Solid State NMR Characterization of Complex Metal Hydrides systems for Hydrogen Storage Applications

Solid state NMR is widely applied in studies of solid state chemistries for hydrogen storage reactions. Use of ^(11)B MAS NMR in studies of metal borohydrides (BH_4) is mainly focused, revisiting the issue of dodecaborane formation and observation of ^(11)B{^1H} Nuclear Overhauser Effect

A method for the estimation of p-mode parameters from averaged solar oscillation power spectra

A new fitting methodology is presented which is equally well suited for the estimation of low-, medium-, and high-degree mode parameters from $m$-averaged solar oscillation power spectra of widely differing spectral resolution. This method, which we call the "Windowed, MuLTiple-Peak, averaged spectrum", or WMLTP Method, constructs a theoretical profile by convolving the weighted sum of the profiles of the modes appearing in the fitting box with the power spectrum of the window function of the observing run using weights from a leakage matrix that takes into account both observational and physical effects, such as the distortion of modes by solar latitudinal differential rotation. We demonstrate that the WMLTP Method makes substantial improvements in the inferences of the properties of the solar oscillations in comparison with a previous method that employed a single profile to represent each spectral peak. We also present an inversion for the internal solar structure which is based upon 6,366 modes that we have computed using the WMLTP method on the 66-day long 2010 SOHO/MDI Dynamics Run. To improve both the numerical stability and reliability of the inversion we developed a new procedure for the identification and correction of outliers in a frequency data set. We present evidence for a pronounced departure of the sound speed in the outer half of the solar convection zone and in the subsurface shear layer from the radial sound speed profile contained in Model~S of Christensen-Dalsgaard and his collaborators that existed in the rising phase of Solar Cycle~24 during mid-2010

LiSc(BH_4)_4 as a Hydrogen Storage Material: Multinuclear High-Resolution Solid-State NMR and First-Principles Density Functional Theory Studies

A lithium salt of anionic scandium tetraborohydride complex, LiSc(BH_4)_4, was studied both experimentally and theoretically as a potential hydrogen storage medium. Ball milling mixtures of LiBH_4 and ScCl_3 produced LiCl and a unique crystalline hydride, which has been unequivocally identified via multinuclear solid-state nuclear magnetic resonance (NMR) to be LiSc(BH_4)_4. Under the present reaction conditions, there was no evidence for the formation of binary Sc(BH_4)_3. These observations are in agreement with our first-principles calculations of the relative stabilities of these phases. A tetragonal structure in space group I (#82) is predicted to be the lowest energy state for LiSc(BH_4)_4, which does not correspond to structures obtained to date on the crystalline ternary borohydride phases made by ball milling. Perhaps reaction conditions are resulting in formation of other polymorphs, which should be investigated in future studies via neutron scattering on deuterides. Hydrogen desorption while heating these Li−Sc−B−H materials up to 400 °C yielded only amorphous phases (besides the virtually unchanged LiCl) that were determined by NMR to be primarily ScB_2 and [B_(12)H_(12)]^(−2) anion containing (e.g., Li_2B_(12)H_(12)) along with residual LiBH_4. Reaction of a desorbed LiSc(BH_4)_4 + 4LiCl mixture (from 4LiBH_4/ScCl_3 sample) with hydrogen gas at 70 bar resulted only in an increase in the contents of Li_2B_(12)H_(12) and LiBH_4. Full reversibility to reform the LiSc(BH_4)_4 was not found. Overall, the Li−Sc−B−H system is not a favorable candidate for hydrogen storage applications

Study of aluminoborane compound AlB_4H_(11) for hydrogen storage

Aluminoborane compounds AlB_4H_(11), AlB_5H_(12), and AlB_6H_(13) were reported by Himpsl and Bond in 1981, but they have eluded the attention of the worldwide hydrogen storage research community for more than a quarter of a century. These aluminoborane compounds have very attractive properties for hydrogen storage: high hydrogen capacity (i.e., 13.5, 12.9, and 12.4 wt % H, respectively) and attractive hydrogen desorption temperature (i.e., AlB_4H_(11) decomposes at ~125 °C). We have synthesized AlB_4H_(11) and studied its thermal desorption behavior using temperature-programmed desorption with mass spectrometry, gas volumetric (Sieverts) measurement, infrared (IR) spectroscopy, and solid state nuclear magnetic resonance (NMR). Rehydrogenation of hydrogen-desorbed products was performed and encouraging evidence of at least partial reversibility for hydrogenation at relatively mild conditions is observed. Our chemical analysis indicates that the formula for the compound is closer to AlB_4H_(12) than AlB_4H_(11)

Rural Hospital Mergers Increased Between 2005 and 2016—What Did Those Hospitals Look Like?

The objective of this study is to determine whether key hospital-level financial and market characteristics are associated with whether rural hospitals merge. Hospital merger status was derived from proprietary Irving Levin Associates data for 2005 through 2016 and hospital-level characteristics from HCRIS, CMS Impact File Hospital Inpatient Prospective Payment System, Hospital MSA file, AHRF, and U.S. Census data for 2004 through 2016. A discrete-time hazard analysis using generalized estimating equations was used to determine whether factors were associated with merging between 2005 and 2016. Factors included measures of profitability, operational efficiency, capital structure, utilization, and market competitiveness. Between 2005 and 2016, 11% (n = 326) of rural hospitals were involved in at least one merger. Rural hospital mergers have increased in recent years, with more than two-thirds (n = 261) occurring after 2011. The types of rural hospitals that merged during the sample period differed from nonmerged rural hospitals. Rural hospitals with higher odds of merging were less profitable, for-profit, larger, and were less likely to be able to cover current debt. Additional factors associated with higher odds of merging were reporting older plant age, not providing obstetrics, being closer to the nearest large hospital, and not being in the West region. By quantifying the hazard of characteristics associated with whether rural hospitals merged between 2005 and 2016, these findings suggest it is possible to determine leading indicators of rural mergers. This work may serve as a foundation for future research to determine the impact of mergers on rural hospitals

Subcellular localization of MC4R with ADCY3 at neuronal primary cilia underlies a common pathway for genetic predisposition to obesity.

Most monogenic cases of obesity in humans have been linked to mutations in genes encoding members of the leptin-melanocortin pathway. Specifically, mutations in MC4R, the melanocortin-4 receptor gene, account for 3-5% of all severe obesity cases in humans1-3. Recently, ADCY3 (adenylyl cyclase 3) gene mutations have been implicated in obesity4,5. ADCY3 localizes to the primary cilia of neurons 6 , organelles that function as hubs for select signaling pathways. Mutations that disrupt the functions of primary cilia cause ciliopathies, rare recessive pleiotropic diseases in which obesity is a cardinal manifestation 7 . We demonstrate that MC4R colocalizes with ADCY3 at the primary cilia of a subset of hypothalamic neurons, that obesity-associated MC4R mutations impair ciliary localization and that inhibition of adenylyl cyclase signaling at the primary cilia of these neurons increases body weight. These data suggest that impaired signaling from the primary cilia of MC4R neurons is a common pathway underlying genetic causes of obesity in humans

Promoter analysis by saturation mutagenesis

Gene expression and regulation are mediated by DNA sequences, in most instances, directly upstream to the coding sequences by recruiting transcription factors, regulators, and a RNA polymerase in a spatially defined fashion. Few nucleotides within a promoter make contact with the bound proteins. The minimal set of nucleotides that can recruit a protein factor is called a cis-acting element. This article addresses a powerful mutagenesis strategy that can be employed to define cis-acting elements at a molecular level. Technical details including primer design, saturation mutagenesis, construction of promoter libraries, phenotypic analysis, data analysis, and interpretation are discussed