Cryogenic Ion Vibrational Predissociation (CIVP) Spectroscopy of Aryl Cobinamides in the Gas Phase: How Good Are the Calculations for Vitamin B12 Derivatives?

Aryl corrins represent a novel class of designed B12 derivatives with biological properties of "antivitamins B12". In our previous study, we experimentally determined bond strength in a series of aryl-corrins by the threshold collision-induced dissociation experiments (T-CID) and compared the measured bond dissociation energies (BDEs) with those calculated with density functional theory (DFT). We found that the BDEs are modulated by the side chains around the periphery of the corrin unit. Given that aryl cobinamides have many side chains that increase their conformational space and that the question of a specific structure, measured in the gas phase, was important for further evaluation of our T-CID experiment, we proceeded to analyze structural properties of aryl cobinamides using cryogenic ion vibrational predissociation (CIVP) spectroscopy, static DFT, and Born-Oppenheimer molecular dynamic (BOMD) simulations. We found that none of the examined DFT models could reproduce the CIVP spectra convincingly; both "static" DFT calculations and "dynamic" BOMD simulations provide a surprisingly poor representation of the vibrational spectra, specifically of the number, position, and intensity of bands assigned to hydrogen-bonded versus non-hydrogen-bonded NH and OH moieties. We conclude that, for a flexible molecule with ca. 150 atoms, more accurate approaches are needed before definitive conclusions about computed properties, specifically the structure of the ground-state conformer, may be made.

Cryogenic ion vibrational predissociation (CIVP) spectroscopy of a gas-phase molecular torsion balance to probe London dispersion forces in large molecules.

We report a gas-phase molecular torsion balance that uses a conformational equilibrium to "weigh" London dispersion against a competing cation-π interaction, for which the readout is the shift in an N-H stretching frequency measured by cryogenic ion vibrational predissociation (CIVP) spectroscopy of electrosprayed pyridinium cations in a Fourier-transform ion cyclotron resonance trap. While frequency calculations with DFT, within the harmonic approximation, assist in the interpretation of the spectra, the observed complex spectrum most likely comes from a Fermi resonance of the N-H stretch with otherwise "dark" overtones of in-plane C-H wagging modes, as argued on the basis of comparison of the spectrum to those for a range of related cations with systematically varied substitution. An equilibrium in favor of the asymmetric conformer would suggest that the dispersion-corrected DFT calculations tested in this work appear to overestimate significantly the stability of the compact conformations favored by London dispersion in the gas phase, which would then pertain to the use of dispersion energy donors in the design of stereoselective reactions.

A 4 K FT-ICR cell for infrared ion spectroscopy.

We present the design of the newly constructed cryogenic Fourier-transform ion cyclotron resonance (FT-ICR) ion trap for infrared ion spectroscopy. Trapped ions are collisionally cooled by the pulsed introduction of buffer gas into the cell. Using different buffer gases and cell temperatures, we record action spectra of weakly bound neutral gas-analyte complexes with an IR laser source. We show for the first time that ion-He complexes can be observed in an ICR cell at temperatures around 4 K. We compare the experimental vibrational spectra of Ag(PPh3)2+ obtained by tagging with different neutral gases: He, Ne, Ar, H2, and N2 to computed vibrational spectra. Furthermore, the conditions necessary for the formation of neutral tags within an ICR ion trap are studied.

Ab initio studies on the photodissociation dynamics of the 1,1-difluoroethyl radical.

Born-Oppenheimer molecular dynamics trajectory calculations at the HCTH147/6-31G** level of theory simulate the dissociation dynamics of photolytically excited 1,1-difluoroethyl radicals. EOMCCSD/AUG-cc-pVDZ calculations show that an excitation energy of 94.82 kcal/mol is necessary to initiate photodissociation reactions. In contrast to photodissociation dynamics of ethyl radicals where a large discrepancy between actual dissociation rates and rates that are predicted by statistical rate theories, we find reaction rates of 5.1 × 1011 s-1 for the dissociation of an H atom, which is in perfect accord with what is predicted by Rice-Ramsperger-Kassel-Marcus (RRKM) calculations and there is no indication of any nonstatistical effects. However, our trajectory calculations show a much larger fraction of C-C bond breakage reaction of 56% occurring than that expected by RRKM (only 16%).

Estimation of human body concentrations of DDT from indoor residual spraying for malaria control.

Inhabitants of dwellings treated with DDT for indoor residual spraying show high DDT levels in blood and breast milk. This is of concern since mothers transfer lipid-soluble contaminants such as DDT via breastfeeding to their children. Focusing on DDT use in South Africa, we employ a pharmacokinetic model to estimate DDT levels in human lipid tissue over the lifetime of an individual to determine the amount of DDT transferred to children during breastfeeding, and to identify the dominant DDT uptake routes. In particular, the effects of breastfeeding duration, parity, and mother's age on DDT concentrations of mother and infant are investigated. Model results show that primiparous mothers have greater DDT concentrations than multiparous mothers, which causes higher DDT exposure of first-born children. DDT in the body mainly originates from diet. Generally, our modeled DDT levels reproduce levels found in South African biomonitoring data within a factor of 3.