Temperature Dependence of Desorbed Ions and Neutrals and Ionization Mechanism of Matrix-Assisted Laser Desorption/Ionization.

Two separate temperature-dependent experiments were performed to investigate the ionization mechanism of ultraviolet matrix-assisted laser desorption/ionization (UV-MALDI) of matrix 2,5-dihydroxybenzoic acid (2,5-DHB). First, the angular resolved intensity and velocity distributions of neutrals desorbed from the 2,5-DHB solid sample through UV laser (355 nm) pulse irradiation were measured using a rotating quadrupole mass spectrometer. Second, the desorbed neutrals, at an angle normal to the surface, and the desorbed ions were simultaneously detected for each laser shot using the quadrupole mass spectrometer and a time-of-flight mass spectrometer, respectively.

Dynamics Insight into Isomerization and Dissociation of Hot Criegee Intermediate CHCHOO.

We study the isomerization and dissociation of syn-CHCHOO with high internal energies by combining electronic structure calculations, ab initio molecular dynamics, and RRKM microcanonical variational transition-state theories. The results show a striking effect of the internal energy on the reaction fate of syn-CHCHOO. With lower internal energies, syn-CHCHOO prefers isomerizing to vinyl hydroperoxide, which then produces hydroxyl radical.

Ion-to-Neutral Ratios and Thermal Proton Transfer in Matrix-Assisted Laser Desorption/Ionization.

The ion-to-neutral ratios of four commonly used solid matrices, α-cyano-4-hydroxycinnamic acid (CHCA), 2,5-dihydroxybenzoic acid (2,5-DHB), sinapinic acid (SA), and ferulic acid (FA) in matrix-assisted laser desorption/ionization (MALDI) at 355 nm are reported. Ions are measured using a time-of-flight mass spectrometer combined with a time-sliced ion imaging detector. Neutrals are measured using a rotatable quadrupole mass spectrometer.

Does decarboxylation make 2,5-dihydroxybenzoic acid special in matrix-assisted laser desorption/ionization?

Rationale: Among the six positional isomers of dihydroxybenzoic acid (DHB), 2,5-DHB is a more favorable matrix for use in matrix-assisted laser desorption/ionization (MALDI) than the other isomers because of its high ion-generation efficiency at 337 and 355 nm. The generation of hydroquinone or p-benzoquinone through the decarboxylation of 2,5-DHB has been suggested to play a crucial role in the ion-generation efficiency of 2,5-DHB.

Methods: The mass spectra of desorbed neutrals generated from MALDI were measured using electron impact ionization (70 eV) and a quadrupole mass spectrometer and vacuum ultraviolet (118 nm) photoionization and a time-of-flight mass spectrometer.

Ion intensity and thermal proton transfer in ultraviolet matrix-assisted laser desorption/ionization.

The ionization mechanism of ultraviolet matrix-assisted laser desorption/ionization (UV-MALDI) was investigated by measuring the total cation intensity (not including sodiated and potasiated ions) as a function of analyte concentration (arginine, histidine, and glycine) in a matrix of 2,4,6-trihydroxyacetophenone (THAP). The total ion intensity increased up to 55 times near the laser fluence threshold as the arginine concentration increased from 0% to 1%. The increases were small for histidine, and a minimal increase occurred for glycine.

Thermal proton transfer reactions in ultraviolet matrix-assisted laser desorption/ionization.

One of the reasons that thermally induced reactions are not considered a crucial mechanism in ultraviolet matrix-assisted laser desorption ionization (UV-MALDI) is the low ion-to-neutral ratios. Large ion-to-neutral ratios (10(-4)) have been used to justify the unimportance of thermally induced reactions in UV-MALDI. Recent experimental measurements have shown that the upper limit of the total ion-to-neutral ratio is approximately 10(-7) at a high laser fluence and less than 10(-7) at a low laser fluence.

Effects of intramolecular hydrogen bonding on the excited state dynamics of phenol chromophores.

The theoretical prediction and experimental confirmation of the 1πσ* excited state of phenol which is repulsive along the O-H bond has a large impact on the interpretation of phenol and tyrosine photochemistry. In this work, we demonstrate that this excited state changes significantly if the OH functional group is involved in the formation of an intramolecular hydrogen bond in the ground state. We investigate the excited state dynamics of 2-, 3-, and 4-hydroxyacetophenone (HAP) separately in a molecular beam at 193 nm using multimass ion imaging techniques.

Photodissociation dynamics of methoxybenzoic acid at 193 nm.

The theoretical prediction and experimental confirmation of the 1πσ* repulsive excited state along O-H bond of phenol have large impact on the interpretation of phenol and tyrosine photochemistry. In this work, we investigated the photodissociation dynamics of 2-, 3-, and 4-methoxybenzoic acid (MOBA) in a molecular beam at 193 nm using multimass ion imaging techniques. In addition, the ground state and the excited state potential energy surfaces of MOBA were investigated using ab initio calculations, and branching ratios were predicted by Rice-Ramsperger-Kassel-Marcus theory.

Photodissociation dynamics of benzyl alcohol at 193 nm.

Photodissociation dynamics of benzyl alcohol, C(6)H(5)CH(2)OH and C(6)H(5)CD(2)OH, in a molecular beam was investigated at 193 nm using multimass ion imaging techniques. Four dissociation channels were observed, including OH elimination and H(2)O elimination from the ground electronic state, H atom elimination (from OH functional group), and CH(2)OH elimination from the triplet state. The dissociation rate on the ground state was found to be 7.

Energy transfer of highly vibrationally excited naphthalene: collisions with CHF3, CF4, and Kr.

Energy transfer of highly vibrationally excited naphthalene in the triplet state in collisions with CHF(3), CF(4), and Kr was studied using a crossed-beam apparatus along with time-sliced velocity map ion imaging techniques. Highly vibrationally excited naphthalene (2.0 eV vibrational energy) was formed via the rapid intersystem crossing of naphthalene initially excited to the S(2) state by 266 nm photons.

Alkylation effects on the energy transfer of highly vibrationally excited naphthalene.

The energy transfer of highly vibrationally excited isomers of dimethylnaphthalene and 2-ethylnaphthalene in collisions with krypton were investigated using crossed molecular beam/time-of-flight mass spectrometer/time-sliced velocity map ion imaging techniques at a collision energy of approximately 300 cm(-1). Angular-resolved energy-transfer distribution functions were obtained directly from the images of inelastic scattering. The results show that alkyl-substituted naphthalenes transfer more vibrational energy to translational energy than unsubstituted naphthalene.

Energy transfer of highly vibrationally excited phenanthrene and diphenylacetylene.

The energy transfer between Kr atoms and highly vibrationally excited, rotationally cold phenanthrene and diphenylacetylene in the triplet state was investigated using crossed-beam/time-of-flight mass spectrometer/time-sliced velocity map ion imaging techniques. Compared to the energy transfer between naphthalene and Kr, energy transfer between phenanthrene and Kr shows a larger cross-section for vibrational to translational (V → T) energy transfer, a smaller cross-section for translational to vibrational and rotational (T → VR) energy transfer, and more energy transferred from vibration to translation. These differences are further enlarged in the comparison between naphthalene and diphenylacetylene.

Photodissociation dynamics of hydroxybenzoic acids.

Aromatic amino acids have large UV absorption cross-sections and low fluorescence quantum yields. Ultrafast internal conversion, which transforms electronic excitation energy to vibrational energy, was assumed to account for the photostability of amino acids. Recent theoretical and experimental investigations suggested that low fluorescence quantum yields of phenol (chromophore of tyrosine) are due to the dissociation from a repulsive excited state.

Photodissociation and photoionization of 2,5-dihydroxybenzoic acid at 193 and 355 nm.

Photodissociation and photoionization of 2,5-dihydroxybenzoic acid (25DHBA), at 193 and 355 nm were investigated separately in a molecular beam using multimass ion imaging techniques. Two channels competed after excitation by one 193 nm photon. One channel is dissociation from the repulsive excited state along O-H bond distance, resulting in H atom elimination from meta-OH functional group.

Energy transfer of highly vibrationally excited biphenyl.

The energy transfer between Kr atoms and highly vibrationally excited, rotationally cold biphenyl in the triplet state was investigated using crossed-beam/time-of-flight mass spectrometer/time-sliced velocity map ion imaging techniques. Compared to the energy transfer of naphthalene, energy transfer of biphenyl shows more forward scattering, less complex formation, larger cross section for vibrational to translational (V→T) energy transfer, smaller cross section for translational to vibrational and rotational (T→VR) energy transfer, larger total collisional cross section, and more energy transferred from vibration to translation. Significant increase in the large V→T energy transfer probabilities, termed supercollisions, was observed.

Photodissociation dynamics of tryptophan and the implication of asymmetric photolysis.

Photodissociation of amino acid tryptophan in a molecular beam at wavelengths of 212.8 and 193 nm, corresponding to excitation to the second and third absorption bands, was investigated using multimass ion imaging techniques. The respective wavelengths also represent excitation to the edge of a positive circular dichroism band and the center of a negative circular dichroism band of L-tryptophan.

Photodissociation dynamics of benzoic acid.

The photodissociation of benzoic acid at 193 and 248 nm was investigated using multimass ion imaging techniques. Three dissociation channels were observed at 193 nm: (1) C(6)H(5)COOH-->C(6)H(5)+COOH, (2) C(6)H(5)COOH-->C(6)H(5)CO+OH, and (3) C(6)H(5)COOH-->C(6)H(6)+CO(2). Only channels, (2) and (3), were observed at 248 nm.

355 nm multiphoton dissociation and ionization of 2, 5-dihydroxyacetophenone.

Multiphoton dissociation and ionization of 2,5-dihydroxyacetophenone (DHAP), an important matrix compound in UV matrix-assisted laser desorption/ionization (MALDI), is studied in a molecular beam at 355 nm using multimass ion imaging mass spectrometer and time-of-flight mass spectrometry. For laser fluence larger than 130 mJ/cm(2), nearly all of the irradiated molecules absorb at least one photon. The absorption cross section was found to be sigma = 1.

Photodissociation dynamics of 2,5-dihydroxyacetophenone.

Photodissociation of 2,5-dihydroxyacetophenone (DHAP), an important matrix compound in matrix-assisted laser desorption/ionization (MALDI), was studied in a molecular beam at 193 nm using multimass ion imaging techniques. Two major dissociation channels were observed, including (1) C(6)H(3)(OH)(2)COCH(3) --> OC(6)H(3)(OH)COCH(3) + H and (2) C(6)H(3)(OH)(2)COCH(3) --> C(6)H(3)(OH)(2) + COCH(3). The minor channels include C(6)H(3)(OH)(2)COCH(3) --> C(6)H(3)(OH)(2)CO + CH(3) and/or C(6)H(3)(OH)(2)COCH(3) --> C(6)H(3)(OH)(2) + CO + CH(3).

Photodissociation dynamics of small aromatic molecules studied by multimass ion imaging.

The photodissociation dynamics of various aromatic molecules, studied using multimass ion imaging techniques, is reviewed. The experimental data reveals new isomerization and dissociation mechanisms. Our investigation of benzene, pyridine, and pyrimidine finds that H-atom elimination thresholds remain the same for the three molecules.

Photodissociation of S atom containing amino acid chromophores.

Photodissociation of 3-(methylthio)propylamine and cysteamine, the chromophores of S atom containing amino acid methionine and cysteine, respectively, was studied separately in a molecular beam at 193 nm using multimass ion imaging techniques. Four dissociation channels were observed for 3-(methylthio)propylamine, including (1) CH(3)SCH(2)CH(2)CH(2)NH(2)-->CH(3)SCH(2)CH(2)CH(2)NH+H, (2) CH(3)SCH(2)CH(2)CH(2)NH(2)-->CH(3)+SCH(2)CH(2)CH(2)NH(2), (3) CH(3)SCH(2)CH(2)CH(2)NH(2)-->CH(3)S+CH(2)CH(2)CH(2)NH(2), and (4) CH(3)SCH(2)CH(2)CH(2)NH(2)-->CH(3)SCH(2)+CH(2)CH(2)NH(2). Two dissociation channels were observed from cysteamine, including (5) HSCH(2)CH(2)NH(2)-->HS+CH(2)CH(2)NH(2) and (6) HSCH(2)CH(2)NH(2)-->HSCH(2)+CH(2)NH(2).

Photostability of amino acids: internal conversion versus dissociation.

Photodissociation dynamics for various tryptophan chromophores was studied at 193 or 248 nm using multimass ion imaging techniques. The competition between internal conversion to the ground electronic state and dissociation from the repulsive excited state reveals size-dependent photostability for these amino acid chromophores. As the size of chromophore increases, internal conversion to the ground state becomes the major nonradiative process.

Karyological evidence for meiosis in the three different types of life cycles existing in Agaricus bisporus.

In Agaricus bisporus all cytological studies performed until now concerned the pseudohomothallic and bisporic var. bisporus. In the past 12 y two tetrasporic varieties have been described, the heterothallic var.

Photodissociation and photoisomerization of alpha-fluorotoluene and 4-fluorotoluene in a molecular beam.

The photodissociation of jet-cooled alpha-fluorotoluene and 4-fluorotoluene at 193 and 248 nm was studied using vacuum ultraviolet (vuv) photoionization/multimass ion imaging techniques as well as electron impact ionization/photofragment translational spectroscopy. Four dissociation channels were observed for alpha-fluorotoluene at both 193 and 248 nm, including two major channels C6H5CH2F-->C6H5CH2 (or C7H7)+F and C6H5CH2F-->C6H5CH (or C7H6)+HF and two minor channels C6H5CH2F-->C6H5CHF+H and C6H5CH2F-->C6H5+CH2F. The vuv wavelength dependence of the C7H7 fragment photoionization spectra indicates that at least part of the F atom elimination channel results from the isomerization of alpha-fluorotoluene to a seven-membered ring prior to dissociation.

Photodissociation dynamics of C6HxF6-x (x = 1-4) at 193 nm.

Photodissociation of fluorine-substituted benzenes, including 1,3-difluorobenzene, 1,2,4-trifluorobenzene, 1,2,4,5-tetrafluorobenzene, and pentafluorobenzene, at 193 nm under collision-free conditions has been studied in separate experiments using multimass ion imaging techniques. HF elimination was found to be the major dissociation channel for all of these molecules. Small amounts of photofragments of C(6)H(3)F(2) and C(6)H(2)F(3) from 1,3-difluorobenzene and 1,2,4-trifluorobenzene, respectively, were also observed.