Analytische Chemie
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- Prozessanalytik (9)
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- Ground penetrating radar (4)
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Eingeladener Vortrag
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The development of innovative medium resolution NMR spectrometers (MR-NMR) is remarkable due to their possible applications in quality control, education, or process monitoring.
The use of compact permanent magnets allows to employ NMR devices in an industrial environment without high maintenance requirements and without the need for cryogenic liquids.
A benchtop 43 MHz MR-NMR spectrometer was used for reaction monitoring. Quasi-simultaneous proton and fluorine NMR spectra were acquired. Automatic data pretreatment and evaluation methods were applied and compared to quantitative 500 MHz HR-NMR spectroscopy
Introducing fluorine into molecules has a wide range of effects on their physicochemical properties, often desirable but in most cases unpredictable. The fluorine atom imparts the C–F bond with low polarizability and high polarity, and significantly affects the behavior of neighboring functional groups, in a covalent or noncovalent manner. Here, we report that fluorine, present in the form of a single fluoroalkyl amino acid side chain in the P1 position of the well-characterized serine-protease inhibitor BPTI, can fully restore inhibitor activity to a mutant that contains the corresponding hydrocarbon side chain at the same site. High resolution crystal structures were obtained for four BPTI variants in complex with bovine b-trypsin, revealing changes in the stoichiometry and dynamics of water molecules in the S1 subsite. These results demonstrate that the introduction of fluorine into a protein environment can result in “chemical complementation” that has a significantly favorable impact on protein–protein interactions.
A new method for sampling wear particles directly from the lubricant reservoir has been developed and applied successfully for analyzing wear particles by high-resolution scanning electron microscopy in transmission mode having coupled energy-dispersive X-ray spectroscopy. The lubricated tribological testing was carried out with fully formulated as well as with non-formulated synthetic base oil. It was possible to analyze individual particles with dimensions as small as about 5–30 nm which are likely the 'primary' wear particles. A majority of the particles, however, are agglomerated and, thus, lead to the formation of larger agglomerates of up to a few micrometers. Chemical analysis led to the conclusion that most of the observed particles generated in formulated oil, especially the larger ones, are composed of the additives of the lubricant oil. In non-formulated base oil, the primary particles are of similar dimensions but contain only iron, chromium and oxygen, but most likely stem from the mating materials. This finding points to the fact that the main wear mechanism under lubricated conditions with fully formulated oil is more like a continuous shearing process rather than a catastrophic failure with the generation of larger primary particles. When the oil is non-formulated, however, several wear mechanisms act simultaneously and the wear rate is increased significantly. Generated larger primary particles are milled down to the nanoscale. When the oil is fully formulated, wear mainly takes places at the additive layer or tribofilm; thus, the steel surface is protected.
Laser-induced breakdown spectroscopy (LIBS) is a combination of plasma generation on the sample surface by a high power laser pulse and optical emission spectroscopy (OES). It is a direct measurement method without an extensive sample preparation. Concrete is a multi phase system. With LIBS it is possible to distinguish the different phases and based on that to correlate the chloride content to the cement mass. This is done by scanning the surface with a resolution of up to 0.1 mm. The high measurement frequency of 100 Hz or even higher allows the in-situ visualization of the chloride content over the measured area. With a calibration a quantification of chloride concentration is possible. As an example the LIBS measurement on a 50 mm by 70 mm area with a resolution of 0.5 mm and the visualization of the chloride distribution takes only 10 minutes. Additionally it is possible to evaluate the carbonation depth from the same measurement. Examples of practical application to determine the chloride-to-cement-content on concrete samples are presented. The possibilities and the limitations of LIBS are discussed.
We present a systematic study on the effect of surface ligands on the luminescence properties and colloidal stability of β-NaYF4:Yb3+,Er3+ upconversion nanoparticles (UCNPs), comparing nine different surface coatings to render these UCNPs water-dispersible and bioconjugatable. A prerequisite for this study was a large-scale synthetic method that yields ~2 g per batch of monodisperse oleate-capped UCNPs providing identical core particles. These ~23 nm sized UCNPs display an upconversion quantum yield of ~0.35% when dispersed in cyclohexane and excited with a power density of 150 W cm-2, underlining their high quality. A comparison of the colloidal stability and luminescence properties of these UCNPs, subsequently surface modified with ligand exchange or encapsulation protocols, revealed that the ratio of the green (545 nm) and red (658 nm) emission bands determined at a constant excitation power density clearly depends on the surface chemistry. Modifications relying on the deposition of additional (amphiphilic) layer coatings, where the initial oleate coating is retained, show reduced non-radiative quenching by water as compared to UCNPs that are rendered water-dispersible via ligand exchange. Moreover, we could demonstrate that the brightness of the upconversion luminescence of the UCNPs is strongly affected by the type of surface modification, i.e., ligand exchange or encapsulation, yet hardly by the chemical nature of the ligand.
Gold nanoparticles (AuNPs) can catalyze the decolorization of organic dyes in the presence of sodium borohydride (NaBH4), which can be utilized for sensitive optical signaling. Here, we monitor the catalytic reduction of a fluorescent substrate, exemplarily chosen uranine, by AuNPs serving as nanocatalysts by absorption and fluorescence spectroscopy. Dye reduction is accompanied by dramatic changes in the absorption and fluorescence properties of uranine. As proposed reaction mechanism, we assume electron transfer between uranine and NaBH4 through the AuNPs nanocatalysts which is currently investigated also by time-resolved fluorescence and detailed spectroscopic studies of the influence of pH, NaBH4, and AuNPs on these effects. As ultimate goal, a model reporter platform with colorimetric andfluorometric signaling is anticipated for the detection of different analytes by coating AuNPs with affinity ligands such as antibodies and aptamers and and special separation methods.
We present the results of several machine learning (ML)- inspired data fusion algorithms applied to multi-sensory nondestructive testing (NDT) data. Our dataset consists of Impact-Echo (IE), Ultrasonic Pulse Echo (US) and Ground Penetrating Radar (GPR) data collected on large-scale concrete specimens with built–in simulated honeycombing defects. The main objective is to improve the detectability of honeycombs by fusing the information from the three different sensors. We describe normalization, feature detection and optimal feature selection. We have used unsupervised and supervised ML, i.e., classification and clustering, for data fusion. We demonstrate the advantage of data fusion in reducing the false positives up to 10% compared to the best single sensor, thus, improving the detectability of the defects. The methods were evaluated on a concrete specimen. The effectiveness of the proposed approach was demonstrated on a separate full-scale concrete specimen. The results indicate the transportability of the conclusions from one specimen to the other.
The kinetic energy of keV electrons backscattered from a rutile (TiO2) surface depends measurably on the mass of the scattering atom. This makes it possible to determine separately the angular distribution of electrons backscattered elastically from either Ti or O. Diffraction effects of these backscattered electrons inside the rutile crystal lead to the formation of Kikuchi patterns. The element-resolved Kikuchi patterns of Ti and O differ characteristically, but each can be described fairly well in terms of the dynamical theory of diffraction. Qualitatively, much of the differences can be understood by considering the relative arrangement of the Ti and O atoms with respect to planes defined by the crystal lattice.
Dieser Bericht beschreibt die Herstellung und Zertifizierung einer Cadmiumlösung mit natürlicher Isotopenzusammensetzung. Für das Isotopen-Referenzmaterial sind sowohl die Isotopenverhältnisse als auch Isotopenhäufigkeiten und die molare Masse von Cadmium zertifiziert. Die Unsicherheiten sind erweiterte Messunsicherheiten U = k.uc mit k = 2. Der Cadmium-Massenanteil in der Lösung wird als indikativer Wert angegeben mit einer erweiterten Messunsicherheit U = k.uc mit k = 4,5.
Isotope dilution mass spectrometry often is applied for the quantification of platinum group elements in environmental and geological samples. In most cases, however, certified spike solutions offering complete uncertainty statements and SI-traceability are missing. This report describes the production and certification of two isotope reference materials, ERM-AE140 and ERM-AE141, serving as calibrated spike solutions for IDMS based quantification of Pd and Pt, respectively. Both materials were produced by dissolving highly enriched isotopes 106Pd and 194Pt and determining the mass fraction of 106Pd and 194Pt in the final solution by reverse IDMS. Two independent back-spikes were produced for each material from high purity Pd and Pt. Characterization measurements were carried out by MC-ICPMS. For ERM-AE140 the certified mass fractions are w(106Pd) = 20.24(5) mg/kg and w(Pd) = 20.54(5) mg/kg. For ERM-AE141 the certified mass fractions are w(194Pt) = 18.18(11) mg/kg and w(Pt) = 19.90(12) mg/kg. These values are traceable to the International System of Units (SI) in the shortest possible way.
The concreting of prefabricated concrete structures can lead to insufficient bonding or even to remaining cavities. Honeycombs (aggregate clusters without cement) represent potential weakening of the structure and need to be detected non-destructively. In our study we tested the capability of ground penetrating radar (GPR) techniques for this purpose. We applied GPR in reflection mode and zero-offset profiling (ZOP) transmission mode on a precast concrete twin wall with built-in honeycombs. GPR measurements were performed as two channel measurement with ground coupled antennas with centre frequencies of 1.5 GHz and 2.6 GHz mounted to an automated scanner system.
Our findings show that ZOP transmission measurements are a more efficient method to detect voids in reinforced concrete structures compared to reflection mode measurements. This holds for both the effort needed for the measurement and the evaluation as well as the validity of the data. Honeycombs (basically representing voids) are usually characterized by strongly reduced amplitudes and earlier arrivals of the transmitted wave.
The concreting of prefabricated concrete structures can lead to insufficient bonding or even to remaining cavities. Honeycombs (aggregate clusters without cement) represent potential weakening of the structure and need to be detected non-destructively. In our study we tested the capability of ground penetrating radar (GPR)techniques for this purpose. We applied GPR in reflection mode and zero-offset profiling (ZOP) Transmission mode on a precast concrete twin wall with built-in honeycombs. GPR measurements were performed as twochannel measurement with ground coupled antennas with centre frequencies of 1.5 GHz and 2.6 GHz mounted to an automated scanner system.
Our findings show that ZOP transmission measurements are a more efficient method to detect voids in reinforced concrete structures compared to reflection mode measurements. This holds for both the effort needed for the measurement and the evaluation as well as the validity of the data. Honeycombs (basically representing voids) are usually characterized by strongly reduced amplitudes and earlier arrivals of the transmitted wave.
An experimental investigation has been carried out to characterize and discriminate seven saffron samples and to verify their declared geographical origin using a voltammetric electronic tongue (VE-tongue). The ability of multivariable analysis methods such as Principal Component Analysis (PCA), Hierarchical Cluster Analysis (HCA) to classify the saffron samples according to their geographical origin have been investigated. A good discrimination has reached using PCA and HCA in the VE-tongue characterization case. Furthermore, cross validation and Partial Least Square (PLS) techniques were applied in order to build suitable management and prediction models for the determination of safranal concentration in saffron samples based on SPME-GC-MS and UV-Vis Spectrophotometry. The obtained results reveals that some relationships were established between the VE-tongue signal, SPMEGC-MS and UV-Vis spectrophotometry methods to predict safranal concentration levels in saffron samples by using the PLS model. In the light of these results, we can say that the proposed electronic system offer a fast, simple and efficient tool to recognize the declared geographical origin of the saffron samples.
In this work, sample losses of silver nanoparticles (Ag NPs) in asymmetrical flow field-flow fractionation (AF4) have been systematically investigated with the main focus on instrumental conditions like focusing and cross-flow parameters as well as sample concentration and buffer composition. Special attention was drawn to the AF4 membrane. For monitoring possible silver depositions on the membrane, imaging laser ablation coupled to inductively coupled plasma mass spectrometry (LA-ICP-MS) was used. Our results show that the sample residue on the membrane was below 0.6% of the total injected amount and therefore could be almost completely avoided at low sample concentrations and optimized conditions. By investigation of the AF4 flows using inductively coupled plasma mass spectrometry (ICP-MS), we found the recovery rate in the detector flow under optimized conditions to be nearly 90%, while the cross-flow, slot-outlet flow and purge flow showed negligible amounts of under 0.5%. The analysis of an aqueous ionic Ag standard solution resulted in recovery rates of over 6% and the ionic Ag content in the sample was found to be nearly 8%. Therefore, we were able to indicate the ionic Ag content as the most important source of sample loss in this study.
High resolution in situ monitoring of the initial cement hydration influenced by organic admixtures
(2015)
Numerous admixtures are used in the building practice to customize the properties of the cement paste during application. The influences of admixtures on the course of cement hydration and formation of hydrate phases have to be considered. Polycarboxylate ether (PCE) based polymeric superplasticizers (SPs) are known to retard the setting of the cement paste. The extent of the retardation differs depending on the molecular structure of the SP. Additionally, the presence of a stabilizing agent (SA) in the cement paste has a retarding side effect on the setting. The initial cement hydration processes and the detailed mechanisms of the retardation influenced by PCEs, as well as their interactions with particular SAs, are insufficiently understood. Up to now, only the results of phenomenological studies were taken into account to describe this retardation process. A detailed structure analysis monitoring the change of the phase composition during the hydration was never applied. Both SP and SA affect the adsorption of the sulphate ions on the clinker particles, causing changes in the formation of ettringite during the initial hydration, and are therefore a crucial part of the setting process itself. Here, the initial hydration of cement influenced by the interaction of SP and SA was monitored in situ by synchrotron X-ray diffraction. The high time resolution of the measurements allowed a continuous detection of the hydrates formed. The hydration was followed from the starting point of water addition and for couple of hours afterwards. The hydration of the levitated cement pellets containing starch as SA was initialized by adding aqueous solutions of different commercial SPs. Changes in the ettringite formation were detected in comparison to the reference hydration of pure cement.
In the near future, it will be important to adopt innovative approaches and technologies in order to further guarantee the reliability and availability of the highway network. New tools are therefore needed in order to obtain in-depth information about the condition of bridges and its development early enough before significant, precarious damage cases occur. In 2011, the research program “Intelligente Brücken (Smart Bridges)” was launched by the BASt together with the BMVI to evolve systems for information and holistic evaluation for Bridge structures as a supplement to the current inspection-based maintenance management. Several projects dealt with the topic in the last few years and provided guidelines and a solid basis to move towards a first implementation considering the input of all research projects carried out so far.
This paper reflects recent progress in the field of fluorescent polymer optical fiber sensors (F-POF) for partial discharge (PD) detection in high voltage (HV) cable accessories using optical-only PD detection by coincidence single photon counting. In experiments with artificial PD sources these sensors show the ability to detect optical emissions from picocoulomb-level PDs in a real-scale model of a translucent high voltage cable accessory. False positives (caused by detector noise) are efficiently suppressedwhile maintaining sufficient sensitivity,even when the sensor is located in an unfavorable position.
The intention of this compilation of articles was to introduce brand-new developments in the field of chemical imaging which have not been discussed in previous review articles. These include the design of new sensor nanomaterials based on photon uponversion crystals which convert near-infrared excitation light into sensor signals in the visible wavelength range highlighted by Christ and Schäferling. Sun, Ungerböck and Mayr describe the state of the art in oxygen imaging in microreactors and microfluidic devices. Miniaturized sensors for the imaging of oxygen, pH and temperature in microchips, microfluidic platforms and microbioreactors are reviewed by Pfeiffer and Nagl. Furthermore, Dmitriev and Papkovsky present a critical assessment of the applicability of probes for intracellular oxygen sensing.
I hope these articles provide an interesting insight into advanced luminescent sensor materials and the applications of optical micro- and nanosensors in fluorescence imaging today and will be inspiring for the reader. Finally, I would like to thank all authors and referees for spending their time to enable this collection of articles.
Ziel dieser Arbeit war die Entwicklung einer Methode zur Hochdurchsatzanalyse von partikelgebundenen Split-and-Mix-Peptidbibliotheken. Dabei wurde ein System entwickelt, das Partikelbibliotheken in kurzer Zeit auf ihre Bindung zu einem Zielmolekül hin untersucht und im nächsten Schritt eine direkte „Ein-Partikel“-Sequenzierung der Peptide von der festen Phase ermöglicht. Die Analyse der Bindung eines Zielmoleküls an ein selektiv bindendes Peptid wurde dabei in einem Modellsystem simuliert. Dazu wurde FITC-markiertes Neutravidin 3 mit festphasengebundenen biotinylierten und nicht-biotinylierten Peptiden inkubiert. Die Bindung von Neutravidin-FITC an die biotinylierten Peptide konnte erfolgreich mittels eines Fluoreszenzmikroskops nachgewiesen werden, wobei diese Methode für eine Hochdurchsatzanalyse ungeeignet war. So wurde die Analyse des Fluoreszenzassays auf einen Microarrayscanner übertragen (siehe Abbildung 33). Dies gelang erfolgreich wobei die hohe Eigenfluoreszenz des Tentagel-Harzes zu falsch positiven Ergebnissen führte. Mit einem Wechsel zum längerwelligen Fluoreszenzfarbstoff ATTO-633 konnten falsch positive Ergebnisse vermieden werden. Somit wurde die zeitintensive Fluoreszenzanalyse von einem Fluoreszenzmikroskop erfolgreich auf einen Microarrayscanner übertragen, welcher in kurzer Zeit (ca. 5 min pro Objektträger) eine Vielzahl an peptidbeladenen Partikeln gleichzeitig analysieren kann.