Cyclobutene photochemistry. Adiabatic photochemical ring opening of alkylcyclobutenes

Abstract: The photochemistry of the cis and trans isomers of a series of dimethylbicyclo[n.2.O]alk-(n+2)-enes (n = 2-5) (bicyclic cyclobutene derivatives in which the C=C bond is shared by the two rings) in pentane solution is described. Irradiation of these compounds using monochromatic 193-or 214-nm light sources results in ring opening to yield the corresponding 1,2-bis(l-ethylidene)cycloalkanes (C,-C,) in high chemical and quantum yields. In all cases, the reaction proceeds with a high (70-90%) degree of disrotatory stereoselectivity. Quantum yields for direct cis,trans photoisomerization of the isomeric E,Eand E,Z-1,2-bis(l-ethylidene)cycloalkanes have also been determined. The product distributions from irradiation of the cyclobutenes are wavelength dependent, but for 214-nm excitation the isomeric diene distributions obtained from cyclobutene ring opening agree fairly closely with those calculated from the quantum yields for cis,trans photoisomerization of the isomeric dienes on the assumption that the process involves purely disrotatory ring opening to yield a single diene isomer in the lowest excited singlet state. The results are consistent with an orbital-symmetry-controlled, adiabatic mechanism for ring opening. Key words: photochemistry, cyclobutene, electrocyclic, adiabatic, conical intersection, orbital symmetry. Resume : On dCcrit la photochimie des isomkres cis et trans d'une sCrie de dimCthylbicyclo[n.2.0]alc-(n+2)-knes (n = 2-5) (dCrivts cyclobutknes bicycliques dans lesquels la liaison C% est partagCe entre deux cycles) en solution dans le pentane. L'irradiation de ces composCs utilisant des sources de lumikre monochromatique (193 ou 214 nm) provoque une ouverture de cycle qui conduit aux 1,2-bis(1-Cthylidbne)cycloalcanes (C,-C,) correspondants avec des rendements chimiques et quantiques tlevCs. Dans tous les cas, la reaction se produit avec un degrC ClevC (70-90%) de stCrCosClectivitt disrotatoire. On a determink les rendements quantiques pour la photoisomtrisation cis/trans des E,E-and E,Z-1,2-bis(1-Cthy1idkne)cycloaIcanes. Les distributions des produits dtrivant de l'irradiation des cyclobutknes dependent de la longueur d'onde, mais, pour l'excitation B 214 nm, les distributions des diknes isomkres obtenues pour l'ouverture de cycle du cyclobutkne sont en assez bon accord avec ceux calculCs ii partir des rendements quantiques pour la photoisomCrisation cis/trans des diknes isomkres en supposant que le processus implique une ouverture de cycle strictement disrotatoire pour conduire B un seul dikne isomkre dans 1'Ctat singulet excitC le plus bas. Les rtsultats sont en accord avec un mCcanisme, pour l'ouverture de cycle, qui serait adiabatique et sous contr6le d'une symCtrie des orbitales

Four Years of Realtime GRB Followup by BOOTES-1B (2005-2008)

Four years of BOOTES-1B GRB follow-up history are summarised for the first time in the form of a table. The successfully followed events are described case by case. Further, the data are used to show the GRB trigger rate in Spain on a per-year basis, resulting in an estimate of 18 triggers and about 51 h of telescope time per year for real time triggers. These numbers grow to about 22 triggers and 77 h per year if we include also the GRBs observable within 2 hours after the trigger.Comment: 16 pages, Accepted into Proceedings of AstroRob Malaga 200

Recent GRBs observed with the 1.23m CAHA telescope and the status of its upgrade

We report on optical observations of Gamma-Ray Bursts (GRBs) followed up by our collaboration with the 1.23m telescope located at the Calar Alto observatory. The 1.23m telescope is an old facility, currently undergoing upgrades to enable fully autonomous response to GRB alerts. We discuss the current status of the control system upgrade of the 1.23m telescope. The upgrade is being done by the ARAE our group, based on members of IAA (Instituto de Astrofiisica de Andalucia). Currently the ARAE group is responsible to develop the BOOTES network of robotic telescopes based on the Remote Telescope System, 2nd Version (RTS2), which controls the available instruments and interacts with the EPICS database of Calar Alto. Currently the telescope can run fully autonomously or under observer supervision using RTS2. The fast reaction response mode for GRB reaction (typically with response times below 3 minutes from the GRB onset) still needs some development and testing. The telescope is usually operated in legacy interactive mode, with periods of supervised autonomous runs under RTS2. We show the preliminary results of several GRBs followed up with observer intervention during the testing phase of the 1.23m control software upgrade.Comment: 15 pages, 7 figures. Accepted for publication in the Special issue "Robotic Astronomy" of Advances in Astronomy. It includes two iterations with the referee

OCTOCAM: A fast multichannel imager and spectrograph for the 10.4m GTC

OCTOCAM is a multi-channel imager and spectrograph that has been proposed for the 10.4m GTC telescope. It will use dichroics to split the incoming light to produce simultaneous observations in 8 different bands, ranging from the ultraviolet to the near-infrared. The imaging mode will have a field of view of 2' x 2' in u, g, r, i, z, J, H and Ks bands, whereas the long-slit spectroscopic mode will cover the complete range from 4,000 to 23,000 {\AA} with a resolution of 700 - 1,700 (depending on the arm and slit width). An additional mode, using an image slicer, will deliver a spectral resolution of over 3,000. As a further feature, it will use state of the art detectors to reach high readout speeds of the order of tens of milliseconds. In this way, OCTOCAM will be occupying a region of the time resolution - spectral resolution - spectral coverage diagram that is not covered by a single instrument in any other observatory, with an exceptional sensitivity.Comment: 11 pages, 10 figures, SPIE 2010 Astronomical Instrumentatio

A decade of GRB follow-up by BOOTES in Spain (2003-2013)

This article covers ten years of GRB follow-ups by the Spanish BOOTES stations: 71 follow-ups providing 23 detections. Follow-ups by BOOTES-1B from 2005 to 2008 were given in the previous article, and are here reviewed, updated, and include additional detection data points as the former article merely stated their existence. The all-sky cameras CASSANDRA have not yet detected any GRB optical afterglows, but limits are reported where available

The Highly Energetic Expansion of SN2010bh Associated with GRB 100316D

We present the spectroscopic and photometric evolution of the nearby (z = 0.059) spectroscopically confirmed type Ic supernova, SN 2010bh, associated with the soft, long-duration gamma-ray burst (X-ray flash) GRB 100316D. Intensive follow-up observations of SN 2010bh were performed at the ESO Very Large Telescope (VLT) using the X-shooter and FORS2 instruments. Owing to the detailed temporal coverage and the extended wavelength range (3000--24800 A), we obtained an unprecedentedly rich spectral sequence among the hypernovae, making SN 2010bh one of the best studied representatives of this SN class. We find that SN 2010bh has a more rapid rise to maximum brightness (8.0 +/- 1.0 rest-frame days) and a fainter absolute peak luminosity (L_bol~3e42 erg/s) than previously observed SN events associated with GRBs. Our estimate of the ejected (56)Ni mass is 0.12 +/- 0.02 Msun. From the broad spectral features we measure expansion velocities up to 47,000 km/s, higher than those of SNe 1998bw (GRB 980425) and 2006aj (GRB 060218). Helium absorption lines He I lambda5876 and He I 1.083 microm, blueshifted by ~20,000--30,000 km/s and ~28,000--38,000 km/s, respectively, may be present in the optical spectra. However, the lack of coverage of the He I 2.058 microm line prevents us from confirming such identifications. The nebular spectrum, taken at ~186 days after the explosion, shows a broad but faint [O I] emission at 6340 A. The light-curve shape and photospheric expansion velocities of SN 2010bh suggest that we witnessed a highly energetic explosion with a small ejected mass (E_k ~ 1e52 erg and M_ej ~ 3 Msun). The observed properties of SN 2010bh further extend the heterogeneity of the class of GRB supernovae.Comment: 37 pages and 12 figures (one-column pre-print format), accepted for publication in Ap

Verbal fluency tests: Normative data for Spanish-speaking pediatric population

OBJECTIVE: To generate normative data for the phonological and semantic verbal fluency tests (VFT) in Spanish-speaking pediatric populations. METHOD: The sample consisted of 4,373 healthy children from nine countries in Latin America (Chile, Cuba, Ecuador, Guatemala, Honduras, Mexico, Paraguay, Peru, and Puerto Rico) and Spain. Each participant was administered the VFT as part of a larger neuropsychological battery. Scores for letters F, A, S, and animals and fruit categories were normed using multiple linear regressions and standard deviations of residual values. Age, age2, sex, and mean level of parental education (MLPE) were included as predictors in the analyses. RESULTS: The final multiple linear regression models showed main effects for age on all scores, such that scores increased linearly as a function of age. Age2 had a significant effect in Chile (animals), Cuba (A letter, fruits), Ecuador (animals, fruits), Honduras (F letter), Mexico (animals, fruits), Peru (fruits), and Spain (S letters, animals, fruits). Models showed an effect for MLPE in Chile (A letters, animals, fruits), Ecuador (S letter, animals, fruits), Guatelama (F, S letter, animals), Honduras (animals), Mexico (F, A, S letters, animals, fruits), Puerto Rico (A, letters, animals), and Spain (all scores). Sex scores were found significant in Chile (animals), Ecuador (A letter, fruits), Mexico (F letter, fruits), Paraguay (F, A, S letters, fruits), Puerto Rico (F letter, animals, fruits), and Spain (F letter, fruits). CONCLUSIONS: This is the largest multi-national Spanish speaking-pediatric normative study in the world, and as such it will allow neuropsychologists from these countries to have a more accurate way to interpret the phonological and semantic VFT in pediatric populations

The NORMAN Suspect List Exchange (NORMAN-SLE): facilitating European and worldwide collaboration on suspect screening in high resolution mass spectrometry

Background: The NORMAN Association (https://www.norman-.network.com/) initiated the NORMAN Suspect List Exchange (NORMAN-SLE; https://www.norman-.network.com/nds/SLE/) in 2015, following the NORMAN collaborative trial on non-target screening of environmental water samples by mass spectrometry. Since then, this exchange of information on chemicals that are expected to occur in the environment, along with the accompanying expert knowledge and references, has become a valuable knowledge base for "suspect screening" lists. The NORMAN-SLE now serves as a FAIR (Findable, Accessible, Interoperable, Reusable) chemical information resource worldwide.Results: The NORMAN-SLE contains 99 separate suspect list collections (as of May 2022) from over 70 contributors around the world, totalling over 100,000 unique substances. The substance classes include per- and polyfluoroalkyl substances (PFAS), pharmaceuticals, pesticides, natural toxins, high production volume substances covered under the European REACH regulation (EC: 1272/2008), priority contaminants of emerging concern (CECs) and regulatory lists from NORMAN partners. Several lists focus on transformation products (TPs) and complex features detected in the environment with various levels of provenance and structural information. Each list is available for separate download. The merged, curated collection is also available as the NORMAN Substance Database (NORMAN SusDat). Both the NORMAN-SLE and NORMAN SusDat are integrated within the NORMAN Database System (NDS). The individual NORMAN-SLE lists receive digital object identifiers (DOIs) and traceable versioning via a Zenodo community (https:// zenodo.org/communities/norman-.sle), with a total of > 40,000 unique views, > 50,000 unique downloads and 40 citations (May 2022). NORMAN-SLE content is progressively integrated into large open chemical databases such as PubChem (https://pubchem.ncbi.nlm.nih.gov/) and the US EPA's CompTox Chemicals Dashboard (https://comptox. epa.gov/dashboard/), enabling further access to these lists, along with the additional functionality and calculated properties these resources offer. PubChem has also integrated significant annotation content from the NORMAN-SLE, including a classification browser (https://pubchem.ncbi.nlm.nih.gov/classification/#hid=101).Conclusions: The NORMAN-SLE offers a specialized service for hosting suspect screening lists of relevance for the environmental community in an open, FAIR manner that allows integration with other major chemical resources. These efforts foster the exchange of information between scientists and regulators, supporting the paradigm shift to the "one substance, one assessment" approach. New submissions are welcome via the contacts provided on the NORMAN-SLE website (https://www.norman-.network.com/nds/SLE/)

The Mars Environmental Dynamics Analyzer, MEDA. A Suite of Environmental Sensors for the Mars 2020 Mission

86 pags, 49 figs, 24 tabsNASA's Mars 2020 (M2020) rover mission includes a suite of sensors to monitor current environmental conditions near the surface of Mars and to constrain bulk aerosol properties from changes in atmospheric radiation at the surface. The Mars Environmental Dynamics Analyzer (MEDA) consists of a set of meteorological sensors including wind sensor, a barometer, a relative humidity sensor, a set of 5 thermocouples to measure atmospheric temperature at ∼1.5 m and ∼0.5 m above the surface, a set of thermopiles to characterize the thermal IR brightness temperatures of the surface and the lower atmosphere. MEDA adds a radiation and dust sensor to monitor the optical atmospheric properties that can be used to infer bulk aerosol physical properties such as particle size distribution, non-sphericity, and concentration. The MEDA package and its scientific purpose are described in this document as well as how it responded to the calibration tests and how it helps prepare for the human exploration of Mars. A comparison is also presented to previous environmental monitoring payloads landed on Mars on the Viking, Pathfinder, Phoenix, MSL, and InSight spacecraft.This work has been funded by the Spanish Ministry of Economy and Competitiveness, through the projects No. ESP2014-54256-C4-1-R (also -2-R, -3-R and -4-R) and AYA2015-65041-P; Ministry of Science, Innovation and Universities, projects No. ESP2016-79612-C3-1-R (also -2-R and -3-R), ESP2016-80320-C2-1-R, RTI2018-098728-B-C31 (also -C32 and -C33) and RTI2018-099825-B-C31; Instituto Nacional de Tecnica Aeroespacial; Ministry of Science and Innovation's Centre for the Development of Industrial Technology; Grupos Gobierno Vasco IT1366-19; and European Research Council Consolidator Grant no 818602.Peer reviewe

The NORMAN Suspect List Exchange (NORMAN-SLE): Facilitating European and worldwide collaboration on suspect screening in high resolution mass spectrometry

Background: The NORMAN Association (https://www.norman-network.com/) initiated the NORMAN Suspect List Exchange (NORMAN-SLE; https://www.norman-network.com/nds/SLE/) in 2015, following the NORMAN collaborative trial on non-target screening of environmental water samples by mass spectrometry. Since then, this exchange of information on chemicals that are expected to occur in the environment, along with the accompanying expert knowledge and references, has become a valuable knowledge base for “suspect screening” lists. The NORMAN-SLE now serves as a FAIR (Findable, Accessible, Interoperable, Reusable) chemical information resource worldwide. Results: The NORMAN-SLE contains 99 separate suspect list collections (as of May 2022) from over 70 contributors around the world, totalling over 100,000 unique substances. The substance classes include per- and polyfluoroalkyl substances (PFAS), pharmaceuticals, pesticides, natural toxins, high production volume substances covered under the European REACH regulation (EC: 1272/2008), priority contaminants of emerging concern (CECs) and regulatory lists from NORMAN partners. Several lists focus on transformation products (TPs) and complex features detected in the environment with various levels of provenance and structural information. Each list is available for separate download. The merged, curated collection is also available as the NORMAN Substance Database (NORMAN SusDat). Both the NORMAN-SLE and NORMAN SusDat are integrated within the NORMAN Database System (NDS). The individual NORMAN-SLE lists receive digital object identifiers (DOIs) and traceable versioning via a Zenodo community (https://zenodo.org/communities/norman-sle), with a total of > 40,000 unique views, > 50,000 unique downloads and 40 citations (May 2022). NORMAN-SLE content is progressively integrated into large open chemical databases such as PubChem (https://pubchem.ncbi.nlm.nih.gov/) and the US EPA’s CompTox Chemicals Dashboard (https://comptox.epa.gov/dashboard/), enabling further access to these lists, along with the additional functionality and calculated properties these resources offer. PubChem has also integrated significant annotation content from the NORMAN-SLE, including a classification browser (https://pubchem.ncbi.nlm.nih.gov/classification/#hid=101). Conclusions: The NORMAN-SLE offers a specialized service for hosting suspect screening lists of relevance for the environmental community in an open, FAIR manner that allows integration with other major chemical resources. These efforts foster the exchange of information between scientists and regulators, supporting the paradigm shift to the “one substance, one assessment” approach. New submissions are welcome via the contacts provided on the NORMAN-SLE website (https://www.norman-network.com/nds/SLE/)