Direct fission versus sequential evaporation mechanism of sputtered caesium iodide cluster ions

A triple stage hybrid mass spectrometer was scanned for the trapping of the reaction intermediates of the over-all loss of two CsI-moieties from size-selected caesium iodide cluster ions of the general formula Cs (CsI)⁺ _n . In addition to appropriate MS/MS/MS-methods an electrically floated collision cell has been applied to trap intermediates of unimolecular and collision-induced evaporations. In comparison with other experimental findings the features of the evaporation mechanism are discussed.     

Method development for the quantitation of ABT-578 in rabbit artery tissue by 96-well liquid-liquid extraction and liquid chromatography/tandem mass spectrometric detection

Quantitative determination of drug concentrations in tissue samples can provide critical information for drug metabolism, kinetics, and toxicity evaluations. For analysis of tissue samples using liquid chromatography/tandem mass spectrometric (LC/MS/MS) detection, homogenization is a critical step in achieving good assay performance. Assay performance can be closely evaluated by spiking the drug directly into tissue samples prior to homogenization. It is especially important to include this assay evaluation for the analysis of artery tissue samples because artery tissue is very elastic, making it quite a challenge to develop an effective procedure for homogenization. An LC/MS/MS assay in 96-well format using liquid-liquid extraction was developed for analyzing ABT-578 in rabbit artery samples. Tissue quality control samples were prepared by spiking ABT-578 stock solutions directly into the tissue before homogenization. The usage of the tissue control samples gives a thorough evaluation of the sample preparation process that includes both homogenization and sample extraction. A 20% blood in saline solution was used as a homogenization solution. Calibration standards were made by spiking ABT-578 into rabbit whole blood. Blood quality control samples were also prepared by spiking ABT-578 into rabbit whole blood. These blood QC samples were used to confirm the validity of the calibration curve. A lower limit of quantitation of 0.050 ng/mL was achieved. The linear dynamic range of blood standards was from 0.050-30.3 ng/mL with the correlation coefficient (r) ranging from 0.9969-0.9996. Overall %CV was between 1.3 and 7.0%, and analytical recovery was between 98.2 and 105.8% for blood QC samples. The %CVs for tissue QC samples were between 6.7 and 13.0%, and analytical recovery after correction was between 93.5 and 114.3%.     

Electron binding energies of aqueous alkali and halide ions: EUV photoelectron spectroscopy of liquid solutions and combined ab initio and molecular dynamics calculations

Photoelectron spectroscopy combined with the liquid microjet technique enables the direct probing of the electronic structure of aqueous solutions. We report measured and calculated lowest vertical electron binding energies of aqueous alkali cations and halide anions. In some cases, ejection from deeper electronic levels of the solute could be observed. Electron binding energies of a given aqueous ion are found to be independent of the counterion and the salt concentration. The experimental results are complemented by ab initio calculations, at the MP2 and CCSD(T) level, of the ionization energies of these prototype ions in the aqueous phase. The solvent effect was accounted for in the electronic structure calculations in two ways. An explicit inclusion of discrete water molecules using a set of snapshots from an equilibrium classical molecular dynamics simulations and a fractional charge representation of solvent molecules give good results for halide ions. The electron binding energies of alkali cations computed with this approach tend to be overestimated. On the other hand, the polarizable continuum model, which strictly provides adiabatic binding energies, performs well for the alkali cations but fails for the halides. Photon energies in the experiment were in the EUV region (typically 100 eV) for which the technique is probing the top layers of the liquid sample. Hence, the reported energies of aqueous ions are closely connected with both structures and chemical reactivity at the liquid interface, for example, in atmospheric aerosol particles, as well as fundamental bulk solvation properties.     

Theoretical implications involved in the DDRP method

The aim of this paper is to prove that safe success in finding reaction paths (RPs) can only be expected from global path-determining methods. Some extensions of the mathematical arguments leading to the introduction of the DDRP (dynamically defined reaction path) method have been sketched. Four cases involving relaxation of analyticity, variability of the gradient field, minimum energy (reaction) paths (MEPs) and golf pocket holes on the potential energy surface (PES), and the rather strange consequences of the main theorem of the DDRP method giving a rigorous mathematical basis to chemical intuition in reaction kinetics have been discussed. The discussions show that the DDRP method - when changing the conditions and parameters - may, in essence, involve all other global methods. It has been shown that the DDRP method works in a stable way even for non-analytic though smooth energy functions; moreover, the gradient field can be replaced by other vector fields resulting in better convergence to the reaction path. As a by-product, the question of the existence of MEPs can safely be handled and golf pocket holes are constructed on the PES in order to prove that local methods have chance to search faithfully the RPs in complicated systems only if the energy function can be restored from its arbitrarily small pieces.This work was presented in parts at the 8th International Congress of Quantum Chemistry, Prague, Czech Republic, June 19–23,1994; Addendum to the Book of Abstracts of the 8ICQC: P/I-129.     

Zu Struktur,Bindung und Ligandenaustauschverhalten von Nitrosyltechnetium(II)-Verbindungen Eine. EPR-Untersuchung

Structure, Bonding, and Ligand Exchange Behaviour of Nitrosyl-Technetium (II) Compounds. An EPR Study EPR investigations on the nitrosyltechnetium(II) compounds (Bu₄N)₂[Tc(NO)Cl₅], (Bu₄N)[Tc(NO)Br₄], (Bu₄N)[Tc(NO)I₄], and (Ph₄As)₂[Tc(NO)(NCS)₅] having a 4 t low-spin configuration are reported. The EPR parameters g?, Ã^Tc as well as ligand hyperfine data are used to analyze the bonding properties. The isotropic parameters g₀ and a are found to be clearly correlated to the composition of the coordination sphere. Therefore, they can be used to characterize mixed-ligand complexes unambiguously. The formation of mixed-ligand complexes was investigated for ligand-exchange reactions on [Tc(NO)Cl₅]^2? and [Tc(NO)Br₄]^?. In these investigations unsaturated dichalcogeno ligands are included.     

An algorithm for determining dynamically defined reaction paths (DDRP)

Summary A numerically stable and well-parallelizable curve variational algorithm is described for determining tangent curves of vector fields between two given stationary points. In particular, the method is suitable for finding reaction paths and saddle points on potential energy hypersurfaces (PHS). The stability of the procedure is illustrated by an artificial mathematical function, showing phases of following the reaction on the PHS.Dedicated to Professor Zoltán G. Szabó, the great teacher and scientist in reaction kinetics and in many other fields of physical chemistry, on his 84th birthday.     

SOCl2 and POCl3 as reducing agents for TcO 4 − formation and EPR detection of Tc(VI)-compounds

Pertechnetate, TcO ₄ ^– , is reduced by thionyl chloride and phosphoryl chloride, respectively, to yield semistable Tc(VI) intermediates which can easily be detected by EPR spectroscopy. Spectra are recorded in liquid and frozen solutions. EPR data as well as chemical behaviour suggest the compounds obtained to be oxochloro complexes of technetium(VI).     

“Comment” on the Reply to the Paper “On the Elber–Karplus Reaction Path-Following Method and Related Procedures”

The flaws in the Reply [1] to our paper [2] have been pointed out. Elber and Karplus (EK) have not disproved our irrefutable global statement that the energy average cannot be minimized which rebuts the theoretical background of EK-type calculations. Another statement of ours has shown that even a curve for which the average energy is locally minimal for all directional perturbations in the sense of classical variational calculus cannot be identical with the reaction path (RP) defined as a steepest descent path (SDP). EK found an error in the early preprint of our theoretical paper [3] and because of this error they qualified our correct variational statement as false for all the SDPs consisting of a straight line each. Mixing global and variational arguments, EK refuted our criticism in a logically incorrect manner. In this Comment we prove that both of our earlier statements invariably remain in force and the criticism included in those has been as well-established and solid as was before.     

Sampling unfolding intermediates in calmodulin by single-molecule spectroscopy

We used single-pair fluorescence resonance energy transfer (spFRET) measurements to characterize denatured and partially denatured states of the multidomain calcium signaling protein calmodulin (CaM) in both its apo and Ca(2+)-bound forms. The results demonstrate the existence of an unfolding intermediate. A CaM mutant (CaM-T34C-T110C) was doubly labeled with fluorescent probes AlexaFlour 488 and Texas Red at opposing globular domains. Single-molecule distributions of the distance between fluorophores were obtained by spFRET at varying levels of the denaturant urea. Multiple conformational states of CaM were observed, and the amplitude of each conformation was dependent on urea concentration, with the amplitude of an extended conformation increasing upon denaturation. The distributions at intermediate urea concentrations could not be adequately described as a combination of native and denatured conformations, showing that CaM does not denature via a two-state process and demonstrating that at least one intermediate is present. The intermediate conformations formed upon addition of urea were different for Ca(2+)-CaM and apoCaM. An increase in the amplitude of a compact conformation in CaM was observed for apoCaM but not for Ca(2+)-CAM upon the addition of urea. The changes in the single-molecule distributions of CaM upon denaturation can be described by either a range of intermediate structures or by the presence of a single unfolding intermediate that grows in amplitude upon denaturation. A model for stepwise unfolding of CaM is suggested in which the domains of CaM unfold sequentially.