Bioassays for bomb-makers: proof of concept.

Clandestine bomb-makers are exposed to significant amounts of explosives and allied materials. As with any ingested xenobiotic substance, these compounds are subject to biotransformation. As such, the potential exists that characteristic suites of biomarkers may be produced and deposited in matrices that can be exploited for forensic and investigative purposes. However, before such assays can be developed, foundational data must be gathered regarding the toxicokinetics, fate, and transport of the resulting biomarkers within the body and in matrices such as urine, hair, nails, sweat, feces, and saliva. This report presents an in vitro method for simulation of human metabolic transformations using human liver microsomes and an assay applicable to representative nitro-explosives. Control and metabolized samples of TNT, RDX, HMX, and tetryl were analyzed using high-performance liquid chromatography coupled to tandem mass spectrometry (LC/MS/MS) and biomarkers identified for each. The challenges associated with this method arise from solubility issues and limitations imposed by instrumentation, specifically, modes of ionization.

Application of a pyroprobe to simulate smoking and metabolic degradation of abused drugs through analytical pyrolysis.

Smoking of illicit drugs can produce unique metabolic biomarkers. Smoking conditions can be partially modeled via pyrolysis, a process that decomposes a chemical compound by extreme heat. Pyrolytic decomposition was found to be useful as a limited metabolic mimic in that analytical pyrolysis can be used to generate some of the same compounds produced by metabolic degradation. This project focused on the pyrolysis of cocaine and methamphetamine using a pyroprobe coupled with a GC/MS and more generally, potential applications of pyrolysis to forensic toxicology. Common diluents including lidocaine, caffeine, and benzocaine were pyrolyzed in mixtures with cocaine and methamphetamine. Correlations between pyrolytic and metabolic degradations revealed that this method has the capability to produce some of the reported metabolites such as norcocaine and cocaethylene for cocaine, and amphetamine for methamphetamine. The results demonstrate that analytical pyrolysis has the potential to identify some metabolic products and to supplement in vivo and enzymatic studies.

Probing affinity via capillary electrophoresis: advances in 2003-2004.

This review addresses recent advances in capillary electrophoresis of biological-based molecular interaction from a broader perspective, based on applications reported during the period 2003-2004. These capillary electrophoresis-based studies of molecular interactions include affinity capillary electrophoresis, electrokinetic chromatography, and free zone electrophoresis. The review is written as a general synopsis of applications and does not cover the theory or protocol involved in the implementation of the analyses.

Rapid assessment of beta-asarone content of Acorus calamus by micellar electrokinetic capillary chromatography.

This report outlines a rapid, reproducible method for the determination of beta-asarone, a known carcinogen, using micellar electrokinetic capillary chromatography (MEKC)-UV-vis absorbance and a simple alcohol extraction. The MEKC method is based on a running buffer comprised of 100 mM sodium dodecyl sulfate (SDS), pH 10. The method is reproducible and provides baseline separation of alpha-asarone and beta-asarone. This protocol was used to determine the beta-asarone content of Acorus calamus rhizome of a diploid variety harvested from the wetlands of the United States and the triploid variety from India obtained commercially. The results indicate raw product that originated from India contained 4.4% w/w beta-asarone, while that from the United States contained 0.2% w/w beta-asarone. Neither sample contained detectable concentrations of alpha-asarone. This is the first report of the use of MEKC to determine asarone in a natural source.

Recent advances in micellar electrokinetic chromatography.

This review contains nearly 200 reference citations, and covers advances in electrokinetic capillary chromatography based on micelles, including stabilized micelle complexes, polymeric and mixed micelles from 2003-2004. Detection strategies, analyte determinations, and applications in micellar electrokinetic capillary chromatography (MEKC) are discussed. Information regarding methods of analyte concentration, analyte specific analyses, and nonstandard micelles has been summarized in tabular form to provide a means of rapid access to information pertinent to the reader.