NMR Chemical Shifts of Trace Impurities: Common Laboratory Solvents, Organics, and Gases in Deuterated Solvents Relevant to the Organometallic Chemist

Tables of ^1H and ^(13)C NMR chemical shifts have been compiled for common organic compounds often used as reagents or found as products or contaminants in deuterated organic solvents. Building upon the work of Gottlieb, Kotlyar, and Nudelman in the Journal of Organic Chemistry, signals for common impurities are now reported in additional NMR solvents (tetrahydrofuran-d_8, toluene-d_8, dichloromethane-d_2, chlorobenzene-d_5, and 2,2,2-trifluoroethanol-d_3) which are frequently used in organometallic laboratories. Chemical shifts for other organics which are often used as reagents or internal standards or are found as products in organometallic chemistry are also reported for all the listed solvents

Nano-Imprinted Thin Films of Reactive, Azlactone-Containing Polymers: Combining Methods for the Topographic Patterning of Cell Substrates with Opportunities for Facile Post-Fabrication Chemical Functionalization

Approaches to the fabrication of surfaces that combine methods for the topographic patterning of soft materials with opportunities for facile, post-fabrication chemical functionalization could contribute significantly to advances in biotechnology and a broad range of other areas. Here, we report methods that can be used to introduce well defined nano- and microscale topographic features to thin films of reactive polymers containing azlactone functionality using nanoimprint lithography (NIL). We demonstrate that NIL can be used to imprint topographic patterns into thin films of poly(2-vinyl-4,4- dimethylazlactone) and a copolymer of methyl methacrylate and 2-vinyl- 4,4-dimethylazlactone using silicon masters having patterns of grooves and ridges ranging in width from 400 nm to 2μm, demonstrating the potential f this method to transfer patterns to films of these reactive polymers over a range of feature sizes and densities. We demonstrate further that the azlactone functionality of these polymers survives temperatures and pressures associated with NIL, and that topographically patterned films can be readily functionalized post-fabrication by treatment of surface-accessible azlactone functionality with small molecules and polymers containing primary amines. The results of experiments in which NIH-3T3 cells were seeded onto films imprinted with lined patterns having a pitch of 4 demonstrated that cells attach and proliferate on these azlactone-containing films and that they align in the direction of the imprinted pattern. Finally, we demonstrate that the treatment of these materials with amine-functionalized poly(ethylene glycol) (PEG) can be used to create regions of topographically patterned films that prevent cell adhesion. The results of this study suggest approaches to the functionalization of topographically patterned surfaces with a broad range of chemical functionality (e.g., peptides, proteins, carbohydrates, etc.) of biotechnological interest. The ability to manipulate and define both the physical topography and chemical functionality of these reactive materials could provide opportunities to investigate the combined effects of substrate topography and chemical functionality on cell behavior and may also be useful in a broad range of other applications

Optical to near-infrared transmission spectrum of the warm sub-Saturn HAT-P-12b

We present the transmission spectrum of HAT-P-12b through a joint analysis of data obtained from the Hubble Space Telescope Space Telescope Imaging Spectrograph (STIS) and Wide Field Camera 3 (WFC3) and Spitzer, covering the wavelength range 0.3-5.0 $\mu$m. We detect a muted water vapor absorption feature at 1.4 $\mu$m attenuated by clouds, as well as a Rayleigh scattering slope in the optical indicative of small particles. We interpret the transmission spectrum using both the state-of-the-art atmospheric retrieval code SCARLET and the aerosol microphysics model CARMA. These models indicate that the atmosphere of HAT-P-12b is consistent with a broad range of metallicities between several tens to a few hundred times solar, a roughly solar C/O ratio, and moderately efficient vertical mixing. Cloud models that include condensate clouds do not readily generate the sub-micron particles necessary to reproduce the observed Rayleigh scattering slope, while models that incorporate photochemical hazes composed of soot or tholins are able to match the full transmission spectrum. From a complementary analysis of secondary eclipses by Spitzer, we obtain measured depths of $0.042\%\pm0.013\%$ and $0.045\%\pm0.018\%$ at 3.6 and 4.5 $\mu$m, respectively, which are consistent with a blackbody temperature of $890^{+60}_{-70}$ K and indicate efficient day-night heat recirculation. HAT-P-12b joins the growing number of well-characterized warm planets that underscore the importance of clouds and hazes in our understanding of exoplanet atmospheres.Comment: 25 pages, 19 figures, accepted for publication in AJ, updated with proof correction

The disruption of Celf6, a gene identified by translational profiling of serotonergic neurons, results in autism-related behaviors

The immense molecular diversity of neurons challenges our ability to understand the genetic and cellular etiology of neuropsychiatric disorders. Leveraging knowledge from neurobiology may help parse the genetic complexity: identifying genes important for a circuit that mediates a particular symptom of a disease may help identify polymorphisms that contribute to risk for the disease as a whole. The serotonergic system has long been suspected in disorders that have symptoms of repetitive behaviors and resistance to change, including autism. We generated a bacTRAP mouse line to permit translational profiling of serotonergic neurons. From this, we identified several thousand serotonergic-cell expressed transcripts, of which 174 were highly enriched, including all known markers of these cells. Analysis of common variants near the corresponding genes in the AGRE collection implicated the RNA binding protein CELF6 in autism risk. Screening for rare variants in CELF6 identified an inherited premature stop codon in one of the probands. Subsequent disruption of Celf6 in mice resulted in animals exhibiting resistance to change and decreased ultrasonic vocalization as well as abnormal levels of serotonin in the brain. This work provides a reproducible and accurate method to profile serotonergic neurons under a variety of conditions and suggests a novel paradigm for gaining information on the etiology of psychiatric disorders

Atomic-Scale Mapping and Quantification of Local Ruddlesden-Popper Phase Variations

The Ruddlesden-Popper (An+1BnO3n+1) compounds are highly tunable materials whose functional properties can be dramatically impacted by their structural phase n. The negligible differences in formation energies for different n can produce local structural variations arising from small stoichiometric deviations. Here, we present a Python analysis platform to detect, measure, and quantify the presence of different n-phases based on atomic-resolution scanning transmission electron microscopy (STEM) images. We employ image phase analysis to identify horizontal Ruddlesden-Popper faults within the lattice images and quantify the local structure. Our semiautomated technique considers effects of finite projection thickness, limited fields of view, and lateral sampling rates. This method retains real-space distribution of layer variations allowing for spatial mapping of local n-phases to enable quantification of intergrowth occurrence and qualitative description of their distribution suitable for a wide range of layered materials

Communication: Analytic continuation of the virial series through the critical point using parametric approximants

The mathematical structure imposed by the thermodynamic critical point motivates an approximant that synthesizes two theoretically sound equations of state: the parametric and the virial. The former is constructed to describe the critical region, incorporating all scaling laws; the latter is an expansion about zero density, developed from molecular considerations. The approximant is shown to yield an equation of state capable of accurately describing properties over a large portion of the thermodynamic parameter space, far greater than that covered by each treatment alone

Quantum Gate Fidelity in Terms of Choi Matrices

We provide new results for computing and comparing the quantum gate fidelity of quantum channels via their Choi matrices. We extend recent work that showed there exist non-dual pairs of quantum channels with equal gate fidelity by providing an explicit characterization of all such channels. We use our characterization to show that when the dimension is 2 (or 3, under slightly stronger hypotheses), the gate fidelity of two channels is equal if and only if their difference equals the difference of some unital map and its dual -- a fact that has been shown to be false when the dimension is 4 or larger. We also present a formula for the minimum gate fidelity of a channel in terms of a well-studied norm on a compression of its Choi matrix. As a consequence, several new ways of bounding and approximating the minimum gate fidelity follow, including a simple semidefinite program to compute it for qubit channels.Comment: Minor corrections and updates since v1. 16 pages, 1 figur

The Evolution of the Stratopause During the 2006 Major Warming: Satellite Data and Assimilated Meteorological Analyses

Microwave Limb Sounder and Sounding of the Atmosphere with Broadband Emission Radiometry data show the polar stratopause, usually higher than and separated from that at midlatitudes, dropping from <55-60 to near 30 km, and cooling dramatically in January 2006 during a major stratospheric sudden warming (SSW). After a nearly isothermal period, a cool stratopause reforms near 75 km in early February, then drops to <55 km and warms. The stratopause is separated in longitude as well as latitude, with lowest temperatures in the transition regions between higher and lower stratopauses. Operational assimilated meteorological analyses, which are not constrained by data at stratopause altitude, do not capture a secondary temperature maximum that overlies the stratopause or the very high stratopause that reforms after the SSW; they underestimate the stratopause altitude variation during the SSW. High-quality daily satellite temperature measurements are invaluable in improving our understanding of stratopause evolution and its representation in models and assimilation systems