Naked-eye Color Change Research Articles

Anthraquinone Schiff base and SDS-based visual detection for environmental safety: Targeting triphosgene and Hg2+ with secondary focus on detection of BSA

New sensing techniques with exceptional performance, i.e., high sensitivity, high selectivity, and dependability, are needed to meet the growing demand for quick and accurate environmental pollution prevention and monitoring. A novel Schiff base probe synthesized from anthraquinone and 4-(diethylamino)-2-hydroxybenzaldehyde (coded as AQHB) was synthesized and subsequently combined with anionic surfactant Sodium dodecyl sulfate (SDS) assemblies to form highly fluorescent AQHB@SDS ensemble. The zeta potential of ensemble AQHB@SDS is −52.6 mV confirm the encapsulation of AQHB (-17.3 mV) in SDS micelles. This formed fluorescent AQHB@SDS ensemble further practical applications in detection of toxic triphosgene and Hg2+ ions via naked eye color change and fluorescence quenching mechanism. The fluorescence of in-situ formed AQHB@SDS+Hg2+ complex restored by the addition of BSA. The optimized system demonstrates detection limits of 0.60, 0.68, and an impressive 0.028 nM for triphosgene, Hg2+, BSA respectively. Control experiments revealed that the -OH and -NH groups in AQHB along with anionic surfactant played crucial roles in the sensing mechanism. Moreover, the ensemble AQHB@SDS system efficiently detected triphosgene and Hg2+ in real samples, such as water and soil, highlighting its practical applicability.

Spectroscopic and Computational Study of Vanillin-Dipyrrin Ligand that Capable of Colorimetric Sensor for Zinc and Copper Ions

Phenolic-dipyrrin is a promising colorimetric chemosensor due to its tautomeric formation (phenolic-hemiquinone forms). In methanol solution, the vanillin-dipyrrin compound exists as a hemiquinone species, whereas the complexes exist in a phenolic form. This molecule showed a red-magenta color in methanol, in contrast to yellowish allyl-protected-dipyrrin. In the presence of zinc or copper ions, the vanillin-dipyrrin solution turned into a pale-yellow complex, similar to that of protected-dipyrrin. A computational study of the ligands and complexes showed a close relevance, where the energy transition between the highest molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) of the ligand in the hemiquinone form had a lower energy transition, and the two complexes showed slightly different transition energies. Apart from naked-eye color changes, vanillin-dipyrrin showed limits of detection of 9.2 × 10–7 M and 4.8×10−7 M for zinc and copper ions, respectively.

A novel naphthalimide-derived “turn-off” chemosensor for the detection of Cu2+, F- and CN- ions

The development of selective chemosensor for the detection of detrimental analytes in the environment is crucial due to their catastrophic effects. In this study, a novel Schiff base derived from naphthalimide and salicylaldehyde was designed and prepared for the detection of Cu2+, F-, and CN- ions in CH3CN as medium. The chemosensor exhibits a red shift in the presence of Cu2+, F-, and CN- ions accompanied by naked eye color change in the presence of F- and CN- ions. On the other hand, a “turn-off” response was observed in the presence of ion Cu2+, F-, and CN- ions in the fluorescent spectrum. The good anti-interference characteristics, strong binding, and low limit of detection (LOD) of the chemosensor revealed its sensitivity against Cu2+, F-, and CN- ions i.e. 1.25 × 10-5 M, 1.07 × 10-6 M, and 0.98 × 10-6 M, respectively. The binding ratio (1:1) was determined by Job's plot between the chemosensor and ions. In addition, the binding of ions with the chemosensor was proposed which was further supported by time-dependent density functional theory (TD-DFT) and IR spectrum data.

Triple modal aptasensor arrays driven by CHA-mediated DNAzyme for signal-amplified atrazine pesticide accumulation monitoring in agricultural crops

Developing sensors with high selectivity and sensitivity is of great significance for pesticide analysis in environmental assessment. Herein, a versatile three-way sensor array was designed for the detection of the pesticide atrazine, based on the integration of catalytic hairpin assembly (CHA) amplification and three-mode signal transducers. With atrazine, CHA was triggered to generate abundant G-quadruplex. The produced G-quadruplex hybrid could assemble with thioflavin T (TFT) or hemin to mimic enzyme and induce the fluorescence enhancement by TFT, or the colorimetric increase by the oxidized chromogenic substrate and the naked-eye color change by inhibiting the L-cysteine-mediated aggregation of gold nanoparticles. A distinctive three-mode array was successfully constructed with convenience, on-site accessibility and high sensitivity for enzyme-free practical analysis of atrazine. It is also effective and reliable for analyzing real samples including paddy water, paddy soil and polished rice. The detection limits for atrazine were as low as 7.4 pg/mL by colorimetric observation and 0.25 pg/mL by fluorescent detection. Furthermore, the array was exploited to monitor the residue, distribution and bioaccumulation of atrazine in maize and rice for food security and environmental assessment. Hence, this work presented a versatile example for sensitive and on-site all-in-one pesticide analysis arrays with multiple signal report modes.

Development of a novel sensory material for rapid detection of mercury ions in various water sources: Solution and solid-state analysis

A xanthene propane nitrile-based sensor material was successfully prepared, and an attempt towards the preparation of polymer bead form was made for the sensitive or selective detection of mercury ions (Hg2+) in water. The sensor material in solution as well as in polymeric form showed amazing selectivity over other added metal ions with a naked eye color change, UV visible spectral and fluorescence spectral change, and a rapid and excellent color change from colorless to purple. The 1H NMR study exposed the probable binding site of the probe with the added mercury ion. In this study, the imine nitrogen and the C = O interact with the mercury ion, resulting in the ring opening of lactam with a vivid color change. The EDTA test was done to verify the reversible behavior of the probe and confirmed its reversibility by UV–visible and fluorescence spectral studies. The polymer bead made using this probe can be used as a tool for monitoring mercury ions in real time in different sources of water samples. The sensor molecule itself senses the mercury ion in its solid state by simple grinding and changes its color from pale yellow to deep purple. The sensor color change response is very rapid towards mercury detection, which is confirmed by the prepared test strip.

Aggregation-induced emission active multianalyte sensor: Detection of pH, carbonate, bi-carbonate and nitroaromatics in water

An aggregation-induced emission (AIE) based multi-tasking probe DAAQ (5-(dimethylamino)-N-(9,10-dioxo-9,10-dihydroanthracen-2-yl)naphthalene-1-sulfonamide) has been reported for detecting multiple analytes such as anions (carbonate and bicarbonate ions) and nitroaromatic compounds (2,4-DNP and TNP). Probe DAAQ displayed the photophysical properties of aggregation-induced emission (AIE) in DMSO-water mixture, acidochromism and detected various analytes, making DAAQ a multi-tasking probe. DAAQ respond to carbonate and bicarbonate (CO32− and HCO3−) with a colour change from pale yellow to dark orange. The limit of detections (LOD) was estimated as 0.486 mg/L and 41.35 mg/L for CO32− and HCO3−, respectively. The applications of DAAQ were also explored to detect CO32− ions in water samples collected from various sources and soft drinks. Further, the probe also explored detecting neural aromatic compounds such as 2,4-DNP and TNP by a naked eye colour change and the LODs were calculated as 12.6 µM and 8.19 µM, respectively. DFT calculations were applied for the confirmation binding studies of DAAQ with multiple analytes. The sensing of 2,4-DNP and TNP were achieved through PET with a Turn-Off response. The sensing mechanisms were confirmed with 1H NMR experiments.

Smartphone-assisted chemosensor based on thiocarbohydrazide Schiff base for selective detection of Hg2+ and Cu2+ ions

A simple and sensitive thiocarbohydrazide Schiff base colorimetric chemosensor (L) was synthesized, and characterized by FTIR, 1H NMR, TOF-MS, and elemental analyses. UV–vis absorption spectra of L in CH3CN:H2O (9:1, v/v) showed a highly selective absorption enhancement response towards Hg2+ and Cu2+ ions, accompanied by distinct color changes from colorless to yellow. The binding stoichiometry of chemosensor L and related metal ions was 2:1 and the binding constant was 2.6 × 105 M−1 for Hg2+ and 2.6 × 104 M−1 for Cu2+. The detection limits for Hg2+ and Cu2+ ions were 0.11 and 0.18 µM, respectively. The effective naked eye color change of L depending on Hg2+ and Cu2+ concentration was integrated with smartphone for real-time applications of chemosensor. Finally, L was successfully applied to determine of Hg2+ and Cu2+ ions in tap water, drinking water, and river water samples.

A mitochondria-targeting fluorescent probe for the dual-emission fluorescence-enhanced detection of hydrogen sulfide and turn-on detection of hydrazine

A fluorescent probe (probe 1) with selectivity and sensitivity for H2S and N2H4 has been developed. Probe 1 exhibits dual-excitation and dual-emission fluorescence response to H2S and fluorescence enhancement toward N2H4 with distinct naked-eye color changes. Moreover, probe 1 displayed low detection limits for H2S and N2H4 of 0.90 nM and 23.6 nM, respectively. The reaction mechanism of probe 1 toward H2S and N2H4 was established using 1H NMR and HR-MS spectroscopy. Additionally, probe 1 was used for monitoring and differentiating H2S and N2H4 in HeLa cells and displays good biocompatibility and low cytotoxicity.

Stimuli-Responsive Properties of a Zinc(II) Salen-Type Schiff-Base Complex and Vapochromic Detection of Volatile Organic Compounds.

This contribution reports, through a combined thermogravimetric analysis, differential scanning calorimetry, UV-vis, powder X-ray diffraction, and Rietveld refinement analysis, on the stimuli-responsive chromic properties of a substituted Zn(salmal) Schiff-base Lewis acidic complex with unique and distinct thermo- and vapochromic characteristics. The solid complex obtained in air or by evaporation of the solvent from their THF solutions shows a marked thermochromism associated with a phase transition, unusually triggered by the reversible desorption/adsorption of one lattice water molecule. In contrast, the anhydrous solid, achieved from THF solutions of the complex by evaporation of the solvent under anhydrous conditions, behaves very differently as it does not show any absorption of water or thermochromism and exhibits varied vapochromic properties. Detection of volatile organic compounds having Lewis basicity is demonstrated by using the anhydrous solid or the related cast films on glass or paper substrates. In both cases, a marked vapochromism is observed upon exposure to vapors of various volatile species and involves well-defined optical absorptions and naked-eye color changes, also allowing the discrimination of primary aliphatic amines. Vapochromic behavior with the formation of stable, stoichiometric adducts is also demonstrated for both the solid obtained in air and the anhydrous solid or for the related cast films after exposure to vapors of pyridine.

A selective colorimetric chemosensor for detecting Ni(II) in aqueous solutions based on 4-[{[4-(3-chlorophenyl)-1,3-thiazol-2-yl]hydrazono}methyl]phenyl 4-methyl benzene sulfonate (CTHMBS).

Among the toxic heavy metals, Ni(II) can cause a variety of side effects on human health, such as allergy, cardiovascular and kidney diseases, lung fibrosis, lung, and nasal cancer. It is therefore critical from a public health and environmental perspective to determine and monitor Ni(II) ions in drinking water, foods, and environmental samples. In this study, a novel selective chemosensor (4-[{[4-(3-Chlorophenyl)-1,3-Thiazol-2-yl]Hydrazono}Methyl]phenyl4-methylBenzene Sulfonate (CTHMBS) was developed for the colorimetric detection of Ni(II) in aqueous medium. The presence of Ni(II) led to a distinct naked-eye color change from yellow to reddish-brown in aqueous solution. To examine the binding mechanism of CTHMBS to Ni(II), UV-vis spectroscopy analysis and DFT calculations were conducted. The detection limit of CTHMBS for Ni(II) was 11.87 µM, and the sensing ability of CTHMBS for Ni(II) was successfully carried out in real water samples.

A coronene diimide based radical anion for detection of picomolar H2O2: a biochemical assay for detection of picomolar glucose in aqueous medium.

Coronene diimide functionalized with 4-(2-nitrovinyl)phenyl (CDI 2) serves as a precursor for generating a stable radical anion (CDI 2˙-) using H2S as a reductant in 40% H2O-THF solution in the NIR region with stability up to >50 min. The optical, cyclic voltammetry (CV), current-voltage (I-V) and electron paramagnetic resonance (EPR) studies revealed the formation of the radical anion (CDI 2˙-). The addition of a strong oxidant NOBF4 quenches the radical anion (CDI 2˙-). The aggregation studies revealed that CDI 2 exists in the aggregated state in 40% H2O-THF solution, which points to the possibility of stabilization of the radical anion in the aggregates. The radical anion (CDI 2˙-) was explored for the detection of 58.27 pM H2O2 in aqueous medium with the naked eye colour change from green to light yellow. The biochemical assay involving the radical anion (CDI 2˙-) and glucose oxidase (GOx) enzyme can be used for the detection of 16 pM (UV-vis method) and 82.4 pM (fluorescence method) glucose. The naked eye colour change from green to light yellow (daylight) and a colorless non-fluorescent solution to a green fluorescent solution (365 nm) allow the detection of 1 nM glucose.

A chromogenic diarylethene-based probe for the detection of Cu2+ in aqueous medium in Drosophila for early diagnosis of Alzheimer

A diarylethene-based probe (Z)-N'-((2-amino-5-chlorophenyl)(phenyl)methylene)-2-hydroxy benzohydrazide (KBH) has been proficiently developed and its structure has been confirmed by single crystal X-ray diffraction technique. It displays a selective and sensitive colorimetric sensing of Cu2+ ions in aqueous medium with a naked eye colour change from colourless to yellow. It exhibits a significantly low limit of detection as 1.5 nM. A plausible binding mechanism has been proposed using Job's plot, FT-IR, 1H NMR titration, HRMS and DFT studies. The chemosensor is effectively reversible and reusable with EDTA. Test strip kit and real water sample analysis have been shown to establish its practical applicability. Further, the potential of KBH for the early diagnosis of Cu2+ ion-induced amyloid toxicity has been investigated in eye imaginal disc of Alzheimer's disease model of Drosophila 3rd instar larvae. The in-vivo interaction of KBH with Cu2+ in gut tissues of Drosophila larvae establishes its sensing capability in biological system. Interestingly, the in-vivo detection of Cu2+ has been done using bright field imaging which eliminates the necessity of a fluorescent label, hence making the method highly economical.

Acid/base responsive pseudo[3]rotaxanes from amine naphthotubes and bis-pyridinium/isoquinolinium guests.

A novel cooperative pseudo[3]rotaxane system was successfully constructed by the inclusion complexation of two identical amine naphthotubes with a bis-pyridinium/isoquinolinium guest. Single crystal structure analysis revealed that weak Csp3-H⋯O hydrogen bonds between the two hosts are responsible for the positive cooperativity during the formation of pseudo[3]rotaxanes. Moreover, intermolecular charge-transfer interactions between the electron-rich host and the electron-poor guests were observed. The pseudo[3]rotaxanes showed pH-controllable association/dissociation processes with naked-eye color changes in solution.

Designing novel benzofuran derived AIE-probes: dual-mode fluorescence turn-off and naked-eye color change for hydrazine detection

We report the molecular engineering of a benzofuran derivative to construct aggregation induced emissive (AIE) luminogens for hydrazine detection through dual mode fluorescence turn-off and naked eye color change mechanisms.

AIE active fluorescent organic nanoparticles based optical detection of Cu2+ ions in pure water: a case of aggregation-disaggregation reversibility.

An AIE-active pyrene-terpyridine derivative, (4'-(pyren-1-yl)-2,2':6',2''-terpyridine) (1) was found to form nanoaggregate in an aqueous medium. The probe involved hydrogen bonding with solvent molecules that modulated the charge transfer behavior and consequently resulted in different spectroscopic behavior due to the formation of fluorescent organic nanoparticles (FONs). In the presence of Cu2+ ions, FONs displayed a ratiometric red shift of the absorption band (360 to 420 nm) accompanied by a prominent naked-eye color change from colorless to light yellow. With a gradual increase in water content, 1 displayed a huge red shift of the emission band (430 to 475 nm) denoting its switching from monomer to FONs. In the presence of Cu2+, the 475 nm emission band of FONs gradually diminished, facilitating the micromolar scale detection of Cu2+ (LOD = 8.57 μM) in a 100% aqueous medium with a fluorogenic color change from cyan to dark. The SEM and DLS data indicated the cation-induced disaggregation of FONs, which was further confirmed by mass spectral analysis and electron paramagnetic resonance measurement. In addition, the high selectivity of FONs towards Cu2+ ions over other potential cations and the 2 : 1 (1-Cu2+) binding stoichiometry were also determined. Moreover, the spectroscopic behavior of the monomeric amphiphilic probe was well supported by extensive DFT study. Such detection of Cu2+ ions in pure aqueous medium denoting an aggregation-disaggregation event is very rare in the literature.

Sequence-Specific Relay Recognition of Multiple Anions: An Interplay between Proton Donors and Acceptors.

Ratiometric detection of analyte is highly deserving since the technique is free from background correction. This work reports the design and synthesis of a pyridine-end oligo p-phenylenevinylene (OPV) derivative, 1 and its application in ratiometric dual-mode (both colorimetric and fluorogenic) recognition of dual anions, bisulfate (LOD=12.5 ppb) followed by fluoride (LOD=18.2 ppb) by sequence-specific relay (SPR) technique. The colorless probe turns brown with addition of bisulfate and again becomes colorless with the sequential addition of fluoride ion. In addition to such naked-eye color change, interestingly the ratiometric spectroscopic signals are reversible and evidently, the probe is reusable for several cycles. Besides, in presence of bisulfate, the protonated probe molecules, owing to their larger amphiphilic characteristics, formed self-assembled nanostructures. In addition to colorimetric and fluorescent changes, 1 H NMR titration and systematic DFT study evidently establish the underneath proton transfer mechanisms. Such reusable OPV-based chemosensor particularly with the capability of naked-eye recognition of dual anions using the SPR technique is seminal and possibly the first report in the literature.

Partially reduced-linked covalent organic frameworks: A new approach for heterogeneous catalysis and naked-eye HCl sensing

Compared to the traditionally made imine-linked covalent organic frameworks (COFs), amine-linked COFs provided by in-situ reduction of the linkages represent significant potential for advanced applications, including catalysis and sensing. The current paper deals with preparing a partially reduced COF with secondary amine groups (IR-COF) via in-situ reduction of imine linkages as a dual-functional material adopted for heterogeneous catalysis and acid-sensing. This COF was synthesized using formic acid as a reductant and catalyst in a solvothermal reaction between 2,4,6-tris-(4-formyl-phenoxy)-1,3,5-triazine and p-phenylenediamine. The IR-COF was used as a basic organocatalyst for the efficient synthesis of tetrahydro-4H-chromenes through the Knoevenagel-Michael cyclocondensation. Excellent yields, short reaction times, easy workup, absence of toxic organic solvents, easy recovery, and reusability of the catalyst are outstanding aspects of this catalytic method, making it convenient and useful for fine chemical synthesis. Moreover, the immediate naked-eye color change of IR-COF upon exposure to the hydrochloric acid by protonating the secondary amine groups was investigated. The (time-dependent) density functional theory (TD)DFT PBE/DNP+ method was used to investigate the mechanism of color change during the sensing. The appearance of a new absorption band at higher wavelengths upon protonation is proved to be due to intermolecular or interlayer electron transitions.

A Handy Chemical Sensor Based on Benzaldehyde and Imidazo[1,2-a]pyridine Mixture for Naked-eye Colorimetric and Fluorescent Detection of F.

Upon the Schiff base condensation reaction of imidazo[1,2-a]pyridine-2-carbohydrazide and 2,5-dihydroxybenzaldehyde, a bimodal colorimetric and fluorescent chemosensor 1o for assaying fluoride (F-) in DMSO was synthesized. The characterization of 1o structure was obtained by 1H NMR, 13C NMR and MS.The structure of 1o was characterized by 1H NMR, 13C NMR and MS. Under the presence of various anions, 1o could be applied for naked-eye and fluorescent detection of F- (naked eye: colorless to yellow; fluorescence: dark to green) and displayed promising performance, such as high selectivity and sensitivity, as well as a low detection limit. Upon calculation, the detection limit of chemosensor 1o for F- was 193.5nM, which is well below the allowed maximum value of F- (1.5mg/L) by WHO. As the intermolecular proton transfer mechanism induced "turn-on" fluorescent signal and naked-eye color change of F- to 1o through deprotonation effect, which was confirmed by Job's plot curve, mass spectrometry and 1H NMR titration. Alternatively, the chemosensor 1o can be effectively manufactured into test strips to detect fluoride in solid state, which is user-friendly with no additional equipment required.

Development of red fluorescent carbon dots for optical and smartphone imaging dual-mode determination of metabisulfite and pH monitoring

A new type of red photoluminescent carbon dots (R-CDs) with high quantum yield of 46.9% was favorably developed by introducing the luminophore of resazurin into the framework. The obtained R-CDs exhibit excitation-independent behavior, advantageous dispersion and outstanding optical performance. It is worth noting that the proposed R-CDs demonstrate a particular response to S2O52- over other competitive species accompanied by a naked-eye color change from red to orange. Fluorescence quenching of R-CDs is determined to be S2O52- concentrations dependence with ultra-fast response time and low detection limit. The as-developed R-CDs is further employed in building a smartphone imaging colorimetry platform for portable recognition of S2O52- in real samples with considerable accuracy. Furthermore, the speciallyprepared R-CDs also display a significant fluorescence enhancement behavior with the increase of pH in the linear range of 5.4–6.2 with a pKa of 5.86. These findings may offer a distinctive strategy for the development of long-wavelength emission carbon dots and help to expand their application in food safety inspection.

A fluorescent probe based on phenothiazine for detection of ClO− with naked-eye color change properties

Hypochlorite (ClO−) plays a key role in life systems and it is necessary to develop an effective detection method. In view of the significant advantages of the fluorescent probe, we have synthesized a naked-eye recognition fluorescent probe NNCF for the detection of ClO− based on phenothiazine and naphthalimide. The probe NNCF is sensitive (LOD = 9.5 nM) and fast for ClO− (within 30 s), and its Stokes shift is as large as 161 nm. In addition, the probe NNCF has been successfully used for imaging detection of exogenous ClO− in MCF-7 cells with low toxicity.