Letter: Complexes of benzyl isocyanide with ferrous phthalocyanine. A model for the heme group and a solar energy storage system.
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Irradiation of Ru(bipy)(3) (2+) (bipy = 2,2'-bipyridine) with light below 560 nm results in the formation of a charge-transfer excited state potentially capable of reducing water to dihydrogen with concomitant production of Ru(bipy)(3) (3+). The latter may be reduced by hydroxide [Formula: see text] to form dioxygen and regenerate the starting complex. The use of these reactions in a cell designed to bring about the photochemical decomposition of water is proposed.The stoichiometry, kinetics, and mechanism of the Ru(bipy)(3) (3+)-hydroxide reaction have been investigated by conventional and stopped-flow spectrophotometry. The dioxygen yield is a sharp function of pH, attaining its maximum value (about 80%) at pH 9. At low pH (3 and 4.8) the production of ruthenium(II) is first order with k(obsd) = (1.41 +/- 0.04) x 10(-4) sec(-1) (25 degrees , ionic strength mu = 1.00 M with sodium sulfate). In the intermediate pH range (7.9-10.0) complex kinetics are observed. In the hydroxide range 0.01-0.50 M, ruthenium(II) production is predominantly first order with k(obsd) = k(a)[OH(-)] + k(b)[OH(-)](2) sec(-1); k(a) = 148 M(-1) sec(-1) and k(b) = 138 M(-2) sec(-1) (25 degrees , mu = 1.00 M, sodium sulfate). For the k(a) term, the activation parameters are DeltaH(double dagger) = 15.3 +/- 1.0 kcal mol(-1) and DeltaS(double dagger) = 7 +/- 3 cal deg(-1) mol(-1) (1 cal = 4.184 J). An intermediate species (lambda(max) 800 nm) forms at the same rate as ruthenium(II) in this hydroxide range. It disappears with k(obsd) = 1.2 + 1.1 x 10(2) [OH(-)] sec(-1) at 25 degrees . Similarly absorbing (lambda(max) 750 to 800 nm) species are generated by the addition of hydroxyl radical to M(bipy)(3) (2+/3+) [M = Fe(II), Os(II), Ru(II), Cr(III), Ru(III)] in pulse radiolysis experiments. The kinetics above pH 7 are described in terms of rate-determining nucleophilic attack by hydroxide on the bound bipyridine ring. The hydroxide adduct so generated is tentatively identified with that observed in the pulse radiolysis experiments with Ru(bipy)(3) (2+).For reduction of Ru(bipy)(3) (3+) by hydrogen peroxide ruthenium(II) production is first order with k(obsd) = k(c)[HO(2) (-)] + k(d)[H(2)O(2)] where k(c) = 5.4 x 10(7) M(-1) sec(-1) and k(d) = 8.3 M(-1) sec(-1) (25 degrees , mu = 1.00 M, pH 3.5 to 9.7). This reaction produces dioxygen in 83 +/- 15% yield at pH 6.8 and in 1.0 N sulfuric acid.
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The synthesis of important prebiotic molecules is fundamentally reliant on basic starting ingredients: water, organic species [e.g., methane (CH(4))], and reduced nitrogen compounds [e.g., ammonia (NH(3)), methyl cyanide (CH(3)CN) etc.]. However, modern studies conclude that the primordial Earth's atmosphere was too rich in CO, CO(2), and water to permit efficient synthesis of such reduced molecules as envisioned by the classic Miller-Urey experiment. Other proposed sources of terrestrial nitrogen reduction, like those within submarine vent systems, also seem to be inadequate sources of chemically reduced C-H-O-N compounds. Here, we demonstrate that nebular dust analogs have impressive catalytic properties for synthesizing prebiotic molecules. Using a catalyst analogous to nebular iron silicate condensate, at temperatures ranging from 500K to 900K, we catalyzed both the Fischer-Tropsch conversion of CO and H(2) to methane and water, and the corresponding Haber-Bosch synthesis of ammonia from N(2) and H(2). Remarkably, when CO, N(2), and H(2) were allowed to react simultaneously, these syntheses also yielded nitrogen-containing organics such as methyl amine (CH(3)NH(2)), acetonitrile (CH(3)CN), and N-methyl methylene imine (H(3)CNCH(2)). A fundamental consequence of this work for astrobiology is the potential for a natural chemical pathway to produce complex chemical building blocks of life throughout our own Solar System and beyond.
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This paper describes the technique of imaging the ionosphere using tomographic principles. It reports on current developments and speculates on the future of this research area. Recent developments in computing and ionospheric measurement, together with the sharing of data via the internet, now allow us to envisage a time when high-resolution, real-time images and 'movies' of the ionosphere will be possible for radio communications planning. There is great potential to use such images for improving our understanding of the physical processes controlling the behaviour of the ionosphere. While real-time images and movies of the electron concentration are now almost possible, forecasting of ionospheric morphology is still in its early stages. It has become clear that the ionosphere cannot be considered as a system in isolation, and consequently new research projects to link together models of the solar-terrestrial system, including the Sun, solar wind, magnetosphere, ionosphere and thermosphere, are now being proposed. The prospect is now on the horizon of assimilating data from the entire solar-terrestrial system to produce a real-time computer model and 'space weather' forecast. The role of tomography in imaging beyond the ionosphere to include the whole near-Earth space-plasma realm is yet to be realized, and provides a challenging prospect for the future. Finally, exciting possibilities exist in applying such methods to image the atmospheres and ionospheres of other planets.
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Growing plants in an enclosed controlled environment is crucial in developing bioregenerative life-support systems (BLSS) for space applications. The major challenge currently facing a BLSS is the extensive use of highly energy-intensive electric light sources, which leads to substantial energy wastes through heat dissipations by these lamps. An alternative lighting strategy is the use of a solar irradiance collection, transmission, and distribution system (SICTDS). Two types of fiber optic-based SICTDS, a Fresnel-lens Himawari and a parabolic-mirror optical waveguide (OW) lighting system, were evaluated. The overall efficiency for the OW SICTDS of 40.5% exceeded by 75% that for the Himawari of 23.2%. The spectral distributions of the light delivered by the Himawari and the OW SICTDS were almost identical and had practically no difference from that of terrestrial solar radiation. The ratios of photosynthetically active radiation (PAR) to total emitted radiation (k) of 0.39 +/- 0.02 for the Himawari and 0.41 +/- 0.04 for the OW SICTDS were statistically indistinguishable, were not significantly different from that of 0.042 +/- 0.01 for terrestrial solar radiation, and were comparable to that of 0.35 for a high-pressure sodium (HPS) lamp. The coefficients of variation (CV) of 0.34 and 0.39 for PPF distributions, both at 50 mm X 50 mm square grid arrays, corresponding to the Himawari and the OW SICTDS, respectively, were comparable with each other but were both significantly greater than the CV of 0.08 corresponding to the HPS lamp. The average fresh weight or dry weight of lettuce grown in the solar chamber with either the Himawari or the OW SICTDS showed no statistical difference from the average fresh weight or dry weight of lettuce grown in the reference chamber with the HPS lamp. The results of this study suggest that an SICTDS could help reduce the electric power demand in a BLSS.
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Under the effect of solar radiation some antibiotics of plant origin (phenylheptatriin, bakuchiol and others) showed antimicrobial phototoxicity differing by the spectrum and activity from the antibiotic action. The highest in vitro antimicrobial phototoxicity was observed with polyacetylene phenylheptatriin: the activation effect of solar radiation on it was due to UV-A and developed in gaseous phase or to a lesser extent in dispersed liquid phase. For comparison, 18 currently used antibiotics of various chemical structure were investigated and no phototoxicity under the effect of solar radiation with respect to the tested microbes was detected. In nature the phenomenon of antimicrobial phototoxicity of plant secondary metabolites due to the effect of solar radiation is probably of large scale. The study of the phenomenon is a new trend in biology (plant antibiotics and phytoncides, phytoimmunity, ecological and evolutionary microbiology, etc.) and a new approach to increase the efficacy of some antibiotics and to develop principally novel photochemotherapeutics for the treatment of infections in humans, animals and plants.
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Solar ultraviolet radiation (UVR, 280-400 nm) is known to cause a number of detrimental effects in aquatic organisms. The area of Patagonia, which is sometimes under the influence of the Antarctic ozone "hole", occasionally receives enhanced levels of ultraviolet B radiation (UV-B, 280-315 nm). Great efforts have been put into creating a database for UVR climatology by installing a variety of instruments in several localities in the region. However, no comparable effort has been made to determine the impact of normal and enhanced levels of solar UVR upon organisms. Most of the photobiological research in aquatic systems of Patagonia has focused on determining the effects of solar UVR in phytoplankton photosynthesis, DNA damage, and mortality, fecundity and repair mechanisms in zooplanktonic species. Some work has also been done with fish larvae and interactions between species at low trophic levels of the aquatic food web. The results of these studies indicate that in order to assess the overall impact of UVR in a certain waterbody, it is also necessary to consider other variables, such as changes in cloudiness, ozone concentrations, differential sensitivity of organisms, and depth of the upper mixed layer/epilimnion. All factors that can preclude or benefit the acclimation of species to solar radiation.
Solar energy driven physical, chemical and biological recycling of nutrients is the characteristic of the Earth-Sun system which permits life on earth to continue. Natural recycle of nutrients on Earth may literally require thousands or even millions of years to be complete, but for modern civilization to continue on Earth or in space, mankind must take charge of, and accelerate, the recycle of all essentials of life. In this paper we describe studies of two accelerated recycle systems; a solar powered energy system and an integrated feed lot. Both systems require special infrastructures permitting the accelerated physical, chemical and biological processing to occur. These systems do not integrate respiratory carbon dioxide as must be done in a complete closed ecological life support system (CELSS). The Algatron, a more complete system involving microalgal bacterial waste treatment with water, oxygen and carbon dioxide recycle was designed for use in Space Stations over 20 years ago.
Exploitation of photosynthetic cells for the production of useful metabolites requires efficient photobioreactors. Many laboratory scale photobioreactors have been reported but most of them are extremely difficult to scale up. Furthermore, the use of open ponds and outdoor tubular photobioreactors is limited by the requirement for large spaces and the difficulty in maintaining sterile conditions. In view of this, we have designed and constructed an internally illuminated stirred tank photobioreactor. The photobioreactor is simple, heat sterilizable and mechanically agitated like the conventional stirred tank bioreactors. Furthermore, it can easily be scaled up while maintaining the light supply coefficient and thus the productivity constant. A device was installed for collecting solar light and distributing it inside the reactor through optical fibers. It was equipped with a light tracking sensor so that the lenses rotate with the position of the sun. This makes it possible to use solar light for photosynthetic cell cultivation in indoor photobioreactors. As a solution to the problems of night biomass loss and low productivity on cloudy days, an artificial light source was coupled with the solar light collecting device. A light intensity sensor monitors the solar light intensity and the artificial light is automatically switched on or off, depending on the solar light intensity. In this way, continuous light supply to the reactor is achieved by using solar light during sunny period, and artificial light at night and on cloudy days.
Protection from the radiation effects of solar particle events for deep space mission crews requires a warning system to observe solar flares and predict subsequent charged particle fluxes. Such a system relates precursor information observed in each flare to the intensity, delay, and duration of the subsequent Solar Particle Event (SPE) at other locations in the solar system. A warning system of this type is now in operation at the NOAA Space Environment Services Center in Boulder, Colorado for support of space missions. It has been used to predict flare particle fluxes at the earth for flares of Solar Cycle 22. The flare parameters used and the effectiveness of the current warning system, based on Solar Cycle 22 experience, are presented, with an examination of the shortcomings. Needed improvements to the system include more complete observations of solar activity, especially information on the occurrences of solar mass ejections; and consideration of the effects of propagation conditions in the solar corona and interplanetary medium. Requirements for solar observations and forecasting systems on board the spacecraft are discussed.
Dynamics of heart rhythm variability (HRV) according to 24-h Holter monitoring of ECG was studied in patients with chronic IHD with paroxysmal cardiac fibrillation (PCF) and controls in response to unfavourable medical weather types and high geomagnetic activity. In unfavourable meteorological conditions IHD patients with PCF show attenuation of a general effect of autonomic nervous system on heart rhythm, changes in correlation of sympathetic and parasympathetic activity. Shifts to relative sympathicotony, parasympathicotony or absence of parasympathicotony or sympathicotony predominance were recorded.