Experimentální studium chemické evoluce biomolekul v podmínkách rané Země

Vznik života na Zemi je jedním z prázdných míst lidského vědění. Tato práce je zaměřena na odhalení několika dílků této skládačky. Prezentujeme současný stav poznání zejména ve spojení se syntézou biomolekul za prebiotických podmínek. V této práci jsou předloženy výsledky experimentů, jež naznačují, že neutrální planetární atmosféra obsahující představitele vulkanických plynů (CO2, N2, H2O) může být působením měkkého UV záření v přítomnosti minerálních katalyzátorů přeměněna na relativně reaktivní směs redukovaných plynů (CH4, CO). Ty mohou být dále transformovány vysoce energetickými procesy za vzniku biomolekul. Směs CH4, CO + N2 představuje prototyp běžné redukční atmosféry, jíž podobné lze nalézt např. na Titanu, největším Saturnově měsíci, nebo také v minulosti na naší planetě coby tzv. sekundární atmosféru. V následných experimentech byla ekvimolární směs CH4 : CO : N2 v přítomnosti vodní páry exponována vysoce energetickému plazmatu, jež simuluje dopad asteroidu - jednu ze série impaktních událostí, kterým byla raná Země vystavena během prvních 600 milionů let své existence. Po dodání celkové energie 3250 J v laserových pulzech byla zjištěna přítomnost organických molekul důležitých pro prebiotickou chemii. Mezi nimi jsou např. báze ribonukleové kyseliny (adenin, uracil, guanin, cytosin),...Origin of life is a still-enduring gap in human knowledge. This work is focused on revealing of several pieces of this puzzle. State of the art scenarios of biomolecules synthesis under prebiotic conditions are presented and discussed. This thesis presents our recent experiments suggesting a novel idea that neutral planetary atmosphere containing a mixture of neutral volcanic-type gasses (CO2, N2, H2O) can be converted over acidic mineral catalysts upon irradiation by a soft UV-radiation into a relatively reactive mixture of reducing gases (CH4, CO), which can be further reprocessed by high-energy chemistry. The resulting mixture (CH4, CO + N2) represents a common reducing atmosphere related e.g. to the chemistry of Titan, the largest moon of Saturn, as well as a possible representation of the secondary atmosphere of our planet. Also, photocatalytic reduction of CO2-rich atmosphere can explain the abiotic origin of methane on current Mars or other terrestrial planets. In our subsequent experiments, corresponding equimolar model mixture of CH4 : CO : N2 in presence of water vapour was subjected to reprocessing by high-power laser plasma simulating an asteroid impact - one of a series of impact events which the young Earth experienced during the first 600 million years of her history. Upon delivery...Katedra fyzikální a makromol. chemieDepartment of Physical and Macromolecular ChemistryPřírodovědecká fakultaFaculty of Scienc

Výzkum transformace atmosfér terestrických planet vlivem impaktů mimozemských těles a UV záření

Keywords: Exoplanets, Earth, Impact, Photochemistry, Infrared Spectroscopy, Atmospheric chemistry Impacts and photochemistry are two very important driving forces for chemical transformation of planetary atmospheres. While strong UV radiation produced by young stars continuously provides a significant amount of energy, impacts are one-time events with far-reaching consequences. Especially important are then impacts on young rocky planets, including the early Earth, because these planets are likely exposed to much higher impact fluxes, commonly called 'heavy bombardment'. This bombardment is the final echo of the turbulent planetary accretion and has prominent significance for planetary environments, e.g., the chemical composition and shape of the planetary surface, the chemistry of atmospheres, aerosol production, and likely the origin of life. Future observations of exoplanets by space telescopes, such as the James Webb Space Telescope or Ariel, as well as ground-based telescopes, such as the Extremely Large Telescope currently under construction in Chile, could determine whether this heavy bombardment represents a common scenario for the evolution of terrestrial planets. Both impacts and photochemistry can be efficiently simulated and studied in laboratory conditions by state-of-the-art methods....Klíčová slova: exoplanety, Země, impakty, fotochemie, infračervená spektroskopie, atmosférická chemie Impakty a fotochemie jsou dvěma významnými hnacími silami pro chemické přeměny v planetárních atmosférách. Zatímco UV záření produkované mladými hvězdami kontinuálně poskytuje energii, impakty jsou jednorázové události s dalekosáhlými důsledky. Zvlášť významné jsou pak impakty na mladých kamenných planetách, protože tyto planety jsou vystavovány mnohem vyšším tokům dopadající hmoty, obvykle nazývané "těžké bombardování". Toto bombardování je posledním dozvukem turbulentní planetární akrece a hraje důležitou roli při formování podmínek na planetách, včetně chemického složení, povrchu, chemie atmosfér, produkce aerosolů a pravděpodobně i vzniku života. Budoucí pozorování vesmírnými teleskopy, jako např. Vesmírný dalekohled Jamese Webba nebo Ariel, či pozemskými dalekohledy, jako např. Extrémně velký dalekohled, který je v současnosti konstruován v Chile, mohou určit, zda je toto těžké bombardování běžnou součástí evoluce terestrických planet. Jak impakty, tak fotochemie mohou být efektivně simulovány a studovány v laboratorních podmínkách pomocí moderních metod. Tato práce shrnuje naše výsledky zaměřené na rozpoznávání markerových molekul impaktů a s tím souvisejících termodynamických nerovnováh v...Department of Inorganic ChemistryKatedra anorganické chemieFaculty of SciencePřírodovědecká fakult

Ariel – a window to the origin of life on early earth?

Is there life beyond Earth? An ideal research program would first ascertain how life on Earth began and then use this as a blueprint for its existence elsewhere. But the origin of life on Earth is still not understood, what then could be the way forward? Upcoming observations of terrestrial exoplanets provide a unique opportunity for answering this fundamental question through the study of other planetary systems. If we are able to see how physical and chemical environments similar to the early Earth evolve we open a window into our own Hadean eon, despite all information from this time being long lost from our planet’s geological record. A careful investigation of the chemistry expected on young exoplanets is therefore necessary, and the preparation of reference materials for spectroscopic observations is of paramount importance. In particular, the deduction of chemical markers identifying specific processes and features in exoplanetary environments, ideally “uniquely”. For instance, prebiotic feedstock molecules, in the form of aerosols and vapours, could be observed in transmission spectra in the near future whilst their surface deposits could be observed from reflectance spectra. The same detection methods also promise to identify particular intermediates of chemical and physical processes known to be prebiotically plausible. Is Ariel truly able to open a window to the past and answer questions concerning the origin of life on our planet and the universe? In this paper, we discuss aspects of prebiotic chemistry that will help in formulating future observational and data interpretation strategies for the Ariel mission. This paper is intended to open a discussion and motivate future detailed laboratory studies of prebiotic processes on young exoplanets and their chemical signatures

Enabling planetary science across light-years. Ariel Definition Study Report

Ariel, the Atmospheric Remote-sensing Infrared Exoplanet Large-survey, was adopted as the fourth medium-class mission in ESA's Cosmic Vision programme to be launched in 2029. During its 4-year mission, Ariel will study what exoplanets are made of, how they formed and how they evolve, by surveying a diverse sample of about 1000 extrasolar planets, simultaneously in visible and infrared wavelengths. It is the first mission dedicated to measuring the chemical composition and thermal structures of hundreds of transiting exoplanets, enabling planetary science far beyond the boundaries of the Solar System. The payload consists of an off-axis Cassegrain telescope (primary mirror 1100 mm x 730 mm ellipse) and two separate instruments (FGS and AIRS) covering simultaneously 0.5-7.8 micron spectral range. The satellite is best placed into an L2 orbit to maximise the thermal stability and the field of regard. The payload module is passively cooled via a series of V-Groove radiators; the detectors for the AIRS are the only items that require active cooling via an active Ne JT cooler. The Ariel payload is developed by a consortium of more than 50 institutes from 16 ESA countries, which include the UK, France, Italy, Belgium, Poland, Spain, Austria, Denmark, Ireland, Portugal, Czech Republic, Hungary, the Netherlands, Sweden, Norway, Estonia, and a NASA contribution

Expression and purification of protein photo-initiated nanoprobe: tool to study clinically relevant protein-protein interactions

Cytochrome b5 is a key protein in the function and regulation of the mixed function monooxygenase (MFO) system in mammalian endoplasmic reticulum and is, therefore, a clinically relevant target for biochemical studies. To study its interactions within the MFO system using photo-initiated crosslinking, we have developed cytochrome b5 mutants with methionine in several key amino acid positions within the primary amino acid sequence, such as serine 23 and leucine 41. Also, naturally presented Met in positions 96, 126 and 131 were mutated to Leu with no effect to cytochrome b5 activity. Our protein was expressed in E. coli B834 auxotrophic type with L-2-amino-5,5-azi-hexanoic acid (photo-Met) present in the cultivation medium. This methionine analogue with photolabile diazirine ring is readily incorporated in Met positions into the primary sequence of proteins by aminoacyl-tRNA synthetases. The whole expression protocol was optimized to achieve maximal percentage of photo-Met incorporation into the expressed protein sequence. Up to 93.4% incorporation of photo-Met was achieved. The expressed protein was isolated and photo-Met incorporation was established with MALDI-TOF mass spectrometry. After reconstitution with its natural interaction partners - full-length cytochrome P450 2B4 (rabbit isoform) or..

Experimental study of chemical evolution of biomolecules under early Earth conditions

Origin of life is a still-enduring gap in human knowledge. This work is focused on revealing of several pieces of this puzzle. State of the art scenarios of biomolecules synthesis under prebiotic conditions are presented and discussed. This thesis presents our recent experiments suggesting a novel idea that neutral planetary atmosphere containing a mixture of neutral volcanic-type gasses (CO2, N2, H2O) can be converted over acidic mineral catalysts upon irradiation by a soft UV-radiation into a relatively reactive mixture of reducing gases (CH4, CO), which can be further reprocessed by high-energy chemistry. The resulting mixture (CH4, CO + N2) represents a common reducing atmosphere related e.g. to the chemistry of Titan, the largest moon of Saturn, as well as a possible representation of the secondary atmosphere of our planet. Also, photocatalytic reduction of CO2-rich atmosphere can explain the abiotic origin of methane on current Mars or other terrestrial planets. In our subsequent experiments, corresponding equimolar model mixture of CH4 : CO : N2 in presence of water vapour was subjected to reprocessing by high-power laser plasma simulating an asteroid impact - one of a series of impact events which the young Earth experienced during the first 600 million years of her history. Upon delivery..

Decomposition of Benzene during Impacts in N2-dominated Atmospheres

Benzene is a simple neutral aromatic compound found in molecular clouds, comets, and planetary atmospheres. It has been confirmed on Jupiter, Saturn, Titan, and is expected on exoplanets. In this paper, the decomposition of benzene in a simulated asteroid or comet impact into an N _2 -dominated atmosphere was investigated. The impact plasma was simulated with laser-induced dielectric breakdown and the gas phase decomposition products were observed using high-resolution Fourier transform infrared spectroscopy. The gas phase decomposition products involve mainly HCN, C _2 H _2 , and smaller amounts of CH _4 with yields of 3.1%–24.0%, 0–11.7%, and 0.5%–3.3%, respectively. Furthermore, in presence of water, benzene also produces CO and CO _2 with yields of 2.4%–35.1% and 0.01%–4.8%, respectively. The oxidation state of the product mixture is proportional to the water content. Apart from that, a black-brownish solid phase is formed during the experiments, which makes up about 60% of the original carbon content. Our results therefore show that in anoxic N _2 -dominated planetary atmospheres, impacts might lead to the depletion of benzene and the formation of HCN, C _2 H _2 , and CH _4 and, in the presence of water, to the formation of CO and CO _2

Photoacoustic spectroscopy with mica and graphene micro-mechanical levers for multicomponent analysis of acetic acid, acetone and methanol mixture

Multilayer graphene and mica cantilevers as part of an optical microphone in combination with CO2 laser emitting in the range of 9-11 mu m were employed in a multicomponent analysis of a mixture of acetone, acetic acid and methanol by photoacoustic spectroscopy. Using these elements, the detection limits of mica circle cantilever were 0.54, 0.80 and 24.8 ppm for acetic acid, methanol and acetone, respectively; these limits were approximately 5 times lower than the detection limit of the highest-class microphone used in this study. The multicomponent analysis was performed using five selected CO2 laser lines and a classical method of least squares. Despite the inaccuracies of our system, very good agreement between the concentration of acetic acid calculated from the photoacoustic signal and from weighing of concentration standards (similar to 3%) was found when measuring the signal in a 10:1:1 mixture of acetone:acetic acid:methanol at five selected laser lines. The absorption coefficient of acetic acid at 10.24 mu m was almost 500 times higher than that of acetone, which showed the good ability of this method to detect acetic acid in a high background of acetone, which can be beneficial in the medical analysis of breath.Web of Science14420820