1,2,3,4-tetrahydro-8-hydroxymanzamines, alkaloids from two different haplosclerid sponges

The isolation and characterization of two new sponge alkaloids, 1,2,3,4-tetrahydro-2-N-methyl-8-hydroxymanzamine A (2) and 1,2,3,4-tetrahydro-8-hydroxymanzamine A (3), is described. These compounds were obtained from Papua New Guinea sponges of the genera Petrosia and Cribochalina, which are in different families of the order Haplosclerida. These new manzamines are close in structure to 8-hydroxymanzamine (4) recently reported from Pachypellina, a Haplosclerid sponge belonging to a different family than that of the two preceding sponges. The cytotoxicity of 2 is described and the biogenetic relationship of 2 or 3 to manzamine A (1) and to nine other related polycyclic diamine and one monoamine type alkaloids is described.     

Absolute proton affinity for acetaldehyde

Dissociative photoionization mass spectrometry has been used to measure appearance energies for the 1-hydroxyethyl cation (CH(3)CH=OH(+)) formed from ethanol and 2-propanol. Molecular orbital calculations for these two unimolecular fragmentation reactions suggest that only methyl loss from ionized 2-propanol does not involve excess energy at the threshold. The experimental appearance energy of 10.31 +/- 0.01 eV for this latter process results in a 298 K heat of formation of 593.1 +/- 1.2 kJ mol(-1) for CH(3)CH=OH(+) and a corresponding absolute proton affinity for acetaldehyde of 770.9 +/- 1.3 kJ mol(-1). This value is supported by both high-level ab initio calculations and a proposed upward revision of the absolute isobutene proton affinity to 803.3 +/- 0.9 kJ mol(-1). A 298 K heat of formation of 52.2 +/- 1.9 kJ mol(-1) is derived for the tert-butyl radical.     

Solid-phase synthesis of 5-substituted amino pyrazoles

An efficient method for the solid-supported synthesis of 5-N-alkylamino and 5-N-arylamino pyrazoles is described. This method is general and mild and utilizes readily accessible resin-immobilized beta-ketoamides 2 as starting materials for the preparation of 1. Resin-immobilized beta-ketoamide, aryl-, or alkylhydazine and Lawesson's reagent are suspended in a mixture of THF/Py and heated at 50-55 degrees C to give a resin-bound 5-aminopyrazole, that is liberated from the solid support by treatment with TFA.     

Hydrogen induced metallicity on the ZnO(1010) surface

Exposure of the mixed-terminated surface to atomic hydrogen at room temperature is found to lead to drastic changes of the electrical properties. The insulator surface is found to become metallic. By employing several experimental techniques (electron energy loss spectroscopy, He-atom scattering, and scanning tunneling microscopy) together with ab initio electronic structure calculations we demonstrate that a low-temperature (1 x 1) phase with two H atoms in the unit cell transforms upon heating to another (1 x 1) phase with only one H atom per unit cell. The odd number of electrons added to the surface per unit cell gives rise to partially filled surface states and thus a metallization of the surface.     

Working group report: Heavy-ion physics and quark-gluon plasma

This is the report of Heavy Ion Physics and Quark-Gluon Plasma at WHEPP-09 which was part of Working Group-4. Discussion and work on some aspects of quark-gluon plasma believed to have created in heavy-ion collisions and in early Universe are reported.     

Methodological inaccuracies in clinical aortic valve severity assessment: insights from computational fluid dynamic modeling of CT-derived aortic valve anatomy

Aortic stenosis is the most common valvular heart disease. Assessing the contribution of the valve as a portion to total ventricular load is essential for the aging population. A CT scan for one patient was used to create one in vivo tricuspid aortic valve geometry and assessed with computational fluid dynamics (CFD). CFD simulated the pressure, velocity, and flow rate, which were used to assess the Gorlin formula and continuity equation, current clinical diagnostic standards. The results demonstrate an underestimation of the anatomic orifice area (AOA) by Gorlin formula and overestimation of AOA by the continuity equation, using peak velocities, as would be measured clinically by Doppler echocardiography. As a result, we suggest that the Gorlin formula is unable to achieve the intended estimation of AOA and largely underestimates AOA at the critical low-flow states present in heart failure. The disparity in the use of echocardiography with the continuity equation is due to the variation in velocity profile between the outflow tract and the valve orifice. Comparison of time-averaged orifice areas by Gorlin and continuity with instantaneous orifice areas by planimetry can mask the errors of these methods, which is a result of the assumption that the blood flow is inviscid.     

Low-energy electron induced restructuring of water monolayers on NaCl(100)

The influence of electron irradiation on the controversially discussed monolayer structure of H(2)O on NaCl(100) is investigated with helium atom diffraction before and after a low-damage low-energy electron diffraction (LEED) experiment. The ordered (1x1) structure observed initially with He atoms is found to be transformed to a stable c(4x2) structure after a 90 eV electron dosage of only 10(15) electrons cm(-2) or about 2 incident electrons per adsorbate molecule. Based on previously reported structure models for the two phases, the transition is attributed to a reorientation, and a possible compression of the water film induced by the electrons.     

Short-term changes in delta(13)C and delta(15)N signatures of water discharged from grazed grasslands

The composition of dissolved organic matter (DOM) in a soil is the product of a variety of soil processes. Changes in the composition of DOM in water discharged from soil should, therefore, give an important insight into modifications in these soil processes. We hypothesise that these processes in soils, under different grassland management regimes, would be affected to different extents by the short-term disturbance of a storm event and that evidence of this could be detected in delta(13)C and delta(15)N signatures in drainage and surface runoff waters. During a storm event we collected discharge waters from 1 ha grassland lysimeters, with or without artificial drainage, which received contrasting fertiliser inputs, and delta(13)C and delta(15)N signatures were determined. Changes in (13)C enrichment during the storm event were clearly identifiable, as were differences between plots for (13)C and (15)N, illustrating that this technique has potential to be a useful tool for identifying and investigating short- and long-term changes in soil organic matter dynamics. Copyright 1999 John Wiley & Sons, Ltd.     

Calculation of inelastic helium atom scattering from H2/NaCl(001)

The one-phonon inelastic low energy helium atom scattering theory is adapted to cases where the target monolayer is a p(1 × 1) commensurate square lattice. Experimental data for para-H(2)/NaCl(001) are re-analyzed and the relative intensities of energy loss peaks in the range 6 to 9 meV are determined. The case of the H(2)/NaCl(001) monolayer for 26 meV scattering energy is computationally challenging and difficult because it has a much more corrugated surface than those in the previous applications for triangular lattices. This requires a large number of coupled channels for convergence in the wave-packet-scattering calculation and a long series of Fourier amplitudes to represent the helium-target potential energy surface. A modified series is constructed in which a truncated Fourier expansion of the potential is constrained to give the exact value of the potential at some key points and which mimics the potential with fewer Fourier amplitudes. The shear horizontal phonon mode is again accessed by the helium scattering for small misalignment of the scattering plane relative to symmetry axes of the monolayer. For 1° misalignment, the calculated intensity of the longitudinal acoustic phonon mode frequently is higher than that of the shear horizontal phonon mode in contrast to what was found at scattering energies near 10 meV for triangular lattices of Ar, Kr, and Xe on Pt(111).     

One-pot two step synthesis of 5-cyano-dihydropyrimidinones using polyphosphate ester

A combination of a modified Biginelli reaction and a polyphosphate ester (PPE)-promoted dehydration reaction provides 5-cyano-dihydropyrimidinones in good to excellent overall yields.