Applications of Direct Injection Soft Chemical Ionisation-Mass Spectrometry for the Detection of Pre-blast Smokeless Powder Organic Additives

Analysis of smokeless powders is of interest from forensics and security perspectives. This article reports the detection of smokeless powder organic additives (in their pre-detonation condition), namely the stabiliser diphenylamine and its derivatives 2-nitrodiphenylamine and 4-nitrodiphenylamine, and the additives (used both as stabilisers and plasticisers) methyl centralite and ethyl centralite, by means of swab sampling followed by thermal desorption and direct injection soft chemical ionisation-mass spectrometry. Investigations on the product ions resulting from the reactions of the reagent ions H3O+ and O2+ with additives as a function of reduced electric field are reported. The method was comprehensively evaluated in terms of linearity, sensitivity and precision. For H3O+, the limits of detection (LoD) are in the range of 41-88 pg of additive, for which the accuracy varied between 1.5 and 3.2%, precision varied between 3.7 and 7.3% and linearity showed R20.9991. For O2+, LoD are in the range of 72 to 1.4 ng, with an accuracy of between 2.8 and 4.9% and a precision between 4.5 and 8.6% and R20.9914. The validated methodology was applied to the analysis of commercial pre-blast gun powders from different manufacturers.(VLID)4826148Accepted versio

Determination of retinol, alpha-tocopherol, and beta-carotene in serum by liquid chromatography with absorbance and electrochemical detection.

Abstract We describe a method for the determination of retinol, alpha-tocopherol, and beta-carotene in serum, using a liquid-chromatographic separation with wavelength-programmed ultraviolet/visible absorbance and amperometric electrochemical detection with a glassy carbon electrode. After protein denaturation and addition of an internal standard, tocol, 250-microL samples are twice extracted with hexane. The reversed-phase, gradient-elution chromatographic separation provides baseline resolution of: the all-trans isomer of retinol from the cis isomers, alpha- from gamma-tocopherol, and all-trans-beta-carotene from alpha-carotene and from cis-beta-carotene isomers. The linearity of response and the detection limits for the two detectors for the three analytes are measured. A comparison of the values obtained for serum extracts shows good agreement between the absorbance and electrochemical detectors.</jats:p

Organic electrochemical techniques having potential clinical application.

Abstract The Organic Electrochemistry Group at the National Bureau of Standards is pursuing several avenues of research of potential application to problems of clinical chemists. With one development, electrochemical detectors for liquid chromatography, organomercury species can be determined in biological tissues and other matrices. Spectroelectrochemistry is being used to characterize the redox behavior of metal complexes of bleomycin, an antitumor drug. Chemically modified electrodes are being developed as selective electrocatalytic sensors for organohalogen compounds and may lead to new sensors for clinically important analytes. Surface-enhanced Raman spectroscopy is helping characterize the polymer films used to modify the electrode surfaces. Another sensor is being developed for the detection of carboxylic acids: after the photocatalytic oxidation of the acids at a semiconductor electrode, the carbon dioxide produced is subsequently determined with a flow-through gas-sensing electrode. Finally, mathematical modeling may provide a better understanding of the fundamental processes involved in several of the above techniques.</jats:p