Showing papers on "Cyanide published in 2010"
TL;DR: This tutorial review focuses on recent developments arising from studies of optical sensors for cyanide ions, which are categorized by approaches involving cyanide selective receptors, the utilization of metal coordinated complexes, and chemodosimeters.
Abstract: This tutorial review focuses on recent developments arising from studies of optical sensors for cyanide ions, which are categorized by approaches involving cyanide selective receptors, the utilization of metal coordinated complexes, and chemodosimeters.
989 citations
TL;DR: In this article, a gold-nanocluster-based fluorescent sensor for cyanide in aqueous solution, which is based on the cyanide etching-induced fluorescence quenching of gold nanoclusters, is reported.
Abstract: A novel, gold-nanocluster-based fluorescent sensor for cyanide in aqueous solution, which is based on the cyanide etching-induced fluorescence quenching of gold nanoclusters, is reported. In addition to offering high selectivity due to the unique Elsner reaction between cyanide and the gold atoms of gold nanoclusters, this facile; environmentally friendly and cost-effective method provides high sensitivity&-With-zthis'sensor, the lowest concentration to quantify cyanide ions ccould be down to 200 x 10(-9) M, which. is approximately 14 times lower tharr-the..moxotim, level (2.7 x 10(-6) M) of cyanide in drinking water permitted by the World Health Organization (WHO). Furthermore, several real water samples spiked with cyanide, including local groundwater, tap water, pond water, and lake water, are analyzed using the sensing system, and experimental results show that this fluorescent sensor exhibits excellent recoveries (over 93%). This highly sensitive and selective detection of cyanide in food, soil, water, and biological samples.
393 citations
TL;DR: The recent methods cover both established and emerging analytical disciplines and include naked eye visual detection, spectrophotometry/colorimetry, capillary electrophoresis with optical absorbance detection, fluorometry, chemiluminescence, near-infrared cavity ring down spectroscopy, atomic absorption spectrometry, electrochemical methods.
318 citations
TL;DR: A new NIR fluorescent sensor based on an amine-substituted heptamethine cyanine dye displayed a highly selective fluorescence enhancement with cyanide in aqueous solutions, and was applied for the imaging of anthropogenic and biogenic cyanide.
285 citations
TL;DR: This work presents an approach that can be used for the rational design of cathode catalysts with potential use in phosphoric acid fuel cells, or in any environments containing strongly adsorbing tetrahedral anions, based on molecular patterning of platinum surfaces with cyanide adsorbates that can efficiently block the sites for adsorption of spectator anions while the oxygen reduction reaction proceeds unhindered.
Abstract: The slow rate of the oxygen reduction reaction in the phosphoric acid fuel cell is the main factor limiting its wide application. Here, we present an approach that can be used for the rational design of cathode catalysts with potential use in phosphoric acid fuel cells, or in any environments containing strongly adsorbing tetrahedral anions. This approach is based on molecular patterning of platinum surfaces with cyanide adsorbates that can efficiently block the sites for adsorption of spectator anions while the oxygen reduction reaction proceeds unhindered. We also demonstrate that, depending on the supporting electrolyte anions and cations, on the same CN-covered Pt(111) surface, the oxygen reduction reaction activities can range from a 25-fold increase to a 50-fold decrease. This behaviour is discussed in the light of the role of covalent and non-covalent interactions in controlling the ensemble of platinum active sites required for high turn over rates of the oxygen reduction reaction.
274 citations
TL;DR: A Co(II)-salen based fluorescent sensor (1.Co) that can selectively recognize cyanide anions in 1:2 binding stoichiometry over other anions has been developed.
217 citations
TL;DR: In this article, a Ce-doped ZnOoxide, prepared by sonochemical wet impregnation method and calcined at 500°C, was characterized by XRD, EDS, XPS, SEM, FT-IR, UV-visible DRS, PL, EIS, and N 2 -adsorption and desorption isotherms.
164 citations
TL;DR: Kinetic evaluation and equilibrium assessment illustrated that the Langmuir model is the best fit for the experimental data, which attains a maximum adsorption capacity of 156.2 mg/g.
143 citations
TL;DR: UV-vis spectral changes which accompany either fluoride or cyanide binding to the boron center are similar and include a 30 nm bathochromic shift of the metal-to-ligand charge transfer band.
Abstract: As part of our ongoing interest in the design of boron-based cyanide anion receptors, we have synthesized a triaryl borane decorated by a cationic Ru(II) complex and have investigated its anion binding properties. This new borane, [(2,2′-bpy)Ru(κ-C,N-2-(dimesitylborylphenyl)pyridinato)]OTf ([2]OTf), binds both fluoride and cyanide anions in organic solvents to afford 2-F and 2-CN whose crystal structures have been determined. UV−vis titrations in 9/1 CHCl3/DMF (vol.) afforded K(F−) = 1.1(±0.1) × 104 M−1 and K(CN−) = 3.0(±1.0) × 106 M−1 indicating that [2]+ has a higher affinity for cyanide than for fluoride in this solvent mixture. These elevated binding constants show that the cationic Ru(II) complex increases the anion affinity of these complexes via Coulombic and inductive effects. The UV−vis spectral changes which accompany either fluoride or cyanide binding to the boron center are similar and include a 30 nm bathochromic shift of the metal-to-ligand charge transfer band. This shift is attributed to a...
133 citations
TL;DR: A number of aromatic heterocycles as well as azulene can be cyanated in reasonable to good yields by using a copper cyanide catalyst and an iodine oxidant.
131 citations
TL;DR: An activated Michael acceptor type of probe by an intramolecular hydrogen bond has shown a selective fluorescence turn-on response to cyanide through a conjugated addition of the nucleophilic anion to the enone probe with a 1300-fold increase in its fluorescence intensity.
TL;DR: A Zn(2+)-specific molecular probe 3 was developed for the selective detection of CN(-) under aqueous conditions and generates a bright blue fluorescence that allows the detection of the latter and is useful for the screening of natural products with and without endogenous cyanide content.
TL;DR: A new SET-driven reaction-based strategy is reported for sensing of cyanide with indicators having low LUMO levels, which exhibits regenerability and dip-stick sensing, and fabrication of an electronic sensing device for cyanide is demonstrated.
TL;DR: A sensory polymeric material for the colorimetric sensing of cyanide in water has been developed based on the reactivity of this anion with a fluorene derivative.
TL;DR: Transcriptional profiling of the cys-c1 mutant reveals that cyanide accumulation acts as a repressive signal for several genes encoding enzymes involved in cell wall rebuilding and the formation of the root hair tip as well as genes involved in ethylene signaling and metabolism.
Abstract: Cyanide is stoichiometrically produced as a coproduct of the ethylene biosynthesis pathway and is detoxified by β-cyanoalanine synthase enzymes. The molecular and phenotypical analysis of T-DNA insertion mutants of the mitochondrial β-cyanoalanine synthase CYS-C1 suggests that discrete accumulation of cyanide is not toxic for the plant and does not alter mitochondrial respiration rates but does act as a strong inhibitor of root hair development. The cys-c1 null allele is defective in root hair formation and accumulates cyanide in root tissues. The root hair defect is phenocopied in wild-type plants by the exogenous addition of cyanide to the growth medium and is reversed by the addition of hydroxocobalamin or by genetic complementation with the CYS-C1 gene. Hydroxocobalamin not only recovers the root phenotype of the mutant but also the formation of reactive oxygen species at the initial step of root hair tip growth. Transcriptional profiling of the cys-c1 mutant reveals that cyanide accumulation acts as a repressive signal for several genes encoding enzymes involved in cell wall rebuilding and the formation of the root hair tip as well as genes involved in ethylene signaling and metabolism. Our results demonstrate that mitochondrial β-cyanoalanine synthase activity is essential to maintain a low level of cyanide for proper root hair development.
TL;DR: The absorption spectra indicated the formation of complex between host and guest is in 1:2 stoichiometric ratios, and both sensors show visual detection, UV-vis and NMR spectral changes in presence of fluoride and cyanide anions in organic solvent as well as in aqueous medium.
TL;DR: The first general catalytic enantioselective conjugate addition of cyanide to beta,beta-disubstituted alpha, beta-unsaturated ketones and N-acylpyrroles was developed using a strontium catalyst derived from Sr(O(i)Pr)(2) and new chiral ligand 5.
Abstract: The first general catalytic enantioselective conjugate addition of cyanide to β,β-disubstituted α,β-unsaturated ketones and N-acylpyrroles was developed using a strontium catalyst derived from Sr(OiPr)2 and new chiral ligand 5. The reaction exhibited excellent enantioselectivity and a wide substrate scope using 0.5−10 mol % catalyst. 1,4-Adducts containing β-quaternary carbons were exclusively produced over 1,2-adducts. ESI-MS analysis of the strontium catalyst indicated that the active catalyst was a trimetallic Sr/5 = 3:5 complex. The exclusive 1,4-selectivity was partly due to the ability of the strontium complex to promote both a retro-cyanation reaction from the 1,2-adducts and highly enantioselective conjugate cyanation.
TL;DR: Current bioanalytical techniques used for the verification of cyanide exposure are discussed, common problems associated with the analysis are identified, and the metabolism and toxicokinetics of cyanides and its breakdown products in biological systems are addressed.
Abstract: Cyanide is a toxic chemical that may be introduced into living organisms as a result of natural processes and/or anthropogenic uses (legal or illicit). Exposure to cyanide can be verified by analysis of cyanide or one of its breakdown products from biological samples. This verification may be important for medical, law-enforcement, military, forensic, research, or veterinary purposes. This review will discuss current bioanalytical techniques used for the verification of cyanide exposure, identify common problems associated with the analysis of cyanide and its biological breakdown products, and briefly address the metabolism and toxicokinetics of cyanide and its breakdown products in biological systems.
TL;DR: Water containing cyanide was biologically detoxified with the bacterial strain Pseudomonas pseudoalcaligenes CECT5344 in a batch reactor, which constitutes an effective alternative to available physico-chemical methods for the purification of wastewater containing cyanides or cyano-metal complexes.
TL;DR: This presented biosensor combined with a resistor and a multimeter demonstrated the general applicability as a fast and simple detection method in the determination of endogenous biological cyanide.
Abstract: In this work we developed a fully integrated biofuel cell on a microchip, which consisted of glucose dehydrogenase supported (carbon nanotubes/thionine/gold nanoparticles)8 multilayer as the anode, and the (carbon nanotubes/polylysine/laccase)15 multilayer as the cathode. The as-obtained biofuel cell produced open circuit potential 620 mV and power density 302 μW cm−2, showing great potential as a small power resource of portable electronics. Most importantly, for the first time we demonstrated the feasibility of developing a self-powered biosensor based on the inhibitive effect on microchip enzyme biofuel cell. With cyanide employed as the model analyte, this method showed a linear range of 3.0 × 10−7 to 5.0 × 10−4 M and a detection limit with 1.0 × 10−7 M under the optimal conditions. The detection limit was lower than the acceptable cyanide concentration in drinking water (1.9 × 10−6 M) according to the World Health Organization (WHO). This self-powered sensor was successfully used to detect the cyanid...
TL;DR: 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.
TL;DR: The atomic displacement parameters, apparent bond lengths, and structure of a low-temperature, low-symmetry phase reveal that the low-energy vibrational modes responsible for this behavior maintain approximately rigid Zn coordination tetrahedra but involve significant distortion of their Cu counterparts.
Abstract: Tetramethylammonium copper(I) zinc(II) cyanide, which consists of N(CH(3))(4)(+) ions trapped within a cristobalite-like metal cyanide framework, has been studied by variable-temperature powder and single-crystal X-ray diffraction. Its coefficient of thermal expansion is approximately zero over the temperature range 200-400 K and comparable with the best commercial zero thermal expansion materials. The atomic displacement parameters, apparent bond lengths, and structure of a low-temperature, low-symmetry phase reveal that the low-energy vibrational modes responsible for this behavior maintain approximately rigid Zn coordination tetrahedra but involve significant distortion of their Cu counterparts.
TL;DR: By the incorporation of an irreversible redox-matched organic dye, a two-component [BMes(2)/B(OR)(2)] dosimeter system can be developed capable of colorimetrically signaling the presence of fluoride and cyanide in organic solution by Boolean AND/NOT logic.
Abstract: Synthetic approaches based on the direct borylation of ferrocene by BBr3, followed by boryl substituent modification, or on the lithiation of ferrocene derivatives and subsequent quenching with the electrophile FBMes2, have given access to a range of ferrocene derivatized Lewis acids with which to conduct a systematic study of fluoride and cyanide binding. In particular, the effects of borane electrophilicity, net charge, and ancillary ligand electronics/cooperativity on the binding affinities for these anions have been probed by a combination of NMR, IR, mass spectrometric, electrochemical, crystallographic, and UV−vis titration measurements. In this respect, modifications made at the para position of the boron-bound aromatic substituents exert a relatively minor influence on the binding constants for both fluoride and cyanide, as do the electronic properties of peripheral substituents at the 1′- position (even for cationic groups). By contrast, the influence of a CH2NMe3+ substituent in the 2- position is found to be much more pronounced (by >3 orders of magnitude), reflecting, at least in part, the possibility in solution for an additional binding component utilizing the hydrogen bond donor capabilities of the methylene CH2 group. While none of the systems examined in the current study display any great differentiation between the binding of F− and CN− (and indeed some, such as FcBMes2, bind both anions with equal affinity within experimental error), much weaker boronic ester Lewis acids will bind fluoride (but give a negative response for cyanide). Thus, by the incorporation of an irreversible redox-matched organic dye, a two-component [BMes2/B(OR)2] dosimeter system can be developed capable of colorimetrically signaling the presence of fluoride and cyanide in organic solution by Boolean AND/NOT logic.
TL;DR: X-ray absorption spectra at the Co L(2,3)-edges were analyzed to evidence different behaviors of the Co(III)(LS) and Co(II)(HS) ions in the three-dimensional structure related to their electronic configurations, and to propose an approach based on the electronic density distribution along the Co-NC-Fe linkage.
Abstract: X-ray absorption spectra at the Co L2,3-edges were analyzed by means of ligand field multiplet calculations in different states of three photomagnetic CoFe Prussian blue analogues of chemical formula Cs2Co4[Fe(CN)6]3.3·11H2O, Rb2Co4[Fe(CN)6]3.3·11H2O and Na2Co4[Fe(CN)6]3.3·11H2O. These simulations of the experimental spectra allowed the quantification of the crystal field parameter (10Dq). This determination led us (i) to evidence different behaviors of the CoIII(LS) and CoII(HS) ions in the three-dimensional structure related to their electronic configurations, (ii) to propose an approach based on the electronic density distribution along the Co−NC−Fe linkage to account for the energy position of the states implied in the switching properties of the compounds, and (iii) to explain the different photomagnetic properties observed as a function of the size of the inserted alkali cation by competing interactions between the cyanide ion and the transition metal ions within the CoFe cyanide bimetallic network ...
TL;DR: A new ratiometric fluorescent cyanide chemosensor was designed and synthesized, in which the anthracene moiety acted as a fluorophore and trifluoroacetyl group as the cyanide acceptor.
Abstract: A new ratiometric fluorescent cyanide chemosensor, N-2-anthracenyl trifluoroacetamide was designed and synthesized, in which the anthracene moiety acted as a fluorophore and trifluoroacetyl group as the cyanide acceptor. Compared with other reported trifluoroacetamide derivative-based cyanide chemosensors, N-2-anthracenyl trifluoroacetamide exhibits a better cyanide probe with higher sensitivity.
TL;DR: The results indicated that EC was very effective treatment for the removals of cadmium, nickel, and cyanide ions from the electroplating rinse water.
Abstract: Treatments of cadmium‐cyanide and nickel‐cyanide electroplating rinse water were investigated in an electrochemical reactor equipped with iron plate electrodes in a batch mode by electrocoagulation (EC). Effects of the process variables such as pH, current density, and operating time were explored with respect to removal efficiencies of cadmium, nickel and cyanide in electroplating rinse water and operating costs as well. Removal efficiencies and operating costs under the optimum conditions (30 A/m2, 30 min and pH 8–10 for cadmium; 60 A/m2, 80 min and pH 8–10 for nickel) for the EC process in electroplating rinse water were determined as 99.4% and 1.05 /m3 for cadmium, 99.1% and 2.45 /m3 for nickel and >99.7% for cyanide, respectively. The results indicated that EC was very effective treatment for the removals of cadmium, nickel, and cyanide ions from the electroplating rinse water.
TL;DR: In this article, the infrared spectra of methyl cyanide coordinated to the monovalent cations, Li, Na, K, Rb, Cu, Ag, Au, Tl and the divalent cations are reported.
Abstract: Infrared spectra are reported of methyl cyanide coordinated to the monovalent cations, Li, Na, K, Rb, Cu, Ag, Au, Tl and the divalent cations, Be, Mg, Ca, Sr, Ba, Mn, Fe, Co, Ni, Cu, Zn, Cd, Pd, in complexes of the types M (CH3CN)pn+ (SbCl6)n- and M (CH3CN)pn+ (SnCl6)n/22−.
The shifts in the different bands are discussed. Metal ions are placed in a series of electronegativity towards methyl cyanide. The sequence is compared with ionization energies of the metals, and with other measures of metal electronegativity.
TL;DR: A colorimetric sensing ensemble was prepared by mixing readily prepared adenosine triphosphate (ATP)-stabilized AuNPs with Cu2+−phenanthroline complexes as discussed by the authors.
TL;DR: These studies demonstrate that Cbi is a highly effective cyanide antidote in mouse models, and suggest it could be used in a mass casualty setting, because it can be given rapidly as an intramuscular injection when administered as Cbi-SO3.
Abstract: Context. Cyanide is a rapidly acting cellular poison, primarily targeting cytochrome c oxidase, and is a common occupational and residential toxin, mostly via smoke inhalation. Cyanide is also a potential weapon of mass destruction, with recent credible threats of attacks focusing the need for better treatments, as current cyanide antidotes are limited and impractical for rapid deployment in mass casualty settings. Objective. We have used mouse models of cyanide poisoning to compare the efficacy of cobinamide (Cbi), the precursor to cobalamin (vitamin B12), to currently approved cyanide antidotes. Cbi has extremely high affinity for cyanide and substantial solubility in water. Materials and Methods. We studied Cbi in both an inhaled and intraperitoneal model of cyanide poisoning in mice. Results. We found Cbi more effective than hydroxocobalamin, sodium thiosulfate, soldium nitrite, and the combination of sodium thiosulfate–sodium nitrite in treating cyanide poisoning. Compared to hydroxocobalamin, Cbi wa...
TL;DR: A novel type of chemodosimeter azo dye developed on the basis of the benzophenone as the electrophilic receptor of the cyanide anion and a saccharidic moiety to render the dye water soluble is found.