Fast and easy detection of hypochlorite by a smartphone-based fluorescent turn-on probe: Applications to water samples, zebrafish and plant imaging.

We have developed a fluorescent probe DBT-Cl ((E)-2-(2-(4-(diphenylamino)benzylidene) hydrazinyl)-N,N,N-trimethyl-2-oxoethan-1-aminium chloride) for ClO- with an aggregation-induced emission (AIE) strategy depending on solvent polarity. DBT-Cl possessed a prominent solvatochromic emission property with intramolecular charge transfer (ICT) from the TPA (triphenylamine) to the amide group, which was studied by spectroscopic analysis and DFT calculations. These unique AIE properties of DBT-Cl led to the recognition of ClO- with high fluorescent selectivity. DBT-Cl quickly detected ClO- in less than 1 sec with a fluorescent color change from green to cyan. DBT-Cl had a low detection limit of 9.67 µM to ClO-. Detection mechanism of DBT-Cl toward ClO- was illustrated to be oxidative cleavage of DBT-Cl by 1H NMR titrations, ESI-mass, and DFT calculations. We established the viability for dependable detection of ClO- in actual water samples, as well as zebrafish and plant imaging. In particular, DBT-Cl was capable of easily monitoring ClO- through a smartphone application. Therefore, DBT-Cl assured a promising approach for a fast-responsive and multi-applicable ClO- probe in environmental and living organism systems.

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.

Selective visual staining of polyurethane microplastics by novel colorimetric and near-infrared (NIR) fluorescent dye: Application to environmental water and natural soil samples.

Microplastics can cause environmental pollution and ecosystem destruction as well as human health problems. Among the types of microplastics, polyurethane (PU) is particularly resistant to heat and difficult to decompose, causing disposal problems, and is evaluated as one of the most hazardous polymers. We present a novel colorimetric and near-infrared (NIR) fluorescence dye, (E)-N-(2-((4-(diphenylamino)benzylidene)amino)phenyl)- 7-nitrobenzo[c][1,2,5]oxadiazol-4-amine (DPNA), designed for selective visual PU microplastic staining. The intramolecular charge transfer (ICT) properties of DPNA are demonstrated through density functional theory (DFT) calculations along with solvatochromic shift. DPNA exhibits red color and red fluorescence emission, showing promising potential as a staining dye. To achieve selective PU microplastic staining, we establish an optimized experimental procedure with the staining dye DPNA by evaluating the staining efficiency under different staining solvent compositions and staining times. DPNA can distinguish PU by both red fluorescence signal and red coloration among different types of microplastics. In addition, DPNA well stain fresh PUs with diverse sizes and at various pH range of 5-9, and the aged PUs can also be dyed as effectively as the fresh PU. Most importantly, DPNA selectively stains PU among 11 types of microplastics and 5 types of natural particles in environmental water and soil with and without any pre-treatments. The adsorption mechanism of DPNA on PU microplastic is demonstrated through field emission scanning electron microscopes (FE-SEM), differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), X-ray photoelectron spectroscopy (XPS), and non-covalent interaction (NCI)-reduced density gradient (RDG) analyses, and proposed that intermolecular hydrogen bonding has a significant effect.

Smartphone-Based Quantitative Measurement of Cu2+: Fluorescent Turn-on Chemosensor via Radical Cation Formation.

We report a unique radical cation formation-based fluorescent chemosensor (E)-N'-(4-(diphenylamino)benzylidene)thiophene-2-carbohydrazide (DBTC) that quantitatively determines Cu2+ based on the RGB model using a smartphone. DBTC exhibited a weak turquoise fluorescence due to fluorescence suppression by amide isomerization. When Cu2+ was added into DBTC, it showed strong light blue fluorescence with a high quantum yield ([Formula: see text] = 0.470). The detection limit of Cu2+ was determined to be 0.40 µM at the concentration range of 0-7.5 µM. In addition, the detection mechanism of DBTC for Cu2+ was demonstrated to be an oxidative cyclization reaction through 1H NMR titration, ESI-MS analysis, and DFT calculation. Remarkably, DBTC could be applied to the quantitative measurement of Cu2+ using a smartphone and RGB analysis. The detection limit was calculated to be 0.05 µM, which is the lowest detection limit among chemosensors that could detect Cu2+ through smartphone-based fluorescence measurements. Additionally, spike and recovery experiments conducted with different concentrations of Cu2+ showed good recovery values. DBTC exhibited its potential as a chemosensor for determining Cu2+ through the application of a smartphone-based platform capable of real-time monitoring.

A Dual-target Fluorescent Chemosensor for Detecting Indium (III) and Hypochlorite with High Selectivity.

A dual-target fluorescent chemosensor BQC (((E)-N-benzhydryl-2-(quinolin-2-ylmethylene)hydrazine-1-carbothioamide) was synthesized for detecting In3+ and ClO-. BQC displayed green and blue fluorescence responses to In3+ and ClO- with low detection limits (0.83 µM for In3+ and 2.50 µM for ClO-), respectively. Importantly, BQC is the first fluorescent chemosensor capable of detecting In3+ and ClO-. The binding ratio between BQC and In3+ was determined to be a 2:1 through Job plot and ESI-MS analysis. BQC could be successfully utilized as a visible test kit to detect In3+. Meanwhile, BQC showed a selective turn-on response to ClO- even in the presence of anions or reactive oxygen species. The sensing mechanisms of BQC for In3+ and ClO- were demonstrated by 1 H NMR titration, ESI-MS and theoretical calculations.

A low-cost TICT-based staining agent for identification of microplastics: Theoretical studies and simple, cost-effective smartphone-based fluorescence microscope application.

A novel staining agent, (5-(4-(diethylamino)benzylidene)- 1,3-dimethylpyrimidine-2,4,6(1 H,3 H,5 H)-trione) (DDB) was developed for the effective detection of environmentally harmful microplastics. DDB has competitive cost advantages, namely its facile synthesis and high yield, over Nile Red (NR), which is commonly used for microplastic staining. The unique photophysical properties of DDB, including emissive twisted intramolecular charge transfer (TICT) and aggregation-induced emission (AIE), were corroborated via spectroscopic investigations and density functional theory (DFT) calculations. Notably, DDB demonstrated superior selectivity for staining microplastics (polyethylene (PE), polyurethane (PU), polypropylene (PP), polyvinyl chloride (PVC), polystyrene (PS), and polyethylene terephthalate (PET)) over non-plastic materials in water. Furthermore, modulation of the solvent environment during the staining process yielded distinct fluorescence in both the green and red channels for specific types of plastic with the interplay between locally excited (LE) and TICT states. Treatment with 5% ethanol results in the selective staining of PE and PET with the emission of red fluorescence, whereas treatment with 30% ethanol facilitates the selective staining of PU, PVC, and PET with the emission of green fluorescence. Additionally, DDB could selectively stain microplastics in spiked soil and river water samples. Furthermore, a smartphone-based fluorescence microscope was developed at a cost below $100, validating the effective detection of microplastics stained with the newly synthesized DDB. The outcomes of this research demonstrate the potential of DDB as an economical and efficient agent for selective microplastic detection.

Dual-channel fluorescence dye: Fluorescent color-dependent visual detection of microplastics and selective polyurethane.

In this study, we developed a dual-channel fluorescent dye ((E)-N'-(4-(diphenylamino)benzylidene)pyrazine-2-carbohydrazide) DPC for visual detection of 8 types of microplastics (MPs; HDPE, MDPE, LDPE, PET, PU, PVC, PS, and PP) and selective PU. The intramolecular charge transfer (ICT) and aggregation-induced emission (AIE) properties of DPC were demonstrated by the spectroscopic analysis, DFT calculations, and Tyndall effect. MPs and nonplastics (cellulose, chitin, sand, shell, and wood) were stained with DPC in water and their respective fluorescence signals in the blue and green channels were analyzed. The staining procedure using DPC was optimized with the concentration of DPC and staining time as parameters. DPC was able to effectively stain 8 types of MPs and only PU in blue and green fluorescence signals, respectively. Furthermore, false positive detections of DPC were minimized through additional ethanol treatment after staining. Moreover, the effects of temperature, pH, and salinity on the staining ability of DPC were investigated. Surprisingly, DPC was able to selectively detect PU through the green fluorescence signal even in a single environment where various MPs existed. Most importantly, DPC is the first fluorescent dye capable of selectively monitoring PU in the green channel as well as staining 8 types of MPs in the blue channel. DPC showed promising potential to be used for MP monitoring on real environmental samples.

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.

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.

An NBD-based fluorescent and colorimetric chemosensor for detecting S2-: Practical application to zebrafish and water samples.

A novel 7-nitro-1,2,3-benzoxadiazole (NBD)-based chemosensor BOP ((5-bromopyridin-2-yl)(4-(7-nitrobenzo[c][1,2,5]oxadiazol-4-yl)piperazin-1-yl)methanone) was synthesized. BOP could detect S2- through fluorescent quenching and colorimetric change. The detection limit was calculated to be 10.9 µM through fluorescence titration. The reaction mechanism of BOP towards S2- was estimated to be thiolysis of NBD amine, producing the cleavage products, NBD-S- and BP ((5-bromopyridin-2-yl)(piperazin-1-yl)methanone). The thiolysis was demonstrated by 1H NMR titrations, ESI-mass analysis and theoretical calculations. Importantly, BOP was able to successfully monitor S2- in zebrafish and water samples. Additionally, test strips coated with BOP were applied to the in-the-field measurements of S2-.

A new sensitive and selective detection of Ga3+ by thiophene-based 'turn-on' fluorescent chemosensor.

We designed a thiophene-based fluorescent chemosensor DHTC ((E)-2-([3,5-dichloro-2-hydroxybenzylidene]amino)thiophene-3-carboxamide) for detecting gallium (Ga3+ ). DHTC could probe Ga3+ using fluorescence enhancement. The limit of detection for Ga3+ by DHTC was 0.39 µM. The binding mode of DHTC to Ga3+ was determined as a 1:1 ratio from analysis by Job's plot and electrospray ionization-mass spectrometry (ESI-MS). In addition, DHTC could selectively detect Ga3+ using test kits. The sensing process of Ga3+ by DHTC was presented using ultraviolet-visible light titration, Job's plot, ESI-MS, 1 H nuclear magnetic resonance titration, and density functional theory calculation.

A benzothiazole-based fluorescent and colorimetric probe for the detection of ClO- and its application to zebrafish and water sample.

A benzothiazole-based fluorescent and colorimetric chemosensor BZD ((E)-2-(benzo[d]thiazol-2-yl)-5-((4-(diethylamino)-2-hydroxybenzylidene)amino)phenol) was applied for detecting ClO-. BZD showed fluorescence quenching and color variation for ClO- via oxidative reaction between ClO- and the imine bond. It could effectively detect ClO- over various competitive analytes. Detection limit for ClO- was calculated to be 1.74 µM by fluorescent method and 16.44 µM by colorimetric one, respectively. Additionally, BZD could be utilized for sensing ClO- in zebrafish, real water sample and paper strip. The photophysical characteristics and sensing mechanism of BZD to ClO- were studied by fluorescent and UV-visible spectroscopy, NMR titration, and ESI-mass spectrometry.

Highly Selective Detection of Al3+ by Carboxamide-Based Fluorescent Chemosensor.

We designed a carboxamide-based fluorescent chemosensor HTPQ ((E)-2-(((8-hydroxy-2,3,6,7-tetrahydro-1H,5H-pyrido[3,2,1-ij]quinolin-9-yl)methylene)amino)thiophene-3-carboxamide) for detecting Al3+. HTPQ could probe Al3+ by fluorescence enhancement. Limit of detection for Al3+ toward HTPQ was 1.4 µM. Binding of HTPQ to Al3+ was determined to be a 1:1 ratio with the analysis of Job plot and ESI-mass. In addition, HTPQ was able to detect Al3+ using the test strip by fluorescent variation. The sensing process of Al3+ by HTPQ was presented by UV-vis titration, ESI-MS, Job plot, 1H NMR titration and DFT calculation.

A chalcone-based fluorescent chemosensor for detecting Mg2+ and Cd2.

SBOD (sodium (E)-2-(3-[5-bromothiophen-2-yl]-3-oxoprop-1-en-1-yl)-4,6-dichlorophenolate) was designed and synthesized as a chalcone-based fluorescent turn-on chemosensor for Mg2+ and Cd2+ . SBOD selectively detected Mg2+ and Cd2+ through the increase in effective fluorescence. Detection limits of SBOD for Mg2+ and Cd2+ were calculated to be 3.8 µM and 2.9 µM, respectively. The binding modes of SBOD for Mg2+ and Cd2+ were determined to be 1:1 by ESI-MS and Job plot. Association mechanisms for SBOD to Mg2+ and Cd2+ were illustrated by ESI-MS, UV-vis, fluorescence spectroscopy, and calculations.

An Acylhydrazone-Based Fluorescent Sensor for Sequential Recognition of Al3+ and H2PO4.

A novel acylhydrazone-based fluorescent sensor NATB was designed and synthesized for consecutive sensing of Al3+ and H2PO4-. NATB displayed fluorometric sensing to Al3+ and could sequentially detect H2PO4- by fluorescence quenching. The limits of detection for Al3+ and H2PO4- were determined to be 0.83 and 1.7 µM, respectively. The binding ratios of NATB to Al3+ and NATB-Al3+ to H2PO4- were found to be 1:1. The sequential recognition of Al3+ and H2PO4- by NATB could be repeated consecutively. In addition, the practicality of NATB was confirmed with the application of test strips. The sensing mechanisms of Al3+ and H2PO4- by NATB were investigated through fluorescence and UV-Visible spectroscopy, Job plot, ESI-MS, 1H NMR titration, and DFT calculations.

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).

An Indole-Based Fluorescent Chemosensor for Detecting Zn2+ in Aqueous Media and Zebrafish.

An indole-based fluorescent chemosensor IH-Sal was synthesized to detect Zn2+. IH-Sal displayed a marked fluorescence increment with Zn2+. The detection limit (0.41 µM) of IH-Sal for Zn2+ was greatly below that suggested by the World Health Organization. IH-Sal can quantify Zn2+ in real water samples. More significantly, IH-Sal could determine and depict the presence of Zn2+ in zebrafish. The detecting mechanism of IH-Sal toward Zn2+ was illustrated by fluorescence and UV-visible spectroscopy, DFT calculations, 1H NMR titration and ESI mass.

A naphthyl thiourea-based effective chemosensor for fluorescence detection of Ag+ and Zn2.

A naphthyl thiourea-based effective chemosensor HNC, (E)-2-(2-hydroxy-3-methoxybenzylidene)-N-(naphthalen-1-yl)hydrazine-1-carbothioamide, was synthesized. HNC showed quick responses toward Ag+ and Zn2+ through marked fluorescence turn-on in different solvent conditions, respectively. Binding proportions of HNC to Ag+ and Zn2+ were found to be 2:1 and 1:1, respectively. Detection limits of HNC for Ag+ and Zn2+ were calculated as 3.82 and 0.21 µM. Binding processes of HNC for Ag+ and Zn2+ were represented using Job's plot, DFT, 1 H NMR titration, and ESI-MS.

A selective fluorescence sensor for hypochlorite used for the detection of hypochlorite in zebrafish.

Hypochlorite is used as a water disinfectant and it is also produced by biological organisms. Its detection and quantification is important and could lead to its mechanism of reactivity in cells. We have synthesized a new fluorescence sensor for hypochlorite based on bithiophene and furan-carbohydrazide. The sensor shows increased fluorescence as a function of hypochlorite and is selective for hypochlorite. Fluorescence enhancement due to hypochlorite is observed when the sensor is used in aqueous solutions at neutral pH values. Using the sensor, the detection limit for hypochlorite is 4.2 µM, making the sensor practical to determine hypochlorite in water. Applying the sensor to aide in the detection of hypochlorite in zebrafish, showed localization of ClO-/HClO in the air bladders and eyes of zebrafish.

A Benzothiazole-Based Fluorescence Turn-on Sensor for Copper(II).

A new benzothiazole-based chemosensor BTN (1-((Z)-(((E)-3-methylbenzo[d]thiazol-2(3H)-ylidene)hydrazono)methyl)naphthalen-2-ol) was synthesized for the detection of Cu2+. BTN could detect Cu2+ with "off-on" fluorescent response from colorless to yellow irrespective of presence of other cations. Limit of detection for Cu2+ was determined to be 3.3 µM. Binding ratio of BTN and Cu2+ turned out to be a 1:1 with the analysis of Job plot and ESI-MS. Sensing feature of Cu2+ by BTN was explained with theoretical calculations, which might be owing to internal charge transfer and chelation-enhanced fluorescence processes.