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Simple, fast, and versatile methods for the quantification of thiol groups are of considerable interest not only for protein analysis but also for the characterization of the surface chemistry of nanomaterials stabilized with thiol ligands or bearing thiol groups for the subsequent (bio-) functionalization via maleimide−thiol chemistry. Here, we compare two simple colorimetric assays, the widely used Ellman’s assay performed at alkaline pH and the aldrithiol assay executed at acidic and neutral pH, with respect to their potential for the quantification of thiol groups and thiol ligands on different types of nanoparticles like polystyrene nanoparticles, semiconductor nanocrystals (SC NC), and noble metal particles, and we derive criteria for their use. In order to assess the underlying reaction mechanisms and to obtain stoichiometry factors mandatory for reliable thiol quantification, both methods were studied photometrically and with electrospray ionization time-of-flight mass spectrometry (ESI-TOF-MS), thereby demonstrating the influence of different thiols on the reaction mechanism. Our results underline the suitability of both methods for the quantification of directly accessible thiol groups or ligands on the surface of 2D- and 3D-supports, here exemplarily polystyrene nanoparticles. Moreover, we could derive strategies for the use of these simple assays for the determination of masked (i.e., not directly accessible) thiol groups like disulfides such as lipoic acid and thiol stabilizing ligands coordinatively bound to Cd and/or Hg surface atoms of II/VI and ternary SC NC and to gold and silver nanoparticles.
Nach den bisherigen Regeln werden Bauwerksprüfungen von Brücken in starr definierten Intervallen durchgeführt. Diese starre, periodische, zustandsbasierte Instandhaltungsstrategie soll zukünftig durch eine flexible und prädiktive Instandhaltung ersetzt werden. Hierbei sollen Inspektionen und Instandhaltungsmaßnahmen unterstützt durch autonome Systeme auf der Grundlage von Monitoringdaten geplant und zusätzlich bei unvorhergesehenen Ereignissen ausgelöst werden. Im Rahmen des Verbundforschungsvorhabens AISTEC wird ein Vorgehen für Großbauwerke und kleinere Regelbauwerke zur Umsetzung eines kombinierten globalen, schwingungsbasierten und quasistatischen Monitorings entworfen. An der Maintalbrücke Gemünden – einer semiintegralen Rahmenbrücke aus Spannbeton auf der Schnellfahrstrecke Hannover–Würzburg – wurde als Demonstrator ein Dauermonitoring realisiert.
Die Infrastruktursysteme der Industriestaaten erfordern heute und in Zukunft ein effizientes Management bei alternder Bausubstanz, steigenden Lasten und gleichbleibend hohem Sicherheitsniveau. Digitale Technologien bieten ein großes Potenzial zur Bewältigung der aktuellen und künftigen Herausforderungen im Infrastrukturmanagement. Im BMBF-geförderten Projekt Bewertung alternder Infrastrukturbauwerke mit digitalen Technologien (AISTEC) wird untersucht, wie unterschiedliche Technologien und deren Verknüpfung gewinnbringend eingesetzt werden können. Am Beispiel der Maintalbrücke Gemünden werden ein sensorbasiertes Bauwerksmonitoring, bildbasierte Inspektion mit durch Kameras ausgestatteten Drohnen (UAS) und die Verknüpfung digitaler Bauwerksmodelle umgesetzt. Die aufgenommenen Bilder dienen u. a. als Grundlage für spätere visuelle Anomaliedetektionen und eine 3D-Rekonstruktion, welche wiederum für die Kalibrierung und Aktualisierung digitaler Tragwerksmodelle genutzt werden. Kontinuierlich erfasste Sensordaten werden ebenfalls zur Kalibrierung und Aktualisierung der Tragwerksmodelle herangezogen. Diese Modelle werden als Grundlage für Anomaliedetektionen und perspektivisch zur Umsetzung von Konzepten der prädiktiven Instandhaltung verwendet. Belastungsfahrten und historische Daten dienen in diesem Beitrag der Validierung von kalibrierten Tragwerksmodellen.
Structural health monitoring (SHM) intends to improve the management of engineering structures. The number of successful SHM projects – especially SHM research projects – is ever growing, yielding added value and more scientific insight into the management of infrastructure asset. With the advent of the data age, the value of accessible data becomes increasingly evident. In SHM, many new data-centric methods are currently being developed at a high pace. A consequent application of research data management (RDM) concepts in SHM projects enables a systematic management of raw and processed data, and thus facilitates the development and application of artificial intelligence (AI) and machine learning (ML) methods to the SHM data. In this contribution, a case study based on an institutional RDM framework is presented. Data and metadata from monitoring the structural health of the Maintalbrücke Gemünden for a period of 16 months are managed with the RDM system BAM Data Store, which makes use of the openBIS data management software. An ML procedure is used to classify the data. Feature engineering, feature training and resulting data are performed and modelled in the RDM system.
Support structures of wind turbines in German offshore wind farms are regularly inspected. Currently, inspection outcomes are generally not systematically recorded. This prevents their consistent handling and processing, which is a key requirement to enable an efficient structural integrity management. As part of the DiMoWind-Inspect project, a data model and reference designation system for such inspection results is developed to facilitate their identification, localization, quantification, tracing and linking throughout the lifetime of a wind farm and beyond. The inspection results together with structural health monitoring results and information on repairs form the basis for assessing and predicting the structural condition, estimating the remaining lifetime, and planning of future inspections, structural health monitoring, and repairs. As a basis for developing a digital structural integrity management, a generic framework is proposed in this paper, which describes the stakeholders, data, models, processes and workflows of the integrity management of support structures in offshore wind farms and their interrelations. The framework adopts a building information modelling approach to describe the information relevant to the structural integrity management. The central digital space of the framework is a common data environment. An implementation of the framework will enable a digital structural integrity management in which inspection, structural health monitoring, repair, assessment and planning outcomes generated throughout the life cycle of a wind farm can be consistently collected, managed, shared and processed by the relevant shareholders.
The optical properties of semiconductor nanocrystals (SC NCs) are largely controlled by their size and surface chemistry, i.e., the chemical composition and thickness of inorganic passivation shells and the chemical nature and number of surface ligands as well as the strength of their bonds to surface atoms.
The latter is particularly important for CdTe NCs, which – together with alloyed CdₓHg₁₋ₓTe – are the only SC NCs that can be prepared in water in high quality without the need for an additional inorganic passivation shell. Aiming at a better understanding of the role of stabilizing ligands for the control of the application-relevant fluorescence features of SC NCs, we assessed the influence of two of the most commonly used monodentate thiol ligands, thioglycolic acid (TGA) and mercaptopropionic acid (MPA),
on the colloidal stability, photoluminescence (PL) quantum yield (QY), and PL decay behavior of a set of CdTe NC colloids. As an indirect measure for the strength of the coordinative bond of the ligands to SC NC surface atoms, the influence of the pH (pD) and the concentration on the PL properties of these colloids was examined in water and D₂O and compared to the results from previous dilution studies with a set of thiol-capped Cd₁₋ₓHgₓTe SC NCs in D₂O. As a prerequisite for these studies, the number of surface ligands was determined photometrically at different steps of purification after SC NC synthesis with Ellman’s test.
Our results demonstrate ligand control of the pH-dependent PL of these SC NCs, with MPA-stabilized CdTe NCs being less prone to luminescence quenching than TGA-capped ones. For both types of CdTe colloids, ligand desorption is more pronounced in H₂O compared to D₂O, underlining also the role of hydrogen bonding and solvent molecules.
Bright and stable near-infrared (NIR) and infrared (IR) emitting chromophores are in high demand for applications in telecommunication, solar cells, security barcodes, and as fluorescent reporters in bioimaging studies. The best choice for wavelengths >750 nm are semiconductor nanocrystals, especially ternary or alloy nanocrystals like CdHgTe, which enable size and composition control of their optical properties. Here, we report on the influence of growth time and surface chemistry on the composition and optical properties of colloidal CdHgTe. Up to now, these are the only NIR and IR emissive quantum dots, which can be synthesized in high quality in water, using a simple one-pot reaction. For this study we utilized and compared three different thiol ligands, thioglycolic acid (TGA), 3-mercaptopropionic acid (MPA), and glutathione (GSH). Aiming at the rational design of bright NIR- and IR-emissive alloy materials, special emphasis was dedicated to a better understanding of the role of the surface ligand and adsorptiondesorption equilibria on the photoluminescence quantum yield and stability. In this respect, dilution and protonation studies were performed. Our results show that with this simple synthetic procedure, strongly fluorescent CdHgTe colloids can be obtained with MPA as stabilizing ligand revealing quantum yields as high as 45% independent of particle concentration.
Für die Berechnung des Crashverhaltens von Fahrzeugstrukturen muss zusätzlich zur Dehnratenabhängigkeit des plastischen Verformungsverhaltens des Grundwerkstoffs auch das Verhalten von Fügestellen bei hoher Beanspruchungsgeschwindigkeit bestimmt werden. Ziel der VDEh-Arbeitsgruppe 'Hochgeschwindigkeitszugversuche an gefügten Stählen' war die Erstellung eines Stahl-Eisen-Prüfblattes (SEP) zur Ermittlung crashrelevanter Kennwerte für gefügte Stahl-Feinbleche unter vereinheitlichten Prüfbedingungen. Zur Erarbeitung der in dieser Richtlinie zu formulierenden Empfehlungen wurden Scherzugversuche bei hoher Geschwindigkeit an punktgeschweißten und lasergeschweißten Proben von elf Prüflaboratorien durchgeführt. Der Beitrag beschreibt die Ergebnisse dieses Ringversuchs und seine Auswirkungen auf das SEP.
Monitoringsysteme erfassen kontinuierlich Bauwerksdaten wie z.B. Bauwerksbeschleunigungen, auf deren Grundlage Bauwerksschäden mit Hilfe von SHM-Methoden quantifiziert werden können. Mit den gewonnenen Informationen über den aktuellen Bauwerkszustand können Vorhersagen des Bauwerkszustandes und der Bauwerkszuverlässigkeit aktualisiert und erforderliche Inspektionen und Instandhaltungsmaßnahmen vorausschauend geplant werden. Im BMBF-Forschungsvorhaben AISTEC entwickeln der Fachbereich 7.2 „Ingenieurbau“ innovative Monitoringverfahren zur Systemidentifikation und automatischen Detektion, Lokalisierung und Quantifizierung von Schäden an Infrastrukturbauwerken anhand von gemessenen dynamischen und statischen Bauwerksdaten. Im Rahmen dieses Projektes werden die Verfahren an der Maintalbrücke bei Gemünden angewendet, welche Teil der ICE-Strecke Hannover-Würzburg ist. In diesem Vortrag wird das für die Maintalbrücke Gemünden geplante und umgesetzte Monitoingsystem vorgestellt.
Inspection and maintenance contribute significantly to the lifetime cost of bridges. There is significant potential in using information obtained through structural health monitoring to update predictive models of the condition and performance of such structures, and thus ena-ble an improved decision-making regarding inspection and maintenance activities. Within the AISTEC project funded by the German Federal Ministry of Education and Research, we develop vibration-based structural health monitoring systems aimed at continuously provid-ing information on the structural condition of bridges. Environmental variations such as changing ambient temperatures can significantly influence the dynamic characteristics of bridges and thus mask the effect of structural changes and damages. It remains a challenge to account for such influences in structural health monitoring. To study the effect of ambient temperatures on the dynamic characteristics of beam structures, we monitor the vibration response of a reinforced concrete beam in the uncracked and cracked state at varying tem-peratures in a climate chamber. We postulate a set of competing parameterized probabilistic structural models, which explicitly account for the effect of varying ambient temperatures on the mechanical properties of the system. We then combine the information provided by the structural models with the information contained in the recorded vibration data to learn the parameters of the temperature-dependent structural models and infer the plausible state of the beam using Bayesian system identification and model class selection.
Investigation and control of protein adsorption for fluorescent nanosilver reference material
(2017)
Upon interaction of nanomaterials like noble metal nanoparticles (NPs) with biological systems like body fluids such as serum, a protein corona is formed.[1] This reversibly bound layer of proteins controls the transport of the NPs and their subsequent interaction with biological components.[2] The plasmonic properties of nobel metal NPs like Au and Ag can considerably affect the fluorescence properties of fluorophores in their vicinity, i.e., within a near field distance. Depending on the chemical composition, size and shape of these noble metal NPs, the spectral properties of the dye, and the particle-fluorophore distance, the fluorescence is quenched or in some cases enhanced.[3,4,5] This can be monitored by fluorescence intensity and lifetime measurements, with the latter effect being accompanied by an increase in fluorescence intensity and reduction in fluorescence lifetime due to an increase in radaiative rate constant. We utilized these effects to study and manipulate noble metal NP-protein interaction exemplarily for fluorophore-labeled bovine serum albumin (BSA) modified e.g. by succinylation, amination and the introduction of thiol groups, resulting in different binding affinities of the proteins.[6] Our results show that the fluorescent corona allows monitoring of the interaction of our accordingly protein-functionalized particles with biological model systems like solutions containing different amounts of various proteins. This can be eventually used for further in vitro and in vivo studies to assess the uptake, digestion, and excretion of surface functionalized noble metal NPs.