The Study of Transient Species and Precursors of Biomolecules using Spectroscopic Techniques

The presented thesis is focused on a spectroscopic study of unstable radicals, ions and molecules in a positive column glow discharge and laser plasma. The research of these fragments is supplemented by a study of biomolecules formation from these species and influence of catalysts. Molecular dynamics of radicals, ions and unstable molecules has been studied using a time resolved Fourier transform infrared spectroscopy. Time resolved spectra of CH4, HCONH2, BrCN, CH3CN, CF3Br, (CF3)2CHBr positive column glow discharges have been measured and simulated using a kinetic model including molecular dynamics, collisions and chemical and radiation transfer processes. The model has been compared with our experimental results and time resolved spectra were described in details. Fit to a complex reaction mechanism has been used to estimate a rate constant of a HCN conversion to HNC by a collision with H radical. The study of precursors of biomolecules was focused on chemical consequences of a laser induced dielectric breakdown in formamide vapor and gaseous carbon monooxide with 18 O labeled water. Dissociation products have been detected using the Fourier transform absorption spectroscopy. The experimental results have been explained by a help of a chemical laser spark dynamics model. Additionally, our the...Předložená dizertační práce je složena ze studií zaměřených na spektroskopický popis, kinetiku a dynamiku molekul, radikálů a iontů v plazmě výboje a laserové jiskry. Výzkum těchto fragmentů je rozšířen o vznik biomolekul z těchto jednoduchých specií včetně vlivu látek s katalytickým účinkem. Dynamika radikálů, iontů a nestabilních molekul byla studována pomocí časově rozlišené spektrometrie s Fourierovou transformací. Byla měřena časově rozlišená emisní spektra výbojů v CH4, HCONH2, BrCN, CH3CN, CF3Br, (CF3)2CHBr a dalších plynech. Následně byl výboj simulován pomocí modelu zahrnujícího molekulární dynamiku, kolizní, chemické a radiační procesy. Modely byly porovnány s experimentálními výsledky a byla vysvětlena získaná emisní časově rozlišená spektra. Fitem na komplexní mechanismus byla experimentálně zjištěna hodnota rychlostní konstanty konverze HCN na HNC kolizí s excitovaným atomem vodíku. V rámci studia prekurzorů biomolekul bylo pomocí vysoce rozlišené infračervené absorpční spektrometrie s Fourierovou transformací analyzováno složení plynných látek vznikajících po expozici par formamidu a plynné směsi oxidu uhelnatého s dusíkem a izotopově značenou vodou laserové jiskře generované vysoce výkonným pražským laserovým systémem Asterix (PALS). Pomocí chemického modelu byla studována dynamika...Department of Physical and Macromolecular ChemistryKatedra fyzikální a makromol. chemieFaculty of SciencePřírodovědecká fakult

Využití spektrometrie s Fourierovou transformací pro měření absorpčních a emisních spekter a její aplikace v problematice životního prostředí

Department of Physical and Macromolecular ChemistryKatedra fyzikální a makromol. chemieFaculty of SciencePřírodovědecká fakult

Infrared Spectra of Small Radicals for Exoplanetary Spectroscopy: OH, NH, CN and CH: The State of Current Knowledge

In this study, we present a current state-of-the-art review of middle-to-near IR emission spectra of four simple astrophysically relevant molecular radicals—OH, NH, CN and CH. The spectra of these radicals were measured by means of time-resolved Fourier transform infrared spectroscopy in the 700–7500 cm−1 spectral range and with 0.07–0.02 cm−1 spectral resolution. The radicals were generated in a glow discharge of gaseous mixtures in a specially designed discharge cell. The spectra of short-lived radicals published here are of great importance, especially for the detailed knowledge and study of the composition of exoplanetary atmospheres in selected new planets. Today, with the help of the James Webb telescope and upcoming studies with the help of Plato and Ariel satellites, when the investigated spectral area is extended into the infrared spectral range, it means that detailed knowledge of the infrared spectra of not only stable molecules but also the spectra of short-lived radicals or ions, is indispensable. This paper follows a simple structure. Each radical is described in a separate chapter, starting with historical and actual theoretical background, continued by our experimental results and concluded by spectral line lists with assigned notation

Konzept OER-Zertifizierung an österreichischen Hochschulen

Das Ergebnis der Arbeitsgruppe „Open Educational Resources“ ist ein Konzept zur OER-Zertifizierung an österreichischen Hochschulen. Dazu wird unterschieden in eine zweistufige Zertifizierung für Hochschullehrende und eine dreistufige Zertifizierung für Hochschulen. Der Umsetzungsvorschlag sieht dafür digitale Open Badges vor, die von einer zentralen Stelle bereits in der nächsten Leistungsvereinbarungsperiode (2019–2021) vergeben werden sollen

UV-Induced Nanoparticles-Formation, Properties and Their Potential Role in Origin of Life

Inorganic nanoparticles might have played a vital role in the transition from inorganic chemistry to self-sustaining living systems. Such transition may have been triggered or controlled by processes requiring not only versatile catalysts but also suitable reaction surfaces. Here, experimental results showing that multicolor quantum dots might have been able to participate as catalysts in several specific and nonspecific reactions, relevant to the prebiotic chemistry are demonstrated. A very fast and easy UV-induced formation of ZnCd quantum dots (QDs) with a quantum yield of up to 47% was shown to occur 5 min after UV exposure of the solution containing Zn(II) and Cd(II) in the presence of a thiol capping agent. In addition to QDs formation, xanthine activity was observed in the solution. The role of solar radiation to induce ZnCd QDs formation was replicated during a stratospheric balloon flight

A chemical survey of exoplanets with ARIEL

Thousands of exoplanets have now been discovered with a huge range of masses, sizes and orbits: from rocky Earth-like planets to large gas giants grazing the surface of their host star. However, the essential nature of these exoplanets remains largely mysterious: there is no known, discernible pattern linking the presence, size, or orbital parameters of a planet to the nature of its parent star. We have little idea whether the chemistry of a planet is linked to its formation environment, or whether the type of host star drives the physics and chemistry of the planet’s birth, and evolution. ARIEL was conceived to observe a large number (~1000) of transiting planets for statistical understanding, including gas giants, Neptunes, super-Earths and Earth-size planets around a range of host star types using transit spectroscopy in the 1.25–7.8 μm spectral range and multiple narrow-band photometry in the optical. ARIEL will focus on warm and hot planets to take advantage of their well-mixed atmospheres which should show minimal condensation and sequestration of high-Z materials compared to their colder Solar System siblings. Said warm and hot atmospheres are expected to be more representative of the planetary bulk composition. Observations of these warm/hot exoplanets, and in particular of their elemental composition (especially C, O, N, S, Si), will allow the understanding of the early stages of planetary and atmospheric formation during the nebular phase and the following few million years. ARIEL will thus provide a representative picture of the chemical nature of the exoplanets and relate this directly to the type and chemical environment of the host star. ARIEL is designed as a dedicated survey mission for combined-light spectroscopy, capable of observing a large and well-defined planet sample within its 4-year mission lifetime. Transit, eclipse and phase-curve spectroscopy methods, whereby the signal from the star and planet are differentiated using knowledge of the planetary ephemerides, allow us to measure atmospheric signals from the planet at levels of 10–100 part per million (ppm) relative to the star and, given the bright nature of targets, also allows more sophisticated techniques, such as eclipse mapping, to give a deeper insight into the nature of the atmosphere. These types of observations require a stable payload and satellite platform with broad, instantaneous wavelength coverage to detect many molecular species, probe the thermal structure, identify clouds and monitor the stellar activity. The wavelength range proposed covers all the expected major atmospheric gases from e.g. H2O, CO2, CH4 NH3, HCN, H2S through to the more exotic metallic compounds, such as TiO, VO, and condensed species. Simulations of ARIEL performance in conducting exoplanet surveys have been performed – using conservative estimates of mission performance and a full model of all significant noise sources in the measurement – using a list of potential ARIEL targets that incorporates the latest available exoplanet statistics. The conclusion at the end of the Phase A study, is that ARIEL – in line with the stated mission objectives – will be able to observe about 1000 exoplanets depending on the details of the adopted survey strategy, thus confirming the feasibility of the main science objectives.Peer reviewedFinal Published versio

Simulating asteroid impacts and meteor events by high-power lasers : from the laboratory to spaceborne missions

Meteor plasmas and impact events are complex, dynamic natural phenomena. Simulating these processes in the laboratory is, however, a challenge. The technique of laser induced dielectric breakdown was first used for this purpose almost 50 years ago. Since then, laser-based experiments have helped to simulate high energy processes in the Tunguska and Chicxulub impact events, heavy bombardment on the early Earth, prebiotic chemical evolution, space weathering of celestial bodies and meteor plasma. This review summarizes the current level of knowledge and outlines possible paths of future development.Czech Science FoundationCzech Academy of Sciences Program of Regional Cooperatio

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