Dual-channel fluorescent probe for discriminative detection of H2S and N2H4: Exploring sensing mechanism and real-time applications.

A highly efficient system incorporates the real-time visualization of the two toxic molecules (H2S and N2H4) and the recognition of corresponding transforms using a fluorescent sensor. In this paper, a dual-responsive probe (QS-DNP) based on methylquinolinium-salicyaldehyde-2,4-dinitrophenyl was developed that can simultaneously detect H2S and N2H4 at two independent fluorescent channels without signal crosstalk. QS-DNP showed excellent anti-interference, high selectivity, outstanding water solubility, low LOD values (H2S: 51 nM; N2H4: 40 nM), low cytotoxicity, and mitochondrial localization properties. The 2,4-dinitrophenyl site was sensitive to H2S, and the CC bridge was reactive to N2H4, with strong fluorescence at 680 and 488 nm, respectively. The wavelength gap between these two channels is 192 nm; verify that there is no signal crosstalk throughout detection. By this means, the probe was used to simultaneously detect H2S and N2H4 in real soil samples, food samples, and living cells. The endogenous H2S and N2H4 were monitored in HeLa cells and investigated the mitochondria organelle of living cells with a positive charge on QS-DNP. Overall, all results emphasize that the QS-DNP probe is a powerful tool for the simultaneous detection of H2S and N2H4 and presents a potential new sensing approach.

A new recognition moiety diphenylborinate in the detection of pyruvate via Lewis acid/base sensing pathway and its bioimaging applications.

Developing new reaction based recognizing units can enhance the specificity of target analyte molecules in practical applications of real samples and biosystems. Therefore, introducing a recognizing moiety diphenylborinate was encountered for the detection of pyruvate biomolecule through Lewis acid-base reaction based sensing strategy. The construction of the Schiff-base back bone between quinoline and N-(diethylamino)salicylaldehyde-diphenylborinate (QSB) were expressed the red shift from blue emission of quinoline in to green as that of dative bond developed between Schiff base nitrogen and boron atoms. The new sensing approach was involved such a way that fluorophore QSB is a Lewis acid while pyruvate acts as Lewis base, where the elimination of Lewis pair produced a weak green fluorescence including the formation of quinoline, N-(diethylamino)salicylaldehyde (QS). The switching products were witnessed through 1H NMR titration, HR-MS and FT-IR studies. The good selectivity and interference ability were achieved in presence of 1000-fold excess of possible interferences with LOD of 16 nM. Moreover, the tracking ability of the probe was employed towards pyruvate in live HeLa cell imaging for evaluating an exogenous and endogenous signals producing ability and its mitochondria targeting property was investigated successfully. Further, the practical utility of the probe was tested with milk samples and obtained good recovery results.

Prostate cancer biomarker citrate detection using triaminoguanidinium carbon dots, its applications in live cells and human urine samples.

Citrate is a tricarboxylate, plays vital role in prostate cancer (PC) and the level of citrate is an indicator for PC identification. Herein, triaminoguanidine carbon dots (TAG-CDs) prepared by one step hydrothermal method and used as a citrate receptor. Notably the TAG-CDs without alkaline treatment were highly fluorescent at pH 7 with high quantum yield (11.3%). TAG-CDs were characterized through TEM, XRD, FT-IR, UV-vis and spectrofluorimetry. It is noted that the average size was of 2.8 nm, the presence of highly disordered carbon, retain the functionality of TAG. The absorbance maxima obtained at 294 nm and good emitting response observed at 396 nm. The Y-aromaticity of receptor guanidinium moiety acts as Lewis acid and have peculiar interaction with Lewis base citrate via electrostatic interaction and also protons in the TAG participate hydrogen bonds with citrate, which causes quenching of TAG-CDs. From the obtained linear quenching equation the LOD was found to be 4 nM. The probe expressed high selectivity, high interference tolerance (500 - fold), fast response in 15 mins and good biocompatible. Finally, TAG-CDs utilized for the intracellular imaging of citrate in live MCF-7 cells, it showed good cytotoxicity and delivered contrast images in presence, absence of citrate. TAG-CDs detected the citrate level in human urine samples, the obtained results are validated with HPLC method.

Quantitative Hg2+ detection via forming three coordination complexes using a lysosome targeting quinoline - Fisher aldehyde fluorophore.

This work describes (Z)-N-((Z)-2-(1,3,3-trimethylindolin-2ylidene)ethylidene)quinoline-8-amine (LYSO-QF), a high-performing and biocompatible dye comprised of quinoline and Fisher aldehyde moieties linked via an imine vinyl backbone with lysosome targeting ability that can be used to quantitatively detect the mercury ion (Hg2+) in biosystems and the natural environment. This is achieved by forming three different tetrameric, trimeric and dimeric complexes between Hg2+ and LYSO-QF with the limit of detection (LOD) of 11 nm. The complexes formed were analyzed with the aid of time-dependent density functional theory (TD-DFT) calculations. The concentration dependence of the Hg2+ complex fluorescence emission changes from grey-green to jade green and then to red as the different types of complex are formed. The favorable sensor properties of the LYSO-QF probe are demonstrated by monitoring different Hg2+ concentrations in buffer solutions, HeLa cells, zebrafish model samples and several different types of water sample. Experiments with Whatman paper strips demonstrate that the cost-effective LYSO-QF also has considerable potential for use in on-site Hg2+ detection with the naked eye.

Tetraphenylethene-based fluorescent probe with aggregation-induced emission behavior for Hg2+ detection and its application.

A tetraphenylethene (TPE) derivative was designed and synthesized upon conjugation with bis(thiophen-2-ylmethyl) amine (BTA) containing a mercury-binding moiety and further characterized by using Nuclear magnetic resonance (NMR), LC-MS, UV-Vis, and fluorescence spectroscopic methods. The resulting TPE-BTA exhibited comprehensive aggregation-induced emission while expressing a high quantum yield and emission intensity at 70% water fraction. The probe exhibited a good photochromic effect with a Stokes shift of 178 nm, and the emission intensity at 550 nm increased considerably with the color turning from dark green to bright green under a UV lamp upon the addition of 5 µM Hg2+. The lowest-energy conformation of the probe showed that two thiophene rings were perpendicular to the phenyl ring, while two BTA molecules were situated in a staggered form to each other. The sulfur and nitrogen atoms present in TPE-BTA were coordinated to the Hg2+ ion, and these binding sites were confirmed by the NMR parameters, X-ray photoelectron spectroscopy signals, and structural calculations. The binding of Hg2+ to TPE-BTA was believed to restrict the intramolecular motion of TPE-BTA, thus inducing it to shine brighter according to the unique aggregation-induced emission effect. The concentration of Hg2+ was determined based on the enhancement of the emission intensity, and the present probe showed an extremely high sensitivity with a limit of detection of 10.5 nM. Furthermore, TPE-BTA enabled selective detection of Hg2+ even in the presence of a 1000-fold excess of other interfering metal ions. The proposed method was successfully employed to determine Hg2+ in living HeLa cells and real water samples.

Successive Detection of Zinc Ion and Citrate Using a Schiff Base Chemosensor for Enhanced Prostate Cancer Diagnosis in Biosystems.

Sensitive and quantitative detection of prostate cancer (PC) requires a chemosensor with an applicable sensing strategy. A star-shaped Schiff base triaminoguanidine-integrated thiophene fluorophore TAT was rationally designed with nitrogen and sulfur atoms to coordinate with Zn2+ as the initial step and to chelate with citrate as the following step. Formation of the complex TAT-Zn2+ induced an intramolecular charge transfer and caused a red-shifted, Zn2+ concentration-dependent fluorescence at 507 nm. Chelation of TAT-Zn2+ with citrate led to an emission band at 692 nm upon an aggregation-induced emission mechanism. The distinctive fluorescence emissions of Zn2+ and citrate biomarkers were demonstrated first in on-site paper-based test strips showing gradually enhanced colors at yellow and red channels and second in both in vitro and in vivo by using PC3 cells and BALB/c nude mouse animal models, respectively. The in vitro test confirmed the mitochondria organelle-targeting property of TAT, and the in vivo performance manifested the successful application of the probe in recognizing the prostate cancer. This is the first applicable chemosensor that could be in continuous recognition of dual PC biomarkers Zn2+ and citrate in cancer diagnosis with a mitochondria organelle-targeting ability.

An azido coumarin-quinoline conjugated fluorogenic dye: Utilizing amide-iminol tautomerism for H2S detection in live MCF-7 cells.

Detection of H2S to analyze some diseases in living lives demands fast response, high selectivity and biocompatibility. Here we designed an azide containing coumarin attached with 8-aminoquinoline via amide backbone (ACAQ) fluorophore as the H2S sensing probe. Excellent response time of 6 min, high sensitivity with the limit of detection (LOD) of 14.6 nM and high selectivity with other possible interferences are revealed for ACAQ after characterized by spectroscopy, 1H NMR titration and LC-MS measurements. The sensing strategy is explained by amide-iminol tautomerism and azide reduction. In addition, the successful visualization measurement suggests the practicability of the probe ACAQ for H2S detection in live samples.

Rapid-Response and Highly Sensitive Boronate Derivative-Based Fluorescence Probe for Detecting H2O2 in Living Cells.

Intracellular H2O2 monitoring is important and has driven researchers to pursue advancements for the rapid identification of H2O2, since H2O2 is short-lived in cell lines. An arylboronate derivative has been investigated as a chemospecific fluorescence recognition agent for H2O2. Triphenylimidazoleoxadiazolephenyl (TPIOP) boronate was contrived as a novel candidate for the rapid and sensitive recognition of H2O2. The probe was conjugated using the TPIOP functional group acting as an excellent fluorescent enhancer. The TPIOP group stimulated the polarization of C-B bond due to its extended π-conjugation, which included heteroatoms, and induced the production of rapid signal because of the highly polar C-B bond along with the corresponding boronate unit. While H2O2 reacts with TPIOP boronate, its nucleophilic addition to the boron generates a charged tetrahedral boronate complex, and then the C-B bond migrates toward one of the electrophilic peroxide oxygen atoms. The resulting boronate ester is then hydrolyzed by water into a phenol, which significantly enhances fluorescence through aggregation-induced emission. The TPIOP boronate probe responded to H2O2 rapidly, within 2 min, and exhibited high sensitivity with a limit of detection of 8 nM and a 1000-fold selectivity in the presence of other reactive oxygen species. Therefore, the developed TPIOP boronate chemodosimeter was successfully utilized to visualize and quantify intracellular H2O2 from human breast cancer (MCF-7) cells, as well as gaseous and aqueous H2O2 from environmental samples using Whatman paper strips coated with TPIOP boronate.

On-off-on relay fluorescence recognition of ferric and fluoride ions based on indicator displacement in living cells.

A new boronic acid derivative functionalized with a 4-(3-(4-(4,5-diphenyl-1H-imidazole-2-yl)phenyl)-1,2,4-oxadiazol-5-yl)phenyl (IOP) moiety was synthesized for use as a sequential "on-off-on"-type relay fluorescence probe for Fe3+ ions and F- ions with high selectivity and sensitivity under physiological conditions. The introduction of Fe3+ to IOP boronic acid (IOPBA) formed an Fe3+IOPBA complex, which led to quenching of the blue fluorescence intensity at 458 nm. The lowest-energy conformation of IOPBA was theoretically predicted to adopt an extended structure, and the Fe3+ ion in the Fe3+IOPBA complex was coordinated to two phenyl groups to form a π-complex. Upon addition of F- to the Fe3+IOPBA complex, the original fluorescence was recovered due to formation of [FeF6]3‒, resulting in "on-off-on"-type sensor behavior. IOPBA showed high selectivity towards Fe3+ among other cations. Moreover, the Fe3+IOPBA complex showed specific selectivity towards F-, with other cations and anions not interfering with detection. Both sensing processes showed 1:1 stoichiometry with binding constants of 6.87 × 106 and 4.49 × 106 mol-1 L for Fe3+ with IOPBA and F- with Fe3+IOPBA, respectively. The limits of detection for Fe3+ and F- were 10 and 1 nM, respectively. The proposed method was successfully applied in real water samples. Furthermore, the probe had low cytotoxicity and was successfully used as a bioimaging reagent to detect intracellular Fe3+ and F- in living HeLa cells.