741 research outputs found
Ir Spectroscopy Of Selected Atmospheric Monoterpenes And Oxydation Products
No full text"Several monoterpenes are biogenic volatile organic compounds (BVOCS) present in the atmosphere. They can react with \chem{OH}, \chem{O_3}, \chem{NO_x}, etc. to give rise to several oxydation and degradation products.
We have studied the gas phase spectroscopy of monocyclic (limonene, -terpinene) and bicyclic (-pinene, -pinene) atmospheric monoterpenes (\chem{C_{10}H_{16}}), as well as two \chem{C_{10}H_{14}O} oxydation products (perillaldehyde, carvone). In the first step of this work, theoretical calculations and microwave spectroscopy were used in order to evidence the most stable conformers and their relative energies. \footnote{J. R. Aviles Moreno, F. Partal Urena, J. J. Lopez Gonzalez and T. R. Huet, {\em C.\ Phys.\ Lett.}~{\bf 473} (2009) 17} \footnote{J. R. Aviles Moreno, T. R. Huet, F. Partal Urena, J. J. Lopez Gonzalez, {\em Struc.\ Chem.}~{\bf 24} (2013) 1163} \footnote{J. R. Aviles Moreno, E. Neeman, T. R. Huet, manuscript in preparation}
In the present communication we will present the results of the IR study. Infrared spectra have been recorded on the FTIR spectrometer of the AILES beamline at synchrotron SOLEIL, using the Jet-AILES molecular beam and a long path cell. Special attention was given to the 700--1300 \wn~atmospheric window, to the \chem{CH} vibration region, and to the ""finger print"" FIR region. Quantum calculations have been performed at different levels of theory (DFT, ab initio). In particular anharmonic force fields were obtained in order to model the vibrational structures.
Support from the French Laboratoire d'Excellence CaPPA (Chemical and Physical Properties of the Atmosphere) through contract ANR-10-LABX-0005 of the Programme d'Investissements d'Avenir is acknowledged.
The experiment on the AILES beam-line at synchrotron SOLEIL was performed under project number 20130192."Made available in DSpace on 2014-09-17T16:55:24Z (GMT). No. of bitstreams: 3
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Previous issue date: 2014-06-17Made available in DSpace on 2015-04-14T18:39:25Z (GMT). No. of bitstreams: 4
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Previous issue date: 2014-06-1
Microwave Spectroscopy Of Monoterpenes Of Atmospheric Interest: Α-pinene, Β-pinene, And Nopinone
No full textSeveral monoterpenes and terpenoids are biogenic volatile organic compounds which are emitted in the atmosphere, and react with \chem{OH}, \chem{O_3}, \chem{NO_x}, etc. to give rise to several oxydation and degradation products. Spectroscopic information on these atmospheric species are still very scarse. Meanwhile we have demonstrated that combining quantum calculations to microwave spectroscopy led to the unambiguous characterization of the most stable conformers for perillaldehyde, \footnote{J.-R. Aviles Moreno, F. Partal Urena, J.-J. Lopez Gonzalez and T. R. Huet, {\em Chem.\ Phys.\ Lett.}~{\bf 473} (2009) 17} limonene and carvone.
\footnote{J.-R. Aviles Moreno, T. R. Huet, F. Partal Urena, J.-J. Lopez Gonzalez, {\em Struct.\ Chem.}~{\bf 24} (2013) 1163} This information can be used to subsequently model accurately the vibrational signature for atmospheric purposes. \footnote{T. R. Huet, J.-R. Aviles Moreno, O. Pirali, M. Tudorie, F. Partal Urena, J.-J. Lopez Gonzalez, {\em JQSRT.}~{\bf 113} (2012) 1261}
We have recorded the pure rotational spectra of -pinene and -pinene (\chem{C_{10}H_{16}}), and of nopinone (\chem{C_{9}H_{14}O}), using the MB-FTMW spectrometer of Lille, in the 2-20 GHz range at temperatures varying between 340 and 380 K. For these three bicyclic molecules only one conformer can be observed, and the rotational structure was observed up to J, K = 8, 3 ; 8, 4 ; 8, 5, respectively. All the spectra were modeled with a semi-rigid rotor Hamiltonian and fitted to obtain a rms value better than 5 kHz using a-, b- and c- type transitions.
All the experimental results were supported by several quantum calculations performed at different levels of theory (DFT and ab initio). In particular no experimental evidence of internal rotation motion was found (methyl groups), in good agreement with the calculated barriers.
Support from the French Laboratoire d'Excellence CaPPA (Chemical and Physical Properties of the Atmosphere) through contract ANR-10-LABX-0005 of the Programme d'Investissements d'Avenir is acknowledged.Made available in DSpace on 2014-09-17T16:55:20Z (GMT). No. of bitstreams: 3
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Previous issue date: 2014-06-18Made available in DSpace on 2015-04-14T18:38:46Z (GMT). No. of bitstreams: 4
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Previous issue date: 2014-06-1
Gas-phase molecular structure of nopinone and its water complexes studied by microwave fourier transform spectroscopy and quantum chemical calculations
No full textSeveral monoterpenes and terpenoids are biogenic volatile organic compounds which are emitted in the atmosphere, where they react with OH, O and NO etc. to give rise to several oxidation and degradation products.\footnote{A. Calogirou, B.R. Larsen, and D. Kotzias, \textit{ Atmospheric Environment}, \textbf{33}, 1423-1439, (1999).} Their decomposition products are a major source of secondray organic aerosol (SOA).\footnote{P. Paasonen et al., \textit{Nat. Geosci.}, \textbf{6}, 438-442 (2013)} Spectroscopic information on these atmospheric species is still very scarce.
The rotational spectrum of nopinone (CHO) one of the major oxidation products of -pinene,\footnote{D. Zhang and R. Zhang \textit{The Journal of Chemical Physics}, \textbf{122}, 114308, (2005).} \footnote{R. Winterhalter et al. \textit{ Journal of Atmospheric Chemistry}, \textbf{35}, 165-197, (2000).} and of its water complexes were recorded in a supersonic jet expansion with a Fourier transform microwave spectrometer over the range 2-20 GHz. The structure of the unique stable conformer of the nopinone was optimized using density functional theory and \textit{ab initio} calculations. Signals from the parent species and from the and isotopomers were observed in natural abundance. A magnetic hyperfine structure associated with the pairs of hydrogen nuclei in the methylene groups was observed and modeled. \\ The structures of several conformers of the nopinone-water complexes with up to three molecules of water were optimized using density functional theory and \textit{ab initio} calculations. The energetically most stable of calculated conformers were observed and anlyzed. The rotational and centrifugal distortion parameters were fitted to a Watson’s Hamiltonian in the A-reduction. The present work provides the first spectroscopic characterization of nopinone and its water complexes in the gas phase.\\Made available in DSpace on 2017-01-26T21:40:27Z (GMT). No. of bitstreams: 3
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Previous issue date: 2016-06-2
Development of a novel and viable knock-in factor V deficiency murine model: Utility for an ultra-rare disease
No full textAuthor contributions Conceptualization:
Juan A. De Pablo-Moreno, Pablo Bermejo-Álvarez, Antonio Liras. Formal analysis: Juan A. De Pablo-Moreno, Leopoldo González-Brusi, Andrea Miguel-Batuecas, Pablo Bermejo-Álvarez, Luis Revuelta, Antonio Liras. Funding acquisition: Pablo Bermejo-Álvarez, Luis Revuelta, Antonio Liras. Investigation: Juan A. De Pablo-Moreno, Leopoldo González-Brusi, Andrea Miguel-Batuecas, Pablo Bermejo-Álvarez, Antonio Liras. Methodology: Juan A. De Pablo-Moreno, Leopoldo González-Brusi, Andrea Miguel-Batuecas, Pablo Bermejo-Álvarez, Luis Revuelta, Antonio Liras. Project administration: Antonio Liras. Resources: Pablo Bermejo-Álvarez, Luis Revuelta, Antonio Liras. Software: Juan A. De Pablo-Moreno, Andrea Miguel-Batuecas. Supervision: Pablo Bermejo-Álvarez, Luis Revuelta, Antonio Liras. Writing – original draft: Juan A. De Pablo-Moreno, Andrea Miguel-Batuecas, Antonio Liras. Writing – review & editing: Juan A. De Pablo-Moreno, Andrea Miguel-Batuecas, Leopoldo González-Brusi, Pablo Bermejo-Álvarez, Luis Revuelta, Antonio LirasFactor V deficiency is a congenital coagulation disorder characterized by the absence or malfunction of factor V (FV). The purpose of this study was to develop a viable FV-deficient mouse model using CRISPR/Cas9 technology. A viable pathological model of the disease was not available to develop new therapies. A previous in silico study was performed to select a mutation causing a mild disease phenotype in humans (Thr1898Met missense). Such mutation was replicated in mice by CRISPR-mediated homology directed repair. Following crossing, homozygous individuals were subjected to coagulometry assays, including FV levels, prothrombin time (PT), and activated partial thromboplastin time (aPTT). The in silico study suggested that the mutation destabilizes FV structure of both mouse and human variants, putatively producing a mild phenotype of the disease in mice. Mendelian inheritance was observed in the offspring. No spontaneous signs of blood clotting disturbances, premature deaths or gestational dysfunctions were observed. FV levels in homozygous animals were 24.5% ± 5.1; 39.7 sec ± 2.8; PT was 61.8% ± 6.3; 23.4 sec ± 1.6 (INR = 1.47 ± 0.12); and aPTT was 46.9 sec ± 3.2. A viable FV-deficient mouse model was generated by introducing a missense mutation in FV. The model exhibits a mild phenotype of the disease, akin to that observed in humans.Comunidad de MadridUniversidad Complutense de Madrid- Banco SantanderMinisterio de Ciencia, Innovación y Universidades ( España)Depto. de FisiologíaDepto. de Producción AnimalDepto. de Genética, Fisiología y MicrobiologíaFac. de VeterinariaFac. de Ciencias BiológicasTRUEpu
Methacrolein In The Ir Atmospheric Window: Mm-wave And Ftir Spectroscopies Complemented By Quantum Calculations
No full textMethacrolein, \chem{CH_2=C(CH_3)CHO} or MAC, is an important atmospheric molecule because it is a major product of the isoprene-OH reaction. Meanwhile the spectroscopic information on MAC is very scarse. \footnote{M. Suzuki and K. Kozima, {\em J.\ Molec.\ Spectrosc.}~{\bf 38} (1971) 314} \footnote{J. R. Durig, J. Qiu, B. Dehoff and T. S. Little, {\em Spectrochimica Acta}~{\bf 42A} (1986) 89}
On the theoretical side, we have performed quantum calculations at different levels of theory (DFT and {\em ab initio}) to model the structure of the two conformers, the large amplitude motion associated with the methyl top, and the anharmonic vibrational structure.
On the experimental side, we have at first characterized the millimeter-wave spectrum of MAC in the 150-465 GHz range using the Lille frequency multiplication chain spectrometer. In particular the ground state has been analyzed up to J, K = 37, 17 and the first excited states are currently investigated.
Secondly, FTIR spectra have been recorded on the AILES beamline of SOLEIL using a long path cell, between 30 and 3500 \wn at medium resolution (0.5 \wn). A few bands of atmospheric interest have also been recorded at higher resolution (0.001 \wn). We will report the details of the vibrational analysis, as well as the molecular parameters derived from the analysis of the high resolution spectrum of the c-type band located around 930 \wn.
Support from the French Laboratoire d'Excellence CaPPA (Chemical and Physical Properties of the Atmosphere) through contract ANR-10-LABX-0005 of the Programme d'Investissements d'Avenir is acknowledged.
The experiment on the AILES beam-line of the synchrotron SOLEIL was performed under project number 20130192.Made available in DSpace on 2014-09-17T16:55:11Z (GMT). No. of bitstreams: 3
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Previous issue date: 2014-06-17Made available in DSpace on 2015-04-14T18:40:29Z (GMT). No. of bitstreams: 4
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Previous issue date: 2014-06-1
Padova e il paesaggio: scenari futuri per il parco Roncajette e la zona industriale = Padova and the landscape: alternative futures for the Roncajette park and the industrial zone
No full textQuesto studio analizza possibili scenari futuri per il Parco Roncajette, per la Zona Industriale di Padova e per il paesaggio della zona orientale della provincia di Padova. E' il prodotto del lavoro condiviso di un gruppo di studenti dell’Università di Harvard - Graduate School of Design, diretto dal Professor Carl Steinitz con Juan Carlos Vargas-Moreno e Laura Cipriani.
[ENGLISH ABSTRACT. This study is of the future of the Parco Roncajette, the industrial zone ZIP, and the landscape of the eastern part of the region of Padova. It is the product of collaborative student work at the Harvard University Graduate School of Design. The class was taught by Professor Carl Steinitz with Juan Carlos Vargas-Moreno and Laura Cipriani]
Torsion - rotation - vibration effects in the ground and first excited states of methacrolein and methyl vinyl ketone
No full textMethacrolein and methyl vinyl ketone are the two major oxidation products of isoprene emitted in the troposphere. New spectroscopic information is provided with the aim to allow unambiguous identification of these molecules, characterized by a large amplitude motion associated with the methyl top. State-of-the-art millimeter-wave spectroscopy experiments coupled to quantum chemical calculations have been performed. Comprehensive sets of molecular parameters have been obtained. The torsion-rotation-vibration effects will be discussed in detail.
From the atmospheric application point of view the results provide precise ground state molecular constants essential as a foundation (by using the Ground State Combination Differences method) for the analysis of high resolution spectrum, recorded from 600 to 1600 \wn. The infrared range can be then refitted using appropriate Hamiltonian parameters.
The present work is funded by the French ANR through the PIA under contract ANR-11-LABX-0005-01 (Labex CaPPA), by the Regional Council Nord-Pas de Calais and by the European Funds for Regional Economic Development (FEDER).Made available in DSpace on 2017-01-26T21:40:02Z (GMT). No. of bitstreams: 3
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Previous issue date: 2016-06-2
María Moreno, una letrada sorora: Maternidades, filiaciones y disidencias
No full textFrom an reading of Oración. Carta a Vicky y otras elegias políticas (2018) by María Moreno, I propose to expose: on the one hand, some of the tensions of the testimonial field in Argentina and to review the procedures with which Moreno transgresses his classical ways. On the other hand, I want to explore how the author resignifies the idea of the "solidarity intellectual" and becomes a "sorority intellectual".A partir de una lectura de Oración. Carta a Vicky y otras elegías políticas (2018) de María Moreno propongo mostrar: por un lado, algunas de las tensiones del campo testimonial en Argentina y revisar los procedimientos con los que Moreno transgrede sus formas clásicas. Por otro lado, explorar de qué manera Moreno resignifica la idea del “letrado solidario” y se transforma en una “letrada sorora”
THE MILLIMETER-WAVE SPECTRUM OF METHACROLEIN. TORSION-ROTATION-VIBRATION EFFECTS IN THE EXCITED STATES
No full textLast year we reported the analysis of the rotational spectrum of emph{s-trans} conformer of methacrolein CH=C(CH)CHO in the ground vibrational statefootnote{Zakharenko O. et al., 69th ISMS, 2014, TI01}. In this talk we report the study of its low lying excited vibrational states. The study is based on room-temperature absorption spectra of methacrolein recorded in the frequency range 150 � 465 GHz using the spectrometer in Lille. The new results include assignment of the first excited torsional state (131 cm), and the joint analysis of the v = 0 and v = 1 states, that allowed us to improve the model in the frame of Rho-Axis-Method (RAM) Hamiltonian and to remove some strong correlations between parameters. Also we assigned the first excited vibrational state of the skeletal torsion mode (170 cm). The inverse sequence of A and E tunneling substates as well as anomalous A-E splittings observed for the rotational lines of v = 1 state clearly indicate a coupling between methyl torsion and skeletal torsion. However we were able to fit within experimental accuracy the rotational lines of v = 1 state using the RAM Hamiltonian. Because of the inversion of the A and E tunneling substates the rotational lines of the v = 1 states were assumed to belong to a virtual first excited torsional state. Finally, we assigned several low-K rotational transitions of the excited vibrational states above 200 cm but their analysis is complicated by different rotation-vibration interactions. In particular there is an evidence of the Fermi-type resonance between the second excited torsional state and the first excited state of the in-plane skeletal bending mode (265 cm). \
em{Support from the French Laboratoire d�Excellence CaPPA (Chemical and Physical Properties of the Atmosphere) through contract ANR-10-LABX-0005 of the Programme d�Investissements d�Avenir is acknowledged. }Made available in DSpace on 2016-01-05T20:01:22Z (GMT). No. of bitstreams: 3
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ROTATIONAL SPECTROSCOPY OF METHYL VINYL KETONE
No full textMethyl vinyl ketone, MVK, along with previously studied by our team methacrolein, is a major oxidation product of isoprene, which is one of the primary contributors to annual global VOC emissions. In this talk we present the analysis of the rotational spectrum of MVK recorded at room temperature in the 50 -- 650 GHz region using the Lille spectrometer. The spectroscopic characterization of MVK ground state will be useful in the detailed analysis of high resolution infrared spectra. Our study is supported by high level quantum chemical calculations to model the structure of the two stable emph{s-trans} and emph{s-cis} conformers and to obtain the harmonic force field parameters, internal rotation barrier heights, and vibrational frequencies. In the Doppler-limited spectra the splittings due to the internal rotation of methyl group are resolved, therefore for analysis of this molecule we used the Rho-Axis-Method Hamiltonian and RAM36 code to fit the rotational transitions. At the present time the ground state of two conformers is analyzed. Also we intend to study some low lying excited states. The analysis is in progress and the latest results will be presented. \
em{Support from the French Laboratoire d�Excellence CaPPA (Chemical and Physical Properties of the Atmosphere) through contract ANR-10-LABX-0005 of the Programme d�Investissements d�Avenir is acknowledged. }Made available in DSpace on 2016-01-05T20:03:31Z (GMT). No. of bitstreams: 3
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