A slowly relaxing rigid biradical for efficient dynamic nuclear polarization surface-enhanced NMR spectroscopy: expeditious characterization of functional group manipulation in hybrid materials

A new nitroxide-based biradical having a long electron spin-lattice relaxation time (T(1e)) has been developed as an exogenous polarization source for DNP solid-state NMR experiments. The performance of this new biradical is demonstrated on hybrid silica-based mesostructured materials impregnated with 1,1,2,2-tetrachloroethane radical containing solutions, as well as in frozen bulk solutions, yielding DNP enhancement factors (ε) of over 100 at a magnetic field of 9.4 T and sample temperatures of ~100 K. The effects of radical concentration on the DNP enhancement factors and on the overall sensitivity enhancements (Σ(?)) are reported. The relatively high DNP efficiency of the biradical is attributed to an increased T(1e), which enables more effective saturation of the electron resonance. This new biradical is shown to outperform the polarizing agents used so far in DNP surface-enhanced NMR spectroscopy of materials, yielding a 113-fold increase in overall sensitivity for silicon-29 CPMAS spectra as compared to conventional NMR experiments at room temperature. This results in a reduction in experimental times by a factor >12,700, making the acquisition of (13)C and (15)N one- and two-dimensional NMR spectra at natural isotopic abundance rapid (hours). It has been used here to monitor a series of chemical reactions carried out on the surface functionalities of a hybrid organic-silica material.     

Joint Scalar versus Joint Velocity-Scalar PDF Simulations of Bluff-Body Stabilized Flames with REDIM

Two transported PDF strategies, joint velocity-scalar PDF (JVSPDF) and joint scalar PDF (JSPDF), are investigated for bluff-body stabilized jet-type turbulent diffusion flames with a variable degree of turbulence–chemistry interaction. Chemistry is modeled by means of the novel reaction-diffusion manifold (REDIM) technique. A detailed chemistry mechanism is reduced, including diffusion effects, with N ₂ and CO ₂ mass fractions as reduced coordinates. The second-moment closure RANS turbulence model and the modified Curl’s micro-mixing model are not varied. Radiative heat loss effects are ignored. The results for mean velocity and velocity fluctuations in physical space are very similar for both PDF methods. They agree well with experimental data up to the neck zone. Each of the two PDF approaches implies a different closure for the velocity-scalar correlation. This leads to differences in the radial profiles in physical space of mean scalars and mixture fraction variance, due to different scalar flux modeling. Differences are visible in mean mixture fraction and mean temperature, as well as in mixture fraction variance. In principle, the JVSPDF simulations can be closer to physical reality, as a differential model is implied for the scalar fluxes, whereas the gradient diffusion hypothesis is implied in JSPDF simulations. Yet, in JSPDF simulations, turbulent diffusion can be tuned by means of the turbulent Schmidt number. In the neck zone, where the turbulent flow field results deteriorate, the joint scalar PDF results are in somewhat better agreement with experimental data, for the test cases considered. In composition space, where results are reported as scatter plots, differences between the two PDF strategies are small in the calculations at hand, with a little more local extinction in the joint scalar PDF results.     

High-temperature limit of Landau-gauge Yang-Mills theory

The infrared properties of the high-temperature limit of Landau-gauge Yang-Mills theory are investigated. In a first step the high-temperature limit of the Dyson-Schwinger equations is taken. The resulting equations are identical to the Dyson-Schwinger equations of the dimensionally reduced theory, a three-dimensional Yang-Mills theory coupled to an effective adjoint Higgs field. These equations are solved analytically in the infrared and ultraviolet, and numerically for all Euclidean momenta. We find infrared enhancement for the Faddeev-Popov ghosts, infrared suppression for transverse gluons and a mass for the Higgs. These results imply long-range interactions and over-screening in the chromomagnetic sector of high-temperature Yang-Mills theory while in the chromoelectric sector only screening is observed.Received: 5 August 2004, Published online: 21 September 2004     

Collision-Induced consecutive dissociation reactions of the monocarboxylate anions generated from the dimethyl and diethyl esters of glutaric acid and its 3,3-dimethyl analogue

The collision-induced dissociation reactions of the monocarboxylate anions, generated from the dimethyl and diethyl esters of glutaric acid and its 3,3-dimetbyl analogue in a chemical ionization source, were studied as a function of the potential applied to the collision cell in combination with ²H labelling experiments. It was shown that many of the product anions are formed in consecutive steps. The mechanisms associated with these steps appear to be initiated by a functional group interaction between the carboxylate anion and the ester group, 1,5-hydrogen migrations both to the carboxylate anion and the uncharged ester group and charge remote fragmentation. In one of the collision-induced dissociation channels a methyl anion is generated as a granddaughter product anion, which contains the hydrogen atoms exclusively originating from positions 2 and 4 as shown by the applied ²H labelling.