Wissenschaftliche Artikel der BAM
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Xenobiotics and their reactive metabolites are conjugated with native biomolecules such as glutathione and glucoside during phase II metabolism. Toxic metabolites are usually detoxified during this step. On the other hand, these reactive species have a potential health impact by disrupting many enzymatic functions. Thus, it is crucial to understand phase II conjugation reactions of xenobiotics in order to address their fate and possible toxicity mechanisms.
Additionally, conventional methods (in vivo and in vitro) have limitation due to matrix complexity and time-consuming. Hence, developing fast and matrix-free alternative method is highly demandable. In this work, oxidative phase I metabolites and reactive species of chlorpyrifos (insecticide) and fluopyram (fungicide) were electrochemically produced by using a boron-doped diamond electrode coupled online to electrospray mass spectrometry (ESI-MS). Reactive species of the substrates were trapped by biomolecules (glutathione and glucoside) and phase II conjugative metabolites were identified using liquid chromatography (LC)-MS/MS, and/or Triple time of flight (TripleTOF)-MS. Glutathione conjugates and glucosylation of chlorpyrifos, trichloropyridinol, oxon, and monohydroxyl fluopyram were identified successfully. Glutathione and glucoside were conjugated with chlorpyrifos, trichloropyridinol, and oxon by losing a neutral HCl. In the case of fluopyram, its monohydroxyl metabolite was actively conjugated with both glutathione and glucoside. In summary, seven bioconjugates of CPF and its metabolites and two bioconjugates of fluopyram metabolites were identified using electrochemistry (EC)/MS for the first time in this work. The work could be used as an alternative approach to identify glutathione and glucosylation conjugation reactions of other organic compounds too. It is important, especially to predict phase II conjugation within a short time and matrix-free environment.
Evidence for the formation of difluoroacetic acid in chlorofluorocarbon-contaminated ground water
(2019)
The concentrations of difluoroacetic acid (DFA) and trifluoroacetic acid (TFA) in rainwater and surface water from Berlin, Germany resembled those reported for similar urban areas, and the TFA/DFA ratio in rainwater of 10:1 was in accordance with the literature. In contrast, nearby ground water historically contaminated with 1,1,2-trichloro-1,2,2-trifluoroethane (R113) displayed a TFA/DFA ratio of 1:3. This observation is discussed versus the inventory of microbial Degradation products present in this ground water along with the parent R113 itself. A microbial Transformation of chlorotrifluoroethylene (R1113) to DFA so far has not been reported for environmental media, and is suggested based on well-established mammalian metabolic pathways.
The phase behavior and molecular ordering of hexakishexyloxy triphenylene (HAT6) DLC under cylindrical nanoconfinement is studied utilizing differential scanning calorimetry (DSC) and dielectric spectroscopy (DS), where cylindrical nanoconfinement is established through embedding HAT6 into the nanopores of anodic aluminum oxide membranes (AAO), and a silica membrane with pore diameters ranging from 161 nm down to 12 nm. Both unmodified and modified pore walls were considered, and in the latter case the pore walls of AAO membranes were chemical treated with n octadecylphosphonic acid (ODPA) resulting in the formation of a 2.2 nm thick layer of grafted alkyl chains. Phase transition enthalpies decrease with decreasing pore size, indicating that a large proportion of the HAT6 molecules within the pores has a disordered structure, which increases with decreasing pore size for both pore walls. In the case of the ODPA modification the amount of ordered HAT6 is increased compared to the unmodified case. The pore size dependencies of the phase transition temperatures were approximated using the Gibbs Thomson equation, where the estimated surface tension is dependent on the molecular ordering of HAT6 molecules within the pores and upon their surface. DS was employed to investigate the molecular ordering of HAT6 within the nanopores. These investigations revealed that with a pore size of around 38 nm, for the samples with the unmodified pore walls, the molecular ordering changes from planar axial to homeotropic radial. However, the planar axial configuration, which is suitable for electronic applications, can be successfully preserved through ODPA modification for most of the pore sizes.
We investigate the nearfield dipole mobility of protein membranes in a wide frequency range from 3 kHz to 10 GHz. The results of our nanoscale dielectric images and spectra of bacteriorhodopsin (bR) reveal Debye relaxations with time constants of τ ∼ 2 ns and τ ∼ 100 ns being characteristic of the Dipole moments of the bR retinal and α-helices, respectively. However, the dipole mobility and therefore the protein biophysical function depend critically on the amount of surface water surrounding the protein, and the characteristic mobility in the secondary structure is only observed for humidity levels <30%. Our results have been achieved by adding the frequency as a second fundamental dimension to quantitative dielectric microscopy. The key elements for the success of this advanced technique are the employed heterodyne detection scheme, the broadband electrical signal source, a high frequency optimized cabling, development of calibration procedures and precise finite element modelling. Our study demonstrates the exciting possibilities of broadband dielectric microscopy for the investigation of dynamic processes in cell bioelectricity at the individual molecular level. Furthermore, the technique may shed light on local dynamic processes in related materials science applications like semiconductor Research or nano-electronics.
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.
Automated modal analysis for tracking structural change during construction and operation phases
(2019)
The automated modal analysis (AMA) technique has attracted significant interest over the last few years, because it can track variations in modal parameters and has the potential to detect structural changes. In this paper, an improved density-based spatial clustering of applications with noise (DBSCAN) is introduced to clean the abnormal poles in a stabilization diagram. Moreover, the optimal system model order is also discussed to obtain more stable poles. A numerical Simulation and a full-scale experiment of an arch bridge are carried out to validate the effectiveness of the proposed algorithm. Subsequently, the continuous dynamic monitoring system of the bridge and the proposed algorithm are implemented to track the structural changes during the construction phase. Finally, the artificial neural network (ANN) is used to remove the temperature effect on modal frequencies so that a health index can be constructed under operational conditions.
We propose to use artificial neural networks (ANNs) for raw measurement data interpolation and signal shift computation and to demonstrate advantages for wavelength-scanning coherent optical time domain reflectometry (WS-COTDR) and dynamic strain distribution measurement along optical fibers. The ANNs are trained with synthetic data to predict signal shifts from wavelength scans. Domain adaptation to measurement data is achieved, and standard correlation algorithms are outperformed. First and foremost, the ANN reduces the data analysis time by more than two orders of magnitude, making it possible for the first time to predict strain in real-time applications using the WS-COTDR approach. Further, strain noise and linearity of the sensor response are improved, resulting in more accurate measurements. ANNs also perform better for low signal-to-noise measurement data, for a reduced length of correlation input (i.e., extended distance range), and for coarser sampling settings (i.e., extended strain scanning range). The general applicability is demonstrated for distributed measurement of ground movement along a dark fiber in a telecom cable. The presented ANN-based techniques can be employed to improve the performance of a wide range of correlation or interpolation problems in fiber sensing data analysis and beyond.
Combining X-ray Absorption Fine Spectroscopy (XAFS) with Anomalous Small-Angle X-ray Scattering (ASAXS) determines the location of Cu2+ ions in silicoaluminophosphate (SAPO-5) frameworks prepared by hydrothermal crystallization or impregnation. As expected, for the hydrothermally prepared sample, incorporation in the SAPO-5 framework was observed. For the first time preferential location of Cu2+ ions at the inner and outer surfaces of the framework is determined. Temperature-Programmed Reduction (TPR) and X-ray Photoelectron Spectroscopy (XPS) investigations demonstrated that such Cu2+ is stable in an argon (Ar) atmosphere up to 550 °C and can only be reduced under a hydrogen atmosphere. In contrast, Cu2+ deposited by impregnation on the pure SAPO-5 framework can be easily reduced to Cu+ in an Ar atmosphere. At lower Cu amounts, mononuclear tetrahedrally coordinated Cu species were formed which are relatively stable in the monovalent form. In contrast, at higher Cu amounts, CuO particles were found which change easily between the mono- and bivalent species.
Simulating fiber-reinforced concrete mechanical performance using CT-based fiber orientation data
(2019)
The main hindrance to realistic models of fiber-reinforced concrete (FRC) is the local materials property variation, which does not yet reliably allow simulations at the structural level. The idea presented in this paper makes use of an existing constitutive model, but resolves the problem of localized material variation through X-ray computed tomography (CT)-based pre-processing. First, a three-point bending test of a notched beam is considered, where pre-test fiber orientations are measured using CT. A numerical model is then built with the zone subjected to progressive damage, modeled using an orthotropic damage model. To each of the finite elements within this zone, a local coordinate system is assigned, with its longitudinal direction defined by local fiber orientations. Second, the parameters of the constitutive damage model are determined through inverse analysis using load-displacement data obtained from the test. These parameters are considered to clearly explain the material behavior for any arbitrary external action and fiber orientation, for the same geometrical properties and volumetric ratio of fibers. Third, the effectiveness of the resulting model is demonstrated using a second, “control” experiment. The results of the “control” experiment analyzed in this research compare well with the model results. The ultimate strength was predicted with an error of about 6%, while the work-of-load was predicted within 4%. It demonstrates the potential of this method for accurately predicting the mechanical performance of FRC components.
This paper describes a novel methodology for quantitative in-situ moisture measurement without tracking agents using X-ray computed tomography (XCT). The high levels of grey-scale precision required for the measurement of moisture without tracking agents resulted in the need for an additional image calibration procedure to correct for water-related X-ray scattering and for equipment-variability related artefacts arising during in-situ testing. This calibration procedure was developed on the basis of existing principles of XCT image cor-rection. Resulting images of moisture distribution exhibit a high level of agreement with expected material behaviour. This research demonstrated that XCT can be successfully used to measure both moisture-front movement over time and changes in 3D moisture distribution within samples. This approach to moisture measurement lays the groundwork for the planned future investigation of the interaction between cracking induced by varying chemical and mechanical processes and water transport in concrete.