Search results for " Dissociation"
showing 10 items of 99 documents
Two- and three-state conical intersections in the electron capture dissociation of disulfides: The importance of multireference calculations
2011
The SS bond cleavage produced upon electron attachment to disulfides was generally assumed to be an adiabatic process because the added electron occupies the σ*(SS) antibonding orbital. This is clearly the case in the parent HSSH compound, but not necessarily in XSSX′ derivatives, where the substituents X and X′ are different. Through the use of MS-CASPT2 calculations, we have shown that the dissociation of the SS two-center-three-electron bond in these asymmetric XSSX′ compounds requires the interaction of at least two states, in order to localize the extra electron in one of the fragments upon dissociation. This is actually the case for the CH3SSNH2 derivative, where the most favorable di…
ETD and ECD Mass Spectrometry Fragmentation for the Characterization of Protein Post Translational Modifications
2012
The introduction of electron capture dissociation (ECD) by McLafferty and co-workers, and further of electron transfer dissociation (ETD), mechanism allows gas-phase fragmentation of multiply charged protein and peptide ions upon capture of a low-energy (<1 eV) electron or electron transfer in a gas phase ion-ion chemistry. The odd-electron species then undergoes rearrangement with subsequent cleavage of N−Cα backbone. Peptide fragmentation can take place inducing the formation of cand ztype fragment ions without loss of the information on the PTM localization. The key to the success of this approach is the selection of intact protein molecular ions and its profound potential for PTM charac…
Do electrospray mass spectra of surfactants mirror their aggregation state in solution?
2011
One important feature in the gas phase chemistry of surfactants is to ascertain whether their aggregates produced by electrospray ionization reflect those formed in the starting solution. With this aim, we have performed ESI-MS, ESI-MS/MS and ER-MS spectra of bis(2-ethylhexyl)sulfosuccinate (AOTNa) solutions in different solvents, i.e. water, water/methanol, methanol and n-hexane. The results clearly indicate that, notwithstanding the strongly different aggregation state in solution (direct micelles in water and in water/methanol, molecular dispersion in methanol and reverse micelles in n-hexane) and marked effects of the solvent polarity on the total ionic current, the surfactant aggregate…
Study of the Fragmentation of D-Glucose and Alkylmonoglycosides in the Presence of Sodium Ions in an Ion-Trap Mass Spectrometer
2009
Abstract Using electrospray ion-trap mass spectrometry, the fragmentation of D-glucose and alkylmonoglycopyranosides (alkyl-GPs) was studied. In the presence of Na+, B1 and 0,2A fragmentations were observed. The alkyl-GPs also showed a 2,5Afragmentation. A cluster containing no carbon atoms and adducts of this cluster with neutral molecules were observed. Standards of alkylmonoglycofuranosides (alkyl-GFs) were not available; however, their fragmentation was studied by high-performace liquid chromatography–mass spectrometry (HPLC-MS) and HPLC-MS2 using an industrial mixture of alkylpolyglycosides. The cluster and its adducts were more easily formed by the alkyl-GPs than by the alkyl-GFs, but…
Colloidal Nanoplatelet/Conducting Polymer Hybrids: Excitonic And Material Properties
2016
WOS:000370678700053 Here we present the first account of conductive polymer/colloidal nanoplatelet hybrids. For this, we developed DEH-PPV-based polymers with two different anchor groups (sulfide and amine) acting as surfactants for CdSe nanoplatelets, which are atomically flat semiconductor nanocrystals. Hybridization of the polymers with the nanoplatelets in the solution phase was observed to cause strong photoluminescence quenching in both materials. Through steady-state photoluminescence and excitation spectrum measurements, photoluminescence quenching was shown to result from dominant exciton dissociation through charge transfer at the polymer/nanoplatelet interfaces that possess a sta…
Ultrafast ionization and rotational dynamics of molecules in strong laser fields
2021
The investigation of ultrafast molecular dynamics is of great importance towards the understanding of a variety of natural phenomena in physical and chemical sciences. With the rapid development of femtosecond laser systems and precision detection technologies, it is possible now to visualize and steer the motion of molecules in matter as well as the ultrafast dynamics of electrons and nuclei in molecules on a microscopic timescale. When a molecule is exposed to a strong laser field, its electrons can be freed or excited, which often triggers a rapid dissociation of the system, in which the released electrons and nuclei exhibit a strong correlation, while the electronic motion on attosecond…
Calcium binding and ionic conduction in single conical nanopores with polyacid chains: model and experiments.
2012
Calcium binding to fixed charge groups confined over nanoscale regions is relevant to ion equilibrium and transport in the ionic channels of the cell membranes and artificial nanopores. We present an experimental and theoretical description of the dissociation equilibrium and transport in a single conical nanopore functionalized with pH-sensitive carboxylic acid groups and phosphonic acid chains. Different phenomena are simultaneously present in this basic problem of physical and biophysical chemistry: (i) the divalent nature of the phosphonic acid groups fixed to the pore walls and the influence of the pH and calcium on the reversible dissociation equilibrium of these groups; (ii) the asym…
The dissociation channels of silver clusters Agn+, 3 ≤ n ≤ 20
1996
Abstract The low energy dissociation channels of silver cluster ions Agn+, 3 ≤ n ≤ 20 are determined by collision-induced dissociation (CID) in a Penning trap. While for most cluster sizes the first fragment cluster ion is produced by monomer evaporation, the fragment ion of small odd-sized clusters has two atoms less than their precursors indicating an evaporation of dimers. The results are compared to similar CID studies on gold cluster ions, photofragmentation patterns, abundance spectra for various silver-cluster production techniques and calculated binding energies.
Collision induced dissociation of stored gold cluster ions
1994
The stability of gold cluster ions Au + (2≦n≦23) has been investigated via collision induced dissociation in a Penning trap. Threshold energies and dissociation channels have been determined. The cluster stability exhibits a pronounced odd — even alternation: Clusters with an odd number of atoms,n, are more stable than the even-numbered ones. Enhanced stabilities are found for Au 3 + , Au 9 + , and Au 19 + in accordance with the Clemenger-Nilsson and the deformed jellium model of delocalized valence electrons. Excited odd cluster ions withn≦15 predominantly decay by evaporation of dimers; all others decay by monomer evaporation. From the dissociation channels estimates of the binding energi…
Fragmentation pattern of gold clusters collided with xenon atoms
1994
Abstract The dissociation channels of gold cluster ions Au n + (2 ≤ n ≤ 23) have been investigated via collision induced dissociation in a Penning trap. Excited odd cluster ions with n ≤ 15 decay by evaporation of dimers, all others decay by monomer evaporation. Information on the binding energies is deduced from these dissociation channels.