Wissenschaftliche Artikel der BAM
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Development of theranostic concepts that include inductively coupled plasma mass spectrometry (ICP-MS) and laser ablation ICP-MS (LA-ICP-MS) imaging can be hindered by the lack of a direct comparison to more standardly used methods for in vitro and in vivo evaluation; e.g. fluorescence or nuclear medicine. In this study a bimodal (or rather, hybrid) tracer that contains both a fluorescent dye and a chelate was used to evaluate the existence of a direct link between mass spectrometry (MS) and in vitro and in vivo molecular imaging findings using fluorescence and radioisotopes. At the same time, the hybrid label was used to determine whether the use of a single isotope label would allow for MS-based diagnostics.
The excitation of localized surface plasmons in noble metal nanoparticles (NPs) results in different nanoscale effects such as electric field enhancement, the generation of hot electrons and a temperature increase close to the NP surface. These effects are typically exploited in diverse fields such as surface-enhanced Raman scattering (SERS), NP catalysis and photothermal therapy (PTT). Halogenated nucleobases are applied as radiosensitizers in conventional radiation cancer therapy due to their high reactivity towards secondary electrons. Here, we use SERS to study the transformation of 8-bromoadenine (8BrA) into adenine on the surface of Au and AgNPs upon irradiation with a low-power continuous wave laser at 532, 633 and 785 nm, respectively. The dissociation of 8BrA is ascribed to a hot-electron transfer reaction and the underlying kinetics are carefully explored. The reaction proceeds within seconds or even milliseconds. Similar dissociation reactions might also occur with other electrophilic molecules, which must be considered in the interpretation of respective SERS spectra. Furthermore, we suggest that hot-electron transfer induced dissociation of radiosensitizers such as 8BrA can be applied in the future in PTT to enhance the damage of tumor tissue upon irradiation.
Distributed measurement of humidity is a sought-after capability for various fields of application, especially in the civil engineering and structural health monitoring sectors. This article presents a method for distributed humidity sensing along polymethyl methacrylate (PMMA) polymer optical fibers (POFs) by analyzing wavelength-dependent Rayleigh backscattering and attenuation characteristics at 500 nm and 650 nm wavelengths. Spatially resolved humidity sensing is obtained from backscatter traces of a dual-wavelength optical time domain reflectometer (OTDR). Backscatter dependence, attenuation dependence as well as the fiber length change are characterized as functions of relative humidity. Cross-sensitivity effects are discussed and quantified. The evaluation of the humidity-dependent backscatter effects at the two wavelength measurements allows for distributed and unambiguous measurement of relative humidity. The technique can be readily employed with low-cost standard polymer optical fibers and commercial OTDR devices.
This article reports on the characterization of four superparamagnetic iron oxide nanoparticles stabilized with dimercaptosuccinic acid, which are suitable candidates for reference materials for magnetic properties. Particles p1 and p2 are single-core particles, while p3 and p4 are multi-core particles. Small-angle X-ray scattering analysis reveals a lognormal type of size distribution for the iron oxide cores of the particles. Their mean radii are 6.9 nm (p1), 10.6 nm (p2), 5.5 nm (p3) and 4.1 nm (p4), with narrow relative distribution widths of 0.08, 0.13, 0.08 and 0.12. The cores are arranged as a clustered network in the form of dense mass fractals with a fractal dimension of 2.9 in the multi-core particles p3 and p4, but the cores are well separated from each other by a protecting organic shell. The radii of gyration of the mass fractals are 48 and 44 nm, and each network contains 117 and 186 primary particles, respectively. The radius distributions of the primary particle were confirmed with transmission electron microscopy. All particles contain purely maghemite, as shown by X-ray absorption fine structure spectroscopy
Ti-6Al-4V bridges were additively fabricated by selective laser melting (SLM) under different scanning speed conditions, to compare the effect of process energy density on the residual stress state. Subsurface lattice strain characterization was conducted by means of synchrotron diffraction in energy dispersive mode. High tensile strain gradients were found at the frontal surface for samples in an as-built condition. The geometry of the samples promotes increasing strains towards the pillar of the bridges. We observed that the higher the laser energy density during fabrication, the lower the lattice strains. A relief of lattice strains takes place after heat treatment.
In granular soils, long-term cyclically loaded structures can lead to an accumulation of irreversible strain by forming closed convective cells in the upper layer of the bedding. The size of the convective cell, its formation and grain migration inside this closed volume have been studied with reference to different stiffness of the embedded structure and different maximum force amplitudes applied at the head of the structure.
This relation was experimentally investigated by applying a cyclic lateral force to a scaled flexible vertical element embedded in a dry granular soil. The model was monitored with a camera in order to derive the displacement field by means of the PIV technique. Furthermore, the ratcheting convective cell was also simulated with DEM with the aim of extracting some micromechanical information. The main results regarded the different development, shape and size of the convection cell and the surface settlements.
A controlled, reproducible, gram-scale method is reported for the covalent functionalization of graphene Sheets by a one-pot nitrene [2+1] cycloaddition reaction under mild conditions. The reaction between commercially available 2,4,6-trichloro-1,3,5-triazine and sodium azide with thermally reduced graphene oxide (TRGO) results in defined dichlorotriazine-functionalized sheets. The different reactivities of the chlorine substituents on the functionalized graphene allow stepwise post-modification by manipulating the temperature.
This new method provides unique access to defined bifunctional 2D nanomaterials, as exemplified by chiral surfaces and multifunctional hybrid architectures.
The duplex stainless steel 1.4062 (X2CrNiN22-2) is used as alternative material to austenitic stainless steels in the construction industry. The corrosion resistance of welded seams is influenced by the base material, the weld filler material, the welding process and also by the final surface treatment. The scale layer next to the weld seam can be removed by grinding, pickling, electro-polished or blasting depending on the application and the requested corrosion resistance. Blasted surfaces are often used in industrial practice due to the easier and cheaper manufacturing process compared to pickled or electro-polished surfaces. Furthermore blasting with corundum-grain is more effective than blasting with glass-beads which also lower the process costs. In recent years, stainless steel surfaces showed an unusually high susceptibility to pitting corrosion after grinding with corundum. For this reason, it is now also questioned critically whether the corrosion resistance is influenced by the applied blasting agent. This question was specifically investigated by comparing grinded, pickled, corundum-grain- and glass-bead-blasted welding seams. Results of the SEM analyses of the blasting agents and the blasted surfaces will be presented and correlated with the different performed corrosion tests (potential measurement, KorroPad-test and pitting potential) on welding seams with different surface treatments.
The novel heat treatment concept, “quenching and partitioning” (Q&P) has been developed for high strength steels with enhanced formability. This heat treatment involves quenching of austenite to a temperature between martensite start and finish, to receive a several amount of retained austenite. During the subsequent annealing treatment, the so called partitioning, the retained austenite is stabilized due to carbon diffusion, which results in enhanced formability and strength regarding strain induced austenite to martensite transformation. In this study a Q&P heat treatment was applied to a Fe-0.45C-0.65Mn-0.34Si-13.95Cr stainless martensite. Thereby the initial quench end temperature and the partitioning time were varied to characterize their influence on microstructural evolution. The microstructural changes were analysed by dilatometer measurements, X-ray diffraction and scanning electron microscopy, including electron backscatter diffraction. Compression testing was made to examine the mechanical behaviour. It was found that an increasing partitioning time up to 30 min leads to an enhanced formability without loss in strength due to a higher amount of stabilized retained and reversed austenite as well as precipitation hardening.
Water and aqueous reagents are essential in any biological process or system. But apart from a few special low vapor-pressure cases, liquids have not been accessible to any technique requiring UHV conditions. EnviroESCA opens up this exciting field of applications.
In this paper first results from water based samples are presented as a proof of concept to demonstrate the special capabilities of EnviroESCA analyzing liquid samples. The following solutions were investigated under near ambient pressure conditions: i.) water, ii.) brine, iii.) an oil in water dispersion, iv.) aqueous iron(II) sulfate heptahydrate, and v.) a suspension of nano silver particles in water.
An UCST-type copolymer of acrylamide (AAm) and acrylonitrile (AN) (poly(AAm-co-AN)) was prepared by reversible addition fragmentation chain transfer (RAFT) polymerization and its temperature-induced phase transition and aggregation behaviour studied by turbidimetry, static and dynamic light scattering, small angle neutron scattering (SANS) and cryo-transmission electron microscopy (cryo-TEM) measurements. The phase transition temperature was found to increase with increasing AN content in the copolymer, concentration of the solutions and copolymer chain length. A significant effect was observed onto the phase transition temperature by addition of different electrolytes into the copolymer solution. The copolymer chains were aggregated below the phase transition temperature and disaggregated above it. The size of the aggregates increases with increasing AN contents and concentration of the copolymer solutions below the phase transition temperature. The copolymer chains were expanded and weekly associated in solution above the phase transition temperature. A model is proposed to explain such association–aggregation behaviour of poly(AAm-co-AN) copolymers depending on AN contents and concentration of the copolymer solutions as a function of temperature.
The paper presents a new method for the determination and evaluation of tafel factors using gel-type electrolytes and electrochemical frequency modulation technique (EFM). This relatively new electrochemical method offers the possibility to determine both polarization resistances and tafel factors within one measurement and in short measuring intervals. Starting from a comprehensive parameter study it is shown that a direct relationship between the two values exists that can be described mathematically. This contribution presents the determined tafel factors for the system gel-type electrolyte/zinc and discusses their applicability and their limits.
The CCQM-K123 key comparison was organized by the Inorganic Analysis Working Group (IAWG) of CCQM to assess and document the capabilities of the national metrology institutes (NMIs) or the designated institutes (DIs) to measure the mass fractions of sodium, calcium, potassium, magnesium phosphorous and sulfur in biodiesel fuel (BDF). The National Metrology Institute of Japan (NMIJ) and National Institute of Standards and Technology (NIST) acted as the coordinating laboratories.
Results were submitted by 11 NMIs and DIs. The participants used different measurement methods, though most of them used inductively coupled plasma-mass spectrometry (ICP-MS), isotope dilution technique with ICP-MS and inductively coupled plasma-optical emission spectrometry (ICP-OES) with microwave acid digestion.
The material was quite challenging and a number of questions were raised at the IAWG meeting. Concerning S, the variation in S results between participants, particularly those using IDMS methods was discussed at the IAWG meeting. BAM, NIST and NMIJ reviewed their experimental conditions, results and/or uncertainty calculations for IDMS. According to the additional evaluation and investigation, the variances between the revised results became smaller than the original one, the revised results were overlapping between IDMS measurements of S content at the k=2 level. It is not possible to calculate a KCRV with values being modified after submission. It was concluded that this KC does not support S measurements.
Accounting for relative expanded uncertainty, comparability of measurement results for each of Na, Ca, K, Mg and P was successfully demonstrated by the participating NMIs or DIs. It is expected that sodium, calcium, potassium, magnesium and phosphorus at mass fractions greater than approximately 0.1 mg/kg, 0.1 mg/kg, 0.05 mg/kg, 0.05 mg/kg and 0.1 mg/kg respectively in biodiesel fuel and similar matrices (fuels and oils etc.) can be determined by each participant using the same technique(s) employed for this key comparison to achieve similar uncertainties mentioned in the present report. Furthermore, the results of this key comparison can be utilized along with the IAWG core capability approach.
This work demonstrates that phase-segregated poly(ester urethane) (PEU) with switching segments of crystallizable poly(1,4-butylene adipate) (PBA) can be programmed to generate two separate stress recovery events upon heating under constant strain conditions. For programming, two elongations are applied at different temperatures, followed by unloading and cooling. During the adjacent heating, two-step stress recovery is triggered. The results indicate that the magnitude of the stress recovery signals corresponds to the recovery of the two deformation stresses in reverse order. As demonstrated by further experiments, twofold stress recovery can be detected as long as the elongation at higher temperature exceeds the strain level of the deformation at lower temperature. Another finding includes that varying the lower deformation temperature enables a control over the stress recovery temperature and thus the implementation of so-called “temperature-memory effects”. Moreover, exerting only one elongation during programming enables a heating-initiated one-step stress recovery close to the deformation temperature. Based on these findings, such polymers may offer new technological opportunities in the fields of active assembly when used as fastening elements and in functional clothing when utilized for compression stockings.
Referee Report 06 March 2017
(2017)
Driven mostly by the search for chemical syntheses under biocompatible conditions, so called "click" chemistry rapidly became a growing field of research. The resulting simple one-pot reactions are so far only scarcely accompanied by an adequate optimization via comparably straightforward and robust analysis techniques possessing short set-up times. Here, we report on a fast and reliable calibration-free online NMR monitoring approach for technical mixtures. It combines a versatile fluidic system, continuous-flow measurement of 1H spectra with a time interval of 20 s per spectrum, and a robust, fully automated algorithm to interpret the obtained data. As a proof-of-concept, the thiol-ene coupling between N-boc cysteine methyl ester and allyl alcohol was conducted in a variety of non-deuterated solvents while its time-resolved behaviour was characterized with step tracer experiments. Overlapping signals in online spectra during thiol-ene coupling could be deconvoluted with a spectral model using indirect hard modeling and were subsequently converted to either molar ratios (using a calibrationfree approach) or absolute concentrations (using 1-point calibration). For various solvents the kinetic constant k for pseudo-first order reaction was estimated to be 3.9 h-1 at 25 °C. The obtained results were compared with direct integration of non-overlapping signals and showed good agreement with the implemented mass balance.
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.
Matrix-assisted laser desorption ionization time of flight mass spectrometry (MALDI-TOF MS) is a well-implemented analytical technique for the investigation of complex biological samples. In MS, the sample preparation strategy is decisive for the success of the measurements. Here, sample preparation processes and target materials for the investigation of different pollen grains are compared. A reduced and optimized sample preparation process prior to MALDI-TOF measurement is presented using conductive carbon tape as target. The application of conductive tape yields in enhanced absolute signal intensities and mass spectral pattern information, which leads to a clear separation in subsequent pattern analysis. The results will be used to improve the taxonomic differentiation and identification, and might be useful for the development of a simple routine method to identify pollen based on mass spectrometry.
This article provides an impression on potentials in applying nowadays welding simulation tools in construction design. This is carried out exemplary on plate girders from two structural steel grades. The calculated residual stresses are compared with measurements by sectioning method. It has been repeatedly stated that present Eurocode models fail to approximate the residual stresses. Especially for high strength steel (HSS) only limited information is available on realistic occurring residual stresses in typical I-girders. The investigations are aimed to give further guidance on these values. A few proposals on advanced models are discussed.
In the quest for finding the ideal synchrotron-radiation-induced imaging method for the investigation of trace element distributions in human bone samples, experiments were performed using both a scanning confocal synchrotron radiation micro X-ray fluorescence (SR-mXRF) (FLUO beamline at ANKA) setup and a full-field color X-ray camera (BAMline at BESSY-II) setup. As zinc is a trace element of special interest in bone, the setups were optimized for its detection. The setups were compared with respect to count rate, required measurement time and spatial resolution. It was demonstrated that the ideal method depends on the element of interest. Although for Ca (a major constituent of the bone with a low energy of 3.69 keV for its K alpha XRF line) the color X-ray camera provided a higher resolution in the plane, for Zn (a trace element in bone) only the confocal SR-µXRF setup was able to sufficiently image the distribution.
Reliable nanomaterial classification of powders using the volume-specific surface area method
(2017)
The volume-specific surface area (VSSA) of a particulate material is one of two apparently very different metrics recommended by the European Commission for a definition of "nanomaterial" for regulatory purposes: specifically, the VSSA metric may classify nanomaterials and non-nanomaterials differently than the median size in number metrics, depending on the chemical composition, size, polydispersity, shape, porosity, and aggregation of the particles in the powder.
Here we evaluate the extent of agreement between classification by electron microscopy (EM) and classification by VSSA on a large set of diverse particulate substances that represent all the anticipated challenges except mixtures of different substances. EM and VSSA are determined in multiple labs to assess also the level of reproducibility. Based on the results obtained on highly characterized benchmark materials from the
NanoDefine EU FP7 project, we derive a tiered screening strategy for the purpose of implementing the definition of nanomaterials. We finally apply the Screening strategy to further industrial materials, which were classified correctly and left only borderline cases for EM.
On platelet-shaped nanomaterials, VSSA is essential to prevent false-negative classification by EM. On porous materials, approaches involving extended Adsorption isotherms prevent false positive classification by VSSA. We find no false negatives by VSSA, neither in Tier 1 nor in Tier 2, despite real-world industrial polydispersity and diverse composition, shape, and coatings. The VSSA screening strategy is recommended for inclusion in a technical guidance for the implementation of the definition.
Halophilic bacteria use a variety of osmoregulatory methods, such as the accumulation of one or more compatible solutes. The wide diversity of compounds that can act as compatible solute complicates the task of understanding the different strategies that halophilic bacteria use to cope with salt. This is specially challenging when attempting to go beyond the pathway that produces a certain compatible solute towards an understanding of how the metabolic network as a whole addresses the problem. Metabolic reconstruction based on genomic data together with Flux Balance Analysis (FBA) is a promising tool to gain insight into this problem. However, as more of these reconstructions become available, it becomes clear that processes predicted by genome annotation may not reflect the processes that are active in vivo. As a case in point, E. coli is unable to grow aerobically on citrate in spite of having all the necessary genes to do it. It has also been shown that the realization of this genetic potential into an actual capability to metabolize citrate is an extremely unlikely event under normal evolutionary conditions. Moreover, many marine bacteria seem to have the same pathways to metabolize glucose but each species uses a different one. In this work, a metabolic network inferred from genomic annotation of the halophilic bacterium Halomonas elongata and proteomic profiling experiments are used as a starting point to motivate targeted experiments in order to find out some of the defining features of the osmoregulatory strategies of this bacterium. This new information is then used to refine the network in order to describe the actual capabilities of H. elongata, rather than its genetic potential.
Experimental and phase field studies of age hardening response of a high purity Al‐4Cu‐1Li‐0.25Mn‐alloy (mass %) during isothermal aging are conducted. In the experiments, two hardening phases are identified: the tetragonal θ′ (Al₂Cu) phase and the hexagonal T1 (Al₂CuLi) phase. Both are plate shaped and of nm size. They are analyzed with respect to the development of their size, number density and volume fraction during aging by applying different analysis techniques in TEM in combination with quantitative microstructural analysis. 3D phase‐field simulations of formation and growth of θ′ phase are performed in which the full interfacial, chemical and elastic energy contributions are taken into account. 2D simulations of T1 phase are also investigated using multi‐component diffusion without elasticity. This is a first step toward a complex phase‐field study of T1 phase in the ternary alloy. The comparison between experimental and simulated data shows similar trends. The still unsaturated volume fraction indicates that the precipitates are in the growth stage and that the coarsening/ripening stage has not yet been reached.
Welding is the most important joining technology. In the steel construction
industry, e.g. production of windmill sections, welding accounts for a
main part of the manufacturing costs and resource consumption. Moreover, social
issues attached to welding involve working in dangerous environments. This aspect
has unfortunately been neglected so far, in light of a predominant focus on economics
combined with a lack of suitable assessment methods. In this chapter,
exemplary welding processes are presented that reduce the environmental and
social impacts of thick metal plate welding. Social and environmental Life Cycle
Assessments for a thick metal plate joint are conducted for the purpose of
expressing and analysing the social and environmental impacts of welding.
Furthermore, it is shown that state-of-the-art technologies like Gas Metal Arc
Welding with modified spray arcs and Laser Arc-Hybrid Welding serve to increase
social and environmental performance in contrast to common technologies, and
therefore offer great potential for sustainable manufacturing.
We report on a study in which plasmid DNA in water was irradiated with 30 keV electrons generated by a scanning electron microscope and passed through a 100 nm thick Si3N4 membrane. The corresponding Monte Carlo simulations suggest that the kinetic energy spectrum of the electrons throughout the water is dominated by low energy electrons (<100 eV). The DNA radiation damage, single-strand breaks (SSB) and double-strand breaks (DSB), was determined by electrophoresis. The median lethal dose of D1/2 = 1.7 ± 0.3 Gy was found to be much smaller compared to partially or fully hydrated DNA irradiated under vacuum conditions. The ratio of DSB to SSB was found to be (1:12) as compared to 1:88) found for hydrated DNA. Our method enables quantitative measurements of radiation damage to biomolecules (DNA, proteins) in solutions under varying conditions (pH, salinity, cosolutes) for an electron energy range which is difficult to probe by standard methods.
We propose the use of alternating pulse wavelengths in a direct-detection coherent optical time domain reflectometry (C-OTDR) setup not only to measure strain and temperature changes but also to determine the correct algebraic sign of the change. The sign information is essential for the intended use in distributed mode shape analysis of civil engineering structures. Correlating relative backscatter signal shifts in the temporal/signal domain allows for measuring with correct magnitude and sign. This novel approach is simulated, experimentally implemented and demonstrated for temperature change measurement at a spatial resolution of 1 m.
Residual stresses and distortions in welded I-girders for steel construction are relevant when evaluating the stability of steel beams and column members. The application of high strength steels allows smaller wall thicknesses compared to conventional steels. Therefore, the risk of buckling has to be considered carefully. Due to the lack of knowledge concerning the residual stresses present after welding in high strength steel components conservative assumptions of their level and distribution is typically applied. In this study I-girders made of steels showing strengths of 355 MPa and 690 MPa were welded with varying heat input. Due to the dimension of the I-girders and the complex geometry the accessibility for residual stress measurement using X-ray diffraction was limited. Therefore, saw cutting accompanied by strain gauge measurement has been used to produce smaller sections appropriate to apply X-ray diffraction. The stress relaxation measured by strain gauges has been added to residual stresses determined by X-ray diffraction to obtain the original stress level and distribution before sectioning. The combination of both techniques can produce robust residual stress values. From practical point of view afford for strain gauge application can be limited to a number of measuring positions solely to record the global amount of stress relaxation. X-ray diffraction can be applied after sectioning to determine the residual stresses with sufficient spatial resolution.
A phosphaphenanthrene and triazinetrione group containing flame retardant (TAD) is combined with organically modified montmorillonite (OMMT) in epoxy resin thermosets (EP) to improve the performance of the flame-retardant system. When only 1 wt% OMMT/4 wt% TAD is introduced into the EP, the limited oxygen index (LOI) rises from 26% to 36.9% and a V-0 rating is achieved in a UL 94 test. The decomposition and pyrolysis products in the gas phase and condensed phase were characterized using thermogravimetry-Fourier transform infrared spectroscopy (TG-FTIR). The influence on the decomposition of EP, such as the increase in char yield, is limited with the incorporation of OMMT; a large amount of the phosphorus is released into the gas phase. The flame-retardant effect evaluation based on cone calorimeter data testified that OMMT improves the protective-barrier effect of the fire residue of OMMT/TAD/EP on the macroscopic scale, while TAD mainly causes flame inhibition. The fire residues showed a corresponding macroscopic appearance (digital photo) and microstructure (scanning electron microscope [SEM] results). The protective barrier effect of OMMT and the flame-inhibition effect of TAD combined to exert a superior flame-retardant effect, resulting in sufficient flame-retardant performance of OMMT/TAD/EP