Chemische Charakterisierung und Spurenanalytik
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The rapid development of portable analytical methods—which has accelerated particularly during the SARS-CoV-2 pandemic—has fundamentally transformed diagnostics and expanded their use beyond healthcare into fields such as food safety, environmental management, and security, including threat detection and forensic analysis. These technologies enable rapid on-site decision-making without relying on a centralized laboratory infrastructure. Their practical applicability is further enhanced by the widespread availability of mobile devices equipped with high-performance cameras and significant computing power. Despite these advances, most existing assays remain limited to the detection of a single analyte. A key challenge therefore lies in the development of reliable multiplexed assays capable of simultaneously identifying multiple target compounds with high sensitivity.
This presentation introduces versatile strategies developed in the Chemical and Optical Sensing Division at BAM, with a focus on supramolecular chemistry, luminescent detection methods, nanomaterials, and the miniaturization of devices. Illustrative examples include mesoporous nanomaterials, gated indicator systems, molecularly imprinted polymers, microfluidic platforms, test strips, and smartphone-based analytical approaches.
Molecularly imprinted polymers (MIPs) containing fluorescent probe monomers or crosslinkers that are covalently polymerized into the MIP network are powerful tools for the direct indication of analytes in a sample or a sample extract [1]. This direct incorporation not only allows the use of the diverse formats in which MIPs can be prepared for analytical applications but also allows the use of MIPs for real-time signal readout as well as for enrichment and readout, depending on the design of the assay. In addition, the presence of a dye in each step of the preparation process, starting with the prepolymerization mixture, provides a useful tool for monitoring the synthetic procedure to determine whether the intended complexes are being imprinted and/or whether unexpected or undesirable events are occurring during preparation.
Naturally, in addition to the general requirement that such a functional dye must survive the polymerization process, the intended application and desired format must also take various factors into account before a specific dye scaffold is selected, i.e., the wavelength range of operation, the type of signal changes to be measured, possible internal referencing as well as possible multiplexing. Based on our experience in the development of fluorescent probe monomers and crosslinkers [2–5], this contribution offers (young) researchers a guide to selecting the appropriate dye for their MIP.
Incineration is currently the only commercial full-scale technology available to destroy per- and polyfluoroalkyl substances (PFAS) in large solid and liquid waste streams. Given previous experience of dioxin formation during halogenated waste incineration, concerns about the emission of products of incomplete destruction (PIDs) from PFAS incineration exist. The overarching objective of this project is to track the fate of fluorine during full-scale hazardous waste incineration in order to demonstrate the readiness, viability, and level of safety for thermal PFAS destruction in various waste streams. The specific objectives of this project are to enhance our understanding of key variables and conditions on PFAS incineration performance, to identify major PIDs under insufficient treatment conditions, to explore the catalytic role of fly ash and other process-relevant surfaces in thermal PFAS decomposition, and to determine the potential formation of polyfluorinated dibenzodioxins and dibenzofurans
Reactive extrusion (REx) is emerging as a powerful technology for the continuous and solventless production of modified lignins. However, the optimization of REx-based processes for modifying lignin relies on offline lignin analytics, which are time-consuming and heavily influenced by sample preparation. This study integrated near- infrared (NIR) spectroscopy into a twin-screw extruder to monitor in real time the modification of softwood kraft lignin via esterification with octenyl succinic anhydride (OSA). The NIR data was processed by means of chemometric methods. Temperature and screw configuration were found to influence the esterification of lignin. Combining these results with offline lignin analytics, 120 ◦ C was selected as the optimal temperature in conjunction with the integration of kneading elements into the screw profile, to yield OSA-lignin esters with ≥ 50% degree of modification. The product output was successfully scaled up sevenfold while using NIR spectroscopy to monitor the extrusion. In addition, the broader applicability of this inline monitoring method was demonstrated by using a biorefinery lignin from hardwood. The target degree of modification was achieved with minimal recalibration of process parameters. A space–time yield of up to 7 x 10 •day was realized, indicating the potential of this REx process for industrial adoption. Overall, this work provides a foundation for the development of a process analytical technology for monitoring lignin modification during REx that can be expanded to other lignin chemistries, thus providing scalable and adaptable solutions for adding value to lignin.
The analysis of paper-based food contact materials (FCM) has gained increasing attention due to the widespread use of per- and polyfluoroalkyl substances (PFAS) and their known toxic effects and environmental persistence. As regulatory frameworks for PFAS in FCM remain limited, sensitive and reliable analytical methods are necessary to ensure food safety. While PFAS analysis is predominantly performed using liquid chromatography coupled to tandem mass spectrometry (LC-MS/MS), a systematic development of gas chromatography coupled to mass spectrometry (GC-MS)-based methods for multiple PFAS classes remains limited. In this study, two pre-column derivatization techniques were optimized and evaluated for GC-MS determination of perfluoroalkyl carboxylic acids (PFCA), fluorotelomer alcohols (FTOH), and fluorotelomer carboxylic acids (FTCA). Both derivatization methods enabled qualification and quantification of the targeted PFAS with comparable limits of detection in the low ng/mL range. N,N-Dimethylformamide dimethyl acetal (DMFDMA) derivatization proved to be more sensitive with a limit of detection down to 0.85 ng/mL. In addition, this derivatization approach was successfully automated within the GC-MS workflow, resulting in sample preparation times comparable to those of LC-MS-based methods. The application of this optimized method to paper-based FCM demonstrated its suitability for real world FCM analysis. Results of PFAS content per targeted PFAS of 26.6 to 261.4 ng/g highlight the potential of GC-MS analysis, particularly when combined with automated derivatization, as a viable alternative or complement to LC-MS for PFAS analysis in FCM.
Over the past three decades, luminescent nanocrystals have evolved from a scientific curiosity into a versatile class of functional materials with applications spanning photonics, bioimaging, sensing, energy conversion, and quantum technologies. Throughout this development, Markus Haase has played a defining role in shaping the field through his pioneering contributions to colloidal semiconductor quantum dots and, in particular, lanthanide-doped upconverting nanocrystals. His work established fundamental synthetic strategies, provided mechanistic insight into particle formation and optical processes, and set new standards for reproducibility, characterization, and scientific rigor.
This commemorative lecture brings together the perspectives of colleagues, former doctoral researchers, collaborators, and long-standing friends from the scientific community to celebrate Markus Haase's remarkable career and lasting scientific legacy. Beyond highlighting key milestones and breakthroughs, the presentation reflects on the qualities that have distinguished his work: intellectual curiosity, creativity, uncompromising scientific integrity, and the willingness to pursue challenging and unconventional research directions. Equally important, it acknowledges the personal values that have inspired generations of researchers—his honesty, loyalty, commitment, passion for science, and distinctive sense of humor. Together, these contributions have not only advanced the field of luminescent nanocrystals but have also left a lasting impact on the people and collaborations that continue to shape it.
There is an increasing interest in molecular and nanoscale with emission > 800 nm and recently also > 1000 nm for bioanalysis, medical diagnostics, bioimaging, and safety barcodes [1]. Mandatory for the comparison of different emitter classes and the rational design of the next generation of reporters for the short wavelength infrared (SWIR) region are reliable and quantitative photoluminescence measurements in this challenging wavelength region. This is of special relevance for nanocrystalline emitters like semiconductor quantum dots and rods as well as lanthanide-based upconversion and downconversion nanocrystals, where surface states and the accessibility of emissive states by quenchers largely control accomplishable photoluminescence quantum yields and hence, signal sizes and detection sensitivities from the reporter side. Such measurements are currently hampered by the lack of suitable methods and standards for instrument calibration and validation and quantum yield standards with emission > 800 nm and especially > 1000 nm [2-4]. In this respect, we present the design of integrating sphere setups for absolute and excitation power density-dependent measurements of emission spectra and photoluminescence quantum yields in the wavelength region of 650 to 1650 nm including calibration strategies and first candidates for potential fluorescence standards [3-5]. Subsequently, the photoluminescence properties of different types of nanocrystals are presented including the upconversion and downconversion emission of differently sized and surface functionalized lanthanide-doped nanoparticles and photoluminescence quenching effects are quantified. Key words: NIR, IR fluorescence, quantum dot, upconversion nanocrystal, lanthanide emitter, integrating sphere spectroscopy, absolute fluorescence quantum yield Kraft.
The use of engineered nanoparticles of different size, shape, and composition is continuously increasing in life and materials sciences. This calls for methods and reference materials enabling the reliable and accurate determination of nanoparticle size, particle size distribution, shape, number concentration, degree of aggregation and agglomeration in different environments as well as for nanoparticle dispersibility and stability.
We are currently building up and exploring a platform of lanthanide-based nanocrystals (LnNCs) and other functional nanoparticles with application-specifically tuned size, shape, composition, architecture, optical properties, and surface chemistry for emerging applications in life sciences and as reference and test materials. As a prerequisite for the broad applicability of these nanomaterials, we assess simple, robust, and easily up-scaleable synthesis protocols for LnNCs with defined morphologies and tunable optical properties [1], and the short-term and long-term stability of LnNCs with selected surface coatings in aqueous environments under different application-relevant conditions.[2] In addition to sensing and encoding applications, we are currently exploring the applicability of our LnNCs which can be prepared in large amounts in different shapes,. i.e., as spheres, bypyramids, or rods with excellent control of size and size distribution, as reference material candidates for sizing methods such as electron microscopy and small-angle X-ray scattering (SAXS) as well as for determination of particle number concentration. For spherical NPs, particle size can be easily determined from measurements of the diameter of by electron microscopy providing 2D information on a large number of dried nanoparticles deposited in vacuo on a solid substrate. However, for NPs with a different shape, this 2D-projection can be misleading. Here, new correlative approaches are needed for the complete 3D characterization for particles with a more complex shape [3] and non-spherical reference particles for establishing such methods and the implementation and validation of the respective data fitting routine. In this context, we are currently exploring the potential of differently sized functional nanoparticles as test and reference materials for size and particle number concentration (PNC) by SAXS and interlaboratory comparisons involving different SAXS expert groups.[4]
In this study, novel polymer/graphene oxide (GO) composites were engineered for the adsorption and recovery of phenolic compounds from olive mill wastewater. A pentafluoropyridine-derived monomer was synthesized and subsequently polymerized via polycondensation to yield pyridine-containing polymers. Composites incorporating 5, 10, and 15 wt% GO were then prepared and evaluated for the adsorption of major phenolic constituents commonly detected in olive mill wastewater, namely hydroxytyrosol (HT), tyrosol (TR), caffeic acid (CA), and ferulic acid (FA). These compounds are recognized for their remarkable antioxidant activity and their broad potential applications in the cosmetic, pharmaceutical, nutraceutical, and food sectors. The materials also demonstrated the capability for the simultaneous co-adsorption of multiple phenolic compounds. Adsorption kinetics and equilibrium studies indicated that the process was best described by the pseudo-first-order kinetic model and the Langmuir isotherm model, respectively, suggesting predominantly monolayer adsorption behavior. Among the synthesized materials, the P-GO10 composite exhibited superior adsorption performance, achieving maximum adsorption capacities of 95.5 mg g1 for hydroxytyrosol and 81.3 mg g1 for tyrosol, with adsorption equilibrium attained within approximately 24 h. Desorption was effectively achieved through methanol washing, and the regenerated adsorbent retained approximately 73% of its initial adsorption efficiency after five consecutive adsorption–desorption cycles, demonstrating satisfactory stability and reusability. Collectively, these findings underscore the significant potential of P–GO composites as efficient, robust, and reusable adsorbent materials for the recovery and valorization of high-value phenolic compounds from agro-industrial wastewater streams.
Luminescent particles such as spectrally shifting lanthanide-based nanocrystals (LnNCs) like NaYF4: Yb, Er, semiconductor quantum dots, and luminophore-labelled or doped silica and polymer particles are broadly applied in the life and material sciences. The identification of optimum particle architectures and surface chemistries for photonic applications requires quantitative spectroscopic studies of the application-relevant optical properties and simple methods for the determination of surface functionalities. In this context, photoluminescence studies of different luminescent nanocrystals are presented with focus on LnNCs. Also, methods for the determination of particle brightness and photoluminescence quantum yield are presented as well as examples for the determination of surface functionalities with optical assays.