An Unusual Hydrogen Migration/C−H Activation Reaction with Group 3 Metals

A novel hydrogen migration from the phenyl ring to the pyridine ring of an yttrium pyridyl complex supported by a 1,1′-ferrocene diamide ligand is reported. Density functional theory calculations were instrumental in probing the mechanism for this transformation

Reaction of Group III Biheterocyclic Complexes

Group III alkyl complexes supported by a ferrocene diamide ligand (1,1′-fc(NSitBuMe_2)_2) have been found to be reactive toward aromatic N-heterocycles such as 1-methylimidazole and pyridines. These reactions were investigated experimentally and computationally. An initial C−H activation event is followed by a coupling reaction to form biheterocyclic complexes, in which one of the rings is dearomatized. In the case of 1-methylimidazole, the biheterocyclic compound could not be isolated and further led to an imidazole ring-opened product; in the case of pyridines, it transformed into an isomer with extended conjugation of double bonds. Mechanisms for both reactions are proposed on the basis of experimental and computational results. DFT calculations were also used to show that an energetically accessible pathway for the ring-opening of pyridines exists

The Earth System Grid Federation: Delivering globally accessible petascale data for CMIP5

The fifth Coupled Model Intercomparison Project (CMIP5) will involve the global production and analysis of petabytes of data. The Program for Climate Model Diagnosis and Intercomparison (PCMDI), with responsibility for archival for CMIP5, has established the global “Earth System Grid Federation” (ESGF) of data producers and data archives to support CMIP5. ESGF will provide a set of globally synchronised views of globally distributed data – including some large cache replicants which will be persisted for (at least) decades. Here we describe the archive requirements and key aspects of the resulting architecture. ESGF will stress international networks, as well as the data archives themselves – but significantly less than would have been the case of a centralised archive. Developing and deploying the ESGF has exploited good will and best efforts, but future developments are likely to require more formalised architecture and management

Extrapulmonary Tuberculosis among Somalis in Minnesota1

To analyze extrapulmonary tuberculosis in Somalis living in Minnesota, we reviewed surveillance and public health case management data on tuberculosis cases in ethnic Somalis in Minnesota from 1993 through 2003. The presence of these recent immigrants substantially affects the local epidemiology and clinical manifestation of tuberculosis

miRNA profiles as a predictor of chemoresponsiveness in Wilms' tumor blastema.

The current SIOP treatment protocol for Wilms' tumor involves pre-operative chemotherapy followed by nephrectomy. Not all patients benefit equally from such chemotherapy. The aim of this study was to generate a miRNA profile of chemo resistant blastemal cells in high risk Wilms' tumors which might serve as predictive markers of therapeutic response at the pre-treatment biopsy stage. We have shown here that unsupervised hierarchical clustering of genome-wide miRNA expression profiles can clearly separate intermediate risk tumors from high risk tumors. A total of 29 miRNAs were significantly differentially expressed between post-treatment intermediate risk and high risk groups, including miRNAs that have been previously linked to chemo resistance in other cancer types. Furthermore, 7 of these 29 miRNAs were already at the pre-treatment biopsy stage differentially expressed between cases ultimately deemed intermediate risk compared to high risk. These miRNA alterations include down-regulation in high risk cases of miR-193a.5p, miR-27a and the up-regulation of miR-483.5p, miR-628.5p, miR-590.5p, miR-302a and miR-367. The demonstration of such miRNA markers at the pre-treatment biopsy stage could permit stratification of patients to more tailored treatment regimens

Astrometry and Photometry for ≈\approx1000 L, T, and Y Dwarfs from the UKIRT Hemisphere Survey

We present positions, proper motions, and near-infrared photometry for 966 known objects with spectral types later than M observed as part of the the UKIRT Hemisphere Survey (UHS). We augment the photometry and astrometry from UHS with information from Gaia DR3, Pan-STARRS DR2, and CatWISE 2020 to produce a database of homogeneous photometry and astrometry for this sample. The multi-epoch survey strategy of UHS allows us to determine proper motions for most sources, with a median proper motion uncertainty of $\sim$3.6 mas yr$^{-1}$. Our UHS proper motion measurements are generally in good agreement with those from Gaia DR3, Pan-STARRS, and CatWISE 2020, with UHS proper motions typically more precise than those from CatWISE 2020 and Pan-STARRS but not Gaia DR3. We critically analyze publicly available spectra for 406 members of this sample and provide updated near-infrared spectral types for $\sim$100 objects. We determine typical colors as a function of spectral type and provide absolute magnitude vs. spectral type relations for UHS $J$- and $K$-band photometry. Using newly determined proper motions, we highlight several objects of interest, such as objects with large tangential velocities, widely separated co-moving companions, and potential members of young nearby associations.Comment: Accepted to A