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- Amino acid (1)
- Aqueous solution (1)
- Biological structure (1)
- Carbon nanotube CNT (1)
- Curing kinetics (1)
- DSC (1)
- Epoxy resins (1)
- Fluorescence labeling (1)
- Gene-5 protein (1)
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In this paper we present results of our recent efforts to understand the mechanical interface behaviour of single-walled carbon nanotubes (CNTs) embedded in metal matrices. We conducted experimental pull-out tests of CNTs embedded in Pd or Au and found Maximum forces in the range 10 - 102 nN. These values are in good agreement with forces obtained from molecular Dynamics simulations taking into account surface functional Groups (SFGs) covalently linked to the CNT material. The dominant failure mode in experiment is a CNT rupture, which can be explained with the presence of SFGs. To qualify the existence of SFGs on our used CNT material, we pursue investigations by means of fluorescence labeling of surface species in combination with Raman imaging. We also report of a tensile test system to perform pull-out tests inside a transmission electron microscope to obtain in situ images of CNT-metal interfaces under mechanical loads at the atomic scale.
Near-infrared spectroscopy (NIR) turned out to be well suited for analyzing the degree of cure for epoxy systems. In contrast to dynamic scanning calorimetry (DSC), where the released heat of reaction determines the degree of epoxy conversion indirectly, NIR spectroscopy is able to determine the conversion directly by analyzing structural changes. Therefore, a new heatable NIR cell was equipped with an integrated thermocouple, which enables the real sample temperature to be controlled and monitored in situ during epoxy curing. Dynamic scans at different heating rates were used for kinetic modelling, to define kinetic parameters and to predict real curing processes. The kinetic models and their parameters were validated with an isothermal and a more complex multi-step curing scenario. Two available commercial epoxy systems based on DGEBA were used with an anhydride and with an amine hardener. NIR results were compared with DSC data. The simulated conversion predicted with a model fitted on the basis of NIR and DSC dynamic scans showed good agreement with the conversion measured in the isothermal curing validation test. Due to the proven reliability of NIR in measuring the reaction progress of curing, it can be considered a versatile measurement system for in situ monitoring of component production in the automotive, aerospace and wind energy sectors.
The thermal molecular degradation of polyamide 66 (PA 66) doped with (partially supported) metal oxide particles (Fe2O3, ZnO, Al2O3) was investigated qualitatively and quantitatively using common analysis techniques like thermogravimetry coupled with IR-spectroscopic evolved gas analysis (TGA-FTIR). Using pyrolysis coupled with gas chromatography mass spectrometry (Py-GC-MS), qualitative conclusions were drawn about the complex hydrocarbon products. However, the combination of TGA with solid-phase extraction, followed by thermal desorption gas chromatography mass spectrometry (TED-GC-MS), allows qualitative and even semi-quantitative conclusions about the decomposition pathway of PA 66 in the presence of various metal oxide particles.
The investigations under inert conditions showed that the presence of metal particles increases the rate of decarboxylation and deamination reactions, as well as the formation rate of cyclopentanone and pyridine derivatives. These species are a consequence of various condensation reactions. The condensation reactions release a large amount of water, thus triggering the hydrolysis of PA 66. Molecular thermal degradation mechanisms were developed for the main decomposition as well as for the condensation reactions and supported by quantum chemical calculations. The catalytic effect of the metal oxides in PA 66 increases in the following order: PA 66 = PA 66 – Al2O3 < PA 66 – Fe2O3 < PA 66 – ZnO.
Microorganisms accumulate molar concentrations of compatible solutes like ectoine to prevent proteins from denaturation. Direct structural or spectroscopic information on the mechanism and about the hydration shell around ectoine are scarce. We combined surface plasmon resonance (SPR), confocal Raman spectroscopy, molecular dynamics simulations, and density functional theory (DFT) calculations to study the local hydration shell around ectoine and its influence on the binding of a gene-S-protein (G5P) to a single-stranded DNA (dT(25)). Due to the very high hygroscopicity of ectoine, it was possible to analyze the highly stable hydration shell by confocal Raman spectroscopy. Corresponding molecular dynamics simulation results revealed a significant change of the water dielectric constant in the presence of a high molar ectoine concentration as compared to pure water. The SPR data showed that the amount of protein bound to DNA decreases in the presence of ectoine, and hence, the protein-DNA dissociation constant increases in a concentration-dependent manner. Concomitantly, the Raman spectra in terms of the amide I region revealed large changes in the protein secondary structure. Our results indicate that ectoine strongly affects the molecular recognition between the protein and the oligonudeotide, which has important consequences for osmotic regulation mechanisms.