TY - JOUR A1 - Xie, Zai-Lai A1 - Taubert, Andreas T1 - Thermomorphic behavior of the ionic liquids [C(4)mim][FeCl4] and [C(12)mim][FeCl4] JF - ChemPhysChem : a European journal of chemical physics and physical chemistry N2 - The iron-containing ionic liquids 1-butyl-3-methylimidazolium tetrachloroferrate(III) [C(4)mim][FeCl4] and 1-dodecyl-3-methylimidazolium tetrachloroferrate(III) [C(12)mim][FeCl4] exhibit a thermally induced demixing with water (thermomorphism). The phase separation temperature varies with IL weight fraction in water and can be tuned between 100 degrees C and room temperature. The reversible lower critical solution temperature (LCST) is only observed at IL weight fractions below ca. 35% in water. UV/Vis, IR, and Raman spectroscopy along with elemental analysis prove that the yellow-brown liquid phase recovered after phase separation is the starting IL [C(4)mim][FeCl4] and [C(12)mim][FeCl4], respectively. Photometry and ICP-OES show that about 40% of iron remains in the water phase upon phase separation. Although the process is thus not very efficient at the moment, the current approach is the first example of an LCST behavior of a metal-containing IL and therefore, although still inefficient, a prototype for catalyst removal or metal extraction. KW - imidazolium KW - ionic liquids KW - phase transitions KW - Raman spectroscopy KW - thermomorphism Y1 - 2011 U6 - https://doi.org/10.1002/cphc.201000808 SN - 1439-4235 VL - 12 IS - 2 SP - 364 EP - 368 PB - Wiley-VCH CY - Weinheim ER - TY - JOUR A1 - Wunder, Bernd A1 - Kutzschbach, Martin A1 - Hosse, Luisa A1 - Wilke, Franziska Daniela Helena A1 - Schertl, Hans-Peter A1 - Chopin, Christian T1 - Synthetic B-[4]-bearing dumortierite and natural B-[4]-free magnesiodumortierite from the Dora-Maira Massif BT - differences in boron coordination in response to ultrahigh pressure JF - European journal of mineralogy N2 - Dumortierite was synthesized in piston-cylinder experiments at 2.5-4.0 GPa, 650-700 degrees C in the Al2O3 -B2O3-SiO2-H2O (ABSH) system. Electron-microprobe (EMP) analyses reveal significant boron-excess (up to 0.26 B-[4] per formula unit, pfu) and silicon-deficiency relative to the ideal anhydrous dumortierite stoichiometry Al7BSi3O18 . The EMP data in conjunction with results from single-crystal Raman spectroscopy and powder X-ray diffraction provide evidence that silicon at the tetrahedral site is replaced by excess boron via the substitution Si-[4] <--> B-[4] + H. The Raman spectrum of synthetic dumortierite in the frequency region 2000 4000 cm(-1) comprises eight bands, of which six are located at frequencies below 3400 cm(-1). This points to strong hydrogen bonding, most likely O2-H center dot center dot center dot O7 and O7-H center dot center dot center dot O2, arising from a high number of octahedral vacancies at the All site and substitution of trivalent Al3+ and B3+ for Si4+ at Si1 and Si2 sites, causing decreasing acceptor-donor distances and lower incident valence at the acceptor oxygen. Contrary to the synthetic high-pressure ABSH-dumortierite, magnesiodumortierite from the Dora-Maira Massif, which is assumed to have formed at similar conditions (2.5-3.0 GPa, 700 degrees C), does not show any B-excess. Tourmaline shows an analogous behaviour in that magnesium-rich (e.g., dravitic) tourmaline formed at high pressure shows no or only minor amounts of tetrahedral boron, whereas natural aluminum-rich tourmaline and synthetic olenitic tourmaline formed at high pressures can incorporate significant amounts of tetrahedral boron. Two mechanisms might account for this discrepancy: (i) Structural avoidance of Mg-[6]-(OR3+)-R-[4] configurations in magnesiodumortierite due to charge deficieny at the oxygens O2 and O7 and strong local distortion of M1 due to decreased O2-O7 bond length, and/or (ii) decreasing fluid mobility of boron in Al-rich systems at high pressures. KW - dumortierite KW - magnesiodumortierite KW - Dora-Maira KW - ultrahigh-pressure (UHP) KW - ABSH-system KW - synthesis KW - tetrahedral boron KW - Raman spectroscopy Y1 - 2018 U6 - https://doi.org/10.1127/ejm/2018/0030-2742 SN - 0935-1221 SN - 1617-4011 VL - 30 IS - 3 SP - 471 EP - 483 PB - Schweizerbart CY - Stuttgart ER - TY - JOUR A1 - Sumpf, Bernd A1 - Maiwald, Martin A1 - Muller, Andre A1 - Ginolas, Arnim A1 - Haeusler, Karl A1 - Erbert, Goetz A1 - Traenkle, Guenther T1 - Reliable operation for 14 500 h of a wavelength-stabilized Diode Laser System on a Microoptical Bench at 671 nm JF - IEEE transactions on components, packaging and manufacturing technology N2 - Reliability tests for wavelength-stabilized compact diode laser systems emitting at 671 nm are presented. The devices were mounted on microoptical benches with the dimensions of 13 mm x 4 mm. Reflecting Bragg gratings were used for wavelength stabilization and emission width narrowing. The reliability tests were performed at 25 degrees C and at an output power up to 10 mW per micrometer stripe width of the gain medium. Reliable operation could be demonstrated over a test time up to 14 500 h at an output power up to 1.0 W. Environmental tests using random vibrations with acceleration up to 29 g were performed without deterioration of the devices. KW - High-power lasers KW - laser resonators KW - Raman spectroscopy KW - reliability KW - semiconductor lasers Y1 - 2012 U6 - https://doi.org/10.1109/TCPMT.2011.2171342 SN - 2156-3950 VL - 2 IS - 1 SP - 116 EP - 121 PB - Inst. of Electr. and Electronics Engineers CY - Piscataway ER - TY - GEN A1 - Sparkes, Robert B. A1 - Hovius, Niels A1 - Galy, Albert A1 - Liu, James T. T1 - Survival of graphitized petrogenic organic carbon through multiple erosional cycles T2 - Postprints der Universität Potsdam : Mathematisch-Naturwissenschaftliche Reihe N2 - Graphite forms the endpoint for organic carbon metamorphism; it is extremely resilient to physical, biological and chemical degradation. Carbonaceous materials (CM) contained within sediments, collected across Taiwan and from the Gaoping submarine canyon, were analyzed using Raman spectroscopy to determine the crystallinity. This allowed the erosional and orogenic movements of petrogenic organic carbon (OCpetro) during the Taiwanese orogeny to be deduced. After automatically fitting and classifying spectra, the distribution of four groups of CM within the sediments provides evidence that many forms of OCpetro have survived at least one previous cycle of erosion, transport and burial before forming rocks in the Western Foothills of the island. There is extensive detrital graphite present in rocks that have not experienced high-grade metamorphism, and graphite flakes are also found in recently deposited marine sediments off Taiwan. The tectonic and geological history of the island shows that these graphite flakes must have survived at least three episodes of recycling. Therefore, transformation to graphite during burial and orogeny is a mechanism for stabilizing organic carbon over geological time, removing biospheric carbon from the active carbon cycle and protecting it from oxidation during future erosion events. T3 - Zweitveröffentlichungen der Universität Potsdam : Mathematisch-Naturwissenschaftliche Reihe - 1223 KW - graphite KW - organic carbon KW - orogeny KW - recycling KW - Raman spectroscopy KW - erosion Y1 - 2022 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus4-533541 SN - 1866-8372 ER - TY - THES A1 - Serrano, Paloma T1 - Methanogens from Siberian permafrost as models for life on Mars : response to simulated martian conditions and biosignature characterization T1 - Methanogene Archaeen aus sibirischen Permafrost als Modelle für Leben auf dem Mars N2 - Mars is one of the best candidates among planetary bodies for supporting life. The presence of water in the form of ice and atmospheric vapour together with the availability of biogenic elements and energy are indicators of the possibility of hosting life as we know it. The occurrence of permanently frozen ground – permafrost, is a common phenomenon on Mars and it shows multiple morphological analogies with terrestrial permafrost. Despite the extreme inhospitable conditions, highly diverse microbial communities inhabit terrestrial permafrost in large numbers. Among these are methanogenic archaea, which are anaerobic chemotrophic microorganisms that meet many of the metabolic and physiological requirements for survival on the martian subsurface. Moreover, methanogens from Siberian permafrost are extremely resistant against different types of physiological stresses as well as simulated martian thermo-physical and subsurface conditions, making them promising model organisms for potential life on Mars. The main aims of this investigation are to assess the survival of methanogenic archaea under Mars conditions, focusing on methanogens from Siberian permafrost, and to characterize their biosignatures by means of Raman spectroscopy, a powerful technology for microbial identification that will be used in the ExoMars mission. For this purpose, methanogens from Siberian permafrost and non-permafrost habitats were subjected to simulated martian desiccation by exposure to an ultra-low subfreezing temperature (-80ºC) and to Mars regolith (S-MRS and P-MRS) and atmospheric analogues. They were also exposed to different concentrations of perchlorate, a strong oxidant found in martian soils. Moreover, the biosignatures of methanogens were characterized at the single-cell level using confocal Raman microspectroscopy (CRM). The results showed survival and methane production in all methanogenic strains under simulated martian desiccation. After exposure to subfreezing temperatures, Siberian permafrost strains had a faster metabolic recovery, whereas the membranes of non-permafrost methanogens remained intact to a greater extent. The strain Methanosarcina soligelidi SMA-21 from Siberian permafrost showed significantly higher methane production rates than all other strains after the exposure to martian soil and atmospheric analogues, and all strains survived the presence of perchlorate at the concentration on Mars. Furthermore, CRM analyses revealed remarkable differences in the overall chemical composition of permafrost and non-permafrost strains of methanogens, regardless of their phylogenetic relationship. The convergence of the chemical composition in non-sister permafrost strains may be the consequence of adaptations to the environment, and could explain their greater resistance compared to the non-permafrost strains. As part of this study, Raman spectroscopy was evaluated as an analytical technique for remote detection of methanogens embedded in a mineral matrix. This thesis contributes to the understanding of the survival limits of methanogenic archaea under simulated martian conditions to further assess the hypothetical existence of life similar to methanogens on the martian subsurface. In addition, the overall chemical composition of methanogens was characterized for the first time by means of confocal Raman microspectroscopy, with potential implications for astrobiological research. N2 - Der Mars ist unter allen Planeten derjenige, der aufgrund verschiedener Faktoren am wahrscheinlichsten Leben ermöglichen kann. Das Vorhandensein von Wasser in Form von Eis und atmosphärischem Dampf zusammen mit der Verfügbarkeit biogener Elemente sowie Energie sind Indikatoren für die Möglichkeit, Leben, wie wir es kennen, zu beherbergen. Das Auftreten von dauerhaft gefrorenen Böden, oder auch Permafrost, ist ein verbreitetes Phänomen auf dem Mars. Dabei zeigen sich vielfältige morphologische Analogien zum terrestrischen Permafrost. Permafrostgebiete auf der Erde, welche trotz extremer, Bedingungen durch eine große Zahl und Vielfalt mikrobieller Gemeinschaften besiedelt sind, sind hinsichtlich möglicher Habitate auf dem Mars die vielversprechendste Analogie. Die meisten methanogenen Archaeen sind anaerobe, chemolithotrophe Mikroorganismen, die auf der Marsoberfläche viele der metabolischen und physiologischen Erfordernisse zum Überleben vorfinden. Methanogene Archaeen aus dem sibirischen Permafrost sind zudem extrem resistent gegenüber unterschiedlichen Formen von physiologischem Stress sowie simulierten thermo-physikalischen Marsbedingungen. Die Hauptziele dieser Untersuchung bestehen darin, das Überleben der methanogenen Archaeen unter Marsbedingungen zu beurteilen, wobei der Fokus auf methanogenen Archaeen aus dem sibirischen Permafrost liegt, sowie deren Biosignaturen mit Hilfe der Raman-Spektroskopie zu charakterisieren, einer starken Technologie zur mikrobiellen Identifikation, welche bei der ExoMars-Mission zum Einsatz kommen wird. Zu diesem Zweck wurden methanogene Archaeen aus dem sibirischen Permafrost sowie aus Nicht-Permafrost-Habitaten in Simulationen Marsbedingungen ausgesetzt, wie Austrocknung durch Langzeitversuche bei ultraniedrigen Temperaturen unter dem Gefrierpunkt (-80ºC), Mars-analogen Mineralien (S-MRS und P-MRS) sowie einer Marsatmosphäre. Weiterhin wurden die Kulturen verschiedenen Konzentrationen von Magnesiumperchlorat, einem starken Oxidant, der im Marsboden nachgewiesenen wurde, ausgesetzt. Ferner wurden die Biosignaturen einzelner Zellen der methanogenen Archaeen mit Hilfe der konfokalen Raman-Mikrospektroskopie (CRM) charakterisiert. Die Ergebnisse zeigten für alle untersuchten methanogenen Stämme Überleben und Methanbildung, nachdem diese simulierten Austrocknungsbedingungen ausgesetzt worden waren. Nach Versuchen mit Temperaturen unter dem Gefrierpunkt zeigten die Stämme aus dem sibirischen Permafrost eine schnellere Wiederaufnahme der Stoffwechseltätigkeit, wohingegen bei den Referenzorganismen aus Nicht-Permafrost-Habitaten die Zell¬membranen im größeren Ausmaß intakt blieben. Der Stamm Methanosarcina soligelidi SMA-21 aus dem sibirischen Permafrost zeigte nach dem Belastungstest mit Marsboden und Mars-analoger Atmosphäre signifikant höhere Methanbildungsraten. Zudem überlebten alle untersuchten Stämme die Zugabe von Magnesiumperchlorat in der entsprechenden Konzentration, die auf dem Mars vorkommt. Weiterhin konnten durch die Raman-Spektroskopie beachtliche Unterschiede in der chemischen Zusammensetzung zwischen methanogenen Archaeen aus Permafrost- und Nicht-Permafrost-Habitaten, trotz ihrer phylogenetischen Verwandtschaft, ermittelt werden. Die Konvergenz der chemischen Zusammensetzung der Permafrost-Stämme könnte das Resultat ihrer Anpassung an die Umgebung sein, was auch die Unterschiede hinsichtlich ihrer Resistenz verglichen mit Nicht-Permafrost-Stämmen erklären könnte. Als Teil dieser Studie wurde die Raman-Spektroskopie als Analyse-Technik zur Ferndetektion von methanogenen Archaeen, welche in eine Mineral-Matrix eingebettet sind, evaluiert. Diese Dissertation trägt zu einem besseren Verständnis hinsichtlich der Grenzen für ein Überleben von methanogenen Archaeen unter simulierten Marsbedingungen bei und damit zu einer Beurteilung der Hypothese, ob es ähnliches Leben unter der Marsoberfläche geben könnte. Darüber hinaus wurde erstmalig die chemische Zusammensetzung von methanogenen Archaeen mit Hilfe der Raman-Mikrospektroskopie charakterisiert. Dieser Technologie kommt eine wesentliche Bedeutung für weitere Forschungstätigkeit in der Astrobiologie zu. KW - Methanogene Archaeen KW - sibirischen Permafrost KW - Mars KW - Raman Spektroskopie KW - Biosignaturen KW - methanogenic archaea KW - Siberian permafrost KW - Mars KW - Raman spectroscopy KW - biosignatures Y1 - 2014 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus-72299 ER - TY - JOUR A1 - Schmälzlin, Elmar Gerd A1 - Moralejo, Benito A1 - Gersonde, Ingo A1 - Schleusener, Johannes A1 - Darvin, Maxim E. A1 - Thiede, Gisela A1 - Roth, Martin M. T1 - Nonscanning large-area Raman imaging for ex vivo/in vivo skin cancer discrimination JF - Journal of biomedical optics N2 - Imaging Raman spectroscopy can be used to identify cancerous tissue. Traditionally, a step-by-step scanning of the sample is applied to generate a Raman image, which, however, is too slow for routine examination of patients. By transferring the technique of integral field spectroscopy (IFS) from astronomy to Raman imaging, it becomes possible to record entire Raman images quickly within a single exposure, without the need for a tedious scanning procedure. An IFS-based Raman imaging setup is presented, which is capable of measuring skin ex vivo or in vivo. It is demonstrated how Raman images of healthy and cancerous skin biopsies were recorded and analyzed. (C) The Authors. Published by SPIE under a Creative Commons Attribution 3.0 Unported License. KW - Raman spectroscopy KW - cancer diagnosis KW - Raman imaging KW - multichannel KW - astronomy KW - epidermis KW - dermis Y1 - 2018 U6 - https://doi.org/10.1117/1.JBO.23.10.105001 SN - 1083-3668 SN - 1560-2281 VL - 23 IS - 10 PB - SPIE CY - Bellingham ER - TY - JOUR A1 - Schmidt, Birgit Angelika A1 - Ziemann, Martin Andreas A1 - Pentzien, Simone A1 - Gabsch, Toralf A1 - Koch, Werner A1 - Krüger, Jörg T1 - Technical analysis of a Central Asian wall painting detached from a Buddhist cave temple on the northern Silk Road JF - Studies in Conservation N2 - A great number of Central Asian wall paintings, archeological materials, architectural fragments, and textiles, as well as painting fragments on silk and paper, make up the so called Turfan Collection at the Asian Art Museum in Berlin. The largest part of the collection comes from the Kucha region, a very important cultural center in the third to ninth centuries. Between 1902 and 1914, four German expeditions traveled along the northern Silk Road. During these expeditions, wall paintings were detached from their original settings in Buddhist cave complexes. This paper reports a technical study of a wall painting, existing in eight fragments, from the Buddhist cave no. 40 (Ritterhohle). Its original painted surface is soot blackened and largely illegible. Gruwedel, leader of the first and third expeditions, described the almost complete destruction of the rediscovered temple complex and evidence of fire damage. The aim of this case study is to identify the materials used for the wall paintings. Furthermore, soot deposits as well as materials from conservation interventions were of interest. Non-invasive analyses were preferred but a limited number of samples were taken to provide more precise information on the painting technique. By employing optical and scanning electron microscopy, energy dispersive X-ray spectroscopy, micro X-ray fluorescence spectroscopy, X-ray diffraction analysis, and Raman spectroscopy, a layer sequence of earthen render, a ground layer made of gypsum, and a paint layer containing a variety of inorganic pigments were identified. KW - Wall paintings KW - Central Asia KW - Silk Road KW - Pigments KW - Microscopy KW - EDX KW - XRF KW - Raman spectroscopy Y1 - 2016 U6 - https://doi.org/10.1179/2047058414Y.0000000152 SN - 0039-3630 SN - 2047-0584 VL - 61 SP - 113 EP - 122 PB - Routledge, Taylor & Francis Group CY - Abingdon ER - TY - JOUR A1 - Sarhan, Radwan Mohamed A1 - Koopman, Wouter-Willem Adriaan A1 - Pudell, Jan-Etienne A1 - Stete, Felix A1 - Rössle, Matthias A1 - Herzog, Marc A1 - Schmitt, Clemens Nikolaus Zeno A1 - Liebig, Ferenc A1 - Koetz, Joachim A1 - Bargheer, Matias T1 - Scaling up nanoplasmon catalysis BT - the role of heat dissipation JF - The journal of physical chemistry : C, Nanomaterials and interfaces N2 - Nanoscale heating by optical excitation of plasmonic nanoparticles offers a new perspective of controlling chemical reactions, where heat is not spatially uniform as in conventional macroscopic heating but strong temperature gradients exist around microscopic hot spots. In nanoplasmonics, metal particles act as a nanosource of light, heat, and energetic electrons driven by resonant excitation of their localized surface plasmon resonance. As an example of the coupling reaction of 4-nitrothiophenol into 4,4′-dimercaptoazobenzene, we show that besides the nanoscopic heat distribution at hot spots, the microscopic distribution of heat dictated by the spot size of the light focus also plays a crucial role in the design of plasmonic nanoreactors. Small sizes of laser spots enable high intensities to drive plasmon-assisted catalysis. This facilitates the observation of such reactions by surface-enhanced Raman scattering, but it challenges attempts to scale nanoplasmonic chemistry up to large areas, where the excess heat must be dissipated by one-dimensional heat transport. KW - Gold KW - Raman spectroscopy KW - Silicon KW - Irradiation KW - Lasers Y1 - 2019 U6 - https://doi.org/10.1021/acs.jpcc.8b12574 SN - 1932-7447 VL - 123 IS - 14 SP - 9352 EP - 9357 PB - American Chemical Society CY - Washington ER - TY - JOUR A1 - Riebe, Daniel A1 - Beitz, Toralf A1 - Dosche, Carsten A1 - Löhmannsröben, Hans-Gerd A1 - Raab, Volker A1 - Raab, Corinna A1 - Unverzagt, Matthias T1 - High-resolution spectrometer using combined dispersive and interferometric wavelength separation for raman and laser-induced Breakdown Spectroscopy (LIBS) JF - Applied spectroscopy : an international journal of spectroscopy ; official publication of the Society for Applied Spectroscopy N2 - In this paper the concept of a compact high-resolution spectrometer based on the combination of dispersive and interferometric elements is presented. Dispersive elements are used to spectrally resolve the light in one direction with coarse resolution (Delta lambda < 0.5 nm), while perpendicular to that direction an etalon provides high spectral resolution (Delta lambda < 50 pm). This concept for two-dimensional spectroscopy has been implemented for the wavelength range lambda = 350-650 nm. Appropriate algorithms for reconstructing spectra from the two-dimensional raw data and for wavelength calibration were established in an analysis software. Potential applications for this new spectrometer are Raman and laser-induced breakdown spectroscopy (LIBS). Resolutions down to 28 pm (routinely 54 pm) could be realized for these applications. KW - Raman spectroscopy KW - Laser-induced breakdown spectroscopy KW - LIBS KW - Fabry-Perot etalon KW - High-resolution spectrometer Y1 - 2014 U6 - https://doi.org/10.1366/13-07426 SN - 0003-7028 SN - 1943-3530 VL - 68 IS - 9 SP - 1030 EP - 1038 PB - Society for Applied Spectroscopy CY - Frederick ER - TY - THES A1 - Pan, Mengdi T1 - Systematic studies on the thermodynamic properties of gas hydrates and their formation/dissociation/transformation behaviors T1 - Systematische Untersuchungen zu den thermodynamischen Eigenschaften von Gashydraten und ihrem Bildungs-/Dissoziations-/Umwandlungsverhalten N2 - Gas hydrates are ice-like crystalline compounds made of water cavities that retain various types of guest molecules. Natural gas hydrates are CH4-rich but also contain higher hydrocarbons as well as CO2, H2S, etc. They are highly dependent of local pressure and temperature conditions. Considering the high energy content, natural gas hydrates are artificially dissociated for the production of methane gas. Besides, they may also dissociate in response to global warming. It is therefore crucial to investigate the hydrate nucleation and growth process at a molecular level. The understanding of how guest molecules in the hydrate cavities respond to warming climate or gas injection is also of great importance. This thesis is concerned with a systematic investigation of simple and mixed gas hydrates at conditions relevant to the natural hydrate reservoir in Qilian Mountain permafrost, China. A high-pressure cell that integrated into the confocal Raman spectroscopy ensured a precise and continuous characterization of the hydrate phase during formation/dissociation/transformation processes with a high special and spectral resolution. By applying laboratory experiments, the formation of mixed gas hydrates containing other hydrocarbons besides methane was simulated in consideration of the effects from gas supply conditions and sediments. The results revealed a preferential enclathration of different guest molecules in hydrate cavities and further refute the common hypothesis of the coexistence of hydrate phases due to a changing feed gas phase. However, the presence of specific minerals and organic compounds in sediments may have significant impacts on the coexisting solid phases. With regard to the dissociation, the formation damage caused by fines mobilization and migration during hydrate decomposition was reported for the first time, illustrating the complex interactions between fine grains and hydrate particles. Gas hydrates, starting from simple CH4 hydrates to binary CH4—C3H8 hydrates and multi-component mixed hydrates were decomposed by thermal stimulation mimicking global warming. The mechanisms of guest substitution in hydrate structures were studied through the experimental data obtained from CH4—CO2, CH4—mixed gas hydrates and mixed gas hydrates—CO2 systems. For the first time, a second transformation behavior was documented during the transformation process from CH4 hydrates to CO2-rich mixed hydrates. Most of the crystals grew or maintained when exposed to CO2 gas while some others decreased in sizes and even disappeared over time. The highlight of the two last experimental simulations was to visualize and characterize the hydrate crystals which were at different structural transition stages. These experimental simulations enhanced our knowledge about the mixed gas hydrates in natural reservoirs and improved our capability to assess the response to global warming. N2 - Gashydrate sind eisähnliche, kristalline Verbindungen bestehend aus Wasserkäfigen, in denen verschiedene Arten von Gastmolekülen eingeschlossen sind. Natürliche Gashydrate sind CH4-reich, enthalten aber auch höhere Kohlenwasserstoffe sowie CO2, H2S usw. Sie sind stark von den lokalen Druck- und Temperaturbedingungen abhängig. Aufgrund ihres hohen Energiegehalts werden natürliche Gashydrate zur Produktion von Methangas kontrolliert zersetzt. Sie können sich aber auch als Reaktion auf die globale Erwärmung zersetzen. Daher ist es von entscheidender Bedeutung, den Hydratnukleation und des Wachstumsprozesses auf molekularer Ebene zu verstehen. Es ist auch von großer Bedeutung zu klären, wie die Gastmoleküle in den Hydratkäftigen auf die Erderwärmung oder die Gasinjektion antworten. Diese Arbeit beschäftigt sich mit einer systematischen Untersuchung von einfachen und gemischten Gashydraten unter Bedingungen, die für die natürlichen Hydratvorkommen im Qilian Mountain Permafrost, China, relevant sind. Eine in die konfokale Raman-Spektroskopie integrierte Hochdruckzelle gewährleistet eine präzise und kontinuierliche Charakterisierung der Hydratphase während des Bildungs-/Dissoziations-/Umwandlungsprozesses mit hoher örtlicher und spektraler Auflösung. Anhand von Laborversuchen wurde der Entstehungsprozess von gemischten Gashydraten unter Berücksichtigung der Auswirkungen unterschiedliches Gaszufuhr und Sedimenten simuliert. Die Ergebnisse zeigten eine bevorzugte Einlagerung verschiedener Gastmoleküle in die Hydratkäfige und widerlegen die gängige Hypothese der Bildung koexistierender Hydratphasen aufgrund einer sich ändernden Gasphase. Das Vorhandensein bestimmter Mineralien und organischer Verbindungen in Sedimenten kann ebenfalls erhebliche Auswirkungen auf die koexistierenden festen Phasen haben. Bezüglich der Hydratzersetzung konnte im Rahmen dieser Arbeit erstmals über die Formationsschädigung durch Feinkornmobilisierung und -migration beim Hydratabbau berichtet werden, was die komplexen Wechselwirkungen zwischen feinen Sedimentkörnern und Hydratpartikeln verdeutlicht. Gashydrate, angefangen von einfachen CH4-Hydraten über binäre CH4-C3H8-Hydrate bis hin zu Mehrkomponenten-Mischhydraten, wurden durch thermische Stimulation zersetzt, um die Reaktion auf die globale Erwärmung nachzuahmen. Die Mechanismen der Substitution der Gasmoleküle in Hydratstrukturen wurden anhand der experimentellen Daten von CH4-CO2-, CH4-Mischgashydraten und Mischgashydraten-CO2-Systemen untersucht. Erstmals wurde ein zweites Umwandlungsverhalten während des Umwandlungsprozesses von CH4-Hydraten zu CO2-reichen Mischhydraten dokumentiert. In den meisten Fällen wird das Modell des Schrumpfenden Kerns (Shrinking-core-model) unterstützt, während in einigen anderen Fällen die Kristalle mit konstanter Geschwindigkeit umwandelten. Der Höhepunkt der beiden letzten experimentellen Simulationen war die Visualisierung und Charakterisierung von Hydratkristallen, die sich in verschiedenen strukturellen Übergangsstadien befanden. Diese experimentellen Simulationen erweiterten unser Wissen über gemischte Gashydrate in natürlichen Lagerstätten und verbesserten unsere Fähigkeit, die Reaktion auf die globale Erwärmung zu bewerten. KW - gas hydrates KW - Raman spectroscopy KW - thermodynamic and kinetic properties KW - Gashydrate KW - Raman-Spektroskopie KW - thermodynamische und kinetische Eigenschaften Y1 - 2022 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus4-554760 ER - TY - JOUR A1 - Machatschek, Rainhard Gabriel A1 - Heuchel, Matthias A1 - Lendlein, Andreas T1 - Thin-layer studies on surface functionalization of polyetherimide BT - hydrolysis versus amidation JF - Journal of materials research : JMR / Materials Research Society N2 - Among the high-performance and engineering polymers, polyimides and the closely related polyetherimide (PEI) stand out by their capability to react with nucleophiles under relatively mild conditions. By targeting the phthalimide groups in the chain backbone, post-functionalization offers a pathway to adjust surface properties such as hydrophilicity, solvent resistance, and porosity. Here, we use ultrathin PEI films on a Langmuir trough as a model system to investigate the surface functionalization with ethylene diamine and tetrakis(4-aminophenyl)porphyrin as multivalent nucleophiles. By means of AFM, Raman spectroscopy, and interfacial rheology, we show that hydrolysis enhances the chemical and mechanical stability of ultrathin films and allows for the formation of EDC/NHS-activated esters. Direct amidation of PEI was achieved in the presence of a Lewis acid catalyst, resulting in free amine groups rather than cross-linking. When comparing amidation with hydrolysis, we find a greater influence of the latter on material properties. KW - Membrane KW - Nanostructure KW - Polymer KW - Raman spectroscopy KW - Scanning probe microscopy (SPM) KW - Surface reaction KW - Thin film Y1 - 2021 U6 - https://doi.org/10.1557/s43578-021-00339-7 SN - 0884-2914 SN - 2044-5326 VL - 37 IS - 1 SP - 67 EP - 76 PB - Springer CY - Berlin ER - TY - JOUR A1 - Klein, Julia A1 - Darvin, Maxim E. A1 - Meinke, Martina C. A1 - Schweigert, Florian J. A1 - Müller, Kerstin E. A1 - Lademann, Jürgen T1 - Analyses of the correlation between dermal and blood carotenoids in female cattle by optical methods JF - Journal of biomedical optics N2 - Herd health programs for the maintenance of welfare and productivity in cattle need efficient tools for monitoring the health of individual animals. Recent reports demonstrate that the oxidative status is related to various stress conditions in dairy cows. Biomarkers, among other carotenoids, could serve as indicators of stress originating from the environment (e.g., heat stress or sun radiation) or from the animal itself (e.g., disease). To date, only invasive in vitro tests are available to assess the oxidative status in cattle. The present study compares the results of optical noninvasive in vivo measurements of dermal carotenoids in cattle udder skin using an LED-based miniaturized spectroscopic system (MSS) with those obtained by photometric analysis of beta carotene in whole blood samples using a portable device. Correlations between the concentrations of dermal and blood carotenoids were calculated under consideration of the nutritional status of the animals. Significant correlation (R = 0.86) was found for cattle with a moderate to obese body condition. Thus, the blood and skin concentrations of the marker substance beta carotene are comparable under stable stress conditions of the cattle. This demonstrates that the MSS is suitable for noninvasive assessment of dermal carotenoid concentrations in cattle. KW - Raman spectroscopy KW - reflection spectroscopy KW - skin KW - antioxidants KW - free radicals Y1 - 2013 U6 - https://doi.org/10.1117/1.JBO.18.6.061219 SN - 1083-3668 VL - 18 IS - 6 PB - SPIE CY - Bellingham ER - TY - JOUR A1 - Grüneberger, Anja Maria A1 - Schmidt, Christian A1 - Jahn, Sandro A1 - Rhede, Dieter A1 - Loges, Anselm A1 - Wilke, Max T1 - Interpretation of Raman spectra of the zircon-hafnon solid solution JF - European journal of mineralogy N2 - Zircon (ZrSiO4), hafnon (HfSiO4) and five intermediate compositions were synthesized from a Pb silicate melt. The resulting crystals were 20-300 mu m in size and displayed sector and growth zoning. Raman spectra were acquired at locations in the sample for which preceding electron microprobe (EMP) analyses revealed sufficient compositional homogeneity. The dataset documents shifts of Raman bands with changing composition. In this study, bands that have previously not been reported were found for the intermediate compositions and for pure hafnon, in particular at wavenumbers less than 200 cm(-1). For these external modes, the dataset provides new insight into the compositional dependence of their frequencies. Density-functional theory calculations support the observations and are used for a detailed interpretation of the spectra. The pitfalls of the EMP analysis along the zircon-hafnon join are highlighted. KW - zircon KW - hafnon KW - solid solution KW - Raman spectroscopy KW - synthesis KW - density-functional theory KW - hafnium analysis Y1 - 2016 U6 - https://doi.org/10.1127/ejm/2016/0028-2551 SN - 0935-1221 SN - 1617-4011 VL - 28 SP - 721 EP - 733 PB - Schweizerbart CY - Stuttgart ER - TY - JOUR A1 - Ermeydan, Mahmut Ali A1 - Cabane, Etienne A1 - Masic, Admir A1 - Koetz, Joachim A1 - Burgert, Ingo T1 - Flavonoid insertion into cell walls improves wood properties JF - ACS applied materials & interfaces N2 - Wood has an excellent mechanical performance, but wider utilization of this renewable resource as an engineering material is limited by unfavorable properties such as low dimensional stability upon moisture changes and a low durability. However, some wood species are known to produce a wood of higher quality by inserting mainly phenolic substances in the already formed cell walls a process so-called heartwood formation. In the present study, we used the heartwood formation in black locust (Robinia pseudoacacia) as a source of bioinspiration and transferred principles of the modification in order to improve spruce wood properties (Picea abies) by a chemical treatment with commercially available flavonoids. We were able to effectively insert hydrophobic flavonoids in the cell wall after a tosylation treatment for activation. The chemical treatment reduced the water uptake of the wood cell walls and increased the dimensional stability of the bulk spruce wood. Further analysis of the chemical interaction of the flavonoid with the structural cell wall components revealed the basic principle of this bioinspired modification. Contrary to established modification treatments, which mainly address the hydroxyl groups of the carbohydrates with hydrophilic substances, the hydrophobic flavonoids are effective by a physical bulking in the cell wall most probably stabilized by pi-pi interactions. A biomimetic transfer of the underlying principle may lead to alternative cell wall modification procedures and improve the performance of wood as an engineering material. KW - wood cell wall KW - heartwood formation KW - chemical modification KW - Raman spectroscopy KW - dimensional stability KW - nanoindentation Y1 - 2012 U6 - https://doi.org/10.1021/am301266k SN - 1944-8244 VL - 4 IS - 11 SP - 5782 EP - 5789 PB - American Chemical Society CY - Washington ER - TY - JOUR A1 - Demetriou, Antri A1 - Pashalidis, Ioannis A1 - Nicolaides, Athanassios V. A1 - Kumke, Michael Uwe T1 - Surface mechanism of the boron adsorption on alumina in aqueous solutions JF - Desalination and water treatment : science and engineering N2 - The adsorption of boron (boric acid) from aqueous solutions on alumina has been investigated at pH 8.0, I=0.1M NaClO4, T=22 +/- 3 degrees C, and under normal atmospheric conditions. The characterization of the adsorbed species was performed by Raman spectroscopy and the spectroscopic speciation was assisted by theoretical DFT calculations. Evaluation of the spectroscopic data points to the formation of inner-sphere surface complexes and indicates the formation of two different types of adsorbed boron species. The theoretical calculations corroborate the spectroscopic data and indicate that at low boron concentration the monodentate surface species dominates, whereas increased boron concentration favors the formation of a bidentate surface species. Assuming low coverage, the conditional formation constant for the monodentate surface species has been evaluated to be log=4.1 +/- 0.1. KW - Boric acid KW - Alumina KW - Raman spectroscopy KW - DFT calculations KW - Surface complexes KW - Formation constant Y1 - 2013 U6 - https://doi.org/10.1080/19443994.2013.764354 SN - 1944-3994 SN - 1944-3986 VL - 51 IS - 31-33 SP - 6130 EP - 6136 PB - Taylor & Francis Group CY - Philadelphia ER -