Highly specific and sensitive chromo-fluorogenic detection of sarin, tabun, and mustard gas stimulants: a multianalyte recognition approach.

Nerve agents are the most notorious substances, which can be fatal to an individual because they block the activity of acetylcholinesterase. Fighting against unpredictable terrorist assaults and wars requires the simple and quick detection of chemical warfare agent vapor. In the present contribution, we have introduced a rhodamine-based chemosensor, BDHA, for the detection of nerve gas-mimicking agents diethylchlorophosphate (DCP) and diethylcyanophosphonate (DCNP) and mustard gas-mimicking agent 2-chloroethyl ethyl sulfide (CEES), both in the liquid and vapor phase. Probe BDHA provides the ability for detection by the naked eye in terms of colorimetric and fluorometric changes. It has been revealed that the interaction between nerve agents mimics and probe BDHA facilitates spirolactam ring opening due to the phosphorylation process. Thus, the highly fluorescent and colored species developed while probe BDHA is colorless and non-fluorescent due to the intramolecular spirolactam ring. Moreover, probe BDHA can effectively recognize DCP, DCNP, and CEES in the µM range despite many toxic analytes and could be identified based on the response times and quantum yield values. Inexpensive, easily carried paper strips-based test kits were developed for the quick, on-location solid and vapor phase detection of these mustard gas imitating agents (CEES) and nerve gas mimicking agents (DCP and DCNP) without needing expensive equipment or skilled personnel. More remarkably, the test strips' color and fluorescence can be rapidly restored, exposing them to triethyl amine (TEA) for cyclic use, suggesting a potential application in the real-time identification of chemical warfare agents. To accomplish the on-location application of BDHA, we have experimented with soil samples to find traces of DCP. Therefore, the chromo-fluorogenic probe BDHA is a promising, instantaneous, and on-the-spot monitoring tool for the selective detection of DCP, DCNP, and CEES in the presence of others.

A Chromogenic Probe for Detection of Biologically Important Anions and its Implications for Designing Molecular Logic Gates.

Detection of fluoride (F-), acetate (AcO-), and cyanide (CN-) anions is vital from the biological and environmental aspects. In the present contributions, we have introduced a simple Salen-type chromogenic sensor, BEN, to detect these biologically important anions. Changes in UV-visible absorption spectra and color of BEN solution from very pale yellow to pink color are similar for each of these anions and found to be reversible only in the case of F- ions in attendance of HSO4- ions. The estimated limit of detection of BEN solution for detecting F-, AcO-, and CN- anions is found to be below the micromolar (µM) concentration level. Our fabricated handy paper test kit is suitable for qualitatively naked-eye detection of the anions. An immediate quantitative estimation of these important anions is possible using our BEN employing a smartphone, avoiding any costly experimental setup.

A Phenanthroimidazole-Based Luminophore for Selective and Specific Identification of Sarin Simulant, Diethylchlorophosphate.

The simplicity of synthesis, significant toxicity of organophosphorus-containing nerve agents, and ease of use of their in-terrorism attacks highlight the necessity to create efficient probes and precise methods for detecting these chemicals. This study developed luminogenic probe 4-(1 H-phenanthrene imidazole-2-yl) benzaldehyde, PB for selectively recognizing lethal chemical sarin mimicking diethylchlorophosphate (DCP) with µM detection limit. Following the addition of DCP to the PB solution, the fluorescence changed from bluish-cyan to green simultaneously; after the insertion of triethylamine (TEA) into the PB-DCP phosphorylated solution, the fluorescence of the original one came back, and it occurred five times. A paper strip-based test kit and dip-stick experiments have been executed to demonstrate the practical applicability of our sensor PB and instant, on-site recognition of the target analyte DCP. An experiment has been investigated using a smartphone and red-green-blue (RGB) color analysis, which offers a novel way for the fast, on-site visual detection and quantification of DCP in actual samples. It also reduces equipment costs, speeds up detection times, and substantially simplifies the operation procedure.

A Julolidine Coupled Azine-based Reversible Chromo-fluorogenic Probe for Specific Detection of Cu2+ Ions.

Among the various essential trace elements for living organisms, the copper (Cu2+) ions are the most important. However, Cu2+ ions are vital for the human body and are associated with necessary physiological processes; insufficient or excessiveness has many hazardous effects on our bodies. In the present contribution, strategically, we have introduced a julolidine-coupled azine-based, 9,9'-((1E,1'E)-hydrazine-1,2-diylidene bis(methanylylidene)) bis(1,2,3,5,6,7-hexahydropyrido [3,2,1-ij] quinolin-8-ol) (HDBQ) reversible chromo-fluorogenic probe for specific detection of Cu2+ ions. Probe HDBQ exhibits observable orange colorimetric change from yellow, which is visible to the naked eye in daylight. The highly green fluorescence HDBQ becomes a non-fluorescent one with the incorporation of Cu2+ ions. Interestingly, the colorimetric change and non-fluorescent HDBQ-Cu2+ complex reverse to the original HDBQ in the presence of ethylenediamine tetraacetic acid (EDTA). The detection and quantification limit of HDBQ towards the detection of Cu2+ ions is found to be in the µM range, which is much lower than the limit (31.5 µM) recommended by WHO. We have also performed a colorimetric and fluorometric paper-based test strips-based experiment employing HDBQ for real-time on-site detection of Cu2+ ions. Using the reversibility characteristics of HDBQ for the consecutive addition of Cu2+ and EDTA, we have established the INHIBIT molecular logic gate. The present report brings a precise and sensitive probe for the detection of Cu2+ ions in real environmental and biological samples.

A pyrene-based chromo-fluorogenic probe for specific detection of sarin gas mimic, diethylchlorophosphate.

Nerve agents are becoming serious issues for the healthy and sustainable environment of modern civilization. Therefore, its detection and degradation are of paramount importance to the scientific community. In the present contribution, we have introduced a chromo-fluorogenic pyrene-based  probe, (E)-2-methoxy-3-(pyren-1-ylimino)-3,8a-dihydro-2H-chromen-4-ol (PMCO) to detect sarin stimulant diethylchlorophosphate (DCP) in solution and gaseous phases. On inserting DCP in PMCO solution, a visual colorimetric change from yellow to clear colourless in daylight and highly intensified blue fluorescence was observed instantly under a 365 nm portable UV lamp light. PMCO has outstanding selectivity and high sensitivity with a limit of detection of 1.32 µM in dimethyl sulfoxide (DMSO) medium and 77.5 nM in 20% H2O-DMSO. A handy strained paper strip-based experiment was demonstrated to recognize DCP in a mixture of similar toxic analytes. A dip-stick experiment was performed to identify DCP vapour, and may be used as an effective photonic tool. We also demonstrated real sample analysis utilizing different DCP-spiked water samples and validating DCP detection even in various types of soils such as sand, field, and mud. Therefore, this present study provides an effective chemosensor for instant and on-site detection of toxic nerve agents in dangerous circumstances.

Spectroscopic and Density Functional Studies on the Interaction of a Naphthalene Derivative with Anions.

This article highlights the investigation of anion interactions and recognition abilities of naphthalene derivative, [(E)-1-(((4-nitrophenyl)imino)methyl)naphthalen-2-ol], (NIMO) by UV-visible spectroscopically and colorimetrically. NIMO shows selective recognition of F- ions colorimetrically, and a visual color change from yellow to pink is observed by the naked eye. The F- ions recognition is fully reversible in the presence of HSO4- ions. The limit of F- ions detection by NIMO could be possible down to 0.033 ppm-level. A paper strips-based test kit has been demonstrated to detect F- ions selectively by the naked eye, and a smartphone-based method for real sample analysis in the non-aqueous medium has also been demostrated. Spectroscopic behavior is well supported by pKa value calculation and DFT analysis, to find a correlation with receptor analyte interaction. The optical response of NIMO towards the accumulation of F- ions and, subsequently, HSO4- ions as chemical inputs provides an opportunity to construct INH and IMP molecular logic gates.

A Chromo-fluorogenic Probe for Selective Detection of Picric Acid Alongside Its Recovery by Aliphatic Amines and Construction of Molecular Logic Gates.

Nitroaromatic compounds are illicit explosive chemicals. For environmental security and homeland safety, selective and sensitive identification of these secondary-class explosives has been a reason for the exhaustive research arena of chemists for about a decade. We introduced a sensitive optical sensor with desalted neutral red (NR) dye. After ingressing picric acid (PA) in acetonitrile, the probe becomes non-fluorescent, displaying a colorimetric change from yellow to pink. The quenched phenomena and the changed color were re-established with aliphatic amine, trimethylamine (TEA). The reversibility is produced cyclically, both in fluorimetrically and spectrophotometrically. The detection limit for PA with our probe comes out as 0.639 µM; this value is significantly lower than many chemosensors available in the literature. Also, NR-stained filter paper strips-based test kit analysis has been deployed as a displayable photonic device for in-situ detection of PA. Furthermore, the whole system was conceptualized to produce single input, single output, and double input single output logic gates, which can be applied to digital devices. The chronological input manner as NTP (NR- TEA-PA) pushed us to configure a molecular keypad lock system, the basis of digital locking devices. The repeatable & reversible detection system exhibits "Write read- Erase-read Write-read' type memory devices.

Highly selective and sensitive chromogenic recognition of sarin gas mimicking diethylchlorophosphate.

The high-level toxic effects of organophosphate (OP) nerve agents severely threaten national security and public health. Generating trustworthy, accurate methods for quickly identifying these poisonous chemicals is urgently necessary. In this study, we have presented an azine-based colorimetric sensor (HBD) for the highly sensitive and selective identification of poisonous sarin gas surrogate diethylchlorophosphate (DCP). Our introduced sensor shows a purple color in contact with DCP, which is fully reversible upon the addition of triethylamine (TEA). The detection limit of our sensor for the toxic nerve agent mimic DCP is in the µM range. We have fabricated a test kit to verify the capability of HBD for on-the-spot identification of DCP to execute its practical use. To prove that HBD is an effective chemosensor, dip-stick investigation was conducted to detect DCP in the vaporous stage in the presence of different OPs, inorganic phosphates (IPs), and many other deadly analytes. A cellphone-based display method was also undertaken for on-the-spot recognition and measurement of DCP in isolated regions.

A benzoxazole-triphenylamine conjugated fluorogenic probe for specific detection of sarin gas mimic diethylchlorophosphate.

In this study, an excellent chromo-fluorogenic PMPA probe, (E)-4-(((4-(benzoxazole-2-yl)phenyl)imino)methyl)-N,N-diphenylamine, is introduced for the detection of sarin gas mimic diethyl chlorophosphate (DCP) in solution and gaseous phases. On adding DCP into PMPA solution in a pure DMSO and water-DMSO (4 : 1) medium, it exhibits a hypsochromic shift from yellow to colorless and from no fluorescence to highly intense blue-violet photoluminescence via the formation of a phosphorylated PMPA-DCP product due to the inhibition of intramolecular charge transfer (ICT) and photoinduced electron transfer (PET) mechanism. The sensor could detect DCP in the presence of several other notorious guest analytes with a detection limit in the µM range. Moreover, to accomplish the on-spot detection of DCP and explore the practical applicability of the probe, a paper strip-based test kit, "dip-stick" method, and, more interestingly, a real sample analysis was demonstrated in spiked soil samples.

Acid-base equilibrium in non-aqueous medium: colorimetric visualization, estimation of acidity constants and construction of molecular logic gates.

A reversible acid-base probe, (N1E, N4E)-N1, N4-bis((Z)-3-(4-(dimethylamino)phenyl)allylidene)benzene-1,4-diamine (MM1), is introduced for the colorimetric visualization of acid-base equilibria in non-aqueous media. MM1 displays reversible acidochromic behavior, showing exciting colorimetric change varying from weak to strong acid. Also, we have fabricated a colorimetric paper strip-based test kit to visualize acid-base equilibria. A dipstick experiment has been demonstrated to visualize the acid-base equilibria in the gaseous state. This acid-base probe has also been employed to estimate the pKa values of several acidic compounds in a non-aqueous medium using overlapping indicator methods. Based on reversible acidochromic UV-visible absorption spectral and colorimetric behavior, we have constructed a reconfigurable dual input and dual output combinational logic circuit and set-reset memorized device employing acid and base as chemically encoded inputs and corresponding optical outputs. The current report evokes a new protocol for developing various reversible acidochromic probes and its implication for constructing opto-chemical molecular logic gates and estimating the acid dissociation constants of various acidic compounds in non-aqueous media.

A benzoxazole-based turn-on fluorosensor for rapid and sensitive detection of sarin surrogate, diethylchlorophosphate.

A benzoxazole-based fluorosensor (IMP) has been synthesized and employed for the selective and sensitive detection of sarin surrogate, diethylchlorophosphate (DCP) in solution, and gas phase, respectively. Remarkable turn-on fluorescence is observed due to the introduction of DCP in the solution of IMP because of inhibition of the intramolecular charge transfer process and disruption of the excited state intramolecular proton transfer (ESIPT) mechanism. The synthesized IMP-based fluorescence sensor exhibits excellent selectivity, high sensitivity, and a wide linear range of 15-60 µM with a detection limit of 44 nM. Low-intense to highly intensified visible violet color could be seen by the naked eye under a portable 365 nm UV lamp due to the addition of DCP in the solution of IMP. IMP-stained paper strips-based test kit experiment has been demonstrated to detect traces of DCP in stockpiles of related analytes. A dip-stick experiment for the detection of DCP vapor has also been demonstrated. The effectiveness of IMP in detecting DCP established that it might be used as a signal tool for real sample analysis.

A PET and ESIPT-communicated ratiometric, turn-on chromo-fluorogenic sensor for rapid and sensitive detection of sarin gas mimic, diethylchlorophosphate.

Fast and precise identification of toxic G-series nerve agents in the solution and vapor phase is urgently needed to save human beings from unwanted wars and terrorist attacks, which is challenging to execute practically. In this article, we have designed and synthesized a sensitive and selective phthalimide-based chromo-fluorogenic sensor, DHAI, by a simple condensation process that shows ratiometric and turns on chromo-fluorogenic behavior towards Sarin gas mimic diethylchlorophosphate (DCP) in liquid and vapor phases, respectively. A colorimetric change, from yellow to colorless, is observed in the DHAI solution due to the introduction of DCP in daylight. A remarkable cyan color photoluminescence enhancement is noticed in the presence of DCP in the DHAI solution, which is observable to the naked under a portable 365 nm UV lamp. The mechanistic aspects of the detection of DCP by employing DHAI have been revealed by time-resolved photoluminescence decay analysis and 1H NMR titration investigation. Our probe DHAI exhibits linear photoluminescence enhancement from 0 to 500 µM with a detection limit of nanomolar range from non-aqueous to semi-aqueous media. For practical utility, a DHAI-stained test kit employing Whatman-41 filter paper has been fabricated and used as a portable and displayable photonic device for on-site detection of Sarin gas surrogate, DCP. Also, a dip-stick experiment has been demonstrated to identify the vapor of Sarin gas mimics DCP colorimetrically and fluorometrically. The concentrations of DCP in various water samples have been evaluated with the help of a standard fluorescence curve for real sample analysis.

Reversible acidochromism of a benzoxazole based scaffold and construction of reconfigurable dual output molecular logic gates.

This report explores the reversible acidochromism of a benzoxazole-based scaffold (BPP), which is highly sensitive to the acid-base in the liquid and gas phases. With the addition of acid, the solution of BPP changes its color from yellow to pink fuchsia due to the transformation of its imine into quinonoid form. Colour change is completely reversible in the presence of the base, confirming the reversible acidochromic behavior of the present BPP system. Further, a paper strips-based test kit has been demonstrated for the practical utility of the present acidochromic BPP to identify a trace amount of acid-base in solution and gas-phase, respectively. The mechanistic aspect of detection of acid-base and colorimetric change in the presence of acid-base have been explored by density functional theoretical investigations and 1H NMR experiments. Moreover, we have constructed a reconfigurable dual-output combinatorial logic circuit by utilizing the spectral shift between two wavelengths at 404 nm and 552 nm, respectively, and colorimetric change of the BPP in the presence and absence of acid-base.