Second-order NMR spectra at high field of common organic functional groups

The proton NMR spectra of aryl n-propyl sulfides gave rise to what may appear to be first-order proton NMR spectra. Upon oxidation to the corresponding sulfone, the spectra changed appearance dramatically and were clearly second-order. A detailed analysis of these second-order spectra, in the sulfone series, provided vicinal coupling constants which indicated that these compounds had a moderate preference for the anti-conformer, reflecting the much greater size of the sulfone over the sulfide. It also emerged, from this study, that the criterion for observing large second-order effects in the proton NMR spectra of 1,2-disubstituted ethanes was that the difference in vicinal coupling constants must be large and the difference in geminal coupling constants must be small. n-Propyl triphenylphosphonium bromide and 2-trimethylsilylethanesulfonyl chloride, and derivatives thereof, also exhibited second-order spectra, again due to the bulky substituents. Since these spectra are second-order due to magnetic nonequivalence of the nuclei in question, not chemical shifts, the proton spectra are perpetually second-order and can never be rendered first-order by using higher field NMR spectrometers.

Source depletion and extent of melting in the Tongan sub-arc mantle

The fluid immobile High Field Strength Elements (HFSE) Nb and Ta can be used to distinguish between the effects of variable extents of melting and prior source depletion of the Tongan sub-arc mantle. Melting of spinel Iherzolite beneath the Lau Basin back-arc spreading centres has the ability to fractionate Nb from Ta due to the greater compatibility of the latter in clinopyroxene. The identified spatial variation in plate velocities and separation of melt extraction zones, combined with extremely depleted lavas make Tonga an ideal setting in which to test models for arc melt generation and the role of back-arc magmatism. We present new data acquired by laser ablation-ICPMS of fused sample glasses produced without the use of a melt fluxing agent. The results show an arc trend towards strongly sub-chondritic Nb/Ta (

Strong parallel magnetic field effects on the hydrogen molecular ion

Equilibrium distances, binding energies and dissociation energies for the ground and low-lying states of the hydrogen molecular ion in a strong magnetic field parallel to the internuclear axis are calculated and refined, by using the two- dimensional pseudospectral method. High-precision results are presented for the binding energies over a wider field regime than already given in the literature (Kravchenko and Liberman 1997 Phys. Rev. A 55 2701). The present work removes a long- standing discrepancy for the R-eq value in the 1sigma(u) state at a field strength of 1.0 x 10(6) T. The dissociation energies of the antibonding 1pi(g) state induced by magnetic fields are determined accurately. We have also observed that the antibonding 1pi(g) potential energy curve develops a minimum if the field is sufficiently strong. Some unreliable results in the literature are pointed out and discussed. A way to efficiently treat vibrational processes and coupling between the nuclear and the electronic motions in magnetic fields is also suggested within a three-dimensional pseudospectral scheme.

Applications of statistical models in proportioning medium strength self-compacting concrete

Self-compacting concrete (SCC) is generally designed with a relatively higher content of finer, which includes cement, and dosage of superplasticizer than the conventional concrete. The design of the current SCC leads to high compressive strength, which is already used in special applications, where the high cost of materials can be tolerated. Using SCC, which eliminates the need for vibration, leads to increased speed of casting and thus reduces labour requirement, energy consumption, construction time, and cost of equipment. In order to obtain and gain maximum benefit from SCC it has to be used for wider applications. The cost of materials will be decreased by reducing the cement content and using a minimum amount of admixtures. This paper reviews statistical models obtained from a factorial design which was carried out to determine the influence of four key parameters on filling ability, passing ability, segregation and compressive strength. These parameters are important for the successful development of medium strength self-compacting concrete (MS-SCC). The parameters considered in the study were the contents of cement and pulverised fuel ash (PFA), water-to-powder ratio (W/P), and dosage of superplasticizer (SP). The responses of the derived statistical models are slump flow, fluidity loss, rheological parameters, Orimet time, V-funnel time, L-box, JRing combined to Orimet, JRing combined to cone, fresh segregation, and compressive strength at 7, 28 and 90 days. The models are valid for mixes made with 0.38 to 0.72 W/P ratio, 60 to 216 kg/m3 of cement content, 183 to 317 kg/m3 of PFA and 0 to 1% of SP, by mass of powder. The utility of such models to optimize concrete mixes to achieve good balance between filling ability, passing ability, segregation, compressive strength, and cost is discussed. Examples highlighting the usefulness of the models are presented using isoresponse surfaces to demonstrate single and coupled effects of mix parameters on slump flow, loss of fluidity, flow resistance, segregation, JRing combined to Orimet, and compressive strength at 7 and 28 days. Cost analysis is carried out to show trade-offs between cost of materials and specified consistency levels and compressive strength at 7 and 28 days that can be used to identify economic mixes. The paper establishes the usefulness of the mathematical models as a tool to facilitate the test protocol required to optimise medium strength SCC.

The velocity distribution of solar photospheric magnetic bright points.

We use high spatial resolution observations and numerical simulations to study the velocity distribution of solar photospheric magnetic bright points. The observations were obtained with the Rapid Oscillations in the Solar Atmosphere instrument at the Dunn Solar Telescope, while the numerical simulations were undertaken with the MURaM code for average magnetic fields of 200 G and 400 G. We implemented an automated bright point detection and tracking algorithm on the data set and studied the subsequent velocity characteristics of over 6000 structures, finding an average velocity of approximately 1 km s(-1), with maximum values of 7 km s(-1). Furthermore, merging magnetic bright points were found to have considerably higher velocities, and significantly longer lifetimes, than isolated structures. By implementing a new and novel technique, we were able to estimate the background magnetic flux of our observational data, which is consistent with a field strength of 400 G.

Characteristics of Transverse Waves in Chromospheric Mottles

Using data obtained by the high temporal and spatial resolution Rapid Oscillations in the Solar Atmosphere instrument on the Dunn Solar Telescope, we investigate at an unprecedented level of detail transverse oscillations in chromospheric fine structures near the solar disk center. The oscillations are interpreted in terms of propagating and standing magnetohydrodynamic kink waves. Wave characteristics including the maximum transverse velocity amplitude and the phase speed are measured as a function of distance along the structure's length. Solar magnetoseismology is applied to these measured parameters to obtain diagnostic information on key plasma parameters (e.g., magnetic field, density, temperature, flow speed) of these localized waveguides. The magnetic field strength of the mottle along the ~2 Mm length is found to decrease by a factor of 12, while the local plasma density scale height is ~280 ± 80 km.

Solar coronal magnetic fields derived using seismology techniques applied to omnipresent sunspot waves

Sunspots on the surface of the Sun are the observational signatures of intense manifestations of tightly packed magnetic field lines, with near-vertical field strengths exceeding 6,000 G in extreme cases1. It is well accepted that both the plasma density and the magnitude of the magnetic field strength decrease rapidly away from the solar surface, making high-cadence coronal measurements through traditional Zeeman and Hanle effects difficult as the observational signatures are fraught with low-amplitude signals that can become swamped with instrumental noise2, 3. Magneto-hydrodynamic (MHD) techniques have previously been applied to coronal structures, with single and spatially isolated magnetic field strengths estimated as 9–55 G (refs 4,5,6,7). A drawback with previous MHD approaches is that they rely on particular wave modes alongside the detectability of harmonic overtones. Here we show, for the first time, how omnipresent magneto-acoustic waves, originating from within the underlying sunspot and propagating radially outwards, allow the spatial variation of the local coronal magnetic field to be mapped with high precision. We find coronal magnetic field strengths of 32 ± 5 G above the sunspot, which decrease rapidly to values of approximately 1 G over a lateral distance of 7,000 km, consistent with previous isolated and unresolved estimations. Our results demonstrate a new, powerful technique that harnesses the omnipresent nature of sunspot oscillations to provide magnetic field mapping capabilities close to a magnetic source in the solar corona.

Time-dependent Suppression of Oscillatory Power in Evolving Solar Magnetic Fields

Oscillation amplitudes are generally smaller within magnetically active regions like sunspots and plage when compared to their surroundings. Such magnetic features, when viewed in spatially resolved power maps, appear as regions of suppressed power due to reductions in the oscillation amplitudes. Employing high spatial- and temporal-resolution observations from the Dunn Solar Telescope (DST) in New Mexico, we study the power suppression in a region of evolving magnetic fields adjacent to a pore. By utilizing wavelet analysis, we study for the first time how the oscillatory properties in this region change as the magnetic field evolves with time. Image sequences taken in the blue continuum, G-band, Ca ii K, and Hα filters were used in this study. It is observed that the suppression found in the chromosphere occupies a relatively larger area, confirming previous findings. Also, the suppression is extended to structures directly connected to the magnetic region, and is found to get enhanced as the magnetic field strength increased with time. The dependence of the suppression on the magnetic field strength is greater at longer periods and higher formation heights. Furthermore, the dominant periodicity in the chromosphere was found to be anti-correlated with increases in the magnetic field strength.

White-light oscillations during a flare on II Peg

We analyse the intensity oscillations observed in the gradual phase of a white-light flare on the RS CV n binary II Peg. Fast Fourier Transform power spectra and Wavelet analysis reveal a period of 220 s. The reliability of the oscillation is tested using several criteria. Oscillating coronal loop models are used to derive physical parameters such as temperature, electron density and magnetic field strength associated with the coronal loop. The derived parameters are consistent with the near-simultaneous X-ray observations of the flare. There is no evidence for oscillations in the quiescent state of the binary.

Quantum manifestations of scattering orbits in the scaled spectrum of a non-hydrogenic atom in crossed fields

Evidence for scattering closed orbits for the Rydberg electron of the singly excited helium atom in crossed electric and magnetic fields at constant scaled energy and constant scaled electric field strength has been found through a quantum calculation of the photo-excitation spectrum. A particular 3D scattering orbit in a mixed regular and chaotic region has been investigated and the hydrogenic 3D closed orbits composing it identified. To the best of our knowledge, this letter reports the first quantum calculation of the scaled spectrum of a non- hydrogenic atom in crossed fields.

The closed orbits and the photo-excitation scaled spectrum of the hydrogen atom in crossed fields

In a recent Letter to the Editor (J Rao, D Delande and K T Taylor 2001 J. Phys. B: At. Mol. Opt. Phys. 34 L391-9) we made a brief first report of our quantal and classical calculations for the hydrogen atom in crossed electric and magnetic fields at constant scaled energy and constant scaled electric field strength. A principal point of that communication was our statement that each and every peak in the Fourier transform of the scaled quantum photo-excitation spectrum for scaled energy value epsilon = -0.586 538 871028 43 and scaled electric value (f) over tilde = 0.068 537 846 207 618 71 could be identified with a scaled action value of a found and mapped-out closed orbit up to a scaled action of 20. In this follow-up paper, besides presenting full details of our quantum and classical methods, we set out the scaled action values of all 317 closed orbits involved, together with the geometries of many.

Characterization of melanoidins from a glucose-glycine model system

The properties of melanoidins prepared from glucose and glycine (GG) were investigated by a three step purification protocol consisting of dialysis, gel filtration at high ionic strength and ion metal affinity chromatography. The high molecular weight fraction obtained in the GG system is responsible for 80% of the total brown colour and its antioxidative ability was about 1/4 of that of Trolox measured by the inhibition of linoleic acid oxidation. GG melanoidins have good affinity towards Cu (II) (32% bound to the resin) while it is much lower towards Pb (II) (10%) and Fe (II) (5%). Capillary zone electrophoresis analysis suggests that GG melanoidins are positively charged, although no signal was observed analysing melanoidins by matrix-assisted laser desorption-ionisation time-of-flight mass spectrometry (MALDI-TOF/MS).

Ruthenium complexes of the 1,4-bis(diphenylphosphino)-1,3-butadiene-bridged diphosphine 1,2,3,4-Me-4-NUPHOS: Solvent-dependent interconversion of four- and six-electron donor coordination and transfer hydrogenation activity

In chloroform, [RuCl2(nbd)(py)(2)] (1) (nbd = norbornadiene; py = pyridine) reacts with 1,4-bis(diphenylphosphino)-1,2,3,4-tetramethyl-1,3-butadiene (1,2,3,4-Me-4-NUPHOS) to give the dimer [Ru2Cl3(eta(4)-1,2,3,4-Me-4-NUPHOS)(2)]Cl (2a), whereas, in THF [RuCl2(1,2,3,4-Me-4-NUPHOS)(PY)(2)] (3) is isolated as the sole product of reaction. Compound 2 exists as a 4:1 mixture of two noninterconverting isomers, the major with C, symmetry and the minor with either C, or C-2 symmetry. A single-crystal X-ray analysis of [Ru2Cl3 (eta(4)-1,2,3,4-Me-4-NUPHOS)(2)] [SbF6] (2b), the hexafluoroantimonate salt of 2a, revealed that the diphosphine coordinates in an unusual manner, as a eta(4)-six-electron donor, bonded through both P atoms and one of the double bonds of the butadiene tether. Compounds 2a and 3 react with 1,2-ethylenediamine (en) in THF to afford [RuCl2(1,2,3,4-Me-4-NUPHOS)(en)] (4), which rapidly dissociates a chloride ligand in chloroform to give [RuCl(eta(4)-1,2,3,4-Me-4-NUPHOS)(en)] [Cl] (5a). Complexes 4 and 5a cleanly and quantitatively interconvert in a solvent-dependent equilibrium, and in THF 5a readily adds chloride to displace the eta(2)-interaction and re-form 4. A single-crystal X-ray structure determination of [RuCl(eta(4)-1,2,3,4-Me-4-NUPHOS)(en)][ClO4] (5b) confirmed that the diphosphine coordinates in an eta(4)-manner as a facial six-electron donor with the eta(2)-coordinated double bond occupying the site trans to chloride. The eta(4)-bonding mode can be readily identified by the unusually high-field chemical shift associated with the phosphorus atom adjacent to the eta(2)-coordinated double bond. Complexes 2a, 2b, 4, and 5a form catalysts that are active for transfer hydrogenation of a range of ketones. In all cases, catalysts formed from precursors 2a and 2b are markedly more active than those formed from 4 and 5a.