Zinc-Ferricyanide Flow Batteries Operating Stably under -10 °C.

Alkaline ferri/ferro-cyanide-based flow batteries are well suited for energy storage because of their features of high electrochemical activity, good kinetics and low material cost. However, they suffer from low energy density and poor temperature adaptability. The ferri/ferro-cyanide catholyte exhibits low solubility (~0.4 M at 25 °C) in NaOH- or KOH-based supporting electrolyte and can easily form precipitates below room temperature. Here we report a lithium-based supporting electrolyte that significantly enhances the solubility of ferrocyanide. The use of LiOH intensifies the ion-dipole interaction between water molecules and solutes and cripples polarization among ferrocyanide ions. Thus, we have achieved a ferrocyanide-based catholyte of 1.7 M at 25 °C and of 0.8 M at -10 °C. A zinc-ferricyanide flow battery based on the lithium-based supporting electrolyte demonstrates a steady charge energy of ~72 Wh L-1catholyte at 25 °C for ~4200 cycles (~4200 hours). Furthermore, it remains stable for ~800 cycles (~800 hours) at -10 °C.

The impact of gold mining activities: understanding the dynamics of cyanide in river ecosystems in Ecuador.

Understanding the behavior of cyanide in rivers is of utmost importance as it has a direct impact on the health of people who depend on these water sources. Cyanide contamination from gold mining activities poses a significant environmental threat to river ecosystems, particularly in southern Ecuador. This study aimed to investigate the behavior of cyanide when it enters contact with other metals in these rivers. Simulations were conducted to determine the speciation of cyanide, mercury, arsenic, lead, and manganese in a study area, taking into account the water temperature and pH at four locations. The findings revealed that CN-and HCN(aq) species were present in the research area. Additionally, mercury-cyanide (Hg(CN)2(aq), Hg(CN)3-), and manganese-cyanide (MnCN+) complexes were identified 3 km downriver from the site where the mining activity is higher. These metal-cyanide complexes tend to dissociate quickly under weak acidic conditions, making them hazardous to the environment. This research is crucial, not only for the environment but also for human health, as it allows to predict toxicity risks for people supplied with this water source, emphasizing the potential harm to human health. This study highlights the importance of stringent regulations and effective monitoring practices to mitigate cyanide contamination and safeguard environmental and occupational health.

Prebiotic thiol-catalyzed thioamide bond formation.

Thioamide bonds are important intermediates in prebiotic chemistry. In cyanosulfidic prebiotic chemistry, they serve as crucial intermediates in the pathways that lead to the formation of many important biomolecules (e.g., amino acids). They can also serve as purine and pyrimidine precursors, the two classes of heterocycle employed in genetic molecules. Despite their importance, the formation of thioamide bonds from nitriles under prebiotic conditions has required large excesses of sulfide or compounds with unknown prebiotic sources. Here, we describe the thiol-catalyzed formation of thioamide bonds from nitriles. We show that the formation of the simplest of these compounds, thioformamide, forms readily in spark-discharge experiments from hydrogen cyanide, sulfide, and a methanethiol catalyst, suggesting potential accumulation on early Earth. Lastly, we demonstrate that thioformamide has a Gibbs energy of hydrolysis ( Δ G r ∘ ) comparable to other energy-currencies on early Earth such as pyrophosphate and thioester bonds. Overall, our findings imply that thioamides might have been abundant on early Earth and served a variety of functions during chemical evolution.

Ratiometric detection and monitoring of cyanide in biological, environmental and food samples by a novel triphenylamine-xhantane based fluorescent probe.

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. SIGNIFICANCE: 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.

Ligand-Enabled Gold-Catalyzed Cyanation of Organohalides.

Herein, we disclose the first report on gold-catalyzed C(sp2)-CN cross-coupling reaction by employing a ligand-enabled Au(I)/Au(III) redox catalysis. This transformation utilizes acetone cyanohydrin as a nucleophilic cyanide source to convert simple aryl and alkenyl iodides into the corresponding nitriles. Combined experimental and computational studies highlighted the crucial role of cationic silver salts in activating the stable (P,N)-AuCN complex towards the oxidative addition of aryl iodides to subsequently generate key aryl-Au(III) cyanide complexes.

Optimization of Cyanide-Free Composite Electrodeposition Based on π-π Interactions Preparation of Silver-Graphene Composite Coatings for Electrical Contact Materials.

With the rapid development of industrial automation and power electronics, the requirements for electrical contact materials are increasing. However, traditional electrical contact materials encountered significant bottlenecks in terms of performance enhancement and production environmental friendliness. Therefore, this paper proposes a new material design idea that utilizes π-π interactions between graphene and compounds with conjugated structures in order to achieve uniform dispersion of graphene in the metal matrix and thus enhance the performance of composites. Based on this design idea, we used nicotinic acid, which has a conjugated structure and is safe, as the complexing agent, and successfully prepared high-quality silver-graphene (Ag-G) composite coatings with graphene uniformly dispersed in the metal matrix on copper substrates by composite electrodeposition technique. Subsequently, the mechanical properties of composite coatings were investigated by hardness test and X-ray diffractometer, and the tribological properties of the composite coatings and the comprehensive performance under the current carrying conditions were systematically evaluated by using friction and wear tester and load key life tester. The results show that the Ag-G composite coatings have significant advantages in mechanical, tribological, and current carrying conditions. This result not only verifies the feasibility of the design idea of the material, but also provides a new direction for the research and development of electrical contact materials.

An affordable, field-deployable detecting system for cyanide ion - Investigating applications in real time uses.

A highly efficient system that incorporates the instantaneous visualization of the cyanide ion in water was synthesized by keeping the fluorophore system (electron donor) as a julolidine-coumarin conjugate and changing the electron acceptor unit. The probes exhibit a notable color change in normal and UV light. The probe interaction modalities are based on the ICT process. With a detection limit in the nM range, it may preferentially react with cyanide, which is less than the tolerable level of 1.9 µM. According to 1H NMR data, the probes detect cyanide ions by nucleophilic addition reaction mechanism. Furthermore, current probe successfully determines real resources, including cyanide containing cassava powder, sprouted potatoes and various water samples. Besides the test strips, an electronic Arduino device was also employed to detect the cyanide ion. As such, the developed probes exhibit outstanding practical application with respect to the cyanide ion.

Elucidation of γ-glutamyl-ß-cyanoalanylglycine biosynthesis in mammalian cells by LC-QTOF-MS.

γ-Glutamyl-ß-cyanoalanylglycine (gEcnAG) is a glutathione analog in which the cysteine moiety in glutathione is replaced with ß-cyanoalanine, a known plant cyanide metabolite. Previously, gEcnAG was detected in the liver of rats and chicks exposed to ß-cyanoalanine. We reported the detection of gEcnAG in naïve mammalian cells using liquid chromatography coupled with tandem quadrupole time-of-flight mass spectrometry (LC-QTOF-MS). LC-QTOF-MS analysis enabled high-resolution confirmation (exact mass determination and MS/MS fragmentation) of the gEcnAG structure. The detection of gEcnAG in rat pheochromocytoma (PC12) cells that were not exposed to ß-cyanoalanine suggests its endogenous production. Furthermore, the inhibition of myeloperoxidase, an enzyme potentially required for endogenous cyanide generation, decreased gEcnAG levels in PC12 cells. This supports the notion that PC12 cells intrinsically produce cyanide, unlike HepG2 cells, which exhibited lower intracellular gEcnAG levels. Notably, ß-cyanoalanine was undetectable in PC12 cells. Moreover, depleting glutathione with buthionine sulfoximine reduced intracellular gEcnAG levels, whereas supplementation with glutathione reduced ethyl ester increased them. These observations suggest that endogenous gEcnAG may be generated from glutathione, potentially through its reaction with endogenous cyanide. Our findings implicate gEcnAG as a possible metabolite of endogenous cyanide.

Cyanohydrin Equilibria Implicate Non-Aromatic Aldehydes in Photochemical Production of Oceanic Carbon Monoxide.

Carbonyls have previously been dismissed as significant precursors for carbon monoxide (CO) photoproduction from natural chromophoric dissolved organic matter (CDOM). Here, we used hydrogen cyanide (HCN), which reacts with carbonyls to form photochemically inert cyanohydrins, as a probe to re-examine the role of carbonyls in CO photoproduction. Adding HCN to low-absorbance euphotic zone seawater decreased CO photoproduction. Modeling [HCN] (∼5 to 364 µM) vs the percent decrease in CO photoproduction (%CO↓) yielded carbonyl-cyanohydrin dissociation equilibrium constants, KD, and maximum %CO↓, %CO↓max values. Four Atlantic and Pacific seawater KDs (66.7 ± 19.6 µM) overlap aqueous aliphatic but not aromatic aldehyde KDs. Phenylacetaldehyde (PA) and other ß,γ-unsaturated aldehydes are proposed as prototypical CO precursors. Direct photolysis of ∼10 nM PA can supply the measured daily production of HCN-sensitive CO at an open-ocean site near Bermuda. HCN's %CO↓max was 31 ± 2.5% in North Atlantic seawater vs the 13 ± 2.5% inhibition of CO photoproduction by borohydride, a dilemma since only borohydride affects most ketones. Borohydride also decreased CDOM absorption much more than did HCN. This puzzle probably reflects differing steric and solvation requirements in HCN- and borohydride-CDOM reactions. This study demonstrates cyanophilic aldehydes to be a significant source of open-ocean CO and reveals new clues regarding CDOM photochemistry mechanisms.

Automated Image-Based Fluorescence Screening of Mitochondrial Membrane Potential in Daphnia magna: An Advanced Ecotoxicological Testing Tool.

This study demonstrated the strengths of in vivo molecular staining coupled with automated imaging analysis in Daphnia magna. A multiwell plate protocol was developed to assess mitochondrial membrane potential using the JC-1 dye. The suitability of five common anesthetics was initially tested, and 5% ethanol performed best in terms of anesthetic effects and healthy recovery. The staining conditions were optimized to 30 min staining with 2 µM JC-1 for best J-aggregate formation. The protocol was validated with the model compound carbonyl cyanide 3-chlorophenylhydrazone (CCCP) and used to measure the effect of four environmental contaminants, 2,4-dinitrophenol, triclosan, n-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine (6PPD), and ibuprofen, on mitochondrial health. Test organisms were imaged using an automated confocal microscope, and fluorescence intensities were automatically quantified. The effect concentrations for CCCP were lower by a factor of 30 compared with the traditional OECD 202 acute toxicity test. Mitochondrial effects were also detected at lower concentrations for all tested environmental contaminants compared to the OCED 202 test. For 2,4-dinitrophenol, mitochondria effects were detectable after 2 h exposure to environmentally relevant concentrations and predicted organism death was observed after 24 h. The high sensitivity and time efficiency of this novel automated imaging method make it a valuable tool for advancing ecotoxicological testing.

Community Perceptions on Health Risks Associated With Toxic Chemical Pollutants in Kwekwe City, Zimbabwe: A Qualitative Study.

Globally, environmental pollution continues to be a significant public health problem, and according to the World Health Organisation, pollution-induced deaths account for 23% of deaths yearly, which could be prevented if people lived in healthier environments. Despite implementing multilateral agreements and international treaties such as the Bamako, Basel, Rotterdam, Minamata, and Stockholm conventions, the United Nations Sustainable Development Goals, and national laws, toxic pollutants remain a serious environmental and public health problem in low-income countries. In the specific context of Kwekwe City, an industrial and mining area in Zimbabwe, where environmental and pollution-induced health problems associated with industries have been widely reported, this study was conducted in close collaboration with the local community. The study aimed to assess community members' perceptions regarding health risks associated with potentially toxic elements and cyanide pollution in Kwekwe City. An explorative cross-sectional study was conducted with key stakeholders and industrial settlements' residents. Face-to-face interviews with key informants and focus group discussions with residents and workers were used to gather data. A thematic approach was utilised in data analysis. Study participants, who played a crucial role in the research process, perceived that industrial pollution principally linked to cyanide, mercury and chromium posed significant environmental and health risks. This participatory approach in risk perception assessment is critical in providing insight into the scope of the problem and formulating intervention strategies. However, given that qualitative study results lack generalisability and replicability, quantitative studies need to be undertaken to determine environmental levels of toxic chemical pollutants as a complementary and validative measure.

Cyanide and cyanidation wastes management in gold leaching plants in Siaya County, Kenya.

This study assesses cyanide and cyanidation wastes management practices among small, medium and large-scale gold leaching plants in Siaya County, Kenya. The socio-economic benefits of gold extraction through cyanidation of mercury-contaminated tailings notwithstanding, the study establishes inadequate cyanide and cyanidation wastes management practices which could potentially cause significant environmental and human health impacts. Through structured key-informant interviews with operators from 15 selected gold leaching plants of varying scales of operation, along with field observations, and quantitative analysis utilizing both bivariate and inferential statistical tools, the study reveals inadequacies in cyanide, cyanidation wastewater, and tailings management practices. Key findings highlight widespread contravention of the international cyanide management standards and lack of adoption of advanced cyanidation wastes treatment technologies. Moreover, the study examines Political, Economic, Social, Technological, Environmental, and Legal factors as external factors affecting the management of cyanidation wastes. Consequently, the study recommends adoption of comprehensive cyanide management practices as outlined in the Cyanide Code and technological upgrades to mitigate potential environmental and human health impacts, and enhance regulatory compliance in gold cyanidation. In a nutshell, this study underscores the urgent need for stringent enforcement of environmental and mining industry laws and regulations in order to protect the environment and public health in gold mining regions. These measures are vitally important to ensure responsible mining practices and uphold environmental stewardship while promoting economic growth.

Dhurrin in Sorghum: Biosynthesis, Regulation, Biological Function and Challenges for Animal Production.

Sorghum (Sorghum bicolor) holds a significant position as the fifth most vital cereal crop globally. Its drought resistance and robust biomass production, coupled with commendable nutritional value, make sorghum a promising choice for animal feed. Nevertheless, the utilization of sorghum in animal production faces hurdles of dhurrin (a cyanogenic glycoside) poisoning. While dhurrin serves as a protective secondary metabolite during sorghum growth, the resulting highly toxic hydrogen cyanide poses a significant threat to animal safety. This review extensively examines the biometabolic processes of dhurrin, the pivotal genes involved in the regulation of dhurrin biosynthesis, and the factors influencing dhurrin content in sorghum. It delves into the impact of dhurrin on animal production and explores measures to mitigate its content, aiming to provide insights for advancing research on dhurrin metabolism regulation in sorghum and its rational utilization in animal production.

Anion-binding-induced selective aggregation and self-degradation: Influence of positional isomerism on the anion selectivity and mode of binding of an imine-based receptor.

Imine based positional isomers (8E)-N-(4-((E)-(perfluorophenylimino)methyl)benzylidene)-2,3,4,5,6-pentafluorobenzenamine, L and (10E)-N-(3-(E-Perfluorophenylimino)methyl)benzylidene)-2,3,4,5,6-pentafluorobenzenamine, L1 have been designed, and synthesized by functionalizing two electron deficient aromatic moieties at the para-para'/ortho-ortho' positions in the phenyl core of the L and L1 respectively. The responses of L and L1 towards various anionic species are examined. The positional isomers L and L1 differs not only by showing distinguishable color change upon addition of anions but also differentiates themselves by the way of self-assembling together upon binding with cyanide anion. The naked-eye colorimetric experiments, UV-Vis, Nuclear Magnetic Resonance, and Infra-Red spectroscopic analyses reveal that the isomer L binds fluoride anion through 2:1 stoichiometry ratio. Unlike fluoride complex, the isomer L form aggregates while binding with cyanide ion. On the other hand, isomer L1 does not show any instant color change upon additions of any anion. Interestingly, after thirty minutes, only the color of the cyanide complex is turned into dark brown. While analyzing the spectroscopic results of cyanide complex of L1, it is found that the cyanide complex begins to decompose and finally it is completely decomposed within 30 min. This unprecedented phenomenon about the colorimetric sensing of cyanide and destruction of cyanide complex with respect to time has not been reported in the literature yet. To the best of our knowledge this is the first example of study of sensing controlling the selectivity, mode of binding, self-aggregating and degradation properties of anionic complexes under the influence of positional isomeric effects. This present investigation provides simple and effective strategy to construct the sensor molecules with tunable binding properties in terms of easy to prepare as well as easy to use as a colorimetric sensor. _____________________________________________________________________________________________________.

Detection of Cyanide in a Decomposed Exhumed Body: A Case Report.

Cyanide is a lethal poison that induces immediate fatality. Infrequently employed as a homicidal poison, it is not an ideal choice for homicide as it causes a 'dramatic' death causing suspicion among others. Cyanide is a rapidly metabolized poison that also rapidly disintegrates after death, posing challenges for chemical analysis, particularly when dealing with decomposed bodies. Detection of cyanide from a decomposed body is infrequent. A suspected case of intentional poisoning resulting in death was interred without conducting a postmortem examination. The exhumation process revealed the presence of hydrogen cyanide in the postmortem fluids collected from the body cavities three years after interment.

Survey of Physicians and Healers Using Amygdalin to Treat Cancer Patients.

Amygdalin is purported to exhibit anti-cancer properties when hydrolyzed to hydrogen cyanide (HCN). However, knowledge about amygdalin efficacy is limited. A questionnaire evaluating the efficacy, treatment, and dosing protocols, reasons for use, HCN levels, and toxicity was distributed to physicians and healers in Germany, providing amygdalin as an anti-cancer drug. Physicians (20) and healers (18) provided amygdalin over 8 (average) years to nearly 80 annually treated patients/providers. Information about amygdalin was predominantly obtained from colleagues (55%). Amygdalin was administered both intravenously (100%) and orally (32%). Intravenous application was considered to maximally delay disease progression (90%) and relieve symptoms (55%). Dosing was based on recommendations from colleagues (71%) or personal experience (47%). If limited success became apparent after an initial 3g/infusion, infusions were increased to 27g/infusion. Treatment response was primarily monitored with established (26%) and non-established tumor markers (19%). 90% did not monitor HCN levels. Negative effects were restricted to a few dizzy spells and nausea. Only 58% were willing to participate in clinical trials or contribute data for analysis (34%). Amygdalin infusions are commonly administered by healers and physicians with few side effects. The absence of standardized treatment calls for guidelines. Since intravenous application bypasses metabolization, re-evaluation of its mode of action is required.

Opportunities for Insight into the Mechanism of Efficient CO2/CO Interconversion at a Nickel-Iron Cluster in CO Dehydrogenase.

The reduction of CO2 with low overpotential and high selectivity is a crucial challenge in catalysis. Fortunately, natural systems have evolved enzymes that achieve this catalytic reaction very efficiently at a complex nickel-iron-sulfur cluster within carbon monoxide dehydrogenase (CODH). Extensive biochemical, crystallographic, and spectroscopic work has been done to understand the structures and mechanism involved in the catalytic cycle, which are summarized here from the perspective of mechanistic organometallic chemistry. We highlight the ambiguities in the data and suggest experiments that could lead to clearer understanding of the mechanism and structures of intermediates at the active-site cluster. These include parallel crystallography and spectroscopy, as well as the preparation of synthetic analogues that help to interpret structural and spectroscopic signatures.

Evaluation of exposure to cyanogenic glycosides and potential hydrogen cyanide release in commercially available foods among the Korean population.

The release of hydrogen cyanide (HCN) after food ingestion can pose a serious health risk to consumers. This study aimed to simultaneously quantify four cyanogenic glycosides (lotaustralin, prunasin, taxiphyllin, and dhurrin) using liquid chromatography-tandem mass spectrometry. The analysis scope extended beyond agricultural products to various consumer foods to estimate dietary exposure to cyanogenic glycosides and assess its risk levels. The major exposure sources are cassava chips (lotaustralin), apples (seeds) (prunasin and dhurrin), and Prunus mume axis (taxiphyllin). In addition to quantifying specific cyanogenic glycosides, this study proposed the development of a preliminary risk assessment framework based on the dietary exposure assessment and the calculation of theoretical levels of HCN derived from cyanogenic glycoside concentrations. In the absence of established guidelines for the permissible intake of foods containing cyanogenic glycosides, this study provides initial guidance for assessing the risks associated with a range of commonly consumed foods.

Evaluation of gold adsorption on activated carbon from real cyanide and thiourea leachate solutions.

The recovery of gold by adsorption using activated carbon from sodium cyanide and thiourea leached solutions are reported in this study. The leached solutions were obtained under real operating conditions from the beneficiation plant "Paz Borja", Machala-Ecuador. Calgon Carbon DG-11 6X12 type, widely used in the local metallurgical industry was used as adsorbent material. The operational parameters varied during the adsorption process experiments included the concentration of leaching agent, agitation speed, dose of activated carbon and initial concentration of gold. The control parameters included density, percentage of solid, pH, temperature, and solution potential. The obtained results were adjusted to mass transfer model by diffusion through the interface and the Freundlich model for the equilibrium isotherms. The analysis of the results indicates a higher adsorption rate of the gold di-cyanide complex on activated carbon compared to gold-thiourea complexes.

Construction of Metal-Organic Framework as a Novel Platform for Ratiometric Determination of Cyanide.

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.