The Absolute Configuration for Inthomycin C: Revision of Previously Published Work with a Reinstatement of the (3R)-Configuration for (-)-Inthomycin C

Abstract Image

Stereochemical evidence is presented to demonstrate that (−)-inthomycin C has (3R)- and not (3S)-stereochemistry. Careful reappraisal of the previously published work2−5 now indicates that the Hatakeyama, Hale, Ryu, and Taylor teams all have synthesized (−)-(3R)-inthomycin C. The newly measured [α]D of pure (−)-(3R)-inthomycin C (98% ee) is −7.9 (c 0.33, CHCl3) and not −41.5 (c 0.1, CHCl3) as was previously reported in 2012.

Absolute Magnitudes of Pan-STARRS PS1 Asteroids

Absolute magnitude (H) of an asteroid is a fundamental parameter describing the size and the apparent brightness of the body. Because of its surface shape, properties and changing illumination, the brightness changes with the geometry and is described by the phase function governed by the slope parameter (G). Although many years have been spent on detailed observations of individual asteroids to provide H and G, vast majority of minor planets have H based on assumed G and due to the input photometry from multiple sources the errors of these values are unknown. We compute H of ~ 180 000 and G of few thousands asteroids observed with the Pan-STARRS PS1 telescope in well defined photometric systems. The mean photometric error is 0.04 mag. Because on average there are only 7 detections per asteroid in our sample, we employed a Monte Carlo (MC) technique to generate clones simulating all possible rotation periods, amplitudes and colors of detected asteroids. Known asteroid colors were taken from the SDSS database. We used debiased spin and amplitude distributions dependent on size, spectral class distributions of asteroids dependent on semi-major axis and starting values of G from previous works. H and G (G12 respectively) were derived by phase functions by Bowell et al. (1989) and Muinonen et al. (2010). We confirmed that there is a positive systematic offset between H based on PS1 asteroids and Minor Planet Center database up to -0.3 mag peaking at 14. Similar offset was first mentioned in the analysis of SDSS asteroids and was believed to be solved by weighting and normalizing magnitudes by observatory codes. MC shows that there is only a negligible difference between Bowell's and Muinonen's solution of H. However, Muinonen's phase function provides smaller errors on H. We also derived G and G12 for thousands of asteroids. For known spectral classes, slope parameters agree with the previous work in general, however, the standard deviation of G in our sample is twice as larger, most likely due to sparse phase curve sampling. In the near future we plan to complete the H and G determination for all PS1 asteroids (500,000) and publish H and G values online. This work was supported by NASA grant No. NNX12AR65G.

Absolute Magnitudes of Pan-STARRS 1 Asteroids

It is well known that the absolute magnitudes (H) in the MPCORB and ASTORB orbital element catalogs suffer from a systematic offset. Juric at al. (2002) found 0.4 mag offset in the SDSS data and detailed light curve studies of WISE asteroids by Pravec et al. (2012) revealed size-dependent offsets of up to 0.5 mag. The offsets are thought to be caused by systematic errors introduced by earlier surveys using different photometric catalogs and filters. The next generation asteroid surveys provide an order of magnitude more asteroids and well-defined and calibrated magnitudes. The Pan-STARRS 1 telescope (PS1) has observed hundreds of thousands asteroids, submitted more than 2 million detections to the Minor Planet Center (MPC) and discovered almost 300 NEOs since the beginning of operations in late 2010. We transformed the observed apparent magnitudes of PS1-detected asteroids from the gP1,rP1,iP1,yP1,zP1 and wP1-bands into Johnson photometric system by assuming the mean S and C-type asteroid color (Fitzsimmons 2011 - personal communication, Schlafly et al. 2012, Magnier et al. 2012 - in preparation) and calculated the absolute magnitude (H) in the V-band and its uncertainty (Bowell et al., 1989) for more than 200,000 known asteroids having on average 6.7 detections per object. The H error with respect to the MPCORB catalog revealed a mean offset of -0.49+0.30 mag in good agreement with published values. We will also discuss the statistical and systematical errors in H and slope parameter G.

Absolute magnitudes and slope parameters of Pan-STARRS PS1 asteroids -preliminary results

We present the study of absolute magnitude (H) and slope parameter (G) of 170,000 asteroids observed by the Pan-STARRS1 telescope during the period of 15 months within its 3-year all-sky survey mission. The exquisite photometry with photometric errors below 0.04 mag and well-defined filter and photometric system allowed to derive H and G with statistical and systematic errors. Our new approach lies in the Monte Carlo technique simulating rotation periods, amplitudes, and colors, and deriving most-likely H, G and their systematic errors. Comparison of H_M by Muinonen's phase function (Muinonen et al., 2010) with the Minor Planet Center database revealed a negative offset of 0.22±0.29 meaning that Pan-STARRS1 asteroids are fainter. We showed that the absolute magnitude derived by Muinonen's function is systematically larger on average by 0.14±0.29 and by 0.30±0.16 when assuming fixed slope parameter (G=0.15, G_{12}=0.53) than Bowell's absolute magnitude (Bowell et al., 1989). We also derived slope parameters of asteroids of known spectral types and showed a good agreement with the previous studies within the derived uncertainties. However, our systematic errors on G and G_{12} are significantly larger than in previous work, which is caused by poor temporal and phase coverage of vast majority of the detected asteroids. This disadvantage will vanish when full survey data will be available and ongoing extended and enhanced mission will provide new data.

Crime, Punishment and Article 3 ECHR: Puzzles and Prospects of Applying an Absolute Right in a Penal Context

Article 3 of the European Convention on Human Rights (ECHR), which provides that ‘No one shall be subjected to torture or to inhuman or degrading treatment or punishment’, is considered to enshrine an absolute right. Yet it contains an under-explored element: inhuman and degrading punishment. While torture has been the subject of extensive academic commentary, and inhuman and degrading treatment has been examined to some extent, the prohibition of inhuman and degrading punishment has not been explored in significant depth, in spite of its considerable potential to alter the penal landscape.

This paper elucidates the key doctrinal elements of inhuman and degrading punishment ‘and treatment associated with it’, in the words of the European Court of Human Rights (ECtHR). It addresses a number of ‘puzzles’ or problems which arise in applying the absolute right enshrined in Article 3 of the ECHR to sentencing and imprisonment, clarifies ECtHR doctrine and highlights some of its key implications. Bringing a theoretically informed understanding to bear on the application of Article 3 of the ECHR in a penal context, the paper provides clarity and coherence to a complex and crucial intersection between human rights and penology.

Absolute magnitudes and slope parameters for 250,000 asteroids observed by Pan-STARRS PS1 - preliminary results

We present the results of a Monte Carlo technique to calculate the absolute magnitudes (H) and slope parameters (G) of about 240,000 asteroids observed by the Pan-STARRS1 telescope during the first 15 months of its 3-year all-sky survey mission. The system's exquisite photometry with photometric errors asteroids rotation period, amplitude and color to derive the most-likely H and G, but its major advantage is in estimating realistic statistical+systematic uncertainties and errors on each parameter. The method was confirmed by comparison with the well-established and accurate results for about 500 asteroids provided by Pravec et al. (2012) and then applied to determining H and G for the Pan-STARRS1 asteroids using both the Muinonen et al. (2010) and Bowell et al. (1989) phase functions. Our results confirm the bias in MPC photometry discovered by ( Jurić et al., 2002).

Interactions between pyrazole derived enantiomers and Chiralcel OJ: Prediction of enantiomer absolute configurations and elution order by molecular dynamics simulations

The separation of enantiomers and confirmation of their absolute configurations is significant in the development of chiral drugs. The interactions between the enantiomers of chiral pyrazole derivative and polysaccharide-based chiral stationary phase cellulose tris(4-methylbenzoate) (Chiralcel OJ) in seven solvents and under different temperature were studied using molecular dynamics simulations. The results show that solvent effect has remarkable influence on the interactions. Structure analysis discloses that the different interactions between two isomers and chiral stationary phase are dependent on the nature of solvents, which may invert the elution order. The computational method in the present study can be used to predict the elution order and the absolute configurations of enantiomers in HPLC separations and therefore would be valuable in development of chiral drugs.

Absolute cross sections for dissociative electron attachment to HCCCN

New absolute cross sections for dissociative electron attachment to HCCCN (cyanoacetylene or propiolonitrile) in the range of 0-10 eV electron energy are presented here, which have been determined from a new analysis of previously reported data (Graupner et al 2006 New J. Phys. 8 117). The highest cross sections are observed for the formation of CN^- at 5.3 eV and CCCN^- at 5.1 eV; approximately 0.06 Ų and 0.05 Ų respectively. As part of the re-analysis, it was necessary to determine absolute cross sections for electron-impact ionization of HCCCN with the binary-encounter Bethe method. These electron-impact ionization absolute cross sections for HCCCN are also presented here; the maximum value was found to be ∼6.6 Ų at ∼80 eV.