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Three chromatographic procedures were investigated regarding their potential for the quantification of aniline and 19 of its methylated and chlorinated derivatives in groundwater. These methods were based on liquid-liquid-extraction in combination with gas chromatography and single quadrupole mass spectrometry (GC/MS) according to German standard DIN 38407-16:1999 and its extension using tandem mass spectrometry (GC/MS-MS), both following liquid-liquid extraction, and as third alternative the direct injection of the water sample into a liquid chromatograph coupled to tandem mass spectrometry (LC/MS-MS). Results were compared using fortified water and real-world contaminated groundwater used in an interlaboratory comparison. It could be shown that GC/MS and GC/MS-MS yielded results deviating less than 10% from each other while all three procedure displayed quantification results deviating less than 15% from the intercomparison reference values in case of each analyte in the concentration range between 1 and 45 µg L-1. Though GC/MS-MS displays a ten-fold higher sensitivity than single quadrupole GC/MS, the precision of both methods in the concentration range was similar. LC/MS-MS has the advantage of no further sample preparation due to the direct injection and leads for methylanilines and meta-, para- substituted chloroanilines to results sufficiently equivalent to the standardised GC/MS method. However, LC/MS-MS is not suitable for ortho-chloroaniline derivates due to significantly lower ion yields than meta- and para-substituted chloroanilines.
Seit 1999 existiert das MIL-HDBK 1823, die us-amerikanische Leitfaden zur Erstellung einer Probability of Detection (POD; Fehlerdetektionswahrscheinlichkeit). Obwohl das Dokument als internationaler Stand der Technik angesehen wird, ist die allgemeine Anwendung in der ZfP-Praxis von einigen Nachteilen begleitet:
1. Die beschriebenen POD‘s bilden ausschließlich die Grundlagen-POD ab, jeweils mit nur einem Fehlerparameter und einem Signalparameter. Modernere Ansätze werden hier nicht adressiert.
2. Die aktuelle Version verzichtet fast vollständig auf konkrete mathematische Formulierungen.
3. Die Richtlinie richtet sich hauptsächlich an die militärische Luftfahrt.
4. Das Dokument ist nur in englischer Sprache verfügbar.
Mit Hilfe eines BMWi-Förderprojekts wird ein weiterführendes Regelwerk auf Basis der MIL-HDBK 1823 unter deutscher Federführung erarbeitet, welches die Anwendung der POD-Berechnung auf eine breitere Basis stellt und die oben genannten Nachteile der MIL-HDBK 1823 behebt.
Das vorgestellte Projekt „normPOD“ wird eine normative, branchenübergreifend einsetzbare Beschreibung des Vorgehens bei der Berechnung einer POD zur Zuverlässigkeitsbewertung zerstörungsfreier Prüfungen entwickeln. Hierbei wird Klarheit über unterschiedliche POD-Ansätze geschaffen und anhand praktischer Beispiele aus Maschinenbau und Bauwesen ein Leitfaden für den Praxiseinsatz erarbeitet.
Das Poster gibt einen Überblick über die geplanten Arbeiten innerhalb des Projekts und lädt die Beteiligten der DGZfP-Jahrestagung zur Diskussion ein, um eine breite Basis und Akzeptanz für die entwickelten Berechnungsverfahren zu schaffen, insbesondere in Hinblick auf ZfP 4.0 und Digitalisierung.
The impact sensitivity (IS) of FOX-7 polymorphs is predicted by phonon up-pumping to decrease as layers of FOX-7 molecules flatten. Experimental validation proved anomalous owing to a phase transition during testing, raising questions regarding Impact sensitivity measurement and highlighting the need for models to predict IS of polymorphic energetic materials.
The successful shift to NDE 4.0 will not only require developing and embracing new technologies associated with the fourth industrial revolution or becoming an integral part of the overall Industry 4.0, but also developing and adopting new ways of working. It is undoubtful that people will remain in charge of the inspections. However, it is arguable if the current “procedure-following” “level I-III” paradigm can withstand the changes that come along NDE 4.0. With the increased autonomy and interconnectedness expected with NDT 4.0, the majority of traditional NDE tasks will no longer be needed. Instead, different skills, such as that of programming and adapting systems, as well as problem solving, will become vital for the inspections. Therefore, we suggest that a new paradigm is needed—one in which inspector roles and, thus, also the requirements will have to be reinvented. We expect the inspectors to be relieved from the tedious and error prone aspects of the current system and to take responsibility for increasingly complex automated systems and work in closer collaboration with other experts. Thus, we propose that the traditional inspector roles will be transformed into that of the system developer, caretaker and problem solver, each requiring a specific set of skills and assuming different responsibilities. In this talk, we will present the new roles and discuss the challenges that may arise with them.
Iron-based catalysts have been reported manifold and studied as platinum group metal (PGM) free alternatives for the catalysis of the oxygen reduction reaction (ORR). However, their sustainable preparation by greener synthesis approaches is usually not discussed. In this work, we propose a new method for the sustainable preparation of such catalysts by using a mechanochemical approach, with no solvents and non-toxic chemicals. The materials obtained from low temperature carbonization (700 °C) exhibit considerable and stable catalytic performance for ORR in alkaline medium. A catalyst obtained
from iron hydroxide, tryptophan, dicyandiamide, and ammonium nitrate shows the best electrocatalytic Performance with an overpotential of 921 mV vs. RHE at 0.1 mA/cm2 and an electron transfer number of 3.4.
Despite considerable advances in synthesizing high-quality core/shell upconversion (UC) nanocrystals (NC; UCNC) and UCNC photophysics, the application of near-infrared (NIR)-excitable lanthanide-doped UCNC in the life and material sciences is still hampered by the relatively low upconversion luminescence (UCL) of UCNC of small size or thin protecting shell. To obtain deeper insights into energy transfer and surface quenching processes involving Yb3+ and Er3+ ions, we examined energy loss processes in differently sized solid core NaYF4 nanocrystals doped with either Yb3+ (YbNC; 20% Yb3+) or Er3+ (ErNC; 2% Er3+) and co-doped with Yb3+ and Er3+ (YbErNC; 20% Yb3+ and 2% Er3+) without a surface protection shell and coated with a thin and a thick NaYF4 shell in comparison to single and co-doped bulk materials. Luminescence studies at 375 nm excitation demonstrate backenergy transfer (BET) from the 4G11/2 state of Er3+ to the 2F5/2 state of Yb3+, through which the red Er3+ 4F9/2 state is efficiently populated. Excitation power density (P)-dependent steady state and time-resolved photoluminescence measurements at different excitation and emission wavelengths enable to separate surface-related and volume-related effects for two-photonic and threephotonic processes involved in UCL and indicate a different influence of surface passivation on the green and red Er3+ emission.
The intensity and lifetime of the latter respond particularly to an increase in volume of the active UCNC core. We provide a threedimensional random walk model to describe these effects that can be used in the future to predict the UCL behavior of UCNC.
In additive manufacturing the powder bed based processes binder jetting and powder bed fusion are increasingly used also for the production of ceramics. Final part properties depend to a high percentage on the powder bed density. Therefore, the aim is to use the best combination of powder deposition method and powder which leads to a high packing of the particles. The influence of flowability, powder properties and deposition process on the powder bed density is discussed and the different deposition processes including slurry-based ones are reviewed.
It turns out that powder bed density reached by slurry-based layer deposition exceeds conventional powder deposition, however, layer drying and depowdering are extra steps or more time-consuming for the slurry route.
Depending on the material properties needed the most suitable process for the part has to be selected.
Bitumen is a crucial building material in road construction, which is exposed to continuously higher stresses due to higher traffic loads and changing climatic conditions. Therefore, various additives are increasingly being added to the bitumen complicating the characterisation of the bituminous binder, especially concerning the reuse of reclaimed asphalt.
Therefore, this work aimed to demonstrate that the combination of Fourier transform infrared (FTIR) spectroscopy with attenuated total reflexion (ATR) technique and multivariate evaluation is a very wellsuited method to reliable identify and quantify additives in bituminous binders. For this purpose, various unmodified and modified binders, directly and extracted from laboratory and reclaimed asphalts, were investigated with FTIR-ATR spectroscopy. The determined spectra, pre-processed by standard normal variate (SNV) transformation and the determination of the 1st derivation, were evaluated using factor Analysis (FA), linear discriminant analysis (LDA) and partial least square regression (PLSR). With this multivariate evaluation, first, a significant model with a very high hit rate of over 90% was developed allowing for the identification of styrene-butadiene copolymers (SBC), ethylene-copolymer bitumen (ECB) and different waxes (e.g. amide and Fischer-Tropsch wax) even if the additives do not show any additional peaks or the samples are multi-modified. Second, a quantification of the content is possible for SBC, ECB, and Amide wax with a mean error of RMSE B 0.4 wt% and a
coefficient of determination of R2[90%. Based on these results, FTIR identification and quantification of additives in bituminous binders is a very promising method with a great potential.
Additive Manufacturing (AM) in terms of laser powder-bed fusion (L-PBF) offers new prospects regarding the design of parts and enables therefore the production of lattice structures. These lattice structures shall be implemented in various industrial applications (e.g. gas turbines) for reasons of material savings or cooling
channels. However, internal defects, residual stress, and structural deviations from the nominal geometry are unavoidable.
In this work, the structural integrity of lattice structures manufactured by means of L-PBF was non-destructively investigated on a multiscale approach.
A workflow for quantitative 3D powder analysis in terms of particle size, particle shape, particle porosity, inter-particle distance and packing density was established.
Synchrotron computed tomography (CT) was used to correlate the packing
density with the particle size and particle shape. It was also observed that at least about 50% of the powder porosity was released during production of the struts.
Struts are the component of lattice structures and were investigated by means of laboratory CT. The focus was on the influence of the build angle on part porosity and surface quality. The surface topography analysis was advanced by the quantitative characterisation of re-entrant surface features. This characterisation was compared with conventional surface parameters showing their complementary
information, but also the need for AM specific surface parameters.
The mechanical behaviour of the lattice structure was investigated with in-situ CT under compression and successive digital volume correlation (DVC). The Deformation was found to be knot-dominated, and therefore the lattice folds unit cell layer wise.
The residual stress was determined experimentally for the first time in such lattice structures. Neutron diffraction was used for the non-destructive 3D stress investigation. The principal stress directions and values were determined in dependence of the number of measured directions. While a significant uni-axial stress state was found in the strut, a more hydrostatic stress state was found in the knot. In both cases, strut and knot, seven directions were at least needed to
find reliable principal stress directions.
Layer-by-layer additive manufacturing (AM) by means of laser-powder bed Fusion (L-PBF) offers many prospects regarding the design of lattice structures used, for example, in gas turbines. However, defects such as bulk porosity, Surface roughness, and re-entrant features are exacerbated in nonvertical structures, such as tilted struts. The characterization and quantification of these kinds of
defects are essential for the correct estimation of fracture and fatigue properties.
Herein, cylindrical struts fabricated by L-PBF are investigated by means of X-ray computed tomography (XCT), with the aim of casting light on the dependence of the three kinds of defects (bulk porosity, surface roughness, and re-entrant features) on the build angle. Innovative analysis methods are proposed to correlate shape and position of pores, to determine the angular-resolved Surface roughness, and to quantify the amount of re-entrant surface features, q. A meshing of the XCT surface enables the correlation of q with the classical Surface roughness Pa. This analysis leads to the conclusion that there is a linear correlation between q and Pa. However, it is conjectured that there must be a threshold of surface roughness, below which no re-entrant features can be build.
While structural ceramics usually display a brittle mechanical behavior, their composites may show nonlinearities, mostly due to microcracking. Herein, the stiffness evolution of a sandwich-like laminate of an Al2O3 15%vol. ZrO2 matrix reinforced with Nextel 610 fibers is studied as a function of number of cycles N in tension. The stiffness of the composite degrades with increasing N, indicating microcracking. However, synchrotron X-ray refraction radiography shows that the internal specific surface of such cracks varies differently. A modeling strategy is developed for the calculation of the equivalent stiffness of mixtures (first the matrix and then the sandwich), based on the Voigt and Reuß schemes. The Bruno–Kachanov model is then used to estimate the initial microcrack density in the matrix (due to the thermal expansion mismatch) and the amount of microcracking increase upon cyclic loading. The stiffness in the composite degrades dramatically already after 20 000 cycles but then remains nearly constant. The combination of mechanical testing, quantitative imaging analysis, and modeling provides insights into the damage mechanisms acting: microcrack propagation is more active than microcrack initiation upon cyclic loading, but the second also occurs. This scenario is similar but not equal to previous results on porous and microcracked ceramics.
The trafficking of illegal drugs by criminal networks at borders, harbors, or airports is an increasing issue for public health as these routes ensure the main supply of illegal drugs. The prevention of drug smuggling, including the installation of scanners and other analytical devices to detect small traces of drugs within a reasonable time frame, remains a challenge. The presented immunosensor is based on a monolithic affinity column with a large excess of immobilized hapten, which traps fluorescently labeled antibodies as long as the analyte cocaine is absent. In the presence of the drug, some binding sites of the antibody will be blocked, which leads to an immediate breakthrough of the labeled protein, detectable by highly sensitive laser-induced fluorescence with the help of a Peltier-cooled complementary metal-oxide-semiconductor (CMOS) camera. Liquid handling is performed with high-precision syringe pumps and microfluidic chip-based mixing devices and flow cells. The biosensor achieved limits of detection of 7 ppt (23 pM) of cocaine with a response time of 90 s and a total assay time below 3 min. With surface wipe sampling, the biosensor was able to detect 300 pg of cocaine. This immunosensor belongs to the most sensitive and fastest detectors for cocaine and offers near-continuous analyte measurement.
High-resolution continuum source graphite furnace molecular absorption spectrometry (HR-CS-GF-MAS) was employed for determining adsorbable organic chlorine (AOCl) in water. Organic chlorine was indirectly quantified by monitoring the molecular absorption of the transient aluminum monochloride molecule (AlCl) around a wavelength of 261.42 nm in a graphite furnace. An aluminum solution was used as the molecularforming modifier. A zirconium coated graphite furnace, as well as Sr and Ag solutions were applied as modifiers for a maximal enhancement of the absorption signal. The pyrolysis and vaporization temperatures were 600 °C and 2300 °C, respectively. Non-spectral interferences were observed with F, Br, and I at concentrations higher than 6 mg L-1, 50 mg L-1, and 100 mg L-1, respectively. Calibration curves with NaCl, 4-chlorophenol, and trichlorophenol present the same slope and dynamic range, which indicates the chlorine atom specificity of the method. This method was evaluated and validated using synthetic water samples, following the current standard DIN EN ISO 9562:2004 for the determination of the sum parameter adsorbable organic halides (AOX) for water quality. These samples contain 4-chlorophenol as the chlorinated organic standard in an inorganic chloride matrix. Prior to analysis, organic chlorine was extracted from the inorganic matrix via solid-phase extraction with a recovery rate >95%. There were no statistically significant differences observed between measured and known values and for a t-test a confidence level of 95% was achieved. The limits of detection and characteristic mass were found to be 48 and 22 pg, respectively. The calibration curve was linear in the range 0.1–2.5 ng with a correlation coefficient R2 = 0.9986.
Due to its large mineral fraction, incineration bottom ash (IBA) from municipal solid waste incineration is an interesting raw material that can be used for road construction or to produce secondary building materials. However, leaching chloride, sulfate, and potentially harmful heavy metals may cause problems in using IBA in civil engineering. Investigating leaching behavior is crucial for the assessment of the environmental compatibility of IBA applications. Various test procedures are available for that purpose. In the present study, a long-term leaching test of a wet-mechanically treated IBA was performed in a lysimeter for almost six years.
While concentrations of chloride, sulfate and the majority of the heavy metals started to decrease rapidly with progressive liquid-to-solid ratio (L/S), antimony (Sb) and vanadium (V) behaved differently. At the beginning of the lysimeter test, the Sb and V concentrations were low, but after approximately one year of operation at an L/S ratio of around 0.8 L/kg, a steady increase was observed. It was shown that this increase is the result of low Ca concentrations due to the formation of CaCO3.
With the data, the solubility products from Ca-antimonate and Ca-vanadate were calculated. The unusual leaching behavior of Sb and V should be kept in mind when considering field scenarios and evaluating the impact on the environment.
Typically, the near-eutectic Al-Si alloys consist of highly interconnected three-dimensional network of the eutectic Silicon (Si) and intermetallics embedded into Aluminium (Al) matrix. For further improvement of the mechanical properties of such alloys, often, one single ceramic reinforcement phase, e.g. silicon carbide (SiC) or aluminium oxide (Al2O3) in the form of fibres or particles is added. However, hybrid reinforcements (fibres and particles) can further improve wear resistance and fracture toughness, and additionally, reduce anisotropy of the material. The engineering of metal matrix composites (MMC) for specific application requirements benefits from a comprehensive knowledge of the failure behaviour. Therefore, damage evolution under compression was investigated on:
- pure near-eutectic AlSi12CuMgNi matrix alloy
- type I: matrix reinforced with random-planar oriented Al2O3 short fibres (15 vol.%)
- type II: matrix reinforced with random-planar oriented Al2O3 short fibres (7 vol.%) and additional SiC particles (15 vol.%)
The analysis of damage mechanism was carried out in two rather independent but complementary studies. First, selected sister samples of every material were exposed to quasi-static compression (traverse control). The compression tests were interrupted at different strain levels. Miniature cylinders with a diameter of 1mm were extracted from the pre-strained samples and investigated by synchrotron computed tomography (SX-µCT) with a spatial resolution of about 0.7 µm. For the pure matrix alloy, microcracks are confined to the intermetallic particles and to the eutectic Si, hence no damage was observed in the Aluminium. The composite type II revealed a more effective strain accumulation (less damage) than type I at low plastic strain (up to 5 %), but a more catastrophic damage development due to cracking of the SiC clusters at higher strain levels.
The second approach to study the damage initiation and accumulation in the materials subjected to compressive load was Acoustic Emission (AE) analysis. In this case the in-situ monitoring of the acoustic emission signal was performed during compression tests on specimens with dimension of several mm. For all three material types, AE activity set at 2% strain. Differences in AE behaviour of the three materials was proven based on AE hitrate, signal peak amplitudes as well as weighted peak frequencies (WPF). Future work focuses on combination of AE and SX-µCT aiming for more detailed knowledge on damage mechanism of metal matrix composites.
The influence of the process gas, laser scan speed, and sample thickness on the build-up of residual stresses and porosity in Ti-6Al-4V produced by laser powder bed fusion was studied. Pure argon and helium, as well as a mixture of those (30% helium), were employed to establish process atmospheres with a low residual Oxygen content of 100 ppm O2. The results highlight that the subsurface residual stresses measured by X-ray diffraction were significantly lower in the thin samples (220 MPa) than in the cuboid samples (645 MPa). This difference was attributed to the shorter laser vector length, resulting in heat accumulation and thus in-situ stress relief. The addition of helium to the process gas did not introduce additional subsurface residual stresses in the simple geometries, even for the increased scanning speed. Finally, larger deflection was found in the cantilever built under helium (after removal from the baseplate), than in those produced under argon and an argon-helium mixture. This result demonstrates that complex designs involving large scanned areas could be subjected to higher residual stress when manufactured under helium due to the gas’s high thermal conductivity, heat capacity, and thermal diffusivity.
The neutron imaging instrument CONRAD was operated as a part of the user program of the research reactor BER‐II at Helmholtz‐Zentrum Berlin (HZB) from 2005 to 2020. The Instrument was designed to use the neutron flux from the cold source of the reactor, transported by a curved neutron guide. The pure cold neutron spectrum provided a great advantage in the use of different neutron optical components such as focusing lenses and guides, solid‐state polarizers, Monochromators and phase gratings. The flexible setup of the instrument allowed for implementation of new methods including wavelength‐selective, dark‐field, phase‐contrast and imaging with polarized neutrons. In summary, these developments helped to attract a large number of scientists and industrial customers, who were introduced to neutron imaging and subsequently contributed to the Expansion of the neutron imaging community.
The SAXS platform at BAM
(2021)
The general understanding has been that PEGs are biologically inert, meaning they pass the human body without any relevant reaction with anything. But recent studies have shown that migth not be correct. Here a retrospective analysis of LC-MS data was performed to determine correlations between blood PEG levels in humans and different experimental factors.
The characterization of technical lignins is a key step for the efficient use and processing of this material into valuable chemicals and for quality control. In this study 31 lignin samples were prepared from different biomass sources (hardwood, softwood, straw, grass) and different pulping processes (sulfite, Kraft, organosolv). Each lignin was analysed by attenuated total reflectance Fourier transform infrared (ATR-FT-IR) spectroscopy. Statistical analysis of the ATR-FT-IR spectra by means of principal component analysis (PCA) showed significant differences between the lignins. Hence, the samples can be separated by PCA according to the original biomass. The differences observed in the ATR-FT-IR spectra result primarily from the relative ratios of the p-hydroxyphenyl, guaiacyl and syringyl units. Only limited influence of the pulping process is reflected by the spectral data. The spectra do not differ between samples processed by Kraft or organosolv processes. Lignosulfonates are clearly distinguishable by ATR-FT-IR from the other samples. For the classification a model was created using the k-nearest neighbor (k NN) algorithm. Different data pretreatment steps were compared for k=1…20. For validation purposes, a 5-fold cross-validation was chosen and the different quality criteria Accuracy (Acc), Error Rate (Err), Sensitivity (TPR) and specificity (TNR) were introduced. The optimized model for k=4 gives values for Acc = 98.9 %, Err = 1.1 %, TPR = 99.2 % and TNR = 99.6 %.
Annexin A5 (anxA5) is a marker for apoptosis, but has also therapeutic potential in cardiovascular diseases, cancer, and, due to apoptotic mimicry, against dangerous viruses, which is limited by the short blood circulation. An 864-amino-acid XTEN polypeptide was fused to anxA5. XTEN864-anxA5 was expressed in Escherichia coli and purified using XTEN as tag.
XTEN864-anxA5 was coupled with DTPA and indium-111. After intravenous or subcutaneous injection of 111In-XTEN864-anxA5, mouse blood samples were collected for blood half-life determination and organ samples for biodistribution using a gamma counter. XTEN864-anxA5 was labeled with 6S-IDCC to confirm binding to apoptotic cells using flow cytometry.
To demonstrate targeting of atherosclerotic plaques, XTEN864-anxA5 was labeled with MeCAT(Ho) and administered intravenously to atherosclerotic ApoE−/−mice. MeCAT(Ho)-XTEN864-anxA5 was detected together with MeCAT(Tm)-MAC-2 macrophage antibodies by imaging mass cytometry (CyTOF) of aortic root sections. The ability of anxA5 to bind apoptotic cells was not affected by XTEN864. The blood half-life of XTEN864-anxA5 was 13 h in mice after IV injection, markedly longer than the 7-min half-life of anxA5. 96 h after injection, highest amounts of XTEN864-anxA5 were found in liver, spleen, and kidney. XTEN864-anxA5 was found to target the adventitia adjacent to atherosclerotic plaques. XTEN864-anxA5 is a long-circulating fusion protein that can be efficiently produced in E. coli and potentially circulates in humans for several days, making it a promising therapeutic drug.
With the aim of identifying the origin and the manufacturer of a cement, a reliable procedure that provides unambiguous results is needed. Such procedure could resolve practical issues in damage research, liability issues and forensic investigations. A substantial number of attempts for fingerprinting of building materials, including cement, has already been carried out during the last decades. Most of them were based on concentration analysis of the main elements/components. This review provides an overview of provenance studies of cement and the main approaches commonly used. Provenance studies of cement via isotope techniques are also presented and discussed as representatives of the state-of-the-art in the field. Due to the characteristic properties and the occurrence of carefully selected isotope ratios, unique fingerprints of different kinds of materials can be provided by these methods. This property has largely been explored in various scientific fields such as geo- and cosmochemistry, food forensics, archaeology, geochronology, biomedical studies, and climate change processes. However, the potential of isotope techniques in cement and concrete research for provenance studies has barely been investigated.
Therefore, the review outlines a suitable approach using isotope ratios, which could lead to reliable provenancing of cementitious materials in the future.
Thermal cycling of a Ni-excess NiTi alloy was conducted between 50 °C and liquid nitrogen temperature to induce martensitic transformations and to reverse them after. The starting point was an annealed and slowly cooled state, the end point a sample thermally cycled 1500 times. Positron annihilation lifetime spectra and Coincidence Doppler Broadening profiles were obtained in various states and at various tem- peratures. It was found that the initial state was low in defects with positron lifetimes close to that of bulk NiTi. Cycling lead to a continuous build-up of a defect structure up to 20 0 −50 0 cycles after which saturation was reached. Two types of defects created during cycling were identified, namely pure dislo- cations and vacancies attached to dislocations.
Background: There is a need for biomarker to identify patients “at risk” for rheumatoid arthritis (risk-RA) and to better predict the therapeutic response and in this study we tested the hypothesis that novel native and citrullinated heterogeneous nuclear ribonucleoprotein (hnRNP)-DL autoantibodies could be possible biomarkers.
Methods: Using protein macroarray and ELISA, epitope recognition against hnRNP-DL was analysed in sera from different developed RA disease and diagnosed SLE patients. Toll-like receptor (TLR) 7/9 and myeloid Differentiation primary response gene 88 (MyD88)-dependency were studied in sera from murine disease models. HnRNP-DL expression in cultivated cells and synovial tissue was analysed by indirect immunofluorescence, immunoblot and immunohistochemistry.
To date, the destructive extraction and analysis of drilling cores is the main possibility to obtain depth information about damaging water ingress in building floors. The time- and costintensive procedure constitutes an additional burden for building insurances that already list piped water damage as their largest item. With its high sensitivity for water, a ground-penetrating radar (GPR) could provide important support to approach this problem in a non-destructive way. In this research, we study the influence of moisture damage on GPR signals at different floor constructions. For this purpose, a modular specimen with interchangeable layers is developed to vary the screed and insulation material, as well as the respective layer thickness. The obtained data set is then used to investigate suitable signal features to classify three scenarios: dry, damaged insulation, and damaged screed. It was found that analyzing statistical distributions of A-scan features inside one B-scan allows for accurate classification on unknown floor constructions. Combining the features with multivariate data analysis and machine learning was the key to achieve satisfying results. The developed method provides a basis for upcoming validations on real damage cases.
Functional nanomaterials (NM) of different size, shape, chemical composition, and surface chemistry are of increasing relevance for many key technologies of the twenty-first century. This includes polymer and silica or silica-coated nanoparticles (NP) with covalently bound surface groups, semiconductor quantum dots (QD), metal and metal oxide NP, and lanthanide-based NP with coordinatively or electrostatically bound ligands, as well as surface-coated nanostructures like micellar encapsulated NP. The surface chemistry can significantly affect the physicochemical properties of NM, their charge, their processability and performance, as well as their impact on human health and the environment. Thus, analytical methods for the characterization of NM surface chemistry regarding chemical identification, quantification, and accessibility of functional groups (FG) and surface ligands bearing such FG are of increasing importance for quality control of NM synthesis up to nanosafety. Here, we provide an overview of analytical methods for FG analysis and quantification with special emphasis on bioanalytically relevant FG broadly utilized for the covalent attachment of biomolecules like proteins, peptides, and oligonucleotides and address methodand material-related challenges and limitations. Analytical techniques reviewed include electrochemical titration methods, optical assays, nuclear magnetic resonance and vibrational spectroscopy, as well as X-ray based and thermal analysis methods, covering the last 5–10 years. Criteria for method classification and evaluation include the need for a signal-generating label, provision of either the total or derivatizable number of FG, need for expensive instrumentation, and suitability for process and production control during NM synthesis and functionalization.
T cells need to adapt their cellular metabolism for effector cell differentiation. This relies on alterations in mitochondrial physiology. Which signals and molecules regulate those alterations remains unclear. We recently reported, that the mitochondrial protein TCAIM inhibits activation-induced changes in mitochondrial morphology and function and thus, CD effector T cell formation. Using conditional TCAIM knock-in (KI) and knockout (KO) mice, w now show that it also applies to CD8+ T cells and more importantly, delineate the molecular processes in mitochondria by which TCAIM controls effector cell differentiation. TCAIM KI resulted in reduced activation-induced HIF1α protein expression. Metabolomics and transcriptional data in combination with mathematical flux modeling revealed an impaired induction of anabolic pathways, especially of the mevalonate pathway and cholesterol biosynthesis in TCAIM KI CD8+ T cells. Addition of cholesterol completely rescued HIF1α protein expression, activation and proliferation of TCAIM KI CD8+ T cells. At the molecular level, TCAIM delayed activation-induced mitochondria-ER contact (MERC) formation by binding to MERC promoting proteins such as RMD3 and VDAC2. In summary, we demonstrate that TCAIM suppresses effector cell differentiation by inhibiting MERC formation, which induce HIF1α-mediated increase in cellular metabolism and cholesterol biosynthesis.
MACC1 is a prognostic and predictive metastasis biomarker for more than 20 solid Cancer entities. However, its role in cancer metabolism is not sufficiently explored. Here, we report on how MACC1 impacts the use of glucose, glutamine, lactate, pyruvate and fatty acids and show the comprehensive analysis of MACC1-driven metabolic networks. We analyzed concentrationdependent changes in nutrient use, nutrient depletion, metabolic tracing employing 13C-labeled substrates, and in vivo studies. We found that MACC1 permits numerous effects on cancer
metabolism. Most of those effects increased nutrient uptake. Furthermore, MACC1 alters metabolic pathways by affecting metabolite production or turnover from metabolic substrates. MACC1 supports use of glucose, glutamine and pyruvate via their increased depletion or altered distribution within metabolic pathways. In summary, we demonstrate that MACC1 is an important regulator of metabolism in cancer cells.
Background: Prevention of metastatic invasion is one of the main challenges in the treatment of alveolar rhabdomyosarcoma. Still the therapeutic options are limited. Therefore, an anti-tumor screening was initiated focusing on the anti-metastatic and anti-invasion properties of selected medicinal plant extracts and phytoestrogens, already known to be effective in the prevention and treatment of different cancer entities.
Methods: Treatment effects were first evaluated by cell viability, migration, invasion, and colony forming assays on the alveolar rhabdomyosarcoma cell line RH-30 in comparison with healthy primary cells.
Results: Initial anti-tumor screenings of all substances analyzed in this study, identified the plant extract of Vincetoxicum arnottianum (VSM) as the most promising candidate, harboring the highest anti-metastatic potential. Those significant anti-motility properties were proven by a reduced ability for migration (60%), invasion (99%) and colony formation (61%) under 48 h exposure to 25 μg/ml VSM. The restricted motility features were due to an induction of the stabilization of the cytoskeleton – actin fibers were 2.5-fold longer and were spanning the entire cell. Decreased proliferation (PCNA, AMT, GCSH) and altered metastasis (e. g. SGPL1, CXCR4, stathmin) marker expression on transcript and protein level confirmed the significant lowered tumorigenicity under VSM treatment. Finally, significant alterations in the cell metabolism were detected for
25 metabolites, with levels of uracil, N-acetyl serine and propanoyl phosphate harboring the greatest alterations. Compared to the conventional therapy with cisplatin, VSM treated cells demonstrated a similar metabolic shutdown of the primary cell metabolism. Primary control cells were not affected by the VSM treatment.
Conclusions: This study revealed the VSM root extract as a potential, new migrastatic drug candidate for the putative treatment of pediatric alveolar rhabdomyosarcoma with actin filament stabilizing properties and accompanied by a marginal effect on the vitality of primary cells.
Lipid droplets, the dynamic organelles that store Triglycerides (TG) and cholesterol esters (CE), are highly accumulated in colon cancer cells. This work studies the TG and CE subspecies profile in colon carcinoma cell lines, SW480 derived from primary tumor, and SW620 derived from a metastasis of the same tumor. It was previously reported that the total TG and CE content is dramatically higher in SW620 cells; however, TG and CE subspecies profile has not been investigated in detail. The work presented here confirms that the total TG and CE Content is significantly higher in the SW620 cells. Moreover, the fatty acid (FA) composition of TG is significantly altered in the SW620 cells, with significant decrease in the abundance of saturated triglycerides. This resulted in a significantly decreased TG saturation index in the SW620 cells. The saturation index of CE was also significantly decreased in the SW620 cells.
Lack of long-time stability of dsDNA-based supramolecular assemblies is an important issue that hinders their applications. In this work, 20 base pairs long dsDNA fragments [(dCdG)20
65%] composed of 65% dCdG and 35% dAdT nucleotides were tethered via a thiol to the surface of a gold electrode. The selfassembled (dCdG)20
-65% monolayer was immersed in solutions
containing ectoine, a compatible solute. Electrochemical results showed that these monolayers were stable for one month. In situ IR spectroscopy indicated that ectoine interacts weakly with the phosphate-ribose backbone, dehydrating the phosphate groups and stabilizing the A-DNA conformation. This structural reorganization led to a reorientation of nucleic acid base pairs and a local disruption of the double-helix structure. However, the conformation and orientation of the dsDNA fragment was stable in the
High-strength fine-grained structural steels have great potential for weight-optimized, efficient structures in many modern steel applications. Further advances in efficiency can be achieved through additive manufacturing and bionic design. Commercial high-strength filler materials for wire arc additive manufacturing (WAAM) are already provided by the consumable producers. Today, application would be strictly limited due to absence of quantitative findings or any guidelines for the industry regarding welding-related stresses and component safety during manufacturing and service. Hence, process- and material-related influences and design-related restraint conditions associated with formation of residual stresses and cold cracking risk are investigated. The aim is the accessibility of special WAAM self-restraining cold cracking tests and easy applicable processing recommendations, enabling an economical, fit-for-purpose and crack-safe WAAM of high-strength steels. This first study focuses on determination of interactions between WAAM process parameters, resulting layer geometry, microstructure and residual stresses, analyzed via X-ray diffraction. Defined reference specimens are automated welded using a special WAAM solid wire (yield strength >820 MPa). Geometric properties can be specifically adjusted by wire feed and welding speed, but cannot be varied arbitrarily, since a high heat input causes local overheating, inadmissible changes of microstructure and mechanical properties, defects and comparable high tensile residual stresses.
For the successful use of lithium-ion batteries in automotive applications, reliable availability of high storage capacity and very short recharging times are essential. In order to develop the perfect battery for a certain application, structure–property relationships of each active material must be fully understood. LiFePO4 is of great interest due to its fast-charging capability and high stability regarding its thermal resistance and chemical reactivity. The anisotropic lithium-ion diffusion through the LiFePO4 crystal structure indicates a strong dependence of the electrochemical performance of a nanostructured active material on particle morphology. In this paper, the relationship of the particle morphology and fast-charging capability of LiFePO4/C core/shell nanoparticles in half-cells was studied. For this purpose, a new multistep synthesis strategy was developed. It involves the combination of a solvothermal synthesis followed by an in situ polymer coating and thermal calcination step. Monodisperse rodlike LiFePO4 nanoparticles with comparable elongation along the b-axis (30–50 nm) and a varying aspect ratio c/a (2.4–6.9) were obtained. A strong correlation of the fast-charging capability with the aspect ratio c/a was observed. When using LiFePO4 nanoparticles with the smallest aspect ratio c/a, the best electrochemical performance was received regarding the specific capacity at high C-rates and the cycling stability. A reduction of the aspect ratio c/a by 30% (3.6 to 2.4) was found to enhance the charge capacity at 10 C up to an order of magnitude (7.4–73 mA h·g–1).
Leather is among the most ancient, widely used materials worldwide. Industrial-scale leather production produces large quantities of organic waste attained during shaving and buffing steps during processing. In this study, leather wastes (LW) are used as fillers in flame retarded polymer composites. LW is investigated as a multifunctional bio-filler that enhances the fire performance of flame retarded poly(ethylene–vinyl acetate) (EVA) containing phosphorus flame retardants (P-FRs) ammonium polyphosphate (APP) or a melamine-encapsulated APP (eAPP). Using LW from tanneries as adjuvants to enhance P-FRs in EVA reduces industrial wastes that otherwise require costly waste management solutions. Materials are characterized multi-methodically via mechanical tests, electron microscopy, rheology, thermogravimetric analysis, evolved gas analysis, and condensed phase FTIR, also reaction-to-small-flames and cone calorimeter tests. EVA containing 10 wt-% LW and 20 wt-% P-FRs achieve 20% reductions in fire loads versus EVA, and up to 10% reduction in effective heats of combustion versus EVA with equal (30 wt-%) P-FR loadings. Enhanced char stabilization of EVA composites with LW and P-FRs lowered peaks of heat release rates up to 53% compared to EVA, and up to 40% compared to equal P-FRs loadings. Synergisms between LW and P-FRs in EVA are quantified. A chemical decomposition mechanism is proposed.
A three-phase transport model for high-temperature concrete simulations validated with X-ray CT data
(2021)
Concrete exposure to high temperatures induces thermo-hygral phenomena, causing water phase changes, buildup of pore pressure and vulnerability to spalling. In order to predict these phenomena under various conditions, a three-phase transport model is proposed. The model is validated on X-ray CT data up to 320 ◦C, showing good agreement of the temperature profiles and moisture changes. A dehydration description, traditionally derived from thermogravimetric analysis, was replaced by a formulation based on data from neutron radiography. In addition, treating porosity and dehydration evolution as independent processes, previous approaches do not fulfil the solid mass balance. As a consequence, a new formulation is proposed that introduces the porosity as an independent variable, ensuring the latter condition.
In the present paper, friction and mechanical properties of AFM-Scan-Induced ripple structures on films of polystyrene and poly-n-(butyl methacrylate) are investigated. Force volume measurements allow a quantitative analysis of the elastic moduli with nanometer resolution, showing a contrast in mechanical response between bundles and troughs. Additionally, analysis of the lateral cantilever deflection shows a clear correlation between friction and the sample topography. Those results support the theory of crack propagation and the formation of voids as a mechanism responsible for the formation of ripples. This paper also shows the limits of the presented measuring methods for soft, compliant, and small structures.
The residual stress (RS) in laser powder bed fusion (LPBF) IN718 alloy samples produced using a 67°-rotation scan strategy is investigated via laboratory X-ray diffraction (XRD) and neutron diffraction (ND). The location dependence of the strain-free (d₀) lattice spacing in ND is evaluated using a grid array of coupons extracted from the far-edge of the investigated specimen. No compositional spatial variation is observed in the grid array. The calculated RS fields show considerable non-uniformity, significant stress gradients in the region from 0.6 to 2 mm below the surface, as well as subsurface maxima that cannot be accounted for via XRD. It is concluded that failure to determine such maxima would hamper a quantitative determination of RS fields by means of the stress balance method.
Machine learning predictions of surface migration barriers in nucleation and non-equilibrium growth
(2021)
Machine learning is playing an increasing role in the discovery of new materials and may also facilitate the search for optimum growth conditions for crystals and thin films. Here, we perform kinetic Monte-Carlo simulations of sub-monolayer growth. We consider a generic homoepitaxial growth scenario that covers a wide range of conditions with different diffusion barriers (0.4–0.55 eV) and lateral binding energies (0.1–0.4 eV). These simulations are used as a training data set for a convolutional neural network that can predict diffusion barriers and binding energies. Specifically, a single Monte-Carlo image of the morphology is sufficient to determine the energy barriers with an accuracy of approximately 10 meV and the neural network is tolerant to images with noise and lower than atomic-scale resolution. We believe this new machine learning method will be useful for fundamental studies of growth kinetics and growth optimization through better knowledge of microscopic parameters.
The therapeutic dose of lithium (Li) compounds, which are widely used for the treatment of psychiatric and hematologic disorders, is close to its toxic level; therefore, drug monitoring protocols are mandatory. Herein, we propose a fast, simple, and low-cost analytical procedure for the traceable determination of Li concentration in human serum, based on the monitoring of the Li isotope dilution through the partially resolved isotope shift in its electronic transition around 670.80 nm using a commercially available high-resolution continuum source graphite furnace atomic absorption spectrometer. With this technique, serum samples only require acidic digestion before analysis. The procedure requires three measurements—an enriched 6Li spike, a mixture of a certified standard solution and spike, and a mixture of the sample and spike with a nominal 7Li/6Li ratio of 0.82. Lanthanum has been used as an internal spectral standard for wavelength correction. The spectra are described as the linear superposition of the contributions of the respective isotopes, each consisting of a spin-orbit doublet, which can be expressed as Gaussian components with constant spectral position and width and different relative intensity, reflecting the isotope ratio in the sample. Both the spectral constants and the correlation between isotope ratio and relative band intensity have been experimentally obtained using commercially available materials enriched with Li isotopes. The Li characteristic mass (mc) obtained corresponds to 0.6 pg. The procedure has been validated using five human serum certified reference materials. The results are metrologically comparable and compatible to the certified values. The measurement uncertainties are comparable to those obtained by the more complex and expensive technique, isotope dilution mass spectrometry.
Fire resistance testing of components made of carbon fibre reinforced polymers (CFRP) usually demands intermediate-scale or full-scale testing. A bench-scale test is presented as a practicable and efficient method to assess how different fire protective systems improve the structural integrity of CFRPs during fire. The direct flame of a fully developed fire was applied to one side of the CFRP specimen, which was simultaneously loaded with compressive force. Three different approaches (film, non-woven, and coatings) were applied: paper with a thickness in the range of μm consisting of cellulose nanofibre (CNF)/clay nanocomposite, nonwoven mats with thickness in the range of cm and intumescent coatings with a thickness in the range of mm. The uncoated specimen failed after just 17 s. Protection by these systems provides fire stability, as they multiply the time to failure by as much as up to 43 times. The reduced heating rates of the protected specimens demonstrate the reduced heat penetration, indicating the coatings’ excellent heat shielding properties. Bench-scale fire stability testing is shown to be suitable tool to identify, compare and assess different approaches to fire protection.
Assembly of permanently porous metal–organic polyhedra/cages (MOPs) with bifunctional linkers leads to soft supramolecular networks featuring both porosity and processability. However, the amorphous nature of such soft materials complicates their characterization and thus limits rational structural control. Here we demonstrate that aging is an effective strategy to control the hierarchical network of supramolecular gels, which are assembled from organic ligands as linkers and MOPs as junctions. Normally, the initial gel formation by rapid gelation leads to a kinetically trapped structure with low controllability. Through a controlled post-synthetic aging process, we show that it is possible to tune the network of the linked MOP gel over multiple length scales. This process allows control on the molecular-scale rearrangement of interlinking MOPs, mesoscale fusion of colloidal particles and macroscale densification of the whole colloidal network. In this work we elucidate the relationships between the gel properties, such as porosity and rheology, and their hierarchical structures, which suggest that porosity measurement of the dried gels can be used as a powerful tool to characterize the microscale structural transition of their corresponding gels. This aging strategy can be applied in other supramolecular polymer systems particularly containing kinetically controlled structures and shows an opportunity to engineer the structure and the permanent porosity of amorphous materials for further applications.
The present work is devoted to the numerical analysis of the high-power laser beam welding of thick sheets at different welding speeds. A three-dimensional transient multi-physics numerical model is developed, allowing for the prediction of the keyhole geometry and the final penetration depth. Two ray tracing algorithms are implemented and compared, namely a standard ray tracing approach and an approach using a virtual mesh refinement for a more accurate calculation of the reflection points. Both algorithms are found to provide sufficient accuracy for the prediction of the keyhole depth during laser beam welding with process speeds of up to 1.5 m/min. However, with the standard algorithm, the penetration depth is underestimated by the model for a process speed of 2.5 m/min due to a trapping effect of the laser energy in the top region. In contrast, the virtually refined ray tracing approach results in high accuracy results for process speeds of both 1.5 m/min and 2.5 m/min. A detailed study on the trapping effect is provided, accompanied by a benchmark including a predefined keyhole geometry with typical characteristics for the high-power laser beam welding of thick plates at high process speed, such as deep keyhole, inclined front keyhole wall, and a hump.
Materials that confer antimicrobial activity, be that by innate property, leaching of biocides or design features (e.g., non-adhesive materials) continue to gain popularity to combat the increasing and varied threats from microorganisms, e.g., replacing inert surfaces in hospitals with copper. To understand how efficacious these materials are at controlling microorganisms, data is usually collected via a standardised test method. However, standardised test methods vary, and often the characteristics and methodological choices can make it difficult to infer that any perceived antimicrobial activity demonstrated in the laboratory can be confidently assumed to an end-use setting. This review provides a critical analysis of standardised methodology used in academia and industry, and demonstrates how many key methodological choices (e.g., temperature, humidity/moisture, airflow, surface topography) may impact efficacy assessment, highlighting the need to carefully consider intended antimicrobial end-use of any product.
Stormwater from urban areas can transport biocidally active substances and related transformation products from buildings into the environment. The occurrence of these substances in urban runoff depends on the availability of water, and on ultraviolet radiation exposure that causes photolytic reactions. In a systematic laboratory study, painted test specimens were exposed to either ultraviolet radiation, water contact, or a combination of both. Leaching of the biocidally active substances carbendazim, diuron, octylisothiazolinone, terbutryn, and selected transformation products of terbutryn and diuron were observed under various exposure conditions. Remaining concentrations of these substances in the paint were quantified. It was demonstrated that the distribution of active substances and transformation products in eluates and in the coatings themselves differs with exposure conditions. Strategies for environmental monitoring of biocide emissions need to consider the most relevant transformation products. However, environmental concentrations of biocidally active substances and transformation products depend on earlier exposure conditions. As a consequence, monitoring data cannot describe emission processes and predict expected leaching of biocidally active substances from buildings if the data are collected only occasionally.
Zeolitic imidazolate framework (ZIF) hybrid fluorescent nanoparticles and ZIF antibody conjugates have been synthesized, characterized, and employed in lateral-flow immunoassay (LFIA). The bright fluorescence of the conjugates and the possibility to tailor their mobility gives a huge potential for diagnostic assays. An enzyme-linked immunosorbent assay (ELISA) with horseradish peroxidase (HRP) as label, proved the integrity, stability, and dispersibility of the antibody conjugates, LC-MS/MS provided evidence that a covalent link was established between these metal-organic frameworks and lysine residues in IgG antibodies.
The localized surface plasmon resonance (LSPR) excitation in plasmonic nanoparticles (NPs) in the visible and near-infrared ranges is currently at the forefront of improving photocatalytic performances via plasmonic photocatalysis. One bottleneck of this field is that the NPs that often display the best optical properties in the visible and near-infrared ranges are based on expensive noble metals such as silver (Ag) and gold (Au). While earth-abundant plasmonic materials have been proposed together with catalytic metals in antenna–reactor systems, their performances remain limited by their optical properties. Importantly, the synthesis of plasmonic photocatalysts remains challenging in terms of scalability while often requiring several steps, high temperatures, and special conditions. Herein, we address these challenges by developing a one-pot, gram-scale, room-temperature synthesis of earth-abundant plasmonic photocatalysts while improving their activities beyond what has been dictated by the LSPR excitation of the plasmonic component. We describe the mechanochemical synthesis of earth-abundant plasmonic photocatalysts by using MoO3 (antenna) and Au (reactor) NPs as a proof-of-concept example and demonstrate that the dual plasmonic excitation of antenna and reactor sites enables the tuning of plasmonic photocatalytic performances toward the reductive coupling of nitrobenzene to azobenzene as a model reaction. In addition to providing a pathway to the facile and gram-scale synthesis of plasmonic photocatalysts, the results reported herein may open pathways to improved activities in plasmonic catalysis.