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Se Pu = Chinese Journal of... Aug 2021Cyanogen chloride (ClCN) has been widely used in industrial production. ClCN is also listed in the Schedule of the Chemical Weapons Convention (CWC). The use of...
Cyanogen chloride (ClCN) has been widely used in industrial production. ClCN is also listed in the Schedule of the Chemical Weapons Convention (CWC). The use of traditional colorimetric analysis or gas chromatography for the detection of ClCN has been characterized by low efficiency and poor sensitivity. In this study, a method was established for the qualitative analysis and quantitative detection of ClCN in organic and water matrices by gas chromatography-mass spectrometry (GC-MS) based on thiol derivatization. 1-Butylthiol was selected as the optimal derivatization reagent. The optimal temperature for thiol derivatization in the organic matrices was 40 ℃ and the reaction time was 10 min. The pH for derivatization was approximately 9. The ClCN in the organic matrices was directly analyzed by GC-MS after derivatization. The conditions of ClCN derivatization in the water matrices were the same as those in the organic matrices. After the derivatization of ClCN, headspace-solid phase microextraction (HS-SPME) was employed during sample preparation for water matrices. Different temperatures for HS-SPME were explored, and the optimal temperature was found to be 55 ℃. The product of thiol derivatization was confirmed as butyl thiocyanate. The main fragmentation patterns and mass spectrometric cleavage pathway were investigated by GC-MS/MS. The quantitative determination of ClCN in organic and water matrices was conducted via the internal standard and external standard methods, respectively. ClCN showed good linearity in the corresponding ranges in the organic and water matrices. The correlation coefficients for both matrices were greater than 0.99. The linearities of ClCN in the organic and water matrices were in the range of 20-2000 μg/L and 20-1200 μg/L, respectively. An organic sample and water samples from different substrates were selected to verify the accuracy and precision of the method at three spiked levels. The average spiked recoveries of ClCN in the organic sample and water samples were 87.3%-98.8% and 97.6%-102.2%, respectively. The corresponding relative standard deviations (RSDs, =6) were 2.1%-4.7% and 2.8%-4.2%. The derivatization method established in this study showed good reaction specificity. The method was successfully applied in the analysis of samples obtained from the Organisation for the Prohibition of Chemical Weapons (OPCW). The method established in this study for the detection of ClCN showed high sensitivity and precision, and could aid in the analysis and detection of ClCN in the environment.
PubMed: 34212592
DOI: 10.3724/SP.J.1123.2020.12004 -
Journal of Pineal Research Apr 2018Hypochlorous acid (HOCl) is a potent cytotoxic oxidant generated by the enzyme myeloperoxidase (MPO) in the presence of hydrogen peroxide (H O ) and chloride (Cl )....
Hypochlorous acid (HOCl) is a potent cytotoxic oxidant generated by the enzyme myeloperoxidase (MPO) in the presence of hydrogen peroxide (H O ) and chloride (Cl ). Elevated levels of HOCl play an important role in various pathological conditions through oxidative modification of several biomolecules. Recently, we have highlighted the ability of HOCl to mediate the destruction of the metal-ion derivatives of tetrapyrrole macrocyclic rings such as hemoproteins and vitamin B (VB ) derivatives. Destruction of cyanocobalamin, a common pharmacological form of VB mediated by HOCl, results in the generation of toxic molecular products such as chlorinated derivatives, corrin ring cleavage products, the toxic blood agents cyanide (CN ) and cyanogen chloride (CNCl), and redox-active free cobalt. Here, we show that melatonin prevents HOCl-mediated cyanocobalamin destruction, using a combination of UV-Vis spectrophotometry, high-performance liquid chromatography analysis, and colorimetric CNCl assay. Identification of several melatonin oxidation products suggests that the protective role of melatonin against HOCl-mediated cyanocobalamin destruction and subsequent CNCl generation is at the expense of melatonin oxidation. Collectively, this work highlights that, in addition to acting as an antioxidant and as a MPO inhibitor, melatonin can also prevent VB deficiency in inflammatory conditions such as cardiovascular and neurodegenerative diseases, among many others.
Topics: Animals; Antioxidants; Chromatography, High Pressure Liquid; Cyanides; Humans; Hypochlorous Acid; In Vitro Techniques; Kinetics; Melatonin; Spectrophotometry; Vitamin B 12
PubMed: 29247550
DOI: 10.1111/jpi.12463 -
The reaction of HOCl and cyanocobalamin: corrin destruction and the liberation of cyanogen chloride.Free Radical Biology & Medicine Feb 2012Overproduction of hypochlorous acid (HOCl) has been associated with the development of a variety of disorders such as inflammation, heart disease, pulmonary fibrosis,...
Overproduction of hypochlorous acid (HOCl) has been associated with the development of a variety of disorders such as inflammation, heart disease, pulmonary fibrosis, and cancer through its ability to modify various biomolecules. HOCl is a potent oxidant generated by the myeloperoxidase-hydrogen peroxide-chloride system. Recently, we have provided evidence to support the important link between higher levels of HOCl and heme destruction and free iron release from hemoglobin and RBCs. Our current findings extend this work and show the ability of HOCl to mediate the destruction of metal-ion derivatives of tetrapyrrole macrocyclic rings, such as cyanocobalamin (Cobl), a common pharmacological form of vitamin B12. Cyanocobalamin is a water-soluble vitamin that plays an essential role as an enzyme cofactor and antioxidant, modulating nucleic acid metabolism and gene regulation. It is widely used as a therapeutic agent and supplement, because of its efficacy and stability. In this report, we demonstrate that although Cobl can be an excellent antioxidant, exposure to high levels of HOCl can overcome the beneficial effects of Cobl and generate proinflammatory reaction products. Our rapid kinetic, HPLC, and mass spectrometric analyses showed that HOCl can mediate corrin ring destruction and liberate cyanogen chloride (CNCl) through a mechanism that initially involves α-axial ligand replacement in Cobl to form a chlorinated derivative, hydrolysis, and cleavage of the phosphonucleotide moiety. Additionally, it can liberate free Co, which can perpetuate metal-ion-induced oxidant stress. Taken together, these results are the first report of the generation of toxic molecular products through the interaction of Cobl with HOCl.
Topics: Chromatography, High Pressure Liquid; Corrinoids; Cyanides; Humans; Hydrolysis; Hypochlorous Acid; Kinetics; Oxidation-Reduction; Plasma; Stereoisomerism; Vitamin B 12
PubMed: 22138102
DOI: 10.1016/j.freeradbiomed.2011.10.496 -
Environmental Health Perspectives Dec 1999We include in this review an assessment of the formation, environmental fate, and mammalian and ecotoxicity of CW agent degradation products relevant to environmental... (Review)
Review
We include in this review an assessment of the formation, environmental fate, and mammalian and ecotoxicity of CW agent degradation products relevant to environmental and occupational health. These parent CW agents include several vesicants: sulfur mustards [undistilled sulfur mustard (H), sulfur mustard (HD), and an HD/agent T mixture (HT)]; nitrogen mustards [ethylbis(2-chloroethyl)amine (HN1), methylbis(2-chloroethyl)amine (HN2), tris(2-chloroethyl)amine (HN3)], and Lewisite; four nerve agents (O-ethyl S-[2-(diisopropylamino)ethyl] methylphosphonothioate (VX), tabun (GA), sarin (GB), and soman (GD)); and the blood agent cyanogen chloride. The degradation processes considered here include hydrolysis, microbial degradation, oxidation, and photolysis. We also briefly address decontamination but not combustion processes. Because CW agents are generally not considered very persistent, certain degradation products of significant persistence, even those that are not particularly toxic, may indicate previous CW agent presence or that degradation has occurred. Of those products for which there are data on both environmental fate and toxicity, only a few are both environmentally persistent and highly toxic. Major degradation products estimated to be of significant persistence (weeks to years) include thiodiglycol for HD; Lewisite oxide for Lewisite; and ethyl methyl phosphonic acid, methyl phosphonic acid, and possibly S-(2-diisopropylaminoethyl) methylphosphonothioic acid (EA 2192) for VX. Methyl phosphonic acid is also the ultimate hydrolysis product of both GB and GD. The GB product, isopropyl methylphosphonic acid, and a closely related contaminant of GB, diisopropyl methylphosphonate, are also persistent. Of all of these compounds, only Lewisite oxide and EA 2192 possess high mammalian toxicity. Unlike other CW agents, sulfur mustard agents (e.g., HD) are somewhat persistent; therefore, sites or conditions involving potential HD contamination should include an evaluation of both the agent and thiodiglycol.
Topics: Animals; Chemical Warfare Agents; Decontamination; Environment
PubMed: 10585900
DOI: 10.1289/ehp.99107933 -
International Journal of Molecular... Aug 2023Impregnated activated carbons (IACs) used in air filtration gradually lose their efficacy for the chemisorption of noxious gases when exposed to humidity due to...
Impregnated activated carbons (IACs) used in air filtration gradually lose their efficacy for the chemisorption of noxious gases when exposed to humidity due to impregnated metal deactivation. In order to stabilize IACs against aging, and to prolong the filters' shelf life, inorganic phosphate compounds (phosphoric acid and its three salts, NaHPO, NaHPO, and NaPO) were used as anti-aging additives for two different chromium-free IACs impregnated with copper, zinc, molybdenum, and triethylenediamine (TEDA). Phosphoric acid, monosodium, and disodium phosphate were found to be very efficient in inhibiting the aging of IACs over long periods against cyanogen chloride (the test agent) chemisorption, with the latter being the most efficient. However, the efficiency of phosphate as an anti-aging additive was not well correlated with its ability to inhibit the migration of metal impregnants, especially copper, from the interior to the external surface of carbon granules. Unlike organic additives, the inorganic phosphate additives did not decrease the surface area of the IAC or its physical adsorption capacity for toluene. Using a phosphate additive in IAC used in collective protection and personal filters can improve the safety of the user and the environment and dramatically reduce the need to replace these filters after exposure to humid environments. This has safety, economic, logistical, and environmental advantages.
Topics: Charcoal; Gases; Copper; Phosphates
PubMed: 37629180
DOI: 10.3390/ijms241613000 -
Molecules (Basel, Switzerland) Mar 2023Cyanogen chloride (CNCl) is highly toxic and volatile, and it is difficult to effectively remove via porous substances such as activated carbon due to the weak...
Cyanogen chloride (CNCl) is highly toxic and volatile, and it is difficult to effectively remove via porous substances such as activated carbon due to the weak interaction between CNCl and the adsorbent surface. Developing a highly effective elimination material against CNCl is of great importance in military chemical protection. In this work, a new metal-organic framework (MOF) CuBTC@PA-PEI (polyacrylate-polyethyleneimine) composite was prepared and exhibited excellent CNCl elimination performance in the breakthrough tests. PEI was used for the functionalization of PA with amino groups, which is beneficial to anchor with metal ions of MOF. Afterward, the growth of MOF occurred on the surface and in the pores of the matrix by molecular self-assembly via our newly proposed stepwise impregnation layer-by-layer growth method. Breakthrough tests were performed to evaluate the elimination performance of the composites against CNCl. Compared with the pristine CuBTC powder, the CuBTC@PA-PEI composite exhibited better adsorption capacity and a longer breakthrough time. By compounding with the PA matrix, a hierarchically porous structure of CuBTC@PA-PEI composite was constructed, which provides a solution to the mass transfer problem of pure microporous MOF materials. It also solves the problems of MOF molding and lays a foundation for the practical application of MOF.
PubMed: 36985410
DOI: 10.3390/molecules28062440 -
RSC Advances Apr 2023Density Functional Theory (DFT) was employed to investigate the interaction between cyanogen chloride (ClCN) and the surface of a carbon nanocone (CNC). The findings of...
Density Functional Theory (DFT) was employed to investigate the interaction between cyanogen chloride (ClCN) and the surface of a carbon nanocone (CNC). The findings of this research revealed that pristine CNC is not an ideal material to detect ClCN gas due to its minimal alterations in electronic properties. In order to enhance the properties of carbon nanocones, multiple methods were implemented. These included functionalizing the nanocones with pyridinol (Pyr) and pyridinol oxide (PyrO) as well as decorating them with metals such as boron (B), aluminium (Al) and gallium (Ga). Additionally, the nanocones were also doped with the same third-group metal (B, Al and Ga). The simulation results indicated that doping it with aluminium and gallium atoms yielded promising results. After a comprehensive optimization process, two stable configurations were obtained between the ClCN gas and the CNC-Al, and CNC-Ga structures (configurations S21, and S22) with values of -29.11, and -23.70 kcal mol respectively, using M06-2X/6-311G(d) level. The adsorption of ClCN on CNC-Al and CNC-Ga surfaces leads to a marked alteration in the electrical properties of these structures. Calculations reveal that the energy gap between the Highest Occupied Molecular Orbital (HOMO) and Lowest Unoccupied Molecular Orbital (LUMO) levels ( ) of these configurations increased in the range of 9.03% and 12.54%, respectively, thereby giving off a chemical signal. An analysis conducted by the NCI confirms that there is a strong interaction between ClCN and Al and Ga atoms in CNC-Al and CNC-Ga structures, which is represented by the red color in the RDG isosurfaces. Additionally, the NBO charge analysis reveals that significant charge transfer is present in S21 and S22 configurations (190 and 191 |me|, respectively). These findings suggest that the adsorption of ClCN on these surfaces impacts the electron-hole interaction, which subsequently alters the electrical properties of the structures. Based on the DFT results, the CNC-Al and CNC-Ga structures, which have been doped with aluminium and gallium atoms, respectively, have the potential to serve as good candidates for detecting ClCN gas. Among these two structures, the CNC-Ga structure emerged as the most desirable one for this purpose.
PubMed: 37101948
DOI: 10.1039/d3ra01231j -
Scientific Reports Feb 2023This study developed a method for the simultaneous determination of volatile phenol, cyanide, anionic surfactant, and ammonia nitrogen in drinking water, using a...
This study developed a method for the simultaneous determination of volatile phenol, cyanide, anionic surfactant, and ammonia nitrogen in drinking water, using a continuous flow analyzer. The samples were first distilled at 145 °C. The phenol in the distillate then subsequently reacted with alkaline ferricyanide and 4-aminoantipyrine to form a red complex that was measured colorimetrically at 505 nm. Cyanide in the distillate subsequently reacted with chloramine T to form cyanogen chloride, which then formed a blue complex with pyridinecarboxylic acid that was measured colorimetrically at 630 nm. The anionic surfactant reacted with basic methylene blue to form a compound that was extracted into chloroform and washed with acidic methylene blue to remove interfering substances. The blue compound in chloroform was determined colorimetrically at 660 nm. Ammonia reacted with salicylate and chlorine from dichloroisocyanuric acid to produce indophenol blue at 37 °C in an alkaline environment that was measured at 660 nm. The relative standard deviations were 0.75-6.10% and 0.36-5.41%, respectively, and the recoveries were 96.2-103.6% and 96.0-102.4% when the mass concentration of volatile phenol and cyanide was in the range of 2-100 μg/L. The linear correlation coefficients were ≥ 0.9999, and the detection limits were1.2 μg/L and 0.9 μg/L, respectively. The relative standard deviations were 0.27-4.86% and 0.33-5.39%, and the recoveries were 93.7-107.0% and 94.4-101.7%. When the mass concentration of anionic surfactant and ammonia nitrogen was 10-1000 μg/L. The linear correlation coefficients were 0.9995 and 0.9999, and the detection limits were 10.7 μg/L and 7.3 μg/L, respectively. When compared to the national standard method, no statistically significant difference was found. This approach saves time and labor, has a lower detection limit, higher precision and accuracy, less contamination, and is more appropriate for the analysis and determination of large-volume samples.
PubMed: 36725871
DOI: 10.1038/s41598-023-28776-w -
Environmental Science and Pollution... Oct 2014Nano-silver is increasingly used in consumer products from washing machines and refrigerators to devices marketed for the disinfection of drinking water or recreational...
Nano-silver is increasingly used in consumer products from washing machines and refrigerators to devices marketed for the disinfection of drinking water or recreational water. The nano-silver in these products may be released, ending up in surface water bodies which may be used as drinking water sources. Little information is available about the stability of the nano-silver in sources of drinking water, its fate during drinking water disinfection processes, and its interaction with disinfection agents and disinfection by-products (DBPs). This study aims to investigate the stability of nano-silver in drinking water sources and in the finished drinking water when chlorine and chloramines are used for disinfection and to observe changes in the composition of DBPs formed when nano-silver is present in the source water. A dispersion of nano-silver particles (10 nm; PVP-coated) was used to spike untreated Ottawa River water, treated Ottawa River water, organic-free water, and a groundwater at concentrations of 5 mg/L. The diluted dispersions were kept under stirred and non-stirred conditions for up to 9 months and analyzed weekly using UV absorption to assess the stability of the nano-silver particles. In a separate experiment, Ottawa River water containing nano-silver particles (at 0.1 and 1 mg/L concentration, respectively) was disinfected by adding sodium hypochlorite (a chlorinating agent) in sufficient amounts to maintain a free chlorine residual of approximately 0.4 mg/L after 24 h. The disinfected drinking water was then quenched with ascorbic acid and analyzed for 34 neutral DBPs (trihalomethanes, haloacetonitriles, haloacetaldehydes, 1,1 dichloro-2-propanone, 1,1,1 trichloro-2-propanone, chloropicrin, and cyanogen chloride). The results were compared to the profile of DBPs obtained under the same conditions in the absence of nano-silver and in the presence of an equivalent concentration of Ag(+) ions (as AgNO3). The stability of the nano-silver dispersions in untreated Ottawa River water, with a dissolved organic carbon concentration of 6 mg/L, was significantly higher than the stability of the nano-silver dispersions in distilled, organic-free water. Nano-silver particles suspended in the groundwater agglomerated and were quickly and quantitatively removed from the solution. Our data confirm previous observations that natural dissolved organic matter stabilizes nano-silver particles, while the high-ionic strength of groundwater appears to favor their agglomeration and precipitation. As expected, nano-silver was not stable in Ottawa River water through the chlorination process, but survived for many days when added to the Ottawa River water after treatment with chlorine or chloramines. Stirring appeared to have minimal effect on nano-silver stability in untreated and treated Ottawa River water. The profile of DBPs formed in the presence of nAg differed significantly from the profile of DBPs formed in the absence of nAg only at the 1 mg/L nAg concentration. The differences observed consisted mainly in reduced formation of some brominated DBPs and a small increase in the formation of cyanogen chloride. The reduced formation of brominated congeners may be explained by the decrease in available bromide due to the presence of Ag(+) ions. It should be noted that a concentration of 1 mg/L is significantly higher than nAg concentrations that would be expected to be present in surface waters, but these results could be significant for the disinfection of some wastewaters with comparably high nano-silver concentrations.
Topics: Canada; Disinfection; Drinking Water; Halogenation; Nanoparticles; Rivers; Silver; Spectrophotometry, Ultraviolet; Water Pollutants, Chemical
PubMed: 24458938
DOI: 10.1007/s11356-014-2508-5 -
Journal of Molecular Modeling Apr 2017The electronic sensitivity and adsorption behavior toward cyanogen halides (X-CN; X = F, Cl, and Br) of a BN nanocluster were investigated by means of density...
The electronic sensitivity and adsorption behavior toward cyanogen halides (X-CN; X = F, Cl, and Br) of a BN nanocluster were investigated by means of density functional theory calculations. The X-head of these molecules was predicted to interact weakly with the BN cluster because of the positive σ-hole on the electronic potential surface of halogens. The X-CN molecules interact somewhat strongly with the boron atoms of the cluster via the N-head, which is accompanied by a large charge transfer from the X-CN to the cluster. The change in enthalpy upon the adsorption process (at room temperature and 1 atm) is about -19.2, -23.4, and -30.5 kJ mol for X = F, Cl, and Br, respectively. The LUMO level of the BN cluster is largely stabilized after the adsorption process, and the HOMO-LUMO gap is significantly decreased. Thus, the electrical conductivity of the cluster is increased, and an electrical signal is generated that can help to detect these molecules. By increasing the atomic number of X, the signal will increase, which makes the sensor selective for cyanogen halides. Also, it was indicated that the BN nanocluster benefits from a short recovery time as a sensor.
Topics: Adsorption; Boron Compounds; Cyanides; Cyanogen Bromide; Fluorides; Models, Chemical; Nanostructures; Thermodynamics
PubMed: 28357691
DOI: 10.1007/s00894-017-3312-1