Analytische Chemie
Filtern
Erscheinungsjahr
Dokumenttyp
- Posterpräsentation (1009) (entfernen)
Sprache
- Englisch (874)
- Deutsch (134)
- Mehrsprachig (1)
Schlagworte
- Nanoparticles (46)
- Fluorescence (41)
- LIBS (33)
- XPS (27)
- DNA (25)
- Nanoparticle (25)
- Mechanochemistry (24)
- Dosimetry (19)
- SAXS (19)
- BAMline (17)
Organisationseinheit der BAM
- 1 Analytische Chemie; Referenzmaterialien (288)
- 8 Zerstörungsfreie Prüfung (172)
- 6 Materialchemie (164)
- 1.2 Biophotonik (59)
- 6.1 Oberflächen- und Dünnschichtanalyse (57)
- 6.3 Strukturanalytik (57)
- 8.1 Sensorik, mess- und prüftechnische Verfahren (53)
- 1.9 Chemische und optische Sensorik (51)
- 1.1 Anorganische Spurenanalytik (50)
- 1.8 Umweltanalytik (44)
Einsatzbereiche des Meßsystems:
- Ortung von Strukturelementen oder Verdichtungsmängeln in Beton
- Dickenbestimmung von Bauteilen bei einseitiger Zugänglichkeit
- Messung des Haftverbundes bei mehrschichtigen Bauteilen
Auswerteverfahren:
- Prinzip der laufzeitkorrigierten Überlagerung
Vorteile:
- Automatischer Meßablauf durch Array-Technik
- Flexibler Einsatz durch lange Kabelverbindungen zwischen Prüfkopfarray und Meßapparatur
Der große Vorteil der vorgestellten Methode liegt in der quasi on-line Bereitstellung der Ergebnisse und in der Möglichkeit des Einsatzes direkt am Bauwerk. Die vorliegenden Meßergebnisse zeigen den erfolgreichen Einsatz von LIBS zur Messung der Betonzusammensetzung. Eine Unterscheidung von Zementen gelingt durch die Einordnung der Meßwerte ins Dreistoffdiagramm.
Neue kleine Laser, handliche Echellespektrographen und neuartige Lichtleiter lassen sich zu mobilen LIBS-Apparaturen kombinieren, die eine Messung undAuswertung vor Ort ermöglicht.
Our aim is the application of LIBS as a simple, quasi on-line method for the non-destructive testing of concrete. Concrete is naturally inhomogeneous. Therefore we must take into account the local variation of the element composition using a statistical analysis. Depending on how much cement and aggregate is measured with each laser pulse, a scan on the surface of a concrete specimen produces a distribution of points in the Rankin diagram which is used to characterise the concrete.
Ziel der Untersuchungen ist die Weiterentwicklung der Impuls-Thermografie als quantitatives zerstörungsfreies Prüfverfahren zur Ortung oberflächennaher Inhomogenitäten in Bauteilen und Bauwerken.
Zur Zeit werden Putzablösungen auf Mauerwerk bzw. Beton, Hohlstellen und Kiesnester in Beton, Ablösungen und Hohlstellen bei Spaltklinkern im Dickbettmörtel auf Beton, Verbundprobleme von CFK-Laminaten auf Beton sowie Ablösungen von Bitumen-Abdichtungsbahnen auf Stahl untersucht.
Die IE-Methode wird seit vielen Jahren zur zerstörungsfreien Prüfung von Betonbauteilen eingesetzt. Bei Anwendung dieses Verfahrens besteht oft das Problem, resultierende Frequenzspektren infolge der vielen Peaks richtig zu interpretieren. Ein wichtiges Bewertungskriterium ist dabei die Amplitudengröße eines Peaks, welche u.a. durch das Anregungsspektrum beeinflusst wird.
Im Rahmen eines FE-Projektes “Inspektion Fester Fahrbahnen“ der BAM und der Deutschen Bahn AG geht es um die Anwendung und weitere Entwicklung zerstörungsfreier Messverfahren zur Beurteilung des Zustandes Fester Fahrbahnen.
Nach ersten Versuchsreihen direkt im Gleis wurden für verschiedene Bauarten die charakteristischen Herstellungsbedingungen simuliert und systematisch untersucht. Die kombinierte Anwendung der drei Messverfahren Ultraschall-Array-, Impakt-Echo- und Impuls-Radar-Verfahren wird hier an dem Beispiel “Betonschwelle in Betoneinbettung” dargestellt.
Die Eignung des Verfahrens der Laser Induzierten Breakdown Spectroscopy (LIBS) zur Kontrolle einer ausreichenden Beschichtung und zur Bestimmung der Schichtdicke von Hydrophobierungsschichten auch im Rahmen wiederholender Messungen sollte untersucht werden. Mit LIBS kann die Elementverteilung orts- und tiefenaufgelöst in oberflächennahen Bereichen quasi on-line bestimmt werden. Es ist keine Probenpräparation notwendig. Wiederholende Messungen würden das vorzeitige Erkennen beschädigter Beschichtungen ermöglichen, wodurch kostspielige Sanierungsmaßnahmen vermieden werden.
In den letzten Jahren hat sich das Impulsradar als zerstörungsfreies Prüfverfahren im Bauwesen insbesondere zur Ortung von metallischen Einbauteilen wie z. B. schlaffer und vorgespannter Bewehrung in Betonbauteilen immer stärker durchgesetzt.
Systematische Laboruntersuchungen und Fallstudien zeigen aber auch, dass das Verfahren sehr gut zur Ortung von Hohlstellen sowohl in Mauerwerk als auch in Betonstrukturen geeignet ist.
Das Radarverfahren arbeitet nach dem Impuls-Echo Prinzip. Dabei wird von der Sendeantenne ein sehr kurzer elektromagnetischer Impuls ausgesendet (ca. 3 Halbwellen), der an Grenzflächen im Material (Änderung der Dielektrizitätskonstanten) und bei nicht zu dicken Bauteilen auch an der Rückseite reflektiert und von der Empfangsantenne detektiert wird. Bei den hier vorgestellten Messergebnissen wurden eine 900 MHz sowie eine 1,5 GHz Antenne in Kombination mit einem kommerziellen Radargerät eingesetzt.
Das Projektziel war die Vermeidung von Schäden bei Erdarbeiten und Ausschachtungen durch Entwicklung eines innovativen Bodenradarsystems mit wesentlicher Verbesserung des räumlichen Auflösungsvermögens bei der zerstörungsfreien Ortung von folgenden Objekten im Untergrund: Gasleitungen, Frisch- und Abwasserleitungen, Leitungen zur Elektrizitäts- und Kommunikationsversorgung aus verschiedenen Materialien und umgeben mit unterschiedlichen Böden mit variierendem Feuchtegehalt. Darüber hinaus ging es um die Reduzierung der Kosten und Erhöhung der Akzeptanz des Verfahrens durch eine schnelle Echtzeit-Interpretation der Messdaten.
Die Risstiefenbestimmung in Festen Fahrbahnen ist hinsichtlich der Dauerhaftigkeit der Konstruktion von wesentlichem Interesse. Im Rahmen eines gemeinsamen Forschungsvorhabens mit der DB AG wurden aus der Literatur bekannte Ansätze bewertet und darauf aufbauend ein Verfahren zur bildgebenden Rissdarstellung entwickelt. Rissüberbrückende Bewehrung sowie Kontaktstellen zwischen den Rissflanken wirken als Schallbrücken und erschweren die Risscharakterisierung, wie bei einem Einsatz an einer Betriebserprobungsstrecke festgestellt wurde. Ein aus der Literatur bekanntes Verfahren der einfachen Laufzeitmessung erwies sich für die Tiefenbestimmung von realen verunreinigten Rissen als ungeeignet.
Das Impaktecho-Verfahren wird seit vielen Jahren zur zerstörungsfreien Untersuchung von Betonbauteilen eingesetzt. Um die Mechanismen der elastischen Wellenausbreitung besser zu verstehen und den Einfluss von Geometrieeffekten auf das Messergebnis herauszuarbeiten, wurden Messungen und numerische Simulationen an einer
Betonplatte mit drei innenliegenden Hüllrohren durchgeführt.
Für die Strukturaufklärung von Betonbauteilen existieren mehrere bildgebende Ultraschallecho-Verfahren, u. a. mit Nutzung des Prinzips der synthetischen Apertur. Die Ergebnisse werden mit unterschiedlichen Verfahren, mit oder ohne Anwendung von Rekonstruktionsrechnungen, ausgewertet und in der Regel als B- bzw. C-Bilder dargestellt.
Ziel ist es, die unterschiedlichen Verfahren anhand von Messreihen an Testkörpern mit bekannten Prüfobjekten in Hinblick auf Ihre Leistungsfähigkeit quantitativ zu fassen und zu vergleichen, um den Einsatz der Prüfverfahren bei Untersuchungen unbekannter Objekte zu optimieren. Dazu wurden drei Kenngrößen definiert. Als erster Schritt erfolgte die Anwendung der Definitionen auf vorliegende Messergebnisse zu einer in einem 50 cm dicken Betontestkörper parallel zur Messfläche eingebrachten Bohrung.
The often poor construction and low maintenance level of tailings dams has caused serious accidents. The EC funded Project TAILSAFE is aimed at the non-destructive assessment of tailings facilities for stabilization analyses and the development of better management methods.
The focus of geophysical field studies was on the discrimination of different layering and construction steps as well as the determination of the spatial (relative) water content in the dams. SIP measurements at three tailings facilities different in their geological backgrounds, composition and age have been conducted.
Dyke breaks - caused by e.g. Overflows or Slop breaks during long lasting high water gauge - Play a great role in a failure potential of extreme flood Events.
Using conventional dyke condition Monitoring dyke messengers can undertake only a visual surface inspection. Thus defective Areas can oftentimes be discovered too late.
A critical area in which failures due to soil displacement and moisture Penetration become more significant is located at a landside dyke foot. Geotextiles are integrated here as a Drainage in case of modern three-zone type of dyke.
For prediction of wave propagation in multilayered structures it is necessary to know the material properties. Important parameters are sound velocity (c) and attenuation ( ). Values found in the literature were not satisfactory mainly due to insufficient accuracy of measured attenuation. Experiments were carried out in Division VI.3 - Durability of Polymers. The ultrasonic test equipment was provided by Divisions VIII.1 - Measurement and Testing Technology; Sensors and VIII.4 - Acoustical and Electromagnetical Methods.
We report on three respiration sensors based on pure optical technologies developed during the FP6 EU project OFSETH. The developed smart medical textiles can sense elongation up to 3%, while maintaining the stretching properties of the textile substrates for a good comfort of the patient. The sensors, based on silica and polymer fibre, are developed for monitoring of patients during MRI examination. The OFSETH harness allows a continuous measurement of respiration movements while all vitals organs are free for medical staff actions. The sensors were tested in MRI environment and on healthy adults.
Mechanische Belastung wie z. B. der Rollkontakt zwischen den Rollen und Lagerringen eines Wälzlagers oder der Rad-Schiene-Kontakt bei der Eisenbahn führen bei ferritischen Stählen zu einer Aufhärtung der Oberfläche. Die mit der Aufhärtung verbundene Versprödung begünstigt die Entstehung von Ermüdungsrissen. Zur Risstiefenbestimmung mit dem Wirbelstromprüfverfahren werden in der Regel Kalibrierkörper mit künstlichen Testfehlern aus dem Grundwerkstoff des Prüfteils verwendet. Die betriebsbedingte Aufhärtung der Prüfteiloberfläche bleibt bei der Kalibrierung unberücksichtigt.
Die lokale Aufhärtung der Oberfläche führt zu einem ortsabhängigen Offset des Wirbelstromsignals in Richtung der Rissanzeigen und somit zu einer Überbewertung der Risstiefe. Bei einzelnen Rissen lässt sich der Effekt kompensieren, in dem das Wirbelstromgerät neben jedem Riss abgeglichen bzw. die Differenz zwischen dem Offset und der Rissanzeige berechnet wird. In der Realität liegen die Ermüdungsrisse jedoch oft so dicht nebeneinander, dass auf Grund der Überlagerung benachbarter Rissanzeigen weder ein Abgleich zwischen den Rissen noch eine Bestimmung des Offsets möglich ist.
Finite-Elemente-Berechnungen ermöglichen es, die in der Realität stets kombiniert auftretenden Wirbelstromsignale der Ermüdungsrisse und der Oberflächenaufhärtung getrennt zu simulieren, um Erkenntnisse für eine Verbesserung der Risstiefenbestimmung zu erlangen.
A long period grating (LPG) mechanically imprinted in a microstructured polymer optical fibre (mPOF) is embedded in a carbon fibre reinforced polymer (CFRP) unidirectional laminate. Processing steps were established in order to ensure that mPOF does not suffer significant degradation. The strain and temperature responses of the embedded mPOF-LPG were then investigated.
A dynamic and quasi-distributed sensor principle for simultaneous measurement of length changes and optical power changes between reflection points in an optical fiber is presented. The technique is based on the incoherent optical frequency domain reflectometry (I-OFDR). The calculation of phase and amplitude changes from few measurement points in the frequency domain yields precise and dynamic length and optical power change results up to 2 kHz and μm-resolution. Test results showing the deformation of a masonry building under seismic load are presented. Promising fields of application for this technique are the structural health monitoring sector and chemical process control.
In a mutual framework agreement, the two German national institutes BAM (Federal Institute of Materials Research and Testing) and PTB (Physikalisch-Technische Bundesanstalt) agreed upon the development, provision, and dissemination of national measurement standards for chemical analysis via primary reference measuring systems.
Traceability to national standards and international comparability is of key importance for the acceptance of measurement results in metrology.
The European research project i-Protect “Intelligent PPE system for personnel in high-risk and complex environments”, supported by the EU 7th Framework Programme, develops an advanced personal protective equipment (PPE) system that will ensure active protection and information support for personnel operating in high risk and complex environments in fire fighting, chemical and mining rescue operations.
Within the project an intelligent underwear for monitoring the rescuers heart rate, body temperature, and respiratory rate will be developed.
PLR Prüftechnik Linke & Rühe Magdeburg und die BAM Bundesanstalt für Materialforschung und -prüfung Berlin haben in Zusammenarbeit mit anderen Partnern im Laufe der letzten Jahre verschiedene Wirbelstromsysteme zur Prüfung verlegter Schienen auf rissartige Fehler des Typs Head Checks entwickelt. Die Entwicklung dieser Systeme erfolgte mit dem Ziel, ein Hilfsmittel für die Planung von Schieneninstandhaltungsmaßnahmen zu schaffen. Die Systeme haben sich im praktischen Prüfeinsatz bewährt. Hierzu wurde regelmäßig auf den vorhergehenden Tagungen berichtet.
Bei der Schieneninstandhaltung kommen unterschiedliche Typen von Schienenbearbeitungsmaschinen zum Einsatz, z. B. Schienenfräs- und Schleifzüge. Seit einiger Zeit wird von Seiten der Schienennetzbetreiber vermehrt ein Qualitätsnachweis nach erfolgter Schienenbearbeitung gefordert. Hierzu wurde ein Wirbelstromprüfsystem entwickelt, dass speziell an die Erfordernisse der Qualitätsüberwachung in Schienenbearbeitungsmaschinen angepasst ist. Das Prüfsystem wird vorgestellt und über erste Erfahrungen aus dem praktischen Einsatz wird berichtet.
One of the important analytical challenges is the fast and reliable trace detection of explosives in the context of security issues, ammunition disposal, and environmental pollution. Antibodies (Ab) are a promising tool for this purpose and the combination with a
surface acoustic wave (SAW) sensor opens the opportunity of highly selective and fast, label-free detection. A robust and sensitive method for the detection of the explosive trinitrotoluene (TNT) was developed. The detection limit was determined to be around 0.5 μg/L. The fast signal response of less than 1 minute shows that this approach is suitable for security and other time-critical applications. In addition, the very low crossreactivity highly reduces the number of false-positives in relation to competing techniques, including sniffer dogs. Due to the multianalyte ability of the SAW system, several explosives might be detected in parallel. Terminal amino groups were functionalized with trinitrophenyl (TNP) groups by reaction with trinitrobenzene sulfonic acid (TNBS). In less than 1 minute, a good signal response was obtained. 50 μL of sample was used. No non-specific interaction with the SAM surface was observed. A complete measuring cycle needed 19 minutes including a surface regeneration step with 50 μL of acetonitrile/water/propionic acid (50:50:1) and 150 μL of SDS solution (0.1 %, pH 1 with 100 mM glycine and 100 mM NaCl). A good long-term stability could be shown for at least 6 hours. Two polyclonal antibodies (R1, R2, affinity purified with Protein A) and a monoclonal antibody (A1.1.1) were tested successfully. A commercially available SAW sensor (sam5 blue, SAW Instruments) was used for liquid handling and detection. Self-assembled monolayers (SAM) of alkanethiol derivatives were
prepared on gold surfaces leading to non-fouling and hydrophilic properties, due to attached polyethylene glycol (PEG) residues. A continuous flow of buffer (phosphate-buffered saline, PBS plus Tween 20) of 100 μL/min was applied to the sensor system. TNT antibodies were pre-incubated with the samples containing traces of explosives. Polyclonal and monoclonal antibodies were tested.
The limit of detection (LOD) was determined to 0.5 μg/L for all three antibodies (3s from 12 replicates).
The writing materials of the Silk Road book cultures in Turfan – Analysis of inks and pigments
(2014)
Manuscript fragments discovered in the oasis of Turfan and in other sites of present-day China in the beginning of the 20th century by A. Grünwedel and A. von Le Coq, represent one of the most fascinating cultural testimonies of people who both lived there and travelled along the trade routes between East and West. To determine the different materials used for writing and painting the Chinese, Sanskrit, Manichaean, Syrian, Sogdian, Tocharian and Uighur fragments of the Berlin collection, analysis of inks and pigments were conducted using non-destructive methods. The research was funded by the German Research Foundation DFG for a period of three years. The identification of specific techniques of preparation allows manuscript groups and sub-groups to be specified, aiding their cultural assignment. This is important for further cultural studies, for the development of conservation strategies and the identification of forgeries.
Surface-enhanced Raman scattering (SERS) exploits the enhancement of electromagnetic fields in close vicinity of plasmonic nanostructures, enabling characterization of analytes at the single-molecule level. The nanometer-scale spatial arrangement of plasmonic metal nanoparticles and analyte molecules has a significant effect on the observed signal enhancements and represents a great challenge in this technique.
In our work, DNA origami is used as platform for precise positioning of gold nanoparticles (AuNPs). Especially high sensitivities are expected for gold nanolenses (AuNLs), consisting of rows of three or more differently-sized AuNPs. We assembled different AuNL designs and determined respective SERS enhancement factors by collecting Raman spectra from single AuNLs. Finite difference time domain calculations estimate attainable electromagnetic field enhancements. Ultimately, we aim to develop a versatile platform for various SERS applications.
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.
Fraunhofer Life Science Day
(2015)
Their high affinity, selectivity and specificity make monoclonal antibodies (mAbs) very important tools in research, diagnostics and therapy. The production of mAbs is routinely performed by hybridoma technique. Hybridomas are generated by fusing antibody-producing B cells with indefinitely proliferating myeloma cells. Both, cell fusion and the indispensable identification and isolation of the desired antibody-producing hybridoma clone is still far from being trivial.
We describe a novel method that should help to optimize the cell fusion, and the screening for antibody-secreting hapten-specific hybridoma cells by using fluorescence activated cell sorting and single-cell fusion. Hybridoma cells specific for a hapten were incubated with a hapten-peroxidase conjugate (hapten-HRP), which was subsequently incubated with a fluorophore-labeled polyclonal anti-peroxidase antibody (anti-HRP-Alexa Fluor® 488). To characterize the expression of membrane-bound immunoglobulin G (IgG) a fluorophore-labeled anti-mouse IgG antibody (anti-IgG-Alexa Fluor® 647) was used. Successful staining was verified by confocal laser scanning microscopy (CLSM). We show that it is possible to specifically label hapten-specific hybridoma cells. It should also be possible to use this labelling approach for the isolation of hapten-specific B cells from the spleen and use these cells for single-cell fusion. Parallelized cell fusion chips were developed to increase fusion efficiencies.
Gravimetrically prepared mono-elemental reference solutions having a well-known mass fraction of approximately 1 g/kg define the very basis of virtually all measurements in inorganic analysis. Serving as the starting materials of all standard/calibration solutions, they link virtually all measurements of inorganic analytes to the purity of the solid materials they were prepared from. In case these solid materials are characterized comprehensively with respect to their purity, this link also establishes direct metrological traceability to The International System of Unit. Within the framework of the European Metrology Research Programme (EMRP), in the Joint Research Project called SIB09 Primary standards for challenging elements, a reference solution of molybdenum was prepared directly from the respective metal with a relative expanded uncertainty associated with the mass fraction of Urel(w) < 0.05 %. A highly accurate and precise ICP OES and MC-ICP-MS method was developed to assist with the preparation and as a dissemination tool.
Reliable analysis of chemical indicators in water, sediment and soil samples for the purpose of environmental pollution assessment poses one of the greatest analytical challenges, having in mind the complexity of sample matrix and low concentrations of pollutants. Organics (pesticides, PAHs, PCBs, etc.) and heavy metals (Hg, Cd, Ni, Pb and As) represent target parameters. Laboratories performing sampling and tests in this field regulated by respective EU directives, need strong support in terms of providing them with appropriate matrix CRMs enabling the process of quality control. NMIs and DIs with proven metrological capabilities for the production and certification of such materials are necessary for the provision of quality data. This project is aiming to develop capacity to produce CRMs for environmental analysis by transferring the theoretical and practical know-how between the partners and combining their skills to focus on environmental CRM production in accordance with ISO Guide 34. Production process includes good manufacturing practices for processing materials, method development and validation for homogeneity, stability and characterisation tests, characterisation of selected analytes together with additional information about matrix constituents, the calculation of individual uncertainties (between units inhomogeneity, long term stability, characterisation) and combination of uncertainties to determine overall uncertainty of the matrix reference materials. Inter laboratory comparison registered as EURAMET project is set as the ultimate project outcome, confirming the partners’ capabilities in applying newly acquired skills.
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.
Here, we summerize our efforts concerning new design concepts and examples for fluorescence standards that can provide traceability to radiometric units and present a first step towards a toolbox of fluorescence standards, currently consisting of:
i) A first set of liquid fluorescence standards enables the determination of a broad variety of fluorescence parameters was developed and certified by BAM and is distributed by Sigma-Aldrich.
ii) Ready-to-use, glass-based fluorescence standards for instrument performance validation (IPV) and determination instrument-to-instrument variations can also be used as wavelength standard for fluorescence instruments with low requirements on spectral resolution and allow monitoring of temporal changes of the wavelength-dependent spectral responsivity.
iii) Novel calibration tools and validation concepts for microarray-based platforms used in molecular diagnostics and food safety control.
iv) We currently develop reference materials, which can be used as reliable quantum yield standards for relative methods for the determination of QY and can be valuable in the evaluation of the performance and sources of uncertainty of absolute, standard-free methods using e.g. integrating spheres.
One of the most important collections of manuscripts and wall paintings from sites of the northern Silk Road, discovered at the beginning of the 20thC, are deposited in Berlin. The fragments represent a broad spectrum of scripts, languages, and painting styles depending on the region of origin and purpose of dissemination. The manufacturing material reflects the various influences in the oasis sites. Based on analyses of some pigments, examples are posed.
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.
N4-acetyl-SMX is the most important cross-reacting compound for the SMX-ELISA with concentrations of 1064 - 2488 ng/L in influent wastewater and 40 - 160 ng/L in effluent wastewater.
The ELISAgrams for estrone show less interfering signals than for SMX.
ELISAgrams of SMX and estrone display in effluent wastewater more interfering signals than in influent wastewater.
Zur Bestimmung von Arzneimittelrückständen in Oberflächengewässern wird häufig die LC-MS/MS als Methode der Wahl eingesetzt. Obwohl sich dieses Nachweisverfahren durch eine hohe Empfindlichkeit und Selektivität auszeichnet, gibt es vor allem bei geringen Substanzkonzentrationen häufig störende Einflüsse durch Matrixeffekte. Diese Matrixeffekte können unterschiedliche Ursachen haben.
Einige Matrixeffekte werden am Beispiel des Wirkstoffs Carbamazepin erläutert. Carbamazepin wird durch Kläranlagen nur partiell aus dem Abwasser entfernt und ist im Spurenbereich auch noch im Trinkwasser nachzuweisen. Wenn für die LC-MS/MS wasserbasierte Anteile in der mobilen Phase genutzt werden, befinden sich trotz Verwendung einer Labor-Reinstwasseranlage in der mobilen Phase noch kleinste Konzentrationen von Carbamazepin, welche einen Blindwert im unteren ppt-Bereich verursachen.
Weitere Matrixeffekte treten durch die unterschiedliche Qualität der Oberflächenwasserproben auf. Koelutionen von weiteren Inhaltstoffen zeitgleich mit dem Zielanalyten führen zu einer Diskriminierung des Meßsignals. Verbindungen, die den gleichen Massenübergang bei nahezu identischer Retentionszeit zeigen, erfordern eine reproduzierbare chromatographische Vortrennung oder die Wahl einer alternativen HPLC-Säule.
Interfaces provide the structural basis for function as, for example, encountered in nature in the membrane-embedded photosystem or in technology in solar cells. Synthetic functional multilayers of molecules cooperating in a coupled manner can be fabricated on surfaces through layer-by-layer self-assembly. Ordered arrays of stimuli-responsive rotaxanes undergoing well-controlled axle shuttling are excellent candidates for coupled mechanical motion. Such stimuli-responsive surfaces may help integrating synthetic molecular machines in larger systems exhibiting even macroscopic effects or generating mechanical work from chemical energy through cooperative action. The present work demonstrates the successful deposition of ordered mono- and multilayers of chemically switchable rotaxanes on gold surfaces. For the first time, rotaxane mono- and multilayers are shown to reversibly switch in a coupled manner between two ordered states as revealed by linear dichroism effects in angle-resolved NEXAFS spectra. Such a concerted switching process is observed only when the surfaces are well packed, while less densely packed surfaces lacking lateral order do not exhibit such effects.
Supplementary cementitious materials (SCMs) are largely used all over the world. The leading SCMs are fly ash (FA) and slag. However, such materials originate from industries that are not well established in sub-Saharan Africa (SSA). Therefore, it becomes extremely challenging and expensive to build up sustainable cement and concrete. For SSA, agriculture is one of the leading economic sectors. Agricultural by-products such as rice husk ash (RHA), can be a potential binder material beneficial for use in a cementitious system. RHA combined with limestone filler (LSF) is an option that can be practised for rice producing countries in Africa.
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
This project aims to develop capacity to produce certified reference materials (CRMs) for environmental analysis by transferring know-how between the partners and combining their skills to focus on environmental CRM production. The production process includes good manufacturing practices for processing materials, method development, the validation and application of homogeneity, stability and characterisation tests, the calculation of individual uncertainties (between-unit inhomogeneity, long term stability, characterisation) and combination of uncertainties to determine overall uncertainty of the matrix reference materials. An inter laboratory comparison registered as a EURAMET project is set as the ultimate project outcome, confirming the partners’ capabilities in applying newly acquired skills.
The NWRimage system is the first elemental imaging-specific laser ablation instrument, offering breakthrough sub-micron spatial resolution and ultra-fast signal response for high throughput rates.
Laser ablation (LA) systems are used in conjunction with Inductively Coupled Plasma Mass Spectrometry (ICP-MS) systems to detect and analyze tiny amounts of material. As ICP-MS systems have become more sensitive, a need has emerged for LA imaging tools with < 1 micron spatial resolution - a capability not previously available on the market. The NWRimage is provided with a carefully designed aerosol path from point of ablation to injection into the ICP itself. This aerosol path combined with a novel Dual Concentric Injector (DCI) ICP torch, yields < 50ms signal response to accelerate the speed of analysis and enabling enhanced sample throughput. The LA system is used for bio imaging of single cells and medical tissue samples.
The laser-induced breakdown spectroscopy (LIBS) is a fast method to provide multi-elemental analysis of any sample. At the Federal Institute for Materials Research and Testing (BAM) the LIBS technique is applied on building materials to measure ingress profiles of harmful species like chloride and alkalis. The ingress depth and the quantitative amount is important for the evaluation of the potential for damage processes like the alkali-silica reaction or chloride-induced corrosion. Concrete as an example is a highly heterogeneous material with 1/7 cement (major component CaO) and 6/7 aggregates (SiO2) with different grain sizes. Due to a scanning procedure a two dimensional element distribution of a concrete surface can be measured. In order to have an automated Separation method to evaluate heterogeneous materials, different cluster algorithm have been tested. Best results have been achieved with the Expectation-Maximization-Algorithm (EM-Algorithm).
In recent years, upconversion nanocrystals (UCNC) have shown great promise for biological and medical applications, mainly because of their excitation in the NIR region, which provides minimum fluorescence background and a rather deep penetration into biological samples, as opposed to excitation in the visible or UV region. Moreover, they show a multitude of characteristic narrow emission bands as basis for ratiometric measurements. Commonly, Yb is the sensitizer of choice, because of a comparatively high absorption cross section, simple energy scheme, and rather efficient energy transfer to the activator, mostly Er, Tm or Ho. A main disadvantage of the use of Yb as sensitizer for biological and medical applications is its absorption band at 976 nm and hence the use of an excitation wavelength at which water has a non-negligible absorption. This can lead to significant sample heating, especially at long illumination times or high excitation power densities, and thus, tissue damage or even cell death. A possible solution is the tri-doping of UCNC with Nd as sensitizer, which can be excited efficiently at around 800 nm, where water absorption is at minimum.
The use of Nd as a sensitizer and Yb as a bridge between Nd and the activator Er in NaYF₄ nanocrystals is a relatively new way to overcome the problems of heating of samples in an aqueous environment. Disadvantages can arise from the tri-doping, which can favor non-radiative relaxation due to the more complicated excitation process compared to e.g., simple Yb,Er-doped UCNC, which might lower the upconversion quantum yields in these tri-doped systems. In order to quantify clear advantages, NaYF₄:Yb,Er,Nd nanoparticles were synthesized and spectroscopically studied using an 8 W 804 nm laser diode and a custom-designed Edinburgh instruments FSP980 spectrometer. Wavelength-dependent studies of the emission intensities and the decay kinetics of these tri-doped UCNC at different excitation power densities and excitation pulse widths revealed the clear advantages of preventing water absorption on measurable luminescence signals.
We were able to show the influence of pulse width and excitation power density on the luminescence intensities and decay kinetics lifetimes at different emission wavelengths. Additionally, we can clearly discern power density-dependent and independent peaks in the emission spectra. In summary, we demonstrate that the tri-doping of NaYF₄:Yb,Er,Nd nanoparticles is a very promising approach to render UCNC more efficient and to make them better suitable for biological and medical applications requiring measurements in aqueous environment.
The steadily increasing number of analytes, especially in bioanalytics and environmental contexts, requires the development of efficient and versatile methods for the simultaneous determination of different parameters within a single run. Additionally, these methods should be applicable in conjunction with established platform technologies like flow cytometry.
Fluorescence techniques have proven to fulfill these requirements. Commonly performed spectral multiplexing utilizing a color code suffers from several problems, such as the sensitivity of fluorescence intensity measurements to fluctuations in excitation light intensity and dye concentration and hence, photobleaching and spectral crosstalk limiting the achievable number of detection channels. Moreover, it typically requires different costly excitation light sources.
The upscaling from small scale academic reactors to large industrial processes typically suffers from a large change in surface-to-volume ratio. A promising approach is the general avoidance of surfaces as in levitated droplet techniques. However, up to now, no mass spectrometric interface for online reaction monitoring in levitated droplets has been provided.
As model reaction the photoinitiated thiol-ene coupling between N-boc cysteine methyl ester and allyl alcohol was studied. A droplet of 5 µL reactand solution was provisioned into an acoustic trap aligned lateral to the MS inlet. Contactless sampling by laser ablation (LA) is followed by dielectric barrier discharge (DBD) postionization. The latter is needed to address non polar reaction partners.
Long-term completely embedded sensor systems offer innovative possibilities for structural health Monitoring of concrete structures. Measuring of relevant parameters, e.g., temperature, humidity, or indication of corrosion can be performed with low energy sensors.
This allows to implement passive RFID sensor systems without cable connection and battery, which are power supplied exclusively by the electromagnetic field from the external Reader device. To evaluate characteristics and conditions of this concept, a systematical Investigation of the transmission characteristics with variation of relevant parameters, as communication frequency, installation depth, type of concrete, moisture content, etc. is currently carried out in an interdisciplinary research project at BAM. First results are presented in this paper.
In respect of modern approaches in material sciences and highly increased requirements on materials on safety relevant components, quality management and non-destructive testing reclaims a steadily increased meaning. The destructive meaning of measuring the degree of purity is defined in DIN EN 10247 through metallurgical investigations, especially microsections. For and comparable, but non-destructive testing due ultrasonic testing, the material the SEP 1927 is a well-defined industry standard. A novel and alternative way of reference block construction was focused by this work. The proposed amendments, regarding the manufactoring and machining, are less time and cost consuming. Verified by measurements the presented reference block fits the same acoustical characteristics and the requirements of the guideline.
Fungal secondary metabolites such as phomopsin A (PHO-A) produced by the fungus Diaporthe toxica are referred to as “emerging” mycotoxins. Recently, we developed a biosynthetic approach to gain access to 15N-isotopically labelled PHO-A as internal standard (IS) for PHO-A matrix independent quantification of PHO-A in various commodities. Aim of the present work was to elucidate the applicability of the new IS for accurate quantification and to investigate the phomopsin formation on various legume seeds as well as plant material. In summary, the applicability of the SIDA-HPLC-MS/MS method could be proven and the potential of D. toxica to produce high amounts of phomopsins under unfavorable conditions on lupins and other legume seeds could be shown. Moreover, a novel toxic methylated PHO-A derivative was unveiled in natural samples infested with D. toxica.
Neue Trends & Alte Probleme: Das Leguminosenmykotoxin Phomopsin A in einer "worst case"-Betrachtung
(2016)
Leguminosen wie z.B. Bohnen, Erbsen, Soja und zunehmend auch die Samen der Süßlupine liefern aufgrund ihres hohen Proteingehaltes einen wertvollen Beitrag zu einer veganen oder vegetarischen Ernährung. Jedoch sind Lupinen anfällig für Infektionen mit dem Pilz Diaporthe toxica, der u.a. Phomopsin A als hepatotoxischen Sekundärmetaboliten bildet. Ziel der Arbeiten waren die Gewinnung und Anwendung eines 15N-isotopenmarkierten internen Standards für die HPLC-MS/MS-Analyse dieses Toxins sowie die Quantifizierung der Toxinbildung in einem „worst case“-Szenario.
Leguminosen wie z.B. Bohnen, Erbsen, Soja und zunehmend auch die Samen der Süßlupine liefern aufgrund ihres hohen Proteingehaltes einen wertvollen Beitrag zu einer veganen oder vegetarischen Ernährung. Jedoch sind Lupinen anfällig für Infektionen mit dem Pilz Diaporthe toxica, der u.a. Phomopsin A als hepatotoxischen Sekundärmetaboliten bildet. Ziel der Arbeiten waren die Gewinnung und Anwendung eines 15N-isotopenmarkierten internen Standards für die HPLC-MS/MS-Analyse dieses Toxins sowie die Quantifizierung der Toxinbildung in einem „worst case“-Szenario.
The NWRiMAGE provides unique technologies for high-speed imaging with genuine sub-micron ablation. In March 2015 ESI installed the first NWR iMAGE at the Bundesanstalt für Materialforschung und –prüfung (BAM) in Berlin, and since then it has undergone extensive use in bio-imaging. The Dual Concentric Injector (DCI), a new interface between laser and plasma, has been integrated into ESI´s TwoVol2 ablation cell. This technology was developed in collaboration with the University of Loughborough, and provides single shot transition at the ICP-MS of < 20 ms with high sample transport efficiency, giving superior signals above background and improve spatial resolution capability. Here we describe some data showing ultra-fast transitions of single shot ablation, sub-micron ablation experiments and rapid acquired imaging.
Immunoassays are analytical methods used to track both clinical and environmental parameters. Antibodies or other proteins with similar recognizing activity, are employed, often immobilized onto a modified surface. Addressable microarrays are based on single-stranded DNA oligonucleotides which are normally used to detect aptamers or relevant gene sequences. The use of antibody-oligonucleotide conjugates allows non-directed antibody immobilization from an immunoassay to be converted into DNA hybridization events on the array. Consequently, the diagnostics platform is multiplexed and addressable. Figure 1 is a model representation of the whole biosensor construct. In brief, a surface is coated with streptavidin, and decorated with biotin-modified oligonucleotides of a controlled size and known sequence. These oligonucleotides on the surface also contain a furan motif, which upon irradiation and in the presence of a photosensitizer, is oxidized via single oxygen to a reactive intermediate which crosslinks the immediate opposing base when hybridized with its complementary strand [1].
Antibody-oligonucleotides conjugates still display several concerns due to their heterogeneicity, difficulty of characterization and high price [2]. The being the case, we aim at developing stable, robust, reproducible and well characterized quimeras for the application on te above described immunoarray. Mild chemical conditions are crucial for the antibody stability, therefore bivalent crosslinkers have been employed [2]. Even though the use of these bilinkers is standard for other substrate conjugation (i.e., enzymes, drug payloads, etc.), there is no literature available on the conjugation of small oligonucleotides (< 30 mer) to antibodies using this method. Several protein-nucleic acid conjugates have been therefore developed, and successfully characterized using MALDI-ToF and gel electrophoresis techniques.
Paper-based SERS test strips
(2016)
For the non-destructive chemical analysis of organic compounds, several different methods such as NMR, UV-vis absorption, IR, Raman, or fluorescence spectroscopy are available. However, all available methods have some restrictions such as the necessity of a large sample amount, interferences in the presence of water, or overlapping signals from the analytes or matrix. Surface enhanced Raman scattering (SERS) allows to observe analytes directly without labelling in low concentrations in aqueous solutions and to identify them by their spectral fingerprint. Therefore, in this work we use SERS as a detection method for different analytes in low concentrations in combination with paper-based test strips as SERS substrates and for sample preparation.
We present a spray method for the preparation of SERS test stripes.[1] With this spray method, nanoparticle solution was deposited on cellulose and glass fibre paper as SERS substrate. The prepared paper-based test strips were tested with classical SERS reporter molecules, e.g. rhodamine 6G, 4-aminothiophenol, and adenine. For the quantification of analytes, highly reproducible signal intensities are necessary, which can be realized with the test strips in acceptable quality. Moreover, employing intensity vs concentration calibration for the analytes, data analysis revealed a behaviour that was best described by a Langmuir isotherm, stressing the strong distance dependence of the SERS effect.
For an easier identification of analytes in a mixture of compounds, the paper-based test strips were functionalised with hydrophobic barriers by wax printing. With these microfluidic paper-based analytical devices (µPAD) the sample mixture can be separated by the chromatographic effects of the paper and the different analytes can be separately detected and identified by SERS.
[1] A. Bolz, U. Panne, K. Rurack, M. Buurman, Glass fibre paper-based test strips for sensitive SERS sensing, Anal. Methods, 2016, 8, 1313-1318.
X-ray powder diffraction (XRD) patterns of the high-temperature (HT) cristobalite form of SiO2 and its isoelectronic AlPO4 analogue are essentially influenced by the dynamic disorder of these crystal structures. The nature of this disorder and of the phase transition between the α- and β-form has been the subject of intensive research during the last four decades [1]. By 1989 it became possible to stabilize the HT-form of cristobalite SiO2 at room temperature in laboratory and engineering ceramic industries by applying solid solution forming techniques [2]. However, for the HT-form of cristobalite AlPO4 nothing similar has been known until 2014 when it was discovered that nanocrystalline and stacking-disordered β-cristobalite AlPO4 is the major component of the fly ash of a large incineration facility operated by the waste water treatment authorities of Frankfurt/M. [3]. Previous comprehensive investigations of this fly ash failed to interpret its complex XRD pattern – presumably mainly due to the lack of a matching experimental digital pattern in the Powder Diffraction Database. The present paper reports on a synthesis route that facilitates the crystallization of nanocrystalline and stacking-disordered β-cristobalite AlPO4 that is free of crystalline impurity phases and long-term stable at ambient. Its room temperature XRD pattern is presented with parameters traced back to certified reference materials.
[1] Yuan F. and Huang L., Phys. Rev, B, 2012, 85, 134114. [2] Perrotta J.A., Grubbs D.K., Martin E.S., Dando N.R., McKinstry H.A. and Huang C.-Y., J. Am. Ceram. Soc., 1989, 72, 441. [3] Peplinski B., Adam C., Adamczyk B., Müller R., Michaelis M., Krahl Th. and Emmerling F., Powder Diffraction Journal, 2015, 30, 2, Supp. 1, S31.
In situ investigations using PXRD coupled with Raman spectroscopy permit the evaluation of the formation pathways of milling reactions. The liquid-assisted grinding cocrystallisation of theophylline with benzamide leading to polymorphic compounds was investigated. The dipole moment of the solvent used in the synthesis determines the structure of the polymorphic product. A detailed investigation allows determining the kinetically and thermodynamically favored product. In situ observations of the formation pathway during the grinding process of both polymorphs show that the thermodynamically favored cocrystal is formed in a two-step mechanism with the kinetic cocrystal as intermediate. The evaluation of the mechanochemical formation pathways reveals the importance of in situ investigations for an in depth understanding of mechanochemical synthesis mechanisms. Our study demonstrates that the choice of the solvent in the LAG synthesis is decisive for the controlled formation of a desired polymorphic final product.
A high-performance fiber Bragg grating-based (FBG) sensor device for the detection of small magnetic fields has been developed. Based on a smart multilayer coating exposed over the physical length of the FBG, magnetic fields exhibited by rotating machine parts, power generators or current cable can easily be detected, analysed and evaluated. Consequently, this innovative, in-process and non-contact inspection method leads to an increase in quality and reliability of high-performing machine parts, devices and cables. The basic physical concept is based on a magnetostrictive multilayer coating system that strains the high-resolution FBG element. Subsequently, a fixed relationship between induced magnetic field and wavelength change of the FBG element forms the characteristic sensitivity curve. Intensive tests regarding the characterisation of the magnetic field FBG sensor have been carried out and its performance has been evaluated.
Core or coating material – What dictates the uptake and translocation of nanoparticles in vitro?
(2016)
Nanoparticle size and shape are crucial parameters regarding the potential of nanoparticles to penetrate cell membranes and epithelial barriers. Current research in this field additionally focuses on the particle coating material. In order to distinguish between core- and coating-related effects in nanoparticle uptake and translocation behavior, this study investigated two nanoparticles equal in size, coating and charge but different in core material.
Silver and iron oxide coated with poly (acrylic acid) (PAS) were extensively characterized by TEM (transmission electron microscopy), SAXS (Small-Angle X-ray Scattering), ZetasizerTM and NanoSightTM. For uptake and transport studies the widely used human intestinal Caco-2 model in a TranswellTM-system with subsequent elemental analysis (AAS) was used. For evaluation and particle visualization transmission electron microscopy (TEM) and Ion Beam Microscopy (IBM) were conducted.
Although similar in size, charge and coating material, the behavior of particles in Caco-2 cells was quite different. The internalized amount was comparable, but PAA-coated iron oxide nanoparticles were additionally transported through the cells. By contrast, PAA-coated silver nanoparticles remained in the cells. Our findings suggest that the coating material influenced only the uptake of the nanoparticles whereas the translocation was determined by the core material.
In summary, a core-dependent effect on nanoparticle translocation was revealed. Both the uptake and transport of nanoparticles in and through cells should be considered when discussing nanoparticle fate and safety.
Lanthanide-doped photon upconversion nanoparticles (UCNPs) exhibit many advantages compared to conventional Stokes-shifted luminescent probes such as organic dyes and quantum dots. Due to the upconversion (UC) process, which describes the conversion of NIR light into shorter wavelength radiation, the limitations of photobleaching, autofluorescence and low penetration depths in tissue shown by classical fluorescent probes absorbing in the UV/vis range are avoided. This makes UCNPs particularly useful for applications in complex samples occurring in bioanalysis, biomedicine and imaging.
Sensing of intracellular pH is of particular interest in biomedical research since structure and function of biomolecules strongly depend on the concentration of protons in their environment. We described previously a UCNP nanosensor for pH based on a resonance energy transfer from hexagonal nanocrystals of NaYF4: Yb3+,Er3+ to a pH-sensitive fluorophore (pHrodoTM Red).[1] The nanocrystals were coated with a thin shell of aminosilane with several nanometer layer thickness for coupling of the pH indicator.
In this contribution we present a new generation of UC nanoprobes that are coated with a layer of highly branched polyethylenimine (PEI). The PEI coating enables a higher coupling of indicator molecules on the particle surface, better signal to reference ratios in ratiometric readout and an improved cellular uptake compared to the aminosilane coated particles due to a more positive zeta potential. Again, pHrodoTM Red is used as pH indicator, sensitized by the 550 nm emission of the UCNPs. The nanoprobes are calibrated by ratiometric dual wavelength readout at 550 nm (reference signal) and 590 nm (sensor signal) and visualized using a scanning confocal fluorescence microscope with 980 nm excitation wavelength. We studied the cellular uptake efficacy of the nanoprobes and determined to which type of compartment, lysosomes, endosomes or cytosol, the probes are targeted to by measuring the pH of their microenvironment. An in situ control was performed in live cells by a treatment with nigericin, whereby the pH of all intracellular compartments is set at extracellular level. Our results suggest that the PEI coating facilitated endosomal escape of the nanoprobes.
Thiols have a high binding affinity to noble metals and semiconductor (SC) materials. Thiol ligands enable size control and tuning of the surface during the synthesis of nanoparticles (NP), significantly influence their physico-chemical and optical properties, and allow for their bioconjugation via further functional groups. Thus, simple, inexpensive, robust, and fast methods for the quantification of thiol groups and the characterization of thiol-modified or - stabilized nanomaterials including polymers are of considerable importance.
Emissive nanoparticles (NP) are of ever increasing importance in nanotechnology, optical industries, and life sciences. Applicationrelevant properties determining particle performance and biocompatibility depend mainly on surface functional groups or ligands. Coating with polyethylene glycol (PEG) ligands enhances hydrophilicity and biocompatibility of nanomaterials, and enables subsequent binding of biomolecules. Hence, PEGylated particles must be carefully engineered and monitored with simple and fast methods.
Resolution of capacitive sensors can be improved enormously by replacement of the dielectric material between the capacitor plates (e.g. air-dielectric) by a dielectric fluid with high permittivity. High dielectric liquid dispersions of ceramic micro and nano powders should be qualified as dielectric fluid with longtime shelf life.
For this purpose it was necessary to produce stabilized ceramic suspensions with high particle concentration and to investigate sedimentation processes of the particles. Characterization of particles was done by use of zeta potential measurement, gas adsorption measurements (BET), density measurement with gas pycnometer as well as particle sizing by ultrasound spectroscopy and by use of an optical centrifuge.
Shelf life of optimized electrostatic and steric stabilized ceramic suspension was investigated by use of an optical centrifuge, a LUMISizer 651 MW (LUM Ltd.) with STEP technology and front tracking analysis. Two different wave lengths – NIR (865 nm) and blue light (470 nm) were available for examination. Centrifugation measurements with different rotation speed were used to study the rheological behavior and the sedimentation process. By this way it was possible to achieve accelerated stability determination. Measured values could be used to simulate the sedimentation process under gravity acceleration and to predict shelf life for suspensions with different dispersants.
Typically, mycotoxigenic moulds and consequently small percentages of extremely contaminated portions (“hot spots”) are randomly distributed in a cereal lot. Therefore, an efficient sampling procedure for mycotoxin analysis represents a complex challenge for operators involving invasive and cost intensive steps. Establishing an in situ analysis of mycotoxins from the homogeneous gas-phase above cereal crops instead of analysing random samples could address this difficult issue. During studies for microbial volatile organic compounds (MVOCs) indicating an infection with Fusarium, trichodiene was identified as a unique biosynthesis intermediate of trichothecenes - one of the largest groups of the mycotoxin family. The sesquiterpene trichodiene is the only volatile biogenic precursor of the trichothecenes, thus, early and fast in situ detection of this biomarker might be of interest for a potential trichothecene infestation. However, there is no commercial trichodiene standard available needed for the quantification of trichodiene in cereal grains.
The aim of the current project is to develop a fast, easy-to-handle and non-invasive gas-phase quantification of trichodiene in the field. Therefore, trichodiene was prepared by total synthesis based on a tandem orthoester Claisen rearrangement - oxidation - Robinson annulation strategy providing the racemic natural product in 9 steps and 8 % overall yield. Its structure was fully elucidated by NMR and MS. With the reference standard in hand, a protocol was established for the quantitative headspace analysis of trichodiene above crop spikes by GC/MS in the < 10 µg/kg range. Besides a sample survey and a trichodiene - trichothecene correlation study, it is aimed to transfer the validated analytical method from the laboratory into a field-portable analytical system.
The fast and reliable in situ detection of trichodiene as a volatile biomarker for trichothecene mycotoxins will contribute to a reduction of food production/analysis costs and to an improvement of food safety.
Surface-enhanced Raman scattering (SERS) exploits the enhancement of electromagnetic fields in close vicinity of plasmonic nanostructures. The nanometer-scale spatial arrangement of plasmonic metal nanoparticles and analyte molecules has a significant effect on the observed signal enhancements and represents a great challenge in this technique. Especially interesting effects are expected for complex gold nanolenses (AuNLs), consisting of three or more differently-sized AuNPs. We use DNA origami to assemble AuNLs with 10, 20 and 60 nm AuNPs, arranged in three different geometries. Using correlated AFM and Raman spectroscopy, and probing single AuNLs, we systematically examined the SERS properties of the three different assemblies.
Coulometric sensors are applied for trace humidity measurements in various technical gases. The use of this sensor type is demanded in some standards by the European Pharmacopoeia for medical gases. Coulometric sensors allow the measurement of water vapour in gases such as e.g. air, Cl2, H2, N2, N2O, CH4 between the concentration ranging from 0.1 to 2,500 µmol∙mol-1 which corresponds to frost point temperature -90 °C to -10 °C, respectively.
The sensing principle is based on Faraday’s law of electrolysis whereby water is decomposed to hydrogen and oxygen. The sensor signal is the measured electrical current which is proportional to the mass of water that is absorbed on the hygroscopic phosphorous pentoxide layer. The signal is dependent on the gas flow at a given voltage, gas pressure and temperature.
The sensors need to be calibrated to measure the accurate signal for humidity in air. However, the signal is dependent on the type of gas matrix. This dependency has not been quantified so far. Therefore, the impact of reactive gases such as hydrogen and nitrous oxide on the calibration curve was investigated. Furthermore, a possible rationale in relation to the interaction of water with the gas matrix and its impact on the electrode reactions is suggested.
The experimental setup consists of a gas supply, dryer, humidifier, test chamber and reference hygrometer. The test gas is generated by mixing the dry and the wet gas flow. First the carrier gas is dried by an activated carbon filter and then split into two flows. One flow is dried again with a molecular sieve. The other flow is humidified by passing it through a bubbler filled with pure water. After this, the rate of both flows is controlled by mass flow controllers and then mixed with the test gas. A calibrated precision chilled mirror dew-point hygrometer is used as a reference instrument.
The coulometric sensors were exposed to different humidified gases and the sensor signal was recorded till a constant value was obtained. Calibration curves were calculated for the frost point temperature in the range of about -70 °C to -10 °C according to the equation, tf = A + B∙ln(I), (I is the electrolysis current and A, B are constants) followed with a linear regression fit.
Comparison of the results of air and nitrogen showed no significant differences. In contrast, there are remarkable differences for humidified hydrogen and nitrous oxide, respectively.
The difference might be due to increased recombination of hydrogen with the produced oxygen to form new water molecules in humidified hydrogen.
In conclusion, coulometric trace humidity sensor is a robust hygrometer for various technical applications. However it needs to be calibrated for the specific gas matrix.
Aluminium and its chemical derivatives are highly abundant in food, food contact materials and consumer products. Up to now little is known about its derivatization and uptake during digestion and its impact on human health. As part of the SolNanoTOX project, different aluminium species were investigated during an artificial digestion process that mimics the saliva, the stomach and the intestine regarding pH-values, duration time, chemical environment and enzymatic composition.
Two different nanomaterials (Al, Al2O3) and a soluble ionic AlCl3 control were digested and investigated by different analytical methods regarding core radius, hydrodynamic diameter, agglomeration and dissolution behavior in biological media.
The fate of nanoparticles during typical pH-values of saliva, gastric and intestinal juice was studied with dynamic light scattering (DLS), small angle X-ray scattering (SAXS) and ICP-MS in the single particle mode. After disappearance at pH 2 the nanoparticles were detected again in the intestinal fluid, as measured by DLS. During all artificial digestion stages Al nanoparticles had a constant average SAXS radius. In contrast, the radii of Al2O3 nanoparticles changed concentration-dependently. Highest radii were observed in the stomach fluid while intestinal fluid was found to cause full recovery of the primary particles. Dissolution of digested nanoparticles in cell culture media showed a bimodal size distribution of primary particles and aggregates.
In summary, simulation of the gastrointestinal tract, mainly the change of pH settings, has provided evidence that the bioavailability of Al is likely to increase during the passage of the gut after oral uptake of aluminium-containing food products.
Although aluminium is one of the most common elements in the biosphere, little is known about its impact on human health. Since aluminium derivatives are highly abundant in food its oral uptake route is of toxicological relevance. Recently aluminium-containing nanomaterials are considered to be linked to cancer and neurodegenerative disorders. Within the frame of the european SolNanoTOX project, we therefore investigated the toxicological effects of Al-containing species in different intestinal cell lines that represent the first biological barrier for food components prior to systemic distribution.
In our in vitro digestion system, nanomaterials have been exposed to different physiological, chemical and biochemical conditions characteristic for saliva, gastric juice and the intestinal fluid. In vitro toxicity assays and cellular impedance measurements demonstrated the absence of cytotoxic effects of nanoparticles during a period of 48h after incubation. This was also observed after the digestion procedure. In contrast, aluminium ions from high concentrations of AlCl3 showed larger effects on cell viability after the digestion procedure.
In summary, the toxicological potential of aluminium-containing nanoparticles and ions to healthy intestinal cells appears to be low. Artificial digestion of these particles does not increase their toxic potential. Only for high doses of ionic aluminium, an increase of toxicity after artificial digestion was observed. Hence, we suggest that the release of Al ions from nanoparticles may lead to toxicity. Due to these observations, other cellular effects of Al-containing nanomaterials are required to be investigated.
Cellular effects of Al-, Ti- and Zn-containing nanomaterials on intestinal cell lines in vitro
(2016)
Aluminium-, titanium- and zinc-containing chemicals are highly abundant in food, food contact materials and consumer products. Physical and chemical conversion might lead to a certain amount of nanoscaled particles that can be taken up by the gastrointestinal tract. Nanospecific effects such as higher reactivity, increased surface or altered uptake can increase hazardous potential for human health. The aim of this study as part of the european SolNanoTOX project is to characterize toxicological effects of Al-, Zn- and Ti-containing nanomaterials on intestinal cell lines.
While toxicological potential of zinc species has been well studied, little is known about the effects of aluminium- and titanium-species. We have performed toxicological experiments on the human intestinal cell line Caco-2 for numerous endpoints: Cellular ATP and glutathione levels, apoptosis, necrosis, vesicular uptake, oxidative stress, growth rate and cell cycle modification. While zinc-containing controls showed toxic responses, our utilized aluminium- (elementary Al, γ-Al2O3) and titanium-species (TiO2, rutile) did not. Nevertheless, we detected some differences between both different aluminium nanoparticle species and aluminium ions with regard to cell viability. We also provide strong evidence for particle-specific uptake of aluminium and titanium in the intestinal cell line Caco-2.
In summary, among the different tested endpoints, Al- and Ti-containing nanomaterials did not show any toxicity in intestinal cell lines in vitro. Nevertheless, this absence of effect was not due to an absence of exposure, since particle-specific uptake was reported. Metal particle uptake over a long time might therefore be relevant for risk assessment of aluminium- and titanium-containing food products.
In the last decade the utilization of silver nanoparticles in consumer related products is enhanced. Therefore, many studies focus on investigations regarding their toxicological potential. This includes investigations concerning uptake, distribution and excretion of the particles. So far, little attention was paid to changes of physical and chemical properties in the human body. During processes like digestion, the question arises whether they can pass this barrier in a nanoscale form. In this study we analytically monitored the changes in the size distribution of colloidal silver during an artificial digestion process with the help of small angle x-ray scattering (SAXS). Therefore, we synthesized polyacrylic acid stabilized ultra-small silver nanoparticles with a radius of 3 nm and a size distribution width of 18%. The artificial digestion process mimics the gastro-intestinal passage and simulates the oral, gastric and small intestinal conditions. Additionally, food components like oil, starch, glucose and skimmed milk powder are used to provide a preferably realistic environment.
In absence of any food components the low pH initiates aggregation of the particles in the stomach. However, the particles unexpectedly stabilize in a defined cluster form with a mean radius of 12 nm. By the use of the food components oil and starch we observed that the particles are dispersed again. Now we found a bimodal size distribution of primary particles and aggregates. In contrast to that, with skimmed milk powder only a slight aggregation occurs in the stomach. In the gastric tract the particle distribution is stabilized at a mean volume weighted radius of 5 nm. Hence, skimmed milk powder acts as a colloidal stabilizer. For comparison we also used silver nitrate as a control substance. Surprisingly, we observed a formation of nanoparticles already in the saliva. During the digestion process the distribution narrows and finally in the intestine it shows a stable distribution with a mean volume weighted radius of 3 nm and a small fraction of aggregates. These results indicate that the silver nanoparticles can pass the digestion process in a nanoscale form but undergo a transformation in the size distribution. However, even from pure silver nitrate nanoparticle formation can be observed. This sketches a complex mechanism in which not only food components but also silver ions cause changes in nanoparticle size and aggregation.
Among major food contaminants agrochemicals (including insecticides, fungicides and herbicides) are a threat for food safety in many countries. Once they entered the food chain or the environment, the parent compound can be transformed into different products by manmade and natural processes. The transformation products (TPs) might be more toxic and stable than the parent compound. In addition to this the transformation products might undergo conjugation with different compounds and/or changed to phase II metabolites.
Conventional in-vivo or in-vitro methods to study phase I and II metabolism have drawbacks of long-time sample preparation and matrix complexity. Online coupling of an electrochemical cell with liquid chromatography-mass spectrometry (EC–LC–MS) is a promising technique to study metabolites, fate and transformation products of pesticides. The new approach enables to identify metabolic transformation products by oxidizing analyte of interest on the EC, separate the metabolites on HPLC and identifying them by MS.
The aim of the present study is to identify/mimic pesticides phase I metabolites using electrochemical cell coupled to liquid chromatography-mass spectrometry (EC-LC-MS). Metabolic transformed products of two model compounds, fluopyram (fungicide) and chlorpyrifos (insecticide) were studied by EC upfront with MS. The results of EC-LC-MS are compared and discussed with those derived from in-vitro assays and the metabolites identified by LC-MS/MS.
Um den Feuchtegehalt von Fußbodenestrich vor der Verlegung von Holz- oder anderen
Bodenbelägen zu bestimmen, werden zerstörende Prüfverfahren wie die Calcium-Carbid
Methode (CM) oder das thermogravimetrische Darr-Verfahren eingesetzt. Diese liefern
jedoch einmalig nur punktuelle Informationen und sind je nach Estrichtyp auch störanfällig.
Zusammen mit Partnern aus Forschung und Industrie wurde an der BAM ein Ringversuch
durchgeführt, dessen Ziel es war, verschiedene nach Möglichkeit zerstörungsfreie oder –
arme Prüfverfahren hinsichtlich ihrer Genauigkeit und Sensitivität vor allem im Bereich der
Belegereife zu testen. Hier dargestellt sind die Ergebnisse aufgenommen an einer
Calciumsulphat-Estrich Probe vom Typ Knauf FE80 Largo mit drei Verfahren, die auch
Aussagen über die Feuchtegradienten in die Tiefe zulassen. Die Proben wurden bei
Konstant-Normklima mit T=23 °C und rH=50 % zur Trocknung gelagert.
This work demonstrates the sub-cellular resolution bio-imaging capabilities of the NWRimage system with Dual Concentric Injector (DCI) technology in a practical application. 3T3 fibroblast cells incubated with gold nanoparticles were imaged, demonstrating the sub-cellular imaging capabilities. A laser ablation system specifically designed for rapid, high resolution imaging was employed. The system´s optical layout is optimized to minimize crater diameters. Sensitivity and speed were achieved using the DCI technology for ultra-fast washout times.
Polymers, such as polystyrene, have been successfully analyzed with matrix-assisted laser desorption/ionization (MALDI) through the addition of e.g. copper or silver salts. This method is often used to establish the polydispersity index of polymer blends.
However, the mechanism of cation addition and the possible interactions between the added salts and the chosen target material are still points of interest. Therefore, the addition of several trifluoroacetate salts to a mixture of polystyrene and matrix
on a range of different target plate materials was systematically investigated, revealing several new interesting aspects of MALDI.
Polystyrene (Mw 1,920 Da) was mixed with a range of trifluoroacetate salts (Li, Na, K, Cs, Ba, Cr, Pd, Cu, Ag, Zn, Al and In, as well as
trifluoroacetic acid) and analyzed with MALDI using 2
-[2E-3-4-tert-butylphenyl)-
2-
methylprop-2-enylidene]ma
lononitrile DCTB) as matrix on different target plate materials (chrome, copper, silver, gold, Ti90/Al6/V4, Inconel® 625, Zinc and stain
less steel) to evaluate the occurrence of redox-reactions.
Polystyrene/salt/matrix solutions were deposited through pneumatic-assisted spraying on microscope slide
-shaped target plate insets of varying material, which, secured with copper tape, fitted a milled out structure from the original target plate. Spectra, obtained on a Bruker Autoflex I MALDI-Time
-of-Flight mass spectrometer, were processed with MATLAB to obtain polystyrene-and matrix
-adduct ion signal intensities for direct comparison between chosen conditions.
The resulting spectra shed light on the MALDI adduct formation process and the cation-polystyrene interactions. It was found
that the following cation
-polystyrene adducts were formed on stainless steel: Al, Li, Na, Cu and Ag, where the yield was found to depend on the sample layer thickness and possibly the cation’s ability to form a complex with either one or two of polystyrene’s phenyl rings, based on the ligand-field and the valence bond theory. With the exception of Al, these salts also formed adducts
and in case of Cu and Ag also sandwich adducts with DCTB. Some alkali salts (e.g. potassium) formed clusters rather than interacting with polystyrene or DCTB, which can be explained with the HSAB theory. Application of TFA salts on a copper surface
led to copper cation formation, resulting in DCTB and polystyrene copper-adduct formation. The same effect occurred for silver substrate. In the absence of copper or silver salts, it is therefore still possible to form their respective adducts by choosing the proper alternative salt (e.g. Li, Cs, Ba, Cr) in combination with either a silver or a copper substrate surface. Incubation tests with copper beads in various salt solutions, before matrix and polystyrene addition, support that copper ions are not generated during the deposition process before the MALDI experiment is carried out, except when trifluoroacetic acid, indium and aluminium
trifluoroacetate are used. For all other salts used on a copper plate, it can therefore be concluded that these copper cation forming redox-reactions are enabled by the input of laser photon energy. Furthermore, it was discovered that copper beads can successfully sequester polystyrene from the sample mixture, indicating the strong bonding of polystyrene to the copper surface.
These findings support that the redox-reactions occur (almost) instantaneously with laser pulse impact at the sample-coated substrate surface.
As groundwork for thickness determination of polymeric surface protection systems for concrete, we present a method for measuring the thickness of isolated semitransparent solids using pulse thermography both in transmission and reflection configuration. An advanced analytical model by Salazar et al. capturing semitransparency is applied. After calibration with samples of well-known thickness, the unknown thickness of samples of the same material can be obtained by fitting.
Characterization of statistical EO-PO copolymers containing different end groups by UPLC/ESI-MS
(2016)
Commercial statistical ethylene oxide (EO) and propylene oxide (PO) copolymers of different monomer compositions and different average molar masses were studied by liquid chromatography under critical conditions (LCCC). Theoretical predictions of the existence of a critical adsorption point (CPA) for statistical copolymers with a given chemical and sequence distribution, could be studied and confirmed. An improved way to determine these critical conditions in a copolymer, alongside the inevitable chemical composition distribution (CCD), with the aid of mass spectrometric detection is described. Shift of the critical eluent composition with the monomer composition of the polymers could be observed. Due to the relatively low average molecular weight, broad molecular weight distribution (MWD) and the presumed existence of different end group functionalities as well as sequence distribution, gradient separation only by CCD was not possible. Therefore isocratic separations at the CPA of definite CCD’s were applied. Although the various present distributions partly superimposed the separation process the goal of separation by end group functionality could still be achieved on the basis of the additional dimension of ESI-MS. The existence of HO-H besides the desired AllylO-H end group functionalities could be confirmed and their amount could be estimated.
Multilayer carbon nanomembrances (CNMs) could pave the way for a new ultrathin functional conductive coatings with tunable electrical, optical, and chemical properties. Due to their molecular thickness, they can also be regarded as “interfaces without bulk” separating regions of different gaseous, liquid, or solid components and controlling the materials exchange between them, making them optimal materials for membranes applications. Furthermore, their physical and chemical properties depend strongly on their structure, molecular composition, and the surroundings of either sides, thus allowing for tailored properties. Here, nanolayers of Aromatic p-terphenylthiol (TPT) self-assembled into 2D carbon monolayers (thickness - 1.6 nm) were synthesized and further crosslinked by ion bombardment, forming CNMs. Here, though a recently developed multilayer nanosheets routine, stacks of 5, 10, 15 and 20 TPT sheets where transferred on top of each other forming a multilayered CNMs. However, this transfer routine could introduce some intrinsic defects to the sheets, which would alter the molecular composition and / or structure, thus consequently the CNMs properties. Therefore, it is essential to characterize defects in “pure” TPT nanomembranes, before tailoring the molecular compositions, e.g. adding functional groups. For this reason, broadband dielectric spectroscopy (BDS) was utilized to characterize any defects that could be rasied during preparation. Due the structure of pure TPT membranes, no dipole moment should exsist. However, the presence of other elements, e.g. water or sulphur, would result in a dipole moment that could be probed by BDS.
As a main result, for all different stacked-layer numbers, a clear relaxation process is seen, which moves to higher frequencies with increasing the temperature. The temperature dependence of the relaxation rate of this process is independent of film thickness and can be well described by a common VFT function, hence a corporative motion. This relaxation process was assigned to intrinisic defects in the membranes, introduced during preparation, which was further confimed by a detailed anaylsis of the dielectric strength. This is the first BDS measurment on TPT CNMs.
Der Beitrag beschreibt Untersuchungen und Entwicklungsarbeiten für einen technisch einfach zu realisierenden Sensor, der die breitbandige kurzzeitige Energieabgabe von Blitzlampen punktuell bestimmen kann. Solche Lampen werden in der zerstörungsfreien Prüfung als Energiequelle für thermografische Untersuchungen genutzt. Dabei soll die zeitliche Entwicklung der Oberflächentemperatur des Sensors mit der ohnehin vorhandenen IR-Kamera aufgenommen und danach ausgewertet werden. Hierzu wurden zwei Konzepte betrachtet: thermisch dünne und thermisch dicke Proben. Der direkte Vergleich zeigt die Vorteile von thermisch dicken Proben, die in der Physik der beteiligten Wärmeausgleichsprozesse begründet sind.
Many engineering structures are made of composite materials or metal foam. To simulate the deformational behaviour of these structures often requires a high number of discretisation elements. This in turn yields a very large system of linear equations that are extremely time and memory consuming or practically impossible to solve. It is therefore desirable to find an approach to overcome this obstacle.
Many engineering structures are made of composite materials or metal foam. To simulate the deformational behaviour of these structures often requires a high number of discretisation elements. This in turn yields a very large system of linear
equations that are extremely time and memory consuming or practically impossible to solve. It is therefore desirable to find an approach to overcome this obstacle.
Within the field of optically excited thermography, full-field thermal imaging is used to characterize materials, to determine thicknesses of layers or to find inhomogeneities such as voids or cracks. Classical light sources, such as flash lamps (impulse heating) or halogen lamps (modulated heating), are hereby specifically used. This has led to the different testing methods lock-in and flash thermography. The VCSEL array promises to merge these excitation methods.
Vertical Cavity Surface Emitting Lasers (VCSELs) are laser diodes emitting light perpendicular to their surface. Due to the vertical structure they can be arranged in large arrays of many thousand individual lasers and still be controlled like ordinary diode lasers. Recently a high-power albeit very compact version of such a VCSEL-array became available which offers both the fast timing behavior of lasers and large illumination areas. Moreover, it allows a spatial and temporal control of the heating because individual parts of the VCSEL-array can be controlled arbitrarily in frequency, amplitude, and phase.
Although the VCSEL-array has a high potential for a new range of applications, it is too early to proclaim them. As one out of very few labs, we already adopted to this new VCSEL technology and show a thorough characterization and first results obtained with a 2.4 kW device. Specifically, we will discuss
- the linearity between control voltage and optical output
- the minimal pulse duration
- the maximal applicable modulation frequency
- optical projection and its influence on the optical output
- spatial control of the illumination and thermal wave shaping
Our results indicate that a VCSEL-array can be used for conventional impulse (aka flash) thermography whereas pulse duration and power are instantaneously accessible compared to flash lamp excitation. In case of lock-in thermography, we can apply frequencies in excess of 200 Hz without a loss in amplitude or an after glowing of the source, making it attractive for photo thermal applications. Consequently, this means that the VCSEL-array is able to merge the two main excitation methods lock-in and impulse thermography.
BODIPY fluorophores are popular functional dyes in a multitude of fields in chemistry, physics, and materials sciences due to their excellent properties such as a good photostability, high fluorescence quantum yields, and almost unlimited possibilities for tailoring their properties by chemical functionalization. In sensing applications, BODIPY dyes are widely employed.
In this work, we present an approach for creating a BODIPY-based pocket-like structure for the recognition of volatile organic compounds (VOC) such as benzene and its derivatives. This may lead to the development of sensing devices for this class of compounds, which receive special attention by environmental chemists and regulatory authorities due to severe adverse effects on humans in particular and the environment in general. The low reactivity of benzene-derived hazardous compounds is thereby a major fact that has to be taken into consideration. While for other reactive gaseous compounds, fluorophore-based detection performance is achieved by the chemical modification of the fluorophore itself, e.g. by bond cleavage, addition, oxidation or reduction reactions; this is not possible for many VOCs. Several metal complexes were described for the sensing of benzene and its derivatives, but no organic dyes such as BODIPYs are known with these capabilities. Our unique concept towards BODIPY-based molecules acting as scavengers for VOCs is supposed to overcome the problem of benzene’s low reactivity by enforcing π-π-interactions between the fluorophore and the volatile aromatic analyte in pocket-like molecular structures.
In Near Edge X-Ray Absorption Fine Structure (NEXAFS) spectroscopy X-Ray photons are used to excite tightly bound core electrons to low-lying unoccupied orbitals of the system. This technique offers insight into the electronic structure of the system as well as useful structural information. In this work, we apply NEXAFS to two kinds of imidazolium based ionic liquids ([CnC1im]+ [NTf2]− and [C4C1im]+ [I]−). A combination of measurements and quantum chemical calculations of C K and N K NEXAFS resonances is presented. The simulations, based on the transition potential density functional theory method (TP-DFT), reproduce all characteristic features observed by the experiment. Further, a detailed assignment of resonance features to excitation centers leads to a consistent interpretation of the spectra.
Background: Fluorescent amplification strategies with nanomaterials are of increasing importance for a wide range of applications in material and life sciences. This includes their use as reporters for optical assays, targeted probes in bioimaging studies and as sensor materials. Some organic dyes with twisted skeleton conformation show enhanced emission upon aggregation (AIE)in contrast to the majority of dyes which reveal aggregation-caused fluorescence quenching (ACQ). Such dyes could be candidates for amplification strategies.
Here we present a series of new hydrophobic pyrrolidinylvinylquinoxaline (PVQ) dyes with different substituents, which are supposed to show AIE. This group of twisted skeleton conformed dyes are emissive in the solid state, as aggregates, and encapsulated in hydrophobic polymer materials.
Results: The PVQ derivatives show strong AIE in ethanol-water-mixtures containing more than 80% water as indicated by the strong increase in fluorescence quantum yields and lifetimes upon dye aggregation and nanoparticle formation. The size of the AIE effect and the observed fluorescence enhancement are in good agreement with DFT- and XRD calculations of the torsion angle between the four different substituents and the planar backbone of the dye. In all cases, particles with diameters smaller than 450 nm were formed. The hydrodynamic diameter of the aggregates was controlled by the water content, with an increasing water content causing a decrease of the hydrodynamic diameter. In the presence of polyelectrolytes or surfactants, μm-sized crystals were obtained. Encapsulation of the dyes in preformed polymer particles provides stabil and strongly emissive nanoparticles.
Conclusion: Based on new PVQ, we yielded highly emissive nanoparticles. The correlation between the torsion angle and the AIE effect underlines structural control of AIE by substitution pattern in this dye class. The loading of a polymer matrix with PVQ resulted in stable nanoparticles with varied surface modification. Applications of these effects in fluorescence assays are currently studied.
A 400 m² soil test field with gas injection system was built up, which enables an experimental validation of linear gas sensors for specific applications and gases in an application-relevant scale. Several injection and soil watering experiments with carbon dioxide (CO2) at different days with varying boundary conditions were performed indicating the potential of the method for, e.g., rapid leakage detection with respect to Carbon Capture and Storage (CCS) issues.
Flow cytometry is a common tool in biological research and clinical analyses. In current developments, there are two different tendencies of interest. Firstly, we face the need for analysis methods that are capable of addressing more and more involved analysis tasks, i.e., an increasing number of fluorescent codes and markers is required. Secondly, low-cost diagnostic tests, e.g. in disease recognition, are needed in routine application.
Lifetime encoding could be an attractive alternative to commonly applied color (spectral) encoding. By combining spectral and lifetime multiplexing, the number of simultaneously detectable codes might be increased by adding lifetime codes to the parameter space. Otherwise, instrumentation costs could be lowered using only lifetime encoding and thus avoiding costly excitation light sources and detectors.
Here, we report on our recent progress in time-resolved flow cytometry using dye-stained lifetime-encoded polymer microparticles as a model system. We could show that the discrimination of two lifetime codes is feasible. Moreover, the simultaneous detection of a spectrally different ligand fluorescence signal excited at the same wavelength as the lifetime code fluorescence could be demonstrated.
Advanced methods for 3D green density characterization like computed tomography and 3D FE sinter modeling can be utilized for increasing the reliability of sintered components. The experimental in situ observation of sintering, however, is currently restricted to silhouette methods, i.e. heating microscopy. For complex shaped samples, in situ shape screening during shrinkage would allow much better validation of 3D sinter simulation models. Further, by revealing temporary sinter warpage, 3D high-temperature shape screening allows to locate potential defects of complex sintered components. Against this background, BAM developed a testing device for in situ 3D high-temperature shape screening for ceramic and glass-ceramic tapes up to 1000°C [1-3]. Current work is focused on dropping this restriction in sample shape and temperature. The poster illustrates the current state of this work and possible applications of the method e.g. in detecting sinter warpage of metallized glass-ceramic LTCC tapes.
Worldwide BAM Certification of Radigraphic Image Detectors for the NDT Market – Status of 2016
(2016)
The Poster shows the status of 2016 in BAM certification of radiographic image detectors for industrial radiology for nondestructive testing. BAM was generating first the basis by worldwide standardization activities and released later certificates on request of the device manufacturers using these Standards a base for certification.