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The development of novel fluorescent probes for real-time detection of cyanides (CN - ) in environmental and biological systems has become a significant focus in chemical sensing. Particularly, ratiometric fluorescence sensing offers a unique method for precise and quantitative detection of cyanides, even under complex conditions. We report herein the design of a new ratiometric fluorescent probe for cyanides based on modulation of Förster resonance energy transfer (FRET) coupled with novel cyanide-induced nucleophilic substitution of aromatic hydrogen (SNArH). The target probe (R1) is developed by introducing coumarin fluorophores as FRET donors into a 3-nitro-naphthalimide acceptor, which is easily synthesized and exhibits a colorimetric change from colorless to faint yellow and a significant ratiometric fluorescence shift (Δλ = 114 nm) upon cyanide binding. A clear ratiometric signal at I 582 /I 468 was obtained, with a limit of detection of 5.69 μM. The sensing mechanism was confirmed through 1 H NMR titration and LC-MS analysis. Additionally, R1-loaded strips were easily prepared, serving as a portable device for detecting CN - with visible color changes. The probe R1 has been successfully utilized for real-time monitoring of cyanide in food materials and water samples. Importantly, fluorescence bioimaging studies in HeLa cells were conducted, demonstrating the probe's capability for ratiometric detection of exogenous CN - in living systems., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024. Published by Elsevier B.V.)

Background: Cyanide poisoning poses a significant threat to burn patients exposed to smoke in residential or workplace fires, leading to central nervous system dysfunction, hemodynamic instability, cardiovascular collapse, and death. Prompt administration of an effective antidote is critical. Hydroxocobalamin, a form of vitamin B12, is the gold standard treatment for cyanide toxicity, by binding to cyanide molecules and converting them into non-toxic cyanocobalamin that is eliminated by the kidneys. This mechanism is distinct from previous cyanide antidotes, which induce the formation of methemoglobin to bind to cyanide. Recent case studies have reported elevated methemoglobin levels after hydroxocobalamin administration, raising concerns regarding its safety. The current study investigates smoke inhalation patients treated with hydroxocobalamin at a single institution Burn Unit in hopes of enhancing our understanding of the complexities surrounding cyanide antidote therapy., Methods: After Institutional Board Approval, a retrospective cohort study was conducted. Our sample comprised burn patients with inhalation injury admitted to a single institution from 2013 to 2023 and treated with hydroxocobalamin for suspected cyanide toxicity. We also analyzed a matched control cohort of similar patients with inhalation injury not treated with hydroxocobalamin. We analyzed changes and peaks in methemoglobin levels, lactate levels, blood urea nitrogen (BUN) and creatinine, ventilator days, % total body surface area (TBSA), various types of medications and dressings, and mortality. Statistical analyses included t-tests, chi-square, linear and logistic regressions, and correlation analysis., Results: In the study, 36 patients with suspected inhalation injury were treated with hydroxocobalamin at the Los Angeles General (LAG) Burn Unit from 2013 to 2023, who were matched to 32 control patients with inhalation injury who were not treated with hydroxocobalamin. Demographic and baseline characteristics showed no statistically significant differences between the groups, including age, gender, BMI, and %TBSA. No significant differences were found in initial, final, peak, or change in methemoglobin levels. The study also revealed no significant disparities in initial lactate levels, mortality, kidney function tests, ventilator days, surgeries, or use of medications/treatments (e.g., Silvadene dressings, Vitamin C) between the two groups. When controlling for covariates, multiple linear regression analysis (age, gender, and %TBSA) indicated that hydroxocobalamin administration was not significantly associated with changes in methemoglobin or mortality. Increased %TBSA, however, was linked to elevated lactate levels., Conclusions: Our investigation sought to assess the potential risks associated with hydroxocobalamin administration in burn patients with concomitant inhalation injury. Contrary to our initial hypothesis, we found no statistically significant differences in methemoglobinemia, lactate levels, mortality, or kidney function. The influence of other factors, such as methemoglobinemia-inducing drugs or hydroxocobalamin's interference with co-oximetry, adds complexity. Although elevated methemoglobin levels were observed in some cases, their clinical significance was limited. However, this study's limitations, particularly the rarity of inhalation injury cases with concern for cyanide toxicity, warrant consideration. Further research is required to comprehensively elucidate the impact of hydroxocobalamin administration on burn patients' outcomes., Competing Interests: Declaration of Competing Interest The authors report no conflicts of interest or financial disclosures related to this manuscript., (Copyright © 2024. Published by Elsevier Ltd.)

Despite a range of methods used to promote modern agriculture with several outcomes, food quality and availability problems remain. This work aims to evaluate the effect of AM fungi inoculation on the growth, yield, nutritional, and antinutritional properties of 7 varieties of cassava. Growth characteristics, yields, rentability, nutritional, and antinutritional of tubers of each treatment were determined at harvest. All the cassava varieties used form a symbiosis with AM fungi at various frequencies, with the I090590 variety being the best (61.66 %). The best amount of chlorophyll, carotenoid, and height of plants were recorded at 9 months old. The 96/1414, TME/693 and MD varieties respectively show the best amount of chlorophyll, size, and carotenoids at 9 months old. Following AM fungi inoculation, an increase in the content of chlorophyll, size, and carotenoids was recorded for all the varieties with the best rate attributed respectively to 92/0326, MD, and 92/0326. Tuber yields vary significantly depending on the cassava varieties, with the best (56.16 t/ha) recorded for the I090590 variety. Following inoculation with AM fungi, a significant increase in yields was recorded, with the best ratio (2.7) obtained with the AE variety. The I090590 variety shows the best yield and by then the most profitable. Inoculation with AM fungi leads to a significant increase in the sugar, protein, fibre, and phosphorus content of all cassava varieties, with the best ratios obtained in 96/1414, 01/1797, and I090590 varieties respectively. Similarly, the inoculation of cassava varieties with AM fungi leads to a significant reduction in the content of cyanides, oxalates, and phytates. The best ratio of reduction for cyanide was 1.91 for the MD variety. AM fungi inoculation is an important way to ensure safe, exponential production and high economic profitability of foodstuffs., Competing Interests: The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (© 2024 The Authors.)

The synthesis and crystal structures of two anionic cadmium dicyanoaurate coordination polymers, [ n Bu 4 N] 6 [(Cd 4 Cl 4 ) 2 (Au(CN) 2 ) 12 ][CdCl 4 ] (TCCA) and [ n Bu 4 N] 2 [Cd(Au(CN) 2 ) 4 ], and their reaction with ammonia vapour is reported. TCCA and the isostructural [ n Bu 4 N] 6 [(Cd 4 Br 4 ) 2 (Au(CN) 2 ) 12 ][CdBr 4 ] form 3-D arrays with [Cd 4 X 4 ] 4+ (X=Cl, Br) cubane clusters linked from each octahedral Cd(II) centre by three bridging [Au(CN) 2 ] - units. TCCA reacts with ammonia with concentrations of 1000 ppm or higher to give a product with a quantum yield of 0.88, while [ n Bu 4 N] 2 [Cd(Au(CN) 2 ) 4 ], which forms a 2-D anionic Cd[Au(CN) 2 ] 2 sheet structure with axially pendant [Au(CN) 2 ] - units, reacts with concentrated ammonia vapour to generate Cd(NH 3 ) 2 [Au(CN) 2 ] 2 ; this has a similar 2-D sheet structure but with axial NH 3 units. Vibrational spectroscopy illustrated that the reaction of both Cd/[Au(CN) 2 ]-based materials with ammonia proceeded by breaking Cd-NC bonds. For [ n Bu 4 N] 2 [Cd(Au(CN) 2 ) 4 ], this results in decomposition into [ n Bu 4 N][Au(CN) 2 ] ⋅ 0.5H 2 O and Cd(NH 3 ) 2 [Au(CN) 2 ] 2 , while the reaction of ammonia with TCCA is reversible by heating the ammonia-bound sample above 110 °C. Cd[Au(CN) 2 ] 2 can be prepared by thermal removal of NH 3 units from Cd(NH 3 ) 2 [Au(CN) 2 ] 2 ., (© 2023 Wiley-VCH GmbH.)

Catalyst design with a "Co-N-C" structure at the atomic level has shown great interest for peroxymonosulfate (PMS) activation toward advanced oxidation water treatment. Here, we present an innovative way of producing cobalt hexacyanocobaltate (Co-HCC) with an abundance of atomically isolated Co II -NC sites at the outer surface. This material allows ultraefficient PMS activation to generate plenty of sulfate and hydroxyl radicals, with a turnover frequency much higher than those of most cobalt-based catalysts reported so far and even the homogeneous catalysis by Co 2+ ions. We gained fundamental insights on its unprecedently high catalytic performance based on experimental results and computational study. Then, we controlled the growth of Co-HCC on a ceramic membrane to form a confined oxidation environment that utilizes the extended surface area and maximal exposure of short-lived radicals for a fast removal of organic pollutants that enter the pores. As a result, this catalytic membrane achieves complete disruption of micropollutants under a water flux up to 10,000 LMH (merely 0.2 s retention time) and further >90% mineralization of organic pollutants in complex industrial wastewater matrices (<100 s retention time), together with the merits of operational simplicity and great longevity (2 weeks continuous run). Our study elicits a new milestone in "Co-N-C" catalyst structure design for PMS activation and highlights the great interest of producing catalytic membranes for a confined treatment of organic pollutants from partial oxidation to complete mineralization as a new benchmark.

Background/Objective : Hydroxocobalamin is indicated for cyanide poisoning and its package insert states it should be given "without delay". We sought to evaluate time to administration and clinical characteristics when hydroxocobalamin was administered in a quaternary care academic medical center. Methods : All hydroxocobalamin administrations from January 1, 2007 to December 31, 2018 were analyzed. Data points recorded were: carboxyhemoglobin, cyanide and methemoglobin levels, hospital time and course, time and dose of hydroxocobalamin administration, lactate and bicarbonate levels, initial and nadir pH, initial heart rate, and initial and lowest systolic blood pressure. Results : Fifty-six cases were identified. One case was excluded as hydroxocobalamin was administered for nitroprusside toxicity. Among 55 cases analyzed, 93% (n = 51) were adults. Median hospital length of stay was 4.3 days (IQR 2.5 to 12). Burn, inhalation injury, and smoke inhalation were 80% of admitting diagnoses. Median time to hydroxocobalamin administration was 208 minutes (IQR 62.5 to 330). Eleven of 55 cases died. Hydroxocobalamin was given within 60 minutes of arrival in 12 cases, of which 3 died. All adults received 5 g of hydroxocobalamin. Time to hydroxocobalamin administration was longer in death cases [median: 221 minutes (IQR 119 to 594)] vs survivors [median: 184.5 minutes (IQR 62.8 to 315)]. Seventeen cases had cyanide levels drawn, with 9 being measurable, but none were toxic. Conclusions : Significant delay in hydroxocobalamin administration was seen in this study. Cases that resulted in death had significantly longer times to hydroxocobalamin administration. Further studies are warranted to identify reasons for delays in hydroxocobalamin administration., Competing Interests: Declaration of Conflicting InterestsThe author(s) declared no potential conflicts of interest with respect to the research, authorship, and/or publication of this article.

Sulfurtransferases transfer of sulfur atoms from thiols to acceptors like cyanide. They are categorized as thiosulfate sulfurtransferases (TSTs) and 3-mercaptopyruvate sulfurtransferases (MSTs). TSTs transfer sulfur from thiosulfate to cyanide, producing thiocyanate. MSTs transfer sulfur from 3-mercaptopyruvate to cyanide, yielding pyruvate and thiocyanate. The present study aimed to isolate and characterize the sulfurtransferase FrST from Frondihabitans sp. PAMC28461 using biochemical and structural analyses. FrST exists as a dimer and can be classified as a TST rather than an MST according to sequence-based clustering and enzyme activity. Furthermore, the discovery of activity over a wide temperature range and the broad substrate specificity exhibited by FrST suggest promising prospects for its utilization in industrial applications, such as the detoxification of cyanide., Competing Interests: The authors have declared that no competing interests exist., (Copyright: © 2024 Do et al. This is an open access article distributed under the terms of the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original author and source are credited.)

The one-pot MAC (Masked Acyl Cyanide) reaction is used to perform the tandem oxyhomologation reaction of N,N -dibenzyl-l-phenylalaninal and coupling with nitrogen nucleophiles to provide a wide selection of amide and peptide derivatives of (2 S ,3 S )-allophenylnorstatin in generally good yields and with high anti selectivity, often with dr >98:2. The procedure works equally well with other selected N,N -dibenzyl α-amino aldehydes, and is used to achieve a very short synthesis of (2 S, 3 S,S )-epibestatin.

The dual-functional heterogeneous Fenton catalyst Cu/Ti co-doped iron-based Fenton catalyst (Cu/Ti -Fe 3 O 4 @FeOOH, FCT) were successfully prepared by precipitation oxidation method and characterized by XRD, XPS and XAFS. The prepared Cu/Ti co-doped Fe 3 O 4 @FeOOH nanoparticles consisted of goethite nanorods and magnetite rod octahedral particles, with Cu and Ti replacing Fe in the catalyst crystal structure, leading to the formation of the goethite structure. The heterogeneous Fenton catalyst FCT exhibited excellent degradation activity for cyanide in wastewater and showed different reaction mechanisms at varying pH levels. When treating 100 mL of 12 mg L -1 NaCN solution, complete degradation occurred within 40 min at 30 °C and pH ranging from 6.5 to 12.5 without external energy. Compared to Fe 3 O 4 , FCT shows superior degradation activity for cyanide. The surface Cu(Ⅰ) facilitated the electron transfer and significantly improved the catalytic activity of the catalyst. Additionally, the magnetic properties of the Ti-doped catalyst samples were greatly enhanced compared to the Cu@FeOOH catalyst doped with Cu, making them favorable for recycling and reuse. FCT maintains 100% degradation of cyanogen after three cycles, indicating its excellent stability. Furthermore, electron spin resonance spectroscopy, free radical quenching experiments and fluorescence probe techniques using terephthalic acid (TA) and benzoic acid (BA) confirmed that the presence of • OH and Fe Ⅳ =O reactive species was responsible for the catalysts exhibiting different mechanisms at different pH conditions. Compared with other heterogeneous Fenton catalysts, FCT exhibits intentional degradation activity for cyanide-containing wastewater under different acid-base conditions, which greatly broadened the pH range of the heterogeneous Fenton reaction., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

The wastewater from underground coal gasification (UCG) process has extremely complex composition and high concentrations of toxic and refractory compounds including phenolics, aliphatic and aromatic hydrocarbons, ammonia, cyanides, hazardous metals and metalloids. So, the development of biological processes for treating UCG wastewater poses a serious challenge in the sustainable coal industry. The aim of the study was to develop an innovative and efficient wetland construction technology suitable for a treatment of UCG wastewater using available and low-cost media. During the bioremediation process the toxicity of the raw wastewater decreased significantly between 74%-99%. The toxicity units (TU) ranged from values corresponding to very high acute toxic for raw wastewater to non-toxic for effluents from wetland columns after 60 days of the experiment. The toxicity results correlated with the decrease of some organic and inorganic compounds such as phenols, aromatic hydrocarbons, cyanides, metals and ammonia observed during the bioremediation process. The removal percentage of organic compounds like BTEX, PAHs and phenol was around 99% just after 14 days of treatment. A similar removal rate was indicated for cyanide and metals (Zn, Cr, Cd and Pb). Concluded, in order to effectively assess remediation technologies, it is desirable to consider combination of physicochemical parameters with ecotoxicity measurements. The present findings show that wetland remediation technology can be used to clean-up the heavily contaminated waters from the UCG process. Wetland technology as a nature-based solution has the potential to turn coal gasification wastewater into usable recycled water. It is economically and environmentally alternative treatment method., Competing Interests: The authors have declared that no competing interests exist., (Copyright: © 2024 Jałowiecki et al. This is an open access article distributed under the terms of the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original author and source are credited.)

Peptidomimetics have been extensively explored in many area due to their ability to improve pharmacological qualities and interesting biological activities. Cycles could be incorporated in peptides to reduce their flexibility, often enhancing the affinity for a certain receptor. Many efforts have been made to synthesize various peptidomimetics. Among them, the Ugi reaction is a popular way for the synthesis of peptidomimetics because it provides peptide-like products. The Ugi reaction consists of the condensation of an aldehyde or ketone, a carboxylic acid, an amine, and an isocyanide usually giving a linear peptidomimetic. In order to obtain other linear, cyclic or polycyclic peptidomimetics, the acyclic products have to undergo additional transformations or cyclizations. This review covers the years from 2018-2023, regarding the synthesis of linear, cyclic and polycyclic peptidomimetics, employing Ugi reactions eventually followed by post-Ugi transformations. Organo-catalyzed reactions, base-promoted reactions, and metal-free reactions toward peptidomimetics are highlighted., (© 2023 Wiley-VCH GmbH.)

The extraordinary accumulation of cyanide ions within biological cells is a severe health risk. Detecting and tracking toxic cyanide ions within these cells by simple and ultrasensitive methodologies are of immense curiosity. Here, continuous tracking of ultimate levels of CN - -ions in HeLa cells was reported employing biocompatible branching molecular architectures (BMAs). These BMAs were engineered by decorating colorant-laden dendritic branch within and around the molecular building hollows of the geode-shelled nanorods of organic-inorganic Al-frameworks. Batch-contact methods were utilized to assess the potential of hollow-nest architecture for inhibition/evaluation of toxicant CN - -ions within HeLa cells. The nanorod BMAs revealed significant potential capabilities in monitoring and tracking of CN - ions (88 parts per trillion) in biological trials within seconds. These results demonstrated sufficient evidence for the compatibility of BMAs during HeLa cell exposure. Under specific conditions, the BMAs were utilized for in-vitro fluorescence tracking/sensing of CN - in HeLa cells. The cliff swallow nest with massive mouths may have the potential to reduce the health hazards associated with toxicant exposure in biological cells., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023. Published by Elsevier B.V.)

The novel glutamic acid crosslinked chitosan membrane (CsG) was fabricated and tested for its adsorption capabilities for the removal of multiple pollutants like Cr (VI), cyanide, fluoride and diclofenac sodium from wastewater. This fabricated CsG membrane was characterized by various techniques like FT-IR, SEM, EDX and XRD, BET to assess its structural, compositional and morphological properties. The working parameters studied by batch experiments were solution pH, CsG dose, contact time, pollutant concentration and solution temperature. The CsG membrane exhibited maximum adsorption capacity of 410.7 mg/g, 310.2 mg/g, 14.3 mg/g, 132.7 mg/g for Cr (VI), cyanide, fluoride and diclofenac respectively. The validation of the operational parameters was performed by Response Surface Methodology (RSM). The experimental data fitted well with Langmuir isotherm model and followed pseudo second order kinetics for all the four targeted contaminants. The spontaneity of the process was checked by thermodynamics studies. The high partition coefficients of 7669 L/kg Cr(VI), 23,309 L/kg (CN - ), 649 L/kg (F - ) and 2613 L/kg (DFC) are the indicators of excellent attractive interaction between CsG membrane and target toxicants. The CsG membrane showed efficient regenerative adsorption properties up to 5 adsorption-desorption cycles. Overall, the developed novel CsG membrane promised as an effective material for the removal of multiple number of pollutants from water., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier Inc. All rights reserved.)

A wide range of platinum(0)-η 2 -( E )-1,2-ditosylethene complexes bearing isocyanide, phosphine and N -heterocyclic carbene ancillary ligands have been prepared with high yields and selectivity. All the novel products underwent thorough characterization using spectroscopic techniques, including NMR and FT-IR analyses. Additionally, for some compounds, the solid-state structures were elucidated through X-ray diffractometry. The synthesized complexes were successively evaluated for their potential as anticancer agents against two ovarian cancer cell lines (A2780 and A2780 cis ) and one breast cancer cell line (MDA-MB-231). The majority of the compounds displayed promising cytotoxicity within the micromolar range against A2780 and MDA-MB-231 cells, with IC 50 values comparable to or even surpassing those of cisplatin. However, only a subset of compounds was cytotoxic against cisplatin-resistant cancer cells (A2780 cis ). Furthermore, the assessment of antiproliferative activity on MRC-5 normal cells revealed certain compounds to exhibit in vitro selectivity. Notably, complexes 3d , 6a and 6b showed low cytotoxicity towards normal cells (IC 50 > 100 µM) while concurrently displaying potent cytotoxicity against cancer cells.

The effect of boron (B) deficiency on mediating the contribution of H + -ATPase in the uptake and assimilation of exogenous cyanide (CN - ) is investigated. Under CN - treatments, rice seedlings with B-deficient (-B) conditions exhibited significantly higher CN - uptake and assimilation rates than B-supplemented (+B) seedlings, whereas NH 4 + uptake and assimilation rates were slightly higher in -B rice seedlings than in +B. In this connection, the expression pattern of genes encoding β-CAS, ST, and H + -ATPase was assessed to unravel their role in the current scenario. The abundances of three β-CAS isogenes (OsCYS-D1, OsCYS-D2, and OsCYS-C1) in rice tissues are upregulated from both "CN - -B" and "CN - +B" treatments, however, only OsCYS-C1 in roots from the "CN - -B" treatments was significantly upregulated than "CN - +B" treatments. Expression patterns of ST-related genes (OsStr9, OsStr22, and OsStr23) are tissue specific, in which significantly higher upregulation of ST-related genes was observed in shoots from "CN - -B" treatments than "CN - +B" treatments. Expression pattern of 7 selected H + -ATPase isogenes, OsA1, OSA2, OsA3, OsA4, OsA7, OsA8, and OsA9 are quite tissue specific between "CN - +B" and "CN - -B" treatments. Among these, OsA4 and OsA7 genes were highly activated in the uptake and assimilation of exogenous CN - in -B nutrient solution. These results indicated that B deficiency disturbs the pattern of N cycles in CN - -treated rice seedlings, where activation of ST during CN - assimilation decreases the flux of the innate pool of NH 4 + produced from CN - assimilation by the β-CAS pathway in plants. Collectively, the B deficiency increased the uptake and assimilation of exogenous CN - through activating H + -ATPase., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

Despite the accessibility of numerous transition metal polyphosphido complexes through transition-metal-mediated activation of white phosphorus, the targeted functionalization of P n ligands to obtain functional monophosphorus species remains challenging. In this study, we introduce a new [3+1] fragmentation procedure for cyclo-P 4 ligands, leading to the discovery of acylcyanophosphanides and -phosphines. Treatment of the complex [K(18c-6)][(Ar*BIAN)Co(η 4 -P 4 )] ([K(18c-6)]3, 18c-6=[18]crown-6, Ar*=2,6-dibenzhydryl-4-isopropylphenyl, BIAN=1,2-bis(arylimino)acenaphthene diimine) with acyl chlorides results in the formation of acylated tetraphosphido complexes [(Ar*BIAN)Co(η 4 -P 4 C(O)R)] (R=tBu, Cy, 1-Ad, Ph; 4 a-d). Subsequent reactions of 4 a-d with cyanide salts yield acylated cyanophosphanides [RC(O)PCN] - (9 a-d - ) and the cyclo-P 3 cobaltate anion [(Ar*BIAN)Co(η 3 -P 3 )(CN)] - (8 - ). Further reactions of 4 a-d with trimethylsilyl cyanide (Me 3 SiCN) and isocyanides provide insight into a plausible mechanism of this [3+1] fragmentation reaction, as these reagents partially displace the P 4 C(O)R ligand from the cobalt center. Several potential intermediates of the [3+1] fragmentation were characterized. Additionally, the introduction of a second acyl substituent was achieved by treating [K(18c-6)]9b with CyC(O)Cl, resulting in the first bis(acyl)monocyanophosphine (CyC(O)) 2 PCN (10)., (© 2023 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

Hydroxocobalamin is used for cyanide toxicity after smoke inhalation, but diagnosis is challenging. Retrospective studies have associated hydroxocobalamin with acute kidney injury (AKI). This is a retrospective analysis of patients receiving hydroxocobalamin for suspected cyanide toxicity. The primary outcome was the proportion of patients meeting predefined appropriate use criteria defined as ≥1 of the following: serum lactate ≥8 mmol/L, systolic blood pressure (SBP) <90 mmHg, new-onset seizure, cardiac arrest, or respiratory arrest. Secondary outcomes included incidence of AKI, pneumonia, resolution of initial neurologic symptoms, and in-hospital mortality. Forty-six patients were included; 35 (76%) met the primary outcome. All met appropriate use criteria due to respiratory arrest, 15 (43%) for lactate, 14 (40%) for SBP, 12 (34%) for cardiac arrest. AKI, pneumonia, and resolution of neurologic symptoms occurred in 30%, 21%, and 49% of patients, respectively. In-hospital mortality was higher in patients meeting criteria, 49% vs. 9% (95% CI 0.16, 0.64). When appropriate use criteria were modified to exclude respiratory arrest in a post-hoc analysis, differences were maintained, suggesting respiratory arrest alone is not a critical component to determine hydroxocobalamin administration. Predefined appropriate use criteria identify severely ill smoke inhalation victims and provides hydroxocobalamin treatment guidance., Competing Interests: Declaration of Competing Interest None., (Copyright © 2023 Elsevier Ltd and ISBI. All rights reserved.)

Cyrene, a green bioderived solvent from waste cellulose, was applied to the synthesis of novel α-acyloxyamide derivatives through a Passerini-3CR with carboxylic acids and isocyanides with good yields and diastereoselectivities under mild conditions. Cyrene showed exceptionally high reactivity and the degree of diastereoselection was dependent mostly on the isocyanide. DFT calculations as well as the experimental findings indicated that both kinetic and thermodynamic effects might explain the results., (© 2023. The Author(s), under exclusive licence to Springer Nature Switzerland AG.)

Background: Amyotrophic lateral sclerosis (ALS) is a neurodegenerative disorder with few risk factors identified and no known cure. Gene-environment interaction is hypothesized especially for sporadic ALS cases (90-95%) which are of unknown etiology. We aimed to investigate risk factors for ALS including exposure to ambient air toxics., Methods: This population-based case-control study included 267 ALS cases (from the United States [U.S.] Centers for Disease Control and Prevention/Agency for Toxic Substances and Disease Registry National ALS Registry and Biorepository) and 267 age, sex, and county-matched controls identified via a commercial database. Exposure assessment for 34 ambient air toxicants was performed by assigning census tract-level U.S. Environmental Protection Agency (EPA) 2011 National Air Toxics Assessment (NATA) data to participants' residential ZIP codes. Conditional logistic regression was used to compute adjusted odds ratios (aORs) and 95% confidence intervals (CIs) for individual compounds, chemical classes, and overall exposure. Sensitivity analyses using both conditional logistic regression and Bayesian grouped weighted quartile sum (GWQS) models were performed to assess the integrity of findings., Results: Using the 2011 NATA, the highest exposure quartile (Q4) compared to the lowest (Q1) of vinyl chloride (aOR = 6.00, 95% CI: 1.87-19.25), 2,4-dinitrotoluene (aOR = 5.45, 95% CI: 1.53-19.36), cyanide (aOR = 4.34, 95% CI: 1.52-12.43), cadmium (aOR = 3.30, 95% CI: 1.11-9.77), and carbon disulfide (aOR = 2.98, 95% CI: 1.00-8.91) was associated with increased odds of ALS. Residential air selenium showed an inverse association with ALS (second quartile [Q2] vs. Q1: aOR = 0.38, 95% CI: 0.18-0.79). Additionally, residential exposure to organic/chlorinated solvents (Q4 vs Q1: aOR = 2.62, 95% CI: 1.003-6.85) was associated with ALS., Conclusions: Our findings using the 2011 NATA linked by census tract to residential area provide evidence of increased ALS risk in cases compared to controls for 2,4-dinitrotoluene, vinyl chloride, cyanide, and the organic/chlorinated solvents class. This underscores the importance of ongoing surveillance of potential exposures for at-risk populations., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier Inc. All rights reserved.)

Stefano Marcaccini was one of the pioneers in the use of isocyanide-based multicomponent reactions in organic synthesis. Throughout his career at the University of Florence he explored many different faces of isocyanide chemistry, especially those geared towards the synthesis of biologically relevant heterocycles. His work inspired many researchers who contributed to other important developments in the field of multicomponent reactions and created a school of synthetic chemists that continues today. In this manuscript we intend to review the articles on isocyanide multicomponent reactions published by Dr. Marcaccini and analyse their influence on the following works by other researchers. With this, we hope to highlight the immense contribution of Stefano Marcaccini to the development of isocyanide chemistry and modern organic synthesis as well as the influence of his research on future generations. We believe that this review will not only be a well-deserved tribute to the figure of Stefano Marcaccini, but will also serve as a useful inspiration for chemists working in this field., (© 2023. The Author(s).)

Cells of most eukaryotic species contain mitochondria, which play a role in physiological processes such as cellular senescence, metabolism, and autophagy. Viscosity is considered a key marker for many illnesses and is involved in several crucial physiological processes. Cyanide (CN - ) can target cytochrome-c oxidase, disrupting the mitochondrial electron transport chain and causing cell death through asphyxiation. In this study, a fluorescent probe named HL-1, which targets mitochondria and measures viscosity and CN - levels, was designed and synthesized. HL-1 is viscosity-sensitive, with a linear correlation coefficient of up to 0.992. In addition, HL-1 was found to change color substantially during a nucleophilic addition reaction with CN - , which has a low detection limit of 47 nM. HL-1 not only detects viscosity and exogenous CN - in SKOV-3 cells and zebrafish but also monitors viscosity changes during mitochondrial autophagy in real time. Furthermore, HL-1 has been used successfully to monitor changes in mitochondrial membrane potential during apoptosis. Endogenous CN - in plant samples was quantified. HL-1 provides new ideas for studying viscosity and CN - ., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier Inc. All rights reserved.)

A new fluorescent sensor for the detection of CN - was developed based on the conjugation of phenothiazine fluorophore and benzofuran unit. By the nucleophilic attacking of CN - to the fluoroacetylamino group in the sensor, the additional reaction of CN - and carbonyl group induced the ICT (intramolecular charge transfer) effect in the molecule and caused the fluorescence quenching sensor. The titration experiments show that the sensor has good sensitivity, selectivity and quick response for CN - . In addition, the fluorescent detection of CN - in the living cell and zebrafish experiments demonstrated the value of the sensor in tracing the CN - in biological systems.

To develop a novel 99m Tc-labeled ubiquicidin 29-41 derivative for bacterial infection single-photon emission computed tomography (SPECT) imaging with improved target-to-nontarget ratio and lower nontarget organ uptake, a series of isocyanide ubiquicidin 29-41 derivatives (CNnUBI 29-41, n = 5-9) with different carbon linkers were designed, synthesized and radiolabeled with the [ 99m Tc]Tc(I) + core, [ 99m Tc][Tc(I)(CO) 3 (H 2 O) 3 ] + core and [ 99m Tc][Tc(V)N] 2+ core. All the complexes are hydrophilic, maintain good stability and specifically bind Staphylococcus aureus in vitro. The biodistribution in mice with bacterial infection and sterile inflammation demonstrated that [ 99m Tc]Tc-CN5UBI 29-41 was able to distinguish bacterial infection from sterile inflammation, which had an improved abscess uptake and a greater target-to-nontarget ratio. SPECT imaging study of [ 99m Tc]Tc-CN5UBI 29-41 in bacterial infection mice showed that there was a clear accumulation in the infection site, suggesting that this radiotracer could be a potential radiotracer for bacterial infection imaging.

A new class of palladium-indenyl complexes characterized by the presence of one bulky alkyl isocyanide and one aryl phosphine serving as ancillary ligands has been prepared, presenting high yields and selectivity. All the new products were completely characterized using spectroscopic and spectrometric techniques (NMR, FT-IR, and HRMS), and, for most of them, it was also possible to define their solid-state structures via X-ray diffractometry, revealing that the indenyl fragment always binds to the metal centre with a hapticity intermediate between ƞ 3 and ƞ 5 . A reactivity study carried out using piperidine as a nucleophilic agent proved that the indenyl moiety is the eligible site of attack rather than the isocyanide ligand or the metal centre. All complexes were tested as potential anticancer agents against three ovarian cancer cell lines (A2780, A2780 cis , and OVCAR-5) and one breast cancer cell line (MDA-MB-231), displaying comparable activity with respect to cisplatin, which was used as a positive control. Moreover, the similar cytotoxicity observed towards A2780 and A2780 cis cells (cisplatin-sensitive and cisplatin-resistant, respectively) suggests that our palladium derivatives presumably act with a mechanism of action different than that of the clinically approved platinum drugs. For comparison, we also synthesized Pd-ƞ 3 -allyl derivatives, which generally showed a slightly higher activity towards ovarian cancer cells and lower activity towards breast cancer cells with respect to their Pd-indenyl congeners.

Presenilin 1 (PS1) is a transmembrane proteolytic subunit of γ -secretase that cleaves amyloid precursor proteins. Mutations in PS1 (mPS1) are associated with early-onset familial Alzheimer's disease (AD). The link between mutated PS1, mitochondrial calcium regulation, and AD has been studied extensively in different test systems. Despite the wide-ranging role of mPS1 in AD, there is a paucity of information on the link between PS1 and neuronal cell death, a hallmark of AD. In the present study, we employed the selective mitochondrial uncoupler carbonyl cyanide chlorophenylhydrazone (CCCP) and compared the reactivity of mPS1-transfected cultured rat hippocampal neurons with PS1 and control neurons in a situation of impaired mitochondrial functions. CCCP causes a slow rise in cytosolic and mitochondrial calcium in all three groups of neurons, with the mPS1 neurons demonstrating a faster rise. Consequently, mPS1 neurons were depolarized by CCCP and measured with TMRM, a mitochondrial voltage indicator, more than the other two groups. Morphologically, CCCP produced more filopodia in mPS1 neurons than in the other two groups, which were similarly affected by the drug. Finally, mPS1 transfected neurons tended to die from prolonged exposure to CCCP sooner than the other groups, indicating an increase in vulnerability associated with a lower ability to regulate excess cytosolic calcium.

For over two hundred years, cyanide has served as the primary reagent for gold extraction. However, due to its high toxicity, the use of cyanide poses significant risks. Traditional low-toxicity leaching reagents have limitations that restrict their widespread industrial application, leading to the necessity for the development of new, efficient, and low-toxic gold leaching reagents to support sustainable gold production. In this study, a novel, efficient, and low-toxicity gold extraction reagent was synthesized at high temperatures by combining urea, sodium carbonate, and a specific iron salt. The research delved into the leaching ability of the reagent under different synthesis conditions and examined the generation of free cyanide content as a by-product. Findings indicated that reagents synthesized with either potassium ferrocyanide or potassium ferricyanide displayed comparable leaching capabilities. Reagents synthesized at 800 °C exhibited lower levels of free cyanide ions and reduced toxicity. Additionally, this reagent demonstrated exceptional selectivity for gold, while in minimal dissolution of copper, iron, nickel, lead, and iron from computer central processing unit (CPU) pins. Under optimal conditions, the efficiency of gold extraction from CPU pins reached 94.65%. Hence, this reagent holds significant potential for the low-toxicity extraction of gold from electronic waste or auriferous concentrates., (© 2023. The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature.)

Cyanide and heavy metals pose significant risks as contaminants in certain industrial effluents. This study aims to concurrently eliminate cyanide and specific heavy metals from synthetic wastewater resembling gold processing effluent, employing an improved electrocoagulation method incorporating ozone and UV-LED. The investigation delves into the effects of pH, electrode type, current density, reaction time, and ozonation. The findings revealed notable removal efficiencies: 98% for cyanide, 76% for nickel, 85% for copper, and 84% for zinc when utilizing a stainless steel electrode as the cathode. Optimal removal rates were achieved at 94% for cyanide, 93% for copper, 92% for zinc, and 83% for nickel, employing the UV-LED-ozone technique with an ozonation flow rate of 4 mg/s at pH = 10. Notably, when Al-Gr-SS-Fe electrodes and a current of 15 mA/cm 2 were applied, these removal efficiencies were observed. Therefore, the most favorable conditions for the concurrent removal of pollutants from synthetic wastewater involved maintaining a pH of 10, utilizing SS-Fe as anode and Al-Gr as cathode electrodes, and employing a current density of 15 mA/cm 2 . The addition of ozonation with a flow rate of 4 mg/s, along with UV-LED, further enhanced the removal process. In summary, it can be inferred that the enhanced electrocoagulation method outperformed conventional electrocoagulation, leading to increased elimination of cyanide and selected heavy metals., (© 2023. The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature.)

Dopamine is an important neurotransmitter, and the disruption of dopaminergic homeostasis causes various neurological diseases such as Parkinson's disease. Analysis of intracellular dopamine levels is important to understand the pathology of neurological diseases. We have developed a new method for the fluorometric detection of dopamine by adopting the König reaction, which is commonly used for the detection of cyanide, thiocyanate, and selenocyanate, and demonstrated that it can be applied to the determination of intracellular dopamine levels. The present method only requires a conventional LC system with isocratic elution and post-column derivatization and is simple to perform. The LOD, LOQ, and linearity range were 10.8 nM, 32.8 nM, and 0.05-10 μM, respectively, with accuracies of 101.8-106.3 % and precisions within 5 %, which are sufficient for the quantification of intracellular dopamine. We also determined dopamine levels in PC12 cells and found that the levels increased and decreased when the cells were exposed to L-dopa and cyanide, respectively, possibly because of the conversion of L-dopa into dopamine and the depletion of intracellular dopamine by exposing cells to cyanide, respectively. These results suggest the applicability of the present method, and that this new use of the König reaction offers a reliable and useful means of quantifying intracellular dopamine., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier B.V. All rights reserved.)

The advantages of microbial induced carbonate precipitation (MICP) as bio-cementation technology for tailings-solidification are under extensive investigation. In order to improve performance of bio-cementation, many strengthening materials were applied to the bio-cementation of tailings. Steel slag (SS) is a kind of industrial solid waste, its chemical composition and mineral composition are similar to cement, and it has a certain application prospect as an auxiliary cementing material. In this study, the properties and mechanism of SS strengthening MICP cementation of cyanide tailings (CT) were investigated. The results showed that Sporosarcina pasteurii growth is not inhibited by SS, and Sporosarcina pasteurii can promote the hydration reaction of SS, providing a suitable alkaline environment and Ca 2+ , promoting the production of more CaCO 3 in the MICP process. When 200 mL of CT leachate was added 1.4 g SS (200-400 mesh), the adsorption of Cu, Pb, Zn, Cd, total cyanide (T-CN), and free cyanide (F-CN) reached 48.05%, 44.28%, 36.25%, 16.67%, 79.05%, and 67.20%, respectively. The maximum unconfined compressive strength（UCS） of the cemented body (with 5%, 150 mesh SS) was 1.97 MPa, which was 3.396 times as high as that without SS. The cemented body with the addition of SS (5%, 150 mesh) contained more carbonate bound Cu (2.75%), Pb (4.89%), Zn (5.37%), and Cd (5.75%), and less exchangeable Cu (3.65%), Pb (6.85%), Zn (2.27%), and Cd (4.42%) than that without SS. In summary, the addition of SS improved the UCS of cemented bodies and the stability of heavy metals and cyanide, reduced the environmental risks existing in the process of CT storage. Meanwhile, it also provides new ideas for resource utilization of industrial solid waste SS and improvement of mine filling materials., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier Ltd. All rights reserved.)

Pakistan is an agricultural country producing plenty of fruits, like: mango, banana, apple, peaches, grapes, plums, variety of citrus fruits including lemon, grapefruit, and oranges. So far the peels of most of the fruits are usually wasted and not properly utilized anywhere. In this work, the peels of banana and grapefruit are converted into biochar by slow pyrolysis under controlled supply of air and used for sequestering cyanide ions from aqueous medium after chemical modification with ZnCl 2 and sodium dodecyl sulfate (SDS). The modified biochar was characterized by various instrumental techniques, like: SEM, FTIR, TGA, and CHNS. Different parameters, like: time, temperature, pH, and dose of adsorbent affecting the adsorption of cyanide ions, onto prepared biochar were optimized and to understand the adsorption phenomenon, kinetic and thermodynamic studies were performed. Concentration of cyanide ions was estimated by employing standard ion selective electrode system and it is found that Sodium Dodecyl Sulfate treated biochar of banana peels shown more adsorption capacity, i.e., : 17.080 mg/g as compared to all samples. Present work revealed that the biochar produced from the fruit waste has sufficient potential to eliminate trace quantities of cyanide from water, especially after treatment with sodium dodecyl sulfate.

Recently, we have described the first supermolecular nanoentities (SMEs) of a vitamin B 12 derivative, viz., a monocyano form of heptabutyl cobyrinate ((CN - ) Bu Cby), unique nanoparticles with strong noncovalent intermolecular interactions, and emerging optical and redox properties. In this work, the fast response of thin films based on the SMEs of the B 12 derivative to gaseous toxins (viz., hydrogen cyanide, ammonia, sulfur dioxide, and hydrogen sulfide) particularly dangerous for humans was demonstrated. The reaction between SMEs of (CN - ) Bu Cby in Langmuir-Schaefer (LS) films and HCN generates dicyano species and proceeds ca. 5-fold more rapidly than the process involving drop-coated films that contain (CN - ) Bu Cby in molecular form. The highest sensitivity toward HCN was achieved by using thicker LS films. The reaction proceeds reversibly: upon exposure to air, the dicyano complex undergoes partial decyanation. The decyanated complex retains reactivity toward HCN for at least four subsequent cycles. The processes involving SMEs of (CN - ) Bu Cby and NH 3 , SO 2 , and H 2 S are irreversible, and the sensitivity of the films toward these gases is lower in comparison with HCN. Presented data provides mechanistic information on the reactions involving solid vitamin B 12 derivatives and gaseous toxins. In the case of NH 3 , deprotonation of the coordinated Co(III)-ion water molecule occurs, and the generated hydroxocyano species exhibit high air stability. After binding of SO 2 , a mixture of sulfito and dicyano species is produced, and the regenerated film contains aquacyano and diaqua or aquahydroxo species, which possess high reactivity toward gaseous toxins. Reaction with H 2 S produces a mixture of the Co(III)-dicyano form and Co(II)-species containing sulfide oxidation products, which are resistant to aerobic oxidation. Our findings can be used for the development of naked-eye, electronic optic, and chemiresistive sensors toward gaseous toxins with improved reactivity for prompt cyanide detection in air, blood, and plant samples and for analysis of exhaled gases for the diagnosis of diseases.

Patients transported from fire sites may exhibit various injury patterns. Major trauma, skin burn, inhalation burn, and carbon monoxide poisoning are typical injuries. However, most physicians may be unfamiliar that cyanide poisoning can frequently occur due to combustion. Cyanide poisoning is highly significant owing to high mortality and the existence of antidotes. I present a 35-year-old man who was transported from a burning building and suffered severe metabolic acidosis despite no major bleeding as well as mild carbon monoxide poisoning. I suspected cyanide poisoning and administered the antidote; subsequently, the patient showed improvement. The next day, sudden airway obstruction developed, and emergency endotracheal intubation was performed. The inhalation damage was detected only in the lower airway tract and not in the upper airway. Physicians should be aware of cyanide poisoning and inhalation burn to avoid missing treatment opportunities., Competing Interests: Conflicts of interest The author has no conflicts of interest to declare., (© 2023 The Korean Society of Traumatology.)

Cyanide is a highly toxic substance present in wastewater from various industries. This study investigates the removal of cyanide species (CS) from aqueous solutions using the ZnTiO 3 /TiO 2 /H 2 O 2 /UVB system. ZnTiO 3 /TiO 2 nanoparticles synthesized by the sol-gel method were characterized by powder X-ray diffractometry (XRD), scanning electron microscopy (SEM), and energy-dispersive X-ray spectroscopy (EDS). The adsorption capacity of nanoparticles was tested by varying the pH of the solution, adsorbent concentration, and contact time. The adsorption of CS on ZnTiO 3 and TiO 2 surfaces was verified by Density Functional Theory (DFT) calculations. Photocatalytic experiments were achieved under UVB irradiation (λ = 310 nm). The response surface methodology (RSM) was used to optimize the CS removal efficiency. The detoxification effect was evaluated by acute toxicity tests with brine shrimp. The theoretical results show that the adsorption of CS is energetically more favorable on the ZnTiO 3 surface than on the TiO 2 surface. The experimental results show that the system consisting of ZnTiO 3 /TiO 2 (200 mg L -1 ), H 2 O 2 (0.1%), and UVB light removes 99% of CS from aqueous solutions after 60 min and reduces the mortality of nauplii in 90% after 90 min. This system was reused in five consecutive cycles with a total loss of efficiency of 30%.

Cytochrome c oxidase (CcO) reduces O 2 in the O 2 -reduction site by sequential four-electron donations through the low-potential metal sites (Cu A and Fe a ). Redox-coupled X-ray crystal structural changes have been identified at five distinct sites including Asp 51 , Arg 438 , Glu 198 , the hydroxyfarnesyl ethyl group of heme a, and Ser 382 , respectively. These sites interact with the putative proton-pumping H-pathway. However, the metal sites responsible for each structural change have not been identified, since these changes were detected as structural differences between the fully reduced and fully oxidized CcOs. Thus, the roles of these structural changes in the CcO function are yet to be revealed. X-ray crystal structures of cyanide-bound CcOs under various oxidation states showed that the O 2 -reduction site controlled only the Ser 382 -including site, while the low-potential metal sites induced the other changes. This finding indicates that these low-potential site-inducible structural changes are triggered by sequential electron-extraction from the low-potential sites by the O 2 -reduction site and that each structural change is insensitive to the oxidation and ligand-binding states of the O 2 -reduction site. Because the proton/electron coupling efficiency is constant (1:1), regardless of the reaction progress in the O 2 -reduction site, the structural changes induced by the low-potential sites are assignable to those critically involved in the proton pumping, suggesting that the H-pathway, facilitating these low-potential site-inducible structural changes, pumps protons. Furthermore, a cyanide-bound CcO structure suggests that a hypoxia-inducible activator, Higd1a, activates the O 2 -reduction site without influencing the electron transfer mechanism through the low-potential sites, kinetically confirming that the low-potential sites facilitate proton pump., Competing Interests: Conflict of interest The authors declare that they have no conflicts of interest with the contents of this article., (Copyright © 2023 The Authors. Published by Elsevier Inc. All rights reserved.)

The chemistry of alkynyl triazenes is an emerging field for organic chemists and especially acid-induced nucleophilic functionalizations, either directly, or after a prior reaction towards aromatic triazenes under extrusion of nitrogen, paved the way for fruitful strategies. In contrast, the chemical behavior of alkynyl triazenes upon irradiation with light is still unknown. Herein we present the first photoactivation of alkynyl triazenes that triggers an uncommon reactivity pattern involving the cleavage of the N1-N2 bond of the triazene moiety resulting in a unique approach to cyanocarbenes from a readily available, stable, and insensitive precursor. This allows to access various nitrile compounds without the use of a toxic cyanating agent by exploiting the reactivity pattern of carbenes. By variation of the reaction conditions and light sources, different substitution patterns can be obtained selectively in good yields under mild and metal-free conditions, thus introducing the alkynyl triazene unit as a photo accessible methylene nitrile synthon. Using this synthon, subclasses like α-alkoxynitriles, α-aminonitriles and α-cyanohydrazones become easily available. These exhibit synthetically valuable substitution patterns for the synthesis of pharmaceuticals, intermediates for total synthesis and amino acid synthesis., (© 2023 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

In recent years, electronic waste (e-waste) production has increased due to the population's growth and high consumption. As a result of the high concentration of heavy elements in these wastes, their disposal has posed many environmental problems. On the other hand, due to the non-renewability of mineral resources and the presence of valuable elements such as Cu and Au in electronic waste, these wastes are considered secondary minerals for recovering valuable elements. Among electronic waste, recovery of metals from spent telecommunication printed circuit boards (STPCBs) is significant, which has not been addressed despite their high production worldwide. This study isolated an indigenous cyanogenic bacterium from alfalfa field soil. The 16S rRNA gene sequencing results showed that the best strain has 99.8% phylogenetic affinity with Pseudomonas atacamenisis M7DI(T) with the accession number SSBS01000008 with 1459 nucleotides. The effect of the culture medium, initial pH, glycine concentration, and methionine on the cyanide production of the best strain was investigated. The results showed that the best strain could produce 12.3 ppm cyanide in NB medium with an initial pH of 7 and a concentration of glycine and methionine of 7.5 g/L and 7.5 g/L , respectively. The one-step bioleaching method was performed, which led to the recovery of 98.2% of Cu from STPCBs powder after 5 days. Finally, XRD, FTIR, and FE-SEM analyses were performed to investigate the structure of the STPCBs powder before and after the bioleaching process, confirming the high Cu recovery., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier Ltd. All rights reserved.)

Switching of multiple physical properties by external stimuli in dynamic materials enables applications in, e.g., smart sensors, biomedical tools, as well as data-storage devices. Among stimuli-responsive materials, inorganic-organic molecular hybrids exhibiting thermal order-disorder phase transitions were tested as promising molecular switches of electrical characteristics, including dielectric constant. We aimed at broadening the multifunctional potential of such hybrid materials towards the switching of not only electrical but also other physical properties, e.g., light emission. We report two ionic salts based on luminescent tetracyanidonitridorhenate(V) anions bearing two different diamine ligands, 1,2-diaminoethane (1) and 1,3-diaminopropane (2), both crystallizing with polar N-methyl-dabconium cations. They exhibit an order-disorder phase transition related to the heating-induced turning-on of the rotation of polar cations. This leads to a unique synchronous switching of the dielectric constant as well as metal-complex-centered photoluminescence, as demonstrated by changes in, e.g., emission lifetime. The roles of organic cations, non-trivial Re(V) complexes, and their interaction in achieving the coupled thermal switching of electrical and optical properties are discussed utilizing experimental and theoretical approaches., (© 2023 Wiley-VCH GmbH.)

Studies of protein folding often involve offline experimental methods such as titrating protein samples with denaturants or equilibrating them in the presence of denaturants. Here, we demonstrate an online analytical approach in which the protein structure is perturbed by a pH ramp evoked by immobilized lipase-catalyzed ester hydrolysis. Changes in the tertiary structure of the protein in response to a pH ramp (from approximately 6.3 to 2.8) are monitored using electrospray ionization mass spectrometry and spectrofluorometry. Interestingly, we discovered a side reaction of ammonium and formate leading to the production of cyanide that occurred during the ionization process. We also found that only certain protein analytes were bound to the formed cyanide species. Nevertheless, this problem was readily overcome by carefully selecting a specific ester substrate. Overall, the alterations in the charge-state distribution and fluorescence intensity─caused by the lipase-induced pH ramp─reveal conformational transitions in different proteins. In line with previous reports, the acid-induced denaturation of holo-myoglobin occurs through a two-step mechanism, which is supported by identification of protein-unfolding intermediates and the loss of noncovalent protein ligand (heme). The results─obtained using the developed catalytic method─are also consistent with the results of equilibrium-based experiments, while sample preparation steps are substantially reduced. The proposed approach simplifies the identification of the pH range that has the greatest impact on the protein structure. Thus, it has the potential to be a useful tool for studying protein conformational transitions in the course of pH changes.

We develop a specific derivatization gas chromatography-mass spectrometry (GC-MS) method for cyanide using 1,2,3,3-tetramethyl-3H-indium iodide as the derivatization reagent. The derivative compounds were synthesized and characterized using 1 H nuclear magnetic resonance (NMR), 13 C NMR, and Fourier transform infrared (FT-IR) spectroscopy. The high selectivity of this derivatization for cyanide is supported by calculations and activation energy comparisons. We applied this method to pure water, green tea, orange juice, coffee cafe au lait, and milk. Derivatization was performed by diluting 20 μL of sample solution with 0.1 M NaOH and adding 100 μL of saturated borax solution and 100 μL of 8 mM TMI solution, each drink was completed in 5 min at room temperature, and selected ion (m/z = 200) monitoring analysis was linear (R 2  > 0.998) at 0.15 to 15 μM, with detection limits of 4-11 μM were shown. This method is expected to be widely used in forensic toxicology analysis and can be applied to beverages, which are forensically important field samples., (© 2023. The Author(s), under exclusive licence to The Japan Society for Analytical Chemistry.)

Various boron-containing isocyanides have been efficiently synthesized from the corresponding enantiopure β-substituted β-amino boronic acid pinacol esters, without need for protecting group interconversion, through a two-step, purification-free procedure. They were employed in a variety of isocyanide-based multicomponent reactions, proving to be reliable components for all of them and allowing the efficient synthesis of unprecedented, boron-containing peptidomimetics and heteroatom-rich small molecules, including biologically relevant cyclic boronates. Jointing together the β-amido boronic acid moiety, deriving from the isocyanide component, with prominent pharmacophoric rings emerging from the multicomponent process, a successful application of the molecular hybridization concept could be realized., (© 2022. The Author(s).)

Premise: β-Cyanoalanine synthase (β-CAS) and alternative oxidase (AOX) play important roles in the ability of plants to detoxify and tolerate hydrogen cyanide (HCN). These functions are critical for all plants because HCN is produced at low levels during basic metabolic processes, and especially for cyanogenic species, which release high levels of HCN following tissue damage. However, expression of β-CAS and Aox genes has not been examined in cyanogenic species, nor compared between cyanogenic and acyanogenic genotypes within a species., Methods: We used a natural polymorphism for cyanogenesis in white clover to examine β-CAS and Aox gene expression in relation to cyanogenesis-associated HCN exposure. We identified all β-CAS and Aox gene copies present in the genome, including members of the Aox1, Aox2a, and Aox2d subfamilies previously reported in legumes. Expression levels were compared between cyanogenic and acyanogenic genotypes and between damaged and undamaged leaf tissue., Results: β-CAS and Aox2a expression was differentially elevated in cyanogenic genotypes, and tissue damage was not required to induce this increased expression. Aox2d, in contrast, appeared to be upregulated as a generalized wounding response., Conclusions: These findings suggest a heightened constitutive role for HCN detoxification (via elevated β-CAS expression) and HCN-toxicity mitigation (via elevated Aox2a expression) in plants that are capable of cyanogenesis. As such, freezing-induced cyanide autotoxicity is unlikely to be the primary selective factor in the evolution of climate-associated cyanogenesis clines., (© 2023 Botanical Society of America.)

Cyanocobalamin (CNCbl), a medicinal form of vitamin B 12 , is resistant to glutathione (GSH), and undergoes intracellular processing via reductive decyanation producing the Co(II)-form of Cbl (Cbl(II)) mediated by the CblC-protein. Alteration of the CblC-protein structure might inhibit CNCbl processing. Here, we showed that introducing a bromine atom to the C10-position of the CNCbl corrin ring facilitates its reaction with GSH leading to the formation of Cbl(II) and cyanide dissociation. In a neutral medium, the reaction between C10-Br-CNCbl and GSH proceeds via the complexation of the reactants further leading to dimethylbenzimidazole (DMBI) substitution and electron transfer from GSH to the Co(III)-ion. The reaction is accelerated upon the GSH thiol group deprotonation. The key factors explaining the higher reactivity of C10-Br-CNCbl compared with unmodified CNCbl towards GSH are increasing the electrode potential of CNCbl two-electron reduction upon meso-bromination and the substantial labilization of DMBI, which was shown by comparing their reactions with cyanide and the pK a values of DMBI protonation (pK a base-off ). Aquacobalamin (H 2 OCbl) brominated at the C10-position of the corrin reacts with GSH to give Cbl(II) via GSH complexation and subsequent reaction of this complex with a second GSH molecule, whereas unmodified H 2 OCbl generates glutathionyl-Cbl, which is resistant to further reduction by GSH., (© 2023. The Author(s), under exclusive licence to Society for Biological Inorganic Chemistry (SBIC).)

Abstract: Background : Increased plasma lactate levels in patients with sepsis may be due to insufficient oxygen delivery, but mitochondrial dysfunction or accelerated glycolysis may also contribute. We studied the effect of the latter on muscle metabolism by using microdialysis in a sepsis model with sustained oxygen delivery and decreased energy consumption or mitochondrial blockade. Methods : Pigs were subjected to continuous Escherichia coli infusion (sepsis group, n = 12) or saline infusion (sham group, n = 4) for 3 h. Protocolized interventions were applied to normalize the oxygen delivery and blood pressure. Microdialysis catheters were used to monitor muscle metabolism (naïve). The same catheters were used to block the electron transport chain with cyanide or the Na + /K + -ATPase inhibitor, ouabain locally. Results: All pigs in the sepsis group had positive blood cultures and a Sequential Organ Failure Assessment score increase by at least 2, fulfilling the sepsis criteria. Plasma lactate was higher in the sepsis group than in the sham group ( P < 0.001), whereas muscle glucose was lower in the sepsis group ( P < 0.01). There were no changes in muscle lactate levels over time but lactate to pyruvate ratio (LPR) was elevated in the sepsis versus the sham group ( P < 0.05). Muscle lactate, LPR, and glutamate levels were higher in the sepsis group than in the sham group in the cyanide catheters ( P < 0.001, all comparisons) and did not normalize in the former group. Conclusions: In this experimental study on resuscitated sepsis, we observed increased aerobic metabolism and preserved mitochondrial function. Sepsis and electron transport chain inhibition led to increased LPR, suggesting a decreased mitochondrial reserve capacity in early sepsis., Competing Interests: The authors report no conflicts of interest., (Copyright © 2023 by the Shock Society.)

Hypochlorite is known to oxidatively degrade the corrin ring of cobalamin. Here, transient reaction intermediates are described in the reaction of aqua as well as of cyano-cobalamin with hypochlorite, using stopped-flow UV-vis kinetics. For aqua-cobalamin, the intermediate is assigned as arising from substitution of the aqua ligand with hypochlorite. For cyano-cobalamin, the intermediate is proposed to arise from substitution of the benzimidazole ligand trans to the cyanide. In both cases, the intermediates would feature a new Co(III)-OCl - bond-which is also supported by density functional theory (DFT) calculations., (© 2023. The Author(s), under exclusive licence to Society for Biological Inorganic Chemistry (SBIC).)

2,3,5,6-Tetramethyl-1,4-diisocyanobenzene ( 1 ), 1,4-diisocyanobenzene ( 2 ), and 1,4-dicyanobenzene ( 3 ) were co-crystallized with 1,3,5-triiodotrifluorobenzene (1,3,5-FIB) to give three cocrystals, 1 ·1,3,5-FIB, 2 ·2(1,3,5-FIB), and 3 ·2(1,3,5-FIB), which were studied by X-ray diffraction. A common feature of the three structures is the presence of I···C isocyanide or I···N nitrile halogen bonds (HaBs), which occurs between an iodine σ-hole and the isocyanide C-(or the nitrile N-) atom. The diisocyanide and dinitrile cocrystals 2 ·2(1,3,5-FIB) and 3 ·2(1,3,5-FIB) are isostructural, thus providing a basis for accurate comparison of the two types of noncovalent linkages of C≡N/N≡C groups in the composition of structurally similar entities and in one crystal environment. The bonding situation was studied by a set of theoretical methods. Diisocyanides are more nucleophilic than the dinitrile and they exhibit stronger binding to 1,3,5-FIB. In all structures, the HaBs are mostly determined by the electrostatic interactions, but the dispersion and induction components also provide a noticeable contribution and make the HaBs attractive. Charge transfer has a small contribution (<5%) to the HaB and it is higher for the diisocyanide than for the dinitrile systems. At the same time, diisocyanide and dinitrile structures exhibit typical electron-donor and π-acceptor properties in relation to the HaB donor.

A major route for the influx of calcium ions into neurons uses the STIM-Orai1 voltage-independent channel. Once cytosolic calcium ([Ca 2+ ]i) elevates, it activates mitochondrial and endoplasmic calcium stores to affect downstream molecular pathways. In the present study, we employed a novel drug, carbonyl cyanide chlorophenylhydrazone (CCCP), a mitochondrial uncoupler, to explore the role of mitochondria in cultured neuronal morphology. CCCP caused a sustained elevation of [Ca 2+ ]i and, quite surprisingly, a massive increase in the density of dendritic filopodia and spines in the affected neurons. This morphological change can be prevented in cultures exposed to a calcium-free medium, Orai1 antagonist 2APB, or cells transfected with a mutant Orai1 plasmid. It is suggested that CCCP activates mitochondria through the influx of calcium to cause rapid growth of dendritic processes.

The products of non-canonical isocyanide synthase (ICS) biosynthetic gene clusters (BGCs) mediate pathogenesis, microbial competition, and metal-homeostasis through metal-associated chemistry. We sought to enable research into this class of compounds by characterizing the biosynthetic potential and evolutionary history of these BGCs across the Fungal Kingdom. We amalgamated a pipeline of tools to predict BGCs based on shared promoter motifs and located 3800 ICS BGCs in 3300 genomes, making ICS BGCs the fifth largest class of specialized metabolites compared to canonical classes found by antiSMASH. ICS BGCs are not evenly distributed across fungi, with evidence of gene-family expansions in several Ascomycete families. We show that the ICS dit1/2 gene cluster family (GCF), which was prior only studied in yeast, is present in ∼30% of all Ascomycetes. The dit variety ICS exhibits greater similarity to bacterial ICS than other fungal ICS, suggesting a potential convergence of the ICS backbone domain. The evolutionary origins of the dit GCF in Ascomycota are ancient and these genes are diversifying in some lineages. Our results create a roadmap for future research into ICS BGCs. We developed a website (https://isocyanides.fungi.wisc.edu/) that facilitates the exploration and downloading of all identified fungal ICS BGCs and GCFs., (Published by Oxford University Press on behalf of Nucleic Acids Research 2023.)

The widespread use of cyanide (CN - ) in industry results in contamination of various effluents such as drain, lake, and tap water, an imminent danger to the environment and human health. We prepared naphthoquinolinedione (cyclized; 1-5) and anthracenedione (un-cyclized) probes (6-7) for selective detection of CN - . The addition of CN - to the probe solutions (1-5) resulted in a color change from pale green to orange under 365 nm illumination. The nucleophilic addition of CN - to C2 of the imidazolium ring of the probes is responsible for selective CN - detection. Among all probes, 1 gave the lowest fluorescence-based LOD of 0.13 pM. In contrast, the un-cyclized probes (6 and 7) were substantially inferior to the cyclized counterparts (1 and 2, respectively) for detecting a trace amount of CN - . The notably low LOD displayed by probe 1 was maintained in the detection of CN - in real food samples, human fluids, and human brain cells. This is the first report studying imidazolium-bearing naphthoquinolinedione-based probes for CN - sensing in 100% water., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier B.V. All rights reserved.)