TY - JOUR A1 - Schütz, Roman A1 - Bertinetti, L. A1 - Rabin, Ira A1 - Fratzl, P. A1 - Masic, A. T1 - Quantifying degradation of collagen in ancient manuscripts: the case of the Dead Sea Temple Scroll N2 - Since their discovery in the late 1940s, the Dead Sea Scrolls, some 900 ancient Jewish texts, have never stopped attracting the attention of scholars and the broad public alike, because they were created towards the end of the Second Temple period and the 'time of Christ'. Most of the work on them has been dedicated to the information contained in the scrolls' text, leaving physical aspects of the writing materials unexamined. They are, however, crucial for both historical insight and preservation of the scrolls. Although scientific analysis requires handling, it is essential to establish the state of degradation of these valued documents. Polarized Raman Spectroscopy (PRS) is a powerful tool for obtaining information on both the composition and the level of disorder of molecular units. In this study, we developed a non-invasive and non-destructive methodology that allows a quantification of the disorder (that can be related to the degradation) of protein molecular units in collagen fibers. Not restricted to collagen, this method can be applied also to other protein-based fibrous materials such as ancient silk, wool or hair. We used PRS to quantify the degradation of the collagen fibers in a number of fragments of the Temple Scroll (11Q19a). We found that collagen fibers degrade heterogeneously, with the ones on the surface more degraded than those in the core. KW - Dead Sea Scrolls KW - Collagen KW - Raman spectroscopy PY - 2013 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-331769 DO - https://doi.org/10.1039/c3an00609c SN - 0003-2654 SN - 1364-5528 VL - 138 IS - 19 SP - 5594 EP - 5599 PB - Royal Society of Chemistry CY - Cambridge AN - OPUS4-33176 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Seuthe, T. A1 - Mermillod-Blondin, A. A1 - Grehn, M. A1 - Bonse, Jörn A1 - Wondraczek, L. A1 - Eberstein, M. T1 - Structural relaxation phenomena in silicate glasses modifed by irradiation with femtosecond laser pulses N2 - Structural relaxation phenomena in binary and multicomponent lithium silicate glasses were studied upon irradiation with femtosecond (fs) laser pulses (800 nm central wavelength, 130 fs pulse duration) and subsequent thermal annealing experiments. Depending on the annealing temperature, micro-Raman spectroscopy analyses evidenced different relaxation behaviours, associated to bridging and non-bridging oxygen structures present in the glass network. The results indicate that the mobility of lithium ions is an important factor during the glass modification with fs-laser pulses. Quantitative phase contrast imaging (spatial light interference microscopy) revealed that these fs-laser induced structural modifications are closely related to local changes in the refractive index of the material. The results establish a promising strategy for tailoring fs-laser sensitivity of glasses through structural mobility. KW - Femtosecond laser KW - Silicate glasses KW - Raman spectroscopy KW - Structural relaxation KW - Refractive index PY - 2017 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-393045 DO - https://doi.org/10.1038/srep43815 SN - 2045-2322 VL - 7 SP - 43815, 1 EP - 43815, 10 PB - Nature Publishing Group CY - London, UK AN - OPUS4-39304 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Hahn, Marc Benjamin A1 - Uhlig, F. A1 - Solomun, Tihomir A1 - Smiatek, J. A1 - Sturm, Heinz T1 - Combined influence of ectoine and salt: spectroscopic and numerical evidence for compensating effects of aqueous solutions N2 - Ectoine is an important osmolyte, which allows microorganisms to survive in extreme environmental salinity. The hygroscopic effects of ectoine in pure water can be explained by a strong water binding behavior whereas a study on the effects of ectoine in salty solution is yet missing. We provide Raman spectroscopic evidence that the influence of ectoine and NaCl are opposing and completely independent of each other. The effect can be explained by the formation of strongly hydrogen-bonded water molecules around ectoine which compensate the influence of the salt on the water dynamics. The mechanism is corroborated by first principles calculations and broadens our understanding of zwitterionic osmolytes in aqueous solution. Our findings allow us to provide a possible explanation for the relatively high osmolyte concentrations in halotolerant bacteria. KW - Ectoine KW - Aqueous solution KW - Biological structure KW - Organic osmolytes KW - Raman spectroscopy KW - Water structure PY - 2016 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-376761 UR - http://pubs.rsc.org/en/content/articlelanding/2016/cp/c6cp05417j#!divAbstract DO - https://doi.org/10.1039/c6cp05417j VL - 18 IS - 41 SP - 28398 EP - 28402 PB - Royal Society of Chemistry CY - UK AN - OPUS4-37676 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Fankhänel, J. A1 - Silbernagl, Dorothee A1 - Ghasem Zadeh Khorasani, Media A1 - Daum, B. A1 - Kempe, A. A1 - Sturm, Heinz A1 - Rolfes, R. T1 - Mechanical properties of Boehmite evaluated by Atomic Force Microscopy experiments and Molecular Dynamic Finite Element simulations N2 - Boehmite nanoparticles show great potential in improving mechanical properties of fiber reinforced polymers. In order to predict the properties of nanocomposites, knowledge about the material parameters of the constituent phases, including the boehmite particles, is crucial. In this study, the mechanical behavior of boehmite is investigated using Atomic Force Microscopy (AFM) experiments and Molecular Dynamic Finite Element Method (MDFEM) simulations. Young’s modulus of the perfect crystalline boehmite nanoparticles is derived from numerical AFM simulations. Results of AFM experiments on boehmite nanoparticles deviate significantly. Possible causes are identified by experiments on complementary types of boehmite, that is, geological and hydrothermally synthesized samples, and further simulations of imperfect crystals and combined boehmite/epoxy models. Under certain circumstances, the mechanical behavior of boehmite was found to be dominated by inelastic effects that are discussed in detail in the present work.The studies are substantiated with accompanying X-ray diffraction and Raman experiments. KW - AFM KW - MDFEM KW - Nanocomposite KW - Epoxy KW - X-ray diffraction KW - Raman spectroscopy KW - Young’s modulus KW - Slippage of weakly linked layers PY - 2016 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-384230 UR - https://www.hindawi.com/journals/jnm/2016/5017213/#B26 DO - https://doi.org/10.1155/2016/5017213 VL - 2016 IS - Article ID 5017213 SP - 1 EP - 13 PB - Hindawi Publishing Corporation AN - OPUS4-38423 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Hahn, Marc Benjamin A1 - Susann, Meyer A1 - Schröter, Maria-Astrid A1 - Kunte, Hans-Jörg A1 - Solomun, Tihomir A1 - Sturm, Heinz T1 - DNA protection by ectoine from ionizing radiation: molecular mechanisms N2 - Ectoine, a compatible solute and osmolyte, is known to be an effective protectant of biomolecules and whole cells against heating, freezing and extreme salinity. Protection of cells (human keratinocytes) by ectoine against ultraviolet radiation has also been reported by various authors, although the underlying mechanism is not yet understood. We present the first electron irradiation of DNA in a fully aqueous environment in the presence of ectoine and at high salt concentrations. The results demonstrate effective protection of DNA by ectoine against the induction of single-strand breaks by ionizing radiation. The effect is explained by an increase in low-energy electron scattering at the enhanced free-vibrational density of states of water due to ectoine, as well as the use of ectoine as an ˙OH-radical scavenger. This was demonstrated by Raman spectroscopy and electron paramagnetic resonance (EPR). KW - Ectoine KW - DNA KW - Radiation protection KW - Ionizing radiation KW - Compatible solute KW - Biomolecules KW - Sodium chloride KW - Aqueous solution KW - Hydroxyectoine KW - Raman spectroscopy KW - Electron irradiation KW - Cancer KW - Radical scavenger KW - Low energy electrons KW - Hydroxyl radical KW - OH-radical KW - Ectoin KW - UV radiation KW - Sun KW - Salt KW - Radiation therapy PY - 2017 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-419332 UR - http://pubs.rsc.org/en/content/articlehtml/2017/cp/c7cp02860a DO - https://doi.org/10.1039/C7CP02860A SN - 1463-9076 VL - 19 IS - 37 SP - 25717 EP - 25722 PB - Royal Society of Chemistry CY - United Kingdom AN - OPUS4-41933 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Batzdorf, Lisa A1 - Emmerling, Franziska T1 - Mechanochemical synthesis and characterisation of cocrystals and metal-organic compounds N2 - The mechanochemical synthesis of two model compounds, a metal organic framework ([Bi(1,4-bdc)2]*(Im) (bdc = benzene dicarboxylate, Im = imidazole cation)) and a cocrystal (Carbamazepine:Indometacin 1:1) were followed ex situ by combined analytical methods. Powder X-ray diffraction (XRD) and Raman spectroscopy data were evaluated for the synthesis of the metal organic framework. XRD measurements and REM images were analysed for the synthesis of the cocrystal. The measurements revealed that both model compounds were synthesised within minutes. The metal organic framework [Bi(1,4-bdc)2]*(Im) is synthesised via an intermediate structure. The cocrystal Carbamazepine:Indometacin 1:1 is formed within few seconds and afterwards the crystallite size decreases extremely. KW - Powder X-ray diffraction (XRD) KW - Raman spectroscopy KW - mechanochemical synthesis PY - 2014 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-306305 UR - http://pubs.rsc.org/en/content/articlepdf/2014/fd/c3fd00163f DO - https://doi.org/10.1039/C3FD00163F SN - 1359-6640 SN - 1364-5498 N1 - Geburtsname von Batzdorf, Lisa: Tröbs, L. - Birth name of Batzdorf, Lisa: Tröbs, L. SP - 109 EP - 119 PB - RSC CY - Cambridge [u.a.] AN - OPUS4-30630 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Hinrichs, R. A1 - Zen Vasconcellos, M.A. A1 - Österle, Werner A1 - Prietzel, C. T1 - Amorphization of graphite flakes in gray cast iron under tribological load N2 - A gray cast iron disc, which had been submitted to a heavy duty automotive brake test, was examined with energy filtered transmission electron microscopy. A graphite flake in a convenient angular position showed the shear interaction of graphite layers with the iron matrix in nano-scale resolution. Atomic layers of graphite were wedged into the ferritic bulk, allowing the entrance of oxygen and the subsequent formation of magnetite. The exfoliated few-layer graphene batches deformed heavily when forced into the matrix. When Raman spectra from the disc surface, which show distinctive carbonaceous bands, were compared with Raman spectra from graphite subjected to deformation in a shaker mill with different milling times, it could be seen that the shear stress on the brake surface was much more effective to induce disorder than the milling, where compressive and impact forces had been additionally exerted on the sample. During shear load the high anisotropy of elastic modulus in the graphite crystalline structure and the low adhesion between graphite basal planes allowed the exfoliation of wrinkled few-layer grapheme batches, causing the formation of more defect related Raman bands than the mechanical stress during high-energy milling. KW - Graphite KW - Shear load KW - Amorphization KW - EFTEM KW - Raman spectroscopy PY - 2018 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-469227 DO - https://doi.org/10.1590/1980-5373-MR-2017-1000 SN - 1516-1439 SN - 1980-5373 VL - 21 IS - 4 SP - e20171000, 1 EP - 6 PB - Universidade Federal de São Carlos CY - São Carlos AN - OPUS4-46922 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Sarhan, R. M. A1 - Koopman, W. A1 - Schuetz, R. A1 - Schmid, Thomas A1 - Liebig, F. A1 - Koetz, J. A1 - Bargheer, M. T1 - The importance of plasmonic heating for the plasmondriven photodimerization of 4-nitrothiophenol N2 - 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. KW - Nanoparticles KW - Plasmonic heating KW - Raman spectroscopy PY - 2019 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-475140 DO - https://doi.org/10.1038/s41598-019-38627-2 SN - 2045-2322 VL - 9 IS - 1 SP - 3060, 1 EP - 8 PB - Nature Publishing Group AN - OPUS4-47514 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Steger, Simon A1 - Oesterle, D. A1 - Bretz, S. A1 - Frenzel, L. A1 - Stege, H. A1 - Winkelmeyer, I. A1 - Hahn, Oliver A1 - Geiger, G. T1 - Kandinsky’s fragile art: a multidisciplinary investigation of four early reverse glass paintings (1911–1914) by Wassily Kandinsky N2 - This work highlights the rediscovery of the technique of reverse glass painting by the artists of the “Blaue Reiter” collective in the early 20th-century and focusses particularly on the role of Wassily Kandinsky (1866–1944). Kandinsky created more than 70 reverse paintings on glass and showed several of them in exhibitions together with paintings on canvas and cardboard, implying a coequal importance of these techniques. Four of his early (1911–1914) reverse glass paintings (Auferstehung, Allerheiligen II, Rudern, Apokalyptischer Reiter II) were selected for investigation and their iconography, painting techniques and painting materials were examined. Two paintings were executed on so-called cathedral glass, revealing a “hammered surface”, whereas Kandinsky used a corrugated glass panel for Rudern. A multi-analytical, non-invasive approach [X-ray fluorescence (XRF), diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), VIS spectroscopy (VIS), Raman spectroscopy] was taken to identify the pigments and classify the binding media. The results reveal a broad palette of materials. Several pigments like lead white, zinc white, Strontium yellow, Prussian blue, viridian, cadmium yellow, ultramarine blue, cinnabar and carbon black were found in most of the four paintings. The use of the rare synthetic organic pigments PR60 and PB52 is discussed. In two works of art, cadmium carbonate is associated with cadmium yellow. The identification of aluminium foil along with tin foils in Rudern indicates an early use of this material for reverse glass paintings. KW - Reverse glass painting KW - Non-invasive analysis KW - Raman spectroscopy KW - DRIFTS PY - 2019 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-480075 DO - https://doi.org/10.1186/s40494-019-0268-8 VL - 7 IS - 27 SP - 1 EP - 17 PB - Springer AN - OPUS4-48007 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Stoch, P. A1 - Szczerba, Wojciech A1 - Bodnar, W. A1 - Ciecinska, M. A1 - Stoch, A. A1 - Burkel, E. T1 - Structural properties of iron-phosphate glasses: spectroscopic studies and ab initio simulations N2 - Vitrification is the most effective method for the immobilization of hazardous waste by incorporating toxic elements into a glass structure. Iron phosphate glasses are presently being considered as matrices for the storage of radioactive waste, even of those which cannot be vitrified using conventional borosilicate waste glass. In this study, a structural model of 60P2O5–40Fe2O3 glass is proposed. The model is based on the crystal structure of FePO4 which is composed of [FeO4][PO4] tetrahedral rings. The rings are optimized using the DFT method and the obtained theoretical FTIR and Raman spectra are being compared with their experimental counterparts. Moreover, the proposed model is in very good agreement with X-ray absorption fine structure spectroscopy (XANES/EXAFS) and Mössbauer spectroscopy measurements. According to the calculations the Fe3+ is in tetrahedral and five-fold coordination. The maximal predicted load of waste constituents into the glass without rebuilding of the structure is 30 mol%. Below this content, waste constituents balance the charge of [FeO4]- tetrahedra which leads to their strong bonding to the glass resulting in an increase of the chemical durability, transformation and melting temperatures and density. KW - Glass KW - Iron KW - DFT simulations KW - Mössbauer spectroscopy KW - XANES/EXAFS KW - FTIR spectroscopy KW - Raman spectroscopy KW - Coordination PY - 2014 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-317351 DO - https://doi.org/10.1039/c4cp03113j SN - 1463-9076 SN - 1463-9084 VL - 16 IS - 37 SP - 19917 EP - 19927 PB - The Royal Soc. of Chemistry CY - Cambridge AN - OPUS4-31735 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER -