Biomedical subjects
Publications and source records attributed to Ismael Cotte-Rodríguez.
Desorption electrospray ionization (DESI) mass spectrometry is used for the selective and sensitive detection of trace amounts of explosives and chemical warfare agent simulants from ambient surfaces at distances of up to 3 meters from the mass spectrometer.
The suitability of atmospheric pressure chemical ionization mass spectrometry as sensing instrumentation for the real-time monitoring of low levels of toxic compounds is assessed, especially with respect to public safety applications. Gaseous samples of nine toxic industrial compounds, NH3, H2S, Cl2, CS2, SO2, C2H4O, HBr, C6H6 and AsH3, and two chemical warfare agent simulants, dimethyl methylphosphonate (DMMP) and methyl salicylate (MeS), were studied. API-MS proves highly suited to this application, with speedy analysis times (<30 seconds), high sensitivity, high selectivity towards analytes, good precision, dynamic range and accuracy. Tandem MS methods were implemented in selected cases for improved selectivity, sensitivity, and limits of detection. Limits of detection in the parts-per-billion and parts-per-trillion range were achieved for this set of analytes. In all cases detection limits were well below the compounds' permissible exposure limits (PELs), even in the presence of added complex mixtures of alkanes. Linear responses, up to several orders of magnitude, were obtained over the concentration ranges studied (sub-ppb to ppm), with relative standard deviations less than 3%, regardless of the presence of alkane interferents. Receiver operating characteristic (ROC) curves are presented to show the performance trade-off between sensitivity, probability of correct detection, and false positive rate. A dynamic sample preparation system for the production of gas phase analyte concentrations ranging from 100 pptr to 100 ppm and capable of admixing gaseous matrix compounds and control of relative humidity and temperature is also described.
Desorption electrospray ionization (DESI) mass spectrometry is used for rapid, specific and sensitive detection of trace amounts of the notorious explosive TATP present on ambient surfaces by alkali metal complexation in a simple spray technique.
Heterogeneous reactions at a solution/solid interface are utilized in an ambient mass spectrometry experiment to recognize the cis-diol functionality by its selective complexation reaction to form a cyclic boronate.
Desorption electrospray ionization (DESI), an ambient mass spectrometry technique, is used for trace detection of the explosives trinitrohexahydro-1,3,5-triazine (RDX), octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX), 2,4,6-trinitrotoluene (TNT), Pentaerythritol tetranitrate (PETN), and their plastic compositions (Composition C-4, Semtex-H, Detasheet) directly from a wide variety of surfaces (metal, plastic, paper, polymer) without sample preparation or pretreatment. Analysis of the explosives is performed under ambient conditions from virtually any surface in very short times (<5 s) including confirmatory tandem mass spectrometry (MS/MS) experiments, while retaining the sensitivity and specificity that mass spectrometry offers. Increased selectivity is obtained both by MS/MS and by performing additional experiments in which additives are included in the spray solvent. These reactive DESI experiments (reactions accompanying desorption) produce such ions as the chloride and trifluoroacetate adducts of RDX and HMX or the Meisenheimer complex of TNT. Desorption atmospheric pressure chemical ionization, a variant of DESI that uses gas-phase ions generated by atmospheric pressure corona discharges of toluene or other organic compounds, provides evidence for a heterogeneous-phase (gaseous ion/absorbed analyte) charge-transfer mechanism of DESI ionization in the case of explosives. Plastic explosives on surfaces were analyzed directly as fingerprints, without sample preparation, to test DESI as a possible method for in situ detection of explosives-contaminated surfaces. DESI also allowed detection of explosives in complex matrixes, including lubricants, household cleaners, vinegar, and diesel fuel. Absolute limits of detection for the neat explosives were subnanogram in all cases and subpicogram in the case of TNT. The DESI response was linear over 3 orders of magnitude for TNT. Quantification of RDX on paper gave a precision (RSD) of 2.3%. Pure water could be used as the spray solution for DESI, and it showed ionization efficiencies for RDX in the negative ion mode similar to that given by methanol/water. DESI represents a simple and rapid way to detect explosives in situ with high sensitivity and specificity and is especially useful when they are present in complex mixtures or in trace amounts on ordinary environmental surfaces.
The use of two methods in tandem, single-sided membrane introduction mass spectrometry (SS-MIMS) and fiber introduction mass spectrometry (FIMS), is presented as a technique for field analysis. The combined SS-MIMS-FIMS technique was employed in both a modified commercial mass spectrometer and a miniature mass spectrometer for the selective preconcentration of the explosive simulant o-nitrotoluene (ONT) and the chemical warfare agent simulant, methyl salicylate (MeS), in air. A home-built FIMS inlet was fabricated to allow introduction of the solid-phase microextraction (SPME) fiber into the mass spectrometer chamber and subsequent desorption of the trapped compounds using resistive heating. The SS-MIMS preconcentration system was also home-built from commercial vacuum parts. Optimization experiments were done separately for each preconcentration system to achieve the best extraction conditions prior to use of the two techniques in combination. Improved limits of detection, in the low ppb range, were observed for the combination compared to FIMS alone, using several SS-MIMS preconcentration cycles. The SS-MIMS-FIMS response for both instruments was found to be linear over the range 50 to 800 ppb. Other parameters studied were absorption time profiles, effects of sample flow rate, desorption temperature, fiber background, memory effects, and membrane fatigue. This simple, sensitive, accurate, robust, selective, and rapid sample preconcentration and introduction technique shows promise for field analysis of low vapor pressure compounds, where analyte concentrations will be extremely low and the compounds are difficult to extract from a matrix like air.