Phototauntomerism of o-nitrobenzyl compounds: o-quinonoid aci-nitro species studied by matrix isolation and DFT calculations

Photolyses of 2-nitrobenzyl methyl ether and 2-nitrotoluene with 254 nm light have been investigated in Ar and N2 matrices at 12 K, and have been found to give o-quinonoid aci-nitro species as the primary photoproducts, along with other products. The o-quinonoid species have UV absorptions at relatively long wavelengths (λmax at 385–430 nm) and undergo facile secondary photolysis when irradiated in these absorption bands. By means of this selective photolysis, fairly complete IR spectra of the o-quinonoids have been obtained. Comparison of the matrix IR spectra of these species with simulated spectra computed using density functional theory (DFT) has confirmed the identity of these reactive intermediates. Moreover, detailed analysis of the fit between the computed and experimental IR spectra has allowed the specific stereoisomers generated to be identified with reasonable confidence. Computations have also been made of the relative energies of the starting compounds, intermediate o-quinonoid isomers and the possible secondary products, together with the transition states connecting them. The results of these computations indicate that the observed stereoisomer of each of the o-quinonoid species cannot arise by photoinduced H-atom transfer followed by isomerizations on the electronic ground-state surfaces, since the energy barriers for reversion to starting compounds are substantially lower than those for the necessary isomerizations. It is therefore concluded that H-atom transfer and conformational interconversion occur in an electronic excited state

Could the Ultra Metal-poor Stars be Chemically Peculiar and Not Related to the First Stars?

Chemically peculiar stars define a class of stars that show unusual elemental abundances due to stellar photospheric effects and not due to natal variations. In this paper, we compare the elemental abundance patterns of the ultra metal-poor stars with metallicities [Fe/H] $\sim -5$ to those of a subclass of chemically peculiar stars. These include post-AGB stars, RV Tauri variable stars, and the Lambda Bootis stars, which range in mass, age, binarity, and evolutionary status, yet can have iron abundance determinations as low as [Fe/H] $\sim -5$. These chemical peculiarities are interpreted as due to the separation of gas and dust beyond the stellar surface, followed by the accretion of dust depleted-gas. Contrary to this, the elemental abundances in the ultra metal-poor stars are thought to represent yields of the most metal-poor supernova and, therefore, observationally constrain the earliest stages of chemical evolution in the Universe. The abundance of the elements in the photospheres of the ultra metal-poor stars appear to be related to the condensation temperature of that element; if so, then their CNO abundances suggest true metallicities of [X/H]~ -2 to -4, rather than their present metallicities of [Fe/H] < -5.Comment: Accepted for ApJ. 17 pages, 10 figure

Discovery of Reflection Nebulosity Around Five Vega-like Stars

Coronagraphic optical observations of six Vega-like stars reveal reflection nebulosities, five of which were previously unknown. The nebulosities illuminated by HD 4881, HD 23362, HD 23680, HD 26676, and HD 49662 resemble that of the Pleiades, indicating an interstellar origin for dust grains. The reflection nebulosity around HD 123160 has a double-arm morphology, but no disk-like feature is seen as close as 2.5 arcsec from the star in K-band adaptive optics data. We demonstrate that uniform density dust clouds surrounding HD 23362, HD 23680 and HD 123160 can account for the observed 12-100 micron spectral energy distributions. For HD 4881, HD 26676, and HD 49662 an additional emission source, such as from a circumstellar disk or non-equilibrium grain heating, is required to fit the 12-25 micron data. These results indicate that in some cases, particularly for Vega-like stars located beyond the Local Bubble (>100 pc), the dust responsible for excess thermal emission may originate from the interstellar medium rather than from a planetary debris system.Comment: The Astrophysical Journal, in press for March, 2002 (32 pages, 13 figures

Skin exposure promotes a Th2-dependent sensitization to peanut allergens

Sensitization to foods often occurs in infancy, without a known prior oral exposure, suggesting that alternative exposure routes contribute to food allergy. Here, we tested the hypothesis that peanut proteins activate innate immune pathways in the skin that promote sensitization. We exposed mice to peanut protein extract on undamaged areas of skin and observed that repeated topical exposure to peanut allergens led to sensitization and anaphylaxis upon rechallenge. In mice, this epicutaneous peanut exposure induced sensitization to the peanut components Ara h 1 and Ara h 2, which is also observed in human peanut allergy. Both crude peanut extract and Ara h 2 alone served as adjuvants, as both induced a bystander sensitization that was similar to that induced by the atopic dermatitisassociated staphylococcal enterotoxin B. In cultured human keratinocytes and in murine skin, peanut extract directly induced cytokine expression. Moreover, topical peanut extract application induced an alteration dependent on the IL-33 receptor ST2 in skin-draining DCs, resulting in Th2 cytokine production from T cells. Together, our data support the hypothesis that peanuts are allergenic due to inherent adjuvant activity and suggest that skin exposure to food allergens contributes to sensitization to foods in early life.The work was supported by NIH grants AI044236 (to H.A. Sampson and M.C. Berin), AI093577 (to M.C. Berin), and AI091655 (to K.M. Järvinen) and Environmental Protection Agency grant R834064 (to M.C. Berin). Clinical specimens were provided by the Jaffe Food Allergy Resource Initiative, funded by Food Allergy Research and Education.Peer Reviewe

Skin exposure promotes a Th2-dependent sensitization to peanut allergens

Sensitization to foods often occurs in infancy, without a known prior oral exposure, suggesting that alternative exposure routes contribute to food allergy. Here, we tested the hypothesis that peanut proteins activate innate immune pathways in the skin that promote sensitization. We exposed mice to peanut protein extract on undamaged areas of skin and observed that repeated topical exposure to peanut allergens led to sensitization and anaphylaxis upon rechallenge. In mice, this epicutaneous peanut exposure induced sensitization to the peanut components Ara h 1 and Ara h 2, which is also observed in human peanut allergy. Both crude peanut extract and Ara h 2 alone served as adjuvants, as both induced a bystander sensitization that was similar to that induced by the a topic dermatitis associated staphylococcal enterotoxin B. In cultured human keratinocytes and in murine skin, peanut extract directly induced cytokine expression. Moreover, topical peanut extract application induced an alteration dependent on the IL-33 receptor ST2 in skin-draining DCs, resulting in Th2 cytokine production from T cells. Together, our data support the hypothesis that peanuts are allergenic due to inherent adjuvant activity and suggest that skin exposure to food allergens contributes to sensitization to foods in early life

Growth in marine mammals : a review of growth patterns, composition and energy investment

Funded under award from Office of Naval Research: N000142012392. DPC and SA were funded under the E&P Sound and Marine Life Joint Industry Programme of the International Association of Oil and Gas Producers (IOGP; grant 00-07-23). CRM is supported by the Australian Integrated Marine Observing System (IMOS), IMOS s enabled by the National Collaborative Research Infrastructure Strategy.Growth of structural mass and energy reserves influences individual survival, reproductive success, population and species life history. Metrics of structural growth and energy storage of individuals are often used to assess population health and reproductive potential, which can inform conservation. However, the energetic costs of tissue deposition for structural growth and energy stores and their prioritization within bioenergetic budgets are poorly documented. This is particularly true across marine mammal species as resources are accumulated at sea, limiting the ability to measure energy allocation and prioritization. We reviewed the literature on marine mammal growth to summarize growth patterns, explore their tissue compositions, assess the energetic costs of depositing these tissues and explore the tradeoffs associated with growth. Generally, marine mammals exhibit logarithmic growth. This means that the energetic costs related to growth and tissue deposition are high for early postnatal animals, but small compared to the total energy budget as animals get older. Growth patterns can also change in response to resource availability, habitat and other energy demands, such that they can serve as an indicator of individual and population health. Composition of tissues remained consistent with respect to protein and water content across species; however, there was a high degree of variability in the lipid content of both muscle (0.1–74.3%) and blubber (0.4–97.9%) due to the use of lipids as energy storage. We found that relatively few well-studied species dominate the literature, leaving data gaps for entire taxa, such as beaked whales. The purpose of this review was to identify such gaps, to inform future research priorities and to improve our understanding of how marine mammals grow and the associated energetic costs.Publisher PDFPeer reviewe

Impact of Spiritual Well-Being, Spiritual Perspective, and Religiosity on the Self-Rated Health of Jordanian Arab Christians

The purpose of this study was to explore associations of spiritual well-being, spiritual perspective, and religiosity with self-rated health in a convenience sample of 340 adult Jordanian Arab Christians. Data were collected through church and community groups. Results indicated that spiritual well-being and religiosity were positively associated with self-rated health, but in the final regression model only spiritual well-being retained a significant association after controlling for the other spiritual and religious measures. In conclusion, spirituality and religiosity are important to Jordanian Arab Christians’ health and well-being, and the implications for nursing practice are explored

Resolved Images of Large Cavities in Protoplanetary Transition Disks

Circumstellar disks are thought to experience a rapid "transition" phase in their evolution that can have a considerable impact on the formation and early development of planetary systems. We present new and archival high angular resolution (0.3" = 40-75 AU) Submillimeter Array (SMA) observations of the 880 micron dust continuum emission from 12 such transition disks in nearby star-forming regions. In each case, we directly resolve a dust-depleted disk cavity around the central star. Using radiative transfer calculations, we interpret these dust disk structures in a homogeneous, parametric model framework by reproducing their SMA visibilities and SEDs. The cavities in these disks are large (R_cav = 15-73 AU) and substantially depleted of small (~um-sized) dust grains, although their mass contents are still uncertain. The structures of the remnant material at larger radii are comparable to normal disks. We demonstrate that these large cavities are common among the millimeter-bright disk population, comprising at least 20% of the disks in the bright half of the millimeter luminosity (disk mass) distribution. Utilizing these results, we assess some of the physical mechanisms proposed to account for transition disk structures. As has been shown before, photoevaporation models do not produce the large cavity sizes, accretion rates, and disk masses representative of this sample. It would be difficult to achieve a sufficient decrease of the dust optical depths in these cavities by particle growth alone: substantial growth (to meter sizes or beyond) must occur in large (tens of AU) regions of low turbulence without also producing an abundance of small particles. Given those challenges, we suggest instead that the observations are most commensurate with dynamical clearing due to tidal interactions with low-mass companions --young brown dwarfs or giant planets on long-period orbits.Comment: ApJ, in pres

Psychomotor control in a virtual laparoscopic surgery training environment: gaze control parameters differentiate novices from experts

Background: Surgical simulation is increasingly used to facilitate the adoption of technical skills during surgical training. This study sought to determine if gaze control parameters could differentiate between the visual control of experienced and novice operators performing an eye-hand coordination task on a virtual reality laparoscopic surgical simulator (LAP Mentor™). Typically adopted hand movement metrics reflect only one half of the eye-hand coordination relationship; therefore, little is known about how hand movements are guided and controlled by vision. Methods: A total of 14 right-handed surgeons were categorised as being either experienced (having led more than 70 laparoscopic procedures) or novice (having performed fewer than 10 procedures) operators. The eight experienced and six novice surgeons completed the eye-hand coordination task from the LAP Mentor basic skills package while wearing a gaze registration system. A variety of performance, movement, and gaze parameters were recorded and compared between groups. Results: The experienced surgeons completed the task significantly more quickly than the novices, but only the economy of movement of the left tool differentiated skill level from the LAP Mentor parameters. Gaze analyses revealed that experienced surgeons spent significantly more time fixating the target locations than novices, who split their time between focusing on the targets and tracking the tools. Conclusion: The findings of the study provide support for the utility of assessing strategic gaze behaviour to better understand the way in which surgeons utilise visual information to plan and control tool movements in a virtual reality laparoscopic environment. It is hoped that by better understanding the limitations of the psychomotor system, effective gaze training programs may be developed. © 2010 The Author(s).published_or_final_versionSpringer Open Choice, 01 Dec 201

EAES and SAGES 2018 consensus conference on acute diverticulitis management:evidence-based recommendations for clinical practice

Background Acute diverticulitis (AD) presents a unique diagnostic and therapeutic challenge for general surgeons. This collaborative project between EAES and SAGES aimed to summarize recent evidence and draw statements of recommendation to guide our members on comprehensive AD management. Methods Systematic reviews of the literature were conducted across six AD topics by an international steering group including experts from both societies. Topics encompassed the epidemiology, diagnosis, management of non-complicated and complicated AD as well as emergency and elective operative AD management. Consensus statements and recommendations were generated, and the quality of the evidence and recommendation strength rated with the GRADE system. Modified Delphi methodology was used to reach consensus among experts prior to surveying the EAES and SAGES membership on the recommendations and likelihood to impact their practice. Results were presented at both EAES and SAGES annual meetings with live re-voting carried out for recommendations with < 70% agreement. Results A total of 51 consensus statements and 41 recommendations across all six topics were agreed upon by the experts and submitted for members’ online voting. Based on 1004 complete surveys and over 300 live votes at the SAGES and EAES Diverticulitis Consensus Conference (DCC), consensus was achieved for 97.6% (40/41) of recommendations with 92% (38/41) agreement on the likelihood that these recommendations would change practice if not already applied. Areas of persistent disagreement included the selective use of imaging to guide AD diagnosis, recommendations against antibiotics in non-complicated AD, and routine colonic evaluation after resolution of non-complicated diverticulitis. Conclusion This joint EAES and SAGES consensus conference updates clinicians on the current evidence and provides a set of recommendations that can guide clinical AD management practice