A new ion source has been developed for rapid, noncontact analysis of materials at ambient pressure and at ground potential. The new source, termed DART (for "Direct Analysis in Real Time"), is based on the reactions of electronic or vibronic excited-state species with reagent molecules and polar or nonpolar analytes. DART has been installed on a high-resolution time-of-flight mass spectrometer (TOFMS) that provides improved selectivity and accurate elemental composition assignment through exact mass measurements. Although DART has been applied to the analysis of gases, liquids, and solids, a unique application is the direct detection of chemicals on surfaces without requiring sample preparation, such as wiping or solvent extraction. DART has demonstrated success in sampling hundreds of chemicals, including chemical agents and their signatures, pharmaceutics, metabolites, peptides and oligosaccharides, synthetic organics, organometallics, drugs of abuse, explosives, and toxic industrial chemicals. These species were detected on various surfaces, such as concrete, asphalt, human skin, currency, airline boarding passes, business cards, fruits, vegetables, spices, beverages, body fluids, horticultural leaves, cocktail glasses, and clothing. DART employs no radioactive components and is more versatile than devices using radioisotope-based ionization. Because its response is instantaneous, DART provides real-time information, a critical requirement for screening or high throughput.

Positive ions in the direct analysis in real time (DART) ion source are commonly formed by proton transfer. However, the DART source is similar to atmospheric pressure photoionization (APPI) in that it can produce molecular ions as well as protonated molecules, although the two sources differ in the initial ion formation process. This report discusses some of the factors that influence molecular ion formation in DART and shows how the DART source can be used to analyze "difficult" or nonpolar compounds such as alkanes and cholesterol. Trace reagent ions including NO(+) and O(2)(+)* formed from atmospheric gases are shown to play important roles in DART ionization. The use of the DART source as a gas chromatography/mass spectrometry (GC/MS) interface is demonstrated to show the difference between mass spectra obtained using conditions that favor proton transfer and those that favor molecular ion formation.

The search for more versatile, sensitive, and robust ionization methods is a recurring theme in mass spectrometry (MS). Since the discovery of electrospray ionization (ESI) [1] and matrix-assisted laser desorption/ionization (MALDI), [2] many developments such as atmospheric pressure MALDI, [3] nanospray ionization, [4] Venturi-assisted electrospray, [5] and ion-funnel atmospheric pressure interfaces, [6] have paved the way to improved characterization of small molecules and biomolecules. One of the bottlenecks in achieving high sample throughput with both ESI and MALDI is the need to dissolve, extract, and/or filter the sample prior to analysis. Moreover, vacuum-incompatible materials cannot be easily investigated by MS without disturbing their innate structure. Recently, two novel methods for the direct ionization of solid samples under atmospheric pressure by MS were reported: desorption electrospray ionization (DESI) [7] and direct analysis in real time (DART). [8] More recently, McEwen et al. described a modified atmospheric pressure chemical ionization (APCI) technique for the direct analysis of solids which they named atmospheric pressure solids analysis probe (ASAP).[9] DESI makes use of a high-speed liquid spray directed at a sample held or deposited on a surface at atmospheric pressure. Ions generated during this process are sampled by a mass spectrometer. Several DESI applications such as the mapping of analytes separated by thin-layer chromatography, [10] the detection of explosives, [11,12] and the screening of pharmaceutical tablets [13][14][15] and illicit drugs [16,17] quickly followed the proof-of-principle description of the method.DART involves an ionizing beam of metastable He atoms ( 3 S 1 , 19.8 eV) generated by a corona discharge. The DART ionization mechanism is still not completely understood. In negative ion mode, the metastable He atoms generate electrons that produce negatively charged oxygen-water clusters, which then form the corresponding adducts. In positive ion mode, metastable He atoms generate protonated gaseous water clusters by Penning ionization.[8] Then, by proton exchange, these clusters form [M+H] + ions, which are generally the predominant species. DART's high throughput coupled with the high mass accuracy now attainable with modern time-of-flight mass (TOF) analyzers and accurate isotopic abundance measurements make it especially suitable for the rapid identification of unknown species in solid materials. One particularly relevant example is counterfeit drug samples. Counterfeit drugs are defined as those that are "deliberately and fraudulently mislabeled with respect to identity and/or source".[18] They may include products with the "wrong" ingredient(s), without active ingredient(s), or with an insufficient amount of active ingredient(s).In recent years, a particularly alarming case of drug counterfeiting has been reported by field researchers [19,20] who have detected counterfeit products that mimic the vital antimalarial, artesunate.[21] The consumption of fake ant...

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In mammals and insects, pheromones strongly influence social behaviors such as aggression and mate recognition. In Drosophila melanogaster, pheromones in the form of cuticular hydrocarbons play prominent roles in courtship. GC/MS is the primary analytical tool currently used to study Drosophila cuticular hydrocarbons. Although GC/MS is highly reproducible and sensitive, it requires that the fly be placed in a lethal solution of organic solvent, thereby impeding further behavioral studies. We present a technique for the analysis of hydrocarbons and other surface molecules from live animals by using direct analysis in real-time (DART) MS. Cuticular hydrocarbons were sampled from the surface of a restrained, awake behaving fly by using several brief, carefully controlled depressions of the abdomen with a small steel probe. DART mass spectral analysis of the probe detected ions with mass-to-charge ratio (m/z) of the protonated molecule corresponding to many of the previously identified unsaturated hydrocarbons. Six additional cuticular hydrocarbons also were identified. Consistent with previous GC/MS studies, male and female differences in chemical composition were evident. Spatial differences in the expression profile also were observed on males. Sampling from an individual female first as a virgin and then 45 and 90 min after successful copulation showed that mass signals likely to correspond to cis-vaccenyl acetate, tricosene, and pentacosene increased in relative intensity after courtship. This method provides near-instantaneous analysis of an individual animal's chemical profile in parallel with behavioral studies and could be extended to other models of pheromone-mediated behavior.behavior ͉ cis-vaccenyl acetate ͉ courtship ͉ pheromones ͉ Drosophila

Through the use of direct analysis in real time mass spectrometry (DART-MS), 2-propenesulfenic acid, an intermediate long postulated as being formed when garlic ( Allium sativum ) is crushed, has been detected for the first time and determined by mass spectrometric methods to have a half-life of <1 s at room temperature. Two other key intermediates, 2-propenesulfinic acid and diallyl trisulfane S-oxide, have also been detected for the first time in volatiles from crushed garlic, along with allicin and related thiosulfinates, allyl alcohol, sulfur dioxide, propene, and pyruvate as coproducts. A commercial dietary supplement containing garlic powder, which was sampled after crushing, was found to contain alliin, methiin, and S-allylcysteine and produced allicin upon addition of water. DART-MS detection of 1-butenesulfenic acid from the ornamental A. siculum is also reported. (Z)-Propanethial S-oxide (onion lachrymatory factor), absent in garlic, is found to be formed from crushed elephant garlic ( Allium ampeloprasum ), consistent with the classification of this plant as a closer relative of leek than of garlic. Mixtures of thiosulfinates, lachrymatory thial S-oxides, and related compounds are directly observed from crushed leek ( Allium porrum ) and Chinese chive ( Allium tuberosum ). Disulfanes and polysulfanes are detected only when the Allium samples are heated, consistent with earlier conclusions that these are not primary products from cut or crushed alliums.

Lachrymatory (Z)-butanethial S-oxide along with several 1-butenyl thiosulfinates was detected by DART mass spectrometry upon cutting Allium siculum , a popular ornamental Allium species used in some cultures as a spice. (Z)-Butanethial S-oxide isolated from the plant was shown to be identical to a synthetic sample. Its likely precursor, (R(S),R(C),E)-S-(1-butenyl)cysteine S-oxide (homoisoalliin), was isolated from homogenates of A. siculum, and a closely related species Allium tripedale , and fully characterized. Through use of LC-MS, a series of related gamma-glutamyl derivatives were tentatively identified in A. siculum and A. tripedale homogenates, including gamma-glutamyl-(E)-S-(1-butenyl)cysteine and its S-oxide, gamma-glutamyl-S-butylcysteine and its S-oxide, and gamma-glutamyl-S-methylcysteine and its S-oxide. Because compounds containing the 1-butenyl group have not been previously identified in genus Allium species, this work extends the range of known Allium sulfur compounds. The general applicability of DART mass spectrometry in identifying naturally occurring, thermally fragile thial S-oxides and thiosulfinates is illustrated with onion, Allium cepa , as well as a plant from a different genus, Petiveria alliacea .

Writing ink analysis is used in establishing document authenticity and the sources and relative ages of written entries. Most analytical methods require removing samples or visibly altering the document. Nondestructive, in situ analysis of writing inks on paper without visible alteration is possible using mass spectrometry with a new ion source called Direct Analysis in Real Time. Forty-three different black and blue ballpoint, black fluid, and black gel inks were examined. Both dyes and persistent but thermally labile components of the inks contribute to the mass spectra, principally as protonated molecules [M1H]1. Numerous ink components were identified from the spectra. The spectra were placed in a searchable library, which was then challenged with two spectra from each of the 43 inks. The best match for each of the challenge spectra was correct for all but one ink, which matched with a very similar ink by the same manufacturer.