Coumarin-Cu(II) ensemble-based cyanide sensing chemodosimeter

An "ensemble"-based chemodosimeter 1-Cu(II) for cyanide detection is reported. 1-Cu(II) can recognize a cyanide ion over other anionic species to show a marked fluorescence enhancement under aqueous conditions. "Off-on" fluorescence change of 1-Cu(II) is proceeded by addition of cyanide, which induces decomplexation of the Cu(II) ion from nonfluorescent 1 followed by hydrolytic cleavage of the resulted Schiff base to give a strongly fluorescent coumarinaldehyde (2). The selective detection of cyanide with 1-Cu(II) for biological application was also performed in HepG2 cells.     

A highly selective colorimetric and “Off-On” fluorescence sensor for CN~- based on Zn(salphenazine) complex

The development of sensors for selective detection of cyanide ion(CN~-) is an important mission to accomplish because of the versatility and toxicity of CN~-. In the present work, an "ensemble"-based colorimetric and fluorescent sensor(L2-Zn~(2+)) for CN~-ion has been developed. The addition of cyanide ions removed Zn~(2+) from the ensemble(L2-Zn~(2+)) in aqueous medium, resulting in a color change of the solution from red to buff and a "turn-on" fluorescent response. Also, the sensitivity of both the fluorescenceand colorimetric-based assay is below the maximum allowable level of cyanide ions in drinking water set by the World Health Organization. In addition, test strips, which served as convenient and efficient CN~- test kits, were fabricated based on the sensor.Notably, the selective detection of cyanide with L2-Zn~(2+) for practical application was also performed in sprouting potatoes.     

Selective recognition of sodium cyanide and potassium cyanide by diaza-crown ether-capped Zn-porphyrin receptors in polar solvents

Two new ditopic porphyrin receptors Zn1, incorporating a diaza-15-crown-5 unit, and Zn2, incorporating a diaza-18-crown-6 unit, have been prepared and characterized. UV-vis study in polar methanol has revealed that Zn1 is able to selectively recognize sodium cyanide over potassium cyanide (the ratio of their binding constant is ca. 56), whereas Zn2 exhibits a higher binding affinity for potassium cyanide over sodium cyanide (the ratio of their binding constant is ca. 12). In contrast, both receptors display substantially weaker binding affinity for sodium thiocyanate and potassium thiocyanate presumably due to a monotopic binding fashion.     

Silica nanoparticles doped with an iridium(III) complex for rapid and fluorometric detection of cyanide

We describe a nanosensor for sensitive and selective detection of cyanide anions. The Ir(III) chlorine bridge complex [Ir(C^N)₂-m-Cl]₂ (Irpq, where pq is C^N = 2-phenyl quinoline) was doped into silica nanoparticles (SiNPs) with a typical size of about 30 nm. The intensity of the yellow emission of the doped SiNPs (under 410 nm exCitation) was strongly enhanced on addition of cyanide ions due to the replacement of chloride by cyanide. The method can detect cyanide ions in the 12.5 to 113 μM concentration range, and the limit of detection is 1.66 μM (at an S/N ratio of 3). The method is simple, sensitive and fast, and this makes it a candidate probe for the fast optical determination of cyanide.

The nanosensor is exploiting the cyanide-induced enhancement of the fluorescence of silica nanoparticles doped with an Ir(III) complex which is the result of the replacement of chloride by cyanide.

     

Detection of cyanide via extended π-conjugation-induced fluorescence enhancement of a metal organic framework composed of terbium(III), bipyridyl and adenosine diphosphate

A metal-organic framework (MOF) was designed and prepared from luminescent Tb(III), adenosine diphosphate (ADP) and bipyridyl (Bipy). Its green fluorescence at 545 nm is shown to enable the fluorometric detection of cyanide ion based on the principle of π-conjugation-induced fluorescence enhancement. The fluorescence of the probe is strongly increased by cyanide due to extended π-conjugation between probe MOF and cyanide which sensitizes the fluorescence of Tb(III). This effect can be used to quantify cyanide at levels as low as 30 nM in aqueous solution. The method was applied to the determination of cyanide in saliva samples. The lack of interference by acetate and fluoride is a specific feature of this method. The method based on the principle of π-conjugation-induced fluorescence enhancement provides a new sensing way for widely used fluorescence assays.

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Graphical abstract A cyanide-selective Tb-ADP-Bipy MOF was designed and synthesized for the detection of cyanide based on the principle of π-conjugation-induced fluorescence enhancement.

     

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.     

Cu and CN-selective fluorogenic sensors based on pyrene-appended thiacalix[4]arenes

Two new fluorescent sensors 1 and 2 based on thiacalix[4]arenes bearing pyrene moieties have been synthesized in cone conformation. The binding abilities of these sensors towards different cations such as lithium, sodium, potassium, nickel, cadmium, copper, zinc, lead, silver, mercury and anions like fluoride, chloride, bromide, iodide, cyanide, acetate, hydrogen sulfate and nitrate have been examined by UV-vis and fluorescence spectroscopies. These receptors show pronounced selectivity for copper and cyanide ions. In CH₂Cl₂/CH₃CN (1:1), the presence of Cu(II) ion induces the formation of 1:1 (H/G) complex with receptor 1 and 1:2 (H/G) complex with receptor 2. The cyanide ions form a 1:1 (H/G) complex with both receptors.     

A Convenient Synthesis of 2,3-Diphenyl-2-cyanooxiranes

Several studies¹ have been reported on the synthesis of 2,3-diphenyl-2-cyanooxiranes. Kohler and Brown^la synthesized the oxirane in ca. 30% yield by reaction of desyl chloride with potassium cyanide in aqueous alcohol. However, the method which they employed seems to be rather complicated. Such reaction of desyl bromide with cyanide ion has not been studied in detail. We now report that cis- and trans-2,3-diphenyl-2-cyanooxiranes (2a-d and 3a-d) are conveniently obtained in good yields by reaction of 4′-substituted desyl bromide (1a-d) with 40% aqueous potassium cyanide in a mixture of dichloromethane and triethylbenzylammonium chloride (TEBAC); the total yield of 2c and 3c, for example, was as high as 86%. When cethyltriethylammonium bromide was used as a     

A novel cyanide chemodosimeter based on trifluoroacetamide benzhydrol-2 as binding motif: importance of substituent positioning on intra-molecular charge transfer

The nucleophilic nature of cyanide is used to develop a simple, sensitive, and highly effective sensor. Azo dye 6a based on 2-(trifluoroacetamide) benzhydrol-2 (2-TFAB) as anions receptor, presents a new way to build molecular color sensors for cyanide in water. The 2-TFAB moiety of the dye 6a is used as receptor group for cyanides and linked directly by dominant reversible covalent bonding over hydrogen bonding, confirmed by the inactivity of the derivative 6b toward cyanides.     

Determination of cyanide using a chemiluminescence system composed of permanganate,rhodamine B,and gold nanoparticles

We describe a new chemiluminescence (CL) system based on the oxidation of rhodamine B (RhoB) with alkaline potassium permanganate in the presence of gold nanoparticles (Au-NPs) and anionic detergent sodium dodecyl sulfate. Free RhoB is weakly chemiluminescent when oxidized with permanganate at alkaline pH values. However, a remarkably strong enhancement of CL is observed in the presence of Au-NPs, probably due to a strong interaction between RhoB and the NPs. The possible mechanism was studied via recording the CL emission. It is also found that the intensity of CL gradually decreases in the presence of cyanide due to its interaction with the Au-NPs. The relation between the decreased CL intensity and cyanide concentration was exploited to develop a method for the determination of cyanide in the 0.01–0.5 μM concentration range, with a detection limit of 2.8 nM. The method was used to determine cyanide in spiked water, urine, and serum.

Alkaline permanganate-rhodamine B-SDS CL reaction is dramatically enhanced by gold nanoparticles. Based on the inhibiting effect of cyanide on this system, a sensitive CL method was developed for its determination

     

Coumarinyl aldehyde as a Michael acceptor type of colorimetric and fluorescent probe for cyanide in water

A simple aldehyde-functionalized coumarin (1) was utilized as a doubly activated Michael acceptor type of chemodosimeter for cyanide in water. The probe has shown a selective and sensitive response to the cyanide anion over other various anions through the Michael addition reaction of the cyanide to 1. When cyanide anions were added, the prominent color changes as well as fluorescence changes of 1 were observed so that millimolar concentrations of cyanides were detectable by the naked eye.     

Spectrophotometric determination of hydrogen cyanide in air using phloroglucinol

Summary A spectrophotometric determination of hydrogen cyanide in air is described. Hydrogen cyanide from air is collected in dilute sodium hydroxide and then reacted with pyridine forming glutaconic aldehyde. The glutaconic aldehyde thus formed is subsequently coupled with aqueous phloroglucinol solution to form a polymethine red-violet dye having absorbance maxima at 540 nm. The colour system obeys Beer's law in the range of 0.45 to 3.6 mg/m³ of hydrogen cyanide (0.4 to 3.2 g/g). Collection efficiency of absorbing solution, molar absorptivity and Sandell's sensitivity have been evaluated. All other important analytical parameters have been studied and applied for the determination/detection of hydrogen cyanide in air samples and cigarette smoke.     

β-环糊精包裹的方酸类化合物在纯水体系中对CN-的选择性识别

利用β-环糊精包裹方酸类化合物(SQ),很好地改善了SQ在纯水体系中的溶解度.包合物中SQ的两个苯环分别嵌入到两个不同的β-环糊精的空腔内,而中间的四元环裸露在外边.方酸类化合物在近红外区强而窄的吸收以及它们对氰化物特有的敏感性使它们成为理想的氰根离子的传感器.β-环糊精的包裹作用使不溶入水的SQ能够直接在纯水体系中选择性识别氰根离子而不需要任何化学修饰.     

An iodide/anion exchange route to benzimidazolylidene silver complexes from benzimidazolium iodide: Crystal structures of N,N′-dibutylbenzimidazolylidene silver chloride, bromide, cyanide and nitrate

Syntheses of N,N′-dibutylbenzimidazolylidene silver complexes having chloride, nitrate or cyanide as an anion part through an iodide/anion exchange from N,N′-dibutylbenzimidazolium iodide are described, representing a practical route to benzimidazolylidene silver complexes from readily accessible benzimidazolium iodide. The crystal structures of N,N′-dibutylbenzimidazolylidene silver chloride, bromide, cyanide and nitrate have been determined, showing a close ligand-unsupported Ag-Ag interaction in [(NHC)₂]Ag⁺[AgX₂]⁻ and a “T” shape geometry about the silver(I) cation in complexes of chloride, bromide and cyanide, but a nearly linear shape in the bis(N,N′-dibutylbenzimidazolylidene) silver complex [ with non-coordinating nitrate anion.     

A Novel Nano-Sensor Based on Rhodamine-β-Isothiocyanate – Doped Silica Nanoparticle for pH Measurement

A novel and simple enzymatic method for the determination of trace cyanide in marine fish is presented. This method is based on the conversion of metal-cyanide complexes by a fungal enzyme extract containing cyanide hydratase (E.C. 4.2.1.66; CyHT) and formamidase (E.C. 3.5.1.49) into formate and ammonia. The formate produced in the sample pretreated with the fungal enzymes was measured by adding formate dehydrogenase (E.C. 1.2.1.2; FDH) and excess NAD⁺. The NADH formed accordingly was monitored at 340nm. The cyanide calibration curve was found to be linear in the range of 10–100µM, and the detection limit was 1.1µM (0.0286ppm). The proposed biotest was successfully applied to the determination of trace cyanide in a tropical marine food fish species (Russells Snapper (Lutjamus russellii)) which had been exposed to cyanide.     

Biosourced 3-formyl chromenyl-azo dye as Michael acceptor type of chemodosimeter for cyanide in aqueous environment

A simple water-soluble aldehyde functionalized chromone 5 was utilized as a doubly activated Michael acceptor type of chemodosimeter for cyanide in water. The water solubility of the probe 5 is due to the incorporation of two glycerol units on the starting prepared chemodosimeter. This sensory system is able to selectively distinguish cyanide among fluoride and many other anions at micromolar concentrations and instantly detect cyanide in water at ambient temperatures with a detection limit down to 1.0 mM. Thus, the chemodosimeter 5 was applied to the quantitative determination of cyanide anion in drinking water sample (drinking water from commence).     

Doubly activated coumarin as a colorimetric and fluorescent chemodosimeter for cyanide

A new α,β-unsaturated nitro group and coumarin conjugate-based fluorescent chemodosimeter 1 was developed for the selective detection of cyanide anions. The chemodosimeter has shown a selective and sensitive response to cyanide anions over other various anions through a nucleophilic aromatic substitution reaction of the cyanide to 1. When cyanide anions were added, the enhanced fluorescence intensity as well as the color changes of 1 was observed so that micromolar concentrations of cyanides were detectable by the naked eye.     

Amperometric sensor for cyanide utilizing cyanidase and formate dehydrogenase

An amperometric sensor for the detection of cyanide integrated in a flow injection analysis (FIA) system is presented. The specificity of the sensor for cyanide is achieved by a reaction cascade involving two enzymes, cyanidase (EC 3.5.5.1) and formate dehydrogenase (FDH, EC 1.2.1.2). The limit of detection (LOD) and the limit of quantification (LOQ) were determined to be in the low micromolar range. The sensor showed very good long term stability and the linear range of detection extends from 0.7 up to 800 M. The sensor’s ability to measure cyanide in complex matrices, such as plant extracts, is demonstrated. Although the sensor is susceptible to formate and to a lesser extent to thiocyanate, sulfide does not interfere significantly.     

Enantioselective O-acetylcyanation/cyanoformylation of aldehydes using catalysts with built-in crown ether-like motif in chiral macrocyclic V(V) salen complexes

Chiral macrocyclic V(V) salen complexes 1a-f derived from macrocyclic ligands obtained by the reaction of 1R,2R-(−) diaminocyclohexane/(1R,2R)-(+)-1,2-diphenylethylenediamine with bis-aldehydes 2 and 3 were synthesized and used as efficient catalysts in asymmetric cyanation reactions. The V(V) catalysts demonstrated excellent performance (product yields and ees up to 99%) with potassium cyanide (KCN) and sodium cyanide (NaCN). The catalytic system also performed very well with a safer source of cyanide-ethyl cyanoformate to give cyanohydrin carbonates in excellent yield and ee (up to 97%). The V(V) macrocyclic salen complex 1b retained its performance at multi-gram level and was conveniently recycled for a number of times.     

Kinetics of the reactions of cyclopropane derivatives. III. Gas-phase unimolecular isomerization of cyclopropyl cyanide to the cyanopropenes

Cyclopropyl cyanide isomerizes in the gas phase at 660°–760°K and 2–89 torr to give mainly cis- and trans-crotonitrile and allyl cyanide, with traces of methacrylonitrile. The reactions are first order, homogeneous, and unaffected by the presence of radical-chain inhibitors. The rate constants are given by Overall: cis-Crotonitrile: trans-Crotonitrile: Allyl cyanide: where the error limits are standard deviations. On the basis of a biradical mechanism, it is deduced that the ? CH? CN radical center is resonance stabilized by ca. 30 kJ mole^?1. Approximate equilibrium data are given for interconversion of the 1- and 3-cyanopropenes.