Capped Mesoporous Silica Nanoparticles for the Selective and Sensitive Detection of Cyanide

The development of easy and affordable methods for the detection of cyanide is of great significance due to the high toxicity of this anion and the potential risks associated with its pollution. Herein, optical detection of cyanide in water has been achieved by using a hybrid organic–inorganic nanomaterial. Mesoporous silica nanoparticles were loaded with [Ru(bipy)₃]²⁺, functionalized with macrocyclic nickel(II) complex subunits, and capped with a sterically hindering anion (hexametaphosphate). Cyanide selectively induces demetallation of nickel(II) complexes and the removal of capping anions from the silica surface, allowing the release of the dye and the consequent increase in fluorescence intensity. The response of the capped nanoparticles in aqueous solution is highly selective and sensitive towards cyanide with a limit of detection of 2 μm .     

New methods for the detection of cyanide based on displacement of the glutathione ligand of glutathionylcobalamin by cyanide

Glutathionylcobalamin (GSCbl) is a vitamin B₁₂ derivative that contains glutathione as the upper axial ligand to cobalt via a Co–S bond. In the present study, we discovered that cyanide reacted with GSCbl, generating cyanocobalamin (CNCbl) and reduced glutathione (GSH) via dicyanocobalamin (diCNCbl) intermediate. This reaction was induced specifically by the nucleophilic attack of cyanide anion displacing the glutathione ligand of GSCbl. Based on the reaction of GSCbl with cyanide, we developed new methods for the detection of cyanide. The reaction intermediate, violet-coloured diCNCbl, could be applied for naked eye detection of cyanide and the detection limit was estimated to be as low as 520 μg L^?1 (20 μM) at pH = 10.0. The reaction product, CNCbl, could be applied for a spectrophotometric quantitative determination of cyanide with a detection limit of 26 μg L^?1 (1.0 μM) at pH = 9.0 and a linear range of 26–520 μg L^?1 (1.0–50 μM). In addition, the other reaction product, GSH, could be applied for a fluorometric quantitative determination of cyanide with a detection limit of 31 μg L^?1 (1.2 μM) at pH = 9.0 and a linear range of 31–520 μg L^?1 (1.2–20 μM). These new GSCbl-based methods are simple, highly specific and sensitive with great applicability for the detection of cyanide in biological and non-biological samples.     

A Reversible Dual Mode Chemodosimeter for the Detection of Cyanide Ions in Natural Sources

Herein, we report the synthesis of two indolium probes 1 and 2 based on anthracene and pyrene derivatives and their interactions with various anions. Of these probes, the pyrene conjugate 2 acts as a dual colorimetric and fluorescent chemodosimeter for the selective and sensitive detection of cyanide ions. The detection limit of probe 2 for CN^? ions was found to be 10 ppb (30 nM ). The nature of interaction has been thoroughly studied through various techniques such as ¹H NMR and IR spectroscopy, HRMS, and isothermal calorimetric (ITC) studies. These studies confirm that probe 2 forms a 1,2‐adduct in the presence of CN^? ions. Kinetic studies using probe 2 showed the completion of the reaction within 15 s with a rate constant of k′=0.522±0.063 s^?1_. This probe can be coated on a solid surface (dipstick) and a polymer matrix for the on‐site analysis and quantification of endogenous cyanide ions in natural sources such as Indian almonds.     

A novel fluorescent and chromogenic probe for cyanide detection in water based on the nucleophilic addition of cyanide to imine group

A fluorescent and colorimetric probe bearing salicylaldehyde hydrazone functionality has been prepared for cyanide sensing. The detection of cyanide was performed via the nucleophilic attack of cyanide anion on the imine group of the probe with a 1:1 binding stoichiometry, which could be confirmed by ¹H NMR and MS studies. The specific reaction results in a prominent fluorescence enhancement and a color change from colorless to yellow.     

Determination of cyanide,thiocyanate, cyanate,hexavalent chromium,and metal cyanide complexes in various mixtures by ion chromatography with conductivity detection

The first aim of this study was to develop a selective, sensitive, and reliable method for direct simultaneous determination of cyanate, thiocyanate, and hexavalent chromium by ion chromatography (IC) with conductivity detection. The other target was to successfully determine cyanides by utilizing same chromatographic system. Yet, since cyanides can not be detected by the direct method, free cyanide ions were converted into cyanate with chloramine-T at alkaline pH. In addition, strongly complexed metal cyanides were converted into cyanate by using photo-oxidation following chloramine-T. Total cyanate ion obtained from developed methods were analyzed with IC. The chromatographic separations on anion exchange column were accomplished by optimized multistep gradient eluent program using NaOH as the eluent. Proposed method was applied for the simultaneous determination of cyanide and hexavalent chromium in electroplating bath solutions and in industrial wastewater. Cyanide and hexavalent chromium could be measured in the linear dynamic ranges of 0.6–961.5 and 0.9–118.5 µmol L^?1, respectively. The limit of detection and limit of quantification of cyanide were 0.18 and 0.61 µmol L^?1, and these values for chromium(VI) were 0.26 and 0.86 µmol L^?1, respectively.     

[2]Pseudorotaxane-Based Supramolecular Optical Indicator for the Visual Detection of Cellular Cyanide Excretion

Cyanide is extremely hazardous to living organisms and the environment. Owing to its wide range of applications and high toxicity, the development of functional materials for cyanide detection and sensing is highly desirable. Host–guest complexation between bis(p-phenylene)-34-crown-10 H and N-methylacridinium salt G remarkably decreases the detection limit for cyanide anions compared with that of the guest itself. The [2]pseudorotaxane selectively recognizes the cyanide anion with high optical sensitivity as a result of the nucleophilic addition of the cyanide anion at the 9-position of G . The host–guest complexation is further incorporated into supramolecular materials for the visual detection of cyanide anions, especially the detection of cellular cyanide excretion with a detection limit of 0.6 μm . This supramolecular method provides an extremely distinct strategy for the visual detection of cyanide anions.     

A Fluorimetric Method for the Determination of Cyanide with Fluorescein and Iodine∗

Abstract

A rapid, simple and sensitive fluorimetric method has been developed for the determination of cyanide with fluorescein as fluorogenic reagent (λ_ex = 494 nm, λ_em = 514 nm) at pH 6.0–7.0. A linear calibration curve was obtained in the range 0.004–2.0 μg CN^?/25 ml. The detection limit is 0.004 μg CN^-/25 ml. The method was successfully applied to the determination of cyanide in waste water.

     

A rapid responsive and highly selective probe for cyanide in the aqueous environment

A colorimetric and fluorescent cyanide probe based on 7-(trifluoroacetamino)coumarin has been prepared. This structurally simple probe displays rapid response and high selectivity for cyanide over other common anions in the aqueous solution. The sensing of cyanide was performed via the nucleophilic attack of cyanide anion to carbonyl of the probe with a 1:1 binding stoichiometry, which could be confirmed by Job’s plot, ¹H NMR, and MS studies. DFT/TDDFT calculations support that the fluorescence enhancement of the probe is mainly due to the ICT process improvement. The detection limit of the fluorescent assay for cyanide is as low as 0.3 μM in a rapid response of less than 30 s. Thus, the present probe should be applicable as a practical system for the monitoring of cyanide concentrations in aqueous samples.     

A simple Schiff base as ‘naked eye’ and fluorescent ‘on–off’ sensor for detecting cyanide in mixed aqueous solution

A simple Schiff base sensor (L₁) derived from N-(1-naphthyl) ethylenediamine dihydrochloride was designed and synthesised by simple chemistry procedures. The sensor exhibited a visible colour change observed by both colorimetric and fluorimetric responses for cyanide ion in aqueous solution. The detection of cyanide was performed via the nucleophilic attack of cyanide anion on the imine group of the sensor with a 1?:?1 binding stoichiometry. Moreover, test strips based on the sensor were fabricated, which served as convenient and efficient CN^? test kits and the sensor L₁ is a good way to detect hydrogen cyanide in aqueous extracts of sprouting potatoes.     

Normal pulse polarographic quantification of cyanide and sulfide by the anodization of mercury

Normal pulse polarography is used to quantify cyanide and sulfide simultaneously by the anodic oxidation of mercury. The detection limit for cyanide is 18 μg l^-1 by the normal pulse polarographic technique. A supporting electrolyte system of 1 M Na₂CO₃ is optimal with regard to background interferences and sample loss. The electrode reaction for the oxidation of mercury in the presence of cyanide can be described by Hg + pCN^- α Hg(CN)_p^2-p + 2e^-, with p having values of 2, 3 and 4 depending on the surface concentration of cyanide. The feasibility of simultaneous cyanide and sulfide quantification is demonstrated with waste-water samples.     

Advantages and disadvantages of various kinds of adsorbents used in industrial extraction of [Au(CN)<Subscript>2</Subscript>]<Superscript>–</Superscript> anions from cyanide solutions and pulps

Comparative study of an industrially used activated carbon of WSC-207C-GR brand, strongly basic anion exchanger MINIX, and weakly basic anion exchanger Purogold S992 in recovery of [Au(CN)₂]^– ions from cyanide aqueous solutions and slurries was carried out. It was found that the strongly basic anion exchanger MINIX has the highest adsorption rate of the cyanide complex of gold(I), whereas the activated carbon and the weakly basic ion exchanger possess a substantially higher selectivity toward the complex of gold(I). Use of each of the three sorbents makes it possible to solve the problem of the cyanide leaching of gold from ores containing natural substances that exhibit adsorbent properties with respect to the dicyanoaurate(I) ion. The influence exerted by the amount of kerosene additive and volume fraction of a sorbent on the efficiency of gold recovery by the sorbent in cyanidation of ores in the “carbon-in-pulp” and “resin-in-pulp” modes.     

A fluorescein-based fluorogenic and chromogenic chemodosimeter for the sensitive detection of sulfide anion in aqueous solution

A highly sensitive chromo- and fluorogenic chemodosimeter for sulfide anion was developed based on its nucleophilicity. 2,4-Dinitrobenzenesulfonyl-fluorescein (I) is a weakly fluorescent compound. Upon mixing with sulfide anion in aqueous acetone solution, the 2,4-dinitrobenzenesulfonyl group of I was efficiently removed and highly fluorescent fluorescein was released, hence leading to the dramatic increases in both fluorescence and absorbance of the reaction solution. The fluorescence increment is linear with sulfide anion concentration in the range 50-1000 nmol L⁻¹ with a detection limit of 4.3 nmol L⁻¹ (3σ). The proposed chemodosimeter showed excellent selectivity toward sulfide anion and was successfully applied to the determination of sulfide anion in synthetic wastewater samples.     

Fluorogenic Ag+–Tetrazolate Aggregation Enables Efficient Fluorescent Biological Silver Staining

Silver staining, which exploits the special bioaffinity and the chromogenic reduction of silver ions, is an indispensable visualization method in biology. It is a most popular method for in‐gel protein detection. However, it is limited by run‐to‐run variability, background staining, inability for protein quantification, and limited compatibility with mass spectroscopic (MS) analysis; limitations that are largely attributed to the tricky chromogenic visualization. Herein, we reported a novel water‐soluble fluorogenic Ag⁺ probe, the sensing mechanism of which is based on an aggregation‐induced emission (AIE) process driven by tetrazolate‐Ag⁺ interactions. The fluorogenic sensing can substitute the chromogenic reaction, leading to a new fluorescence silver staining method. This new staining method offers sensitive detection of total proteins in polyacrylamide gels with a broad linear dynamic range and robust operations that rival the silver nitrate stain and the best fluorescent stains.     

Quantification of free and metal-complexed cyanide by tetrathionate derivatization

A sensitive and robust method for detection of free and metal-complexed cyanide in solutions is described. The method does not require a distillation step and is applicable for both low ionic strength and sea-water samples. The method is based on the reaction of cyanide with potassium tetrathionate followed by high-performance liquid chromatography (HPLC) separation and UV detection of formed thiocyanate. The detection limit of the method is 250?nmol?L^?1 cyanide (6.5?µg?L^?1 CN^?) without a pre-concentration step. Storage for three days does not significantly change the results. The sum of free and weak metal-complexed cyanide can be measured by tetrathionate derivatization at a pH of 10. The sum of free, weak metal-complexed cyanide, iron(II) and iron(III)-complexed cyanides may be measured by tetrathionate derivatization at pH 4.4. Derivatization requires heating to 90°C for 20?min at pH?=?10 and for 12 h at pH?=?4.4. Weighted mean recoveries for free, iron(II), iron(III), nickel(II), silver(I), Cd(II) and Zn(II) complexed cyanide were in the range of 87 to 112% and weighted standard deviations were in the range of 1.7 to 10.0%. The method is not applicable for cyanide complexes of gold and cobalt. We illustrate an application of cyanide quantification using pore-waters from the Delaware Great Marsh.     

New Insight into the Mode of Action of Nickel Superoxide Dismutase by Investigating Metallopeptide Substrate Models

For the first time, the existence of a substrate adduct of a nickel superoxide dismutase (NiSOD) model, based on the first nine residues from the N terminus of the active form of Streptomyces coelicolor NiSOD, has been proven and the adduct has been isolated. This adduct is based on the cyanide anion (CN^?), as a substrate analogue of the superoxide anion (O₂^.?), and the nickel metallopeptide H‐HCDLPCGVY‐NH₂‐Ni. Spectroscopic studies, including IR, UV/Vis, and liquid‐ and solid‐state NMR spectroscopy, show a single nickel‐bound cyanide anion, which is embedded in the metallopeptide structure. This complex sheds new light on the question of whether the mode of action of the NiSOD enzyme is an inner‐ or outer‐sphere mechanism. Whereas discussion was previously biased in favor of an outer‐sphere electron‐transfer mechanism due to the fact that binding of cyanide or azide moieties to the nickel active site had never been observed, our results are a clear indication in favor of the inner‐sphere electron‐transfer mechanism for the disproportionation of the O₂^.? ion, whereby the substrate is attached to the Ni atom in the active site of the NiSOD.     

Reaction‐Based Colorimetric and Ratiometric Fluorescence Sensor for Detection of Cyanide in Aqueous Media

A stilbene‐based compound ( 1 ) has been prepared and was highly selective for the detection of cyanide anion in aqueous media even in the presence of other anions, such as F^?, Cl^?, Br^?, I^?, ClO₄^?, H₂PO₄^?, HSO₄^?, NO₃^?, and CH₃CO₂^?. A noticeable change in the color of the solution, along with a prominent fluorescence enhancement, was observed upon the addition of cyanide. The color change was observed upon the nucleophilic addition of the cyanide anion to the electron‐deficient cyanoacrylate group of 1 . The spectral changes induced by the reaction were analyzed by comparison with two model compounds, such as compound 2 with dimethyl substituents and compound 3 without a cyanoacrylate group. An intramolecular charge‐transfer (ICT) mechanism played a key role in the sensing properties, and the mechanism was supported by DFT/TDDFT calculations.     

Detection of Contaminants of High Environmental Impact by Means of Fluorogenic Probes

This personal account describes our contribution to the design of selective fluorogenic probes for contaminants of high environmental impact. For this purpose, we have developed a new family of highly versatile fluorogenic reagents that were able to show large differences in their fluorescence in the presence of selected analytes. They were used in the preparation of fluorogenic probes for the detection of contaminants of high environmental impact which currently have no good solutions: phosphorylating agents, such as chemical weapons; methyl mercury(II); the cyanide anion; amino‐acid metabolites, such as doping substances; and biogenic amine mimics, such as drugs of abuse and recreational drugs. The development of new materials for specific sensing was achieved by anchoring selected probes to silica nanomaterials, suitable for the selective detection of organic analytes in water for immediate application to toxicological or environmental purposes.

     

Indirect quantification of trace levels cyanide in environmental waters through flame atomic absorption spectrometry coupled with cloud point extraction

Cloud point extraction (CPE) has been used for the preconcentration and indirect quantification of cyanide after the formation of a ion-associate complex with 3-amino-7-diethylamino-8,9-benzo-2-phenoxazine chloride (Nile blue, NB⁺) in the presence of copper (II) ions, and later analysis by flame atomic absorption spectrometry (FAAS) using polyethyleneglycolmono-p-nonylphenylether (PONPE 7.5) as extracting surfactant. The chemical variables affecting the separation phase and the viscosity affecting the detection process were optimized. At pH 5.5, preconcentration of only 50 mL of sample in the presence of 0.04 % (w/v) PONPE 7.5 and 5.64 × 10^?5 mol L^?1 Nile blue permitted the detection of 3.75 μg L^?1 cyanide. The enhancement factor was 64.7 for cyanide. The proposed method was successfully applied to the determination of free cyanide in environmental water samples. The method was compared with the pyridine–barbituric acid method and the paired t test was used to determine whether the results obtained by the two methods differ significantly.     

Rapid colorimetric sensing of cyanide anion in aqueous media with a spiropyran derivative containing a dinitrophenolate moiety

A spiropyran derivative containing a dinitrophenolate moiety (2: 1′,3′,3′-trimethyl-6,8-dinitro-spiro-[2H-1-benzopyran-2,2′-indoline]) behaves as a receptor for selective detection of cyanide anion (CN⁻) in aqueous media. Compound 2, when dissolved in aqueous media, spontaneously produces the spirocycle-opened merocyanine (MC) form even in dark condition. The absorption band of the MC form decreases selectively upon addition of CN⁻, via a nucleophilic addition of CN⁻ to the spirocarbon of the MC form. The nucleophilic addition occurs very rapidly (within 1 min) and enables rapid and selective quantification of very low levels of CN⁻ (>0.8 μM) by an absorption analysis.     

Application of hydrocyanic acid vapor generation via focused microwave radiation to the preparation of industrial effluent samples prior to free and total cyanide determinations by spectrophotometric flow injection analysis

A sample preparation procedure for the quantitative determination of free and total cyanides in industrial effluents has been developed that involves hydrocyanic acid vapor generation via focused microwave radiation. Hydrocyanic acid vapor was generated from free cyanides using only 5 min of irradiation time (90 W power) and a purge time of 5 min. The HCN generated was absorbed into an accepting NaOH solution using very simple glassware apparatus that was appropriate for the microwave oven cavity. After that, the cyanide concentration was determined within 90 s using a well-known spectrophotometric flow injection analysis system. Total cyanide analysis required 15 min irradiation time (90 W power), as well as chemical conditions such as the presence of EDTA–acetate buffer solution or ascorbic acid, depending on the effluent to be analyzed (petroleum refinery or electroplating effluents, respectively). The detection limit was 0.018 mg CN l⁻¹ (quantification limit of 0.05 mg CN l⁻¹), and the measured RSD was better than 8% for ten independent analyses of effluent samples (1.4 mg l⁻¹ cyanide). The accuracy of the procedure was assessed via analyte spiking (with free and complex cyanides) and by performing an independent sample analysis based on the standard methodology recommended by the APHA for comparison. The sample preparation procedure takes only 10 min for free and 20 min for total cyanide, making this procedure much faster than traditional methodologies (conventional heating and distillation), which are time-consuming (they require at least 1 h). Samples from oil (sour and stripping tower bottom waters) and electroplating effluents were analyzed successfully.