A Universal Descriptor for the Entropy of Adsorbed Molecules in Confined Spaces

Confinement of hydrocarbons in nanoscale pockets and pores provides tunable capability for controlling molecules in catalysts, sorbents, and membranes for reaction and separation applications. While computation of the enthalpic interactions of hydrocarbons in confined spaces has improved, understanding and predicting the entropy of confined molecules remains a challenge. Here we show, using a set of nine aluminosilicate zeolite frameworks with broad variation in pore and cavity structure, that the entropy of adsorption can be predicted as a linear combination of rotational and translational entropy. The extent of entropy lost upon adsorption is predicted using only a single material descriptor, the occupiable volume (Vocc). Predictive capability of confined molecular entropy permits an understanding of the relation with adsorption enthalpy, the ability to computationally screen microporous materials, and an understanding of the role of confinement on the kinetics of molecules in confined spaces

Strain Modulated Electronic Properties of Ge Nanowires - A First Principles Study

We used density-functional theory based first principles simulations to study the effects of uniaxial strain and quantum confinement on the electronic properties of germanium nanowires along the [110] direction, such as the energy gap and the effective masses of the electron and hole. The diameters of the nanowires being studied are up to 50 {\AA}. As shown in our calculations, the Ge [110] nanowires possess a direct band gap, in contrast to the nature of an indirect band gap in bulk. We discovered that the band gap and the effective masses of charge carries can be modulated by applying uniaxial strain to the nanowires. These strain modulations are size-dependent. For a smaller wire (~ 12 {\AA}), the band gap is almost a linear function of strain; compressive strain increases the gap while tensile strain reduces the gap. For a larger wire (20 {\AA} - 50 {\AA}), the variation of the band gap with respect to strain shows nearly parabolic behavior: compressive strain beyond -1% also reduces the gap. In addition, our studies showed that strain affects effective masses of the electron and hole very differently. The effective mass of the hole increases with a tensile strain while the effective mass of the electron increases with a compressive strain. Our results suggested both strain and size can be used to tune the band structures of nanowires, which may help in design of future nano-electronic devices. We also discussed our results by applying the tight-binding model.Comment: 1 table, 8 figure

A cryogenic liquid-mirror telescope on the moon to study the early universe

We have studied the feasibility and scientific potential of zenith observing liquid mirror telescopes having 20 to 100 m diameters located on the moon. They would carry out deep infrared surveys to study the distant universe and follow up discoveries made with the 6 m James Webb Space Telescope (JWST), with more detailed images and spectroscopic studies. They could detect objects 100 times fainter than JWST, observing the first, high-red shift stars in the early universe and their assembly into galaxies. We explored the scientific opportunities, key technologies and optimum location of such telescopes. We have demonstrated critical technologies. For example, the primary mirror would necessitate a high-reflectivity liquid that does not evaporate in the lunar vacuum and remains liquid at less than 100K: We have made a crucial demonstration by successfully coating an ionic liquid that has negligible vapor pressure. We also successfully experimented with a liquid mirror spinning on a superconducting bearing, as will be needed for the cryogenic, vacuum environment of the telescope. We have investigated issues related to lunar locations, concluding that locations within a few km of a pole are ideal for deep sky cover and long integration times. We have located ridges and crater rims within 0.5 degrees of the North Pole that are illuminated for at least some sun angles during lunar winter, providing power and temperature control. We also have identified potential problems, like lunar dust. Issues raised by our preliminary study demand additional in-depth analyses. These issues must be fully examined as part of a scientific debate we hope to start with the present article.Comment: 35 pages, 11 figures. To appear in Astrophysical Journal June 20 200

Steam-Induced Coarsening of Single-Unit-Cell MFI Zeolite Nanosheets and Its Effect on External Surface Brønsted Acid Catalysis.

Commonly used methods to assess crystallinity, micro-/mesoporosity, Brønsted acid site density and distribution (in micro- vs. mesopores), and catalytic activity suggest nearly invariant structure and function for aluminosilicate zeolite MFI two-dimensional nanosheets before and after superheated steam treatment. Yet, pronounced reaction rate decrease for benzyl alcohol alkylation with mesitylene, a reaction that cannot take place in the zeolite micropores, is observed. Transmission electron microscopy images reveal pronounced changes in nanosheet thickness, aspect ratio and roughness indicating that nanosheet coarsening and the associated changes in the external (mesoporous) surface structure are responsible for the changes in the external surface catalytic activity. Superheated steam treatment of hierarchical zeolites can be used to alter nanosheet morphology and regulate external surface catalytic activity while preserving micro- and mesoporosity, and micropore reaction rates

Expansion of the Parkinson disease-associated SNCA-Rep1 allele upregulates human alpha-synuclein in transgenic mouse brain.

Alpha-synuclein (SNCA) gene has been implicated in the development of rare forms of familial Parkinson disease (PD). Recently, it was shown that an increase in SNCA copy numbers leads to elevated levels of wild-type SNCA-mRNA and protein and is sufficient to cause early-onset, familial PD. A critical question concerning the molecular pathogenesis of PD is what contributory role, if any, is played by the SNCA gene in sporadic PD. The expansion of SNCA-Rep1, an upstream, polymorphic microsatellite of the SNCA gene, is associated with elevated risk for sporadic PD. However, whether SNCA-Rep1 is the causal variant and the underlying mechanism with which its effect is mediated by remained elusive. We report here the effects of three distinct SNCA-Rep1 variants in the brains of 72 mice transgenic for the entire human SNCA locus. Human SNCA-mRNA and protein levels were increased 1.7- and 1.25-fold, respectively, in homozygotes for the expanded, PD risk-conferring allele compared with homozygotes for the shorter, protective allele. When adjusting for the total SNCA-protein concentration (endogenous mouse and transgenic human) expressed in each brain, the expanded risk allele contributed 2.6-fold more to the SNCA steady-state than the shorter allele. Furthermore, targeted deletion of Rep1 resulted in the lowest human SNCA-mRNA and protein concentrations in murine brain. In contrast, the Rep1 effect was not observed in blood lysates from the same mice. These results demonstrate that Rep1 regulates human SNCA expression by enhancing its transcription in the adult nervous system and suggest that homozygosity for the expanded Rep1 allele may mimic locus multiplication, thereby elevating PD risk

Characterization of Silica-Based and Borate-Based, Titanium-Containing Bioactive Glasses for Coating Metallic Implants

Bioactive glasses have found applications in diverse fields, including orthopedics and dentistry, where they have been utilized for the fixation of bone and teeth and as scaffolds for drug delivery. The present work outlines the characterization of two novel titanium-containing glass series, one silica-based and one borate-based. For the silica-based series, titanium is added at the expense of silicon dioxide whereas for the borate-based series, it is added at the expense of boron oxide as confirmed by Energy Dispersive Spectroscopy. Amorphous structures are obtained for silica-based glass at 15 mol% TiO2 and for borate-based glasses at 0 mol% and 5 mol%, with low crystal peak intensities exhibited within the remaining glasses. MAS-NMR proves the role of P2O5 as a network modifier for both glass series by evidencing only Q0 structures (and Q1 structures for the silica-based glasses with crystal structures), whereas FTIR proves that Ti acted as a network modifier in the glass as there was an absence of peaks assignable to titanium bonding. This implies that the two glass series will degrade in-situ and release ions at the site of implantation. Additionally, thermal data sourced from these glasses indicate processing windows which make them suitable for enameling onto implants, with the borate-based series exhibiting greater processing windows over the silica-based series, hence making the borate glasses more suitable for coating metallic implants compared to their silica-based counterparts

An experimental testbed for the study of hydrodynamic issues in supernovae

More than a decade after the explosion of supernova 1987A, unresolved discrepancies still remain in attempts to numerically simulate the mixing processes initiated by the passage of a very strong shock through the layered structure of the progenitor star. Numerically computed velocities of the radioactive 56Ni56Ni and 56Co,56Co, produced by shock-induced explosive burning within the silicon layer, for example, are still more than 50% too low as compared with the measured velocities. To resolve such discrepancies between observation and simulation, an experimental testbed has been designed on the Omega Laser for the study of hydrodynamic issues of importance to supernovae (SNe). In this paper, results are presented from a series of scaled laboratory experiments designed to isolate and explore several issues in the hydrodynamics of supernova explosions. The results of the experiments are compared with numerical simulations and are generally found to be in reasonable agreement. © 2001 American Institute of Physics.Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/69986/2/PHPAEN-8-5-2446-1.pd