Structural Properties, Order-Disorder Phenomena and Phase Stability of Orotic Acid Crystal Forms

Orotic acid (OTA) is reported to exist in the anhydrous (AH), monohydrate (Hy1) and dimethylsulfoxide monosolvate (SDMSO) forms. In this study we investigate the (de)hydration/desolvation behavior, aiming at an understanding of the elusive structural features of anhydrous OTA by a combination of experimental and computational techniques, namely, thermal analytical methods, gravimetric moisture (de)sorption studies, water activity measurements, X-ray powder diffraction, spectroscopy (vibrational, solid-state NMR), crystal energy landscape and chemical shift calculations. The Hy1 is a highly stable hydrate, which dissociates above 135°C and loses only a small part of the water when stored over desiccants (25°C) for more than one year. In Hy1, orotic acid and water molecules are linked by strong hydrogen bonds in nearly perfectly planar arranged stacked layers. The layers are spaced by 3.1 Å and not linked via hydrogen-bonds. Upon dehydration the X-ray powder diffraction and solid-state NMR peaks become broader indicating some disorder in the anhydrous form. The Hy1 stacking reflection (122) is maintained, suggesting that the OTA molecules are still arranged in stacked layers in the dehydration product. Desolvation of SDMSO, a non-layer structure, results in the same AH phase as observed upon dehydrating Hy1. Depending on the desolvation conditions different levels of order-disorder of layers present in anhydrous OTA are observed, which is also suggested by the computed low energy crystal structures. These structures provide models for stacking faults as intergrowth of different layers is possible. The variability in anhydrate crystals is of practical concern as it affects the moisture dependent stability of AH with respect to hydration

Accretion variability of Herbig Ae/Be stars observed by X-Shooter. HD 31648 and HD 163296

This work presents X-Shooter/VLT spectra of the prototypical, isolated Herbig Ae stars HD 31648 (MWC 480) and HD 163296 over five epochs separated by timescales ranging from days to months. Each spectrum spans over a wide wavelength range covering from 310 to 2475 nm. We have monitored the continuum excess in the Balmer region of the spectra and the luminosity of twelve ultraviolet, optical and near infrared spectral lines that are commonly used as accretion tracers for T Tauri stars. The observed strengths of the Balmer excesses have been reproduced from a magnetospheric accretion shock model, providing a mean mass accretion rate of 1.11 x 10^-7 and 4.50 x 10^-7 Msun yr^-1 for HD 31648 and HD 163296, respectively. Accretion rate variations are observed, being more pronounced for HD 31648 (up to 0.5 dex). However, from the comparison with previous results it is found that the accretion rate of HD 163296 has increased by more than 1 dex, on a timescale of ~ 15 years. Averaged accretion luminosities derived from the Balmer excess are consistent with the ones inferred from the empirical calibrations with the emission line luminosities, indicating that those can be extrapolated to HAe stars. In spite of that, the accretion rate variations do not generally coincide with those estimated from the line luminosities, suggesting that the empirical calibrations are not useful to accurately quantify accretion rate variability.Comment: 14 pages, 7 Figures, Accepted in Ap

TRUNK AND UPPER EXTREMITY KINEMATICS OF THE OFFSIDE FOREHAND POLO SWING IN PROFESSIONAL POLO ATHLETES

The purpose of this study was to examine trunk (flexion, lateral flexion, rotation) and upper extremity (shoulder horizontal abduction, elevation, and elbow flexion) kinematics of the offside forehand polo swing between professional male and female polo athletes. Kinematic data were collected while participants performed the offside forehand polo swing on a stationary wooden horse. The polo swing was analyzed at three events: take away (TA), top of back swing (TOB) and ball contact (BC). Results revealed significant differences in trunk and upper extremity kinematics between the male and female professional polo athlete. Further investigation into these mechanical differences, along with the influence of live play and performance variables are necessitated to understand mechanics for the most powerful swin

Panchromatic Imaging of a Transitional Disk: The Disk of GM Aur in Optical and FUV Scattered Light

We have imaged GM Aur with HST, detected its disk in scattered light at 1400A and 1650A, and compared these with observations at 3300A, 5550A, 1.1 microns, and 1.6 microns. The scattered light increases at shorter wavelengths. The radial surface brightness profile at 3300A shows no evidence of the 24AU radius cavity that has been previously observed in sub-mm observations. Comparison with dust grain opacity models indicates the surface of the entire disk is populated with sub-micron grains. We have compiled an SED from 0.1 microns to 1 mm, and used it to constrain a model of the star+disk system that includes the sub-mm cavity using the Monte Carlo Radiative Transfer code by Barbara Whitney. The best-fit model image indicates that the cavity should be detectable in the F330W bandpass if the cavity has been cleared of both large and small dust grains, but we do not detect it. The lack of an observed cavity can be explained by the presence of sub-microns grains interior to the sub-mm cavity wall. We suggest one explanation for this which could be due to a planet of mass <9 Jupiter masses interior to 24 AU. A unique cylindrical structure is detected in the FUV data from the Advanced Camera for Surveys/Solar Blind Channel. It is aligned along the system semi-minor axis, but does not resemble an accretion-driven jet. The structure is limb-brightened and extends 190 +/- 35 AU above the disk midplane. The inner radius of the limb-brightening is 40 +/- 10 AU, just beyond the sub-millimeter cavity wall.Comment: 40 pages, 11 figures, 4 tables, accepted to Ap

High-resolution Br γ spectro-interferometry of the transitional Herbig Ae/Be star HD 100546: a Keplerian gaseous disc inside the inner rim

We present spatially and spectrally resolved Br γ emission around the planet-hosting, transitional Herbig Ae/Be star HD 100546. Aiming to gain insight into the physical origin of the line in possible relation to accretion processes, we carried out Br γ spectro-interferometry using AMBER/VLTI from three different baselines achieving spatial and spectral resolutions of 2–4 mas and 12 000. The Br γ visibility is larger than that of the continuum for all baselines. Differential phases reveal a shift between the photocentre of the Br γ line – displaced ∼0.6 mas (0.06 au at 100 pc) NE from the star – and that of the K-band continuum emission – displaced ∼0.3 mas NE from the star. The photocentres of the redshifted and blueshifted components of the Br γ line are located NW and SE from the photocentre of the peak line emission, respectively. Moreover, the photocentre of the fastest velocity bins within the spectral line tends to be closer to that of the peak emission than the photocentre of the slowest velocity bins. Our results are consistent with a Br γ-emitting region inside the dust inner rim ( ≲ 0.25 au) and extending very close to the central star, with a Keplerian, disc-like structure rotating counter-clockwise, and most probably flared (∼25°). Even though the main contribution to the Br γ line does not come from gas magnetically channelled on to the star, accretion on to HD 100546 could be magnetospheric, implying a mass accretion rate of a few 10−7 M⊙ yr−1. This value indicates that the observed gas has to be replenished on time-scales of a few months to years, perhaps by planet-induced flows from the outer to the inner disc as has been reported for similar systems

Thermal and in situ x-ray diffraction analysis of a dimorphic co-crystal 1:1 caffeine-glutaric acid

YesSpurred by the enormous interest in co-crystals from the pharmaceutical industry, many novel co-crystals of active pharmaceutical ingredients have been discovered in recent years and this has in turn led to an increasing number of reports on polymorphs of co-crystals. Hence, a thorough characterization and understanding of co-crystal polymorphs is a valuable step during drug development. The purpose of this study is to perform in situ structural analysis and to determine thermodynamic stability of a dimorphic co-crystal system, 1:1 caffeine-glutaric acid (CA-GA, Forms I and II). We performed thermal and structural characterizations by differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), hot-stage microscopy (HSM), slurry and in situ variable temperature X-ray diffraction (VTXRD). For completeness, we have also re-determined crystal structures of CA-GA Forms I and II at 180 K using single crystal X-ray diffraction. Our results revealed that Form II is stable and Form I is metastable at ambient conditions. Further, the results suggest that the dimorphs are enantiotropically related and the transition temperature is estimated to be 79 Celcius degrees.This work was supported by Science and Engineering Research Council of A*STAR (Agency for Science, Technology and Research), Singapore

Synthesis of atropisomeric phosphino-triazoles and their corresponding gold(i) complexes

The synthesis of atropisomeric phoshino-triazoles is disclosed. It was found that the introduction of a phosphine functionality onto the 5-position of a 1,2,3-triazole ring could be highly restrictive towards the rotation around a triazole-aryl bond. VT NMR and chiral HPLC studies demonstrated that rotation was restricted even at high temperatures. Gold(I) chloride complexes of single-enantiomer phosphines were prepared and again demonstrated to be conformationally stable

Independent estimation of T\u3csup\u3e*\u3c/sup\u3e2 for water and fat for improved accuracy of fat quantification

Noninvasive biomarkers of intracellular accumulation of fat within the liver (hepatic steatosis) are urgently needed for detection and quantitative grading of nonalcoholic fatty liver disease, the most common cause of chronic liver disease in the United States. Accurate quantification of fat with MRI is challenging due the presence of several confounding factors, including T z.ast;2 decay. The specific purpose of this work is to quantify the impact of Tz.ast;2decay and develop a multiexponential Tz.ast;2 correction method for improved accuracy of fat quantification, relaxing assumptions made by previous T z.ast;2 correction methods. A modified Gauss-Newton algorithm is used to estimate the Tz.ast;2 for water and fat independently. Improved quantification of fat is demonstrated, with independent estimation of Tz.ast;2 for water and fat using phantom experiments. The tradeoffs in algorithm stability and accuracy between multiexponential and single exponential techniques are discussed. © 2010 Wiley-Liss, Inc