A dual-function fluorescence 'turn-on' probe that allows Zn (II) bioimaging and quantification of water in the organic solvent.

Herein, a Eugenol-derived fluorescence 'turn-on' probe FLHE was synthesized by condensing 2-((3-(trifluoromethyl)phenyl)amino)benzohydrazide with 5-allyl-2-hydroxy-3-methoxybenzaldehyde. FLHE demonstrated very low fluorescence in the studied organic solvents of varying polarities. However, upon titration with Zn2+ in HEPES buffer (pH = 7.4, 50% ACN, v/v), FLHE showed 40-fold higher fluorescence signals indicating the formation of the FLHE-Zn2+ complex. The fluorescence turn-on phenomenon upon FLHE-Zn2+ complex formation results from a chelation-enhanced fluorescence (CHEF) effect. The FLHE-Zn2+ complexation demonstrated a stokes shift of 156 nm (λex = 350 nm, λem = 506 nm) and an about 33-fold increase in the quantum yield (FLHE, Φ = 0.007; FLHE-Zn2+ complex, Φ = 0.23). The binding constant (Ka) determined by the Benesi-Hildebrand plot for interaction between FLHE and Zn2+ was 5.33 × 103 M-1. FLHE demonstrated a LOD of 31.8 nM for detecting Zn2+ in the environmental samples without interference from other cations and anions. FLHE-based paper strip (FLHE-PS) assay was developed to quantify the Zn2+ ions in water and the water content of organic solvent. FLHE-PS allows the detection of Zn2+ in aqueous solutions with a LOD of 63.2 nM and quantifying water in acetonitrile with a LOD of 0.14%. These results indicate that the FLHE has high applicability for detecting Zn2+ in living cells and environmental samples and detecting the presence of water in the organic solvents.

Exploration of Molecular Structure, DFT Calculations, and Antioxidant Activity of a Hydrazone Derivative.

The hydrazine derivatives are known to possess several biological activities including anticancer, antibacterial and anti-fungal, anticonvulsant, and antioxidant. This communication presents the synthesis, X-ray crystal structure analysis, DFT calculations, cell cytotoxicity, and antioxidant activity of the Schiff base 4,4'-((1E,1'E)-hydrazine-1,2-diylidenebis(ethan-1-yl-1-ylidene))bis(benzene-1,3-diol) (compound 2). We have also isolated the side product compound 1 and characterized it using single X-ray crystallography. The crystal structure of compound 1 depicts that the ensuing C-H···N hydrogen bonding interaction is presented and discussed herein. In addition, the calculations using density functional theory (DFT) approximation supported by experimental 1H and 13C NMR studies on the key compound 2 are reported. The results of theoretical and experimental 1H and 13C NMR were concordant. The antioxidant activity of compound 2 was determined by using 2,2'-azinobis(3-ethylbenzthiazoline-6-sulfonic acid) (ABTS•+) radical cation assays and 2,2-diphenyl-1-picrylhydrazyl (DPPH) radical assay. Compound 2 demonstrated excellent antioxidant activity in ABTS assay (IC50 = 4.30 ± 0.21 µM) and DPPH assay (IC50 = 81.06 ± 0.72 µM) with almost no cytotoxicity below 25 µM.

Elimination Reaction-Based Benzimidazole Probe for Cysteine Detection and Its Application in Serum Sample Analysis.

Benzimidazole-based compound 2-(p-tolyl)-1H-benzo[d]imidazole (3) and its derivative probe A-B have been synthesized for the highly selective detection and quantification of Cys in human serum. The photophysical properties of A-B and compound 3 were evaluated by UV-vis absorption and fluorescence spectroscopy. A-B showed high selectivity and sensitivity for Cys among tested analytes, including amino acids, anions, and cations. A-B selectively reacts with Cys and results in compound 3 with fluorescence turn-on effect. A-B did not show any interference from the components in the serum matrix for Cys detection in the human serum sample. A-B detects Cys in serum samples with 2.3-5.4-fold better LOD than reported methods. The detection limit of 86 nM and 43 nM in HEPES buffer using UV-visible and fluorescence spectroscopy, respectively, makes A-B an excellent chemosensor for Cys detection.

Exploration of highly selective fluorogenic 'on-off' chemosensor for H2 PO4 - ions: ICT-based sensing and ATPase activity profiling.

In this study, the recognition contour of Chemosensor 1 was investigated using semiaqueous methanol (XH , mole fraction = 0.31) for a range of anions and bioactive species. Host-receptor signalling based on the internal charge transfer mechanism for Chemosensor 1 was explored and reported. Structure of Chemosensor 1 and its plausible anion coordination based on hydrogen bonding is complemented with density functional theory. Consequently, we investigated the applicability of the synthesized probe in blood plasma, urine, tap water samples, and for monitoring of ATP in lysosomes by apyrase enzyme.

High Performance Fluorescent Turn-On Probe for Amitriptyline Based on Hybrid Nanoassembly of Organic-Inorganic Nanoparticles.

Fluorescence methods have gained enormous attention due to their ease in use, simplicity, selectivity and sensitivity. Fluorescent chemosensors respond instantly by converting molecular recognition to fluorescent signals. The consumption of pharmaceutical products by living beings is on great increase. The disposal of such compounds in the environment is a matter of great concern as these compounds enter aquatic environment and show accumulation in tissues of aquatic organisms. In the present study, we have utilized naphthalimide based receptors to fabricate organic nanoparticles (ONPs). These ONPs were used for the development of hybrid nanoassemblies, and the developed nanoassemblies were characterized with the help of transmission electron microscopy and dynamic light scattering studies. The photophysical studies were performed and the hybrid assembly developed using receptor 2 demonstrated a turn-on fluorescence emission behavior on binding with Amitriptyline. The present sensing system acted as promising candidate for determination of Amitriptyline among other contending drug molecules. The established system can recognize Amitriptyline up to a detection limit of 48 nM in aqueous medium. Electrochemical recognition studies show binding of hybrid nanoassembly of receptor 2 with Amitriptyline with limit of detection of 21 nM.

Chemosensors for biogenic amines and biothiols.

There is burgeoning interest among supramolecular chemists to develop novel molecular systems to detect biogenic amines and bio-thiols in aqueous and non-aqueous media due to their potential role in biological processes. Biogenic amines are biologically important targets because of their involvement in the energy metabolism of human biological systems and their requirement is met through food and nutrition. However, the increasing instances of serious health problems due to food toxicity have raised the quality of food nowadays. Biogenic amines have been frequently considered as the markers or primary quality parameters of foods like antioxidant properties, freshness and spoilage. For instance, these amines such as spermine, spermidine, cadavarine, etc. may originate during microbial decarboxylation of amino acids of fermented foods/beverages. These amines may also react with nitrite available in certain meat products and concomitantly produce carcinogenic nitrosamine compounds. On the other hand, it is also well established that biothiols, particularly, thiol amino acids, provide the basic characteristics to food including flavor, color and texture that determine its acceptability. For instance, the reduction of thiol groups produces hydrogen sulfide which reduces flavour as in rotten eggs and spoiled fish, and the presence of hydrogen sulfide in fish is indicative of spoilage. Thus, biogenic amines and bio-thiols have attracted the profound interest of researchers as analytical tools for their quantification. Much scientific and technological information is issued every year, where the establishment of precise interactions of biogenic amines and bio-thiols with other molecules is sought in aqueous and non-aqueous media. This review summarizes the optical chemosensors developed for the selective detection of biogenic amines and bio-thiols.

Fe(III) conjugated fluorescent organic nanoparticles for ratiometric detection of tyramine in aqueous medium: A novel method to determine food quality.

A tetrapodal receptor was synthesized and was processed into fluorescent organic nanoparticles (FONs) for determination of important analytes in aqueous medium. The receptor was fully characterized using characterization techniques. Recognition behavior of FONs towards different metal ions was investigated with fluorescence spectroscopy, amongst them Fe3+ ions showed quenching behavior in the emission spectra. The Fe3+ ion complex of FONs based sensor was further tested with different biogenic amines and ratiometric response was obtained for tyramine. Fluorescence emission profile of FONs. Fe3+ ion complex showed no change in the pH in wide range; thereby increasing their utility in biological and environmental samples. Tyramine detection was linearly proportional in response with the detection limit of 377 nM.

A novel terephthalaldehyde based turn-on fluorescent chemosensor for Cu2+ and its application in imaging of living cells.

A new terephthaldehyde-based chemosensor 1 bearing an aminophenol recognition unit has been synthesized and applied to the fluorescent sensing of metal ions. Molecular system 1 acts as a highly selective and sensitive fluorescence turn-on sensor for Cu2+. The sensing mechanism has been explored. It is proposed that Cu2+ binds with the imine and hydroxyl moiety of 1 in 1 : 2 binding stoichiometry, thereby enhancing the fluorescence at 386 nm. The detection limit and association constant (Ka) of 1 with Cu2+ were found to be 0.62 µM and 6.67 × 104 M-1, respectively. Chemosensor 1 has shown excellent specificity towards Cu2+ and has been successfully applied to the determination of Cu2+ in live L929 cells.

A new Schiff base as a turn-off fluorescent sensor for Cu2+ and its photophysical properties.

A new Schiff base receptor 1 was synthesized and its photophysical properties were investigated by absorption, emission and excitation techniques. Furthermore, its chromogenic and fluorogenic sensing abilities towards various metal ions were examined. Receptor 1 selectively detects Cu2+ ion through fluorescence quenching and detection was not inhibited in the presence of other metal ions. From fluorescence titration, the limit of detection of receptor 1 as a fluorescent 'turn-off' sensor for the analysis of Cu2+ was estimated to be 0.35 µM.

Highly selective optical and reversible dual-path chemosensor for cyanide detection and its application in live cells imaging.

A new biocompatible fluorescent receptor 1 was synthesized by conjugating diaminomaleonitrile (DMN) with benzothiazole unit, and characterized by single X-ray. In DMF/water (1:1, v/v), the receptor 1 showed a selectivity turn-on fluorescence at 517nm in the presence of CN-. Receptor 1 showed a detection limit down to 0.16µM without any interference from other tested anions. The reversibility and reusability of 1 for the detection of CN- ion was also tested for five cycles indicating the probe 1 could be used in a reversible manner. Importantly, the receptor 1 showed excellent cells viability and was successfully applied for the detection of CN- in live mouse fibroblast cells L929 cells.

Selective ciprofloxacin antibiotic detection by fluorescent siderophore pyoverdin.

Fluorescent siderophore pyoverdin (PVD) was produced from a soil isolate Pseudomonas monteilii strain MKP 213. The PVD was purified near to homogeneity and applied for the fluorescent chemosensing of various antibiotics in aqueous solution (pH=7.0). Upon addition of ciprofloxacin, PVD showed new UV-vis absorption bands at 252 and 321nm due to an internal charge transfer mechanism. Also, the addition of ciprofloxacin induced a highly selective fluorescence enhancement of PVD with a 13nm blue shift from 458 to 445nm. The combination of a long peptide chain along with the chromophore unit of PVD generates a converging cleft for ciprofloxacin recognition with LOD and LOQ of 7.13µM and 21.6µM, respectively without interference from other studied antibiotics. The association constant (Ka) of PVD with ciprofloxacin was calculated to be as low as 1.40×10(5)M(-1) using Benesi-Hildebrand plot depicting its significance in detection. The pharmaceutical tablet analysis measures the sensing with negligible matrix effect and quantitative recovery.

A novel zinc(II) and hydrogen sulphate selective fluorescent "turn-on" chemosensor based on isonicotiamide: INHIBIT type's logic gate and application in cancer cell imaging.

We have developed a novel isonicotiamide-based fluorescent "turn-on" chemosensor 1 for the selective detection of Zn(2+) and HSO4(-). The sensor 1 can detect Zn(2+) and HSO4(-) with a detection limit down to the nanomolar level by forming a complex in 1 : 1 stoichiometry in the presence of other anions and 2 : 1 in presence of cations in aqueous solution. Density functional theory calculations on 1 and the 1-Zn(2+)/HSO4(-) complexes are consistent with the experimental results. We have successfully utilized the above cation and anion for the fabrication of INHIBIT molecular logic gates. Furthermore the receptor 1 successfully detected the Zn(2+) and HSO4(-) ions in HeLa cells cultured in Zn(2+) and HSO4(-) enriched medium.

Acetate selective fluorescent turn-on sensors derived using vitamin B6 cofactor pyridoxal-5-phosphate.

Two new Schiff base receptors have been synthesized by condensation of pyridoxal-5-phosphate with 2-aminophenol (L(1)) or aniline (L(2)). In DMSO, the receptors showed both chromogenic and 'turn-on' fluorescence responses selectively in the presence of AcO(-) and F(-). However, in mixed DMSO-H2O medium, the receptors showed AcO(-) selective 'turn-on' fluorescence without any interference from other tested anions including F(-). The detection limit for AcO(-) was found to be 7.37 µM and 22.9 µM using the receptors L(1) and L(2), respectively.

Fluorescence Chemosensor for HSO4 (-) Ion Based on Pyrrole-Substituted Salicylimine Zn (2+) Complex: Nanomolar Detection.

A novel pyrrole-substituted salicylimine zinc (II) ion complex has been synthesized and evaluated its anion binding affinity. The probe 4 has high selectivity for HSO4 (-) over other anions in CH3OH:H2O (70:30, v/v) solvent system. The emission intensity of 4 was quenched upon addition of HSO4 (-). The probe 4 is highly selective for HSO4 (-) with a detection limit of 40 nm. Photoinduced electron transfer (PET) is responsible for observed change. The binding affinity of 4 for HSO4 (-) was further authenticated through ratiometric change in absorbance profile.

Virgin silver nanoparticles as colorimetric nanoprobe for simultaneous detection of iodide and bromide ion in aqueous medium.

A simple colorimetric nanoprobe based on virgin silver nanoparticles (AgNPs) was developed for the selective detection of iodide and bromide ions via aggregation and anti-aggregation mechanism. With addition of I(-) ions, virgin AgNPs, in presence of Fe(3+), showed perceptible color change from yellow to colorless along with disappearance of surface plasmon resonance (SPR) band of AgNPs at 400 nm. But in presence of Cr(3+), AgNPs turned yellow upon addition of I(-)and Br(-) anions. The developed virgin AgNPs probe showed high specificity and selectivity with the detection limits down to 0.32 µM and 1.32 µM for I(-) ions via two different mechanistic routes. Also, the designed probe detects Br(-) with a detection limit down to 1.67 µM.

A chemosensor showing discriminating fluorescent response for highly selective and nanomolar detection of Cu²âº and Zn²âº and its application in molecular logic gate.

A fluorescent based receptor (4Z)-4-(4-diethylamino)-2-hydroxybenzylidene amino)-1,2dihydro-1,5-dimethyl-2-phenylpyrazol-3-one (receptor 3) was developed for the highly selective and sensitive detection of Cu(2+) and Zn(2+) in semi-aqueous system. The fluorescence of receptor 3 was enhanced and quenched, respectively, with the addition of Zn(2+) and Cu(2+) ions over other surveyed cations. The receptor formed host-guest complexes in 1:1 stoichiometry with the detection limit of 5 nM and 15 nM for Cu(2+) and Zn(2+) ions, respectively. Further, we have effectively utilized the two metal ions (Cu(2+) and Zn(2+)) as chemical inputs for the manufacture of INHIBIT type logic gate at molecular level using the fluorescence responses of receptor 3 at 450 nm.

Pyrrole-coupled salicylimine-based fluorescence "turn on" probe for highly selective recognition of Zn²âº ions in mixed aqueous media: Application in living cell imaging.

Cation sensing behaviour of a pyrrole-based derivative (2-hydroxyl 3 methyl 6 isopropyl benzaldehyde}-3,4-dimethyl-1H-pyrrole-2-carbohydrazide (receptor 3) has been explored and is found to be selective towards Zn(2+) over a variety of tested cations. The receptor 3 has shown high selectivity and sensitivity towards Zn(2+) over the other alkali, alkaline earth and transition metal ions. In the presence of Zn(2+), absorption band of receptor 3 has shown the red shift. The sensing behaviour has been suggested to continue via enhancement process which has further been supported by UV-vis absorption and theoretical density functional theory (DFT) calculations indicating the formation of a 1:1 complex between the pyrrole based receptor 3 and Zn(2+). The present work is presenting a highly selective dual channel colorimetric sensor for zinc with great sensitivity. The developed sensor was successfully applied to image intracellular Zn(2+) in living cells.

A novel phthalazine based highly selective chromogenic and fluorogenic chemosensor for Co(2+) in semi-aqueous medium: application in cancer cell imaging.

A new phthalazine based chemosensor was developed for the highly selective and sensitive detection of Co(2+) in the mixed solvent system, CH3CN-H2O (1 : 1, v/v). In the presence of Co(2+), the colour of the solution changed from yellow to green; the absorption maxima of was red-shifted from 383 nm to 435 nm, and the fluorescence of at 550 nm was significantly enhanced. The sensor showed a detection limit down to 25 nM by forming a complex species with Co(2+) in 1 : 1 stoichiometry. Furthermore, by means of confocal laser scanning microscopy experiments, it has demonstrated that it can be used as a fluorescent probe for monitoring Co(2+) in living cells.

A highly selective fluorescent 'turn-on' chemosensor for Zn(2+) based on a benzothiazole conjugate: their applicability in live cell imaging and use of the resultant complex as a secondary sensor of CN(-).

A benzothiazole derivative linked "off-on" multi-responsive and selective chemosensor has been synthesized and evaluated for cation recognition properties. The receptor shows a high sensitivity and selectivity for Zn(2+) through a 'turn-on' fluorescence response over the other tested cations with a detection limit as low as 0.67 µM. The receptor was successfully applied for the detection of Zn(2+) in live HeLa cells. Then, the Zn(2+) complex of receptor was also used for cyanide detection and recognition.

Fluorogenic ratiometric dipodal optode containing imine-amide linkages: exploiting subtle thorium (IV) ion sensing.

The (13E,19E)-N1',N3'-bis[4-(diethylamino)-2-hydroxybenzylidene]malonohydrazide (L) has been developed for the detection of Th(4+) ions using dual channel signalling system. The UV-vis absorbance and fluorescence spectroscopic data revealed the formation of L-Th(4+) complex in 1:1 equilibrium. The density functional theory (DFT) also confirms the optimum binding cavity for the recognition of metal ion. The binding constant computed from different mathematical models for an assembly of L-Th(4+). The detection limit of L for Th(4+) recognition is to a concentration down to 0.1 µM (0.023 µg g(-1)). The present sensing system is also successfully applied for the detection of Th(4+) ion present in soil near nuclear atomic plants.