TY - THES A1 - Hildebrandt, Niko T1 - Lanthanides and quantum dots : time-resolved laser spectroscopy of biochemical Förster Resonance Energy Transfer (FRET) systems T1 - Lanthanide und Quantenpunkte : zeitaufgelöste Laserspektroskopie an biochemischen Förster-Resonanzenergietransfer (FRET) Systemen N2 - Förster Resonance Energy Transfer (FRET) plays an important role for biochemical applications such as DNA sequencing, intracellular protein-protein interactions, molecular binding studies, in vitro diagnostics and many others. For qualitative and quantitative analysis, FRET systems are usually assembled through molecular recognition of biomolecules conjugated with donor and acceptor luminophores. Lanthanide (Ln) complexes, as well as semiconductor quantum dot nanocrystals (QD), possess unique photophysical properties that make them especially suitable for applied FRET. In this work the possibility of using QD as very efficient FRET acceptors in combination with Ln complexes as donors in biochemical systems is demonstrated. The necessary theoretical and practical background of FRET, Ln complexes, QD and the applied biochemical models is outlined. In addition, scientific as well as commercial applications are presented. FRET can be used to measure structural changes or dynamics at distances ranging from approximately 1 to 10 nm. The very strong and well characterized binding process between streptavidin (Strep) and biotin (Biot) is used as a biomolecular model system. A FRET system is established by Strep conjugation with the Ln complexes and QD biotinylation. Three Ln complexes (one with Tb3+ and two with Eu3+ as central ion) are used as FRET donors. Besides the QD two further acceptors, the luminescent crosslinked protein allophycocyanin (APC) and a commercial fluorescence dye (DY633), are investigated for direct comparison. FRET is demonstrated for all donor-acceptor pairs by acceptor emission sensitization and a more than 1000-fold increase of the luminescence decay time in the case of QD reaching the hundred microsecond regime. Detailed photophysical characterization of donors and acceptors permits analysis of the bioconjugates and calculation of the FRET parameters. Extremely large Förster radii of more than 100 Å are achieved for QD as acceptors, considerably larger than for APC and DY633 (ca. 80 and 60 Å). Special attention is paid to interactions with different additives in aqueous solutions, namely borate buffer, bovine serum albumin (BSA), sodium azide and potassium fluoride (KF). A more than 10-fold limit of detection (LOD) decrease compared to the extensively characterized and frequently used donor-acceptor pair of Europium tris(bipyridine) (Eu-TBP) and APC is demonstrated for the FRET system, consisting of the Tb complex and QD. A sub-picomolar LOD for QD is achieved with this system in azide free borate buffer (pH 8.3) containing 2 % BSA and 0.5 M KF. In order to transfer the Strep-Biot model system to a real-life in vitro diagnostic application, two kinds of imunnoassays are investigated using human chorionic gonadotropin (HCG) as analyte. HCG itself, as well as two monoclonal anti-HCG mouse-IgG (immunoglobulin G) antibodies are labeled with the Tb complex and QD, respectively. Although no sufficient evidence for FRET can be found for a sandwich assay, FRET becomes obvious in a direct HCG-IgG assay showing the feasibility of using the Ln-QD donor-acceptor pair as highly sensitive analytical tool for in vitro diagnostics. N2 - Förster Resonanzenergietransfer (FRET) spielt eine wichtige Rolle in biochemischen Anwendungen, wie z.B. DNA-Sequenzierung, intrazellulären Protein-Protein-Wechselwirkungen, molekularen Bindungsstudien, in-vitro-Diagnostik und vielen anderen. Zur quantitativen und qualitativen Analyse werden FRET Systeme normalerweise durch molekulare Erkennung von Biomolekülen, die mit Donator- und Acceptorluminophoren markiert sind, ermöglicht. Durch die besonderen photophysikalischen Eigenschaften sowohl von Lanthanidkomplexen (Ln-Komplexen), als auch Halbleiternanokristallen (sog. Quantenpunkten oder Quantumdots - QD), sind diese besonders für FRET Anwendungen geeignet. In der vorliegenden Arbeit wird effizienter FRET zwischen Ln-Komplexen und QD in biochemischen Systemen demonstriert. Die notwendigen theoretischen und praktischen Grundlagen über FRET, Ln-Komplexe, QD und die verwendeten biochemischen Modelle werden dargestellt, und wissenschaftliche als auch kommerzielle Anwendungen werden präsentiert. FRET kann zur Messung von strukturellen Veränderungen und Dynamiken im Bereich von ca. 1 bis 10 nm verwendet werden. Der sehr starke und gut charakterisierte Bindungsprozess zwischen Streptavidin (Strep) und Biotin (Biot) wird als biomolekulares Modellsystem eingesetzt. Ein FRET System wird durch Streptavidinkonjugation mit Ln-Komplexen und QD-Biotinylierung etabliert. Drei Ln-Komplexe (einer mit Tb3+ und zwei mit Eu3+ als Zentralion) werden als Donatoren verwendet, und neben QD werden zwei weitere Acceptoren, das lumineszierende, quervernetzte Protein Allophycocyanin (APC) und ein kommerzieller Fluoreszenzfarbstoff (DY633), untersucht. FRET kann für alle Donator-Acceptor Paare nachgewiesen werden, zum einen durch sensibilisierte Acceptorlumineszenz und zum anderen durch eine über 1000-fach erhöhte Lumineszenzabklingzeit der QD mit über 100 Mikrosekunden. Mittels detailierter photophysikalischer Charakterisierung der Donatoren und Acceptoren können die Biokonjugate analysiert und die FRET Parameter berechnet werden. Für die QD FRET Systeme ergeben sich extrem große Försterradien von über 100 Å, die wesentlich größer sind als für APC und DY633 (ca. 80 bzw. 60 Å). Besondere Aufmerksamkeit gilt der Wechselwirkung mit den Zusatzreagenzien Boratpuffer, Bovines Serumalbumin (BSA), Natriumazid und Kaliumfluorid (KF) in den wässrigen Lösungen. Im Vergleich zum ausgiebig charakterisierten und vielfach verwendeten Donator-Acceptor Paar aus Europium-tris(Bipyridin) (Eu-TBP) und APC wird eine mehr als 10-fache Senkung der Nachweisgrenze für das FRET-System, bestehend aus Tb-Komplex und QD, erreicht. In azidfreiem Boratpuffer (pH 8,3) mit 2 % BSA und 0,5 M KF wird eine subpicomolare QD-Nachweisgrenze für dieses System aufgezeigt. Um den Transfer des Strep-Biot Modellsystems in eine echte in-vitro-diagnostische Anwendung zu demonstrieren, werden zwei Immuntests zum HCG-(Humanes Choriongonadotropin)-Nachweis untersucht. Sowohl HCG als auch monoklonale anti-HCG Maus-IgG-(Immunoglobulin G)-Antikörper werden mit dem Tb-Komplex bzw. mit QD markiert. Obwohl kein ausreichender Nachweis für FRET in einem immunometrischen Assay (oder Sandwichassay) erbracht werden kann, wird FRET in einem direkten HCG-IgG Assay erzielt, wodurch die Realisierbarkeit von Ln-QD Donator-Acceptor Paaren zur hochsensitiven Anwendung in der in-vitro-Diagnostik gezeigt werden kann. KW - FRET KW - Lanthanide KW - Quantenpunkte KW - Zeitaufgelöster Immunoassay KW - Spektroskopie KW - FRET KW - Lanthanides KW - Quantum Dots KW - Time-resolved Immunoassay KW - Spectroscopy Y1 - 2006 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus-12686 ER - TY - THES A1 - Boeche, Corrado T1 - Chemical gradients in the Milky Way from unsupervised chemical abundances measurements of the RAVE spectroscopic data set T1 - Chemische Gradienten in der Milchstraße aus unüberwachten chemischen Häufigkeitsmessungen aus dem RAVE spektroskopischen Datenset N2 - The present thesis was born and evolved within the RAdial Velocity Experiment (RAVE) with the goal of measuring chemical abundances from the RAVE spectra and exploit them to investigate the chemical gradients along the plane of the Galaxy to provide constraints on possible Galactic formation scenarios. RAVE is a large spectroscopic survey which aims to observe spectroscopically ~10^6 stars by the end of 2012 and measures their radial velocities, atmospheric parameters and chemical abundances. The project makes use of the UK Schmidt telescope at Australian Astronomical Observatory (AAO) in Siding Spring, Australia, equipped with the multiobject spectrograph 6dF. To date, RAVE collected and measured more than 450,000 spectra. The precision of the chemical abundance estimations depends on the reliability of the atomic and atmosphere parameters adopted (in particular the oscillator strengths of the absorption lines and the effective temperature, gravity, and metallicity of the stars measured). Therefore we first identified 604 absorption lines in the RAVE wavelength range and refined their oscillator strengths with an inverse spectral analysis. Then, we improved the RAVE stellar parameters by modifying the RAVE pipeline and the spectral library the pipeline rely on. The modifications removed some systematic errors in stellar parameters discovered during this work. To obtain chemical abundances, we developed two different processing pipelines. Both of them perform chemical abundances measurements by assuming stellar atmospheres in Local Thermodynamic Equilibrium (LTE). The first one determines elements abundances from equivalent widths of absorption lines. Since this pipeline showed poor sensibility on abundances relative to iron, it has been superseded. The second one exploits the chi^2 minimization technique between observed and model spectra. Thanks to its precision, it has been adopted for the creation of the RAVE chemical catalogue. This pipeline provides abundances with uncertains of about ~0.2dex for spectra with signal-to-noise ratio S/N>40 and ~0.3dex for spectra with 20>S/N>40. For this work, the pipeline measured chemical abundances up to 7 elements for 217,358 RAVE stars. With these data we investigated the chemical gradients along the Galactic radius of the Milky Way. We found that stars with low vertical velocities |W| (which stay close to the Galactic plane) show an iron abundance gradient in agreement with previous works (~-0.07$ dex kpc^-1) whereas stars with larger |W| which are able to reach larger heights above the Galactic plane, show progressively flatter gradients. The gradients of the other elements follow the same trend. This suggests that an efficient radial mixing acts in the Galaxy or that the thick disk formed from homogeneous interstellar matter. In particular, we found hundreds of stars which can be kinetically classified as thick disk stars exhibiting a chemical composition typical of the thin disk. A few stars of this kind have already been detected by other authors, and their origin is still not clear. One possibility is that they are thin disk stars kinematically heated, and then underwent an efficient radial mixing process which blurred (and so flattened) the gradient. Alternatively they may be a transition population" which represents an evolutionary bridge between thin and thick disk. Our analysis shows that the two explanations are not mutually exclusive. Future follow-up high resolution spectroscopic observations will clarify their role in the Galactic disk evolution. N2 - Die vorliegende Doktorarbeit wurde im Rahmen des RAdial Velocity Experiment (RAVE) angefertigt. Ihr Ziel ist es, chemische Elementhäufigkeiten an RAVE-Spektren zu messen und zur Untersuchung chemischer Gradienten in der Milchstrassenebene zu benutzen, um verschieden Szenarien der Galaxienentstehung einzugrenzen. RAVE ist eine große spektrokopische Durchmusterung, deren Ziel es ist, bis zum Ende des Jahres 2012 insgesamt 10^6 Sterne zu spektroskopieren, um deren Radialgeschwindigkeiten, sternatmosphärische Parameter und chemische Häufigkeiten zu messen. Das Projekt benutzt das UK Schmidt Teleskop am Australian Astronomical Observatory (AAO) in Siding Spring, Australien, welches mit dem Multiobjekt-Spektrographen 6dF bestückt ist. Bis heute hat RAVE die Spektren von mehr als 450,000 Sternen gesammelt und untersucht. Die Genauigkeit, mit der die Elementhäufigkeiten abgeschätzt werden können, hängt von der Zuverlässigkeit der verwendeten Parameter, (insbesondere der Oszillatorstärken der Absorptionslinien sowie von der effektiven Temperatur, Schwerebeschleunigung und der Metallizität des gemessenen Sterns) ab. Daher identifizierten wir zunächst 604 Absorptionslinien im Wellenlängenbereich von RAVE und verbesserten deren Oszillatorstärken durch eine inverse Spektralanalyse. Dann wurden die stellaren Parameter von RAVE verbessert, indem die RAVE Pipeline und die stellaren Parameter, auf denen sie beruht, modifiziert wurden. Die Änderungen eliminierten einen Teil der systematischen Fehler von stellaren Parametern, die im Laufe dieser Arbeit gefunden wurden. Um Elementhäufigkeiten zu bestimmen, haben wir zwei verschiedene Prozessierungs-Pipelines entwickelt. Beide berechnen die Elementhäufigkeiten unter der Annahme von Sternatmosphären im lokalen thermischen Gleichgewicht (local thermal equilibrium, LTE). Die erste Pipeline berechnete Elemenhäufigkeiten anhand der Äquivalentbreiten von Absorptionslinien. Da diese Methode eine geringe Empfindlichkeit für die Elementhäufigeiten relativ zu Eisen erreichte, wurde sie ersetzt. Die neue Pipeline benutzt chi^2-Fits von Modellspektren an die beobachteten Spektren. Dank Ihrer Präzision wurde diese für die Erstellung des RAVE-Katalogs von Elementhäufigkeiten verwendet. Diese Pipeline liefert Elementhäufigkeiten mit einer Genauigkeit von ~0.2dex, während für Spektren mit 20>S/N>40 immerhin noch ~0.3dex Genauigkeit erreicht werden. Für die vorliegende Arbeit wurden für 217.358 Sterne die Häufigkeiten von sieben chemischen Elementen bestimmt. Mit diesen Daten wurde der radiale chemische Gradient unserer Milchstraße untersucht. Wir finden, dass Sterne mit kleinen vertikalen Geschwindigkeiten |W|, die also nahe der galaktischen Ebene bleiben, einen radialen Gradienten der Eisenhäufigkeit zeigen, der mit früheren Studien übereinstimmt (~-0.07 dex Kpc^-1), während Sterne mit großen |W|, also solche, die größere galaktische Höhen erreichen, einen progressiv flachere Gradienten zeigen. Die Gradienten der anderen Element folgen dem gleichen Trend. Das lässt darauf schließen, dass entweder die Durchmischung der galaktischen dicken Scheibe effizient arbeitet oder aber dass die dicke Scheibe aus interstellarer Materie gebildet wurde, die chemisch recht homogen war. Speziell fanden wir hunderte von Sternen, die zwar kinematisch als zur dicken Scheibe zugehörig klassifiziert werden können, die aber die typische chemische Zusammensetzung der dünnen Scheibe aufweisen. Einige wenige dieser Sterne wurden bereits von anderen Autoren entdeckt, aber ihre Herkunft bleibt immer noch unklar. Eine Möglichkeit ist, dass die Sterne der dünnen Scheibe kinematische geheizt werden, sodass sie effizienter radial gemischt werden, was die chemischen Gradienten verwischt und auch flacher macht. Alternativ dazu könnten diese Sterne einer "Übergangspopulation" angehören, welche hinsichtlich der Scheibenevolution die Verbindung zwischen der dünnen und der dicken Scheibe darstellt. Unsere Untersuchung zeigt, dass sich diese beiden Erklärungen gegenseitig nicht ausschließen. Künftige Nachspektroskopierung mit hoher Auflösung wird die Rolle dieser Sterne in der Entwicklungsgeschichte der galaktischen Scheibe aufklären. KW - Galaxie KW - Milchstraße KW - Spektroskopie KW - chemische Häufigkeiten KW - Galaxy KW - Milky Way KW - Spectroscopy KW - Chemical Abundances Y1 - 2011 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus-52478 ER - TY - JOUR A1 - Zude, Manuela A1 - Pflanz, Michael A1 - Spinelli, Lorenzo A1 - Dosche, Carsten A1 - Torricelli, Alessandro T1 - Non-destructive analysis of anthocyanins in cherries by means of Lambert-Beer and multivariate regression based on spectroscopy and scatter correction using time-resolved analysis JF - Journal of food engineering N2 - In high-value sweet cherry (Prunus avium), the red coloration - determined by the anthocyanins content - is correlated with the fruit ripeness stage and market value. Non-destructive spectroscopy has been introduced in practice and may be utilized as a tool to assess the fruit pigments in the supply chain processes. From the fruit spectrum in the visible (Vis) wavelength range, the pigment contents are analyzed separately at their specific absorbance wavelengths. A drawback of the method is the need for re-calibration due to varying optical properties of the fruit tissue. In order to correct for the scattering differences, most often the spectral intensity in the visible spectrum is normalized by wavelengths in the near infrared (NIR) range, or pre-processing methods are applied in multivariate calibrations. In the present study, the influence of the fruit scattering properties on the Vis/NIR fruit spectrum were corrected by the effective pathlength in the fruit tissue obtained from time-resolved readings of the distribution of time-of-flight (DTOF). Pigment analysis was carried out according to Lambert-Beer law, considering fruit spectral intensities, effective pathlength, and refractive index. Results were compared to commonly applied linear color and multivariate partial least squares (PLS) regression analysis. The approaches were validated on fruits at different ripeness stages, providing variation in the scattering coefficient and refractive index exceeding the calibration sample set. In the validation, the measuring uncertainty of non-destructively analyzing fruits with Vis/NIR spectra by means of PLS or Lambert-Beer in comparison with combined application of Vis/NIR spectroscopy and DTOF measurements showed a dramatic bias reduction as well as enhanced coefficients of determination when using both, the spectral intensities and apparent information on the scattering influence by means of DTOF readings. Corrections for the refractive index did not render improved results. KW - Cherry KW - DTOF KW - Effective pathlength KW - Fruit maturity KW - Lambert-Beer KW - NIR KW - Non-invasive KW - Pigments KW - PLS KW - Ripeness KW - Sensor fusion KW - Spectroscopy KW - Time-resolved spectroscopy KW - TIRF KW - Vis KW - Scattering Y1 - 2011 U6 - https://doi.org/10.1016/j.jfoodeng.2010.09.021 SN - 0260-8774 VL - 103 IS - 1 SP - 68 EP - 75 PB - Elsevier CY - Oxford ER - TY - JOUR A1 - de Vera, Jean-Pierre Paul A1 - Böttger, Ute A1 - de la Torre Nötzel, Rosa A1 - Sanchez, Francisco J. A1 - Grunow, Dana A1 - Schmitz, Nicole A1 - Lange, Caroline A1 - Hübers, Heinz-Wilhelm A1 - Billi, Daniela A1 - Baque, Mickael A1 - Rettberg, Petra A1 - Rabbow, Elke A1 - Reitz, Günther A1 - Berger, Thomas A1 - Möller, Ralf A1 - Bohmeier, Maria A1 - Horneck, Gerda A1 - Westall, Frances A1 - Jänchen, Jochen A1 - Fritz, Jörg A1 - Meyer, Cornelia A1 - Onofri, Silvano A1 - Selbmann, Laura A1 - Zucconi, Laura A1 - Kozyrovska, Natalia A1 - Leya, Thomas A1 - Foing, Bernard A1 - Demets, Rene A1 - Cockell, Charles S. A1 - Bryce, Casey A1 - Wagner, Dirk A1 - Serrano, Paloma A1 - Edwards, Howell G. M. A1 - Joshi, Jasmin Radha A1 - Huwe, Björn A1 - Ehrenfreund, Pascale A1 - Elsaesser, Andreas A1 - Ott, Sieglinde A1 - Meessen, Joachim A1 - Feyh, Nina A1 - Szewzyk, Ulrich A1 - Jaumann, Ralf A1 - Spohn, Tilman T1 - Supporting Mars exploration BIOMEX in Low Earth Orbit and further astrobiological studies on the Moon using Raman and PanCam technology JF - Planetary and space science N2 - The Low Earth Orbit (LEO) experiment Biology and Mars Experiment (BIOMEX) is an interdisciplinary and international space research project selected by ESA. The experiment will be accommodated on the space exposure facility EXPOSE-R2 on the International Space Station (ISS) and is foreseen to be launched in 2013. The prime objective of BIOMEX is to measure to what extent biomolecules, such as pigments and cellular components, are resistant to and able to maintain their stability under space and Mars-like conditions. The results of BIOMEX will be relevant for space proven biosignature definition and for building a biosignature data base (e.g. the proposed creation of an international Raman library). The library will be highly relevant for future space missions such as the search for life on Mars. The secondary scientific objective is to analyze to what extent terrestrial extremophiles are able to survive in space and to determine which interactions between biological samples and selected minerals (including terrestrial, Moon- and Mars analogs) can be observed under space and Mars-like conditions. In this context, the Moon will be an additional platform for performing similar experiments with negligible magnetic shielding and higher solar and galactic irradiation compared to LEO. Using the Moon as an additional astrobiological exposure platform to complement ongoing astrobiological LEO investigations could thus enhance the chances of detecting organic traces of life on Mars. We present a lunar lander mission with two related objectives: a lunar lander equipped with Raman and PanCam instruments which can analyze the lunar surface and survey an astrobiological exposure platform. This dual use of testing mission technology together with geo- and astrobiological analyses will significantly increase the science return, and support the human preparation objectives. It will provide knowledge about the Moon's surface itself and, in addition, monitor the stability of life-markers, such as cells, cell components and pigments, in an extraterrestrial environment with much closer radiation properties to the surface of Mars. The combination of a Raman data base of these data together with data from LEO and space simulation experiments, will lead to further progress on the analysis and interpretation of data that we will obtain from future Moon and Mars exploration missions. KW - Moon KW - Mars KW - Low Earth Orbit KW - Astrobiology KW - Instrumentation KW - Spectroscopy KW - Biosignature Y1 - 2012 U6 - https://doi.org/10.1016/j.pss.2012.06.010 SN - 0032-0633 VL - 74 IS - 1 SP - 103 EP - 110 PB - Elsevier CY - Oxford ER - TY - JOUR A1 - Brosinsky, Arlena A1 - Förster, Saskia A1 - Segl, Karl A1 - Lopez-Tarazon, José Andrés A1 - Pique, Gemma A1 - Bronstert, Axel T1 - Spectral fingerprinting: characterizing suspended sediment sources by the use of VNIR-SWIR spectral information JF - Journal of soils and sediments : protection, risk assessment and remediation N2 - Knowledge of sediment sources is a prerequisite for sustainable management practices and may furthermore improve our understanding of water and sediment fluxes. Investigations have shown that a number of characteristic soil properties can be used as "fingerprints" to trace back the sources of river sediments. Spectral properties have recently been successfully used as such characteristics in fingerprinting studies. Despite being less labour-intensive than geochemical analyses, for example, spectroscopy allows measurements of small amounts of sediment material (> 60 mg), thus enabling inexpensive analyses even of intra-event variability. The focus of this study is on the examination of spectral properties of fluvial sediment samples to detect changes in source contributions, both between and within individual flood events. Sediment samples from the following three different origins were collected in the Isabena catchment (445 km(2)) in the central Spanish Pyrenees: (1) soil samples from the main potential source areas, (2) stored fine sediment from the channel bed once each season in 2011 and (3) suspended sediment samples during four flood events in autumn 2011 and spring 2012 at the catchment outlet as well as at several subcatchment outlets. All samples were dried and measured for spectral properties in the laboratory using an ASD spectroradiometer. Colour parameters and physically based features (e.g. organic carbon, iron oxide and clay content) were calculated from the spectra. Principal component analyses (PCA) were applied to all three types of samples to determine natural clustering of samples, and a mixing model was applied to determine source contributions. We found that fine sediment stored in the river bed seems to be mainly influenced by grain size and seasonal variability, while sampling location-and thus the effect of individual tributaries or subcatchments-seem to be of minor importance. Suspended sediment sources were found to vary between, as well as within, flood events; although badlands were always the major source. Forests and grasslands contributed little (< 10 %), and other sources (not further determinable) contributed up to 40 %. The analyses further suggested that sediment sources differ among the subcatchments and that subcatchments comprising relatively large proportions of badlands contributed most to the four flood events analyzed. Spectral fingerprints provide a rapid and cost-efficient alternative to conventional fingerprint properties. However, a combination of spectral and conventional fingerprint properties could potentially permit discrimination of a larger number of source types. KW - Isabena river KW - Mixing models KW - Northeast Spain KW - Sediment fingerprinting KW - Spectroscopy KW - Suspended sediment Y1 - 2014 U6 - https://doi.org/10.1007/s11368-014-0927-z SN - 1439-0108 SN - 1614-7480 VL - 14 IS - 12 SP - 1965 EP - 1981 PB - Springer CY - Heidelberg ER - TY - JOUR A1 - Brosinsky, Arlena A1 - Förster, Saskia A1 - Segl, Karl A1 - Kaufmann, Hermann T1 - Spectral fingerprinting: sediment source discrimination and contribution modelling of artificial mixtures based on VNIR-SWIR spectral properties JF - Journal of soils and sediments : protection, risk assessment and remediation N2 - Knowledge of the origin of suspended sediment is important for improving our understanding of sediment dynamics and thereupon support of sustainable watershed management. An direct approach to trace the origin of sediments is the fingerprinting technique. It is based on the assumption that potential sediment sources can be discriminated and that the contribution of these sources to the sediment can be determined on the basis of distinctive characteristics (fingerprints). Recent studies indicate that visible-near-infrared (VNIR) and shortwave-infrared (SWIR) reflectance characteristics of soil may be a rapid, inexpensive alternative to traditional fingerprint properties (e.g. geochemistry or mineral magnetism). To further explore the applicability of VNIR-SWIR spectral data for sediment tracing purposes, source samples were collected in the Isabena watershed, a 445 km(2) dryland catchment in the central Spanish Pyrenees. Grab samples of the upper soil layer were collected from the main potential sediment source types along with in situ reflectance spectra. Samples were dried and sieved, and artificial mixtures of known proportions were produced for algorithm validation. Then, spectral readings of potential source and artificial mixture samples were taken in the laboratory. Colour coefficients and physically based parameters were calculated from in situ and laboratory-measured spectra. All parameters passing a number of prerequisite tests were subsequently applied in discriminant function analysis for source discrimination and mixing model analyses for source contribution assessment. The three source types (i.e. badlands, forest/grassland and an aggregation of other sources, including agricultural land, shrubland, unpaved roads and open slopes) could be reliably identified based on spectral parameters. Laboratory-measured spectral fingerprints permitted the quantification of source contribution to artificial mixtures, and introduction of source heterogeneity into the mixing model decreased accuracies for some source types. Aggregation of source types that could not be discriminated did not improve mixing model results. Despite providing similar discrimination accuracies as laboratory source parameters, in situ derived source information was found to be insufficient for contribution modelling. The laboratory mixture experiment provides valuable insights into the capabilities and limitations of spectral fingerprint properties. From this study, we conclude that combinations of spectral properties can be used for mixing model analyses of a restricted number of source groups, whereas more straightforward in situ measured source parameters do not seem suitable. However, modelling results based on laboratory parameters also need to be interpreted with care and should not rely on the estimates of mean values only but should consider uncertainty intervals as well. KW - Artificial mixture KW - Mixing model KW - Sediment fingerprinting KW - Spectroscopy Y1 - 2014 U6 - https://doi.org/10.1007/s11368-014-0925-1 SN - 1439-0108 SN - 1614-7480 VL - 14 IS - 12 SP - 1949 EP - 1964 PB - Springer CY - Heidelberg ER - TY - JOUR A1 - Zehbe, Rolf A1 - Zehbe, Kerstin T1 - Strontium doped poly-epsilon-caprolactone composite scaffolds made by reactive foaming JF - The European journal of the history of economic thought N2 - In the reconstruction and regeneration of bone tissue, a primary goal is to initiate bone growth and to stabilize the surrounding bone. In this regard, a potentially useful component in biomaterials for bone tissue engineering is strontium, which acts as cationic active agent, triggering certain intracellular pathways and acting as so called dual action bone agent which inhibits bone resorption while stimulating bone regeneration. In this study we established a novel processing for the foaming of a polymer (poly-epsilon-caprolactone) and simultaneous chemical reaction of a mixture of calcium and strontium hydroxides to the respective carbonates using supercritical carbon dioxide. The resultant porous composite scaffold was optimized in composition and strontium content and was characterized via different spectroscopic (infrared and Raman spectroscopy, energy dispersive X-ray spectroscopy), imaging (SEM, mu CT), mechanical testing and in vitro methods (fluorescence vital staining, MTT-assay). As a result, the composite scaffold showed good in vitro biocompatibility with partly open pore structure and the expected chemistry. First mechanical testing results indicate sufficient mechanical stability to support future in vivo applications. (C) 2016 Elsevier B.V. All rights reserved. KW - Strontium KW - Poly-epsilon-caprolactone KW - Porous scaffold KW - CAL-72 osteoblasts KW - L-929 fibroblasts KW - Reactive foaming KW - mu CT imaging KW - Spectroscopy Y1 - 2016 U6 - https://doi.org/10.1016/j.msec.2016.05.045 SN - 0928-4931 SN - 1873-0191 VL - 67 SP - 259 EP - 266 PB - Elsevier CY - Amsterdam ER - TY - JOUR A1 - Rousseau, Batiste A1 - Erard, Stéphane A1 - Beck, P. A1 - Quirico, Eric A1 - Schmitt, B. A1 - Brissaud, O. A1 - Montes-Hernandez, G. A1 - Capaccioni, F. A1 - Filacchione, Gianrico A1 - Bockelee-Morvan, Dominique A1 - Leyrat, C. A1 - Ciarniello, M. A1 - Raponi, Andrea A1 - Kappel, David A1 - Arnold, G. A1 - Moroz, L. V. A1 - Palomba, Ernesto A1 - Tosi, Federico T1 - Laboratory simulations of the Vis-NIR spectra of comet 67P using sub-mu m sized cosmochemical analogues JF - Icarus : international journal of solar system studies N2 - Laboratory spectral measurements of relevant analogue materials were performed in the framework of the Rosetta mission in order to explain the surface spectral properties of comet 67P. Fine powders of coal, iron sulphides, silicates and their mixtures were prepared and their spectra measured in the Vis-IR range. These spectra are compared to a reference spectrum of 67P nucleus obtained with the VIRTIS/Rosetta instrument up to 2.7 mu m, excluding the organics band centred at 3.2 mu m. The species used are known to be chemical analogues for cometary materials which could be present at the surface of 67P. Grain sizes of the powders range from tens of nanometres to hundreds of micrometres. Some of the mixtures studied here actually reach the very low reflectance level observed by VIRTIS on 67P. The best match is provided by a mixture of sub-micron coal, pyrrhotite, and silicates. Grain sizes are in agreement with the sizes of the dust particles detected by the GIADA, MIDAS and COSIMA instruments on board Rosetta. The coal used in the experiment is responsible for the spectral slope in the visible and infrared ranges. Pyrrhotite, which is strongly absorbing, is responsible for the low albedo observed in the NIR. The darkest components dominate the spectra, especially within intimate mixtures. Depending on sample preparation, pyrrhotite can coat the coal and silicate aggregates. Such coating effects can affect the spectra as much as particle size. In contrast, silicates seem to play a minor role. (c) 2017 Elsevier Inc. All rights reserved. KW - Comets KW - Comets nucleus KW - Comets composition KW - Spectroscopy KW - Experimental techniques Y1 - 2018 U6 - https://doi.org/10.1016/j.icarus.2017.10.015 SN - 0019-1035 SN - 1090-2643 VL - 306 SP - 306 EP - 318 PB - Elsevier CY - San Diego ER - TY - JOUR A1 - Picconi, David T1 - Nonadiabatic quantum dynamics of the coherent excited state intramolecular proton transfer of 10-hydroxybenzo[h]quinoline JF - Photochemical & photobiological sciences N2 - The photoinduced nonadiabatic dynamics of the enol-keto isomerization of 10-hydroxybenzo[h]quinoline (HBQ) are studied computationally using high-dimensional quantum dynamics. The simulations are based on a diabatic vibronic coupling Hamiltonian, which includes the two lowest pi pi* excited states and a n pi* state, which has high energy in the Franck-Condon zone, but significantly stabilizes upon excited state intramolecular proton transfer. A procedure, applicable to large classes of excited state proton transfer reactions, is presented to parametrize this model using potential energies, forces and force constants, which, in this case, are obtained by time-dependent density functional theory. The wave packet calculations predict a time scale of 10-15 fs for the photoreaction, and reproduce the time constants and the coherent oscillations observed in time- resolved spectroscopic studies performed on HBQ. In contrast to the interpretation given to the most recent experiments, it is found that the reaction initiated by 1 pi pi* <- S-0 photoexcitation proceeds essentially on a single potential energy surface, and the observed coherences bear signatures of Duschinsky mode-mixing along the reaction path. The dynamics after the 2 pi pi* <- S-0 excitation are instead nonadiabatic, and the n pi* state plays a major role in the relaxation process. The simulations suggest a mainly active role of the proton in the isomerization, rather than a passive migration assisted by the vibrations of the benzoquinoline backbone.
[GRAPHICS]
. KW - Excited state proton transfer KW - Quantum dynamics KW - Nonadiabatic effects KW - Spectroscopy KW - Coherences Y1 - 2021 U6 - https://doi.org/10.1007/s43630-021-00112-z SN - 1474-905X SN - 1474-9092 VL - 20 IS - 11 SP - 1455 EP - 1473 PB - Springer CY - Heidelberg ER - TY - THES A1 - Bouma, Sietske T1 - The circum- and intergalactic medium and its connection to the large scale structure in the nearby universe T1 - Das zirkum- und intergalaktisches Medium und sein Zusammenhang mit der großräumigen Struktur im dem nahen Universum N2 - The majority of baryons in the Universe is believed to reside in the intergalactic medium (IGM). This makes the IGM an important component in understanding cosmological structure formation. It is expected to trace the same dark matter distribution as galaxies, forming structures like filaments and clusters. However, whereas galaxies can be observed to be arranged along these large-scale structures, the spatial distribution of the diffuse IGM is not as easily unveiled. Absorption line studies of quasar (QSO) spectra can help with mapping the IGM, as well as the boundary layer between IGM and galaxies: the circumgalactic medium (CGM). By studying gas in the Local Group, as well as in the IGM, this study aims to get a better understanding of how the gas is linked to the large-scale structure of the local Universe and the galaxies residing in that structure. Chapter 1 gives an introduction to the CGM and IGM, while the methods used in this study are explained in Chapter 2. Chapter 3 starts on a relatively small cosmological scale, namely that of our Local Group, which includes i.a. the Milky Way (MW) and the M31. Within the CGM of the MW, there exist denser clouds, some of which are infalling while others are moving away from the Galactic disc. To study these clouds, 29 QSO spectra obtained with the Cosmic Origins Spectrograph (COS) aboard the Hubble Space Telescope (HST) were analysed. Abundances of Si II, Si III, Si IV, C II, and C IV were measured for 69 HVCs belonging to two samples: one in the direction of the LG’s barycentre and the other in the anti-barycentre direction. Their velocities range from -100 ≥ vLSR ≥ -400 km/s for the barycentre sample and between +100 ≤ vLSR ≤ +300 km/s for the anti-barycentre sample. By using Cloudy models, these data could then be used to derive gas volume densities for the HVCs. Because of the relationship between density and pressure of the ambient medium, which is in turn determined by the Galactic radiation field, the distances of the HVCs could be estimated. From this, a subsample of absorbers located in the direction of M31 was found to exist outside of the MW’s virial radius, their low densities (log nH ≤ -3.54) making it likely for them to be part of the gas in between the MW and M31. No such low-density absorbers were found in the anti-barycentre sample. Our results thus hint at gas following the dark matter potential, which would be deeper between the MW and M31 as they are by far the most massive members of the LG. From this bridge of gas in the LG, this study zooms out to the large-scale structure of the local Universe (z ~ 0) in Chapter 4. Galaxy data from the V8k catalogue and QSO spectra from COS were used to study the relation between the galaxies tracing large-scale filaments and the gas existing outside of those galaxies. This study used the filaments defined in Courtois et al. (2013). A total of 587 Lyman α (Lyα) absorbers were found in the 302 QSO spectra in the velocity range 1070 - 6700 km/s. After selecting sightlines passing through or close to these filaments, model spectra were made for 91 sightlines and 215 (227) Lyα absorbers (components) were measured in this sample. The velocity gradient along each filament was calculated and 74 absorbers were found within 1000 km/s of the nearest filament segment. In order to find whether the absorbers are more tied to galaxies or to the large-scale structure, equivalent widths of the Lyα absorbers were plotted against both galaxy and filament impact parameters. While stronger absorbers do tend to be closer to either galaxies or filaments, there is a large scatter in this relation. Despite this large scatter, this study found that the absorbers do not follow a random distribution either. They cluster less strongly around filaments than galaxies, but stronger than random distributions, as confirmed by a Kolmogorov-Smirnov test. Furthermore, the column density distribution function found in this study has a slope of -β = 1.63±0.12 for the total sample and -β =1.47±0.24 for the absorbers within 1000 km/s of a filament. The shallower slope for the latter subsample could indicate an excess of denser absorbers within the filament, but they are consistent within errors. These values are in agreement with values found in e.g. Lehner et al. (2007); Danforth et al. (2016). The picture that emerges from this study regarding the relation between the IGM and the large-scale structure in the local Universe fits with what is found in other studies: while at least part of the gas traces the same filamentary structure as galaxies, the relation is complex. This study has shown that by taking a large sample of sightlines and comparing the data gathered from those with galaxy data, it is possible to study the gaseous large-scale structure. This approach can be used in the future together with simulations to get a better understanding of structure formation and evolution in the Universe. N2 - Sterne und Galaxien, die das Universum füllen, haben sich alle aus Gas gebildet. Bis heute bleibt der Großteil der baryonischen Materie im Universum im gasförmigen Zustand, und nur ein geringer Anteil davon ist kollabiert, um Sterne und Galaxien entstehen zu lassen. Der Gravitationskollaps folgt den Potentialtöpfen der Dunklen Materie, wodurch sich die großräumige Struktur (large-scale structures, LSS) des Universums formt. Die Galaxien innerhalb dieser Struktur ordnen sich entlang der Schichten, Filamenten und um die Knotenpunkte, wobei die Regionen niedriger Dichte (Voids) dazwischen liegen. Das diffuse Gas füllt diese Strukturen ebenfalls und stellt somit ein Reservoir der baryonischen Materie den Galaxien für die weitere Sternbildung zur Verfügung. Galaxien wiederum reichen das umgebende diffuse Gas an. Darum spielt das Gas um und zwischen Galaxien, das zirkum- bzw. intergalaktisches Medium (circum-/intergalactic medium, CGM/IGM), eine wichtige Rolle in der Entstehung und Entwicklung der Galaxien und LSS im Universum. Ziel dieses Promotionsprojektes ist es, ein besseres Verständnis über die Zusammenhänge zwischen demintergalaktischen Gas und LSS mit darin befindlichen Galaxien im lokalen Universum zu erhalten. Die Verteilung de Gases im IGM ist aufgrund der diffusen Beschaffenheit schwer nachzuweisen. Eine der Möglichkeiten es zu untersuchen, ist die Betrachtung der Absorptionsmerkmale in den Spektren der weitentfernten Quasare (QSOs). IGM, das vom Licht dieser QSOs auf dem Weg zum Beobachter durchquert wird, hinterlässt im Spektrum die charakteristischen Absoprtionslinien. Wir analysieren in diesem Promotionsprojekt eine große Anzahl von QSO-Spektren, die vom Cosmic Origin Spectrograph an Bord des Hubble-Weltraumteleskop stammen, um den physikalischen Zustand des intervenierenden intergalaktischen und zirkumgalaktischen Gas im nahen Universumzu untersuchen. Im ersten Teil dieser Dissertation untersuchen wir anhand der sogenannten Hochgeschwindigkeitswolken (high-velocity clouds, HVCs) das CGM um die Milchstraße in Richtung des Baryzentrums und Anti-Baryzentrums der Galaxien der Lokalen Gruppe (LG). Die HVCs haben Radialgeschwindigkeiten von über 80 kms¡1 und können sehr unterschiedliche Herkunft haben. Wir vermessen die Häufigkeiten verschiedener Ionen von Si und C für 69 HVCs sowie deren Kinematik. Daraus werden physikalische Eigenschaften der Wolken abgeleitet, die auf eine Teilstichprobe besonders interessanter Absorber in Richtung des Baryzentrums hinweisen. Diese Teilstichprobe besteht aus HVCs mit sehr geringen Gasdichten (log n(H) < -3.54), was darauf hindeutet, dass diese Wolken sich höchstwahrscheinlich außerhalb des Virialradius der Milchstraße in der gasförmigen Brücke befinden, die die Milchstraße und die Nachbargalaxie M31 verbindet. Ausgehend von dieser gasförmigen Brücke in unserer LG zoomen wir im zweiten Teil des Dissertation heraus, um einen Überblick über die Gasverteilung im lokalen Universum auf größeren Skalen zu erhalten. Wir analysieren die Lyman-α (Lyα) -Absorption des neutralen Wasserstoffs (H I) in 302 QSO-Spektren aus allen Himmelsrichtungen und kombinieren diese Daten mit denen von Galaxiefilamenten, die im V8k Katalog von Courtois et al. (2013) identifiziert wurden. Von den 587 HI Lyα-Absorptionssystemen befinden sich 215 in der Nähe von Galaxiefilamenten. Die stärkeren Absorber befinden sich häufig in der Nähe von Galaxien oder näher an den Mittelachsen der Filamente, aber diese Beziehung zeigt eine große Streuung. Die Lyα-Absorber neigen dazu, sich stärker um die Filamentachsen zu gruppieren im Vergleich zu einer zufälligen Population von Absorbern, wenn auch nicht so stark wie Galaxien. Dies weist darauf hin, dass die Lyα-Absorber zwar der großräumigen Struktur folgen, jedoch auf ihre eigene Weise. Schließlich zeigt eine statistische Analyse der Absorberstärken, dass sich die Verteilung der HI-Säulendichten von Region außerhalb zu Regionen innerhalb der Filamente ändert, was die grundsätzlich höhere Dichte der Materie in letzteren widerspiegelt. DasGesamtergebnis dieser Dissertation stimmt gut mit den Ergebnissen anderer Studien überein: auch wenn ein Teil des intergalaktischen Gases denselben kosmologischen Filamentstrukturen wie Galaxien folgt, bleibt die Beziehung zwischen Gas, Galaxien und großräumigen Struktur komplex. Die hochauflösende kosmologische Simulationen zusammen mit den zukünftigen Beobachtungen werden helfen diesen Zusammenhang besser zu verstehen. KW - Astrophysics KW - Spectroscopy KW - Circumgalactic Medium KW - Intergalactic Medium KW - Large-scale Structure KW - Astrophysik KW - zirkumgalaktisches Medium KW - intergalaktisches Medium KW - großräumige Struktur KW - Spektroskopie Y1 - 2021 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus4-520852 ER - TY - JOUR A1 - Carvalho, Thayslan A1 - Brosinsky, Arlena A1 - Foerster, Saskia A1 - Teixeira, Adunias A1 - Medeiros, Pedro Henrique Augusto T1 - Reservoir sediment characterisation by diffuse reflectance spectroscopy in a semiarid region to support sediment reuse for soil fertilization JF - Journal of soils and sediments : protection, risk assessment and remediation N2 - Purpose: Soil erosion by water yields sediment to surface reservoirs, reducing their storage capacities, changing their geometry, and degrading water quality. Sediment reuse, i.e., fertilization of agricultural soils with the nutrient-enriched sediment from reservoirs, has been proposed as a recovery strategy. However, the sediment needs to meet certain criteria. In this study, we characterize sediments from the densely dammed semiarid Northeast Brazil by VNIR-SWIR spectroscopy and assess the effect of spectral resolution and spatial scale on the accuracy of N, P, K, C, electrical conductivity, and clay prediction models. Methods Sediment was collected in 10 empty reservoirs, and physical and chemical laboratory analyses as well as spectral measurements were performed. The spectra, initially measured at 1 nm spectral resolution, were resampled to 5 and 10 nm, and samples were analysed for both high and low spectral resolution at three spatial scales, namely (1) reservoir, (2) catchment, and (3) regional scale. Results Partial least square regressions performed from good to very good in the prediction of clay and electrical conductivity from reservoir (<40 km(2)) to regional (82,500 km(2)) scales. Models for C and N performed satisfactorily at the reservoir scale, but degraded to unsatisfactory at the other scales. Models for P and K were more unstable and performed from unsatisfactorily to satisfactorily at all scales. Coarsening spectral resolution by up to 10 nm only slightly degrades the models' performance, indicating the potential of characterizing sediment from spectral data captured at lower resolutions, such as by hyperspectral satellite sensors. Conclusion: By reducing the costly and time-consuming laboratory analyses, the method helps to promote the sediment reuse as a practice of soil and water conservation. KW - Sediment characterization KW - Spectroscopy KW - Sediment reuse KW - Surface KW - reservoirs KW - Semiarid KW - Brazil Y1 - 2022 U6 - https://doi.org/10.1007/s11368-022-03281-1 SN - 1439-0108 SN - 1614-7480 VL - 22 SP - 2557 EP - 2577 PB - Springer CY - Heidelberg ER -