Analytische Chemie
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Solution doping of off-the-shelf plastic optical fibers (POFs) represents rather simple and cheap way for preparing custom cladding-doped POFs (CD-POFs) with short to medium lengths. CD-POFs are especially attractive for environmental sensing applications, but might be of interest for illumination task as well. In this work, the proposed doping technique is tested with three different commercial low-cost polymethyl methacrylate (PMMA) POFs; Eska CK-40 and Eska GK-40 from Mitsubishi Rayon and Raytela PGU-FB1000 from Toray. The aim of the work is to aid the selection of the most suitable fiber yielding highest optical quality of prepared CD-POFs. Firstly, the optimal doping times are determined for the individual fiber types using short fiber samples. Secondly, longer 10 m CD-POFs are prepared from all tested fibers using the optimized doping procedure. Finally, attenuation of pristine POFs and prepared CD-POFs is measured using optical time domain reflectometry in order to characterize the impacts of the doping on fiber optical properties. In addition, the importance of post-doping drying procedure for CD-POF optical performance is investigated as well. The results suggest that, although doping of all tested fibers is generally feasible, Eska CK-40 is the most suitable candidate with regard to the doping efficiency and fiber post-doping performance.
The damage caused by ionizing radiation to DNA and proteins is the reason to treat cancer by radiation therapy. A better understanding of the molecular processes and quantification of the different damaging mechanisms is the prerequisite to develop more efficient therapies. Hereby the understanding of the processes involved in the damage to DNA are of key interest due to its central role in reproduction and mutation.
For radiation with low linear energy transfer (LET), most of the damage is caused by the secondary particles produced by scattering of the ionizing radiation with water. Thereby a multitude of species are produced, whereby especially kinetic low energy electrons, prehydrated electrons, OH-radicals and ions are of importance. With higher LET the relative amount of the direct damaging effects increases. This is especially important considering the increased usage of high LET nucleons in radiation therapy. Therefore, the quantification of the contribution to DNA damage of direct and indirect effects and the different secondary species is of high interest due to the increase of radio biological efficiency when applying high LET radiation.
Here we present an approach to investigate the relative contributions to DNA strand break yield for radiation of different LET within a single electron microscope in combination with electron scattering simulations.
Universität Berlin Radiation damage to biomolecules such as DNA, is the reason to treat cancer via radiation therapy. The understanding of the molecular processes and the quantification of the underlying damaging mechanisms is necessary to develope more efficient irradiation protocols for cancer therapy. Thereby damage to DNA is of key interest due to its central role in reproduction and mutation. Due to the high amount of water in biological tissue, most of the damage is caused by the secondary particles which are produced by the interaction of ionizing radiation with water. Thereby a multitude of species are produced, e.g. kinetic low energy electrons, prehydrated electrons, OH-radicals and ions. The quantification of the contribution to DNA damage by the various species is of interest. Here we present an experimental approach to disentangle their relative DNA strand break yields. Plasmid DNA (pUC19 ) is irradiated in water with electrons under the presence of different scavengers. The presented preliminary results reveal the relative contributions of OH-radicals, low energy electrons and prehydrated electrons and their DNA single and double strand break yields.
Quantifizierung der Schädigung von DNA in wässriger Lösung unter direkter Elektronenbestrahlung
(2018)
To cure cancer radiation therapy is used to kill tumor cells.
It is based on radiation induced damage to biomolecules.
Especially DNA damage is of key interest due to its central role in apoptosis and mutation.
Because of the high amount of water in biological tissue, most of the damage is caused by the secondary particles produced by the inelastic scattering of ionizing radiation and water.
A detailed understanding of the underlying molecular processes under physiological conditions is the prerequisite to develop more efficient therapies.
Goal of this work is to quantify the DNA damage caused by ionizing radiation in dependence of the inelastic scattering events and the energy deposit within the microscopic target volume of biological relevance.
The irradiations have to be performed in liquid, under consideration of the chemical environment.
Therefore, a new combination of experiment and Monte-Carlo simulations was developed and tested.
To make it possible to irradiate liquids with electrons within scanning electron microscopes a new sample holder was constructed incorporating an electron transparent nanomembrane.
It makes it possible to irradiate DNA, proteins or cells at different pH, salinity and in the presence of cosolutes.
%The most important results of this work are as follows:
The median lethal dose for a model system of plasmid DNA and water was determined by the combination of experimental data, particle scattering simulations (Geant4-DNA) and diffusion calculations as D0.5=(1.7+-0.3) Gy.
From the convolution of plasmid positions and the spatially resolved energy deposit, as determined by electron scattering simulations, the histogram of the energy deposit within the target volume of the plasmids and the microscopic median lethal energy deposit was calculated as E0.5=6+-4eV.
It could be deduced that on average less than two ionization events are sufficient to cause a single-strand-break.
The relation of single-strand-breaks (SSB) to double-strand-breaks (DSB), which is of importance for microdosimetric modeling, was determined as SSB:DSB = 12:1.
The presented method for the determination of microscopic dose-damage relations was further extended to be applicable for general irradiation experiments.
It becomes independent of the type of primary radiation used, the experimental geometry, and the diffusional properties of the molecules under investigation.
This way different experimental systems with varying, inhomogeneous energy deposit characteristics become comparable with each other, which is not possible when only macroscopic averaged values are taken into account.
In addition, the radiation protection properties of the compatible solute ectoine, as well as its influence on the water properties and biomolecules were investigated.
%In addition, the influence of the compatible solute ectoine on water, biomolecules and its radiation protection properties were investigated.
Raman spectroscopy revealed a concentration dependent increase of the collective water modes in the OH-stretching region, which was found to be independent of the sodium chloride concentration.
Molecular dynamic simulations showed that the zwitterionic properties of ectoine lead to its half-chair conformation.
The hydrogen bonds in the first hydration shell are more stable and have an increased lifetime compared to the bulk water.
Irradiation experiments with DNA in the presence of 1M ectoine revealed an increase of the survival rate by a factor of 1.41 as compared to the absence of ectoine.
The protective properties of ectoine result from the increase of the inelastic scattering probabilities of low energy electrons at the acoustic vibrational modes of water and its properties as OH-radical scavenger.
This was shown by Raman spectroscopy and electron paramagnetic resonance measurements (EPR).
Photoelectron spectroscopy
(2018)
Gold ist eines der sieben schon im Altertum bekannten Metalle und wurde wg. seines Glanzes und seiner Seltenheit von alters her als Tauschmittel und zur Herstellung von Schmuck benutzt. Außerdem ist es einfach bearbeitbar und weitestgehend gegen chemische Einflüsse resistent. Die Untersuchungen von Gold mit synchrotronstrahlungsangeregter Röntgenfluoreszenzanalyse sind zerstörungsfrei und geben Auskunft über die in der untersuchten Probe vorhandenen chemischen Elemente. Bei den hier vorgestellten Untersuchungen an der BAMline stehen Fragestellungen wie Herkunft, Herstellungsverfahren und Zusammengehörigkeit von Goldfunden im Vordergrund. Die verschiedenen Fragestellungen werden an einer Reihe von Beispielen erläutert die vom Wikingerschatz aus Hiddensee über die Himmelsscheibe von Nebra bis hin zu Funden aus Ägypten langen. Zusätzlich werden die modernen Messmethoden vorgestellt, die am Synchrotron heutzutage zur Verfügung stehen.
X-ray absorption fine structure spectroscopy (XAFS) is a frequently employed technique in order to investigate structural composition and change of chemical compounds such as catalytic species. These structural properties are essential (i) to understand underlying reaction mechanism and (ii) to further improve the design of efficient catalysts.
This investigation is based on a newly developed XAFS setup comprising both time- and lateral-resolved XAFS information simultaneously in a single-shot (S2XAFS). The primary broadband beam is generated by a filter/X-ray-mirror combination (bandpass). The transmitted beam through the sample is diffracted by a convexly bent Si (111) crystal, producing a divergent beam. This, in turn, is collected by an area sensitive detector with a theta to 2 theta geometry. This facile, stable and scanningless setup was tested at the BAMline @ BESSY-II (Berlin, Germany).
This contribution focuses on further experimental optimizations allowing the characterization of supported vanadium oxide (VOx) based catalysts at the lower hard X-ray regime (5 to 6 keV). First S2XAFS measurements of these catalysts are presented herein. Supported VOx catalysts show promising results in the oxidation of methane to formaldehyde.
S2XAFS allows determining the structural composition of the metal (i.e. vanadium) based on a fast and smart setup. It is therefore an ideal tool to identify crucial roles of chemical compounds in catalytic reactions.
Ferritic high temperature alloys are widely used as boiler tube and heat exchanger materials in coal, biomass and co-fired power plants. All technologies have in common that the applied materials are exposed to different temperatures, process pressures and reactive atmospheres that lead to a change of the material properties and a further degradation of the material. Material changes caused by aging in highly corrosive and toxic gases such as SO2 are mainly studied ex situ after the reaction is finished. The solid material is deposited in the atmosphere for a certain period of time, and material changes are then examined by various microscopic techniques such as optical microscopy (OM), electron microprobe analysis (EMPA), scanning electron microscopy (SEM and TEM) and X-ray diffraction (XRD). Nevertheless, extensive efforts were made to study material changes of high temperature alloys under oxidizing and reducing atmospheres by environmental scanning electron microscopy or in situ TEM techniques However, the possibilities of microscopic in situ techniques are very limited for the use of highly corrosive and toxic gases such as SO2. Since Sulfur induced corrosion at temperatures relevant for coal and biomass fired power plants, which is causing breakaway oxidation and sulfide precipitation at grain boundaries, is still of scientific interest, the current work focuses on the effect of SO2 in an initial stage of corrosion of ferritic alloys. For the analysis of early stages of combined oxidation and sulphidation processes of Fe-Cr model alloys the usage of a light furnace to conduct a rapid reactive annealing experiment is feasible. Previous studies presented distinct results of the influence of chromium on early high temperature corrosion by SO2 by this technique and subsequent classical metallographic analyses. However, it is still not possible to trace the corrosion mechanism in real time by conducting single aging experiments. The current work introduces two different approaches to study the initial stages of high temperature oxidation processes by applying above state of the art X-ray diffraction and spectroscopy methods. One part focuses on the real time observation of the formation of corrosion products such as oxides and sulfides by energy dispersive X-ray diffraction (EDXRD). The potential of this technique to study crystallization and growth processes of thin films in a reactive environment in real time was previously shown for different compound semiconductors. This approach was now applied to follow oxidation and sulphidation processes of ferritic model alloys in SO2 and SO2/H2O environments. The diffraction signals of the X-rays were detected during the corrosion process and the peak area and positions were analyzed as a function of time. This procedure enables monitoring external oxide growth and material loss in real time in an early stage of corrosion.
The other part of the current work presents the possibilities of X-ray absorption near edge structure spectroscopy (XANES) to characterize oxide scales and their growth mechanisms. Precise phase identification and quantification of corrosion products in a multi-phase oxide/sulfide scale is a pre-requisite to understand diffusion paths of metal ions and gas components. It is a challenging task to distinguish structurally similar reaction products such as Fe3O4 and FeCr2O4 especially in thin films with texture effects by diffraction. To illustrate for example Cr-out diffusion of an alloy throughout an inner and external oxide scale the differentiation of Fe3O4 and FeCr2O4 is indispensable. XANES uses the photoionization effect at the metal absorption edge in an aging product and accesses by this structural and chemical information. The current work uses XANES at the Fe-K and Cr-K absorption edge to identify various aging products grown as thin layers on alloys after short time aging experiments. A reaction chamber for combining high temperature oxidation experiments with surface sensitive X-ray absorption near edge structure spectroscopy will be introduced and first results of XANES on scales at high temperatures will be presented.
In-Situ SAXS Techniques
(2018)
Our project's aim is to enhance the capabilities of additive manufacturing techniques, where enabling a Two-Photon-Polymerization (TPP) 3D printer of producing arrays of precisely aligned nanoparticles is of an enormous value. As heterogeneous functional nanostructures with arrays of oriented nanoparticles are very promising in many fields; electrochemistry, energy storage, nanoelectronics among other vital fields.
The feasibility and the convenience of orienting nanoparticles using magnetic, electric fields and ultrasonic vibrations will be systematically investigated, using Small Angle X-ray Scattering (SAXS), since SAXS can provide detailed information about the orientation characteristics of nano-Ensembles. Corresponding to our prerequisites, a set ad hoc functional sample holders, sample stages and other In-Situ SAXS solutions were developed, and incorporated to be compatible with a state-of-the-arts SAXS machine, called Multi-scale Analyzer for Ultrafine Structures (MAUS).
The MAUS has been customized and engineered to serve as a miniaturized synchrotron, and that is exactly what we need.
Experiments attempting to orient superparamagnetic nanoparticles will be discussed, where the outcomes will not only help in understanding the mechanics of field-particle interactions, it will also help in further developing the adequate needed set of corrections to the SAXS data, that is especially regards oriented samples.
Analytical Sciences has developed from Ostwald’s “unentbehrlichen Dienstmagd” to a chemical discipline at the core of many of today’s fundamental and applied scientific problems and innovations. An atomic or molecular understanding of basic processes in chemistry, soft matter physics, materials and life science is enabled only through new analytical methods and instrumentation. Similar observations can be found for pressing sociopolitical conflicts of the future: A rational discussion of global climate change or new energy sources is only possible with reliable analytical results. Progress in Analytical Sciences is only possible if the underlying interdisciplinary character is acknowledged and valued. The talk will illustrate the scope of modern Analytical Science through examples from process analysis relevant to modern process intensification and industry 4.0 to bioanalysis and the use of synchrotron radiation to elucidate fundamental reactions materials.
In well-annealed thin polymer films, with non-repulsive polymer/substrate interactions, an irreversibly adsorbed layer is expected to from. These adsorbed layers have shown greate potential for technological applications. However, their growth kinetics and molecular dynamics are still not fully understood. This is partly due to the hard accessibility of these layers in thin films. Here, the irreversibly adsorbed layers of homopolymer thin films are revealed by solvent-leaching experiments. First, the growth kinetics of these layers is investigated as a function of annealing time, annealing temperature, leaching time and the original filme thickness. The film thickness, topography and the quality of the adsorbed layer is controlled by Atomic Force Microscopy (AFM). Secondly, the molecular mobility of the adsorbed layer is investigated by Broadband Dielectric Spectroscopy (BDS). A recently developed nanostructured capacitor arrangement is employed to measure the layer with a free surface. The results are quantitatively compared and discussed with respect to recently published work.
The structure and molecular dynamics of thin polymer films are of topical interest of soft matter-physics. Commonly, spatial structural heterogeneities of 1D confined thin films (surface, bulk-like and adsorbed layer), are expected to alter the glassy dynamics, compared to the bulk. Here, Specific Heat Spectroscopy (SHS) was used, to investigate the glassy dynamics of thin films of an asymmetric miscible PVME/PS 25/75 wt% blend. SHS measurements showed a non-monotonous thickness dependence of the dynamic Tg, on the contrary to the previously investigated PVME/PS 50/50 wt%. For PVME/PS 25/75 wt% thin films (> 30 nm), due to the presence of PVME-rich adsorbed and surface layers, the bulk-like layer experienced a thickness dependent increase of PS concentration. This led to a systematic increase of dynamic Tg. Further decrease of the film thickness (< 30 nm), resulted in a decrease of dynamic Tg, ascribed to the influence of the surface layer, which has a high molecular mobility. This is the first study, which shows deviations of dynamic Tg of thin films, compared to the bulk, resulting from the counterbalance of the free surface and adsorbed layer.
Dielectric spectroscopy (BDS) was employed to investigate the dynamics of thin films (7 – 200 nm) of a Poly (vinyl methyl ether) (PVME) / Polystyrene (PS) blend (50:50 wt%). For the BDS measurements Nano-Structured Capacitors (NSC) were employed, where films have a free surface. This method was applied for film thicknesses up to 36 nm. Thicker films were prepared between Crossed Electrodes Capacitors (CEC). The spectra of the films showed multiple processes. The first process was assigned to the -relaxation of a bulk-like layer. For films measured by NSC, its rates were higher compared to that of the bulk blend. This behavior was related to a PVME-rich free-surface layer. A second process was observed for films measured by CEC (process X) and the 36 nm film measured by NSC (process X2). This process was assigned to fluctuations of PVME constraint by PS. Its activation energy was found to be thickness dependent, due to the evidenced thickness dependency of the compositional heterogeneity. Finally, a third process with an activated temperature-dependence was observed for all films measured by NSC (process X1). It resembled the molecular fluctuations in an adsorbed layer found for films of pure PVME.
Die Bundesanstalt für Materialforschung und -prüfung (BAM) ist eine Ressortforschungseinrichtung, die zum Schutz von Mensch, Umwelt und Sachgüter, forscht, prüft und berät. Im Fokus aller Tätigkeiten in der Materialwissenschaft, der Werkstofftechnik und der Chemie steht dabei die technische Sicherheit von Produkten und Prozessen. Dazu werden Substanzen, Werkstoffe, Bauteile, Komponenten und Anlagen sowie natürliche und technische Systeme erforscht und auf sicheren Umgang oder Betrieb geprüft und bewertet. Schwerpunkt des Vortrages sind multimodale Polymeranalytik, nanoskalige Sensormaterialien und die Charakterisierung von technischen Eigenschaften von Polymeren sowie ihre Alterung und Umweltrelevanz.
From simple molar mass disperse homopolymers over copolymers to functionalized, 3-dimensional structures containing various distributions, the complexity of polymeric materials has become more and more sophisticated in recent years. With applications in medicine, pharmacy, smart materials or for the semiconductor industry the requirements for the characterization have risen with the complexity of the used polymers. For each additional distribution, an additional dimension in analysis is needed. Small, often isobaric heterogeneities in topology or microstructure can usually not be simply separated chromatographically or distinguished by any common detector. Instead of a complicated, time consuming and/or expensive 2d-chromatography or ion mobility spectrometry (IMS) method, that also has its limitations, here a simple approach using size exclusion chromatography (SEC) coupled with electrospray ionization mass spectrometry (ESI) is proposed. We used SEC for the separation because unlike other separation modes the separation in this mode solely should occur due to the hydrodynamic volume with no interference of other interactions. This simplifies the interpretation and the above mentioned heterogeneities should show a slight difference in hydrodynamic volume. ESI mass spectrometry can offer more than an access to mass dependent information like MMD, end group masses or CCD in polymer analysis. The online coupling to SEC allows the analysis of reconstructed ion chromatograms (RIC) of each degree of polymerization. While a complete separation often cannot be achieved, the derived retention times and peak widths lead to information on the existence and dispersity of heterogeneities in microstructure or topology, that are otherwise inaccessible or accessible only by time consuming or expensive methods. Because these heterogeneities might vary with the molar mass, analysis of the whole MMD-Peak (here the total ion current (TIC)) would not lead to the desired information. The broadening of the chromatographic peaks in this case does not origin from the already well known band broadening factors in chromatography from diffusion. This band broadening is attributed to the nature and composition of the analyte itself. Surprisingly there is very little investigation into the peak width or peak shape due to analyte structure itself found in literature. It is also shown, that with proper calibration even quantitative information could be obtained. This method is suitable to detect small differences in e. g. branching, topology, monomer sequence or tacticity and could potentially be used in production control of oligomeric products or other routinely done analyses to quickly indicate deviations from set parameters. Based on a variety of examples we demonstrate the possibilities and limitations of this approach.