Detection of Hg2+ with NBD-based colorimetric chemosensor: Practical application to water samples and test strips

A new nitrobenzoxadiazole (NBD)-based chemosensor N′-(7-nitrobenzo[c][1,2,5]oxadiazol-4-yl)thiophene-2-carbohydrazide ( NTCH) was synthesized for detecting Hg²⁺. NTCH could sense Hg²⁺ through a color change method from pale yellow to pink. Binding ratio of NTCH and Hg²⁺ was determined to be 1:1 with the analysis of electrospray ionization mass spectrometry and Job plot. Detection limit turned out to be 0.69 μM. In addition, NTCH could be successfully utilized for detecting Hg²⁺ in real water samples and visible color test strips. The probing mechanism of NTCH to Hg²⁺ was explained with ¹H nuclear magnetic resonance (NMR) titration, Job plot, electrospray ionization mass spectrometry (ESI-MS), and theoretical calculations.     

Acridinium salt based fluorescent and colorimetric chemosensor for the detection of cyanide in water

A new, selective chemosensor has been developed to detect cyanide in water at micromolar concentrations. The acridinium salt used in this sensor system is prepared in a single step from an acridine orange base. Detection is based on the irreversible, 1:1 stoichiometric, nucleophilic addition of cyanide to the 9-position of the acridinium ion. This process induces a large decrease in fluorescence intensity and a marked color change. The selectivity of the system in aqueous media for CN- over other anions is remarkably high. Also, the sensitivity of both the fluorescence- and colorimetric-based assay is below the 1.9 microM suggested by the World Health Organization (WHO) as the maximum allowable cyanide concentration in drinking water. Thus, the chemodosimeter should be applicable as a practical system for the monitoring of CN- concentrations in aqueous samples. [structure: see text]     

A colorimetric and fluorescent chemosensor for detection of Hg2+ using counterion exchange of cationic polydiacetylene

In this study, a colorimetric and fluorescent chemosensor for mercury ions (Hg²⁺) was developed. Cationic polydiacetylene (PDA) vesicles with a quaternary ammonium cation and iodide as a counterion show a blue-to-red color transition; the color change is accompanied by a fluorescence enhancement in selective response to Hg²⁺ ions because of a perturbation of the ene–yne conjugated backbone induced by counterion exchange. It allows for selective detection of Hg²⁺ with the naked eye and the sensor is used to determine Hg²⁺ concentrations in tap water samples.     

Pyrylium-containing polymers as sensory materials for the colorimetric sensing of cyanide in water

A sensory polymeric material for the colorimetric sensing of cyanide in water has been developed based on the reactivity of this anion with the pyrylium cation.     

Indirect spectrophotometric determination of cyanide

A spectrophotometric method for cyanide based on its inhibition of the colour formation reaction between nickel(II) and 3-(4,5-dimethyl-2-thiazolylazo)-2,6-dihydroxybenzoic acid has been developed, and allows the determination of down to 0.1 g of cyanide. Most of the interferences can be avoided by displacement of the hydrogen cyanide using an arsine generator.     

硝基取代苯腙类荧光受体的阴离子识别与传感性能

合成了含萘荧光基团的硝基取代苯腙类受体,利用紫外-可见分光光度法、荧光发射光谱法和核磁等方法研究了受体的阴离子识别与光化学传感性能. 结果表明,在DMSO有机溶剂体系中,单硝基取代受体选择性比色和荧光识别氟离子,而双硝基取代受体可以比色和荧光识别氟离子和醋酸根离子. 归因于腙=N-NH基团质子酸性的进一步增强,双硝基取代受体能够在DMSO-H2O体系中实现对氟离子的比色和荧光识别. 此类受体是有效的“off-on”型阴离子荧光传感分子.     

Salicylaldehyde fluorescein hydrazone: a colorimetric logic chemosensor for pH and Cu(II)

In this work, salicylaldehyde fluorescein hydrazone (1) was synthesized and characterized. Exhibiting reversible color changes responding to different pH in the presence of Cu(II) in buffered media, 1 could be applied as a colorimetric chemosensor for the detection of pH and Cu(II) bi-functionally. It presented a tunable system integrated with a Cu(II)-driven YES logic gate as well as an INHIBIT logic gate, with pH and Cu(II) as its chemical inputs based on encoding binary digits of logical conventions.     

Electroanalytical and spectral investigation of organic receptors as colorimetric and absorption ratiometric anion chemosensor

Colorimetric receptors R1 and R2 have been designed and synthesized by Schiff base condensation and characterised by standard spectroscopic techniques. Anion binding ability of the receptors have been investigated quantitatively through optical, electrochemical and ¹HNMR titration studies. UV-vis spectra of receptor R1 and R2 exhibited a significant red shift for F^? and AcO^? ions with a visual color response. Receptor R1 exhibited selective response towards AcO^? ion in the presence of HEPES buffer media. Incremental color change of receptor R2 with the higher equivalence of AcO^? ions clearly represent the ratiometric response. Cyclic voltammetric studies of R1 and R2 exhibits shift in oxidation and reduction peak with successive addition of AcO^? ions indicating the anion induced oxidation of -NH and reduction of the keto group and nitro species. Electrooptical and ¹H NMR titration studies of R2 collectively reflects the anion induced change of chromophore from C=N to N=N indicative of azo-hydrazone tautomeric signaling in the presence of AcO^? ions. Lower detection limit of 2.1 and 0.41 ppm achieved with sodium salt of AcO^? ion with R1 and R2 reflects their utility as colorimetric chemosensor.     

李春艳1,李建华1,申贵隽2*

氰化物是一种快速、剧毒的化合物,能够引起组织衰竭以至机体死亡。氰化物一旦污染环境及食用源,会严重危害人体健康,当吸入或口服较大剂量氰化物时,会引起“闪电式”骤死,中毒者在10~60S内突然发出尖叫随即昏倒,出现强直性与阵发性痉挛,2-3min后呼吸停止而死亡[1]。因此加强对氰化物检测是一项重要的安全检测指标,为此,建立准确、快速,特别是能用于现场操作的氰化物测定方法有重要意义。     

A highly selective and sensitive dual-channel chemosensor for cyanide based on sulfahydrazone derivative

A colorimetric and fluorescent cyanide probe bearing naphthol and sulfahydrazone groups has been designed and synthesized. This structurally simple probe displays a rapid response and high selectivity for cyanide in DMSO/EtOH (v/v = 2:8) solution. The addition of CN^? to the sensor p-toluenesulfonyl-2-hydroxy-1-naphthylhydrazone (L3) induced a remarkable color change from pale-yellow to yellow, and green fluorescence changed to yellow. The ¹H NMR titration and DFT calculations suggested that the selective sensing process is based on a nucleophilic addition reaction of cyanide to imine. Test strips based on sensor L3 were fabricated, which could act as a convenient and efficient test kit to detect CN^? for “in-the-field” measurements.     

Optical detection of cyanide by palladium(II)-dithiazolopyridine probe at the parts per billion level

Abstract

The ensemble of 2,6-bis(2-chlorophenyl)dithiazolo[4,5-b:5',4'-e]pyridine 1 with Pd²⁺ ions (1?Pd²⁺) was prepared for the detection of cyanide ions (CN^¯) in 50% aqueous methanol. Among the tested metal ions, only Pd²⁺ sensitively induced the red shift of the absorption bands and the complete decrease of fluorescence emission. The detection limit toward Pd²⁺ was 2?ppb. The ensemble 1?Pd²⁺ selectively and rapidly detected a low concentration of cyanide ions by a colorimetric change (40?ppb) as well as a “turn-on” fluorescent response (5?ppb). Job’s plot revealed the complex formation with 1:1 stoichiometry. The binding and replacement mode of 1?Pd²⁺ and CN^¯ were also confirmed by ¹H NMR titrations and IR analysis. In general, a fast and selective recognition of CN^¯ is reported.     

A pyrene-based dual chemosensor for colorimetric detection of Cu2+ and fluorescent detection of Fe3+

A pyrene based chemosensor was designed and synthesized. The pyrene fluorophore was connected with a pyridine unit through a Schiff base structure to give the sensor (L). L was tested with a variety of metal ions and exhibited high colorimetric selectivities for Cu²⁺ and Fe³⁺ over other ions. Upon binding with Cu²⁺ or Fe³⁺, L showed an obvious optical color change from colorless to pink for Cu²⁺ or orange for Fe³⁺ over a wide pH range from 3 to 12. Moreover, the fluorescence of L at 370 nm decreased sharply after bonding with Fe³⁺, while other metal ions including Cu²⁺ had no apparent interference. Thus, using such single chemosensor, Cu²⁺ and Fe³⁺ can be detected independently with high selectivity and sensitivity. The limits of detection toward Cu²⁺ and Fe³⁺ were 8.5 and 2.0 μM, respectively. DFT calculation results also proved the formation of stable coordination complexes and the phenomenon of fluorescence quenching by Fe³⁺. Furthermore, L was also successfully used as a bioimaging reagent for detection of Fe³⁺ in living cells.     

A gold nanoparticle-based colorimetric sensing ensemble for the colorimetric detection of cyanide ions in aqueous solution

A colorimetric sensing ensemble was prepared by mixing readily prepared adenosine triphosphate (ATP)-stabilized AuNPs with Cu²⁺-phenanthroline complexes. The sensing mechanism of the ensemble was examined by UV-vis spectrometry and transmission electron microscopy. The studies showed that the Cu²⁺-phenanthroline complex was converted to free phenanthroline when exposed to cyanide anions and the free phenanthroline caused the ATP-stabilized AuNPs to aggregate, which in turn, resulted in a visible color change in the AuNP solution. The ensemble could detect cyanide ions in aqueous solution at physiological pH, either spectrophotometrically or visually, with high selectivity toward cyanide anions over a range of mono- and di-anions commonly found in biological and environmental systems. This sensing ensemble also allows a quantitative assay of the analyte in a neutral aqueous solution, down to a concentration of 10⁻⁵ M.     

A new ratiometric and colorimetric chemosensor for cyanide anion based on coumarin-hemicyanine hybrid

A hybrid coumarin-hemicyanine dye, Cou-BT, was developed as a new ratiometric and colorimetric sensor for cyanide with a sensing mechanism via nucleophilic addition of cyanide anion to the benzothiolium group. Cou-BT shows high sensitivity and selectivity for cyanide detection over other common anion species in aqueous acetonitrile solution. The calculated pseudo-first-order rate constant for cyanide anion addition was (2.13 ± 0.08) × 10(-2) s(-1) at 298 K, and the detection limit was estimated to be 0.64 μM. The DFT and TDDFT calculation results suggest that the ratiometric and colorimetric sensing behavior of Cou-BT upon its reaction with cyanide was due to the interrupted π-conjugation and blocked ICT progress.     

Salicylaldehyde-indole-2-acylhydrazone: a simple,colorimetric and absorption ratiometric chemosensor for acetate ion

A simple anion receptor (i.e. salicylaldehyde-indole-2-acylhydrazone) was synthesised and its recognition properties were investigated by naked-eye observation, UV–vis titration spectra, ¹H NMR spectroscopy and DFT calculations. The obtained results indicated that this receptor could realise the selective colorimetric sensing and absorption ratiometric response towards AcO^?  in CH₃CN–DMSO medium, by virtue of threefold intermolecular hydrogen bonding interactions formed with phenolic OH, indole NH and amide NH.     

Novel fluorescent cyanide-selective chemosensor based on a functionalised pillar[5]arene copper(II) complex

As a novel macrocyclic host, pillar[5]arene can selectively recognise guest molecules in organic solvents. In this study, a fluorescent chemosensor composed of a functionalised-pillar[5]arene and Cu²⁺ metal complex (PN–Cu), which shows good selectivity for CN^? anions, has been designed and synthesised. Complexation between PN–Cu and anions has been probed by means of various fluorescence-based methods. PN–Cu, as a turn-on fluorescence chemosensor showed high selectivity towards CN^? ions in comparison to other anions, and its detection limit for CN^? was calculated as 9.03 × 10^?7 M. The PN–Cu sensor can serve as a recyclable component in sensing materials. Moreover, the interaction between the singly functionalised pillar[5]arene and Cu²⁺ has been probed through various tests. Based on the remarkable selectivity of the chemosensor PN–Cu, we propose that it might be used as a potential material for CN^? recognition.     

Exploiting the deprotonation mechanism for the design of ratiometric and colorimetric Zn fluorescent chemosensor with a large red-shift in emission

The design, synthesis, and photophysical evaluation of a new naphthalimide-based fluorescent chemosensor, N-butyl-4-[di-(2-picolyl)amino]-5-(2-picolyl)amino-1,8-naphthalimide (1), were described for the detection of Zn²⁺ in aqueous acetonitrile solution at pH 7.0. Probe 1 showed absorption at 451 nm and a strong fluorescence emission at 537 nm (Φ_F=0.33). The capture of Zn²⁺ by the receptor resulted in the deprotonation of the secondary amine conjugated to 1,8-naphthalimide so that the electron-donating ability of the N atom would be greatly enhanced; thus probe 1 showed a 56 nm red-shift in absorption (507 nm) and fluorescence spectra (593 nm, Φ_F=0.14), respectively, from which one could sense Zn²⁺ ratiometrically and colorimetrically. The deprotonated complex, [(1-H)/Zn]⁺, was calculated at m/z 619.1800 and measured at m/z 618.9890. In contrast to these results, the emission of 1 was thoroughly quenched by Cu²⁺, Co²⁺, and Ni²⁺. The addition of other metal ions such as Li⁺, Na⁺, K⁺, Mg²⁺, Ca²⁺, Fe³⁺, Mn²⁺, Al³⁺, Cd²⁺, Hg²⁺, Ag⁺, and Pb²⁺ produced a nominal change in the optical properties of 1 due to their low affinity to probe 1. This means that probe 1 has a very high fluorescent imaging selectivity to Zn²⁺ among metal ions.     

A highly selective chemosensor derived from benzamide hydrazones for the detection of cyanide ion in organic and organic-aqueous media: design,synthesis, sensing and computational studies

ABSTRACT

A new, highly sensitive and selective chemosensing method has been developed for the detection of cyanide ion using benzamide hydrazone receptors (R1-R4). The sensing ability of these compounds towards CN^? in the presence of Br ^?, HSO₄ ^?, Cl^?, OH^?, I^?, F^?, AcO^?, NO₂ ^? and NO₃ ^? in DMF and DMF-Aqueous mixture (DMF:H₂O, 9:1 v/v) was investigated. The binding characteristics of the probe with cyanide ions carried out by ¹ H NMR titrations indicated the deprotonation of N-H group through H-bond interactions between benzamide hydrazones and cyanide ions; it has been theoretically supported by DFT. The binding constant (Ka) and stoichiometry of the host–guest complex formed was calculated by the Benesi–Hildebrand (B–H) plot, and strong interaction of the probe with CN^- ions forming a 1:2 binding stoichiometry has been noted in this study. In a DMF and aqueous medium for CN^? ion, the lower limit of detection (LOD in ppm) is compared to the limit of quantification (LOQ in ppm), which is quite better in terms of sensitivity.