Concurrent determination of cyanide and thiocyanate in human and swine antemortem and postmortem blood by high-performance liquid chromatography–tandem mass spectrometry

Alluhayb, Abdullah H.; Severance, Carter; Hendry-Hofer, Tara; Bebarta, Vikhyat S.; Logue, Brian A.

doi:10.1007/s00216-023-04939-6

Cited by 4 publications

(2 citation statements)

References 47 publications

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“…1e). We confirmed the glycine-mediated stimulation of cyanide generation in liver homogenates using two additional methods which measure volatile HCN in the gaseous form: an LC-MS/MS method where HCN is trapped in a chamber containing naphthalene dialdehyde and taurine 10 (Fig. 1b, Extended Data Fig.…”

Section: Cyanide Is Enzymatically Produced In Mammalian Cells and Tis...supporting

confidence: 52%

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Endogenously produced hydrogen cyanide serves as a novel mammalian gasotransmitter

Zuhra,

Petrosino,

Janickova

et al. 2024

Preprint

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Small, gaseous molecules, known as gasotransmitters (NO, CO, H2S), are produced endogenously in mammalian cells and serve important biological roles. Hydrogen cyanide, traditionally considered a cytotoxic molecule in mammals, serves as an endogenous mediator in several plants and bacterial species. Here we show that low concentrations of cyanide are generated endogenously in mouse liver and human hepatocytes. Cyanide production is stimulated by glycine, occurs at the low pH of lysosomes and requires peroxidase activity. Cyanide, in turn, is detectable in several cellular compartments. Cyanide is also detectable basally in the blood of mice; its levels increase after treatment of the animals with glycine. Rhodanese activity regulates endogenous cyanide levels. Cyanide, when generated endogenously at an optimal level, exerts stimulatory effects on mitochondrial bioenergetics, cell metabolism and cell proliferation. Dysregulation of endogenous cyanide, either below or above optimal levels, impairs cellular bioenergetics. The regulatory effects of cyanide are in part mediated by posttranslational modification of cysteine residues via protein cyanylation; cyanylated protein residues can be detected basally, and increase after treatment with glycine. Controlled low-dose cyanide supplementation exhibits cytoprotective effects, as demonstrated in hypoxia and reoxygenation modelsin vitroandin vivo. However, pathologically elevated cyanide production, as demonstrated in nonketotic hyperglycinemia – an autosomal recessive disease of glycine metabolism – is deleterious to the cells.

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Section: Cyanide Is Enzymatically Produced In Mammalian Cells and Tis...supporting

confidence: 52%

“…5b). Likewise, significant changes in gene expression were observed both with TST overexpression and TST silencing, including effects on multiple key biochemical pathways relevant for cell metabolism and proliferation and viability (Extended Data Table 9,10).…”

Section: Cyanide Exerts Cytoprotective and Organ-protective Effects I...mentioning

confidence: 99%

Endogenously produced hydrogen cyanide serves as a novel mammalian gasotransmitter

Zuhra,

Petrosino,

Janickova

et al. 2024

Preprint

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Dual Fluorometric and Colorimetric Chemosensor Based on Poly(Arylene Ether Nitrile)s Functionalized Zn(II)Porphyrins for Selective Detection of Cyanide

Sivakumar,

Babu,

Ghanti

et al. 2024

Adv Funct Materials

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Poly(arylene ether nitrile)s (PAENs) appended with Zn(II)‐porphyrin in varied molar percentages (5% and 10%) are developed as dual colorimetric and fluorometric sensors for highly sensitive and selective cyanide (CN−) detection. The materials, DP‐5%PAEN@Zn and DP‐10%PAEN@Zn, exhibit significant Soret band shifts at 420 ± 2 nm, accompanied by the appearance of a new absorption band at 436 ± 2 nm, indicating strong CN− binding with high association constants of 1.3 × 10⁴ M−¹ and 2.3 × 10⁴ M−¹, respectively. A prominent color change from purple to green allowed for naked eye detection. Spectrofluorimetric studies revealed turn‐off fluorescence with Stern‐Volmer constants (Ksv) of 99.85 × 103 M−¹ for DP‐5%PAEN@Zn and 121.08 × 103 M−¹ for DP‐10%PAEN@Zn, achieving limit of detection (LOD) of 0.177 and 0.099 ppb, respectively. DP‐10%PAEN@Zn demonstrated excellent sensitivity and selectivity toward CN−, and also reusability, as it remained functional after ten TFA treatment cycles. The mechanistic investigation, supported by photophysical, electrochemical, and DFT analyses, revealed a photoinduced electron transfer process via static quenching. Material stability is confirmed through photodegradability, prolonged time, temperature, and humidity testing. Prototype test kits are developed for real‐time visual CN− detection in remote and environmental samples (tap, lake, sewage, and soil). Additionally, a smartphone‐based color recognition assay is implemented for qualitative and quantitative analysis.

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Can the cyanide metabolite, 2-aminothiazoline-4-carboxylic acid, be used for forensic verification of cyanide poisoning?

Alluhayb,

Severance,

Hendry-Hofer

et al. 2024

Forensic Toxicol

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Purpose Forensic verification of cyanide (CN) poisoning by direct CN analysis in postmortem blood is challenging due to instability of CN in biological samples. CN metabolites, thiocyanate (SCN−) and 2-aminothiazoline-4-carboxylic acid (ATCA), have been proposed as more stable biomarkers, yet it is unclear if either is appropriate for this purpose. In this study, we evaluated the behavior of CN biomarkers in postmortem swine and postmortem blood to determine which serves as the best biomarker of CN exposure. Methods CN, SCN−, and ATCA were measured in postmortem swine (N = 8) stored at 4 °C and postmortem blood stored at 25 °C (room temperature, RT) and 37 °C (typical human body temperature, HBT). Results Following CN poisoning, the concentration of each CN biomarker increased well above the baseline. In postmortem swine, CN concentrations declined rapidly (t1/2 = 34.3 h) versus SCN− (t1/2 = 359 h, 15 days) and ATCA (t1/2 = 544 h, 23 days). CN instability in postmortem blood increased at RT (t1/2 = 10.7 h) and HBT (t1/2 = 6.6 h). SCN− and ATCA were more stable than CN at all storage conditions. In postmortem swine, the t1/2s of SCN− and ATCA were 15 and 23 days, respectively. While both the t1/2s of SCN− and ATCA were relatively lengthy, endogenous levels of SCN− were much more variable than ATCA. Conclusion While there are still questions to be answered, ATCA was the most adept forensic marker of CN poisoning (i.e., ATCA produced the longest half-life, the largest increase above baseline levels, and most stable background concentrations).

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Concurrent determination of cyanide and thiocyanate in human and swine antemortem and postmortem blood by high-performance liquid chromatography–tandem mass spectrometry

Cited by 4 publications

References 47 publications

Endogenously produced hydrogen cyanide serves as a novel mammalian gasotransmitter

Endogenously produced hydrogen cyanide serves as a novel mammalian gasotransmitter

Dual Fluorometric and Colorimetric Chemosensor Based on Poly(Arylene Ether Nitrile)s Functionalized Zn(II)Porphyrins for Selective Detection of Cyanide

Can the cyanide metabolite, 2-aminothiazoline-4-carboxylic acid, be used for forensic verification of cyanide poisoning?

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