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1.
Int J Mol Sci ; 25(12)2024 Jun 12.
Article in English | MEDLINE | ID: mdl-38928184

ABSTRACT

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


Subject(s)
Amines , Cyanides , Ethanol , Cyanides/chemistry , Cyanides/isolation & purification , Adsorption , Amines/chemistry , Ethanol/chemistry , Porosity , Cobalt/chemistry , Magnetite Nanoparticles/chemistry , Nanostructures/chemistry
2.
Biosensors (Basel) ; 14(6)2024 May 27.
Article in English | MEDLINE | ID: mdl-38920580

ABSTRACT

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.


Subject(s)
Cyanides , Electrochemical Techniques , Limit of Detection , Metal-Organic Frameworks , Cyanides/analysis , Metal-Organic Frameworks/chemistry , Electrodes , Biosensing Techniques , Nickel/chemistry , Ferrous Compounds/chemistry , Metallocenes/chemistry , Cobalt/chemistry
3.
Biochim Biophys Acta Bioenerg ; 1865(3): 149048, 2024 Aug 01.
Article in English | MEDLINE | ID: mdl-38723704

ABSTRACT

The effect of mitochondrial membrane potential (ΔΨm) on the absorbance of the reduced cytochrome c oxidase (COX) was evaluated in isolated rabbit heart mitochondria using integrating sphere optical spectroscopy. Maximal reduction of the mitochondrial cytochromes was achieved by either blowing nitrogen to remove oxygen, or by adding cyanide. Gradual depolarization of ΔΨm by adding increasing concentrations of uncoupler resulted in an increase of up to 50 % in the absorbance of cytochrome aa3 under nitrogen saturation, and of 25 % with cyanide. Cytochrome aa3 absorbance increases were also observed in the presence of cyanide with apyrase (20 %) or oligomycin (12 %). The bL heme absorbance also decreased as expected from ΔΨm depolarization. A ~ 1 nm red shift in the peak wavelength of cytochrome aa3 was observed under anoxic conditions as ΔΨm was depolarized. Importantly, cytochrome c and c1 absorbances remained constant at levels corresponding to full reduction under all experimental manipulations of ΔΨm, especially with cyanide. These data suggest that ΔΨm-dependent changes in the absorbance of reduced COX were due to a variable extinction coefficient of heme a and/or a3 as a function of ΔΨm. A similar increase in the reduced cytochrome aa3 absorbance without changes in cytochrome c and c1 was observed in the perfused rabbit heart when decreasing ΔΨm with uncoupler. Our results imply that COX absorbance in its fully reduced state does not simply reflect the oxygen tension but also the ΔΨm. This may prove useful in monitoring ΔΨm under anoxic or ischemic conditions in intact tissue.


Subject(s)
Electron Transport Complex IV , Membrane Potential, Mitochondrial , Mitochondria, Heart , Animals , Electron Transport Complex IV/metabolism , Rabbits , Membrane Potential, Mitochondrial/drug effects , Mitochondria, Heart/enzymology , Mitochondria, Heart/metabolism , Oxidation-Reduction , Cyanides/pharmacology , Cyanides/metabolism
4.
Toxicon ; 245: 107764, 2024 Jul.
Article in English | MEDLINE | ID: mdl-38802050

ABSTRACT

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


Subject(s)
Cyanides , Dog Diseases , Prunus armeniaca , Animals , Female , Dogs , Cyanides/poisoning , Dog Diseases/chemically induced , Seeds , Antidotes/therapeutic use
5.
J Hazard Mater ; 472: 134540, 2024 Jul 05.
Article in English | MEDLINE | ID: mdl-38733787

ABSTRACT

Cyanide is a typical toxic reducing agent prevailing in wastewater with a well-defined chemical mechanism, whereas its exploitation as an electron donor by microorganisms is currently understudied. Given that conventional denitrification requires additional electron donors, the cyanide and nitrogen can be eliminated simultaneously if the reducing HCN/CN- and its complexes are used as inorganic electron donors. Hence, this paper proposes anaerobic cyanides oxidation for nitrite reduction, whereby the biological toxicity and activity of cyanides are modulated by bimetallics. Performance tests illustrated that low toxicity equivalents of iron-copper composite cyanides provided higher denitrification loads with the release of cyanide ions and electrons from the complex structure by the bimetal. Both isotopic labeling and Density Functional Theory (DFT) demonstrated that CN--N supplied electrons for nitrite reduction. The superposition of chemical processes reduces the biotoxicity and enhances the biological activity of cyanides in the CN-/Fe3+/Cu2+/NO2- coexistence system, including complex detoxification of CN- by Fe3+, CN- release by Cu2+ from [Fe(CN)6]3-, and NO release by nitrite substitution of -CN groups. Cyanide is the smallest structural unit of C/N-containing compounds and serves as a probe to extend the electron-donating principle of anaerobic cyanides oxidation to more electron-donor microbial utilization.


Subject(s)
Copper , Cyanides , Iron , Nitrites , Oxidation-Reduction , Cyanides/toxicity , Cyanides/chemistry , Nitrites/chemistry , Nitrites/toxicity , Copper/chemistry , Copper/toxicity , Anaerobiosis , Iron/chemistry , Water Pollutants, Chemical/toxicity , Water Pollutants, Chemical/chemistry , Wastewater/chemistry , Wastewater/toxicity , Denitrification/drug effects
6.
Biosensors (Basel) ; 14(5)2024 May 13.
Article in English | MEDLINE | ID: mdl-38785718

ABSTRACT

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


Subject(s)
Cyanides , Fluorescent Dyes , Indoles , Spectrometry, Fluorescence , Fluorescent Dyes/chemistry , Indoles/chemistry , Cyanides/analysis , Biosensing Techniques
7.
Sci Total Environ ; 934: 173250, 2024 Jul 15.
Article in English | MEDLINE | ID: mdl-38761928

ABSTRACT

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


Subject(s)
Cyanides , Isocyanates , Isocyanates/toxicity , Cyanides/chemistry , Humans , Environmental Pollutants/toxicity , Environmental Exposure
8.
Chem Res Toxicol ; 37(5): 698-710, 2024 May 20.
Article in English | MEDLINE | ID: mdl-38619497

ABSTRACT

Reactive metabolite formation is a major mechanism of hepatotoxicity. Although reactive electrophiles can be soft or hard in nature, screening strategies have generally focused on the use of glutathione trapping assays to screen for soft electrophiles, with many data sets available to support their use. The use of a similar assay for hard electrophiles using cyanide as the trapping agent is far less common, and there is a lack of studies with sufficient supporting data. Using a set of 260 compounds with a defined hepatotoxicity status by the FDA, a comprehensive literature search yielded cyanide trapping data on an unbalanced set of 20 compounds that were all clinically hepatotoxic. Thus, a further set of 19 compounds was selected to generate cyanide trapping data, resulting in a more balanced data set of 39 compounds. Analysis of the data demonstrated that the cyanide trapping assay had high specificity (92%) and a positive predictive value (83%) such that hepatotoxic compounds would be confidently flagged. Structural analysis of the adducts formed revealed artifactual methylated cyanide adducts to also occur, highlighting the importance of full structural identification to confirm the nature of the adduct formed. The assay was demonstrated to add the most value for compounds containing typical structural alerts for hard electrophile formation: half of the severe hepatotoxins with these structural alerts formed cyanide adducts, while none of the severe hepatotoxins with no relevant structural alerts formed adducts. The assay conditions used included cytosolic enzymes (e.g., aldehyde oxidase) and an optimized cyanide concentration to minimize the inhibition of cytochrome P450 enzymes by cyanide. Based on the demonstrated added value of this assay, it is to be initiated for use at GSK as part of the integrated hepatotoxicity strategy, with its performance being reviewed periodically as more data is generated.


Subject(s)
Chemical and Drug Induced Liver Injury , Cyanides , Cyanides/metabolism , Cyanides/chemistry , Humans , Chemical and Drug Induced Liver Injury/metabolism , Chemical and Drug Induced Liver Injury/etiology , Imines/chemistry , Imines/metabolism , Liver/metabolism , Liver/drug effects , Molecular Structure
9.
Anal Chim Acta ; 1305: 342582, 2024 May 29.
Article in English | MEDLINE | ID: mdl-38677838

ABSTRACT

BACKGROUND: Detecting and neutralizing Pd2+ ions are a significant challenge due to their cytotoxicity, even at low concentrations. To address this issue, various chemosensors have been designed for advanced detection systems, offering simplicity and the potential to differentiate signals from different analytes. Nonetheless, these chemosensors often suffer from limited emission response and complex synthesis procedures. As a result, the tracking and quantification of residual palladium in biological systems and environments remain challenging tasks, with only a few chemosensing probes available for commercial use. RESULTS: In this paper, a straightforward approach for the selective detection of Pd2+ ions is proposed, which involves the design, synthesis, and utilization of a propargylated naphthalene-derived probe (E)-N'-((2-(prop-2-yn-1-yloxy)naphthalen-1-yl)methylene)benzohydrazide (NHP). The NHP probe exhibits sensitive dual-channel colorimetry and fluorescence Pd2+ detection over other tested metal ions. The detection process is performed through a catalytic depropargylation reaction, followed by an excited state intramolecular proton transfer (ESIPT) process, the detection limit is as low as 11.58 × 10-7 M under mild conditions. Interestingly, the resultant chemodosimeter adduct (E)-N'-((2-hydroxynaphthalen-1-yl)methylene)benzohydrazide (NHH) was employed for the consecutive detection of CN- ions, exhibiting an impressive detection limit of 31.79 × 10-8 M. Validation of both detection processes was achieved through 1H nuclear magnetic resonance and density functional theory calculations. For real-time applications of the NHP and NHH probes, smartphone-assisted detection, and intracellular detection of Pd2+ and CN- ions within HeLa cells were studied. SIGNIFICANCE: This research presents a novel naphthalene derivative for visually detecting environmentally toxic Pd2+ and CN- ions. The synthesized probe selectively binds to Pd2+, forming a chemodosimeter. It successfully detects CN- ions through colorimetry and fluorimetry, offering a low detection limit and quick response. Notably, it's the first naphthalene-based small molecule to serve as a dual probe for toxic analytes - palladium and cyanide. Moreover, it effectively detects Pd2+ and CN- intracellularly in cancer cells.


Subject(s)
Fluorescent Dyes , Palladium , Palladium/chemistry , Humans , Fluorescent Dyes/chemistry , Fluorescent Dyes/chemical synthesis , Cyanides/analysis , Naphthalenes/chemistry , Naphthalenes/toxicity , HeLa Cells , Optical Imaging , Limit of Detection , Colorimetry/methods , Molecular Structure , Spectrometry, Fluorescence
10.
Int J Mol Sci ; 25(8)2024 Apr 18.
Article in English | MEDLINE | ID: mdl-38674043

ABSTRACT

Molecular studies about cyanide biodegradation have been mainly focused on the hydrolytic pathways catalyzed by the cyanide dihydratase CynD or the nitrilase NitC. In some Pseudomonas strains, the assimilation of cyanide has been linked to NitC, such as the cyanotrophic model strain Pseudomonas pseudoalcaligenes CECT 5344, which has been recently reclassified as Pseudomonas oleovorans CECT 5344. In this work, a phylogenomic approach established a more precise taxonomic position of the strain CECT 5344 within the species P. oleovorans. Furthermore, a pan-genomic analysis of P. oleovorans and other species with cyanotrophic strains, such as P. fluorescens and P. monteilii, allowed for the comparison and identification of the cioAB and mqoAB genes involved in cyanide resistance, and the nitC and cynS genes required for the assimilation of cyanide or cyanate, respectively. While cyanide resistance genes presented a high frequency among the analyzed genomes, genes responsible for cyanide or cyanate assimilation were identified in a considerably lower proportion. According to the results obtained in this work, an in silico approach based on a comparative genomic approach can be considered as an agile strategy for the bioprospection of putative cyanotrophic bacteria and for the identification of new genes putatively involved in cyanide biodegradation.


Subject(s)
Biodegradation, Environmental , Cyanides , Genome, Bacterial , Phylogeny , Pseudomonas , Cyanides/metabolism , Pseudomonas/genetics , Pseudomonas/metabolism , Genomics/methods , Bacterial Proteins/genetics , Bacterial Proteins/metabolism , Aminohydrolases/genetics , Aminohydrolases/metabolism , Pseudomonas pseudoalcaligenes/metabolism , Pseudomonas pseudoalcaligenes/genetics
11.
Environ Sci Technol ; 58(14): 6444-6454, 2024 Apr 09.
Article in English | MEDLINE | ID: mdl-38551318

ABSTRACT

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 CoII-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 Co2+ 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.


Subject(s)
Carcinoma, Hepatocellular , Environmental Pollutants , Liver Neoplasms , Humans , Cobalt/chemistry , Cyanides , Peroxides/chemistry , Catalysis
12.
Methods ; 225: 13-19, 2024 May.
Article in English | MEDLINE | ID: mdl-38438060

ABSTRACT

A new molecular structure 1 has been developed on naphthalimide motif. The amine and triazole binding groups have been employed at the 4-position of naphthalimide to explore the sensing behavior of molecule 1. Single crystal x-ray diffraction and other spectroscopic techniques confirm the identity of 1. Compound 1 exhibits high selectivity and sensitivity for Cu2+ ions in CH3CN. The binding of Cu2+ shows âˆ¼ 70-fold enhancement in emission at 520 nm. The binding follows 1:1 interaction and the detection limit is determined to be 6.49 × 10-7 M. The amine-triazole binding site in 1 also corroborates the detection of F- through a colour change in CH3CN. Initially H-bonding and then deprotonation of amine -NH- in the presence of F- are the sequential steps involved in F- recognition with a detection limit of 4.13 × 10-7 M. Compound 1 is also sensible to CN- like F- ion and they are distinguished by Fe3+ ion. Cu2+-ensemble of 1 fluorimetrically recognizes F- among the tested anions and vice-versa. The collaborative effect of amine and triazole motifs in the binding of both Cu2+ and F-/CN- has been explained by DFT calculation.


Subject(s)
Colorimetry , Copper , Naphthalimides , Spectrometry, Fluorescence , Naphthalimides/chemistry , Copper/chemistry , Copper/analysis , Colorimetry/methods , Spectrometry, Fluorescence/methods , Cyanides/analysis , Cyanides/chemistry , Limit of Detection , Fluorides/analysis , Fluorides/chemistry , Fluorescent Dyes/chemistry , Crystallography, X-Ray/methods , Hydrogen Bonding
13.
Org Lett ; 26(11): 2207-2211, 2024 Mar 22.
Article in English | MEDLINE | ID: mdl-38457925

ABSTRACT

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 (2S,3S)-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 (2S,3S,S)-epibestatin.


Subject(s)
Amides , Peptides , Amides/chemistry , Stereoisomerism , Amino Acids/chemistry , Cyanides
14.
Plant Cell Rep ; 43(4): 92, 2024 Mar 11.
Article in English | MEDLINE | ID: mdl-38466441

ABSTRACT

KEY MESSAGE: Pepper fruits contain two leucine aminopeptidase (LAP) genes which are differentially modulated during ripening and by nitric oxide. The LAP activity increases during ripening but is negatively modulated by nitration. Leucine aminopeptidase (LAP) is an essential metalloenzyme that cleaves N-terminal leucine residues from proteins but also metabolizes dipeptides and tripeptides. LAPs play a fundamental role in cell protein turnover and participate in physiological processes such as defense mechanisms against biotic and abiotic stresses, but little is known about their involvement in fruit physiology. This study aims to identify and characterize genes encoding LAP and evaluate their role during the ripening of pepper (Capsicum annuum L.) fruits and under a nitric oxide (NO)-enriched environment. Using a data-mining approach of the pepper plant genome and fruit transcriptome (RNA-seq), two LAP genes, designated CaLAP1 and CaLAP2, were identified. The time course expression analysis of these genes during different fruit ripening stages showed that whereas CaLAP1 decreased, CaLAP2 was upregulated. However, under an exogenous NO treatment of fruits, both genes were downregulated. On the contrary, it was shown that during fruit ripening LAP activity increased by 81%. An in vitro assay of the LAP activity in the presence of different modulating compounds including peroxynitrite (ONOO-), NO donors (S-nitrosoglutathione and nitrosocyteine), reducing agents such as reduced glutathione (GSH), L-cysteine (L-Cys), and cyanide triggered a differential response. Thus, peroxynitrite and reducing compounds provoked around 50% inhibition of the LAP activity in green immature fruits, whereas cyanide upregulated it 1.5 folds. To our knowledge, this is the first characterization of LAP in pepper fruits as well as of its regulation by diverse modulating compounds. Based on the capacity of LAP to metabolize dipeptides and tripeptides, it could be hypothesized that the LAP might be involved in the GSH recycling during the ripening process.


Subject(s)
Capsicum , Nitric Oxide , Nitric Oxide/metabolism , Fruit/metabolism , Capsicum/genetics , Capsicum/metabolism , Leucine/metabolism , Leucyl Aminopeptidase/genetics , Leucyl Aminopeptidase/metabolism , Peroxynitrous Acid/metabolism , Cyanides/metabolism , Dipeptides/metabolism
15.
Extremophiles ; 28(2): 19, 2024 Mar 01.
Article in English | MEDLINE | ID: mdl-38427139

ABSTRACT

Organic and inorganic cyanides are widely distributed in nature, yet not much is known about the ability of microorganisms to use these compounds as a source of nitrogen and/or carbon at high temperatures (>80 °C). Here we studied the capacity of organic and inorganic cyanides to support growth of an hyperthermophilic Pyrococcus strain isolated from Deception Island, Antarctica. This microorganism was capable of growing with aromatic nitriles, aliphatic nitriles, heterocyclic nitriles, amino aromatic nitriles and inorganic cyanides as nitrogen and/or carbon source. This is the first report of an hyperthermophilic microorganism able to incorporate these compounds in its nitrogen and carbon metabolism. Based on enzymatic activity and genomic information, it is possibly that cells of this Pyrococcus strain growing with nitriles or cyanide, might use the carboxylic acid and/or the ammonia generated through the nitrilase enzymatic activity, as a carbon and/or nitrogen source respectively. This work expands the temperature range at which microorganisms can use organic and inorganic cyanides to growth, having important implications to understand microbial metabolisms that can support life on Earth and the possibility to support life elsewhere.


Subject(s)
Cyanides , Pyrococcus , Cyanides/metabolism , Antarctic Regions , Nitriles , Carbon , Nitrogen
16.
PLoS One ; 19(3): e0298999, 2024.
Article in English | MEDLINE | ID: mdl-38526988

ABSTRACT

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.


Subject(s)
Cysteine/analogs & derivatives , Thiocyanates , Thiosulfates , Sulfurtransferases/chemistry , Thiosulfate Sulfurtransferase , Pyruvic Acid , Cyanides , Sulfur
17.
Molecules ; 29(5)2024 Mar 01.
Article in English | MEDLINE | ID: mdl-38474631

ABSTRACT

A wide range of platinum(0)-η2-(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 A2780cis) 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 IC50 values comparable to or even surpassing those of cisplatin. However, only a subset of compounds was cytotoxic against cisplatin-resistant cancer cells (A2780cis). 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 (IC50 > 100 µM) while concurrently displaying potent cytotoxicity against cancer cells.


Subject(s)
Antineoplastic Agents , Breast Neoplasms , Coordination Complexes , Methane/analogs & derivatives , Ovarian Neoplasms , Phosphines , Female , Humans , Cisplatin/chemistry , Platinum/chemistry , Cell Line, Tumor , Cyanides , Spectroscopy, Fourier Transform Infrared , Coordination Complexes/chemistry , Antineoplastic Agents/chemistry , Ligands
18.
PLoS One ; 19(3): e0300485, 2024.
Article in English | MEDLINE | ID: mdl-38470886

ABSTRACT

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.


Subject(s)
Wastewater , Water Pollutants, Chemical , Coal , Ammonia , Wetlands , Phenols , Metals , Cyanides , Waste Disposal, Fluid/methods , Water Pollutants, Chemical/analysis
19.
J Agric Food Chem ; 72(10): 5318-5324, 2024 Mar 13.
Article in English | MEDLINE | ID: mdl-38477042

ABSTRACT

Cyanase is a possible solution to reduce the environmental impact of cyanide. However, the enzyme's dependence on HCO3- limits its industrial applications. To overcome this problem, carbonic anhydrase is utilized in this study. Three types of Catcher/Tag systems were introduced into the cyanase (psCYN) from Pseudomonas stutzeri and the carbonic anhydrase (hmCA) from Hydrogenovibrio marinus to construct enzyme complexes via irreversible covalent bonds. Initially, a cyanase complex with the aid of scaffolding proteins was designed. The results of cyanase complexes using scaffolding proteins were similar to or inferior to those of the two free enzymes. To address this, the two enzymes were manipulated to form a direct bioconjugation without the need for scaffolding proteins. The two enzymes forming a direct conjugation showed activity more than 2.5 times higher than that of cyanase alone. In conclusion, this outcome will contribute to solving problems related to residual cyanides in food and the environment.


Subject(s)
Carbonic Anhydrases , Cyanides/metabolism , Cyanates/metabolism , Carbon-Nitrogen Lyases/metabolism , Multienzyme Complexes
20.
Spectrochim Acta A Mol Biomol Spectrosc ; 314: 124198, 2024 Jun 05.
Article in English | MEDLINE | ID: mdl-38552540

ABSTRACT

Polarity is a significant intracellular environmental parameter associated with cancer, while cyanide (CN-) is known to be highly toxic to humans. In this work, we designed a dual-functional fluorescent probe (TPABT) for simultaneous detection of polarity and CN-. As a polarity sensor, the probe exhibits NIR emission at 766 nm in 1,4-dioxane (non-polar solvent), whose emission intensity is 71-fold stronger than that in water (polar solvent). Meanwhile, the fluorescence intensity and quantum yield are linearly related to solvent polarity, confirming the polarity response ability of TPABT. For cell polarity detection, low cytotoxicity and polarity sensitivity of probe enable the applications for differentiating cancer cells (HeLa, 4TI) from normal cells (HUV, 3 T3) and monitoring the polarity changes of 4TI cells. As a CN- sensor, TPABT displays a turn-on fluorescence at 640 nm upon the addition of CN-, with advantages of anti-interference, response in aqueous media and low detection limit (22 nM). Additionally, we further explored the practical applications of TPABT for CN- determination in three types of real water samples (drinking water, tap water and lake water) and living cells. Notably, TPABT responses to polarity and CN- in two independent fluorescence channels of 766 and 640 nm, respectively, ensuring the dual functions for polarity and CN- sensing. Consequently, this multi-responsive fluorescent probe TPABT is promising to diagnose polarity-related diseases and detect CN- in real environments.


Subject(s)
Drinking Water , Fluorescent Dyes , Thiophenes , Humans , Cyanides/toxicity , Spectrometry, Fluorescence , Solvents
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