Infrared matrix isolation study of the thermal and photochemical reactions of ozone with dimethylcadmium

The matrix isolation technique has been combined with infrared spectroscopy and theoretical calculations to explore the reaction of (CH(3))(2)Cd with O(3) over a range of time scales and upon irradiation. During twin jet deposition, multiple novel product species were observed along with several stable "late" products. Following annealing of these matrices to 35 K, absorptions due to two novel product species increased in intensity. In addition, new bands appeared, indicating the formation of an additional product. Subsequent UV irradiation destroyed several of the initial products and produced a new photoproduct. On the basis of (18)O and (16,18)O spectroscopic data and theoretical calculations, the novel intermediates H(3)COCdCH(3), H(3)CCdCH(2)OH, H(3)COCdOOCH(3), and H(3)CCdCHO were identified. Merged jet deposition led to a number of stable "late" products, including H(2)CO, CH(3)OH, and C(2)H(6), identifications that were confirmed by (18)O substitution. Mechanistic inferences for this reaction are discussed.     

Quantitative analysis of Fermi resonances by harmonic derivatives of perturbation theory corrections

Vibrational perturbation theory has proven to be a highly accurate and efficient method for extending the harmonic approximation in the treatment of polyatomic molecular vibrations. Unfortunately, accidental near-degeneracies of the harmonic vibrational levels can lead to resonance and a breakdown of the perturbation approximation. These resonances can be resolved by the diagonalization of a small effective Hamiltonian derived from either of the usual Rayleigh–Schrödinger or van Vleck perturbation theories. However, the proper choice of states for inclusion in the effective Hamiltonian is crucial to the accuracy of the results, and is not often clearly evident. It is proposed that the analytical partial derivatives of the anharmonic vibrational correction with respect to the various harmonic frequencies, called ‘Harmonic Derivatives’ in this work, can be used as a tool to quantitatively assess the existence and strength of first-order, or Fermi, resonances. These derivatives are shown to concisely and clearly reflect the quality of the perturbation approximation and the effect of its breakdown on the computed vibrational levels.     

Atoms and bonds in molecules from radial densities

Radial densities are explored as an alternative method for partitioning the molecular density into atomic regions and bonding regions. The radial densities for atoms in molecules are similar to those of an isolated atom. The method may also provide an alternative to Bragg-Slater radii.     

Catalytic Dehydrogenation of Amine-Boranes using Geminal Phosphino-Boranes

The reaction of the intramolecular frustrated Lewis pair (FLP) tBu₂PCH₂BPh₂ with the amine-boranes NH₃ · BH₃ and Me₂NH · BH₃ leads to the formation of the corresponding FLP-H₂ adducts as well as novel five-membered heterocycles that result from capturing the in situ formed amino-borane by a second equivalent of FLP. The sterically more demanding tBu₂PCH₂BMes₂ does not form such a five-membered heterocycle when reacted with Me₂NH · BH₃ and its H₂ adduct liberates dihydrogen at elevated temperatures, promoting the metal-free catalytic dehydrogenation of amine-boranes.     

Use of potentiometric detection in (ultra) high performance liquid chromatography and modelling with adsorption/desorption binding kinetics

Observation of a potentiometric sensor's response behaviour after injection in flow injection analysis at different concentrations allowed studying “on” and “off” kinetics of the analyte's adsorption/diffusion behaviour. The alkaloid metergoline was mostly used as an example. k_on and k_off rate constant values were measured, and the association constant K_ass, and ΔG values of the analyte–surface interaction were calculated with an adsorption-based model which proved to be fully applicable. k_on increased by decreasing the sensor dimensions, while k_off was unaffected by miniaturization. Increasing acetonitrile concentrations in the running buffer increased k_off, while k_on was unaffected. The experimentally determined ΔG values of the analyte–surface interaction showed a linear relation to the response of the sensor, in mV. This knowledge was applied to optimize the potentiometric detection of plant alkaloids in (U)HPLC. Sub-micromolar detection limits were obtained with the potentiometric detector/(U)HPLC combination. This is the first time that the response rates and the response itself can be modelled accurately for coated wire potentiometric sensors, and it is the first application of a potentiometric detector in UPLC.     

Nitrimines as Reagents for Metal‐Free Formal C(sp2)–C(sp2) Cross‐Coupling Reactions

Nitrimines are employed as powerful reagents for metal‐free formal C(sp²)–C(sp²) cross‐coupling reactions. The new chemical process is tolerant of a wide array of nitrimine and heterocyclic coupling partners giving rise to the corresponding di‐ or trisubstituted alkenes, typically in high yield and with high stereoselectivity. This method is ideal for the metal‐free construction of heterocycle‐containing drug targets, such as phenprocoumon.     

Grand canonical Monte Carlo simulations of the 129Xe NMR line shapes of xenon adsorbed in (+/-)-[Co(en)3]Cl3

The 129Xe NMR line shapes of xenon adsorbed in the nanochannels of the (+/-)-[Co(en)3]Cl3 ionic crystal have been calculated by grand canonical Monte Carlo (GCMC) simulations. The results of our GCMC simulations illustrate their utility in predicting 129Xe NMR chemical shifts in systems containing a transition metal. In particular, the nanochannels of (+/-)-[Co(en)3]Cl3 provide a simple, yet interesting, model system that serves as a building block toward understanding xenon chemical shifts in more complex porous materials containing transition metals. Using only the Xe-C and Xe-H potentials and shielding response functions derived from the Xe@CH4 van der Waals complex to model the interior of the channel, the GCMC simulations correctly predict the 129Xe NMR line shapes observed experimentally (Ueda, T.; Eguchi, T.; Nakamura, N.; Wasylishen, R. E. J. Phys. Chem. B 2003, 107, 180-185). At low xenon loading, the simulated 129Xe NMR line shape is axially symmetric with chemical-shift tensor components delta(parallel) = 379 ppm and delta(perpendicular) = 274 ppm. Although the simulated isotropic chemical shift, delta(iso) = 309 ppm, is overestimated, the anisotropy of the chemical-shift tensor is correctly predicted. The simulations provide an explanation for the observed trend in the 129Xe NMR line shapes as a function of the overhead xenon pressure: delta(perpendicular) increased from 274 to 292 ppm, while delta(parallel) changed by only 3 ppm over the entire xenon loading range. The overestimation of the isotropic chemical shifts is explained based upon the results of quantum mechanical 129Xe shielding calculations of xenon interacting with an isolated (+/-)-[Co(en)3]Cl3 molecule. The xenon chemical shift is shown to be reduced by about 12% going from the Xe@[Co(en)3]Cl3 van der Waals complex to the Xe@C2H6 fragment.     

Modeling of an insurance system and its large deviations analysis

We model an insurance system consisting of one insurance company and one reinsurance company as a stochastic process in R². The claim sizes {X_i} are an iid sequence with light tails. The interarrival times {τ_i} between claims are also iid and exponentially distributed. There is a fixed premium rate c₁ that the customers pay; c<c₁ of this rate goes to the reinsurance company. If a claim size is greater than R the reinsurance company pays for the claim. We study the bankruptcy of this system before it is able to handle N number of claims. It is assumed that each company has initial reserves that grow linearly in N and that the reinsurance company has a larger reserve than the insurance company. If c and c₁ are chosen appropriately, the probability of bankruptcy decays exponentially in N. We use large deviations (LD) analysis to compute the exponential decay rate and approximate the bankruptcy probability. We find that the LD analysis of the system decouples: the LD decay rate γ of the system is the minimum of the LD decay rates of the companies when they are considered independently and separately. An analytical and numerical study of γ as a function of (c,R) is carried out.     

Quantifying the Initial Unfolding of Bacteriorhodopsin Reveals Retinal Stabilization

The forces that stabilize membrane proteins remain elusive to precise quantification. Particularly important, but poorly resolved, are the forces present during the initial unfolding of a membrane protein, where the most native set of interactions is present. A high‐precision, atomic force microscopy assay was developed to study the initial unfolding of bacteriorhodopsin. A rapid near‐equilibrium folding between the first three unfolding states was discovered, the two transitions corresponded to the unfolding of five and three amino acids, respectively, when using a cantilever optimized for 2 μs resolution. The third of these states was retinal‐stabilized and previously undetected, despite being the most mechanically stable state in the whole unfolding pathway, supporting 150 pN for more than 1 min. This ability to measure the dynamics of the initial unfolding of bacteriorhodopsin provides a platform for quantifying the energetics of membrane proteins under native‐like conditions.