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We have used negative ion photoelectron spectroscopy to measure the electron affinities of diazocarbene and the diazomethyl radical: EA(Ì̃ 3ΣCNN) ) 1.771 ( 0.010 eV, EA(Ì̃ 2A′′ HCNN) ) 1.685 ( 0.006 eV, and EA(Ì̃ 2A′′ DCNN) ) 1.678 ( 0.006 eV. Our experimental findings are accurately reproduced by complete basis set (CBS) ab initio electronic structure(More)
Selected ion flow tube-chemical ionization mass spectrometry was used to measure formaldehyde levels in human breast cancer cells in comparison with levels in cells treated with the antitumor drugs doxorubicin (DOX) and daunorubicin (DAU) and the daunorubicin-formaldehyde conjugate Daunoform (DAUF). The measurement was performed on cell lysates and showed(More)
A rapid and highly sensitive method for the detection of formaldehyde utilizing selected ion flow tube-chemical ionization mass spectrometry is reported. Formaldehyde in aqueous biological samples is preconcentrated by distillation and directly analyzed using gas-phase thermal energy proton transfer from H30+; this procedure can be performed in 30 min. The(More)
A selected ion flow tube-chemical ionization mass spectrometric method is presented for the first determination of acrolein metabolically produced in biological tissues. Acrolein in aqueous samples (2.5 ml) is preconcentrated by distillation and directly analyzed using gas-phase proton transfer from H3O+. This method provides sensitive detection of acrolein(More)
The reaction of F(-) with CH(3)OOH has been studied in the gas phase using a tandem flowing afterglow-selected ion flow tube apparatus. The reaction is rapid (k = 1.23 x 10(-9) cm(3) s(-1), 49% efficiency), and formation of HO(-) + CH(2)O + HF is the major reaction channel observed (85%). Isotopic labeling, reactions of F(-) with larger alkyl(More)
Methyl, methyl-d(3), and ethyl hydroperoxide anions (CH(3)OO(-), CD(3)OO(-), and CH(3)CH(2)OO(-)) have been prepared by deprotonation of their respective hydroperoxides in a stream of helium buffer gas. Photodetachment with 364 nm (3.408 eV) radiation was used to measure the adiabatic electron affinities: EA[CH(3)OO, X(2)A' '] = 1.161 +/- 0.005 eV,(More)
The E(CO)2 elimination reactions of alkyl hydroperoxides proceed via abstraction of an alpha-hydrogen by a base: X(-) + R(1)R(2)HCOOH --> HX + R(1)R(2)C=O + HO(-). Efficiencies and product distributions for the reactions of the hydroxide anion with methyl, ethyl, and tert-butyl hydroperoxides are studied in the gas phase. On the basis of experiments using(More)
A combination of experimental methods, photoelectron-imaging spectroscopy, flowing afterglow-photoelectron spectroscopy and the flowing afterglow-selected ion flow tube technique, and electronic structure calculations at the B3LYP/6-311++G(d,p) level of density functional theory (DFT) have been employed to study the mechanism of the reaction of the(More)
The 351.1 nm photoelectron spectrum of imidazolide anion has been measured. The electron affinity (EA) of the imidazolyl radical is determined to be 2.613 +/- 0.006 eV. Vibrational frequencies of 955 +/- 15 and 1365 +/- 20 cm(-1) are observed in the spectrum of the (2)B1 ground state of the imidazolyl radical. The main features in the spectrum are(More)