An analytical approach for on-site analysis of breath samples for Δ9-tetrahydrocannabinol (THC).

Increased acceptance of cannabis containing the psychoactive component, Δ9-tetrahydrocannabinol (THC), raises concerns about the potential for impaired drivers and increased highway accidents. In contrast to the "breathalyzer" test, which is generally accepted for determining the alcohol level in a driver, there is no currently accepted roadside test for THC in a motorist. There is a need for an easily collectible biological sample from a potentially impaired driver coupled with an accurate on-site test to measure the presence and quantity of THC in a driver.

Open port sampling interface mass spectrometry of wipe-based explosives, oxidizers, and narcotics for trace contraband detection.

Rapid screening for chemical traces of explosives and narcotics is widely used to support homeland security and law enforcement. These target compounds span a range of physicochemical properties from organic to inorganic, with preferential ionization pathways in both negative and positive mode operation. Nonvolatile inorganic oxidizers present in homemade fuel-oxidizer mixtures, pyrotechnics, and propellants create a unique challenge to traditional thermal desorption-based technologies.

Performance and attributes of liquid chromatography-mass spectrometry with targeted charge separation in quantitative analysis of therapeutic peptides.

Herein we describe a new method, targeted enhanced multiply charged scans (tEMC), for the quantification of therapeutic peptides in tandem mass spectrometry on the linear ion trap mass spectrometer. Therapeutic peptides with chain lengths between eight and 39 amino acid residues and charge states from 2+ to 6+ were used to evaluate and illustrate the method which relies on the ability to separate ions trapped in a linear ion trap according to their charges. In particular, interference from singly charged ions on multiply charged ions can be effectively minimized.

Ultraviolet photodissociation of protonated pharmaceuticals in a pressurized linear quadrupole ion trap.

Ultraviolet photodissociation (UVPD) was evaluated as a technique for generating ion fragmentation information that is alternative and/or complementary to the information obtained by collision-induced dissociation (CID). Ions trapped in a pressurized linear ion trap were dissociated using a 355 nm or a 266 nm pulsed laser. Comparisons of UVPD and CID spectra using a set of aromatic chromophore-containing compounds (desmethyl bosentan, haloperidol, nelfinavir) demonstrated distinct characteristic fragmentation patterns resulting from photodissociation.

Electron super-rich radicals. III. On the peculiar behavior of the aminodihydroxymethyl radical in the gas phase.

In contrast to previously reported electron-super-rich trihydroxy-, triamino- and diaminohydroxymethyl radicals, the title aminodihydroxymethyl radical (1) generates a fraction of metastable species in the form of their deuterium isotopologues. The lifetimes of metastable radicals produced by femtosecond collisional electron transfer to aminodihydroxymethyl cations exceed 4 mus. The main fraction of 1 dissociates by fast loss of a hydroxyl hydrogen atom to form carbamic acid.

Host-guest hydrogen atom transfer induced by electron capture.

1,n-Alkanediammonium cations in noncovalent complexes with two dibenzo-18-crown-6-ether (DBCE) ligands undergo an unusual intramolecular tandem hydrogen atom and proton transfer to the crown ether ligand upon charge reduction by electron capture. Deuterium labeling established that both migrating hydrogens originated from the ammonium groups. The double hydrogen transfer was found to depend on the length of the alkane chain connecting the ammonium groups.

Where does the electron go? Electron distribution and reactivity of peptide cation radicals formed by electron transfer in the gas phase.

We report the first detailed analysis at correlated levels of ab initio theory of experimentally studied peptide cations undergoing charge reduction by collisional electron transfer and competitive dissociations by loss of H atoms, ammonia, and N-C alpha bond cleavage in the gas phase. Doubly protonated Gly-Lys, (GK + 2H) (2+), and Lys-Lys, (KK + 2H) (2+), are each calculated to exist as two major conformers in the gas phase. Electron transfer to conformers with an extended lysine chain triggers highly exothermic dissociation by loss of ammonia from the Gly residue, which occurs from the ground ( X ) electronic state of the cation radical.

Electron super-rich radicals in the gas phase. A neutralization-reionization mass spectrometric and ab initio/RRKM study of diaminohydroxymethyl and triaminomethyl radicals.

Diaminohydroxymethyl (1) and triaminomethyl (2) radicals were generated by femtosecond collisional electron transfer to their corresponding cations (1+ and 2+, respectively) and characterized by neutralization-reionization mass spectrometry and ab initio/RRKM calculations at correlated levels of theory up to CCSD(T)/aug-cc-pVTZ. Ion 1+ was generated by gas-phase protonation of urea which was predicted to occur preferentially at the carbonyl oxygen with the 298 K proton affinity that was calculated as PA = 875 kJ mol-1. Upon formation, radical 1 gains vibrational excitation through Franck-Condon effects and rapidly dissociates by loss of a hydrogen atom, so that no survivor ions are observed after reionization.

Bonding and electronic structure of XeF3-.

The xenon-fluoride bond dissociation energy in XeF3- has been measured by using energy-resolved collision-induced dissociation studies of the ion. The measured value, 0.84 +/- 0.

Effect of substituents on the strength of A-Cl- (A = Si, Ge, and Sn) bonds in hypervalent systems: ACl5-, ACl4F-, and A(CH3)3Cl2-.

The gas-phase strengths of the A-Cl(-) bonds in ACl(5)(-), ACl(4)F(-), and A(CH(3))(3)Cl(2)(-) (A = Si, Ge, and Sn) have been determined by measuring thresholds for collision-induced dissociation in a flowing afterglow-tandem mass spectrometer. Bond dissociation energies increase in the order Si < Ge < Sn. Replacement of the three equatorial chlorides with methyl groups weakens the bonds, while replacing one axial chloride with a fluoride strengthens the bonds.