Vibronic Spectra of Jet-Cooled 2-Aminopurine center dot H2O Clusters Studied by UV Resonant Two-Photon Ionization Spectroscopy and Quantum Chemical Calculations

For understanding the major- and minor-groove hydration patterns of DNAs and RNAs, it is important to understand the local solvation of individual nucleobases at the molecular level. We have investigated the 2-aminopurine center dot H2O. monohydrate by two-color resonant two-photon ionization and UV/UV hole-burning spectroscopies, which reveal two isomers, denoted A and B. The electronic spectral shift delta nu of the S-1 <- S-0 transition relative to bare 9H-2-aminopurine (9H-2AP) is small for isomer A (-70 cm(-1)), while that of isomer B is much larger (delta nu = 889 cm(-1)). B3LYP geometry optimizations with the TZVP basis set predict four cluster isomers, of which three are doubly H-bonded, with H2O acting as an acceptor to a N-H or -NH2 group and as a donor to either of the pyrimidine N sites. The "sugar-edge" isomer A is calculated to be the most stable form with binding energy D-e = 56.4 kJ/mol. Isomers B and C are H-bonded between the -NH2 group and pyrimidine moieties and are 2.5 and 6.9 kJ/mol less stable, respectively. Time-dependent (TD) B3LYP/TZVP calculations predict the adiabatic energies of the lowest (1)pi pi* states of A and B in excellent agreement with the observed 0(0)(0) bands; also, the relative intensities of the A and B origin bands agree well with the calculated S-0 state relative energies. This allows unequivocal identification of the isomers. The R2PI spectra of 9H-2AP and of isomer A exhibit intense low-frequency out-of-plane overtone and combination bands, which is interpreted as a coupling of the optically excited (1)pi pi* state to the lower-lying (1)n pi* dark state. In contrast, these overtone and combination bands are much weaker for isomer B, implying that the (1)pi pi* state of B is planar and decoupled from the (1)n pi* state. These observations agree with the calculations, which predict the (1)n pi* above the (1)pi pi* state for isomer B but below the (1)pi pi* for both 9H-2AP and isomer A.

Retrieval of tropospheric water vapour by using spectra of a 22 GHz radiometer

In this paper, we present an approach to retrieve tropospheric water vapour profiles from pressure broadened emission spectra at 22 GHz, measured by a ground based microwave radiometer installed in the south of Bern at 905 m. Classical microwave instruments concentrating on the troposphere observe several channels in the center and the wings of the water vapour line (20–30 Ghz), whereas our retrieval approach uses spectra with a bandwidth of 1 GHz and a high resolution around the center of the 22 GHz water vapour line. The retrieval is sensitive up to 7 km with a vertical resolution of 3–5 km. Comparisons with profiles from operational balloon soundings, performed at Payerne, 40 km away from the radiometer location, showed a good agreement up to 7 km with a correlation of above 0.8. The retrievals shows a wet bias of 10–20% compared to the sounding.

Pain and swelling after periapical surgery related to the hemostatic agent used: anesthetic solution with vasoconstrictor or aluminum chloride

To assess pain and swelling in the first 7 days after periapical surgery and their relationship with the agent used for bleeding control.

Study of the Compressive Strength of Aluminum Curved Elements

Currently, the Specification for Aluminum Structures (Aluminum Association, 2010) shows thin-walled aluminum plate sections with radii greater than eight inches have a lower compressive strength capacity than a flat plate with the same width and thickness. This inconsistency with intuition, which suggests any degree of folding a plate should increase its elastic buckling strength, inspired this study. A wide range of curvatures are studied—from a nearly flat plate to semi-circular. To quantify the curvature, a single non-dimensional parameter is used to represent all combinations of width, thickness and radius. Using the finite strip method (CU-FSM), elastic local buckling stresses are investigated. Using the ratio of stress values of curved plates compared to flat plates of the same size, equivalent plate-buckling coefficients are calculated. Using this data, nonlinear regression analyses are performed to develop closed form equations for five different edge support conditions. These equations can be used to calculate the elastic critical buckling stress for any curved aluminum section when the geometric properties (width, thickness, and radius) and the material properties (elastic modulus and Poisson’s ratio) are known. This procedure is illustrated in examples, each showing the applicability of the derived equations to geometries other than those investigated in this study and also providing comparisons with theoretically exact numerical analysis results.

Corrosion Characteristics And Mechanical Properties Of Aluminum Coatings Applied By The Cold Spray Process

Aluminum coatings were applied to 2024-T3 and 7075-T6 aluminum alloys via the Cold Spray process. The coatings were applied to substrateswith various surface preparation and Cold Spray carrier gas combinations. Some samples were coated with an additional sealant with and without a chromate conversion layer. An exhaustive corrosion analysis was then performed which utilized a number of long termand accelerated tests in order to characterize the corrosion protection of the coatings.

Sensitivity Gains, Linearity, and Spectral Reproducibility in Nonuniformly Sampled Multidimensional MAS NMR Spectra of High Dynamic Range

Recently, we have demonstrated that considerable inherent sensitivity gains are attained in MAS NMR spectra acquired by nonuniform sampling (NUS) and introduced maximum entropy interpolation (MINT) processing that assures the linearity of transformation between the time and frequency domains. In this report, we examine the utility of the NUS/MINT approach in multidimensional datasets possessing high dynamic range, such as homonuclear C-13-C-13 correlation spectra. We demonstrate on model compounds and on 1-73-(U-C-13,N-15)/74-108-(U-N-15) E. coli thioredoxin reassembly, that with appropriately constructed 50 % NUS schedules inherent sensitivity gains of 1.7-2.1-fold are readily reached in such datasets. We show that both linearity and line width are retained under these experimental conditions throughout the entire dynamic range of the signals. Furthermore, we demonstrate that the reproducibility of the peak intensities is excellent in the NUS/MINT approach when experiments are repeated multiple times and identical experimental and processing conditions are employed. Finally, we discuss the principles for design and implementation of random exponentially biased NUS sampling schedules for homonuclear C-13-C-13 MAS correlation experiments that yield high-quality artifact-free datasets.