoring their quality. In this study, we develop an organic chemosensor probe, 4-(2-(3-(dicyanomethylene)- 5,5-dimethylcyclohex-1-en-1-yl)vinyl)-N,N-diethylbenzenaminium chloride (DEAH), to effectively detect amines through discernible bimodal (colorimetric and fluorometric) changes. By exploiting the amine-triggered intramolecular charge transfer behavior, DEAH exhibits rapid color changes (<1 s) with an excellent detection limit (36.9 nM) and also fluorescence turn-on in response to amine gas. Moreover, it possesses detection capabilities in versatile conditions, including solutions, solids, and coated films, suggesting its practical applicability. In particular, DEAH shows dramatic color change from yellow to violet with exceptional color difference (△Eab) over 98, repeatable usability, and excellent selectivity to amines. Based on these compelling advantages, we successfully demonstrate real-time monitoring of amine gas generated from spoiled protein foods using DEAH-coated films.

Highly selective and sensitive colorimetric chemosensor using PVA/chitosan ion-imprinted nanofibers for copper ion detection and removal.

Herein, a highly efficient colorimetric chemosensor incorporating ion-imprinted electrospun nanofiber was developed for the removal and detection of Cu2+ ions. In this regard, PVA/chitosan composites were used as the polymeric matrix, and 1-(2-pyridylazo)-2-naphthol was employed for complex formation. The prepared naked-eye sensor was characterized using Fourier transform infrared spectroscopy, energy-dispersive X-ray spectroscopy, scanning electron microscopy, atomic force microscopy, differential scanning calorimetry, thermogravimetric analysis, and X-ray diffraction analysis, revealing the morphological, structural, and molecular properties of the sensor. The results showed that the colorimetric chemosensor based on copper-imprinted nanofiber (Cu-INF) possesses higher selectivity for Cu2+ compared to interference ions. The selectivity coefficient (k) and relative selectivity coefficient (K') indicated the selective behavior of Cu-INF in the adsorption of Cu2+ in binary systems including Cu2+/Co2+, Cu2+/Ni2+, and Cu2+/Zn2+. Furthermore, the ion-imprinted nanofiber was used for the preconcentration of copper ions, demonstrating a high adsorption capacity of 128.205 mg g-1 for Cu2+. The equilibrium adsorption isotherm and adsorption kinetics of Cu2+ on Cu-INF followed the Freundlich adsorption isotherm and a pseudo-second-order model, respectively. The developed sensor exhibited a linear detection range of 5 × 10-8 - 2 × 10-7 M with a limit of detection (LOD) of 1.07 × 10-8 M for copper ions. The results indicated satisfactory adsorption and successful detection of Cu2+ at trace concentrations.

Facile and rapid determination of oxalic acid by fading spectrophotometry based on Fe(III)-sulfosalicylate as colorimetric chemosensor.

Spectrophotometry is an economic and rapid method for detecting oxalic acid (OA), while the reported methods have some drawbacks, such as narrow linear range, long response time, delicate operation and required expensive reagents. Herein, we found that the as-synthesized Fe(III)-sulfosalicylate (FeSSA) could be used as an efficient colorimetric chemosensor to detect OA, and the established FeSSA-based fading spectrophotometry showed prominent advantages over the existing ones in detecting OA. The as-established method has wider linear range of 0.80-160 mg/L with regression coefficient ≥ 0.999, while the widest linear range is just 2.7-54 mg/L among the reported ones. Moreover, the method has low limit of detection (0.74 mg/L), extremely fast response (several seconds), satisfactory selectivity, high accuracy and precision. Most importantly, its reliability was further verified by employing it to determine OA concentration during the degradation process of organic pollutants. The measured OA concentration at any time interval was perfectly consistent with those determined by the well-recognized high performance liquid chromatography (HPLC). These confirmed that the FeSSA-based fading spectrophotometry is an efficient, simple, fast, accurate and economic method to determine OA in a wide concentration range.

Colorimetric chemosensors for the selective detection of arsenite over arsenate anions in aqueous medium: Application in environmental water samples and DFT studies.

Novel organic receptors N3R1- N3R3 were developed for the selective colorimetric recognition of arsenite ions in the organo-aqueous media. In the 50% aq. acetonitrile media and 70% aq. DMSO media, receptors N3R2 and N3R3 showed specific sensitivity and selectivity towards arsenite anions over arsenate anions. Receptor N3R1 showed discriminating recognition of arsenite in the 40% aq. DMSO medium. All three receptors formed a 1:1 complex with arsenite and stable for a pH range of 6-12. The receptors N3R2 and N3R3 achieved a detection limit of 0.008 ppm (8 ppb) and 0.0246 ppm, respectively, for arsenite. Initial hydrogen bonding on binding with the arsenite followed by the deprotonation mechanism was well supported by the UV-Vis titration, 1H- NMR titration, electrochemical studies, and the DFT studies. Colorimetric test strips were fabricated using N3R1- N3R3 for the on-site detection of arsenite anion. The receptors are also employed for sensing arsenite ions in various environmental water samples with high accuracy.

Colorimetric Chemosensor Based on Fe3O4 Magnetic Molecularly Imprinted Nanoparticles for Highly Selective and Sensitive Detection of Norfloxacin in Milk.

Long-term use of norfloxacin (NOR) will cause NOR residues in foods and harm human bodies. The determination of NOR residues is important for guaranteeing food safety. In this study, a simple, selective, and label-free colorimetric chemosensor for in situ NOR detection was developed based on Fe3O4 magnetic molecularly imprinted nanoparticles (Fe3O4 MMIP NPs). The Fe3O4 MMIP NPs showed good peroxidase-like catalytic activity to 3,3',5,5'-tetramethylbenzidine (TMB) and selective adsorption ability to NOR. The colorimetric chemosensor was constructed based on the Fe3O4 MMIP NPs-H2O2-TMB reaction system. The absorbance differences were proportional to the concentrations of NOR in the range of 10-300 ng/mL with a limit of detection at 9 ng/mL. The colorimetric chemosensor was successfully applied to detect NOR residue in milk. The recovery range was 78.2-95.81%, with a relative standard deviation of 2.1-9.88%. Together, the proposed colorimetric chemosensor provides a reliable strategy for the detection of NOR residues in foods.