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Description

The catalytic hydrogenation of nitroarenes is an environmentally benign technology for the production of anilines, which are key intermediates for manufacturing agrochemicals, pharmaceuticals and dyes. Most of the precious metal catalysts, however, suffer from low chemoselectivity when one or more reducible groups are present in a nitroarene molecule. Herein we

The catalytic hydrogenation of nitroarenes is an environmentally benign technology for the production of anilines, which are key intermediates for manufacturing agrochemicals, pharmaceuticals and dyes. Most of the precious metal catalysts, however, suffer from low chemoselectivity when one or more reducible groups are present in a nitroarene molecule. Herein we report FeOx-supported platinum single-atom and pseudo-single-atom structures as highly active, chemoselective and reusable catalysts for hydrogenation of a variety of substituted nitroarenes. For hydrogenation of 3-nitrostyrene, the catalyst yields a TOF of ~1,500 h-1, 20-fold higher than the best result reported in literature, and a selectivity to 3-aminostyrene close to 99%, the best ever achieved over platinum group metals. The superior performance can be attributed to the presence of positively charged platinum centres and the absence of Pt–Pt metallic bonding, both of which favour the preferential adsorption of nitro groups.

ContributorsWei, Haisheng (Author) / Liu, Xiaoyan (Author) / Wang, Aiqin (Author) / Zhang, Leilei (Author) / Qiao, Botao (Author) / Yang, Xiaofeng (Author) / Huang, Yanqiang (Author) / Miao, Shu (Author) / Liu, Jingyue (Author) / Zhang, Tao (Author) / College of Liberal Arts and Sciences (Contributor)
Created2014-12-03
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Description

The Mars Science Laboratory landed in Gale crater on Mars in August 2012, and the Curiosity rover then began field studies on its drive toward Mount Sharp, a central peak made of ancient sediments. CheMin is one of ten instruments on or inside the rover, all designed to provide detailed

The Mars Science Laboratory landed in Gale crater on Mars in August 2012, and the Curiosity rover then began field studies on its drive toward Mount Sharp, a central peak made of ancient sediments. CheMin is one of ten instruments on or inside the rover, all designed to provide detailed information on the rocks, soils and atmosphere in this region. CheMin is a miniaturized X-ray diffraction/X-ray fluorescence (XRD/XRF) instrument that uses transmission geometry with an energy-discriminating CCD detector. CheMin uses onboard standards for XRD and XRF calibration, and beryl:quartz mixtures constitute the primary XRD standards. Four samples have been analysed by CheMin, namely a soil sample, two samples drilled from mudstones and a sample drilled from a sandstone. Rietveld and full-pattern analysis of the XRD data reveal a complex mineralogy, with contributions from parent igneous rocks, amorphous components and several minerals relating to aqueous alteration. In particular, the mudstone samples all contain one or more phyllosilicates consistent with alteration in liquid water. In addition to quantitative mineralogy, Rietveld refinements also provide unit-cell parameters for the major phases, which can be used to infer the chemical compositions of individual minerals and, by difference, the composition of the amorphous component.

ContributorsBish, David (Author) / Blake, David (Author) / Vaniman, David (Author) / Sarrazin, Philippe (Author) / Bristow, Thomas (Author) / Achilles, Cherie (Author) / Dera, Przemyslaw (Author) / Chipera, Steve (Author) / Crisp, Joy (Author) / Downs, R. T. (Author) / Farmer, Jack (Author) / Gailhanou, Marc (Author) / Ming, Doug (Author) / Morookian, John Michael (Author) / Morris, Richard (Author) / Morrison, Shaunna (Author) / Rampe, Elizabeth (Author) / Treiman, Allan (Author) / Yen, Albert (Author) / College of Liberal Arts and Sciences (Contributor)
Created2014-10-21
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Description

Agassiz’s desert tortoise (Gopherus agassizii) is a long-lived species native to the Mojave Desert and is listed as threatened under the US Endangered Species Act. To aid conservation efforts for preserving the genetic diversity of this species, we generated a whole genome reference sequence with an annotation based on dee

Agassiz’s desert tortoise (Gopherus agassizii) is a long-lived species native to the Mojave Desert and is listed as threatened under the US Endangered Species Act. To aid conservation efforts for preserving the genetic diversity of this species, we generated a whole genome reference sequence with an annotation based on deep transcriptome sequences of adult skeletal muscle, lung, brain, and blood. The draft genome assembly for G. agassizii has a scaffold N50 length of 252 kbp and a total length of 2.4 Gbp. Genome annotation reveals 20,172 protein-coding genes in the G. agassizii assembly, and that gene structure is more similar to chicken than other turtles. We provide a series of comparative analyses demonstrating (1) that turtles are among the slowest-evolving genome-enabled reptiles, (2) amino acid changes in genes controlling desert tortoise traits such as shell development, longevity and osmoregulation, and (3) fixed variants across the Gopherus species complex in genes related to desert adaptations, including circadian rhythm and innate immune response. This G. agassizii genome reference and annotation is the first such resource for any tortoise, and will serve as a foundation for future analysis of the genetic basis of adaptations to the desert environment, allow for investigation into genomic factors affecting tortoise health, disease and longevity, and serve as a valuable resource for additional studies in this species complex.

ContributorsTollis, Marc (Author) / DeNardo, Dale (Author) / Cornelius, John (Author) / Dolby, Greer (Author) / Edwards, Taylor (Author) / Henen, Brian T. (Author) / Karl, Alice E. (Author) / Murphy, Robert W. (Author) / Kusumi, Kenro (Author) / College of Liberal Arts and Sciences (Contributor)
Created2017-05-31
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Description

Insects communicate with pheromones using sensitive antennal sensilla. Although trace amounts of pheromones can be detected by many insects, context-dependent increased costs of high sensitivity might lead to plasticity in sensillum responsiveness. We have functionally characterized basiconic sensilla of the ant Harpegnathos saltator for responses to general odors in comparison

Insects communicate with pheromones using sensitive antennal sensilla. Although trace amounts of pheromones can be detected by many insects, context-dependent increased costs of high sensitivity might lead to plasticity in sensillum responsiveness. We have functionally characterized basiconic sensilla of the ant Harpegnathos saltator for responses to general odors in comparison to cuticular hydrocarbons which can act as fertility signals emitted by the principal reproductive(s) of a colony to inhibit reproduction by worker colony members. When released from inhibition workers may become reproductive gamergates. We observed plasticity in olfactory sensitivity after transition to reproductive status with significant reductions in electrophysiological responses to several long-chained cuticular hydrocarbons. Although gamergates lived on average five times longer than non-reproductive workers, the shift to reproductive status rather than age differences matched the pattern of changes in olfactory sensitivity. Decreasing sensillum responsiveness to cuticular hydrocarbons could potentially reduce mutually inhibitory or self-inhibitory effects on gamergate reproduction.

ContributorsGhaninia Tabarestani, Majid (Author) / Haight, Kevin (Author) / Berger, Shelley L. (Author) / Reinberg, Danny (Author) / Zwiebel, Laurence J. (Author) / Ray, Anandasankar (Author) / Liebig, Juergen (Author) / College of Liberal Arts and Sciences (Contributor)
Created2017-06-16
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Description

Plastids are supported by a wide range of proteins encoded within the nucleus and imported from the cytoplasm. These plastid-targeted proteins may originate from the endosymbiont, the host, or other sources entirely. Here, we identify and characterise 770 plastid-targeted proteins that are conserved across the ochrophytes, a major group of

Plastids are supported by a wide range of proteins encoded within the nucleus and imported from the cytoplasm. These plastid-targeted proteins may originate from the endosymbiont, the host, or other sources entirely. Here, we identify and characterise 770 plastid-targeted proteins that are conserved across the ochrophytes, a major group of algae including diatoms, pelagophytes and kelps, that possess plastids derived from red algae. We show that the ancestral ochrophyte plastid proteome was an evolutionary chimera, with 25% of its phylogenetically tractable nucleus-encoded proteins deriving from green algae. We additionally show that functional mixing of host and plastid proteomes, such as through dual-targeting, is an ancestral feature of plastid evolution. Finally, we detect a clear phylogenetic signal from one ochrophyte subgroup, the lineage containing pelagophytes and dictyochophytes, in plastid-targeted proteins from another major algal lineage, the haptophytes. This may represent a possible serial endosymbiosis event deep in eukaryotic evolutionary history.

ContributorsDorrell, Richard G. (Author) / Gile, Gillian (Author) / McCallum, Giselle (Author) / Meheust, Raphael (Author) / Bapteste, Eric P. (Author) / Klinger, Christen M. (Author) / Brillet-Gueguen, Loraine (Author) / Freeman, Katalina (Author) / Richter, Daniel J. (Author) / Bowler, Chris (Author) / College of Liberal Arts and Sciences (Contributor)
Created2017-05-12
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Description

The Smoothened receptor (SMO) belongs to the Class Frizzled of the G protein-coupled receptor (GPCR) superfamily, constituting a key component of the Hedgehog signalling pathway. Here we report the crystal structure of the multi-domain human SMO, bound and stabilized by a designed tool ligand TC114, using an X-ray free-electron laser

The Smoothened receptor (SMO) belongs to the Class Frizzled of the G protein-coupled receptor (GPCR) superfamily, constituting a key component of the Hedgehog signalling pathway. Here we report the crystal structure of the multi-domain human SMO, bound and stabilized by a designed tool ligand TC114, using an X-ray free-electron laser source at 2.9 Å. The structure reveals a precise arrangement of three distinct domains: a seven-transmembrane helices domain (TMD), a hinge domain (HD) and an intact extracellular cysteine-rich domain (CRD). This architecture enables allosteric interactions between the domains that are important for ligand recognition and receptor activation. By combining the structural data, molecular dynamics simulation, and hydrogen-deuterium-exchange analysis, we demonstrate that transmembrane helix VI, extracellular loop 3 and the HD play a central role in transmitting the signal employing a unique GPCR activation mechanism, distinct from other multi-domain GPCRs.

ContributorsZhang, Xianjun (Author) / Zhao, Fei (Author) / Wu, Yiran (Author) / Yang, Jun (Author) / Han, Gye Won (Author) / Zhao, Suwen (Author) / Ishchenko, Andrii (Author) / Ye, Lintao (Author) / Lin, Xi (Author) / Ding, Kang (Author) / Dharmarajan, Venkatasubramaniam (Author) / Griffin, Patrick R. (Author) / Gati, Cornelius (Author) / Nelson, Garrett (Author) / Hunter, Mark S. (Author) / Hanson, Michael A. (Author) / Cherezov, Vadim (Author) / Stevens, Raymond C. (Author) / Tan, Wenfu (Author) / Tao, Houchao (Author) / Xu, Fei (Author) / College of Liberal Arts and Sciences (Contributor)
Created2017-05-17
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Description

Nursing behavior is notoriously difficult to study in arboreal primates, particularly when offspring suckle inconspicuously in nests. Orangutans have the most prolonged nursing period of any mammal, with the cessation of suckling (weaning) estimated to occur at 6 to 8 years of age in the wild. Milk consumption is hypothesized

Nursing behavior is notoriously difficult to study in arboreal primates, particularly when offspring suckle inconspicuously in nests. Orangutans have the most prolonged nursing period of any mammal, with the cessation of suckling (weaning) estimated to occur at 6 to 8 years of age in the wild. Milk consumption is hypothesized to be relatively constant over this period, but direct evidence is limited. We previously demonstrated that trace element analysis of bioavailable elements from milk, such as barium, provides accurate estimates of early-life diet transitions and developmental stress when coupled with growth lines in the teeth of humans and nonhuman primates. We provide the first detailed nursing histories of wild, unprovisioned orangutans (Pongo abelii and Pongo pygmaeus) using chemical and histological analyses. Laser ablation inductively coupled plasma mass spectrometry was used to determine barium distributions across the teeth of four wild-shot individuals aged from postnatal biological rhythms. Barium levels rose during the first year of life in all individuals and began to decline shortly after, consistent with behavioral observations of intensive nursing followed by solid food supplementation. Subsequent barium levels show large sustained fluctuations on an approximately annual basis. These patterns appear to be due to cycles of varying milk consumption, continuing until death in an 8.8-year-old Sumatran individual. A female Bornean orangutan ceased suckling at 8.1 years of age. These individuals exceed the maximum weaning age reported for any nonhuman primate. Orangutan nursing may reflect cycles of infant demand that relate to fluctuating resource availability.

ContributorsSmith, Tanya M. (Author) / Austin, Christine (Author) / Hinde, Katie (Author) / Vogel, Erin R. (Author) / Arora, Manish (Author) / College of Liberal Arts and Sciences (Contributor)
Created2017-05-17
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Description

Course-based undergraduate research experiences (CUREs) meet national recommendations for integrating research experiences into life science curricula. As such, CUREs have grown in popularity and many research studies have focused on student outcomes from CUREs. Institutional change literature highlights that understanding faculty is also key to new pedagogies succeeding. To begin

Course-based undergraduate research experiences (CUREs) meet national recommendations for integrating research experiences into life science curricula. As such, CUREs have grown in popularity and many research studies have focused on student outcomes from CUREs. Institutional change literature highlights that understanding faculty is also key to new pedagogies succeeding. To begin to understand faculty perspectives on CUREs, we conducted semi-structured interviews with 61 faculty who teach CUREs regarding why they teach CUREs, what the outcomes are, and how they would discuss a CURE with a colleague. Using grounded theory, participant responses were coded and categorized as tangible or intangible, related to both student and faculty-centered themes. We found that intangible themes were prevalent, and that there were significant differences in the emphasis on tangible themes for faculty who have developed their own independent CUREs when compared with faculty who implement pre-developed, national CUREs. We focus our results on the similarities and differences among the perspectives of faculty who teach these two different CURE types and explore trends among all participants. The results of this work highlight the need for considering a multi-dimensional framework to understand, promote, and successfully implement CUREs.

ContributorsShortlidge, Erin (Author) / Bangera, Gita (Author) / Brownell, Sara (Author) / College of Liberal Arts and Sciences (Contributor)
Created2017-05-26
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Description

A mixed design was created using text and game-like multimedia to instruct in the content of physics. The study assessed which variables predicted learning gains after a 1-h lesson on the electric field. The three manipulated variables were: (1) level of embodiment; (2) level of active generativity; and (3) presence

A mixed design was created using text and game-like multimedia to instruct in the content of physics. The study assessed which variables predicted learning gains after a 1-h lesson on the electric field. The three manipulated variables were: (1) level of embodiment; (2) level of active generativity; and (3) presence of story narrative. Two types of tests were administered: (1) a traditional text-based physics test answered with a keyboard; and (2) a more embodied, transfer test using the Wacom large tablet where learners could use gestures (long swipes) to create vectors and answers. The 166 participants were randomly assigned to four conditions: (1) symbols and text; (2) low embodied; (3) high embodied/active; or (4) high embodied/active with narrative. The last two conditions were active because the on-screen content could be manipulated with gross body gestures gathered via the Kinect sensor. Results demonstrated that the three groups that included embodiment learned significantly more than the symbols and text group on the traditional keyboard post-test. When knowledge was assessed with the Wacom tablet format that facilitated gestures, the two active gesture-based groups scored significantly higher. In addition, engagement scores were significantly higher for the two active embodied groups. The Wacom results suggest test sensitivity issues; the more embodied test revealed greater gains in learning for the more embodied conditions. We recommend that as more embodied learning comes to the fore, more sensitive tests that incorporate gesture be used to accurately assess learning. The predicted differences in engagement and learning for the condition with the graphically rich story narrative were not supported. We hypothesize that a narrative effect for motivation and learning may be difficult to uncover in a lab experiment where participants are primarily motivated by course credit. Several design principles for mediated and embodied science education are proposed.

Created2017-05-24
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Description

This study explores the capabilities of the Coherent X-ray Imaging Instrument at the Linac Coherent Light Source to image small biological samples. The weak signal from small samples puts a significant demand on the experiment. Aerosolized Omono River virus particles of ∼40 nm in diameter were injected into the submicrometre X-ray

This study explores the capabilities of the Coherent X-ray Imaging Instrument at the Linac Coherent Light Source to image small biological samples. The weak signal from small samples puts a significant demand on the experiment. Aerosolized Omono River virus particles of ∼40 nm in diameter were injected into the submicrometre X-ray focus at a reduced pressure. Diffraction patterns were recorded on two area detectors. The statistical nature of the measurements from many individual particles provided information about the intensity profile of the X-ray beam, phase variations in the wavefront and the size distribution of the injected particles. The results point to a wider than expected size distribution (from ∼35 to ∼300 nm in diameter). This is likely to be owing to nonvolatile contaminants from larger droplets during aerosolization and droplet evaporation. The results suggest that the concentration of nonvolatile contaminants and the ratio between the volumes of the initial droplet and the sample particles is critical in such studies. The maximum beam intensity in the focus was found to be 1.9 × 1012 photons per µm2 per pulse. The full-width of the focus at half-maximum was estimated to be 500 nm (assuming 20% beamline transmission), and this width is larger than expected. Under these conditions, the diffraction signal from a sample-sized particle remained above the average background to a resolution of 4.25 nm. The results suggest that reducing the size of the initial droplets during aerosolization is necessary to bring small particles into the scope of detailed structural studies with X-ray lasers.

ContributorsDaurer, Benedikt J. (Author) / Okamoto, Kenta (Author) / Bielecki, Johan (Author) / Maia, Filipe R. N. C. (Author) / Muhlig, Kerstin (Author) / Seibert, M. Marvin (Author) / Hantke, Max F. (Author) / Nettelblad, Carl (Author) / Benner, W. Henry (Author) / Svenda, Martin (Author) / Timneanu, Nicusor (Author) / Ekeberg, Tomas (Author) / Loh, N. Duane (Author) / Pietrini, Alberto (Author) / Zani, Alessandro (Author) / Rath, Asawari D. (Author) / Westphal, Daniel (Author) / Kirian, Richard (Author) / Awel, Salah (Author) / Wiedorn, Max O. (Author) / van der Schot, Gijs (Author) / Carlsson, Gunilla H. (Author) / Hasse, Dirk (Author) / Sellberg, Jonas A. (Author) / Barty, Anton (Author) / Andreasson, Jakob (Author) / Boutet, Sebastien (Author) / Williams, Garth (Author) / Koglin, Jason (Author) / Andersson, Inger (Author) / Hajdu, Janos (Author) / Larsson, Daniel S. D. (Author) / College of Liberal Arts and Sciences (Contributor)
Created2017-04-07