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Integrating fluorescent probes with sensing matrices presents a major challenge because usually, when confined in a rather rigid matrix, fluorophores tend to behave completely different than for instance in the molecular state in solution. The lecture reviews the major strategies that have been devised recently to circumvent such issues with special focus on the works carried out in this field by BAM’s Chemical and Optical Sensing Division. Moreover, it will be shown that by using certain strategies not only can the response behavior be retained but synergistic effects can even endow the hybrid with a much better performance than the probe molecule alone.
Sensor systems are widely used in hydrogen technologies. The lecture presents requirements and properties of sensor systems and shows application examples of these technologies for safety and process control for hydrogen technologies. The focus is on gas sensors as well as sensors for pressure, temperature and gas flow. These systems are applied, among other things, for monitoring and control of operating conditions, indication of hazardous conditions and triggering of alarms.
Two nanosensors for simultaneous optical measurements of temperature (“T”), oxygen (“O”), and pH (“P”) have been designed. These “TOP” nanosensors are based on 100 nm-sized silica-coated polystyrene nanoparticles (PS-NPs) doped with the near infrared emissive oxygen- and temperature-sensitive chromium(III) complex ([Cr(ddpd)2][BPh4]3 CrBPh4)[1][2] and an inert reference fluorescence dye (Nile Red NR or 5,10,15,20-tetrakis-(pentafluorophenyl) porphyrin TFPP) and are covalently labeled with the pH-sensitive fluorophore fluorescein isothiocyanate (FITC). These emitters can be excited at the same wavelength and reveal distinguishable emission spectra suitable for ratiometric intensity-based and time-resolved studies in the visible and near infrared spectral region. The core-shell nanostructure of these sensors reveals high colloidal stability in various aqueous media. Studies in PBS buffer solutions and in a model body liquid demonstrate the applicability of the TOP nanosensors for optically detecting the three bioanalytically and biologically relevant analytes temperature, oxygen and pH simultaneously at the same position.
Photoluminescence applications in the life and material sciences require bright molecular and nanocrystalline emitters, stimuli-responsive optical probes, signal enhancement, multiplexing, and barcoding strategies and traceable methods to quantify the signal-relevant optical properties of luminescent materials at the ensemble and single molecule/particle level. In this context, current research at Division Biophotonics of BAM is presented ranging from dye and nanocrystal photophysics, absolute measurements of photoluminescence quantum yields in the UV/vis/NIR/SWIR, lifetime multiplexing, and the development of different types of fluorescence standards for validating optical-spectroscopic measurements.
A vast number of emerging pollutants is being detected in the environment. Another lingering problem are health-threatening contaminants, such as mycotoxins, that deteriorate food and feed, and the pathogens themselves. Analytical methods, suitable for trace analysis, are needed that are desirably also fast, inexpensive and, if possible, robust and portable. It is set out, how immunoana-lytical, i.e., antibody-based methods, which are elaborated in a broad range of formats, can be profitably used to gain insights on the distribution and concentration trends of the target analytes at the point-of-need.
Macrocycle-containing fluorescent probes continue to be one of the most popular classes of indicator molecules for the sensitive optical detection of ionic inorganic analytes, in particular metal ions, since the first integration of crown ether building blocks into chromophoric π systems more than 30 years ago. However, whereas a large multitude of such probes have been described for operation in organic or mixed aqueous environments, the step to realistic analytical media such as water samples, aqueous food extracts or body fluids is still scarce. On one hand, this is due to considerably low complex stability constants for instance for alkali and alkaline-earth metal ions. On the other hand, many classes of organic dyes that show favourable spectroscopic properties and ion-induced responses in organic solvents are not soluble in neat aqueous media and/or exhibit only significantly quenched fluorescence, even if transition metal ions are binding strongly to the receptor unit. A way to circumvent such problems in a rather simple manner is the steric incorporation of fluorescent probes into mesoporous silica nanomaterials. The local polarity in such pores, whether nascent or modified appropriately with functional silanes, resembles much more a quasi-organic environment while at the same time allowing for free diffusion of water and its cargo.
Two examples of powerful hybrid signalling systems will be presented, utilizing charge transfer-type indicator molecules that show inferior sensing properties in their molecular state. One example discusses mercury(II) determination over an extended concentration range and the other discusses silver(I) and mercury(II) discrimination simply on the basis of photophysical effects retained in the hybrid materials.
The success of this energy transition and the efficient utilization of green hydrogen as a pristine energy carrier hinge upon the cultivation of hydrogen readiness, swift market expansion, and the establishment of crucial value chains within national and European contexts. Paramount to these objectives are reliable quality and safety standards, essential for ensuring supply safety, environmental compatibility, and instilling confidence in these technologies.
In the realm of safety management systems, gas sensors emerge as vital components for detecting hydrogen. This presentation delves into the imperative role of hydrogen systems, emphasizing their capability to monitor and control operations, issue warnings, signal hazardous conditions, and sound alarms. It explores the intricate landscape of functional safety considerations and addresses the challenges associated with measurement uncertainty in sensor testing.
A diverse array of sensors catering to hydrogen, pressure, temperature, and flow are available, each contributing significantly to the safety and efficiency of hydrogen technologies. Applications are envisaged to adhere meticulously to quality infrastructural regulations, codes, and standards, ensuring seamless integration and operation within the broader hydrogen ecosystem.
This discussion underscores the ubiquitous presence of sensor systems across various fields within hydrogen technologies, illustrating their multifaceted contributions to safety, reliability, and overall success in realizing the transformative potential of green hydrogen.
Die Bundesanstalt für Materialforschung und -prüfung (BAM) ist eine forschende Bundesoberbehörde und Einrichtung der Ressortforschung der Bundesrepublik Deutschland. Unter ihrer Leitlinie „Sicherheit in Technik und Chemie“ ist sie zuständig für die öffentliche technische Sicherheit und für metrologische Aufgaben in der Chemie. Das Aufgabenspektrum der BAM, das sich an aktuellen Fragestellungen aus Wissenschaft, Wirtschaft, Politik und Normung orientiert, bietet sehr viele interessante Tätigkeitsfelder für Naturwissenschaftler*Innen und Ingenieur*Innen.
Contamination of natural bodies of water with oil and lubricants (or generally, hydrocarbon derivatives such as petrol, fuel and others) is a commonly found phenomenon around the world due to the extensive production, transfer and use of fossil fuels. The timely identification of these contaminants is of utmost importance, since they directly affect water quality and represent a risk for wildlife and human health even in trace amounts.
In this work, we develop a simple system for the on-field detection of total petroleum hydrocarbons (TPH) in water and soil, the "Spectrocube". The test is based on the measurement of the fluorescence signal emitted by the molecular rotor 4-DNS-OH dye. This dye is embedded in a hydrophobic polymeric matrix (PVDF), avoiding interactions of water with the dye and providing a robust support for use in test-strip fashion. The test-strip’s fluorescence intensity increases linearly at low concentrations of TPH, reaching a saturation value at higher concentrations.
For excitation and evaluation of the test-strip fluorescence, a simple miniature optical system was designed. The system works semi-quantitatively as solvent-free TPH detection kit, as well as quantitatively when using a simple cyclopentane extraction step. To simplify the fluorescence read-out, the device is coupled to a tablet computer via Bluetooth, running a self-programmed software ("app").
Due to the promising combination of chemical, thermal and mechanical properties, springs made of advanced ceramics have attracted much attention as a replacement for metal springs in highly demanding applications, operating at high temperatures and in harsh environments when hardened metals can no longer be used. A further application was recently proposed by using ceramic springs with metalized surfaces as capacitive force sensors. Prior to any design of an instrument, application-specific static and/or dynamic loading experiments are necessary to investigate the stability of spring properties under the given conditions. These experiments can also be used to determine seldom measured material properties like the shear modulus of ceramics.
Helical Springs with a rectangular cross-section have been machined from straight tubes of alumina (99.99% α-AI203,) and zirconia (Y/Ce-TZP). The sintered density of both materials was above 99% of the theoretical density.
The stress/displacement curves turned out to be extremely linear and the spring constants were not altered, even after more than one million cycles of compression loading at various temperatures from -15°C to +60°C. This means that such springs can be a far more reproducible and reliable source of an elastic response to applied forces than handmade springs from molten quartz wires. The behavior found for in-house fabricated springs contrasts to the behavior found for a commercial ceramic spring, which was produced by injection molding and exhibits a less linear response.
Furthermore, high-temperature displacement behavior of fabricated alumina and zirconia springs was tested under static loading conditions in different atmospheres (air, N2 and H2) at temperatures up to 1000 °C.