Refine
Has Fulltext
- no (1992) (remove)
Year of publication
- 2019 (1992) (remove)
Document Type
- Article (1541)
- Other (155)
- Doctoral Thesis (127)
- Monograph/Edited Volume (63)
- Review (58)
- Part of a Book (28)
- Conference Proceeding (7)
- Habilitation Thesis (6)
- Course Material (3)
- Journal/Publication series (2)
Keywords
- climate change (9)
- diffusion (8)
- Germany (7)
- stars: evolution (7)
- stars: winds, outflows (7)
- methods: numerical (6)
- quasars: absorption lines (6)
- stars: massive (6)
- Climate change (5)
- Deutschland (5)
Institute
- Institut für Biochemie und Biologie (304)
- Institut für Physik und Astronomie (283)
- Institut für Geowissenschaften (240)
- Institut für Chemie (152)
- Department Psychologie (108)
- Institut für Ernährungswissenschaft (76)
- Institut für Umweltwissenschaften und Geographie (66)
- Historisches Institut (65)
- Department Sport- und Gesundheitswissenschaften (57)
- Sozialwissenschaften (55)
Anthracyclines like daunorubicin (DRN) and doxorubicin (DOX) play an undisputed key role in cancer treatment, but their chronic administration can cause severe side effects. For precise anthracycline analytical systems, aptamers are preferable recognition elements. Here, we describe the detailed characterisation of a single-stranded DNA aptamer DRN-10 and its truncated versions for DOX and DRN detection. Binding affinities were determined from surface plasmon resonance (SPR) and microscale thermophoresis (MST) and combined with conformational data from circular dichroism (CD). Both aptamers displayed similar nanomolar binding affinities to DRN and DOX, even though their rate constants differed as shown by SPR recordings. SPR kinetic data unravelled a two-state reaction model including a 1 : 1 binding and a subsequent conformational change of the binding complex. This model was supported by CD spectra. In addition, the dissociation constants determined with MST were always lower than that from SPR, and especially for the truncated aptamer they differed by two orders of magnitude. This most probably reflects the methodological difference, namely labelling for MST vs. immobilisation for SPR. From CD recordings, we suggested a specific G-quadruplex as structural basis for anthracycline binding. We concluded that the aptamer DRN-10 is a promising recognition element for anthracycline detection systems and further selected aptamers can be also characterised with the combined methodological approach presented here.
The importance of plasmonic heating for the plasmondriven photodimerization of 4-nitrothiophenol
(2019)
Metal nanoparticles form potent nanoreactors, driven by the optical generation of energetic electrons and nanoscale heat. The relative influence of these two factors on nanoscale chemistry is strongly debated. This article discusses the temperature dependence of the dimerization of 4-nitrothiophenol (4-NTP) into 4,4′-dimercaptoazobenzene (DMAB) adsorbed on gold nanoflowers by Surface-Enhanced Raman Scattering (SERS). Raman thermometry shows a significant optical heating of the particles. The ratio of the Stokes and the anti-Stokes Raman signal moreover demonstrates that the molecular temperature during the reaction rises beyond the average crystal lattice temperature of the plasmonic particles. The product bands have an even higher temperature than reactant bands, which suggests that the reaction proceeds preferentially at thermal hot spots. In addition, kinetic measurements of the reaction during external heating of the reaction environment yield a considerable rise of the reaction rate with temperature. Despite this significant heating effects, a comparison of SERS spectra recorded after heating the sample by an external heater to spectra recorded after prolonged illumination shows that the reaction is strictly photo-driven. While in both cases the temperature increase is comparable, the dimerization occurs only in the presence of light. Intensity dependent measurements at fixed temperatures confirm this finding.
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.
Silver-Iron Hierarchical Microflowers for Highly Efficient H2O2 Nonenzymatic Amperometric Detection
(2019)
This study addresses the fabrication of monodispersed iron-doped silver meso-hierarchical flower-like structures via a facile chemical procedure. The morphology of the obtained silver particles has been tuned by changing the concentration of the structure-directing agent (malonic acid). Ball-shaped silver particles were formed in the absence of malonic acid (MA), while silver particles with craspedia-globosa, chrysanthemum, and dahlia flower-like structures were obtained in the presence of 0.2, 0.5, and 1 mM malonic acid, respectively. The doping of these dahlia flower-like structures with trace amounts of iron (<= 5% Fe weight percent) led to the formation of globe-amaranth iron-doped microflowers (AgFeamaranth). The as-prepared AgFeamaranth exhibited better performance as a nonenzymatic H2O2 sensor compared to undoped silver particles as demonstrated by their higher catalytic activity and stability together with superior sensitivity (1350 mu M-1 cm(-2), 61 times higher) and lower detection limit (0.1 mu M). These enhancements are attributed to the AgFe unique flower-like structures and to the fact that the iron dopants provide a higher number of electroactive sites and reduce the charge transfer resistance of H2O2 reduction. Additionally, the good stability of AgFe is believed to originate from the faster detachment rate of the in situ-formed gas bubbles from their surfaces compared to undoped silver structures.
Hydroxyl terminated oligo(epsilon-caprolactone) (OCL) monolayers were reversibly cross-linked forming two dimensional networks (2D) at the air-water interface. The equilibrium reaction with glyoxal as the cross-linker is pH-sensitive. Pronounced contraction in the area of the prepared 2DOCL films in dependence of surface pressure and time revealed the process of the reaction. Cross-linking inhibited crystallization and retarded enzymatic degradation of the OCLfilm. Altering the subphase pH led to a cleavage of the covalent acetal cross-links. The reversibility of the covalent acetal cross-links was proved by observing an identical isotherm as non-cross-linked sample. Besides as model systems, these customizable reversible OCL2D networks are intended for use as pHresponsive drug delivery systems or functionalized cell culture substrates.
A novel and efficient metal- and solvent-free regioselective para-C-H cyanation of hydroxy-, alkoxy-, and benzyloxyarene derivatives has been introduced, using nontoxic potassium thiocyanate as a cyanating reagent in the presence of silica sulfuric acid (SSA). The desired products are obtained in good to high yields without any toxic byproducts.
Classical Wolf-Rayet (cWR) stars are at a crucial evolutionary stage for constraining the fates of massive stars. The feedback of these hot, hydrogen-depleted stars dominates their surrounding by tremendous injections of ionizing radiation and kinetic energy. The strength of a Wolf-Rayet (WR) wind decides the eventual mass of its remnant, likely a massive black hole. However, despite their major influence and importance for gravitational wave detection statistics, WR winds are particularly poorly understood. In this paper, we introduce the first set of hydrodynamically consistent stellar atmosphere models for cWR stars of both the carbon (C) and the nitrogen (N) sequence, i.e. WC and WN stars, as a function of stellar luminosity-to-mass ratio (or Eddington Gamma) and metallicity. We demonstrate the inapplicability of the CAK wind theory for cWR stars and confirm earlier findings that their winds are launched at the (hot) iron (Fe) opacity peak. For log Z/Z(circle dot) > -2, Fe is also the main accelerator throughout the wind. Contrasting previous claims of a sharp lower mass-loss limit forWR stars, we obtain a smooth transition to optically thin winds. Furthermore, we find a strong dependence of the mass-loss rates on Eddington Gamma, both at solar and subsolar metallicity. Increases inWCcarbon and oxygen abundances turn out to slightly reduce the predicted mass-loss rates. Calculations at subsolar metallicities indicate that below the metallicity of the Small Magellanic Cloud, WR mass-loss rates decrease much faster than previously assumed, potentially allowing for high black hole masses even in the local Universe.
The Galactic WC and WO stars
(2019)
Wolf-Rayet stars of the carbon sequence (WC stars) are an important cornerstone in the late evolution of massive stars before their core collapse. As core-helium burning, hydrogen-free objects with huge mass-loss, they are likely the last observable stage before collapse and thus promising progenitor candidates for type Ib/c supernovae. Their strong mass-loss furthermore provides challenges and constraints to the theory of radiatively driven winds. Thus, the determination of the WC star parameters is of major importance for several astrophysical fields. With Gaia DR2, for the first time parallaxes for a large sample of Galactic WC stars are available, removing major uncertainties inherent to earlier studies. In this work, we re-examine a previously studied sample of WC stars to derive key properties of the Galactic WC population. All quantities depending on the distance are updated, while the underlying spectral analyzes remain untouched. Contrasting earlier assumptions, our study yields that WC stars of the same subtype can significantly vary in absolute magnitude. With Gaia DR2, the picture of the Galactic WC population becomes more complex: We obtain luminosities ranging from log L/L-circle dot = 4.9-6.0 with one outlier (WR 119) having log L/L-circle dot = 4.7. This indicates that the WC stars are likely formed from a broader initial mass range than previously assumed. We obtain mass-loss rates ranging between log(M) over dot = -5.1 and -4.1, with (M) over dot proportional to L-0.68 and a linear scaling of the modified wind momentum with luminosity. We discuss the implications for stellar evolution, including unsolved issues regarding the need of envelope inflation to address the WR radius problem, and the open questions in regard to the connection of WR stars with Gamma-ray bursts. WC and WO stars are progenitors of massive black holes, collapsing either silently or in a supernova that most-likely has to be preceded by a WO stage.
High-precision observations of the present-day geomagnetic field by ground-based observatories and satellites provide unprecedented conditions for unveiling the dynamics of the Earth’s core. Combining geomagnetic observations with dynamo simulations in a data assimilation (DA) framework allows the reconstruction of past and present states of the internal core dynamics. The essential information that couples the internal state to the observations is provided by the statistical correlations from a numerical dynamo model in the form of a model covariance matrix. Here we test a sequential DA framework, working through a succession of forecast and analysis steps, that extracts the correlations from an ensemble of dynamo models. The primary correlations couple variables of the same azimuthal wave number, reflecting the predominant axial symmetry of the magnetic field. Synthetic tests show that the scheme becomes unstable when confronted with high-precision geomagnetic observations. Our study has identified spurious secondary correlations as the origin of the problem. Keeping only the primary correlations by localizing the covariance matrix with respect to the azimuthal wave number suffices to stabilize the assimilation. While the first analysis step is fundamental in constraining the large-scale interior state, further assimilation steps refine the smaller and more dynamical scales. This refinement turns out to be critical for long-term geomagnetic predictions. Increasing the assimilation steps from one to 18 roughly doubles the prediction horizon for the dipole from about tree to six centuries, and from 30 to about 60 yr for smaller observable scales. This improvement is also reflected on the predictability of surface intensity features such as the South Atlantic Anomaly. Intensity prediction errors are decreased roughly by a half when assimilating long observation sequences.
Swimming performance can be improved not only by in-water sport-specific training but also by means of dry land-training (e.g., plyometric jump training [PJT]). This study examined the effects of an 8-week PJT on proxies of muscle power and swimming performance in prepubertal male swimmers. Participants were randomly allocated to a PJT group (PJT; n = 14; age: 10.3 +/- 0.4 years, maturity-offset = -3 +/- 0.3) or a control group (CG; n = 12; age: 10.5 +/- 0.4 years, maturity-offset = -2.8 +/- 0.3). Swimmers in PJT and CG performed 6 training sessions per week. Each training session lasted between 80 and 90 minutes. Over the 8 weeks in-season training period, PJT performed two PJT sessions per week, each lasting between 25 to 30 minutes (similar to 1 hour per week) in replacement of sport-specific swimming drills. During that time, CG followed their regular sport-specific swimming training (e.g., coordination, breathing, improving swimming strokes). Overall training volume was similar between groups. Pre- and post-training, tests were conducted to assess proxies of muscle power (countermovement-jump [CMJ]), standing-long-jump [SLJ]) and sport-specific swimming performances (15-, 25-, and 50-m front-crawl, 25-m kick without push [25-m kick WP], and 25-m front-crawl WP). No training or test-related injuries were detected over the course of the study. Between-group analyses derived from magnitude-based inferences showed trivial-to-large effects in favour of PJT for all tests (ES = 0.28 to 1.43). Within-group analyses for the PJT showed small performance improvements for CMJ (effect-size [ES] = 0.53), 25-m kick WP (ES = 0.25), and 50-m front crawl (ES = 0.56) tests. Moderate performance improvements were observed for the SLJ, 25-m front-crawl WP, 15-m and 25-m front-crawl tests (ES = 0.95, 0.60, 0.99, and 0.85, respectively). For CG, the within-group results showed trivial performance declines for the CMJ (ES=-0.13) and the 50-m front-crawl test (ES = -0.04). In addition, trivial-to-small performance improvements were observed for the SLJ (ES = 0.09), 25-m kick WP (ES = 0.02), 25-m front-crawl WP (ES = 0.19), 25-m front-crawl (ES = 0.2), (SLJ [ES = 0.09, and 15-m front crawl (ES = 0.36). Short-term in-season PJT, integrated into the regular swimming training, was more effective than regular swimming training alone in improving jump and sport-specific swimming performances in prepubertal male swimmers.