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We report on attempts towards the synthesis of titanium nanoparticles using a wet chemical approach in imidazolium-based ionic liquids (ILs) under reducing conditions. Transmission electron microscopy finds nanoparticles in all cases. UV/Vis spectroscopy confirms the nanoparticulate nature of the precipitate, as in all cases an absorption band between ca. 280 and 300 nm is visible. IR spectroscopy shows that even after extensive washing and drying, some IL remains adsorbed on the nanoparticles. Raman spectroscopy suggests the formation of anatase nanoparticles, but X-ray diffraction reveals that, possibly, amorphous titania forms or that the nanoparticles are so small that a clear structure assignment is not possible. The report thus shows that (possibly amorphous) titanium oxides even form under reducing conditions and that the chemical synthesis of titanium nanoparticles in ILs remains elusive.
Background
Micrometer resolution placement and immobilization of probe molecules is an important step in the preparation of biochips and a wide range of lab-on-chip systems. Most known methods for such a deposition of several different substances are costly and only suitable for a limited number of probes. In this article we present a flexible procedure for simultaneous spatially controlled immobilization of functional biomolecules by molecular ink lithography.
Results
For the bottom-up fabrication of surface bound nanostructures a universal method is presented that allows the immobilization of different types of biomolecules with micrometer resolution. A supporting surface is biotinylated and streptavidin molecules are deposited with an AFM (atomic force microscope) tip at distinct positions. Subsequent incubation with a biotinylated molecule species leads to binding only at these positions. After washing streptavidin is deposited a second time with the same AFM tip and then a second biotinylated molecule species is coupled by incubation. This procedure can be repeated several times. Here we show how to immobilize different types of biomolecules in an arbitrary arrangement whereas most common methods can deposit only one type of molecules. The presented method works on transparent as well as on opaque substrates. The spatial resolution is better than 400 nm and is limited only by the AFM's positional accuracy after repeated z-cycles since all steps are performed in situ without moving the supporting surface. The principle is demonstrated by hybridization to different immobilized DNA oligomers and was validated by fluorescence microscopy.
Conclusions
The immobilization of different types of biomolecules in high-density microarrays is a challenging task for biotechnology. The method presented here not only allows for the deposition of DNA at submicrometer resolution but also for proteins and other molecules of biological relevance that can be coupled to biotin.
There is growing evidence that aging and muscle fatigue result in impaired postural reflexes in humans. Therefore, the objective of this study was to examine the effects of ankle fatigue on functional reflex activity (ERA) during gait perturbations in young and elderly men. Twenty-eight young (27.0 +/- 3.1 years, n = 14) and old (67.2 +/- 3.7 years, n = 14) healthy active men participated in this study. Fatigue of the plantarflexors and dorsiflexors was induced by isokinetic contractions. Pre and post-fatigue, subjects were tested for their ability to compensate for decelerating gait perturbations while walking on a treadmill. Latency, ERA of lower extremity muscles and angular velocity of the ankle joint complex were analysed by means of surface electromyography and goniometry. After the fatigue protocol, no significant main and interaction effects were detected for the parameter latency in m. tibialis anterior (TA). For both groups, a significant pre to post-test decrease in ERA in TA (P<.001) was observed coming along with increases in antagonist coactivity (P=.013) and maximal angular velocity of the ankle joint (p=.007). However, no significant group x test interactions were found for the three parameters. Ankle fatigue has an impact on the ability to compensate for gait perturbations in young and elderly adults. However, no significant differences in all analysed parameters were detected between young and elderly subjects. These results may imply that age-related deteriorations in the postural control system do not specifically affect the ability to compensate for gait perturbations under fatigued condition.
The red clover isoflavone irilone is largely resistant to degradation by the human gut microbiota
(2010)
Intestinal bacteria may influence bioavailability and physiological activity of dietary isoflavones. We therefore investigated the ability of human intestinal microbiota to convert irilone and genistein in vitro. In contrast to genistein, irilone was largely resistant to transformation by fecal slurries of ten human subjects. The fecal microbiota converted genistein to dihydrogenistein, 6'-hydroxy-O-desmethylangolensin, and 2-(4-hydroxyphenyl)- propionic acid. However, considerable interindividual differences in the rate of genistein degradation and the pattern of metabolites formed from genistein were observed. Only one metabolite, namely dihydroirilone, was formed from irilone in minor amounts. In further experiments, Eubacterium ramulus, a prevalent flavonoid-degrading species of the human gut, was tested for transformation of irilone. In contrast to genistein, irilone was not converted by E. ramulus. Irilone only differs from genistein by a methylenedioxy group attached to the A-ring of the isoflavone skeleton. This substitution obviously restricts the degradability of irilone by human intestinal bacteria.
Das Dokument ist eine Zusammenfassung der wesentlichen Aspekte zu Rosh Sukka.
Sikum Hilkhot Shabat
(2010)
This document summarises the commandments of Shabbat.
The depositional geometry and facies distribution of an Early Miocene (Burdigalian) carbonate system in the Perfugas Basin (NW Sardinia) comprise a well-exposed example of a transition from a ramp to a steep-flanked platform. The carbonate succession (Sedini Limestone Unit) is composed of two depositional sequences separated by a major erosional unconformity. The lower (sequence 1) records a ramp dominated by heterozoan producers and the upper (sequence 2) is dominated by photozoan producers and displays a gradual steepening of the depositional profile into a steep- flanked platform. This paper shows the process of creating a digital outcrop model including a facies model. This process consists of combining field data sets, including 17 sedimentary logs, and a spatial dataset consisting of differential global positioning system data points measured along key stratigraphic surfaces and sedimentary logs, with the goal of locking traditional field observations into a 3D spatial model. Establishing a precise geometrical framework and visualizing the overall change in the platform geometry and the related vertical and lateral facies variations of the Sedini carbonate platform, allows us to better understand the sedimentary processes leading to the geometrical turn- over of the platform. Furthermore, a detailed facies modeling helps us to gain insight into the detailed depositional dynamics. The final model reproduces faithfully the depositional geometries observed in the outcrops and helps in understanding the relationships between facies and architectural framework at the basin scale. Moreover, it provides the basis to characterize semiquantitatively regional sedimentological features and to make further reservoir and subsurface analogue studies.
This study models maximum temperatures in Switzerland monitored in twelve locations using the generalised extreme value (GEV) distribution. The parameters of the GEV distribution are determined within a Bayesian framework. We find that the parameters of the underlying distribution underwent a substantial change in the beginning of the 1980s. This change is characterised by an increase both in the level and the variability. We assess the likelihood of the heat wave of the summer 2003 using the fitted GEV distribution by accounting for the presence of a structural break. The estimation results do suggest that the heat wave of 2003 is not that statistically improbable if an appropriate methodology is used for dealing with nonstationarity.
Amphibole and mica Ar-40/Ar-39 ages as well as zircon, rutile and titanite U-Pb geochronology of eclogites and associated host rocks from the Higher Himalayan Crystalline Nappes (Indian Plate) in the Upper Kaghan Valley, Pakistan allow distinction of a multistage exhumation history. An Eocene age for peak-pressure metamorphism has been obtained by phengite Ar-40/Ar-39 (47.3 +/- 0.3 Ma) and zircon U-Pb (47.3 +/- 0.4 and 47.4 +/- 0.3 Ma) ages from cover and basement gneisses. A very short-lived metamorphic peak and rapid cooling is documented by an amphibole Ar-40/Ar-39 age of 46.6 +/- 0.5 Ma and a rutile U-Pb age of 44.1 +/- 1.3 Ma from eclogites. Phengite and biotite ages from cover and basement sequences metamorphosed during the Himalayan orogeny are 34.5 +/- 0.2 to 28.1 +/- 0.2 Ma whereas youngest biotites, yielding 23.6 +/- 0.1 and 21.7 +/- 0.2 Ma, probably reflect argon partial resetting. The amphibole age, together with those derived from phengite and zircon demonstrate a rate of initial exhumation of 86-143 mm/a i.e. an extremely rapid transport of the Indian Plate continental crust from ultra-high pressure (UHP) conditions back to crustal levels (47-46 Ma for transport from 140 to 40 km depth). Subsequent exhumation (46-41 Ma, 40-35 km) slowed to about 1 mm/a at the base of the continental crust but increased again later towards slightly higher exhumation rates of ca. 2 mm/a (41-34 Ma, 35- 20 km). This indicates a change from buoyancy-driven exhumation at mantle depths to compression forces related to continent-continent collision and accompanied crustal folding, thrusting and stacking that finally exposed the former deeply-buried rocks.
The Eastern Cordillera of the Colombian Andes represents an inverted Cretaceous basin where Cretaceous magmatism is characterized by rare mafic dykes and sills. We use Ar-40/Ar-39, Sr-Nd-Pb isotopes, as well as major and trace elements analyses of Cretaceous intrusions from both flanks of the Eastern Cordillera in combination with structural data to document the complex evolution of the basin. Magmatism, which is diachronous and geochemically diverse, seems to be related to mantle melting beneath the most subsiding segments of each sub-basin during enhanced extensional tectonics. The mafic intrusions display two different compositional series: an alkaline one with OIB-like pattern and a tholeiitic one with MORB-like features. This indicates at least two diverse mantle sources. Trace-element patterns suggest that the intrusions were emplaced in an extensional setting. Ar-40/Ar-39 dating on primary plagioclase and hornblende provides plateau ages between similar to 136 and similar to 74 Ma. The geochemical and temporal diversities show that the emplacement of the magmas was tectonically controlled, each sub-basin reflecting an individual subsidence event.
Jahresbericht 2009
(2010)
Inhalt: 1. Allgemeiner Überblick 2. Organisationsstruktur des MRZ 2.1 Status des Zentrums 2.2 Leitung und Mitarbeiter 2.3 Beirat 2.4 Förderverein 3. Aktivitäten im Berichtszeitraum 3.1 Forschung 3.2 Promotionen 3.3 Wissenschaftliche Veranstaltungen 3.4 Lehre und Weiterbildung 3.5 Publikationen – Neuerscheinungen 2009 3.6 Bibliothek 3.7 Chronologie der Aktivitäten 4. Anhang 4.1 Bisherige Tagungen 4.2 Schriften des MenschenRechtsZentrums 4.3 Satzung des MRZ 4.4 Hinweise auf Web-Seiten anderer Einrichtungen 4.5 Abstract
Within our research group Bayesian Risk Solutions we have coined the idea of a Bayesian Risk Management (BRM). It claims (1) a more transparent and diligent data analysis as well as (2)an open-minded incorporation of human expertise in risk management. In this dissertation we formulize a framework for BRM based on the two pillars Hardcore-Bayesianism (HCB) and Softcore-Bayesianism (SCB) providing solutions for the claims above. For data analysis we favor Bayesian statistics with its Markov Chain Monte Carlo (MCMC) simulation algorithm. It provides a full illustration of data-induced uncertainty beyond classical point-estimates. We calibrate twelve different stochastic processes to four years of CO2 price data. Besides, we calculate derived risk measures (ex ante/ post value-at-risks, capital charges, option prices) and compare them to their classical counterparts. When statistics fails because of a lack of reliable data we propose our integrated Bayesian Risk Analysis (iBRA) concept. It is a basic guideline for an expertise-driven quantification of critical risks. We additionally review elicitation techniques and tools supporting experts to express their uncertainty. Unfortunately, Bayesian thinking is often blamed for its arbitrariness. Therefore, we introduce the idea of a Bayesian due diligence judging expert assessments according to their information content and their inter-subjectivity.
The temperature range of the apatite fission-track partial annealing zone (PAZ) varies as a function of the kinetic characteristics of the apatite crystal as well as the cooling rate. These kinetic characteristics are controlled largely by the chemical composition of the apatites; fission-track etch pit diameter (D-par) has been shown to be a proxy for quantifying these characteristics. Since some annealing models explicitly use D-par as a kinetic indicator, the question of whether D-par varies according to either operator variability or etching conditions has serious implications. The influence of etching conditions includes both minor variations in temperature and etch time as well as larger variations between the three popular concentrations of nitric acid that are presently in use within the fission- track community: 5 and 5.5 M HNO3 at 21 degrees C for 20 s, and 1.6 M (7 vol.%) HNO3 at 21 degrees C for 45 or 50 s. We have conducted a systematic study of D-par in two widely used apatite age standards: Durango and Fish Canyon Tuff (FCT). Samples were analyzed by at least 2 operators in 2 laboratories; over 15,000 etch pits were measured. Operator imprecision is small compared to other effects both within and between operators. The measured D-par parameters depend primarily on etching conditions including concentration of etchant, and the time and temperature of etching. D-par size increases linearly with time but non-linearly with temperature. Differences between D-par size of Durango and FCT are significantly smaller for the 1.6 M etch compared to the other two etches, implying that the weak etch has less resolving power for D-par measurements. In addition, when etching conditions are changed, confined track lengths for different apatite compositions and D-par values co-vary in a complex fashion. Therefore, the 5 or 5.5 M etch is recommended for studies that employ D-par as a proxy for chemistry; the 1.6 M etch and other weak etches are not recommended. We propose a linear correction for D-par based on measuring D-par in two widely available AFT age standards, Durango and FCT, and cross-plotting the results with those obtained by R. Donelick. The slope of the resulting curve, which passes through the origin, provides a correction factor. This system yields reasonably good corrected values for 3 test samples using the 5 M and 5.5 M HNO3 etches.
We show that Scattering Infrared Near-field Microscopy (SNIM) allows chemical mapping of polymer monolayers that can serve as designed nanostructured surfaces with specific surface chemistry properties on a nm scale. Using s- SNIM a minimum volume of 100 nm x 100 nm x 15 nm is sufficient for a recording of a "chemical'' IR signature which corresponds to an enhancement of at least four orders of magnitudes compared to conventional FT-IR microscopy. We could prove that even in cases where it is essentially difficult to distinguish between distinct polymer compositions based solely on topography, nanophase separated polymers can be clearly distinguished according to their characteristic near-field IR response.
This thesis contains quantum chemical models and force field calculations for the RuBisCO isotope effect, the spectral characteristics of the blue-light sensor BLUF and the light harvesting complex II. The work focuses on the influence of the environment on the corresponding systems. For RuBisCO, it was found that the isotopic effect is almost unaffected by the environment. In case of the BLUF domain, an amino acid was found to be important for the UV/vis spectrum, but unaccounted for in experiments so far (Ser41). The residue was shown to be highly mobile and with a systematic influence on the spectral shift of the BLUF domain chromophore (flavin). Finally, for LHCII it was found that small changes in the geometry of a Chlorophyll b/Violaxanthin chromophore pair can have strong influences regarding the light harvesting mechanism. Especially here it was seen that the proper description of the environment can be critical. In conclusion, the environment was observed to be of often unexpected importance for the molecular properties, and it seems not possible to give a reliable estimate on the changes created by the presence of the environment.
Seven experiments using self-paced reading and eyetracking suggest that omitting the middle verb in a double centre embedding leads to easier processing in English but leads to greater difficulty in German. One commonly accepted explanation for the English pattern-based on data from offline acceptability ratings and due to Gibson and Thomas (1999)- is that working-memory overload leads the comprehender to forget the prediction of the upcoming verb phrase (VP), which reduces working-memory load. We show that this VP-forgetting hypothesis does an excellent job of explaining the English data, but cannot account for the German results. We argue that the English and German results can be explained by the parser's adaptation to the grammatical properties of the languages; in contrast to English, German subordinate clauses always have the verb in clause-final position, and this property of German may lead the German parser to maintain predictions of upcoming VPs more robustly compared to English. The evidence thus argues against language- independent forgetting effects in online sentence processing; working-memory constraints can be conditioned by countervailing influences deriving from grammatical properties of the language under study.
Near edge X-ray absorption. ne structure and X-ray photoelectron spectroscopy have been employed to follow the reversible trans to cis isomerization of tetra-tert-butyl-azobenzene (TBA) adsorbed on Au(111). For one monolayer the molecules adopt an adsorption geometry characteristic of the trans-TBA isomer. The azo-bridge (N = N) is aligned nearly parallel to the surface and the phenyl rings exhibit a planar orientation with a small tilt angle <= 4 degrees with respect to the surface normal. Illumination of the molecular layer at 455 nm triggers the trans to cis isomerization which is associated with a pronounced change of the geometrical and electronic structure. The N1s to pi* transition of the central azo-bridge shifts by 0.45 +/- 0.05 eV to higher photon energy and the transition dipole moment (TDM) is tilted by 59 +/- 5 degrees with respect to the surface normal. The pi-system of one phenyl ring is tilted by about 30 degrees with respect to the surface normal, while the second ring plane is oriented nearly perpendicular to the surface. This reorientation is supported by a shift and broadening of the C-H resonances associated with the tert-butyl legs of the molecule. These findings support a configuration of the photo-switched TBA molecule on Au(111) which is comparable to the cis-isomer of the free molecule. In the photo-stationary state 53 +/- 5% of the TBA molecules are switched to the cis configuration. Thermal activation induces the back reaction to trans-TBA.