TY - CONF A1 - Bell, Jérémy A1 - Tillo, Adam A1 - Chauhan, Vraj P. A1 - Bartelmeß, Jürgen A1 - Rurack, Knut T1 - Microfluidic analytical tool coupling a fluorescent molecular probe and a micro-hydrocyclone for the detection of water chlorination level N2 - Chlorination of pool water and wastewater, in food and pharmaceutical production, as well as in pesticide and paper manufacturing is a routinely used technique. However, the amount of chlorine in water must be strictly adjusted, to ensure enough concentration to kill pathogenic bacteria and viruses, while preventing too high concentrations inducing negative effects on human health. As an indicator, a molecular fluorescent probe based on a BODIPY structure was designed. This indicator exhibits a sensitive and selective fluorescence response upon increasing concentrations of hypochlorite in aqueous solvent mixtures. Real-time analyses became possible after the integration of this fluorescent indicator into newly designed 2D & 3D microfluidic chips incorporating a passive sinusoidal mixer and a micro-hydrocyclone, respectively. A comparison of the two microfluidic systems, including their ability to prevent accumulation or circulation of microbubbles, has shown excellent fluidic behaviour for the micro-hydrocyclone device. This system was distinctly more robust against gas bubbles, showed a higher signal gain and allowed to halve the limit of detection to 0.02 mg L–1. The use of the 3D system to quantify the chlorine content of pool water samples for sensitive and quantitative chlorine monitoring has been demonstrated. T2 - Konferenz CY - Ioannina, Greece DA - 22.09.2019 KW - Chlorine KW - Fluorescence KW - Microfluidics KW - Water KW - Chlor KW - Fluoreszenz KW - Mikrofluidik KW - Wasser PY - 2019 UR - https://media.conferre.gr/index.php/photos-videos/ima2019 AN - OPUS4-49130 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Bartelmeß, Jürgen A1 - Valderrey, Virginia A1 - Rurack, Knut T1 - Development of a “Turn-on” Fluorescent Probe-Based Sensing System for Hydrogen Sulfide in Liquid and Gas Phase N2 - A “turn-on” fluorescence sensing system based on a BODIPY-cobaloxime complex for the detection of H2S in liquid and gas phase was developed. To that aim, two cobaloxime complexes bearing an axial pyridyl-BODIPY ligand were initially evaluated as sensitive fluorescent HS− indicators in aqueous solution. The sensing mechanism involves the selective substitution of the BODIPY ligand by the HS− anion at the cobalt center, which is accompanied by a strong fluorescence enhancement. The selection of a complex with an ideal stability and reactivity profile toward HS− relied on the optimal interaction between the cobalt metal-center and two different pyridyl BODIPY ligands. Loading the best performing BODIPY-cobaloxime complex onto a polymeric hydrogel membrane allowed us to study the selectivity of the probe for HS− against different anions and cysteine. Successful detection of H2S by the fluorescent “light-up” membrane was not only accomplished for surface water but could also be demonstrated for relevant H2S concentrations in gas phase. KW - Sulfide sensing KW - Fluorescence KW - BODIPYs KW - Cobaloxime complex KW - Gas sensing PY - 2019 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:b43-492186 SN - 2296-2646 VL - 7 SP - Art. Nr. 641 PB - Frontiers Media CY - Lausanne AN - OPUS4-49218 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Carl, Peter A1 - Sarma, Dominik A1 - Gregório, Bruno J. R. A1 - Hoffmann, Kristin A1 - Lehmann, Andreas A1 - Rurack, Knut A1 - Schneider, Rudolf T1 - Wash-Free Multiplexed Mix-and-Read Suspension Array Fluorescence Immunoassay for Anthropogenic Markers in Wastewater N2 - Pharmaceuticals, certain food ingredients, and mammalian endogenous metabolic products in wastewater are mostly of human origin. They are anthropogenic markers. Proper knowledge of their levels in wastewater helps to track sources of pollutants in natural waters and allows for calculation of removal efficiencies in wastewater Treatment plants. Here, we describe the development and application of an indirect competitive, multiplexing suspension Array fluorescence immunoassay (SAFIA) for the detection of carbamazepine (CBZ), diclofenac (DCF), caffeine (CAF), and isolithocholic acid (ILA) in wastewater, covering those classes of anthropogenic markers. The assay consists of haptens covalently conjugated to fluorescence-encoded polystyrene core/silica shell microparticles to create a site for competitive binding of the antibodies (Abs). Bound Abs are then stained with fluorophore-labeled Abs. Encoding and signaling fluorescence of the particles are determined by an automated flow cytometer. For compatibility of the immunoassay with the 96-well microtiter plate format, a stop reagent, containing formaldehyde, is used. This enables a wash-free procedure while decreasing time-to-result. Detection limits of 140 ± 40 ng/L for CBZ, 180 ± 110 ng/L for CAF, 4 ± 3 ng/L for DCF, and 310 ± 70 ng/L for ILA are achieved, which meet the sensitivity criteria of wastewater analysis. We demonstrate the applicability of SAFIA to real wastewater samples from three different wastewater Treatment plants, finding the results in good agreement with LC-MS/MS. Moreover, the accuracy in general exceeded that from classical ELISAs. We therefore propose SAFIA as a quick and reliable approach for wastewater analysis meeting the requirements for process analytical technology. KW - Suspension Array KW - Immunoassay KW - Carbamazepine KW - Caffeine KW - Diclofenac KW - SAFIA PY - 2019 U6 - https://doi.org/10.1021/acs.analchem.9b03040 SN - 0003-2700 VL - 91 IS - 20 SP - 12988 EP - 12966 PB - ACS Publications AN - OPUS4-49305 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Tillo, Adam A1 - Bartelmeß, Jürgen A1 - Chauhan, Vraj P. A1 - Bell, Jérémy A1 - Rurack, Knut T1 - Microfluidic Device for the Determination of Water Chlorination Levels Combining a Fluorescent meso-Enamine Boron Dipyrromethene Probe and a Microhydrocyclone for Gas Bubble Separation N2 - Chlorination procedures are commonly applied in swimming pool water and wastewater treatment, yet also in food, pharmaceutical, and paper production. The amount of chlorine in water needs to be strictly controlled to ensure efficient killing of pathogens but avoid the induction of negative health effects. Miniaturized microfluidic fluorescence sensors are an appealing approach here when aiming at online or at-site measurements. Two meso-enamine-substituted boron dipyrromethene (BODIPY) dyes were found to exhibit favorable indication properties, their reaction with hypochlorite leading to strong fluorescence enhancement. Real-time assays became possible after integration of these fluorescent probes with designed two-dimensional (2D) and three-dimensional (3D) microfluidic chips, incorporating a passive sinusoidal mixer and a microhydrocyclone, respectively. A comparison of the two microfluidic systems, including their abilities to prevent accumulation or circulation of microbubbles produced by the chemical indication reaction, showed excellent fluidic behavior for the microhydrocyclone-based device. After coupling to a miniaturized optical reader for fluorescence detection, the 2D microfluidic system showed a promising detection range of 0.04−0.5 mg L−1 while still being prone to bubble-induced fluctuations and suffering from considerably low signal gain. The microhydrocyclone-based system was distinctly more robust against gas bubbles, showed a higher signal gain, and allowed us to halve the limit of detection to 0.02 mg L−1. The use of the 3D system to quantify the chlorine content of swimming pool water samples for sensitive and quantitative chlorine monitoring was demonstrated. KW - Chlorine KW - BODIPY KW - Fluorescence KW - Micro-Hydrocyclone KW - Microfluidic Chip PY - 2019 U6 - https://doi.org/10.1021/acs.analchem.9b03039 SN - 0003-2700 VL - 91 IS - 20 SP - 12980 EP - 12987 PB - American Chemical Society CY - Washington, DC AN - OPUS4-49393 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Liu, H. A1 - Song, W. A1 - Gröninger, Delia A1 - Zhang, L. A1 - Lu, Y. A1 - Chan, K. S. A1 - Zhou, Z. A1 - Rurack, Knut A1 - Shen, Z. T1 - Real-time monitoring of newly acidified organelles during autophagy enabled by reaction-based BODIPY dyes N2 - Real-time monitoring of newly acidified organelles during autophagy in living cells is highly desirable for a better understanding of intracellular degradative processes. Herein, we describe a reaction-based boron dipyrromethene (BODIPY) dye containing strongly electron-withdrawing diethyl 2-cyanoacrylate groups at the α-positions. The probe exhibits intense red fluorescence in acidic organelles or the acidified cytosol while negligible fluorescence in other regions of the cell. The underlying mechanism is a nucleophilic reaction at the central meso-carbon of the indacene core, resulting in the loss of π-conjugation entailed by dramatic spectroscopic changes of more than 200 nm between its colorless, non-fluorescent leuco-BODIPY form and its red and brightly emitting form. The reversible transformation between red fluorescent BODIPY and leuco-BODIPY along with negligible cytotoxicity qualifies such dyes for rapid and direct intracellular lysosome imaging and cytosolic acidosis detection simultaneously without any washing step, enabling the real-time monitoring of newly acidified organelles during autophagy. KW - Autophagy KW - BODIPY KW - Fluorescence KW - Lysosome KW - Real-time imaging PY - 2019 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:b43-498358 UR - https://www.nature.com/articles/s42003-019-0682-1 SN - 23993642 VL - 2 SP - 442 PB - Nature Research CY - London AN - OPUS4-49835 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Descalzo, Ana B. A1 - Ashokkumar, Pichandi A1 - Shen, Z. A1 - Rurack, Knut T1 - On the Aggregation Behaviour and Spectroscopic Properties of Alkylated and Annelated BoronDipyrromethene (BODIPY) Dyes in Aqueous Solution N2 - The tendency of boron-dipyrromethene (BODIPY) dyes to associate in water is well known, and usually a cause for inferior fluorescence properties. Synthetic efforts to chemically improve BODIPYs’ water solubility and minimize this problem have been numerous in the past. However, a deeper understanding of the phenomena responsible for fluorescence quenching is still required. Commonly, the spectroscopic behaviour in aqueous media has been attributed to aggregate or excimer formation, with such works often centring on a single BODIPY family. Herein, we provide an integrating discussion including very diverse types of BODIPY dyes. Our studies revealed that even subtle structural changes can distinctly affect the association behaviour of the fluorophores in water, involving different photophysical processes. The palette of behaviour found ranges from unperturbed emission, to the formation of H or J aggregates and excimers, to the involvement of tightly bound, preformed excimers. These results are a first step to a more generalized understanding of spectroscopic properties vs. structure, facilitating future molecular design of BODIPYs, especially as probes for biological applications. KW - Aggregates KW - BODIPY KW - Excimers KW - Fluorescence KW - Photophysics PY - 2019 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:b43-497771 SN - 2367-0932 VL - 4 IS - 2 SP - 120 EP - 131 PB - WILEY-VCH CY - Weinheim AN - OPUS4-49777 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Sarma, Dominik A1 - Carl, Peter A1 - Climent Terol, Estela A1 - Schneider, Rudolf A1 - Rurack, Knut T1 - Multifunctional polystyrene core/silica shell microparticles with antifouling properties for bead-based multiplexed and quantitative analysis N2 - Commercial bead-based assays are commonly built upon polystyrene particles. The polymeric carrier can be encoded with organic dyes and has ideal material properties for cytometric applications such as low density and high refractive index. However, functional groups are conventionally integrated during polymerization and subsequent modification is limited to the reactivity of those groups. Additionally, polystyrene as the core material leads to many hydrophobic areas still being present on the beads’ surfaces even after functionalization, Rendering the particles prone to nonspecific adsorption during an application. The latter calls for several washing steps and the use of additives in (bio)analytical assays. In this contribution, we show how these limitations can be overcome by using monodisperse polystyrene (PS) core/silica (SiO2) shell particles (SiO2@PS). Two different hydrophobic BODIPY (boron−dipyrromethene) dyes were encapsulated inside a poly(vinylpyrrolidone) (PVP) -stabilized polystyrene core in different concentrations to create 5-plex arrays in two separate detection channels of a cytometer. A subsequent modification of the silica shell with an equimolar APTES/PEGS (aminopropyltriethoxysilane/polyethylene glycol silane) blend added multifunctional properties to the hybrid core/Shell microparticles in a single step: APTES provides amino groups for the attachment of a caffeine derivative (as a hapten) to create antigen-coupled microspheres; the PEG moiety effectively suppresses nonspecific binding of antibodies, endowing the surface with antifouling properties. The particles were applied in a competitive fluorescence immunoassay in suspension, and a highly selective wash-free assay for the detection of caffeine in beverages was developed as a proof of concept. KW - Core−shell particles KW - Bead-based assay KW - Multiplex KW - Antifouling surface KW - Mixed surface PY - 2019 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:b43-472931 UR - https://pubs.acs.org/doi/10.1021/acsami.8b10306 SN - 1944-8244 VL - 11 IS - 1 SP - 1321 EP - 1334 PB - American Chemical Society CY - Online Library AN - OPUS4-47293 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Gotor, Raúl A1 - Bell, Jérémy A1 - Rurack, Knut T1 - Tailored fluorescent solvatochromic test strips for quantitative on-site detection of gasoline fuel adulteration N2 - Gasoline adulteration is a frequent problem world-wide, because of the chance of quick, maximized profits. However, addition of cheaper ethanol or hydrocarbons like kerosene does not only result in economic damage but also poses problems for vehicles and the environment. To enable law enforcement forces, customers or enterprises to uncover such a fraudulent activity directly upon suspicion and without the need to organize for sampling and laboratory analysis, we developed a simple strip-based chemical test. Key to the favorable performance was the dedicated materials tailoring, which led to test strips that consisted of a cellulose support coated with silica, passivated with hexamethyldisilazane and functionalized covalently with a molecular probe. The probe fluoresces brightly across a broad solvent polarity range, enabling reliable quantitative measurements and data analysis with a conventional smartphone. The assays showed high reproducibility and accuracy, allowing not only for the detection of gasoline adulteration but also for the on-site monitoring of the quality of commercial E10 gasoline. KW - Gasoline KW - Adulteration KW - Test strips KW - Benzin KW - Teststreifen KW - Fluorescence KW - Cellulose KW - Zellulose KW - Fluoreszenz PY - 2019 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:b43-479231 UR - https://pubs.rsc.org/en/content/articlelanding/2019/tc/c8tc04818e SN - 2050-7526 VL - 7 IS - 8 SP - 2250 EP - 2256 PB - Royal Society of Chemistry CY - London, UK AN - OPUS4-47923 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER -