Highly sensitive fluorescent probes for selective detection of hypochlorite: Applications in blood serum and cell imaging.

Being one of the vital reactive oxygen species (ROS), abnormal level of hypochlorite ion (ClO-) may pose detrimental threats to living organisms. Therefore, highly selective, and rapid monitoring of ClO- in living system is of prime importance to protect living organisms from its harmful effects. In this regard, design of synthetic fluorescent probes for ClO- has garnered considerable attention. However less fluorescence emission in aggregated state and less photostability of several existing probes for ClO- inspired us to design aggregation induced emission (AIE) active fluorescent probes SH1 and SH2. Probes were rationally designed by introducing thiourea moiety that selectively reacted through desulfurization reaction and resulted in highly selective detection of ClO-. Hypochlorite induced desulfurization reaction was validated through 1H NMR titration and DFT studies. Fine tuning of probes SH1 and SH2 prompted highly sensitive nanoscale (55 nM and 77 nM) and rapid (15 and 35 sec) detection of ClO-. Probe SH1 displayed less cytotoxic effect to live cells before it was successfully applied for bioimaging of ClO- in live MCF-7 cells. Moreover, probes displayed excellent sensing potential for ClO- in blood serum and real water samples. Advantageously, probe coated portable fluorescent films were fabricated for the easy and fast monitoring of ClO-. Of note, this work offers excellent design strategy for highly selective detection of ClO- that may lead to clinical trials.

AIEE active sensors for fluorescence enhancement based detection of Ni2+ in living cells: Mechanofluorochromic and photochromic properties with reversible sensing of acid and base.

Stimuli responsive sensors QI 1 and QI 2 were rationally developed which exhibited diverse features of mutable mechanofluorochromism, reversible photochromism, solvatochromism, aggregation induced emission enhancement (AIEE), and metal ion sensing. After observing the exceptional structural property relationship, sensors were applied for reversible colorimetric and fluorometric determination of Ni2+ with low detection limits of 12 and 17 nM, respectively. Fluorescence emission enhancement based Ni2+ sensing was induced by chelation enhanced fluorescence (CHEF) mechanism. CHEF is triggered by the inhibition of excited state intramolecular proton transfer (ESIPT) and -C=N isomerization. The proposed Ni2+ sensing mechanism was investigated through 1H NMR, FT-IR titration, theoretical studies, and Jobs plots. Further, the developed sensors successfully demonstrated the selective acid-base induced absorption/emission switching through reversible ring-opening/closing and keto-enol tautomerization, evidenced by 1H NMR titration experiments. Additionally, the sensitivity of the sensor QI 1 towards Ni2+ was effectively mimicked in live MCF-7 cells and industrial effluents. Furthermore, monitoring of Ni2+ ions was also accessed through inexpensive and portable sensors' coated fluorescent films. Finally, an INHIBIT logic gate was fabricated imputing Ni2+ and EDTA as input signals to electronically scrutinize the targeted Ni2+.

Sulfonamides as Optical Chemosensors.

Sulfonamides are auspicious chemosensors which are capable to bind with ionic species through various ways like complexation, charge transfer, proton transfer etc. and produce a detection signal in the form of an optical change either in visible or UV-light and for electronic as well as fluorimetric spectra. Sulfonamides have gained much attention of analytical chemists these days as these are inexpensive, robust, green in nature and some what sensitive and selective to many anionic and cationic species. Due to their promising versatility in sensing properties, these are under great consideration in forensic, environmental, analytical and biochemistry laboratories. This review narrates how sulfonamides are being used to optically sense ionic species.

HIGHLIGHTSOptical sensors are of great importance these days because of their optical detection properties rather using Hi-tech techniques.Optical sensors are economical, robust, selective, sensitive and green in nature.The color change, shifts in electronic spectra or alterations in fluorescence pattern may be attributed by interaction between species to be sensed and Sulfonamides by different mechanism i.e. electron transfer, fluorescence energy transfer, charge transfer, hydrogen bonding, etc.LOD data is a proof of their prodigious efficiency of Sulfonamides as optical sensors.

Aggregation induced emission based fluorenes as dual-channel fluorescent probes for rapid detection of cyanide: applications of smartphones and logic gates.

Rational modification of molecular structure by incorporating electron donating groups can play a potential role for designing aggregation induced emission (AIE) active fluorescent probes. Based on this principle, fluorescent probes (1a-c) were synthesized, and they displayed excellent aggregation induced emission (AIE) behavior in a H2O/DMF (4 : 1, v/v) mixture due to restrictions in intramolecular charge transfer (ICT). As a comparison, probe 1d was synthesized by installing an electron withdrawing (-NO2) group that surprisingly quenched the aggregation behaviour. Additionally, AIE active probes 1a-c displayed a highly sensitive dual channel (fluorometric and colorimetric) response towards rapid detection of CN-, which is an active toxic material. Probes 1a-c showed selectively enhanced fluorescence emission behavior towards CN- with detection limits of 1.34 ppb, 1.38 ppb, and 1.54 ppb, respectively. The sensing mechanism involves Michael type adduct formation due to the nucleophilic addition reaction of cyanide with probes and was confirmed through 1H NMR titration experiments. In contrast, probe 1d containing an electron withdrawing moiety showed insensitivity towards CN-. Therefore, this study provides the efficient strategy to induce AIE character in fluorescent probes and expands the mechanistic approach toward the sensing of toxic CN-.

Development of AIEE active fluorescent and colorimetric probe for the solid, solution, and vapor phase detection of cyanide: smartphone and food applications.

Apart from environmental implications, the extreme toxicity of cyanide can lead to sudden human death upon prolonged exposure to it. Hence, rapid and low-level on-site detection of cyanide has earned paramount significance in the present era. Therefore, an AIEE active and piezofluorochromic Schiff base (probe 2) was synthesized which exhibited highly selective fluorescence enhancement based nanoscale (LOD; 6.17 nM) detection of CN-. The interaction mode was attributed to the deprotonation of the probe by the cyanide that was confirmed through 1H NMR titration, pH, theoretical studies, and switchable fluorescence response upon the addition of HCl. Advantageously, probe 2 displayed solid and vapor phase recognition of cyanide which is the first of its kind as far as we know. The excellent sensing potential of the probe was satisfactorily applied for the detection of cyanide in food, natural soil, and industrial wastewater. Additionally, probe 2 showed an immediate colorimetric response towards cyanide which was favorably integrated through a smartphone. Finally, the switchable fluorescence response of the probe was used to design an INHIBIT logic gate. Therefore, the multifunctional probe 2 displayed excellent practical potential for cyanide detection which was the ultimate goal of our work.

Fluorenone-Based Fluorescent and Colorimetric Sensors for Selective Detection of I- Ions: Applications in HeLa Cell Imaging and Logic Gate.

Fluorenone-based fluorescent and colorimetric sensors 1 and 2 have been developed that displayed selective detection of iodide ions in the presence of interferences. Sensors displayed the fluorescence emission enhancement response toward I- with detection limits of 8.0 and 11.0 nM, respectively, which is accomplished through inhibition of intramolecular charge transfer and C=N isomerization. Excellent sensitivity and unique fluorescence enhancement response of sensors toward I- make them superior because most of the previously reported iodide sensors are based on the fluorescence quenching mechanism and are less sensitive. The sensing potential of sensors toward I- ions was investigated through 1H NMR titration, dynamic light scattering, Job's plots, and density functional theory analysis. Further, sensors displayed reversible behavior by the alternate addition of I- and Cu2+ ions that substantiate their role as recyclable sensors for the on-site detection of I- ions. Advantageously, fluorescence enhancement response of sensors was favorably used for fluorescence imaging of I- in live HeLa cells and the design of the logic gate. These sensors were successfully applied in diversified applications such as the preparation of sensors' coated paper strips and the determination of I- ions in blood serum, food, and real water samples.

Fluorescein based fluorescent and colorimetric sensors for sensitive detection of TNP explosive in aqueous medium: Application of logic gate.

Rapid detection of 2,4,6-trinitrophenol (TNP) in real samples has recently attained considerable attention from the perspective of national security, human health, and environmental safety. In this context, cost-effective and convenient detection of TNP explosive was accomplished through two new fluorescein based sensors F2 and F3. Sensors displayed effective fluorescence quenching response towards TNP in the aqueous medium. Highly sensitive fluorescence detection of TNP explosive (detection limit, 0.73 (F2) and 1.7 nM (F3)) was governed by ground-state charge transfer complex formation, facilitated by favorable H-bonding between sensor and TNP explosive. Fluorescence quenching mechanism for the detection of TNP explosive was investigated through UV-Visible absorption, dynamic light scattering (DLS), density functional theory (DFT) calculations, the Benesi-Hildebrand, and Job's plots. Advantageously, sensors displayed selective and immediate colorimetric recognition of TNP explosive. Importantly, sensors exhibited quick response time towards TNP even in the presence of potential interferences that make them highly suitable for practical applications. Sensors were successfully applied for fluorescent and colorimetric detection of TNP explosive in industrial water samples and fabrication of logic gates. Further, convenient contact mode and instant surface sensing of TNP explosive were achieved through the fabrication of fluorescent strips and explosive responsive test kits.

Fluorene-Based Fluorometric and Colorimetric Conjugated Polymers for Sensitive Detection of 2,4,6-Trinitrophenol Explosive in Aqueous Medium.

Nitroaromatic explosives are a class of compounds that are responsible for various health hazards and terrorist outrages. Among these, sensitive detection of 2,4,6-trinitrophenol (TNP) explosive has always been highly desirable considering public health and national security. In this regard, three fluorene-based conjugated polymers (CP 1, CP 2, and CP 3) were synthesized through the Suzuki-Miyaura coupling reaction and were found to be highly sensitive for fluorescence detection of TNP with detection limits of 3.2, 5.7, and 6.1 pM, respectively. Excellent selectivity of CPs toward TNP was attributed to their unique π-π interactions based on fluorescence studies and density functional theory (DFT) calculations. The high sensitivity of CPs to TNP was attributed to the static quenching mechanism based on the photoinduced electron transfer process and was evaluated by fluorescence, UV-visible absorption, dynamic light scattering, Job's plots, the Benesi-Hildebrand plots, and DFT calculations. CPs were also used for colorimetric and real-water sample analysis for the detection of TNP explosive. Meanwhile, sensor-coated test strips were fabricated for on-site detection of TNP, which makes them convenient solid-supported sensors.

Naked Eye Chemosensing of Anions by Schiff Bases.

Spectacular color change during a chemical reaction is always fascinating. A variety of chemosensors including Schiff bases have been reported for selective as well as sensitive recognition of ions. This review explains the use of Schiff bases as color changing agents in the detection of anions. This magic of colors is attributed to change in the electronic structure of the system during reaction. Schiff base chemosensors are easy to synthesize, inexpensive and can be used for visual sensing of different ions. Development of Schiff base chemosensors is commonly based on the interactions between polar groups of Schiff bases and ionic species and the process of charge transfer, electron transfer and hydrogen bonding between Schiff bases and ionic species cause the color of the resultant to be changed. Therefore, designing of simple Schiff base chemosensors which are capable of selective sensing of different anions has attracted considerable interest. In particular, naked eye sensing through color change is important and useful since it allows sensing of ions through color changes without using any instrumental technique.HighlightsNaked eye sensors are of much interest these days due to their visual detection properties rather employing complex instrumentation.Optical sensors are sensitive, selective, cost effective and robust.The magic of color change is fascinating factor in detection by these sensors.The color change may be attributed by interaction between anion and Schiff base by different mechanism i.e. electron transfer, charge transfer, hydrogen bonding, ICT etc.LOD data is an evidence of their great efficiency.

Metal Ion Detection by Carbon Dots-A Review.

Development of economical, sensitive, selective and robust sensors for metal ion sensing is always fascinating for a chemist because traditional routs for their detection involve complicated instrumentation and critical sample preparation procedures. A large number of metal ion detectors including carbon dots (CDs) have been reported for sensitive and selective detection of metal ions. This review comprehensively explores the use of CDs as metallic cation sensors. CDs are being fabricated from variety of carbon sources by employing various synthetic channels. CDs are proved to be efficient colorimetric and fluorimetric detectors due to surface oxygen moieties which are responsible to co-ordinate with metal ions. Doping of CDs with hetero atom such as N, S, B etc. may further enhance their activity toward metal detection. Therefore, designing of CDs having selective sensing properties with low detection limits has gained significant interest.HighlightsCDs have gained much attention as chemical sensors due to their dynamic features i.e. less toxicity, stability, solubility in various solvents, absorption in UV/Vis. region, fluorescence and tunable physico-chemical properties.These are coast effective, sensitive and selective colorimetric and fluorimetric metal ion sensors.Detection of metal ions by CDs involves different mechanisms such as complexation, aggregation, electron transfer, inner filter effect etc.LOD data is an evidence of their greater efficiency.

Carbon dots as naked eye sensors.

Optical sensors are always fascinating for chemists due to their selectivity, sensitivity, robustness and cost-effective nature. Moreover, these sensors provide the facility of onsite detection without employing any instrumental technique. A number of such visual sensors including carbon dots (CDs) have been reported for selective detection of many ionic and molecular species. This review elaborates the utilization of CDs as colorimetric sensors. Carbon dots (CDs) are being synthesized from a large number of natural and synthetic carbon source materials using a variety of methods. CDs can also be tuned chemically by doping, to impart the desired sensing properties. Therefore, the development of CDs with selective sensing properties enables extremely low detection limits and has thus gained substantial attention.