End-to-End Assessment of a Large Aperture Segmented Ultraviolet Optical Infrared (UVOIR) Telescope Architecture

Key challenges of a future large aperture, segmented Ultraviolet Optical Infrared (UVOIR) Telescope capable of performing a spectroscopic survey of hundreds of Exoplanets will be sufficient stability to achieve 10^-10 contrast measurements and sufficient throughput and sensitivity for high yield Exo-Earth spectroscopic detection. Our team has collectively assessed an optimized end to end architecture including a high throughput coronagraph capable of working with a segmented telescope, a cost-effective and heritage based stable segmented telescope, a control architecture that minimizes the amount of new technologies, and an Exo-Earth yield assessment to evaluate potential performance. These efforts are combined through integrated modeling, coronagraph evaluations, and Exo-Earth yield calculations to assess the potential performance of the selected architecture. In addition, we discusses the scalability of this architecture to larger apertures and the technological tall poles to enabling it

Effects of chloride ions in acid-catalyzed biomass dehydration reactions in polar aprotic solvents

The use of polar aprotic solvents in acid-catalyzed biomass conversion reactions can lead to improved reaction rates and selectivities. We show that further increases in catalyst performance in polar aprotic solvents can be achieved through the addition of inorganic salts, specifically chlorides. Reaction kinetics studies of the Brønsted acid-catalyzed dehydration of fructose to hydroxymethylfurfural (HMF) show that the use of catalytic concentrations of chloride salts leads to a 10-fold increase in reactivity. Furthermore, increased HMF yields can be achieved using polar aprotic solvents mixed with chlorides. Ab initio molecular dynamics simulations (AIMD) show that highly localized negative charge on Cl− allows the chloride anion to more readily approach and stabilize the oxocarbenium ion that forms and the deprotonation transition state. High concentrations of polar aprotic solvents form local hydrophilic environments near the reactive hydroxyl group which stabilize both the proton and chloride anions and promote the dehydration of fructose

Reconstruction of the Talkeetna intraoceanic arc of Alaska through thermobarometry

Author Posting. © American Geophysical Union, 2008. This article is posted here by permission of American Geophysical Union for personal use, not for redistribution. The definitive version was published in Journal of Geophysical Research 113 (2008): B03204, doi:10.1029/2007JB005208.The Talkeetna arc is one of two intraoceanic arcs where much of the section from the upper mantle through the volcanic carapace is well exposed. We reconstruct the vertical section of the Talkeetna arc by determining the (re)crystallization pressures at various structural levels. The thermobarometry shows that the tonalites and quartz diorites intruded at ∼5–9 km into a volcanic section estimated from stratigraphy to be 7 km thick. The shallowest, Tazlina and Barnette, gabbros crystallized at ∼17–24 km; the Klanelneechena Klippe crystallized at ∼24–26 km; and the base of the arc crystallized at ∼35 km depth. The arc had a volcanic:plutonic ratio of ∼1:3–1:4. However, many or most of the felsic plutonic rocks may represent crystallized liquids rather than cumulates so that the liquid:cumulate ratio might be 1:2 or larger. The current 5- to 7-km structural thickness of the plutonic section of the arc is ∼15–30% of the original 23- to 28-km thickness. The bulk composition of the original Talkeetna arc section was ∼51–58 wt % SiO2.Funded by NSF EAR-9910899

Technology Development for the Advanced Technology Large Aperture Space Telescope (ATLAST) as a Candidate Large UV-Optical-Infrared (LUVOIR) Surveyor

The Advanced Technology Large Aperture Space Telescope (ATLAST) team has identified five key technologies to enable candidate architectures for the future large-aperture ultraviolet/optical/infrared (LUVOIR) space observatory envisioned by the NASA Astrophysics 30-year roadmap, Enduring Quests, Daring Visions. The science goals of ATLAST address a broad range of astrophysical questions from early galaxy and star formation to the processes that contributed to the formation of life on Earth, combining general astrophysics with direct-imaging and spectroscopy of habitable exoplanets. The key technologies are: internal coronagraphs, starshades (or external occulters), ultra-stable large-aperture telescopes, detectors, and mirror coatings. Selected technology performance goals include: 1x1010 raw contrast at an inner working angle of 35 milli-arcseconds, wavefront error stability on the order of 10 pm RMS per wavefront control step, autonomous on-board sensing & control, and zero-read-noise single-photon detectors spanning the exoplanet science bandpass between 400 nm and 1.8 m. Development of these technologies will provide significant advances over current and planned observatories in terms of sensitivity, angular resolution, stability, and high-contrast imaging. The science goals of ATLAST are presented and flowed down to top-level telescope and instrument performance requirements in the context of a reference architecture: a 10-meter-class, segmented aperture telescope operating at room temperature (~290 K) at the sun-Earth Lagrange-2 point. For each technology area, we define best estimates of required capabilities, current state-of-the-art performance, and current Technology Readiness Level (TRL) - thus identifying the current technology gap. We report on current, planned, or recommended efforts to develop each technology to TRL 5

U-Pb dating of interspersed gabbroic magmatism and hydrothermal metamorphism during lower crustal accretion, Vema lithospheric section, Mid-Atlantic Ridge

New U/Pb analyses of zircon and xenotime constrain the timing of magmatism, magmatic assimilation, and hydrothermal metamorphism during formation of the lower crust at the Mid-Atlantic Ridge. The studied sample is an altered gabbro from the Vema lithospheric section (11°N). Primary gabbroic minerals have been almost completely replaced by multiple hydrothermal overprints: cummingtonitic amphibole and albite formed during high-temperature hydration reactions and are overgrown first by kerolite and then prehnite and chlorite. In a previous study, clear inclusion-free zircons from the sample yielded Th-corrected 206Pb/238U dates of 13.528 ± 0.101 to 13.353 ± 0.057 Ma. Ti concentrations, reported here, zoning patterns and calculated Th/U of the dated grains are consistent with these zircons having grown during igneous crystallization. To determine the timing of hydrothermal metamorphism, we dated a second population of zircons, with ubiquitous <1–20 µm chlorite inclusions, and xenotimes that postdate formation of metamorphic albite. The textures and inclusions of the inclusion-rich zircons suggest that they formed by coupled dissolution-reprecipitation of metastable igneous zircon during or following hydrothermal metamorphism. Th-corrected 206Pb/238U dates for the inclusion-rich zircons range from 13.598 ± 0.012 to 13.503 ± 0.018 Ma and predate crystallization of all but one of the inclusion-free zircons, suggesting that the inclusion-rich zircons were assimilated from older hydrothermally altered wall rocks. The xenotime dates are sensitive to the Th correction applied, but even using a maximum correction, 206Pb/238U dates range from 13.341 ± 0.162 to 12.993 ± 0.055 Ma and postdate crystallization of both the inclusion-rich zircons and inclusion-free igneous zircons, reflecting a second hydrothermal event. The data provide evidence for alternating magmatism and hydrothermal metamorphism at or near the ridge axis during accretion of the lower crust at a ridge-transform intersection and suggest that hydrothermally altered crust was assimilated into younger gabbroic magmas. The results of this study show that high-precision U-Pb dating is a powerful method for studying the timing of magmatic and hydrothermal processes at mid-ocean ridges

Insight into the photodynamics of photostabilizer molecules

Solar exposure of avobenzone, one of the most widely used commercial UVA filters on the market, is known to cause significant degradation. This finding has fueled research into developing photostabilizer molecules. In an effort to provide insight into their stand-alone photoprotection properties, the excited state dynamics of the photostabilizer, 3-(3,4,5-trimethoxybenzylidene) pentane-2,4-dione (TMBP), and its phenolic derivative, 3-(4-hydroxy-3,5-dimethoxybenzylidene) pentane-2,4-dione (DMBP), were studied with ultrafast transient absorption spectroscopy. Solutions of TMPB and DMBP in ethanol and in an industry-standard emollient, as well as TMBP and DMBP deposited on synthetic skin mimic, were investigated. These experiments were allied with computational methods to aid interpretation of the experimental data. Upon photoexcitation, these photostabilizers repopulate the electronic ground state via nonradiative decay within a few picoseconds involving a twisted intramolecular charge transfer configuration in the excited state, followed by internal conversion and subsequent vibrational cooling in the ground state. This finding implies that, aside from acting as a photostabilizer to certain UV filters, TMBP and DMBP may offer additional photoprotection in a sunscreen formulation as a stand-alone UV filter. Finally, TMBP and DMBP could also find applications as molecular photon-to-heat converters

A Future Large-Aperture UVOIR Space Observatory: Key Technologies and Capabilities

We present the key technologies and capabilities that will enable a future, large-aperture ultravioletopticalinfrared (UVOIR) space observatory. These include starlight suppression systems, vibration isolation and control systems, lightweight mirror segments, detector systems, and mirror coatings. These capabilities will provide major advances over current and near-future observatories for sensitivity, angular resolution, and starlight suppression. The goals adopted in our study for the starlight suppression system are 10-10 contrast with an inner working angle of 20 milliarcsec and broad bandpass. We estimate that a vibration and isolation control system that achieves a total system vibration isolation of 140 dB for a vibration-isolated mass of 5000 kg is required to achieve the high wavefront error stability needed for exoplanet coronagraphy. Technology challenges for lightweight mirror segments include diffraction-limited optical quality and high wavefront error stability as well as low cost, low mass, and rapid fabrication. Key challenges for the detector systems include visible-blind, high quantum efficiency UV arrays, photon counting visible and NIR arrays for coronagraphic spectroscopy and starlight wavefront sensing and control, and detectors with deep full wells with low persistence and radiation tolerance to enable transit imaging and spectroscopy at all wavelengths. Finally, mirror coatings with high reflectivity ( 90), high uniformity ( 1) and low polarization ( 1) that are scalable to large diameter mirror substrates will be essential for ensuring that both high throughput UV observations and high contrast observations can be performed by the same observatory

Intermediate to felsic middle crust in the accreted Talkeetna arc, the Alaska Peninsula and Kodiak Island, Alaska : an analogue for low-velocity middle crust in modern arcs

Author Posting. © American Geophysical Union, 2010. This article is posted here by permission of American Geophysical Union for personal use, not for redistribution. The definitive version was published in Tectonics 29 (2010): TC3001, doi:10.1029/2009TC002541.Seismic profiles of several modern arcs have identified thick, low-velocity midcrustal layers (Vp = 6.0–6.5 km/s) that are interpreted to represent intermediate to felsic plutonic crust. The presence of this silicic crust is surprising given the mafic composition of most primitive mantle melts and could have important implications for the chemical evolution and bulk composition of arcs. However, direct studies of the middle crust are limited by the restricted plutonic exposures in modern arcs. The accreted Talkeetna arc, south central Alaska, exposes a faulted crustal section from residual subarc mantle to subaerial volcanic rocks of a Jurassic intraoceanic arc and is an ideal place to study the intrusive middle crust. Previous research on the arc, which has provided insight into a range of arc processes, has principally focused on western exposures of the arc in the Chugach Mountains. We present new U-Pb zircon dates, radiogenic isotope data, and whole-rock geochemical analyses that provide the first high-precision data on large intermediate to felsic plutonic exposures on Kodiak Island and the Alaska Peninsula. A single chemical abrasion–thermal ionization mass spectrometry analysis from the Afognak pluton yielded an age of 212.87 ± 0.19 Ma, indicating that the plutonic exposures on Kodiak Island represent the earliest preserved record of Talkeetna arc magmatism. Nine new dates from the extensive Jurassic batholith on the Alaska Peninsula range from 183.5 to 164.1 Ma and require a northward shift in the Talkeetna arc magmatic axis following initial emplacement of the Kodiak plutons, paralleling the development of arc magmatism in the Chugach and Talkeetna mountains. Radiogenic isotope data from the Alaska Peninsula and the Kodiak archipelago range from $\varepsilon$Nd(t) = 5.2 to 9.0 and 87Sr/86Srint = 0.703515 to 0.703947 and are similar to age-corrected data from modern intraoceanic arcs, suggesting that the evolved Alaska Peninsula plutons formed by extensive differentiation of arc basalts with little or no involvement of preexisting crustal material. The whole-rock geochemical data and calculated seismic velocities suggest that the Alaska Peninsula represents an analogue for the low-velocity middle crust observed in modern arcs. The continuous temporal record and extensive exposure of intermediate to felsic plutonic rocks in the Talkeetna arc indicate that evolved magmas are generated by repetitive or steady state processes and play a fundamental role in the growth and evolution of intraoceanic arcs

Direct structural observation of ultrafast photoisomerization dynamics in sinapate esters

Sinapate esters have been extensively studied for their potential application in ‘nature-inspired’ photoprotection. There is general consensus that the relaxation mechanism of sinapate esters following photoexcitation with ultraviolet radiation is mediated by geometric isomerization. This has been largely inferred through indirect studies involving transient electronic absorption spectroscopy in conjunction with steady-state spectroscopies. However, to-date, there is no direct experimental evidence tracking the formation of the photoisomer in real-time. Using transient vibrational absorption spectroscopy, we report on the direct structural changes that occur upon photoexcitation, resulting in the photoisomer formation. Our mechanistic analysis predicts that, from the photoprepared ππ* state, internal conversion takes place through a conical intersection (CI) near the geometry of the initial isomer. Our calculations suggest that different CI topographies at relevant points on the seam of intersection may influence the isomerization yield. Altogether, we provide compelling evidence suggesting that a sinapate ester’s geometric isomerization can be a more complex dynamical process than originally thought

Genetic risk and a primary role for cell-mediated immune mechanisms in multiple sclerosis.

Multiple sclerosis is a common disease of the central nervous system in which the interplay between inflammatory and neurodegenerative processes typically results in intermittent neurological disturbance followed by progressive accumulation of disability. Epidemiological studies have shown that genetic factors are primarily responsible for the substantially increased frequency of the disease seen in the relatives of affected individuals, and systematic attempts to identify linkage in multiplex families have confirmed that variation within the major histocompatibility complex (MHC) exerts the greatest individual effect on risk. Modestly powered genome-wide association studies (GWAS) have enabled more than 20 additional risk loci to be identified and have shown that multiple variants exerting modest individual effects have a key role in disease susceptibility. Most of the genetic architecture underlying susceptibility to the disease remains to be defined and is anticipated to require the analysis of sample sizes that are beyond the numbers currently available to individual research groups. In a collaborative GWAS involving 9,772 cases of European descent collected by 23 research groups working in 15 different countries, we have replicated almost all of the previously suggested associations and identified at least a further 29 novel susceptibility loci. Within the MHC we have refined the identity of the HLA-DRB1 risk alleles and confirmed that variation in the HLA-A gene underlies the independent protective effect attributable to the class I region. Immunologically relevant genes are significantly overrepresented among those mapping close to the identified loci and particularly implicate T-helper-cell differentiation in the pathogenesis of multiple sclerosis