BACKGROUND: As cyanide (CN-) is a significant hazard to the environment and human health, it is essential to monitor cyanide levels in water and food samples. Moreover, real-time visualization of CN-could provide an additional understanding of its critical physiological and toxicological roles in living cells. The fluorescence approach based on small organic probes is an effective way for the detection of CN-. In this approach, a triphenylamine-xhantane conjugate was applied to detect in many samples such as sewage water, soil, sprouted potato, apricot seed, and living cells.
RESULTS: We report a new ratiometric near-infrared fluorescent probe based on a triphenylamine-xhantane derivative for CN-sensing in many samples. The probe displays high selectivity for only CN- ions among a series of analytes. The addition of cyanide to the dicyanovinyl moiety of the probe disrupts π-conjugation followed by the interruption of internal charge transfer. Consequently, the emission peak of the probe shifts hypsochromically from 655 to 495 nm. There is a linear correlation between the emission intensity (I495) and cyanide level, with a detection limit of 0.036 μM. The probe has many advantages over many probes, such as NIR fluorescence, ratiometric response, low cytotoxicity (85.0 % cell viability up to 50.0 μM of the probe), good membrane permeability, fast response time (4.0 min), high selectivity, good photostability, and anti-interference capability.
CONCLUSIONS: Although various probes have been reported in the literature, the use of triphenylamine-xhantane unit as CN- probe has yet to be explored. The probe can detect trace levels of cyanide in many samples such as sewage water, soil, sprouted potatoes, and apricot seeds. Furthermore, it is successfully utilized for the ratiometric fluorescent bioimaging of cyanide in living cells.

Cytochrome c (CytC), a one-electron carrier, transfers electrons from complex bc1 to cytochrome c oxidase (CcO) in the electron-transport chain. Electrostatic interaction with the partners, complex bc1 and CcO, is ensured by a lysine cluster near the heme forming the Universal Binding Site (UBS). We constructed three mutant variants of mitochondrial CytC with one (2Mut), four (5Mut), and five (8Mut) Lys->Glu substitutions in the UBS and some compensating Glu->Lys substitutions at the periphery of the UBS for charge compensation. All mutants showed a 4-6 times increased peroxidase activity and accelerated binding of cyanide to the ferric heme of CytC. In contrast, decomposition of the cyanide complex with ferrous CytC, as monitored by magnetic circular dichroism spectroscopy, was slower in mutants compared to WT. Molecular dynamic simulations revealed the increase in the fluctuations of Cα atoms of individual residues of mutant CytC compared to WT, especially in the Ω-loop (70-85), which can cause destabilization of the Fe…S(Met80) coordination link, facilitation of the binding of exogenous ligands cyanide and peroxide, and an increase in peroxidase activity. It was found that only one substitution K72E is enough to induce all these changes, indicating the significance of K72 and the Ω-loop (70-85) for the structure and physiology of mitochondrial CytC. In this work, we also propose using a ferro-ferricyanide buffer as a substrate to monitor the peroxidase activity of CytC. This new approach allows us to determine the rate of peroxidase activity at moderate (200 µM) concentrations of H2O2 and avoid complications of radical formation during the reaction.

Cytochrome bd-I from Escherichia coli belongs to the superfamily of prokaryotic bd-type oxygen reductases. It contains three hemes, b558, b595 and d, and couples oxidation of quinol by dioxygen with the generation of a proton-motive force. The enzyme exhibits resistance to various stressors and is considered as a target protein for next-generation antimicrobials. By using electronic absorption and MCD spectroscopy, this work shows that cyanide binds to heme d2+ in the isolated fully reduced cytochrome bd-I. Cyanide-induced difference absorption spectra display changes near the heme d2+ α-band, a minimum at 633 nm and a maximum around 600 nm, and a W-shaped response in the Soret region. Apparent dissociation constant (Kd) of the cyanide complex of heme d2+ is ∼0.052 M. Kinetics of cyanide binding is monophasic, indicating the presence of a single ligand binding site in the enzyme. Consistently, MCD data show that cyanide binds to heme d2+ but not to b5582+ or b5952+. This agrees with the published structural data that the enzyme\'s active site is not a di-heme site. The observed rate of binding (kobs) increases as the concentration of cyanide is increased, giving a second-order rate constant (kon) of ∼0.1 M-1 s-1.

Simple and efficient sample pretreatment methods are important for analysis and detection of chemical warfare agents (CWAs) in environmental and biological samples. Despite many commercial materials or reagents that have been already applied in sample preparation, such as SPE columns, few materials with specificity have been utilized for purification or enrichment. In this study, ionic magnetic mesoporous nanomaterials such as poly(4-VB)@M-MSNs (magnetic mesoporous silicon nanoparticles modified by 4-vinyl benzene sulfonic acid) and Co2+@M-MSNs (magnetic mesoporous silicon nanoparticles modified by cobalt ions) with high absorptivity for ethanol amines (EAs, nitrogen mustard degradation products) and cyanide were successfully synthesized. The special nanomaterials were obtained by modification of magnetic mesoporous particles prepared based on co-precipitation using -SO3H and Co2+. The materials were fully characterized in terms of their composition and structure. The results indicated that poly(4-VB)@M-MSNs or Co2+@M-MSNs had an unambiguous core-shell structure with a BET of 341.7 m2·g-1 and a saturation magnetization intensity of 60.66 emu·g-1 which indicated the good thermal stability. Poly(4-VB)@M-MSNs showed selective adsorption for EAs while the Co2+@M-MSNs were for cyanide, respectively. The adsorption capacity quickly reached the adsorption equilibrium within the 90 s. The saturated adsorption amounts were MDEA = 35.83 mg·g-1, EDEA = 35.00 mg·g-1, TEA = 17.90 mg·g-1 and CN-= 31.48 mg·g-1, respectively. Meanwhile, the adsorption capacities could be maintained at 50-70% after three adsorption-desorption cycles. The adsorption isotherms were confirmed as the Langmuir equation and the Freundlich equation, respectively, and the adsorption mechanism was determined by DFT calculation. The adsorbents were applied for enrichment of targets in actual samples, which showed great potential for the verification of chemical weapons and the destruction of toxic chemicals.

Metal-organic frameworks (MOFs) are frequently utilized as sensing materials. Unfortunately, the low conductivity of MOFs hinder their further application in electrochemical determination. To overcome this limitation, a novel modification strategy for MOFs was proposed, establishing an electrochemical determination method for cyanides in Baijiu. Co and Ni were synergistically used as the metal active centers, with meso-Tetra(4-carboxyphenyl)porphine (TCPP) and Ferrocenecarboxylic acid (Fc-COOH) serving as the main ligands, synthesizing Ni/Co-MOF-TCPP-Fc through a hydrothermal method. The prepared MOF exhibited improved conductivity and stable ratio signals, enabling rapid and sensitive determination of cyanides. The screen-printed carbon electrodes (SPCE) were suitable for in situ and real-time determination of cyanide by electrochemical sensors due to their portability, low cost, and ease of mass production. A logarithmic linear response in the range of 0.196~44 ng/mL was demonstrated by this method, and the limit of detection (LOD) was 0.052 ng/mL. Compared with other methods, the sensor was constructed by a one-step synthesis method, which greatly simplifies the analysis process, and the determination time required was only 4 min. During natural cyanide determinations, recommended readouts match well with GC-MS with less than 5.9% relative error. Moreover, this electrochemical sensor presented a promising method for assessing the safety of cyanides in Baijiu.

Given the growing concern over the deployment of toxic chemicals in warfare, the rapid and accurate removal and detection of cyanogen chloride (CK) as a blood agent has become increasingly critical. However, conventional physisorbents and chemisorbents used in military respirators are insufficient for the effective removal of CK. In this study, we demonstrate the chemisorption and sensing abilities of Co2(m-DOBDC) (m-DOBDC4- = 4,6-dioxo-1,3-benzenedicarboxylate) for CK via electrophilic aromatic substitution (EAS) in humid environments. Unlike the chemisorption in triethylenediamine (TEDA) impregnated carbon materials, which generates by-products through hydrolysis, the electron-rich C5 sites in m-DOBDC4- ligands give rise to cyano substitution with CK. This leads to the formation of stable C-C bonds and chloride ions (Cl-) coordinating with open Co2+ sites. Such a mechanism prevents the generation of toxic by-products like cyanic acid and hydrochloric acid. Breakthrough experiments conducted in a packed-bed system conclusively demonstrated the superior CK removal capacity of Co2(m-DOBDC) (1662 min/g), compared to TEDA-impregnated activated carbon (323 min/g) under humid conditions. Considering that MOF-74 series, isostructural with Co2(m-DOBDC), barely adsorb CK under similar conditions, this finding marks a significant advancement in developing novel sorbents for CK removal. Moreover, this chemisorption not only exhibited rapid and highly efficient CK removal but also enabled colorimetric monitoring via the distinctive color change induced by the coordination of Cl- acting as σ donors. These findings facilitate the development of adsorption and sensing equipment to protect military personnel from toxic chemical threats.

Cyanide is one of the most rapidly acting, lethal poisons in human and veterinary medicine. This case report discusses a novel case of cyanide toxicity from apricot (Prunus armeniaca) kernel ingestion in a canine and alternative treatment modalities. A 9.5-year-old female spayed Golden Retriever presented for vomiting and collapse after ingestion of apricot kernel meal. Laboratory findings, including a high anion gap metabolic acidosis with severe hyperlactatemia, clinical signs, and known ingestion of apricot kernels, were suggestive of cyanide toxicity. The dog was treated with crystalloid and synthetic colloids for stabilization and antidote therapy with hydroxocobalamin. The dog\'s metabolic acidosis and hyperlactemia worsened despite antidote therapy, and the dog progressed to CPA during gastric decontamination efforts. The dog did not respond to CPR efforts. This report will review the mechanism of cyanide toxicity, treatment options, and considerations for future cases.

A novel indolium-based fluorescent probe for the detection of CN- was developed based on the conjugation of 1, 2, 3, 3-Tetramethyl-3H-indolium iodide and 2-acetyl benzothiophene. The introduction of external CN- caused a nucleophilic attack to the quaternary amine salt structure in the probe and resulted in the departure of iodide ions and the steric rotation of the index salt group, which caused fluorescence quenching. The titration experiments showed that the probe had rapid qualitative and quantitative analysis capabilities for CN-. Moreover, the relevant biocompatibility experiments also demonstrated the potential application value of the probe.

BACKGROUND: Cyanide anion can be found in foodstuffs, tobacco smoke and a variety of types of waters, mainly originating from anthropogenic activities. Due to its highly toxic nature, several agencies have established limits for cyanide levels in water. Additionally, monitoring cyanide levels in biological samples, such as blood and urine, is crucial for obtaining clinical information about the health condition of patients. Therefore, there is a pressing need for the development of simple, cost-effective, and reliable analytical methods capable of quantifying cyanide at low concentrations.
RESULTS: This study presents a novel analytical method for the selective and sensitive determination of cyanide based on analyte volatilization, pre-concentration via single-drop microextraction (SDME) using a selective reagent, and colorimetric quantification using a paper-based analytical device. For this, 10 mL of a liquid sample was acidified with phosphoric acid and the generated HCN was collected using a single drop of 3 μL of a palladium dimethylglyoximate solution (Pd (DMG)22-) positioned in the flask headspace using a syringe. The reaction of Pd (DMG)22- leads to the formation of Pd(CN)42- and the demasking of the organic ligand. After 15 min of extraction time, the reagent drop was added to a paper-based analytical device that has been previously impregnated with 3 μL of nickel chloride, resulting in the formation of a red precipitate of nickel (II) dimethylglyoximate. Digital images of the paper-based device were captured and the red channel (R) was used for quantification purposes. Under optimized conditions, the method demonstrates a suitable linear relation (r2 > 0.99) ranging from 26 to 286 μg L-1 and a limit of detection of 5 μg L-1.
CONCLUSIONS: As a proof of concept, cyanide levels were quantified in water and urine samples using this method. The proposed approach offers high sensitivity and selectivity while requiring only a small volume of reagents. Furthermore, it exhibits a high degree of portability for in-situ applications.

Isocyanides and isocyanates are some of the most reactive compounds in organic chemistry, making them perceived as compounds with high potential for use in both the laboratory and industry. With their high reactivity also comes several disadvantages, most notably their potentially high toxicity. The following article is a collection of information on the toxic effects of the isocyanide group on the human body and the environment. Information on the mechanism of how these harmful substances affect living tissues and the environment, worldwide information on how to protect against these chemicals, current regulations, and exposure limits for specific countries is compiled. The latest research on the application uses of isocyanates and isocyanides is also outlined, as well as the latest safer and greener methods and techniques to work with these compounds. Additionally, the presented article can serve as a brief guide to the organic toxicity of a group of isocyanates and isocyanates.