PMCC PMCC

Search tips
Search criteria

Advanced
Results 1-25 (164255)

Clipboard (0)
None

Related Articles

1.  Models of very-low-mass stars, brown dwarfs and exoplanets 
Within the next few years, GAIA and several instruments aiming to image extrasolar planets will be ready. In parallel, low-mass planets are being sought around red dwarfs, which offer more favourable conditions, for both radial velocity detection and transit studies, than solar-type stars. In this paper, the authors of a model atmosphere code that has allowed the detection of water vapour in the atmosphere of hot Jupiters review recent advances in modelling the stellar to substellar transition. The revised solar oxygen abundances and cloud model allow the photometric and spectroscopic properties of this transition to be reproduced for the first time. Also presented are highlight results of a model atmosphere grid for stars, brown dwarfs and extrasolar planets.
doi:10.1098/rsta.2011.0269
PMCID: PMC3350648  PMID: 22547243
PHOENIX; CO5BOLD; very-low-mass stars; brown dwarfs; stars; opacities
2.  Directed Evolution and In Silico Analysis of Reaction Centre Proteins Reveal Molecular Signatures of Photosynthesis Adaptation to Radiation Pressure 
PLoS ONE  2011;6(1):e16216.
Evolutionary mechanisms adopted by the photosynthetic apparatus to modifications in the Earth's atmosphere on a geological time-scale remain a focus of intense research. The photosynthetic machinery has had to cope with continuously changing environmental conditions and particularly with the complex ionizing radiation emitted by solar flares. The photosynthetic D1 protein, being the site of electron tunneling-mediated charge separation and solar energy transduction, is a hot spot for the generation of radiation-induced radical injuries. We explored the possibility to produce D1 variants tolerant to ionizing radiation in Chlamydomonas reinhardtii and clarified the effect of radiation-induced oxidative damage on the photosynthetic proteins evolution. In vitro directed evolution strategies targeted at the D1 protein were adopted to create libraries of chlamydomonas random mutants, subsequently selected by exposures to radical-generating proton or neutron sources. The common trend observed in the D1 aminoacidic substitutions was the replacement of less polar by more polar amino acids. The applied selection pressure forced replacement of residues more sensitive to oxidative damage with less sensitive ones, suggesting that ionizing radiation may have been one of the driving forces in the evolution of the eukaryotic photosynthetic apparatus. A set of the identified aminoacidic substitutions, close to the secondary plastoquinone binding niche and oxygen evolving complex, were introduced by site-directed mutagenesis in un-transformed strains, and their sensitivity to free radicals attack analyzed. Mutants displayed reduced electron transport efficiency in physiological conditions, and increased photosynthetic performance stability and oxygen evolution capacity in stressful high-light conditions. Finally, comparative in silico analyses of D1 aminoacidic sequences of organisms differently located in the evolution chain, revealed a higher ratio of residues more sensitive to oxidative damage in the eukaryotic/cyanobacterial proteins compared to their bacterial orthologs. These results led us to hypothesize an archaean atmosphere less challenging in terms of ionizing radiation than the present one.
doi:10.1371/journal.pone.0016216
PMCID: PMC3020971  PMID: 21249156
3.  A Scientometric Prediction of the Discovery of the First Potentially Habitable Planet with a Mass Similar to Earth 
PLoS ONE  2010;5(10):e13061.
Background
The search for a habitable extrasolar planet has long interested scientists, but only recently have the tools become available to search for such planets. In the past decades, the number of known extrasolar planets has ballooned into the hundreds, and with it, the expectation that the discovery of the first Earth-like extrasolar planet is not far off.
Methodology/Principal Findings
Here, we develop a novel metric of habitability for discovered planets and use this to arrive at a prediction for when the first habitable planet will be discovered. Using a bootstrap analysis of currently discovered exoplanets, we predict the discovery of the first Earth-like planet to be announced in the first half of 2011, with the likeliest date being early May 2011.
Conclusions/Significance
Our predictions, using only the properties of previously discovered exoplanets, accord well with external estimates for the discovery of the first potentially habitable extrasolar planet and highlight the the usefulness of predictive scientometric techniques to understand the pace of scientific discovery in many fields.
doi:10.1371/journal.pone.0013061
PMCID: PMC2949384  PMID: 20957226
4.  Using electron beam radiation to simulate the dose distribution for whole body solar particle event proton exposure 
As a part of the near solar system exploration program, astronauts may receive significant total body proton radiation exposures during a solar particle event (SPE). In the Center for Acute Radiation Research (CARR), symptoms of the acute radiation sickness syndrome induced by conventional radiation are being compared to those induced by SPE-like proton radiation, to determine the relative biological effectiveness (RBE) of SPE protons. In an SPE, the astronaut’s whole body will be exposed to radiation consisting mainly of protons with energies below 50 MeV. In addition to providing for a potentially higher RBE than conventional radiation, the energy distribution for an SPE will produce a relatively inhomogeneous total body dose distribution, with a significantly higher dose delivered to the skin and subcutaneous tissues than to the internal organs. These factors make it difficult to use a 60Co standard for RBE comparisons in our experiments. Here, the novel concept of using megavoltage electron beam radiation to more accurately reproduce both the total dose and the dose distribution of SPE protons and make meaningful RBE comparisons between protons and conventional radiation is described. In these studies, Monte Carlo simulation was used to determine the dose distribution of electron beam radiation in small mammals such as mice and ferrets as well as large mammals such as pigs. These studies will help to better define the topography of the time-dose-fractionation versus biological response landscape for astronaut exposure to an SPE.
doi:10.1007/s00411-010-0315-z
PMCID: PMC3575686  PMID: 20725839
5.  Chemistry of Personalized Solar Energy 
Inorganic Chemistry  2009;48(21):10001-10017.
Personalized energy (PE) is a transformative idea that provides a new modality for the planet’s energy future. By providing solar energy to the individual, an energy supply becomes secure and available to people of both legacy and non-legacy worlds, and minimally contributes to increasing the anthropogenic level of carbon dioxide. Because PE will be possible only if solar energy is available 24 hours a day, 7 day a week, the key enabler for solar PE is an inexpensive storage mechanism. HX (X = halide or OH−) splitting is a fuel-forming reaction of sufficient energy density for large scale solar storage but the reaction relies on chemical transformations that are not understood at the most basic science level. Critical among these are multielectron transfers that are proton-coupled and involve the activation of bonds in energy poor substrates. The chemistry of these three italicized areas is developed, and from this platform, discovery paths leading to new HX and H2O splitting catalysts are delineated. For the case of the water splitting catalyst, it captures many of the functional elements of photosynthesis. In doing so, a highly manufacturable and inexpensive method has been discovered for solar PE storage.
doi:10.1021/ic901328v
PMCID: PMC3332084  PMID: 19775081
6.  How does the Earth system generate and maintain thermodynamic disequilibrium and what does it imply for the future of the planet? 
The Earth's chemical composition far from chemical equilibrium is unique in our Solar System, and this uniqueness has been attributed to the presence of widespread life on the planet. Here, I show how this notion can be quantified using non-equilibrium thermodynamics. Generating and maintaining disequilibrium in a thermodynamic variable requires the extraction of power from another thermodynamic gradient, and the second law of thermodynamics imposes fundamental limits on how much power can be extracted. With this approach and associated limits, I show that the ability of abiotic processes to generate geochemical free energy that can be used to transform the surface–atmosphere environment is strongly limited to less than 1 TW. Photosynthetic life generates more than 200 TW by performing photochemistry, thereby substantiating the notion that a geochemical composition far from equilibrium can be a sign for strong biotic activity. Present-day free energy consumption by human activity in the form of industrial activity and human appropriated net primary productivity is of the order of 50 TW and therefore constitutes a considerable term in the free energy budget of the planet. When aiming to predict the future of the planet, we first note that since global changes are closely related to this consumption of free energy, and the demands for free energy by human activity are anticipated to increase substantially in the future, the central question in the context of predicting future global change is then how human free energy demands can increase sustainably without negatively impacting the ability of the Earth system to generate free energy. This question could be evaluated with climate models, and the potential deficiencies in these models to adequately represent the thermodynamics of the Earth system are discussed. Then, I illustrate the implications of this thermodynamic perspective by discussing the forms of renewable energy and planetary engineering that would enhance the overall free energy generation and, thereby ‘empower’ the future of the planet.
doi:10.1098/rsta.2011.0316
PMCID: PMC3261436  PMID: 22291221
habitability; free energy; thermodynamics; global change; geoengineering
7.  Earth as an Extrasolar Planet: Earth Model Validation Using EPOXI Earth Observations 
Astrobiology  2011;11(5):393-408.
Abstract
The EPOXI Discovery Mission of Opportunity reused the Deep Impact flyby spacecraft to obtain spatially and temporally resolved visible photometric and moderate resolution near-infrared (NIR) spectroscopic observations of Earth. These remote observations provide a rigorous validation of whole-disk Earth model simulations used to better understand remotely detectable extrasolar planet characteristics. We have used these data to upgrade, correct, and validate the NASA Astrobiology Institute's Virtual Planetary Laboratory three-dimensional line-by-line, multiple-scattering spectral Earth model. This comprehensive model now includes specular reflectance from the ocean and explicitly includes atmospheric effects such as Rayleigh scattering, gas absorption, and temperature structure. We have used this model to generate spatially and temporally resolved synthetic spectra and images of Earth for the dates of EPOXI observation. Model parameters were varied to yield an optimum fit to the data. We found that a minimum spatial resolution of ∼100 pixels on the visible disk, and four categories of water clouds, which were defined by using observed cloud positions and optical thicknesses, were needed to yield acceptable fits. The validated model provides a simultaneous fit to Earth's lightcurve, absolute brightness, and spectral data, with a root-mean-square (RMS) error of typically less than 3% for the multiwavelength lightcurves and residuals of ∼10% for the absolute brightness throughout the visible and NIR spectral range. We have extended our validation into the mid-infrared by comparing the model to high spectral resolution observations of Earth from the Atmospheric Infrared Sounder, obtaining a fit with residuals of ∼7% and brightness temperature errors of less than 1 K in the atmospheric window. For the purpose of understanding the observable characteristics of the distant Earth at arbitrary viewing geometry and observing cadence, our validated forward model can be used to simulate Earth's time-dependent brightness and spectral properties for wavelengths from the far ultraviolet to the far infrared. Key Words: Astrobiology—Extrasolar terrestrial planets—Habitability—Planetary science—Radiative transfer. Astrobiology 11, 393–408.
doi:10.1089/ast.2011.0642
PMCID: PMC3133830  PMID: 21631250
8.  Cosmic Carbon Chemistry: From the Interstellar Medium to the Early Earth 
Astronomical observations have shown that carbonaceous compounds in the gas and solid state, refractory and icy are ubiquitous in our and distant galaxies. Interstellar molecular clouds and circumstellar envelopes are factories of complex molecular synthesis. A surprisingly large number of molecules that are used in contemporary biochemistry on Earth are found in the interstellar medium, planetary atmospheres and surfaces, comets, asteroids and meteorites, and interplanetary dust particles. In this article we review the current knowledge of abundant organic material in different space environments and investigate the connection between presolar and solar system material, based on observations of interstellar dust and gas, cometary volatiles, simulation experiments, and the analysis of extraterrestrial matter. Current challenges in astrochemistry are discussed and future research directions are proposed.
Complex organic molecules are present in cosmic dust, comets, and meteorites, which could have delivered material necessary for the emergence of life on Earth and other planets.
doi:10.1101/cshperspect.a002097
PMCID: PMC2982172  PMID: 20554702
9.  Biological Effects of High-Energy Neutrons Measured In Vivo Using a Vertebrate Model 
Radiation research  2009;172(4):473-480.
Interaction of solar protons and galactic cosmic radiation with the atmosphere and other materials produces high-energy secondary neutrons from below 1 to 1000 MeV and higher. Although secondary neutrons may provide an appreciable component of the radiation dose equivalent received by space and high-altitude air travelers, the biological effects remain poorly defined, particularly in vivo in intact organisms. Here we describe the acute response of Japanese medaka (Oryzias latipes) embryos to a beam of high-energy spallation neutrons that mimics the energy spectrum of secondary neutrons encountered aboard spacecraft and high-altitude aircraft. To determine RBE, embryos were exposed to 0–0.5 Gy of high-energy neutron radiation or 0–15 Gy of reference γ radiation. The radiation response was measured by imaging apoptotic cells in situ in defined volumes of the embryo, an assay that provides a quantifiable, linear dose response. The slope of the dose response in the developing head, relative to reference γ radiation, indicates an RBE of 24.9 (95% CI 13.6–40.7). A higher RBE of 48.1 (95% CI 30.0–66.4) was obtained based on overall survival. A separate analysis of apoptosis in muscle showed an overall nonlinear response, with the greatest effects at doses of less than 0.3 Gy. Results of this experiment indicate that medaka are a useful model for investigating biological damage associated with high-energy neutron exposure.
doi:10.1667/RR1556.1
PMCID: PMC2796447  PMID: 19772468
10.  Analysis of White Blood Cell Counts in Mice after Gamma- or Proton-Radiation Exposure 
Radiation research  2011;176(2):170-176.
In the coming decades human space exploration is expected to move beyond low-Earth orbit. This transition involves increasing mission time and therefore an increased risk of radiation exposure from solar particle event (SPE) radiation. Acute radiation effects after exposure to SPE radiation are of prime importance due to potential mission-threatening consequences. The major objective of this study was to characterize the dose–response relationship for proton and γ radiation delivered at doses up to 2 Gy at high (0.5 Gy/min) and low (0.5 Gy/h) dose rates using white blood cell (WBC) counts as a biological end point. The results demonstrate a dose-dependent decrease in WBC counts in mice exposed to high- and low-dose-rate proton and γ radiation, suggesting that astronauts exposed to SPE-like radiation may experience a significant decrease in circulating leukocytes.
doi:10.1667/RR2413.1
PMCID: PMC3575683  PMID: 21476859
11.  Effect of Solar Particle Event Radiation on Gastrointestinal Tract Bacterial Translocation and Immune Activation 
Radiation research  2011;175(4):485-492.
Space flight conditions within the protection of Earth’s gravitational field have been shown to alter immune responses, which could lead to potentially detrimental pathology. An additional risk of extended space travel outside the Earth’s gravitational field is the effect of solar particle event (SPE) radiation exposure on the immune system. Organisms that could lead to infection include endogenous, latent viruses, colonizing pathogenics, and commensals, as well as exogenous microbes present in the spacecraft or other astronauts. In this report, the effect of SPE-like radiation on containment of commensal bacteria and the innate immune response induced by its breakdown was investigated at the radiation energies, doses and dose rates expected during an extravehicular excursion outside the Earth’s gravitational field. A transient increase in serum lipopolysaccharide was observed 1 day after irradiation and was accompanied by an increase in acute-phase reactants and circulating proinflammatory cytokines, indicating immune activation. Baseline levels were reestablished by 5 days postirradiation. These findings suggest that astronauts exposed to SPE radiation could have impaired containment of colonizing bacteria and associated immune activation.
doi:10.1667/RR2373.1
PMCID: PMC3572900  PMID: 21294608
12.  Delivery of Complex Organic Compounds from Evolved Stars to the Solar System 
Stars in the late stages of evolution are able to synthesize complex organic compounds with aromatic and aliphatic structures over very short time scales. These compounds are ejected into the interstellar medium and distributed throughout the Galaxy. The structures of these compounds are similar to the insoluble organic matter found in meteorites. In this paper, we discuss to what extent stellar organics has enriched the primordial Solar System and possibly the early Earth.
doi:10.1007/s11084-011-9254-1
PMCID: PMC3296952  PMID: 22139515
Interstellar medium; Planetary nebulae; Asymptotic giant branch stars; Solar system; Meteorites; Pre-solar grains; Interplanetary dust particles
13.  From Mice and Men to Earth and Space: Joint NASA-NCI Workshop on Lung Cancer Risk Resulting from Space and Terrestrial Radiation 
Cancer research  2011;71(22):6926-6929.
On June 27–28, 2011 scientists from the National Cancer Institute (NCI), NASA, and academia met in Bethesda to discuss major lung cancer issues confronting each organization. For NASA – available data suggest lung cancer is the largest potential cancer risk from space travel for both men and women and quantitative risk assessment information for mission planning is needed. In space the radiation risk is from high energy and charge (HZE) nuclei (such as Fe) and high energy protons from solar flares and not from gamma radiation. By contrast the NCI is endeavoring to estimate the increased lung cancer risk from the potential wide-spread implementation of computed tomography (CT) screening in individuals at high risk for developing lung cancer based on the National Lung Cancer Screening Trial (NLST). For the latter, exposure will be x-rays from CT scans from the screening (which uses “low dose” CT scans) and also from follow-up scans used to evaluate abnormalities found during initial screening. Topics discussed included the risk of lung cancer arising after HZE particle, proton, and low dose Earth radiation exposure. The workshop examined preclinical models, epidemiology, molecular markers, “omics” technology, radiobiology issues, and lung stem cells (LSC) that relate to the development of lung cancer.
doi:10.1158/0008-5472.CAN-11-2546
PMCID: PMC3217106  PMID: 21900398
14.  Acute Biological Effects of Simulating the Whole-Body Radiation Dose Distribution from a Solar Particle Event Using a Porcine Model 
Radiation Research  2011;176(5):649-659.
In a solar particle event (SPE), an unshielded astronaut would receive proton radiation with an energy profile that produces a highly inhomogeneous dose distribution (skin receiving a greater dose than internal organs). The novel concept of using megavoltage electron-beam radiation to more accurately reproduce both the total dose and the dose distribution of SPE protons and make meaningful RBE comparisons between protons and conventional radiation has been described previously. Here, Yucatan minipigs were used to determine the effects of a superficial, SPE-like proton dose distribution using megavoltage electrons. In these experiments, dose-dependent increases in skin pigmentation, ulceration, keratinocyte necrosis and pigment incontinence were observed. Five of 18 animals (one each exposed to 7.5 Gy and 12.5 Gy radiation and three exposed to 25 Gy radiation) developed symptomatic, radiation-associated pneumonopathy approximately 90 days postirradiation. The three animals from the highest dose group showed evidence of mycoplasmal pneumonia along with radiation pneumonitis. Moreover, delayed-type hypersensitivity was found to be altered, suggesting that superficial irradiation of the skin with ionizing radiation might cause immune dysfunction or dysregulation. In conclusion, using total doses, patterns of dose distribution, and dose rates that are compatible with potential astronaut exposure to SPE radiation, animals experienced significant toxicities that were qualitatively different from toxicities previously reported in pigs for homogeneously delivered radiation at similar doses.
PMCID: PMC3382987  PMID: 21859326
15.  Climate Change and Mitigation 
Ambio  2010;39(Suppl 1):11-17.
Planet Earth has experienced repeated changes of its climate throughout time. Periods warmer than today as well as much colder, during glacial episodes, have alternated. In our time, rapid population growth with increased demand for natural resources and energy, has made society increasingly vulnerable to environmental changes, both natural and those caused by man; human activity is clearly affecting the radiation balance of the Earth. In the session “Climate Change and Mitigation” the speakers offered four different views on coal and CO2: the basis for life, but also a major hazard with impact on Earth’s climate. A common denominator in the presentations was that more than ever science and technology is required. We need not only understand the mechanisms for climate change and climate variability, we also need to identify means to remedy the anthropogenic influence on Earth’s climate.
doi:10.1007/s13280-010-0058-8
PMCID: PMC3357646  PMID: 20873680
Climate change; Carbon sequestration; Methanol economy; Artificial climate control
16.  The evolution of organellar metabolism in unicellular eukaryotes 
Metabolic innovation has facilitated the radiation of microbes into almost every niche environment on the Earth, and over geological time scales transformed the planet on which we live. A notable example of innovation is the evolution of oxygenic photosynthesis which was a prelude to the gradual transformation of an anoxic Earth into a world with oxygenated oceans and an oxygen-rich atmosphere capable of supporting complex multicellular organisms. The influence of microbial innovation on the Earth's history and the timing of pivotal events have been addressed in other recent themed editions of Philosophical Transactions of Royal Society B (Cavalier-Smith et al. 2006; Bendall et al. 2008). In this issue, our contributors provide a timely history of metabolic innovation and adaptation within unicellular eukaryotes. In eukaryotes, diverse metabolic portfolios are compartmentalized across multiple membrane-bounded compartments (or organelles). However, as a consequence of pathway retargeting, organelle degeneration or novel endosymbiotic associations, the metabolic repertoires of protists often differ extensively from classic textbook descriptions of intermediary metabolism. These differences are often important in the context of niche adaptation or the structure of microbial communities. Fundamentally interesting in its own right, the biochemical, cell biological and phylogenomic investigation of organellar metabolism also has wider relevance. For instance, in some pathogens, notably those causing some of the most significant tropical diseases, including malaria, unusual organellar metabolism provides important new drug targets. Moreover, the study of organellar metabolism in protists continues to provide critical insight into our understanding of eukaryotic evolution.
doi:10.1098/rstb.2009.0260
PMCID: PMC2817233  PMID: 20124338
adaptation; cellular metabolism; endosymbiosis; organellar genomes; organellogenesis; protein targeting
17.  Earth’s Earliest Atmospheres 
Earth is the one known example of an inhabited planet and to current knowledge the likeliest site of the one known origin of life. Here we discuss the origin of Earth’s atmosphere and ocean and some of the environmental conditions of the early Earth as they may relate to the origin of life. A key punctuating event in the narrative is the Moon-forming impact, partly because it made Earth for a short time absolutely uninhabitable, and partly because it sets the boundary conditions for Earth’s subsequent evolution. If life began on Earth, as opposed to having migrated here, it would have done so after the Moon-forming impact. What took place before the Moon formed determined the bulk properties of the Earth and probably determined the overall compositions and sizes of its atmospheres and oceans. What took place afterward animated these materials. One interesting consequence of the Moon-forming impact is that the mantle is devolatized, so that the volatiles subsequently fell out in a kind of condensation sequence. This ensures that the volatiles were concentrated toward the surface so that, for example, the oceans were likely salty from the start. We also point out that an atmosphere generated by impact degassing would tend to have a composition reflective of the impacting bodies (rather than the mantle), and these are almost without exception strongly reducing and volatile-rich. A consequence is that, although CO- or methane-rich atmospheres are not necessarily stable as steady states, they are quite likely to have existed as long-lived transients, many times. With CO comes abundant chemical energy in a metastable package, and with methane comes hydrogen cyanide and ammonia as important albeit less abundant gases.
Life probably arose on Earth after the moon-forming impact. It and subsequent impacts probably created transient reducing methane- or CO-rich atmospheres that provided abundant chemical energy.
doi:10.1101/cshperspect.a004895
PMCID: PMC2944365  PMID: 20573713
18.  Comment on “Strong signature of the active Sun in 100 years of terrestrial insolation data” by W. Weber 
Annalen Der Physik  2011;523(11):946-950.
An analysis of ground-based observations of solar irradiance was recently published in this journal, reporting an apparent increase of solar irradiance on the ground of the order of 1% between solar minima and maxima [1]. Since the corresponding variations in total solar irradiance on top of the atmosphere are accurately determined from satellite observations to be of the order of 0.1% only [2], the one order of magnitude stronger effect in the terrestrial insolation data was interpreted as evidence for cosmic-ray induced aerosol formation in the atmosphere. In my opinion, however, this result does not reflect reality. Using the energy budget of Earth's surface, I show that changes of ground-based insolation with the solar cycle of the order of 1% between solar minima and maxima would result in large surface air temperature variations which are inconsistent with the instrumental record. It would appear that the strong variations of terrestrial irradiance found by [1] are due to the uncorrected effects of volcanic or local aerosols and seasonal variations. Taking these effects into account, I find a variation of terrestrial insolation with solar activity which is of the same order as the one measured from space, bringing the surface energy budget into agreement with the solar signal detected in temperature data.
doi:10.1002/andp.201100179
PMCID: PMC3263400  PMID: 22279242
Climate; solar activity; solar irradiance; cosmic rays
19.  Exploration of the Potential Energy Surfaces, Prediction of Atmospheric Concentrations, and Prediction of Vibrational Spectra for the HO2···(H2O)n (n=1-2) Hydrogen Bonded Complexes 
The journal of physical chemistry. A  2006;110(10):3686-3691.
The hydroperoxy radical (HO2) plays a critical role in Earth’s atmospheric chemistry as a component of many important reactions. The self-reaction of hydroperoxy radicals in the gas phase is strongly affected by the presence of water vapor. In this work we explore the potential energy surfaces of hydroperoxy radicals hydrogen bonded to one or two water molecules, and predict atmospheric concentrations and vibrational spectra of these complexes. We predict that when the HO2 concentration is on the order of 108 molecules·cm-3 at 298K, that the number of HO2···H2O complexes is on the order of 107 molecules·cm-3 and the number of HO2···(H2O)2 complexes is on the order of 106 molecules·cm-3. Using the computed abundance of HO2···H2O, we predict that, at 298K, the bimolecular rate constant for HO2···H2O + HO2 is about ten times that for HO2 + HO2.
doi:10.1021/jp057165k
PMCID: PMC2548419  PMID: 16526652
20.  The Hydrogen Catalyst Cobaloxime – a Multifrequency EPR & DFT Study of Cobaloxime’s Electronic Structure 
The Journal of Physical Chemistry. B  2012;116(9):2943-2957.
Solar fuels research aims to mimic photosynthesis and devise integrated systems that can capture, convert, and store solar energy in the form of high-energy molecular bonds. Molecular hydrogen is generally considered an ideal solar fuel as its combustion is essentially pollution-free. Cobaloximes rank among the most promising earth-abundant catalysts for the reduction of protons to molecular hydrogen. We have used multifrequency EPR spectroscopy at X-band, Q-band, and D-band combined with DFT calculations to reveal electronic structure and establish correlations between structure, surroundings and catalytic activity of these complexes. To assess the strength and nature of ligand cobalt interactions, the BF2-capped cobaloxime, Co(dmgBF2)2, was studied in a variety of different solvents with a range of polarities and stoichiometric amounts of potential ligands to the cobalt ion. This allows the differentiation of labile and strongly coordinating axial ligands for the Co(II) complex. Labile, or weakly coordinating, ligands like methanol result in larger g-tensor anisotropy than strongly coordinating ligands like pyridine. Additionally, a coordination number effect is seen for the strongly coordinating ligands with both singly-ligated LCo(dmgBF2)2 and doubly-ligated L2Co(dmgBF2)2. The presence of two strongly coordinating axial ligands leads to the smallest g-tensor anisotropy. The relevance of the strength of the axial ligand(s) to the catalytic efficiency of Co(dmgBF2)2 is discussed. Finally, the influence of molecular oxygen and formation of Co(III) superoxide radicals LCo(dmgBF2)2O2• is studied. The experimental results are compared with a comprehensive set of DFT calculations on Co(dmgBF2)2 model systems with various axial ligands. Comparison with experimental values for the “key” magnetic parameters like g-tensor and 59Co hyperfine coupling tensor allows the determination of the conformation of the axially ligated Co(dmgBF2)2 complexes. The data presented here are vital for understanding the influence of solvent and ligand coordination on the catalytic efficiency of cobaloximes.
doi:10.1021/jp209395n
PMCID: PMC3303608  PMID: 22375846
21.  A Neural Network Based Intelligent Predictive Sensor for Cloudiness, Solar Radiation and Air Temperature 
Sensors (Basel, Switzerland)  2012;12(11):15750-15777.
Accurate measurements of global solar radiation and atmospheric temperature, as well as the availability of the predictions of their evolution over time, are important for different areas of applications, such as agriculture, renewable energy and energy management, or thermal comfort in buildings. For this reason, an intelligent, light-weight and portable sensor was developed, using artificial neural network models as the time-series predictor mechanisms. These have been identified with the aid of a procedure based on the multi-objective genetic algorithm. As cloudiness is the most significant factor affecting the solar radiation reaching a particular location on the Earth surface, it has great impact on the performance of predictive solar radiation models for that location. This work also represents one step towards the improvement of such models by using ground-to-sky hemispherical colour digital images as a means to estimate cloudiness by the fraction of visible sky corresponding to clouds and to clear sky. The implementation of predictive models in the prototype has been validated and the system is able to function reliably, providing measurements and four-hour forecasts of cloudiness, solar radiation and air temperature.
doi:10.3390/s121115750
PMCID: PMC3522983  PMID: 23202230
intelligent sensor; sensor fusion; neural networks; cloudiness estimation; solar radiation prediction; temperature prediction; genetic algorithms
22.  How micron-sized dust particles determine the chemistry of our Universe 
Scientific Reports  2013;3:1338.
In the environments where stars and planets form, about one percent of the mass is in the form of micro-meter sized particles known as dust. However small and insignificant these dust grains may seem, they are responsible for the production of the simplest (H2) to the most complex (amino-acids) molecules observed in our Universe. Dust particles are recognized as powerful nano-factories that produce chemical species. However, the mechanism that converts species on dust to gas species remains elusive. Here we report experimental evidence that species forming on interstellar dust analogs can be directly released into the gas. This process, entitled chemical desorption (fig. 1), can dominate over the chemistry due to the gas phase by more than ten orders of magnitude. It also determines which species remain on the surface and are available to participate in the subsequent complex chemistry that forms the molecules necessary for the emergence of life.
doi:10.1038/srep01338
PMCID: PMC3581832  PMID: 23439221
23.  Improved production of biohydrogen in light-powered Escherichia coli by co-expression of proteorhodopsin and heterologous hydrogenase 
Background
Solar energy is the ultimate energy source on the Earth. The conversion of solar energy into fuels and energy sources can be an ideal solution to address energy problems. The recent discovery of proteorhodopsin in uncultured marine γ-proteobacteria has made it possible to construct recombinant Escherichia coli with the function of light-driven proton pumps. Protons that translocate across membranes by proteorhodopsin generate a proton motive force for ATP synthesis by ATPase. Excess protons can also be substrates for hydrogen (H2) production by hydrogenase in the periplasmic space. In the present work, we investigated the effect of the co-expression of proteorhodopsin and hydrogenase on H2 production yield under light conditions.
Results
Recombinant E. coli BL21(DE3) co-expressing proteorhodopsin and [NiFe]-hydrogenase from Hydrogenovibrio marinus produced ~1.3-fold more H2 in the presence of exogenous retinal than in the absence of retinal under light conditions (70 μmole photon/(m2·s)). We also observed the synergistic effect of proteorhodopsin with endogenous retinal on H2 production (~1.3-fold more) with a dual plasmid system compared to the strain with a single plasmid for the sole expression of hydrogenase. The increase of light intensity from 70 to 130 μmole photon/(m2·s) led to an increase (~1.8-fold) in H2 production from 287.3 to 525.7 mL H2/L-culture in the culture of recombinant E. coli co-expressing hydrogenase and proteorhodopsin in conjunction with endogenous retinal. The conversion efficiency of light energy to H2 achieved in this study was ~3.4%.
Conclusion
Here, we report for the first time the potential application of proteorhodopsin for the production of biohydrogen, a promising alternative fuel. We showed that H2 production was enhanced by the co-expression of proteorhodopsin and [NiFe]-hydrogenase in recombinant E. coli BL21(DE3) in a light intensity-dependent manner. These results demonstrate that E. coli can be applied as light-powered cell factories for biohydrogen production by introducing proteorhodopsin.
doi:10.1186/1475-2859-11-2
PMCID: PMC3311610  PMID: 22217184
biohydrogen; Escherichia coli; proteorhodopsin; light-driven proton pump; light-powered cell factory
24.  Self-assembled photosystem-I biophotovoltaics on nanostructured TiO2 and ZnO 
Scientific Reports  2012;2:234.
The abundant pigment-protein membrane complex photosystem-I (PS-I) is at the heart of the Earth’s energy cycle. It is the central molecule in the “Z-scheme” of photosynthesis, converting sunlight into the chemical energy of life. Commandeering this intricately organized photosynthetic nanocircuitry and re-wiring it to produce electricity carries the promise of inexpensive and environmentally friendly solar power. We here report that dry PS-I stabilized by surfactant peptides functioned as both the light-harvester and charge separator in solar cells self-assembled on nanostructured semiconductors. Contrary to previous attempts at biophotovoltaics requiring elaborate surface chemistries, thin film deposition, and illumination concentrated into narrow wavelength ranges the devices described here are straightforward and inexpensive to fabricate and perform well under standard sunlight yielding open circuit photovoltage of 0.5 V, fill factor of 71%, electrical power density of 81 µW/cm2 and photocurrent density of 362 µA/cm2, over four orders of magnitude higher than any photosystem-based biophotovoltaic to date.
doi:10.1038/srep00234
PMCID: PMC3270499  PMID: 22355747
25.  Gaia as a complex adaptive system. 
We define the Gaia system of life and its environment on Earth, review the status of the Gaia theory, introduce potentially relevant concepts from complexity theory, then try to apply them to Gaia. We consider whether Gaia is a complex adaptive system (CAS) in terms of its behaviour and suggest that the system is self-organizing but does not reside in a critical state. Gaia has supported abundant life for most of the last 3.8 Gyr. Large perturbations have occasionally suppressed life but the system has always recovered without losing the capacity for large-scale free energy capture and recycling of essential elements. To illustrate how complexity theory can help us understand the emergence of planetary-scale order, we present a simple cellular automata (CA) model of the imaginary planet Daisyworld. This exhibits emergent self-regulation as a consequence of feedback coupling between life and its environment. Local spatial interaction, which was absent from the original model, can destabilize the system by generating bifurcation regimes. Variation and natural selection tend to remove this instability. With mutation in the model system, it exhibits self-organizing adaptive behaviour in its response to forcing. We close by suggesting how artificial life ('Alife') techniques may enable more comprehensive feasibility tests of Gaia.
doi:10.1098/rstb.2001.1014
PMCID: PMC1692971  PMID: 12079529

Results 1-25 (164255)