Broad band high resolution rotational spectroscopy for Laboratory Astrophysics.

We present a new experimental setup devoted to the study of gas phase molecules and processes using broad band high spectral resolution rotational spectroscopy. A reactor chamber has been equipped with radio receivers similar to those used by radio astronomers to search for molecular emission in space. The whole Q (31.5-50 GHz) and W bands (72-116.5 GHz) are available for rotational spectroscopy observations. The receivers are equipped with 16×2.5 GHz Fast Fourier Transform spectrometers with a spectral resolution of 38.14 kHz allowing the simultaneous observation of the complete Q band and one third of the W band. The whole W band can be observed in three settings in which the Q band is always observed. Species such as CH3CN, OCS, and SO2 are detected, together with many of their isotopologues and vibrationally excited states, in very short observing times. The system permits automatic overnight observations and integration times as long as 2.4×105 seconds have been reached. The chamber is equipped with a radiofrequency source to produce cold plasmas and with four ultraviolet lamps to study photochemical processes. Plasmas of CH4, N2, CH3CN, NH3, O2, and H2, among other species, have been generated and the molecular products easily identified by their rotational spectrum, and mass spectrometry and optical spectroscopy. Finally, the rotational spectrum of the lowest energy conformer of CH3CH2NHCHO (N-Ethylformamide), a molecule previously characterized in microwave rotational spectroscopy, has been measured up to 116.5 GHz allowing the accurate determination of its rotational and distortion constants and its search in space.

The fate of aerosols on the surface of Titan.

A laboratory study based on the chemical transformation that Titan's aerosol analogues suffer when placed under putative surface conditions of the satellite was performed. In order to understand the role that aqueous ammonia may play on the chemical transformation of atmospheric aerosols once they reach the surface, we synthesized laboratory analogues of Titan's aerosols from an N2 : CH4 (98 : 2) mixture irradiated at low temperatures under a continuous flow regime by a cold plasma discharge of 180 W. The analogues were recovered, partitioned in several 10.0 mg samples and placed inside different ammonia concentrations during 10 weeks at temperatures as low as those reported for Titan's surface. After a derivatization process performed to the aerosols' refractory phase with MTBSTFA in DMF, the products were identified and quantified using a GC-MS system. We found derived residues related to amino acids as well as urea. The simplest amino acids aminoethanoic acid (glycine) and 2-aminopropanoic acid (alanine) as well as diaminomethanal (urea), are found regardless of the ammonia concentration and temperature value to which the aerosol analogues were exposed. Our results have important astrobiological implications to Titan's environment particularly if the existence of the suggested subsurface water-ammonia mixture and its deposition on the satellite's surface is validated.

Possible contribution of different energy sources to the production of organics in Titan's atmosphere.

A quantitative comparison of the products arising from the irradiation of a Titan's simulated atmosphere is presented. The energy sources used represent some of the main events that occur in the satellite's atmosphere. All of the compounds identified are classified in the hydrocarbon and nitrile chemical families. Almost all of the detected compounds in Titan's atmosphere are produced by one or more energy sources. The compounds with the highest energy yields include the C2 hydrocarbons, methanonitrile and ethanonitrile. The possibility of using some of the produced organics as tracer compounds during the Huygens descend to identify the leading energy form in the different atmospheric levels remains open.

Production of hydrocarbons and nitriles by electrical processes in Titan's atmosphere.

Although lightning has not been observed in Titan's atmosphere, the presence of methane rain in the troposphere suggests the possibility of electrical activity in the form of corona and/or lightning discharges. Here we examine the chemical effects of these electrical processes on a Titan simulated atmosphere composed of CH4 in N2 at various mixing ratios. Corona discharges were simulated in two different experimental arrays. For the detection of reactive intermediates we used a mass spectrometer to study the main positive ions arising by bombarding low-energy electrons from a hot filament into low-pressure methane. The final stable products, generated by applying a high voltage in a coaxial reactor with either positive or negative polarity, were separated and detected by gas chromatography-Fourier transform infrared spectroscopy and electron impact mass spectrometry (GC-FTIR-MS). Lightning discharges were simulated by a hot and dense plasma generated by a Nd-YAG laser and the final products were separated and detected by GC-FTIR-MS. Corona discharges produce linear and branched hydrocarbons as well as nitriles whereas lightning discharges generate mainly unsaturated hydrocarbons and nitriles. Lightning discharges are about 2 orders of magnitude more efficient in product formation than corona discharges.

Chemical and optical behaviour of tholins, laboratory analogues of Titan aerosols.

Since 1997, after having identified for the first time C4N2 (the only molecule detected on Titan and undetected in the laboratory at this date) in a simulated atmosphere of Titan, our group intended to determine several properties (including optical behavior) of laboratory analogues of Titan's tholins. This article summarizes the results obtained in the frame of that program (observation by microscopy, solubility in hydrocarbons and nitriles, chemical composition, and optical behavior in the 200-900nm range), and finally investigates the following items: what are the key questions still remaining?; how to answer them?

Corona chemistry in Titan.

The atmosphere of Titan is constantly bombarded by galactic cosmic rays and Saturnian magnetospheric electrons causing the formation of free electrons and primary ions, which are then stabilized by ion cluster formation and charging of aerosols. These charged particles accumulate in drops in cloud regions of the troposphere. Their abundance can substantially increase by friction, fragmentation or collisions during convective activity. Charge separation occurs with help of convection and gravitational settling leading to development of electric fields within the cloud and between the cloud and the ground. Neutralization of these charged particles leads to corona discharges which are characterized by low current densities. We have therefore, experimentally studied the corona discharge of a simulated Titan's atmosphere (10% methane and 2% argon in nitrogen) at 500 Torr and 298 K by GC-FTIR-MS techniques. The main products have been identified as hydrocarbons (ethane, ethyne, ethene, propane, propene+propyne, cyclopropane, butane, 2-methylpropane, 2-methylpropene, n-butane, 2-butene, 2,2-dimethylpropane, 2-methylbutane, 2-methylbutene, n-pentane, 2,2-dimethylbutane, 2-methylpentane, 3-methylpentane, n-hexane, 2,2-dimethylhexane, 2,2-dimethylpentane, 2,2,3-trimethylbutane, 2,3-dimethylpentane and n-heptane), nitriles (hydrogen cyanide, cyanogen, ethanenitrile, propanenitrile, 2-methylpropanenitrile and butanenitrile) and a highly branched hydrocarbon deposit. We present the trends of hydrocarbons and nitriles formation as a function of discharge time in an ample interval and have derived their initial yields of formation. The results clearly demonstrate that a complex organic chemistry can be initiated by corona processes in the lower atmosphere. Although photochemistry and charged particle chemistry occurring in the stratosphere can account for many of the observed hydrocarbon species in Titan, the predicted abundance of ethene is too low by a factor of 10 to 40. While some ethene will be produced by charged-particle chemistry, the production of ethene by corona processes and its subsequent diffusion into the stratosphere appears to be an adequate source. Because little UV penetrates to the lower atmosphere to destroy the molecules formed there, the corona-produced species may be long-lived and contribute significantly to the composition of the lower atmosphere and surface.

Corona discharge of Titan's troposphere.

The atmosphere of Titan is constantly bombarded by galactic cosmic rays and Saturnian magnetospheric electrons causing the formation of free electrons and primary ions, which are then stabilized by ion cluster formation and charging of aerosols. These charged particles accumulate in drops in cloud regions of the troposphere. Their abundance can substantially increase by friction, fragmentation or collisions during convective activity. Charge separation occurs with help of convection and gravitational settling leading to development of electric fields within the cloud and between the cloud and the ground. Neutralization of these charge particles leads to corona discharges which are characterized by low current densities. These electric discharges could induce a number of chemical reactions in the troposphere and hence it is of interest to explore such effects. We have therefore, experimentally studied the corona discharge of a simulated Titan's atmosphere (10% methane and 2% argon in nitrogen) at 500 Torr and 298 K by GC-FTIR-MS techniques. The main products have been identified as hydrocarbons (ethane, ethyne, ethene, propane, propene + propyne, cyclopropane, butane, 2-methylpropane, 2-methylpropene, n-butene, 2-butene, 2,2-dimethylpropane, 2-methylbutane, 2-methylbutene, n-pentane, 2,2-dimethylbutane, 2-methylpentane, 3-methylpentane, n-hexane, 2,2-dimethylhexane, 2,2-dimethylpentane, 2,2,3-trimethylbutane, 2,3-dimethylpentane and n-heptane), nitriles (hydrogen cyanide, cyanogen, ethanenitrile, propanenitrile, 2-methylpropanenitrile and butanenitrile) and an uncharacterized film deposit. We present their trends of formation as a function of discharge time in an ample interval and have derived their initial yields of formation. These results clearly demonstrate that a complex organic chemistry can be initiated by corona processes in the lower atmosphere. Although photochemistry and charged particle chemistry occurring in the stratosphere can account for many of the observed hydrocarbon species in Titan, the predicted abundance of ethene is to low by a factor of 10 to 40. While some ethene will be produced by charged-particle chemistry, its production by corona processes and subsequent diffusion into the stratosphere appears to be an adequate source. Because little UV penetrates to the lower atmosphere to destroy the molecules formed there, the corona-produced species may be long-lived and contribute significantly to the composition of the lower atmosphere and surface.

[Cytologic response of the irradiated vagina to estriol succinate]. / Respuesta citológica de la vagina irradiada al succinato de estriol.

The vaginal response to estriol succinate was studied in 40 oncogynecological patients, 20 with irradiation (study group) and 20 without irradiation (control group). Both groups had artificial established menopause at the beginning of the treatment. The previous clinical and cytological patterns to estrogen therapy were more severe in the irradiated group; they presented the highest degree of vaginal atrophy which was related to the type and therapeutic dose used. Response of the study group to a continuous 4 mg of estriol as well as the control group, both has a positive effect in vaginal cytology and alleviates postmenopausal symptoms and improve the quality of life.