Regioselectivity of the photochemical addition of phosphine to unsaturated hydrocarbons in the atmospheres of Jupiter and Saturn.

Phosphine (PH3) has been observed in the atmospheres of Jupiter and Saturn. We have studied the regioselectivity in the gaseous phase of the photochemical addition of PH3 to propene 1, propadiene 2, propyne 3, 1,3-butadiene 4 and 1,3-butadiyne 5. The photolysis were performed at 185 and 254 nm. The volatile products formed in these reactions were characterized by 1H and 31P NMR. The n-propylphosphine 6 and the isopropylphosphine 7 were the major products observed in the photolysis of PH3 with propene. The allylphosphine 8 was obtained when most of the light was absorbed by propene. This allylphosphine was the main product formed in the photolysis of PH3 in the presence of propadiene; the methylvinylphosphine 10 being not detected in these experiments, the reaction presents a very high regioselectivity. When most of the light was absorbed by propadiene, the propargylphosphine 9 was also observed. The photolysis of PH3 in the presence of propyne led to the E- and Z-1-propenylphosphines 12a,b and small amounts of methylvinylphosphine 10. Even when most of the light was absorbed by propyne, the propargylphosphine 9 was not observed. The Z-1-butene-3-ynylphosphine 13a and a mixture of primary phosphines containing the E-and Z-2-butenylphosphines 14a,b were obtained as major products when 1,3-butadiyne and 1,3-butadiene respectively where photolyzed with PH3. A high regioselectivity was thus observed in the photolysis of PH3 with an alkyne or an allene but alkenes led to mixtures of products.     

Model simulations of the impact of the 27-day solar rotation period on stratospheric ozone and temperature

Results are presented from two-year simulations of the effects of short-term solar ultraviolet (UV) variability using the Met. Office coupled chemistry-climate model. The model extends from the ground to 0.1 mbar and contains a complete range of chemical reactions allowing representation of all the main ozone formation and destruction processes in the stratosphere. The simulations were achieved by incorporating a 27-day oscillation in the pre-calculated model photolysis rates. Amplitudes for this signal were determined using solar spectral UV observations from the SOLar STellar Irradiance Comparison Experiment (SOLSTICE) instrument. Two experiments were carried out, one in which the UV variability was included in both the photolysis and radiation schemes and one in which only the photolysis scheme was modified.

The model reproduced several main features of observed correlations between short-term solar UV variability and both ozone and temperature in the tropical upper stratosphere, including the downward propagation of the phase lag and sensitivities of ozone and temperature to solar UV which are similar in magnitude to those observed. In the lower stratosphere, the ozone response to solar UV variability has not been well characterised from observations. Both model runs show a reversal of the propagation of phase lag below 10mb. The model response was found to be different between the two runs indicating that radiatively induced dynamical effects may play a significant role in the ozone response to solar UV variability.     

Photolysis of phosphine in the presence of acetylene and propyne, gas mixtures of planetary interest.

Phosphine (PH3) 1 has been observed in the atmospheres of Jupiter and Saturn. We have studied the photochemical reactions of this compound with acetylene (C2H2), an alkyne also detected in these atmospheres. The volatile products formed in these reactions were characterized by H, 31P and 13C NMR. The ethenylphosphine 2 is the first product formed in the photolysis of PH3 in the presence Of C2H2. Photolysis of PH3 in the presence of propyne (C3H4) led to the formation of the Z- and E-prop-1-enylphosphines and traces of 1-methylethenylphosphine. A reaction pathway is proposed. The initial step is the dissociation of PH3 to hydrogen and PH2 radicals. Addition of the phosphinyl radical on alkyne occurs as the next step. Vinylphosphines are then formed by radical combination. This proposed reaction pathway takes into account the nature of the products and studies devoted to the photolysis of germane (GeH4) or hydrogen sulfide (H2S) in the presence of alkyne. Attempts to detect the methylidynephosphine HC triple bond P (the isoelectronic compound of HC triple bond N), in the photolysis products of PH3-C2H2 mixtures were unsuccessful. The application of these findings to Jovian and Saturn atmospheric chemistry is discussed.     

Synthesis,chemistry and photochemistry of cyanobutadiyne (HCCCCCN)

Cyanobutadiyne has been synthesized starting from the mono or bistributylstannyl derivative of 1,3-butadiyne and p-toluenesulfonyl cyanide. The UV spectrum of HC₅N and the ¹³C NMR spectrum of the deuterocyanobutadiyne DC₅N have been recorded for the first time. Cyanobutadiyne has been detected in the photolysis of mixtures of gases observed on Titan. Its formation starting from cyanoacetylene and acetylene also occurs in the presence of huge amounts of dinitrogen, the major constituent of the Titan’s atmosphere. The application of these findings to the atmosphere of Titan is discussed. The chemistry and photochemistry of cyanobutadiyne have been investigated. A photoadduct has been observed in the photolysis of cyanoacetylene and ethanethiol and, a univocal synthesis of this compound was performed by a nucleophilic addition reaction.     

Formation of bioorganic compounds in simulated planetary atmospheres by high energy particles or photons.

Various types of organic compounds have been detected in Jupiter, Titan, and cometary coma. It is probable that organic compounds were formed in primitive Earth and Mars atmospheres. Cosmic rays and solar UV are believed to be two major energy sources for organic formation in space. We examined energetics of organic formation in simulated planetary atmospheres. Gas mixtures including a C-source (carbon monoxide or methane) and a N-source (nitrogen or ammonia) was irradiated with the followings: High energy protons or electrons from accelerators, gamma-rays from 60Co, UV light from a deuterium lamp, and soft X-rays or UV light from an electron synchrotron. Amino acids were detected in the products of particles, gamma-rays and soft X-rays irradiation from each gas mixture examined. UV light gave, however, no amino acid precursors in the gas mixture of carbon monoxide, nitrogen and nitrogen. It gave only a trace of them in the gas mixture of carbon monoxide, ammonia and water or that of methane, nitrogen and water. Yield of amino acid precursors by photons greatly depended on their wavelength. These results suggest that nitrogen-containing organic compounds like amino acid precursors were formed chiefly with high energy particles, not UV photons, in Titan or primitive Earth/Mars atmospheres where ammonia is not available as a predominant N-source.     

Numerical modelling of radiance of the presumed dust torus around Mars in the 0.350–1 μm spectral range

With the use of high performance liquid chromatography the products of abiogenic synthesis of adenine nucleotides in solid films were indentified and estimated quantitatively. The main products of photosynthesis appeared to be adenosine and deoxyadenosine monophosphates. Maximal yield of these products in case of adenosine has been 0.36 for 5′AMP, 0.41% for 2′(3′)AMP, 0.20 for 2′3′cAMP; in case of deoxyadenosine 0.13% for 5′dAMP, 0.15% for 3′dAMP, 0.24% for 3′5′cdAMP. The destruction of initial adenosine and deoxyadenosine by the end of the experiment was 10 and 15%, respectively. By the increasing of irradiation dose, 5′AMP and 5′dAMP synthesized in the cource of VUV photolysis were destructed up to adenine, its yield being 15% in both cases.     

Simulation experiments of the effect of space environment on bacteriophage and DNA thin films.

The main goal of PUR experiment (phage and uracil response) is to examine and quantify the effect of specific space conditions on nucleic acid models. To achieve this an improved method was elaborated for the preparation of DNA and bacteriophage thin films. The homogeneity of the films was controlled by UV spectroscopy and microscopy. To provide experimental evidence for the hypothesis that interplanetary transfer of the genetic material is possible, phage T7 and isolated T7 DNA thin films have been exposed to selected space conditions: intense UVC radiation (lambda=254 nm) and high vacuum (10(-4) Pa). The effects of DNA hydration, conformation and packing on UV radiation damage were examined. Characteristic changes in the absorption spectrum, in the electrophoretic pattern of DNA and the decrease of the amount of PCR products have been detected indicating the photodamage of isolated and intraphage DNA.     

IUE and Einstein observations of supernovae

In this paper IUE observations of two type II and three type I Supernovae (see Table I and Table II) are reviewed. The type II events were also observed by Einstein and SN 1980k was detected in the soft X-ray energy band. Combining UV spectra available of the same events one has the elements to construct a physical picture which accounts for all observations. For the type II events it appears that the progenitor star was a massive supergiant which underwent a severe mass loss before becoming Supernova. For the type I events there is neither X-ray nor, for the time being, radio detection. The high similarity of the optical and UV spectra for the three events indicates that type I Supernovae are the end products of one and the same phenomenon.     

Laboratory simulation of the photoprocessing and warm-up of cometary and pre-cometary ices: production and analysis of complex organic molecules.

The possibility that the organic molecules that have been found near comets could have formed by UV photolysis of interstellar ices was investigated by simulating this process in the laboratory. It is found that oxygen rich organics containing C-OH, C-H and C=O groups are readily produced in this way. These results indicate that part of the organic material in comets may have formed by UV irradiation of ices, either in the pre-solar nebula or in the interstellar phase.     

Monitoring of biologically effective UV irradiance at El Arenosillo (INTA), Andalucia, in Spain.

Biological UV (ultraviolet) dosimetry was applied using the biofilm-technique (DLR patent) to determine the UV levels weighted of biologically weighted UV radiation at the INTA Sounding Station of El Arenosillo at Huelva, Spain (37 degrees 06'N, 6 degrees 44'W, 50 m a s 1=above sea level) on 2 days in 1997 [correction of 1977] (April 1, and May 5). Exposure periods were calculated for clear sky days using a radiative transfer model for erythemal doses to reach 1.3 to 1.5 MED (minimal erythemal dose). Reliability of the radiative transfer model was demonstrated by the doses registered by a Yankee-UV biometer for the same exposure periods as used for the biosensor. This work presents the methodology employed (biofilm-technique utilized [correction of utiliced], calculation of exposing periods with radiative transfer model, etc) and the results obtained with the Yankee biometer and the biofilm. At noon, the ratio of biofilm measurements (Ieff, W/m2=biological effective irradiance, in W/m2) to the UV Biometer data (in MED/h) was 3-4.     

Biological UV dosimeters in simulated space conditions.

Polycrystalline uracil thin layers participate in the phage and uracil response (PUR) experiment, assigned to the biological dosimetry of the extraterrestrial solar radiation on the International Space Station (ISS). In ground based experiments (experiment verification tests), the following space parameters were simulated and studied: temperature, vacuum and short wavelength UV (UV-C, down to 200 nm) radiation. The closed uracil samples proved to be vacuum-tight for 7 days. In the tested temperature range (from -20 to +40 degrees C) the uracil samples are stable. The kinetic of dimer formation (dimerization) and reversion (monomerization) of uracil dimers due to short wavelength UV radiation was detected, the monomerization efficiency of the polychromatic deuterium lamp is higher than that of the germicidal lamp. A mathematical model describing the kinetic of monomerization-dimerization was constructed. Under the influence of UV radiation the dimerization-monomerization reactions occur simultaneously, thus the additivity law of the effect of the various wavelengths is not applicable.     

Development of an extreme ultraviolet imaging spectrometer for the BepiColombo mission

Extreme and far ultraviolet imaging spectrometers are proposed for the low-altitude orbiter of the BepiColombo mission. The UV instrument, consisting of the two spectrometers with common electronics, aims at measuring (1) emission lines from molecules, atoms and ions present in the Mercury’s tenuous atmosphere and (2) the reflectance spectrum of Mercury’s surface. The instrument pursues a complete coverage in UV spectroscopy. The extreme UV spectrometer covers the spectral range of 30–150 nm with the field of view of 5.0°, and the spectrum from 130 to 430 nm is obtained by the far UV spectrometer. The extreme UV spectrometer employs multi-layer coating technology to enhance its sensitivity at particular emission lines. This technology enables us to identify small ionospheric signatures such as He II (30.4 nm) and Na II (37.2 nm), which could not be detected with conventional optics.     

Thymine photoproduct formation and inactivation of intact spores of Bacillus subtilis irradiated with short wavelength UV (200-300nm) at atmospheric pressure and in vacuo.

Vacuum exposure renders the survival of spores of Bacillus subtilis approximately five times more sensitive to ultraviolet light irradiation than exposure under atmospheric conditions. The photoproduct formation in spores irradiated under ultrahigh vacuum (UHV) conditions is compared to the photoproduct formation in spores irradiated at atmospheric pressure. Compared to irradiation at atmospheric pressure, where only the "spore photoproduct" 5-thyminyl-5,6-dihydrothymine (TDHT) can be detected, two additional photoproducts, known as the c,s and t,s isomers of thymine dimer (T<>T) are produced in vacuo. The spectral efficiencies for photoproduct formation in spores under atmospheric and vacuum conditions are compared. Since there is no increased formation of TDHT after irradiation in vacuum, TDHT cannot be made responsible for the observed vacuum effect. "Vacuum specific" photoproducts may cause a synergistic response of spores to the simultaneous action of ultraviolet light (UV) and UHV. Three different mechanisms are discussed for the enhanced sensitivity of B. subtilis spores to UV radiation in vacuum. The experiments described contribute valuable research information on the chance for survival of microorganisms in outer space.     

XANES analysis of organic residues produced from the UV irradiation of astrophysical ice analogs

Organic residues formed in the laboratory from the ultraviolet (UV) photo-irradiation or ion bombardment of astrophysical ice analogs have been extensively studied for the last 15 years with a broad suite of techniques, including infrared (IR) and UV spectroscopies, as well as mass spectrometry. Analyses of these materials show that they consist of complex mixtures of organic compounds stable at room temperature, mostly soluble, that have not been fully characterized. However, the hydrolysis products of these residues have been partly identified using chromatography techniques, which indicate that they contain molecular precursors of prebiotic interest such as amino acids, nitrile-bearing compounds, and amphiphilic compounds. In this study, we present the first X-ray absorption near-edge structure (XANES) spectroscopy measurements of three organic residues made from the UV irradiation of ices having different starting compositions. XANES spectra confirm the presence of different chemical functions in these residues, and indicate that they are rich in nitrogen- and oxygen-bearing species. These data can be compared with XANES measurements of extraterrestrial materials. Finally, this study also shows how soft X rays can alter the chemical composition of samples.     

Inhibition of denitrification by ultraviolet radiation.

It has been shown that UV-A (lambda=320-400 nm) and UV-B (lambda=280-320 nm) inhibit photosynthesis, nitrogen fixation and nitrification. The purpose of this study was to determine the effects, if any, on denitrification in a microbial community inhabiting the intertidal. The community studied is the microbial mat consisting primarily of Lyngbya that inhabits the Pacific marine intertidal, Baja California, Mexico. Rates of denitrification were determined using the acetylene blockage technique. Pseudomonas fluorescens (ATCC #17400) was used as a control organism, and treated similarly to the mat samples. Samples were incubated either beneath a PAR transparent, UV opaque screen (OP3), or a mylar screen to block UV-B, or a UV transparent screen (UVT) for 2 to 3 hours. Sets of samples were also treated with nitrapyrin to inhibit nitrification, or DCMU to inhibit photosynthesis and treated similarly. Denitrification rates were greater in the UV protected samples than in the UV exposed samples the mat samples as well as for the Ps fluorescens cultures. Killed controls exhibited no activity. In the DCMU and nitrapyrin treated samples denitrification rates were the same as in the untreated samples. These data indicate that denitrification is directly inhibited by UV radiation.     

Chemical evolution of RNA under hydrothermal conditions and the role of thermal copolymers of amino acids for the prebiotic degradation and formation of RNA.

The roles of thermal copolymers of amino acids (TCAA) were studied for the prebiotic degradation of RNA. A weak catalytic ability of TCAA consisted of Glu, L-Ala, L-Val, L-Glu, L-Asp, and optionally L-His was detected for the cleavage of the ribose phosphodiester bond of a tetranucleotide (5'-dCrCdGdG) in aqueous solution at 80 degees C. The rate constants of the disappearance of 5'-dCrCdGdG were determined in aqueous solutions using different pH buffer and TCAA. The degradation rates were enhanced 1.3-3.0 times in the presence of TCAA at pH 7.5 and 8.0 at 80 degrees C, while the hydrolysis of oligoguanylate (oligo(G)) was accelerated about 1.6 times at pH 8.0. A weak inhibitory activity for the cleavage of oligo(G) was detected in the presence of 0.055 M TCAA-Std. On the other hand, our recent study on the influences of TCAA for the template-directed reaction of oligo(G) on a polycytidylic acid template showed that TCAA has an acceleration activity for the degradation of the activated nucleotide monomer and an acceleration activity for the formation of G5' ppG capped oligo(G). This series of studies suggest that efficient and selective catalytic or inhibitory activities for either the degradation or formation of RNA under hydrothermal conditions could have hardly emerged from the simple thermal condensation products of amino acids. A scenario is going to be deduced on the chemical evolution of enzymatic activities and RNA molecules concerning hydrothermal earth conditions.     

Photoproducts in DNA irradiated in vitro and in vivo under extreme environmental conditions.

UV-irradiated DNA forms different photoproducts in accordance with its state of hydration, and the environment in which the irradiation takes place. Photoproducts in addition to the well-known thymine dimer are produced, some of which probably not recognized due to being heat or acid labile, and milder methods for DNA hydrolysis are needed. The isolation, structure and properties of photoproducts which are formed in UV-irradiated frozen thymine solutions are described. Urea, n-propylurea and dihydrothymine are obtained as photolytic products by high radiation doses in low concentrations of thymine. The cyclobutane cis-anti thymine dimer is obtained at high concentrations of thymine, following several cycles of freezing, thawing and irradiations. A trimer is obtained with 290 nm UV light filtered through Pyrex. It reverts back to thymine dimer and thymine when reirradiated in solution. The cis-syn dimer is obtained at all concentrations of frozen thymine and in a dose dependent form. The adduct 5-hydroxy-6-4' (5'-methylpyrimid 2'-1) dihydrothymine is also obtained. In vacuum-dried thymine or DNA, other photoproducts are formed, including the spore-product, TDHT. Several solvent systems were used to develop chromatograms that allow separation of photoproducts.     

Biological dosimetry to determine the UV radiation climate inside the MIR station and its role in vitamin D biosynthesis

The vitamin D synthesis in the human skin, is absolutely dependent on UVB radiation. Natural UVB from sunlight is normally absent in the closed environment of a space station like MIR. Therefore it was necessary to investigate the UV radiation climate inside the station resulting from different lamps as well as from occasional solar irradiation behind a UV-transparent quartz window. Biofilms, biologically weighting and integrating UV dosimeters successfully applied on Earth (e.g. in Antarctica) and in space (D-2, Biopan I) were used to determine the biological effectiveness of the UV radiation climate at different locations in the space station. Biofilms were also used to determine the personal UV dose of an individual cosmonaut. These UV data were correlated with the concentration of vitamin D in the cosmonaut's blood and the dietary vitamin D intake. The results showed that the UV radiation climate inside the Mir station is not sufficient for an adequate supply of vitamin D, which should therefore be secured either by vitamin D supplementat and/or by the regular exposure to special UV lamps like those in sun-beds. The use of natural solar UV radiation through the quartz window for ‘sunbathing’ is dangerous and should be avoided even for short exposure periods.     

The ROSAT all-sky survey

The ROSAT (Röntgensatellit) X-ray astronomy satellite has completed the first all-sky X-ray and XUV survey with imaging telescopes. About 60,000 new X-ray and 400 new XUV /1/ sources were detected. This contribution will deal with preliminary results from the ROSAT ALL-SKY X-RAY SURVEY. The ROSAT diffuse and point-source X-ray skymaps, the positional accuracy obtained for the X-ray sources, and a few results from correlations performed with available catalogues in various energy bands like the Radio, Infrared, Visible, UV, and hard X-rays as well as identifications from optical follow-up observations are presented.     

环氧共混树脂的光固化及其表面化学反应

研究了双酚A型环氧树脂与有机硅环氧树脂紫外光辐照共混改性的工艺条件,并采用扫描电镜和X射线光电子能谱等分析手段对树脂改性效果和表面的物理和化学变化进行了研究.结果表明,采用二苯基碘鎓六氟磷酸盐为光引发剂,当质量分数为5％时,随着E-44含量的增加,共混树脂体系的光固化速度加快.当两者质量比为1∶ 2时,经15min的紫外光辐照后,共混树脂体系的凝胶率可达93％.X射线光电子能谱分析结果表明,在光固化的同时,试样的表面被紫外光辐照时产生的臭氧和原子氧部分氧化,转化为一层含C的氧化硅(SiO _{x )膜.}