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Full-Text Articles in Physical Sciences and Mathematics

Determination Of Dimethyl Trisulfide In Rabbit Blood Using Stir Bar Sorptive Extraction Gas Chromatography-Mass Spectrometry, Erica Mananadhar, Nujud Maslamani, Ilona Petrikovics, Gary A. Rockwood, Brian A. Logue Aug 2016

Determination Of Dimethyl Trisulfide In Rabbit Blood Using Stir Bar Sorptive Extraction Gas Chromatography-Mass Spectrometry, Erica Mananadhar, Nujud Maslamani, Ilona Petrikovics, Gary A. Rockwood, Brian A. Logue

Chemistry and Biochemistry Faculty Publications

Cyanide poisoning by accidental or intentional exposure poses a severe health risk. The current Food and Drug Administration approved antidotes for cyanide poisoning can be effective, but each suffers from specific major limitations concerning large effective dosage, delayed onset of action, or dependence on enzymes generally confined to specific organs. Dimethyl trisulfide (DMTS), a sulfur donor that detoxifies cyanide by converting it into thiocyanate (a relatively nontoxic cyanide metabolite), is a promising next generation cyanide antidote. Although a validated analytical method to analyze DMTS from any matrix is not currently available, one will be vital for the approval of DMTS …


Cyanide Toxicokinetics: The Behavior Of Cyanide, Thiocyanate And 2-Amino-2-Thiazoline-4-Carboxylic Acid In Multiple Animal Models, Raj K. Bhandari, Robert P. Oda, Ilona Petrikovics, David E. Thompson, Matthew Brenner, Sari B. Mahon, Vikhyat S. Bebarta, Gary A. Rockwood, Brian A. Logue May 2014

Cyanide Toxicokinetics: The Behavior Of Cyanide, Thiocyanate And 2-Amino-2-Thiazoline-4-Carboxylic Acid In Multiple Animal Models, Raj K. Bhandari, Robert P. Oda, Ilona Petrikovics, David E. Thompson, Matthew Brenner, Sari B. Mahon, Vikhyat S. Bebarta, Gary A. Rockwood, Brian A. Logue

Chemistry and Biochemistry Faculty Publications

Cyanide causes toxic effects by inhibiting cytochrome c oxidase, resulting in cellular hypoxia and cytotoxic anoxia, and can eventually lead to death. Cyanide exposure can be verified by direct analysis of cyanide concentrations or analyzing its metabolites, including thiocyanate (SCN) and 2-amino-2-thiazoline-4-carboxylic acid (ATCA) in blood. To determine the behavior of these markers following cyanide exposure, a toxicokinetics study was performed in three animal models: (i) rats (250–300 g), (ii) rabbits (3.5–4.2 kg) and (iii) swine (47–54 kg). Cyanide reached a maximum in blood and declined rapidly in each animal model as it was absorbed, distributed, metabolized and …


Simultaneous High-Performance Liquid Chromatography-Tandem Mass Spectrometry (Hplc-Ms-Ms) Analysis Of Cyanide And Thiocyanate From Swine Plasma, Raj K. Bhandari, Erica Manandhar, Robert P. Oda, Gary A. Rockwood, Brian A. Logue Jan 2014

Simultaneous High-Performance Liquid Chromatography-Tandem Mass Spectrometry (Hplc-Ms-Ms) Analysis Of Cyanide And Thiocyanate From Swine Plasma, Raj K. Bhandari, Erica Manandhar, Robert P. Oda, Gary A. Rockwood, Brian A. Logue

Chemistry and Biochemistry Faculty Publications

An analytical procedure for the simultaneous determination of cyanide and thiocyanate in swine plasma was developed and validated. Cyanide and thiocyanate were simultaneously analyzed by high-performance liquid chromatography tandem mass spectrometry in negative ionization mode after rapid and simple sample preparation. Isotopically labeled internal standards, Na13C15N and NaS13C15N, were mixed with swine plasma (spiked and nonspiked), proteins were precipitated with acetone, the samples were centrifuged, and the supernatant was removed and dried. The dried samples were reconstituted in 10 mM ammonium formate. Cyanide was reacted with naphthalene-2,3-dicarboxaldehyde and taurine to form N-substituted …


The Analysis Of Protein-Bound Thiocyanate In Plasma Of Smokers And Non-Smokers As A Marker Of Cyanide Exposure, Stephanie L. Youso, Gary A. Rockwood, Brian A. Logue May 2012

The Analysis Of Protein-Bound Thiocyanate In Plasma Of Smokers And Non-Smokers As A Marker Of Cyanide Exposure, Stephanie L. Youso, Gary A. Rockwood, Brian A. Logue

Chemistry and Biochemistry Faculty Publications

When cyanide is introduced into the body, it quickly transforms through a variety of chemical reactions, normally involving sulfur donors, to form more stable chemical species. Depending on the nature of the sulfur donor, cyanide may be transformed into free thiocyanate, the major metabolite of cyanide transformation, 2-amino-2-thiazoline-4-carboxylic acid or protein-bound thiocyanate (PB-SCN) adducts. Because protein adducts are generally stable in biological systems, it has been suggested that PB-SCN may have distinct advantages as a marker of cyanide exposure. In this study, plasma was analyzed from 25 smokers (chronic low-level cyanide exposure group) and 25 non-smokers for PB-SCN. The amount …


Organ-Distribution Of The Metabolite 2-Aminothiazoline-4-Carboxylic Acid In A Rat Model Following Cyanide Exposure, Ilona Petrikovics, David E. Thompson, Gary A. Rockwood, Brian A. Logue Dec 2011

Organ-Distribution Of The Metabolite 2-Aminothiazoline-4-Carboxylic Acid In A Rat Model Following Cyanide Exposure, Ilona Petrikovics, David E. Thompson, Gary A. Rockwood, Brian A. Logue

Chemistry and Biochemistry Faculty Publications

The reaction of cyanide (CN) with cystine to produce 2-aminothiazoline-4-carboxylic acid (ATCA) is one of the independent detoxification pathways of cyanide in biological systems. In this report, in vivo production of ATCA and its distributions in plasma and organs were studied after a subcutaneous sublethal dose of 4 mg/kg body weight potassium cyanide (KCN) administration to rats. At this sublethal dose of KCN, ATCA concentration was not significantly increased in the plasma samples, however, it was found significantly increased in liver samples. These results suggested that ATCA might not be a good diagnostic biomarker in plasma for sublethal …


Determination Of Cyanide Exposure By Gas Chromatography–Mass Spectrometry Analysis Of Cyanide-Exposed Plasma Proteins, Stephanie L. Youso, Gary A. Rockwood, John A. Lee, Brian A. Logue Sep 2010

Determination Of Cyanide Exposure By Gas Chromatography–Mass Spectrometry Analysis Of Cyanide-Exposed Plasma Proteins, Stephanie L. Youso, Gary A. Rockwood, John A. Lee, Brian A. Logue

Chemistry and Biochemistry Faculty Publications

Exposure to cyanide can occur in a variety of ways, including exposure to smoke from cigarettes or fires, accidental exposure during industrial processes, and exposure from the use of cyanide as a poison or chemical warfare agent. Confirmation of cyanide exposure is difficult because, in vivo, cyanide quickly breaks down by a number of pathways, including the formation of both free and protein-bound thiocyanate. A simple method was developed to confirm cyanide exposure by extraction of protein-bound thiocyanate moieties from cyanide-exposed plasma proteins. Thiocyanate was successfully extracted and subsequently derivatized with pentafluorobenzyl bromide for GC–MS analysis. Thiocyanate levels as low …


The Analysis Of Cyanide And Its Breakdown Products In Biological Samples, Brian A. Logue, Diane M. Hinkens, Steven I. Baskin, Gary A. Rockwood Jan 2010

The Analysis Of Cyanide And Its Breakdown Products In Biological Samples, Brian A. Logue, Diane M. Hinkens, Steven I. Baskin, Gary A. Rockwood

Chemistry and Biochemistry Faculty Publications

Cyanide is a toxic chemical that may be introduced into living organisms as a result of natural processes and/or anthropogenic uses (legal or illicit). Exposure to cyanide can be verified by analysis of cyanide or one of its breakdown products from biological samples. This verification may be important for medical, law-enforcement, military, forensic, research, or veterinary purposes. This review will discuss current bioanalytical techniques used for the verification of cyanide exposure, identify common problems associated with the analysis of cyanide and its biological breakdown products, and briefly address the metabolism and toxicokinetics of cyanide and its breakdown products in biological …


The Analysis Of 2-Amino-2-Thiazoline-4-Carboxylic Acid In The Plasma Of Smokers And Non-Smokers, Brian A. Logue, Wendy K. Maserek, Gary A. Rockwood, Michael W. Keebaugh, Steven I. Baskin Mar 2009

The Analysis Of 2-Amino-2-Thiazoline-4-Carboxylic Acid In The Plasma Of Smokers And Non-Smokers, Brian A. Logue, Wendy K. Maserek, Gary A. Rockwood, Michael W. Keebaugh, Steven I. Baskin

Chemistry and Biochemistry Faculty Publications

ATCA (2-amino-2-thiazoline-4-carboxylic acid) is a promising marker to assess cyanide exposure because of several advantages of ATCA analysis over direct determination of cyanide and alternative cyanide biomarkers (i.e. stability in biological matrices, consistent recovery, and relatively small endogenous concentrations). Concentrations of ATCA in the plasma of smoking and non-smoking human volunteers were analyzed using gaschromatography mass-spectrometry to establish the feasibility of using ATCA as a marker for cyanide exposure. The levels of ATCA in plasma of smoking volunteers, 17.2 ng/ml, were found to be significantly (p < 0.001) higher than that of non-smoking volunteers, 11.8 ng/ml. Comparison of ATCA concentrations of smokers relative to nonsmokers in both urine and plasma yielded relatively similar results. The concentration ratio of ATCA for smokers versus non-smokers in plasma and urine was compared to similar literature studies of cyanide and thiocyanate, and correlations are discussed. This study supports previous evidence that ATCA can be used to determine past cyanide exposure and indicates that further studies should be pursued to validate the use of ATCA as a marker of cyanide exposure.


Determination Of The Cyanide Metabolite 2-Aminothiazoline-4-Carboxylic Acid In Urine And Plasma By Gas Chromatography–Mass Spectrometry, Brian A. Logue, Nicholas P. Kirschten, Ilona Petrikovics, Matthew A, Moser, Gary A. Rockwood, Steven I. Baskin May 2005

Determination Of The Cyanide Metabolite 2-Aminothiazoline-4-Carboxylic Acid In Urine And Plasma By Gas Chromatography–Mass Spectrometry, Brian A. Logue, Nicholas P. Kirschten, Ilona Petrikovics, Matthew A, Moser, Gary A. Rockwood, Steven I. Baskin

Chemistry and Biochemistry Faculty Publications

The cyanide metabolite 2-aminothiazoline-4-carboxylic acid (ATCA) is a promising biomarker for cyanide exposure because of its stability and the limitations of direct determination of cyanide and more abundant cyanide metabolites. A simple, sensitive, and specific method based on derivatization and subsequent gas chromatography–mass spectrometry (GC–MS) analysis was developed for the identification and quantification of ATCA in synthetic urine and swine plasma. The urine and plasma samples were spiked with an internal standard (ATCA-d2), diluted, and acidified. The resulting solution was subjected to solid phase extraction on a mixed-mode cation exchange column. After elution and evaporation of the solvent, a silylating …