Complex organics in laboratory simulations of interstellar/cometary ices.

We present the photochemical and thermal evolution of both non-polar and polar ices representative of interstellar and pre-cometary grains. Ultraviolet photolysis of the non-polar ices comprised of O2, N2, and CO produces CO2, N2O, O3, CO3, HCO, H2CO, and possibly NO and NO2. When polar ice analogs (comprised of H2O, CH3OH, CO, and NH3) are exposed to UV radiation, simple molecules are formed including: H2, H2CO, CO2, CO, CH4, and HCO (the formyl radical). Warming produces moderately complex species such as CH3CH2OH (ethanol), HC(=O)NH2 (formamide), CH3C(=O)NH2 (acetamide), R-CN and/or R-NC (nitriles and/or isonitriles). Several of these are already known to be in the interstellar medium, and their presence indicates the importance of grain processing. Infrared spectroscopy, 1H and 13C nuclear magnetic resonance (NMR) spectroscopy, and gas chromatography-mass spectrometry demonstrate that after warming to room temperature what remains is an organic residue composed primarily of hexamethylenetetramine (HMT, C6H12N4) and other complex organics including the amides above and polyoxymethylene (POM) and its derivatives. The formation of these organic species from simple starting mixtures under conditions germane to astrochemistry may have important implications for the organic chemistry of interstellar ice grains, comets and the origins of life.     

贫燃型汽车尾气NOx的催化净化

用溶胶-凝胶混合法制备了Al₂O₃,Ag/Al₂O₃,Sn/Al₂O₃,Ga/Al₂O₃,Co/Al₂O₃和Pt/Al₂O₃等催化剂.在相同实验条件下,比较了C₃H₆在这些催化剂上还原NO的活性,并考察了反应条件对C₃H₆和CH₃OH在Ag/Al₂O₃上还原NO性能的影响.结果表明,Ag/Al₂O₃的还原NO活性优于其它催化剂.H₂O对Ag/Al₂O₃催化剂的NO还原具有可逆抑制作用,SO₂降低C₃H₆在Ag/Al₂O₃上还原NO的活性,但会显著提高CH₃OH还原NO的活性.     

Gravity wave mixing effects on the OH*-layer

Based on an advanced numerical model for excited hydroxyl (OH*) we simulate the effects of gravity waves (GWs) on the OH*-layer in the upper mesosphere. The OH* model takes into account (1) production by the reaction of atomic hydrogen (H) with ozone (O₃), (2) deactivation by atomic oxygen (O), molecular oxygen (O₂), and molecular nitrogen (N₂), (3) spontaneous emission, and (4) loss due to chemical reaction with O. This OH* model is part of a chemistry-transport model (CTM) which is driven by the high-resolution dynamics from the KMCM (Kühlungsborn Mechanistic general Circulation Model) which simulates mid-frequency GWs and their effects on the mean flow in the MLT explicitly. We find that the maximum number density and the height of the OH*-layer peak are strongly determined by the distribution of atomic oxygen and by the temperature. As a results, there are two ways how GWs influence the OH*-layer: (1) through the instantaneous modulation by O and T on short time scales (a few hours), and (2) through vertical mixing of O (days to weeks). The instantaneous variations of the OH*-layer peak altitude due to GWs amount to 5–10 km. Such variations would introduce significant biases in the GW parameters derived from airglow when assuming a constant pressure level of the emission height. Performing a sensitivity experiment we find that on average, the vertical mixing by GWs moves the OH*-layer down by ~2 to 7 km and increases its number density by more than 50%. This effect is strongest at middle and high latitudes during winter where secondary GWs generated in the stratopause region account for large GW amplitudes.     

Sterilisation properties of the Mars surface and atmospheric environment.

The radiative and chemical conditions at the surface and in the lower Martian atmosphere are computed at various latitudes and seasons combining a 2D photochemical model and radiation simulations. In most situations, the solar UV B and C radiations reach the surface however, suspended dust and, in polar cases, ozone can constitute an effective UV shield. The daytime and night time concentrations of the sterilizing oxidants: OH, H2O2 and O3 are determined, as well as the concentration of the substances which could influence the metabolism of microorganisms. The possible habitats of a remaining Mar's life as well as the possibilities of contamination by resistant earth life forms will be described.     

New considerations of the oxygen effects in radiation biology.

The original demonstration in the bacterial spore of the multiple actions of oxygen in modifying the responses of cells to ionizing radiation has now been verified in mammalian systems, pointing up the need for separate inquiry into each of the several components if the responses of mammalian cells are to be understood. We have provided physico-chemical explanations for only two of the four (at least) oxygen elements recognized in the spore: the reaction of diatomic oxygen with organic free radicals in dry spores; and an action of the hydroxy radical (OH) in spores at low [O2]. This paper will discuss newly recognized features of the oxygen responses that could reveal the nature of the other components. It will examine modulation of response by oxides of nitrogen, the similarities and differences among them and explanations for them that suggest further experiment, the importance of concentration of additive in determining both quantity and quality of response, and a general model that explains sensitizer action in terms of inhomogeneous chemistry.     

Oxygen effect, hydrogen peroxide yields, and time scale of interaction of potentially damaging species in electron pulse irradiated bacterial spores.

A given integrated radiation dose delivered from a LINAC as a train of pulses (50/s), characteristically of 0.1 to 5 microseconds pulse length with dose rates within the pulse between 0.38 and 38 krads/microsecond, inactivates bacterial spores in water suspension more effectively than the same dose given as Co60 gamma rays. This enhancement of radiation damage occurs both in the presence and in the absence of oxygen and is not explained by either pulse dose rate or pulse length alone, but is monotonically related to the product of these pulse parameters, pulse dose. The enhancement appears to result from the interaction, within individual spores, of free radical species of average lifetime of about 2-5 microseconds. The time scale over which these species operate suggests that they are freely diffusable. Prevention, in part, of their damaging effect by the presence of selective scavenging agents is evidence that OH radicals are involved. Measurements of H2O2 yield for irradiation conditions that show a gradation of enhancement of damage correlate strongly with the extent of damage observed.     

Potential vascular damage from radiation in the space environment.

Cultured endothelial cells of blood vessels have a Do of 2 Gy for X-rays. A dose of 0.5 Gy of X-rays has an acute effect on vessel diameter. The vessels may show other acute effects such as change in permeability including a change in the blood brain barrier. Changes occurring from late effects of chronic exposure in vascular architecture include telangiectasia and decrease in vascular density. Changes in the perivascular connective tissue particularly collagen may play a role in these changes. After charged particle exposure of 15 and 30 Gy, radiation changes in the blood brain barrier and vascular changes are noted in the nervous system. These long term changes are recorded by PET, MRI, and CT imaging. Chronic exposure to alpha particles causes vascular damage in compact bone resulting in bone infarcts. Using tandem scanning confocal microscopy in-situ imaging of the capillaries and collagen of the papillary dermis provides a non-invasive method of serial recording of changes in irradiated microvasculature.     

Radiolysis of aqueous formaldehyde relevant to cometary environments.

The radiation chemistry of aqueous solutions of formaldehyde was studied in order to obtain an insight into the possible role of ionizing radiation on cometary environments. Aqueous solutions of 1.0 mol dm-3 formaldehyde were exposed to gamma-radiation in the dose range from 0.01 to 1200 kGy at 298 K. The radiation chemical yield of decomposition of formaldehyde was determined to be: G(-CH2(OH)2)-26.3 +/- 1.2. The high radiation chemical yield of decomposition was explained by a chain reaction initiated by the radical CH(OH)2 with formaldehyde. Computer fitting of the experimental data gives k(CH(OH)2 + CH2(OH)2)- 8.0xl0(1) dm3 mol-1 s-1. In the computer treatment of experimental findings we used 54 equations to consider the radiolysis of water and 11 reactions for the radiolysis of aqueous formaldehyde. Based on previous estimates of the total dose of ionizing radiation that comets have accumulated over 4.6 billion years, we predict a radiation damage-depth curve of formaldehyde in comet nuclei.     

Radiation effects on late cytopathological parameters in the murine lens relative to particle fluence.

Lenses of mice irradiated with 250 MeV protons, 670 MeV/amu 20Ne, 600 MeV/amu 56Fe, 600 MeV/amu 93Nb and 593 MeV/amu 139La ions were evaluated by analyzing cytopathological indicators which have been implicated in the cataractogenic process. The LETs ranged from 0.40 keV/micrometer to 953 keV/micrometer and fluences from 1.31 10(3)/mm2 to 4.99 x 10(7)/mm2. 60Co gamma-rays were used as the reference radiation. The doses ranged from 10 to 40 cGy. The lenses were assessed 64 weeks post irradiation in order to observe the late effects of LET and dose on the target cell population of the lens epithelium. Our study shows that growth dependent pathological changes occur at the cellular level as a function of dose and LET. The shapes of the RBE-LET and RBE-dose curves are consistent with previous work on eye and other biological systems done in both our laboratory and others. The RBEmax's were estimated, for the most radiation cataract related cytological changes, MN frequency and MR disorganization, by calculating the ratio of the initial slopes of dose effect curve for various heavy ions to that of 60Co gamma-ray. For each ion studied, the RBEmax derived from micronucleus (MN) frequency is similar to that derived from meridional row (MR) disorganization, suggesting that heavy ions are equally efficient at producing each type of damage. Furthermore, on a per particle basis (particle/cell nucleus), both MN frequency and MR disorganization are LET dependent indicating that these classic precataractogenic indicators are multi-gene effects. Poisson probability analysis of the particle number traversing cell nuclei (average area = 24 micrometers2) suggested that single nuclear traversals determine these changes. By virtue of their precataractogenic nature the data on these endpoints intimate that radiation cataract may also be the consequence of single hits. In any case, these observations are consistent with the current theory of the mechanism of radiation cataractogenesis, which proposes that genomic damage to the epithelial cells surviving the exposure is responsible for opacification.     

DNA-lesion and cell death by alpha-particles and nitrogen ions.

When the natural logarithm of the surviving fraction is plotted against the dose of radiation, curves with shoulders at relatively high survival levels are obtained after gamma-rays. The curves were practically linear in case of HMV-I and HA-1 cells irradiated by charged particle beams. These cells were derived from human malignant melanoma and Chinese hamster cells, respectively. The amount of DNA single strand breaks (ssb) by gamma-rays or nitrogen-ions (LET=530KeV/micrometers) in HMV-I cells increases linearly with increment in dose, when the ssb is detected using the alkaline elution technique. There is no close relationship between the dose-response curve of the ssb and the dose-survival curves after gamma-rays or N-ions. The amount of DNA double strand breaks (dsb) by gamma-rays increases quadratically with increment of dose, in both HMV-I cells and HA-1 cells, when the dsb is detected using the neutral elution technique. The survival fraction for HA-1 cells is slightly higher than that for HMV-I cells, at the same dose, and the amount of dsb for HA-1 cells is considerably greater than that for HMV-I cells. These results suggest that the radiosensitivities to gamma-rays in different cell lines do not correspond to the number of DNA strand breaks. The amount of both non-repairable ssb and dsb also increases quadratically with increment of dose for gamma-rays and almost linearly with increment of dose for N-ions and alpha-particles (LET=36keV/micrometers for HA-1 cells and LET=77keV/micrometers for HMV-I cells). The dose-response curves for non-repairable dsb in case of these radiations seemed to mirror image the dose-survival curves for these radiations, in both cell lines. The number of non-repairable DNA strand breaks in the two cell lines, at the same level of survival was much the same. These results show the close relationship between the induction of non-repairable DNA strand breaks and cell killing.     

In vivo and in vitro measurements of complex-type chromosomal exchanges induced by heavy ions.

Heavy ions are more efficient in producing complex-type chromosome exchanges than sparsely ionizing radiation, and this can potentially be used as a biomarker of radiation quality. We measured the induction of complex-type chromosomal aberrations in human peripheral blood lymphocytes exposed in vitro to accelerated H-, He-, C-, Ar-, Fe- and Au-ions in the LET range of approximately 0.4-1400 keV/micrometers. Chromosomes were analyzed either at the first post-irradiation mitosis, or in interphase, following premature condensation by phosphatase inhibitors. Selected chromosomes were then visualized after FISH-painting. The dose-response curve for the induction of complex-type exchanges by heavy ions was linear in the dose-range 0.2-1.5 Gy, while gamma-rays did not produce a significant increase in the yield of complex rearrangements in this dose range. The yield of complex aberrations after 1 Gy of heavy ions increased up to an LET around 100 keV/micrometers, and then declined at higher LET values. When mitotic cells were analyzed, the frequency of complex rearrangements after 1 Gy was about 10 times higher for Ar- or Fe- ions (the most effective ions, with LET around 100 keV/micrometers) than for 250 MeV protons, and values were about 35 times higher in prematurely condensed chromosomes. These results suggest that complex rearrangements may be detected in astronauts' blood lymphocytes after long-term space flight, because crews are exposed to HZE particles from galactic cosmic radiation. However, in a cytogenetic study of ten astronauts after long-term missions on the Mir or International Space Station, we found a very low frequency of complex rearrangements, and a significant post-flight increase was detected in only one out of the ten crewmembers. It appears that the use of complex-type exchanges as biomarker of radiation quality in vivo after low-dose chronic exposure in mixed radiation fields is hampered by statistical uncertainties.     

Effects of gamma-ray and high energy carbon ion irradiation on swimming velocity of Euglena gracilis.

The effects of gamma-ray and high energy carbon ion irradiation on the swimming velocity of the photosynthetic flagellate Euglena gracilis strain Z were studied, focusing on a dose-effect relationship. Cells were exposed to 60Co gamma-rays at 6 doses of 10, 15, 20, 40, 100 and 200 Gy for water, and also to 290 MeV/amu carbon ions from the Heavy Ion Medical Accelerator in Chiba at 7 doses (5, 10, 15, 20, 50, 100 and 200 Gy for water). The swimming velocity was measured by a biomonitoring system, called ECOTOX. The swimming velocities of Euglena gracilis cells were significantly decreased by >40 Gy gamma-rays and >5 Gy carbon ions, respectively. The 50% effective doses for inhibition, 34 +/- 4 Gy (gamma-rays) and 13 +/- 1 Gy (290 MeV/amu carbon ions), were estimated from the best fit to data of the logistic model. The relative biological effectiveness (2.6 +/- 0.4) was calculated by the ratio of 50% effective doses. The inhibition of the swimming velocity of the cells irradiated with gamma-rays was still present after 3 days, while recovery of the swimming velocity was shown in the cells exposed to 290 MeV/amu carbon ions. It is suggested that ionizing radiation inhibits ATP production and/or increases frictional drag on beating of the flagellum, thus decreasing swimming velocity.     

Survival of irradiated mice treated with WR-151327, synthetic trehalose dicorynomycolate, or ofloxacin.

Spaceflight personnel need treatment options that would enhance survival from radiation and would not disrupt task performance. Doses of prophylactic or therapeutic agents known to induce significant short-term (30-day) survival with minimal behavioral (locomotor) changes were used for 180-day survival studies. In protection studies, groups of mice were treated with the phosphorothioate WR-151327 (200 mg/kg, 25% of the LD(10)) or the immunomodulator, synthetic trehalose dicorynomycolate (S-TDCM; 8 mg/kg), before lethal irradiation with reactor-generated fission neutrons and gamma-rays (n/gamma=1) or 60Co gamma-rays. In therapy studies, groups of mice received either S-TDCM, the antimicrobial ofloxacin, or S-TDCM plus ofloxacin after irradiation. For WR-151327 treated-mice, survival at 180 days for n/gamma=1 and gamma-irradiated mice was 90% and 92%, respectively; for S-TDCM (protection), 57% and 78%, respectively; for S-TDCM (therapy), 20% and 25%, respectively; for ofloxacin, 38% and 5%, respectively; for S-TDCM combined with ofloxacin, 30% and 30%, respectively; and for saline, 8% and 5%, respectively. Ofloxacin or combined ofloxacin and S-TDCM increased survival from the gram-negative bacterial sepsis that predominated in n/gamma=1 irradiated mice. The efficacies of the treatments depended on radiation quality, treatment agent and its mode of use, and microflora of the host.     

The influence of dose, dose-rate and particle fragmentation on cataract induction by energetic iron ions.

Because activities in space necessarily involve chronic exposure to a heterogeneous charged particle radiation field it is important to assess the influence of dose-rate and the possible modulating role of heavy particle fragmentation on biological systems. Using the well-studied cataract model, mice were exposed to plateau 600 MeV/amu 56Fe ions either as acute or fractionated exposures at total doses of 5 - 504 cGy. Additional groups of mice received 20, 360 and 504 cGy behind 50 mm of polyethylene, which simulates body shielding. The reference radiation consisted of 60Co gamma radiation. The animals were examined by slit lamp biomicroscopy over their three year life spans. In accordance with our previous observations with heavy particles, the cataractogenic potential of the 600 MeV/amu 56Fe ions was greater than for low-LET radiation and increased with decreasing dose relative to gamma-rays. Fractionation of a given dose of 56Fe ions did not reduce the cataractogenicity of the radiation compared to the acute regimen. Fragmentation of the beam in the polyethylene did not alter the cataractotoxicity of the ions, either when administered singly or in fractions.     

Neuroimmune response and sleep studies after whole body irradiation with high-LET particles

In order to investigate the biological effects of galactic rays on astronaut cerebral functions after space flight, mice were exposed to different heavy ions (HZE) in whole-body conditions at doses comparable to the galactic flux: ¹²C, ¹⁶O and ²⁰Ne (95 MeV/u, at 42–76 mGy). Animals were also exposed to 42 mGy of ⁶⁰Co radiation for comparison with HZE. The neuroimmune response, evaluated by interleukin-1 (IL-1) measurement, showed that this cytokine was produced 3 h after irradiation by ¹⁶O or ⁶⁰Co. In contrast, neither ¹²C (56.7 mGy) nor ²⁰Ne (76 mGy) induced IL-1 production. However, immunohistochemical staining of ¹²C-irradiated mouse brain tissue showed 2 months later a marked inflammatory reaction in the hippocampus and a diffuse response in parenchyma. Sleep studies were realized before and after exposure to 42 mGy of ¹⁶O and 76 mGy of ²⁰Ne: only the ²⁰Ne radiation displayed a small effect. A slight decrease in paradoxical sleep, corresponding to a reduction in the number of episodes of paradoxical sleep, was manifested between 8 and 22 days after exposure. Exposure to ¹²C and ¹⁶O induced no changes either in cellularity of spleen or thymus, or in caspase 3 activity (as much as four months after irradiation). Taken together, these data indicate that the CNS could be sensitive to heavy ions and that responses to HZE impact depend on the nature of the particle, the dose threshold and the time delay to develop biological processes. Differences in responses to different HZE highlight the complex biological phenomena to which astronauts are submitted during space flight.     

Crystallization of calcium phosphate in microgravity.

Dilute solutions of CaCl2 and KH2PO4 + K2HPO4 were diffusing from either side into a mixing chamber with KCl solution. The microgravity experiment yielded aggregates of large crystals of OCP (Ca8H2(PO4)3,5H2O) and spherolites of smaller, but still visible crystals of HAP (Ca5OH(PO4)3), the stable final phase. Ground-based experiments yielded submicroscopic HAP crystals. Results of calculations of diffusion and crystal growth on the basis of previous knowledge agree well with observations.     

Mutagenic effects of heavy ions in bacteria.

The peculiarities and mechanisms of the mutagenic action of gamma-rays and heavy ions on bacterial cells have been investigated. Direct mutations in the lac-operon of E. coli in wild type cells and repair deficient strains have been detected. Furthermore, the induction of revertants in Salmonella tester strains was measured. It was found that the mutation rate was a linear-quadratic function of dose in the case of both gamma-rays and heavy ions with LET up to 200 keV/micrometer. The relative biological effectiveness (RBE) increased with LET up to 20 keV/micrometer. Low mutation rates were observed in repair deficient mutants with a block of SOS-induction. The induction of SOS-repair by ionizing radiation has been investigated by means of the "SOS-chromotest" and lambda-prophage induction. It was shown that the intensity of the SOS-induction in E. coli increased with increasing LET up to 40-60 keV/micrometer.     

Peroxides and the survivability of microorganisms on the surface of Mars.

Results of the Viking mission seem to indicate that there is a ubiquitous layer of highly oxidizing aeolian material covering the Martian surface. This layer is thought to oxidize organic material that may settle on it, and is therefore responsible for the lack of detection of organic matter on the planet's surface by Viking. The mechanism that creates the oxidizing condition is not well understood, nor is the extent of the oxidation potential of this material. It has been suggested that the oxidizing nature of the soil is due to photochemical reactions which create hydrogen peroxide and superoxides in the surface soil. One question of importance to planetary protection regarding this material is, what is its potential for destroying terrestrial microorganisms, thus making the surface of Mars "self-sterilizing"? Using data obtained by the gas exchange experiment on Viking, and for simplicity assuming that all of the O2 released came from H2O2, the concentration range for H2O2 on the surface of Mars can be calculated to be 25-250 ppm. The microbial disinfection rate by H2O2 is concentration dependent, and is highly variable within the microbial community. Data from our laboratory indicate that certain soil bacteria survive and grow to stationary phase in 30,000 ppm H2O2. However, the total number of organisms decreases in the presence of H2O2. These results indicate that it is doubtful that the presence of H2O2 alone on Mars would make the surface "self-sterilizing".     

The effect of space radiation of the nervous system.

The long-term effects of irradiation by accelerated heavy ions on the structure and function of the nervous system have not been studied extensively. Although the adult brain is relatively resistant to low LET radiation, cellular studies indicate that individual heavy ions can produce serious membrane lesions and multiple chromatin breaks. Capillary hemorrhages may follow high LET particle irradiation of the developing brain as high RBE effects. Evidence has been accumulating that the glial system and blood-brain barrier (BBB) are relatively sensitive to injury by ionizing radiation. While DNA repair is active in neural systems, it may be assumed that a significant portion of this molecular process is misrepair. Since the expression of cell lethality usually requires cell division, and nerve cells have an extremely low rate of division, it is possible that some of the characteristic changes of premature aging may represent a delayed effect of chromatin misrepair in brain. Altered microcirculation, decreased local metabolism, entanglement and reduction in synaptic density, premature loss of neurons, myelin degeneration, and glial proliferation are late signs of such injuries. HZE particles are very efficient in producing carcinogenic cell transformation, reaching a peak for iron particles. The promotion of viral transformation is also efficient up to an energy transfer of approximately 300 keV/micron. The RBE for carcinogenesis in nerve tissues remains unknown. On the basis of available information concerning HZE particle flux in interplanetary space, only general estimates of the magnitude of the effects of long-term spaceflight on some nervous system parameters may be constructed.     

Probability of cell hits in selected organs and tissues by high-LET particles at the ISS orbit.

The fluence of high-LET particles (HLP) with LET infinity H2O greater than 15 keV micrometers-1 in selected organs and tissues were measured with plastic nuclear track detectors using a life-size human phantom on the 9th Shuttle-Mir Mission (STS-91). The planar-track fluence of HLP during the 9.8-day mission ranged from 1.9 x 10(3) n cm-2 (bladder) to 5.1 x 10(3) n cm-2 (brain) by a factor of 2.7. Based on these data, a probability of HLP hits to a matured cell of each organ or tissue was roughly estimated for a 90-day ISS mission. In the calculation, all cells were assumed to be spheres with a geometric cross-sectional area of 500 micrometers2 and the cell-hit frequency from isotropic space radiation can be described by the Poisson-distribution function. As results, the probability of one or more than 1 hit to a single cell by HLP for 90 days ranged from 17% to 38%; that of two or more than 2 hits was estimated to be 1.3-8.2%.