Nitrogen direct analysis in real time time-of-flight mass spectrometry (N DART-TOFMS) for rapid screening of forensic drugs.

Rationale: Over the last ten years, helium direct analysis in real time time-of-flight mass spectrometry (He DART-TOFMS) has become an established technique in rapid screening of forensic drugs to decrease the time necessary to triage forensic drug cases, therefore contributing to backlog reduction and more timely criminal prosecution. Recently, we demonstrated that N DART was able to efficiently ionize all polar compounds except for a few extremely small ones such as methanol and acetonitrile. Therefore, N DART-TOFMS should be a suitable technique for rapid screening of forensic drugs.

Ionization Mechanism of Positive-Ion Nitrogen Direct Analysis in Real Time.

Nitrogen can be an inexpensive alternative to helium used by direct analysis in real time (DART), especially in consideration of the looming helium shortage. Therefore, the ionization mechanism of positive-ion N DART has been systematically investigated. Our experiments suggest that a range of metastable nitrogen species with a variety of internal energies existed and all of them were less energetic than metastable helium atoms.

A photochemical mechanism for homochirogenesis. Part 2.

A theoretical investigation of the photochemistry of racemic compounds with circularly polarized light was undertaken. The exact solutions of the differential equations by numerical integration to the approximate solutions used in an earlier article were compared. The exact solutions showed that sequential reactions yield enhanced optical activities in the products.

Quantitative real-time monitoring of chemical reactions by autosampling flow injection analysis coupled with atmospheric pressure chemical ionization mass spectrometry.

Although qualitative and/or semiquantitative real-time monitoring of chemical reactions have been reported with a few mass spectrometric approaches, to our knowledge, no quantitative mass spectrometric approach has been reported so far to have a calibration valid up to molar concentrations as required by process control. This is mostly due to the absence of a practical solution that could well address the sample overloading issue. In this study, a novel autosampling flow injection analysis coupled with an atmospheric pressure chemical ionization mass spectrometry (FIA/APCI-MS) system, consisting of a 1 μL automatic internal sample injector, a postinjection splitter with 1:10 splitting ratio, and a detached APCI source connected to the mass spectrometer using a 4.

Differentiation of underivatized monosaccharides by atmospheric pressure chemical ionization quadrupole time-of-flight mass spectrometry.

Rationale: Differentiation of underivatized monosaccharides is essential in the structural elucidation of oligosaccharides which are closely involved in many life processes. So far, such differentiation has been usually achieved by electrospray ionization mass spectrometry (ESI-MS). As an alternative to ESI-MS, atmospheric pressure chemical ionization mass spectrometry (APCI-MS) should provide complementary results.

Ionization mechanism of positive-ion direct analysis in real time: a transient microenvironment concept.

A transient microenvironment mechanism (TMEM) is proposed to address matrix effects for direct analysis in real time (DART). When the DART gas stream is in contact with the sample, a transient microenvironment (TME), which can shield analytes from direct ionization, may be generated through the desorption of the matrix containing the analyte. The DART gas stream can directly ionize the matrix molecules, but the analytes will be ionized primarily through gas-phase ion/molecule reactions with the matrix ions.

Liquid chromatography/negative ion atmospheric pressure photoionization mass spectrometry: a highly sensitive method for the analysis of organic explosives.

Gas chromatography/mass spectrometry (GC/MS) is applied to the analysis of volatile and thermally stable compounds, while liquid chromatography/atmospheric pressure chemical ionization mass spectrometry (LC/APCI-MS) and liquid chromatography/electrospray ionization mass spectrometry (LC/ESI-MS) are preferred for the analysis of compounds with solution acid-base chemistry. Because organic explosives are compounds with low polarity and some of them are thermally labile, they have not been very well analyzed by GC/MS, LC/APCI-MS and LC/ESI-MS. Herein, we demonstrate liquid chromatography/negative ion atmospheric pressure photoionization mass spectrometry (LC/NI-APPI-MS) as a novel and highly sensitive method for their analysis.

Ionization mechanism of negative ion-direct analysis in real time: a comparative study with negative ion-atmospheric pressure photoionization.

The ionization mechanism of negative ion-direct analysis in real time (NI-DART) has been investigated using over 42 compounds, including fullerenes, perfluorocarbons (PFC), organic explosives, phenols, pentafluorobenzyl (PFB) derivatized phenols, anilines, and carboxylic acids, which were previously studied by negative ion-atmospheric pressure photoionization (NI-APPI). NI-DART generated ionization products similar to NI-APPI, which led to four ionization mechanisms, including electron capture (EC), dissociative EC, proton transfer, and anion attachment. These four ionization mechanisms make both NI-DART and NI-APPI capable of ionizing a wider range of compounds than negative ion-atmospheric pressure chemical ionization (APCI) or negative ion-electrospray ionization (ESI).

Negative ion-atmospheric pressure photoionization: electron capture, dissociative electron capture, proton transfer, and anion attachment.

To better guide the development of liquid chromatography/electron capture-atmospheric pressure photoionization-mass spectrometry (LC/EC-APPI-MS) in analysis of low polarity compounds, the ionization mechanism of 19 compounds was studied using dopant assisted negative ion-APPI. Four ionization mechanisms, i.e.