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Micro- and nanoplastics are emerging pollutants with a concerning persistence in the environment. Research into their environmental impact requires addressing challenges related to sensitively and selectively detecting them in complex ecological media. One solution with great potential for alleviating these issues is using radiolabeling strategies. Here, we report the successful introduction of a 64Cu radiotracer into common microplastics, namely polyethylene, polyethylene terephthalate, polystyrene, polyamide, and polyvinylidene dichloride, which allows the sensitive detection of mere nanograms of substance. Utilizing a Hansen Solubility Parameter screening, we developed a swelling and in-diffusion process for tetraphenylporphyrin-complexed 64Cu, which permits one-pot labeling of polymer particles.

A key prerequisite for the successful application of protein crystallography in drug discovery is to establish a robust crystallization system for a new drug‐target protein fast enough to deliver crystal structures when the first inhibitors have been identified in the hit‐finding campaign or, at the latest, in the subsequent hit‐to‐lead process. The first crucial step towards generating well folded proteins with a high likelihood of crystallizing is the identification of suitable truncation variants of the target protein. In some cases an optimal length variant alone is not sufficient to support crystallization and additional surface mutations need to be introduced to obtain suitable crystals. In this contribution, four case studies are presented in which rationally designed surface modifications were key to establishing crystallization conditions for the target proteins (the protein kinases Aurora‐C, IRAK4 and BUB1, and the KRAS–SOS1 complex). The design process which led to well diffracting crystals is described and the crystal packing is analysed to understand retrospectively how the specific surface mutations promoted successful crystallization. The presented design approaches are routinely used in our team to support the establishment of robust crystallization systems which enable structure‐guided inhibitor optimization for hit‐to‐lead and lead‐optimization projects in pharmaceutical research. [ABSTRACT FROM AUTHOR]

The safe disposal of high-level radioactive waste in a deep geological repository is a huge social and technical challenge. So far, one of the less considered factors needed for a long-term risk assessment, is the impact of microorganisms occurring in the different host rocks. Even under the harsh conditions of salt formations different bacterial and archaeal species were found, e. g. Halobacterium sp. GP5 1-1, which has been isolated from a German rock salt sample. The interactions of this archaeon with uranium(VI), one of the radionuclides of major concern for the long-term storage of high-level radioactive waste, were investigated. Different spectroscopic techniques, as well as microscopy, were used to examine the occurring mechanisms on a molecular level leading to a more profound process understanding. Batch experiments with different uranium(VI) concentrations showed that the interaction is not only a simple, but a more complex combination of different processes. With the help of in situ attenuated total reflection Fourier-transform infrared spectroscopy the association of uranium(VI) onto carboxylate groups was verified. In addition, time-resolved laser-induced luminescence spectroscopy revealed the formation of phosphate and carboxylate species within the cell pellets as a function of the uranium(VI) concentration and incubation time. The association behavior differs from another very closely related halophilic archaeon, especially with regard to uranium(VI) concentrations. This clearly demonstrates the importance of studying the interactions of different, at first sight very similar, microorganisms with uranium(VI). This work provides new insights into the microbe-uranium(VI) interactions at highly saline conditions relevant to the long-term storage of radioactive waste in rock salt.

The hydrolytic hydrogenation of xylan to xylitol by a one-pot process was studied in detail in a batch reactor. The reaction was catalyzed by a combination of diluted sulfuric acid and precious metal Ru on carbon powder. Process parameters were varied between 120–150°C, while maintaining constant hydrogen pressure at 20 bar and an acid concentration equivalent to pH 2. The xylan solution consisted of 1 wt% beechwood powder (Carl Roth, >90%) in deionized water. Sulfuric acid was added to the solution until pH two was reached, then the 0.3 wt% catalyst powder (5% Ru on Act. C) was added and the solution was put into the batch reactor. The first approach of kinetic modeling began with conventional first-order kinetics and compared this to a more complex model based on Langmuir–Hinshelwood kinetics. The xylan and xylitol data reached a good fit. However, the modeling results also showed that the rate-limiting step of xylose-formation was still not represented in a satisfactory manner. Therefore, the model was adapted and developed further. The advanced model finally showed a good fit with the intermediate product xylose and the target product xylitol. The overall modeling methods and results are presented and discussed.

A new approach for biomass liquefaction was developed and evaluated in a joint research project. Focus of the project, called FEBio@H2O, lies on a two-step hydrothermal conversion. Within step 1, the input biomass is converted employing a hydrothermal degradation without added catalyst or by homogeneous catalysis. Within step 2, the hydrogen accepting products of step 1, e.g., levulinic acid (LA) are upgraded by a heterogeneously catalyzed hydrogenation with hydrogen donor substances, e.g., formic acid (FA). As a result, components with an even lower oxygen content in comparison to step 1 products are formed; as an example, γ-valerolactone (GVL) can be named. Therefore, the products are more stable and contained less oxygen as requested for a possible application as liquid fuel. As a hydrothermal process, FEBio@H2O is especially suitable for highly water-containing feedstock. The evaluation involves hydrothermal conversion tests with model substances, degradation of real biomasses, transfer hydrogenation or hydrogenation with hydrogen donor of model substances and real products of step 1, catalyst selection and further development, investigation of the influence of reactor design, the experimental test of the whole process chain, and process assessment.

Micro- and nanoplastics are emerging pollutants with a concerning persistence in the environment. Research into their environmental impact requires addressing challenges related to sensitively and selectively detecting them in complex ecological media. One solution with great potential for alleviating these issues is using radiolabeling strategies. Here, we report the successful introduction of a 64Cu radiotracer into common microplastics, namely polyethylene, polyethylene terephthalate, polystyrene, polyamide, and polyvinylidene dichloride, which allows the sensitive detection of mere nanograms of substance. Utilizing a Hansen Solubility Parameter screening, we developed a swelling and in-diffusion process for tetraphenylporphyrin-complexed 64Cu, which permits one-pot labeling of polymer particles. [ABSTRACT FROM AUTHOR]

The safe disposal of high-level radioactive waste in a deep geological repository is a huge social and technical challenge. So far, one of the less considered factors needed for a long-term risk assessment, is the impact of microorganisms occurring in the different host rocks. Even under the harsh conditions of salt formations different bacterial and archaeal species were found, e. g. Halobacterium sp. GP5 1–1, which has been isolated from a German rock salt sample. The interactions of this archaeon with uranium(VI), one of the radionuclides of major concern for the long-term storage of high-level radioactive waste, were investigated. Different spectroscopic techniques, as well as microscopy, were used to examine the occurring mechanisms on a molecular level leading to a more profound process understanding. Batch experiments with different uranium(VI) concentrations showed that the interaction is not only a simple, but a more complex combination of different processes. With the help of in situ attenuated total reflection Fourier-transform infrared spectroscopy the association of uranium(VI) onto carboxylate groups was verified. In addition, time-resolved laser-induced luminescence spectroscopy revealed the formation of phosphate and carboxylate species within the cell pellets as a function of the uranium(VI) concentration and incubation time. The association behavior differs from another very closely related halophilic archaeon, especially with regard to uranium(VI) concentrations. This clearly demonstrates the importance of studying the interactions of different, at first sight very similar, microorganisms with uranium(VI). This work provides new insights into the microbe-uranium(VI) interactions at highly saline conditions relevant to the long-term storage of radioactive waste in rock salt. [ABSTRACT FROM AUTHOR]

BACKGROUND: Acidic hydrolysis of a birch (Betula pendula) xylan produced by a novel semi‐industrial‐scale aqueous‐based and highly sustainable method was studied in a batch reactor. Five commercial acidic heterogeneous catalysts were screened and significant differences in their performance were observed. Dowex 50WX2‐100 was selected for further studies and the influence of the reaction parameters, including stirring speed, pH (0.5–1.5), temperature (115–145 °C) and catalyst particle size (50–400 mesh) were studied. The goal was to maximize xylose yield by balancing between the kinetics of hydrolysis and the undesired degradation of monosaccharides. RESULTS: The results show that the maximum achieved yield of xylose was 76%, but higher yields were hindered by the consecutive dehydration of sugars. It was also observed that the hydrolysis and dehydration reactions do not follow the same dependence on the experimental parameters, which leaves room for optimization of the yield. A kinetic model was developed based on the data, which takes into account the consecutive reaction pathway and the influence of the experimental conditions, and a very good fit of the model to the experimental data was achieved. An activation energy of 119 and 88 kJ mol–1 was obtained for the hydrolysis and dehydration steps, respectively. CONCLUSION: Hydrolysis results of this novel, well‐characterized hemicellulose extract have not been published previously, and they contribute significantly to the understanding of the hydrolysis and dehydration of real feedstock, instead of highly purified and typically very deacetylated model compounds with different characteristics and behaviour in hydrolysis. © 2021 The Authors. Journal of Chemical Technology and Biotechnology published by John Wiley & Sons Ltd on behalf of Society of Chemical Industry (SCI). [ABSTRACT FROM AUTHOR]

Wild‐type human glutathione peroxidase 4 (GPX4) was co‐expressed with SBP2 (selenocysteine insertion sequence‐binding protein 2) in human HEK cells to achieve efficient production of this selenocysteine‐containing enzyme on a preparative scale for structural biology. The protein was purified and crystallized, and the crystal structure of the wild‐type form of GPX4 was determined at 1.0 Å resolution. The overall fold and the active site are conserved compared with previously determined crystal structures of mutated forms of GPX4. A mass‐spectrometry‐based approach was developed to monitor the reaction of the active‐site selenocysteine Sec46 with covalent inhibitors. This, together with the introduction of a surface mutant (Cys66Ser), enabled the crystal structure determination of GPX4 in complex with the covalent inhibitor ML162 [(S)‐enantiomer]. The mass‐spectrometry‐based approach described here opens the path to further co‐complex crystal structures of this potential cancer drug target in complex with covalent inhibitors. [ABSTRACT FROM AUTHOR]

In the present study we have investigated the complexation of uranyl(VI) with chloride and fluoride using luminescence spectroscopy (TRLFS, time-resolved laser-induced fluorescence spectroscopy). At 25 °C (298.15 K), in the presence of 0–0.175 M fluoride, the first single-component emission spectra for all four uranyl(VI)-fluoride complexes, i.e. UO2F+, UO2F2, UO2F3−, and UO2F42− could be extracted. Based on the aqueous speciation derived from the TRLFS data, log K* values at I = 1 M were calculated for all these complexes and extrapolated to infinite dilution using the SIT approach. In the case of chloride, however, quenching of the uranyl(VI)-luminescence hampered the experiments. Thus, uranyl(VI)-complexation was studied with TRLFS at liquid nitrogen temperatures. Samples were prepared at 25 °C (298.15 K) with chloride concentrations ranging from 0 to 1.0 M followed by instantaneous freezing and subsequent luminescence spectroscopic measurements at −120 °C (153.15 K). This allowed for the determination of the first luminescence spectra for the UO2Cl+ complex with the TRLFS method. The chloride quench reaction was further studied in the temperature range 1–45 °C (274.15–318.15 K) using Stern–Volmer analysis. By applying the Arrhenius and the Eyring equations we obtained the first thermodynamic parameters for the dynamic quench process, i.e. the activation energy (Ea = 55.0 ± 12.9 kJ mol−1), enthalpy (ΔH‡ = 52.5 ± 13.0 kJ mol−1), and entropy (ΔS‡ = 103.9 ± 42.8 J mol−1 K−1). [ABSTRACT FROM AUTHOR]

In the present study we have investigated the complexation of uranyl(VI) with chloride and fluoride using luminescence spectroscopy (TRLFS, time-resolved laser-induced fluorescence spectroscopy). At 25 °C (298.15 K), in the presence of 0–0.175 M fluoride, the first single-component emission spectra for all four uranyl(VI)-fluoride complexes, i.e. UO2F+, UO2F2, UO2F3−, and UO2F42− could be extracted. Based on the aqueous speciation derived from the TRLFS data, log K* values at I = 1 M were calculated for all these complexes and extrapolated to infinite dilution using the SIT approach. In the case of chloride, however, quenching of the uranyl(VI)-luminescence hampered the experiments. Thus, uranyl(VI)-complexation was studied with TRLFS at liquid nitrogen temperatures. Samples were prepared at 25 °C (298.15 K) with chloride concentrations ranging from 0 to 1.0 M followed by instantaneous freezing and subsequent luminescence spectroscopic measurements at −120 °C (153.15 K). This allowed for the determination of the first luminescence spectra for the UO2Cl+ complex with the TRLFS method. The chloride quench reaction was further studied in the temperature range 1–45 °C (274.15–318.15 K) using Stern–Volmer analysis. By applying the Arrhenius and the Eyring equations we obtained the first thermodynamic parameters for the dynamic quench process, i.e. the activation energy (Ea = 55.0 ± 12.9 kJ mol−1), enthalpy (ΔH‡ = 52.5 ± 13.0 kJ mol−1), and entropy (ΔS‡ = 103.9 ± 42.8 J mol−1 K−1). [ABSTRACT FROM AUTHOR]

Structured catalysts are a widely discussed approach for process intensification of chemical multiphase reactors. But equal to common catalyst structures, homogeneous educt distribution along the catalytic surface is mandatory for high reactor performance. Especially monolithic structures require a homogeneous initial fluid distribution. A novel distribution concept for gas-liquid flow through arbitrary channel matrices is presented. It is based on the injection principle where gas and liquid are inserted directly into the channels. A prototype for different cell densities was built and tested by various measurement techniques: gravimetry, X-ray tomography, and an optical fiber sensor. Additionally, the flow regime per channel was detected as equal to single-channel conditions. [ABSTRACT FROM AUTHOR]

The continuous hydrogenation of a mixture of L-arabinose and D-galactose over a Ru/C catalyst was investigated in a miniaturized packed-bed reactor. The reaction is one important step of the transformation of the naturally occurring hemicellulose arabinogalactan into valuable sugar alcohols. Process intensification was accomplished by reducing the reactor dimensions to a few millimeters; thus leading to better mass and heat transfer performance. The effects of temperature, pressure, and liquid flow rate on the yield and by-product formation are discussed. Based on a kinetic model derived from batch experiments, a model of the continuous reactor was developed and used for scale-up purposes. [ABSTRACT FROM AUTHOR]

Microbiological photosynthesis is a promising tool for producing hydrogen in an ecologically friendly and economically efficient way. Certain microorganisms (e.g. algae and bacteria) can produce hydrogen using hydrogenase and/or nitrogenase enzymes. However, their natural capacity to produce hydrogen is relatively low. Thus, there is a need to optimize their core photosynthetic processes as well as their cultivation, for more efficient hydrogen production. This review aims to provide a holistic overview of the recent technological and research developments relating to photobiological hydrogen production and downstream processing. First we cover photobiological hydrogen synthesis within cells and the enzymes that catalyze the hydrogen production. This is followed by strategies for enhancing bacterial hydrogen production by genetic engineering, technological development, and innovation in bioreactor design. The remaining sections focus on hydrogen as a product, that is, quantification via (in-process) gas analysis, recent developments in gas separation technology. Finally, a discussion of the sociological (market) barriers to future hydrogen usage is provided as well as an overview of methods for life cycle assessment that can be used to calculate the environmental consequences of hydrogen production. [ABSTRACT FROM AUTHOR]

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A new approach for biomass liquefaction was developed and evaluated in a joint research project. Focus of the project, called FEBio@H2O, lies on a two-step hydrothermal conversion. Within step 1, the input biomass is converted employing a hydrothermal degradation without added catalyst or by homogeneous catalysis. Within step 2, the hydrogen accepting products of step 1, e.g., levulinic acid (LA) are upgraded by a heterogeneously catalyzed hydrogenation with hydrogen donor substances, e.g., formic acid (FA). As a result, components with an even lower oxygen content in comparison to step 1 products are formed; as an example, γ-valerolactone (GVL) can be named. Therefore, the products are more stable and contained less oxygen as requested for a possible application as liquid fuel. As a hydrothermal process, FEBio@H2O is especially suitable for highly water-containing feedstock. The evaluation involves hydrothermal conversion tests with model substances, degradation of real biomasses, transfer hydrogenation or hydrogenation with hydrogen donor of model substances and real products of step 1, catalyst selection and further development, investigation of the influence of reactor design, the experimental test of the whole process chain, and process assessment. [ABSTRACT FROM AUTHOR]

Rock salts are considered as potential host rocks for the long-term storage of highly radioactive waste in a deep geological repository. In addition to bacteria and fungi, extremely halophilic archaea, e.g. Halobacterium species, are predominantly present in this habitat. For long-term risk assessment it is of high interest to study how these microorganisms can potentially interact with radionuclides if the radionuclides are released from the waste repository. Given this fact, the interactions of extremely halophilic archaea from the genus Halobacterium and the moderately halophilic bacterium Brachybacterium sp. G1 with uranium, one of the major radionuclides of concern in the geological repository of radioactive wastes, were investigated in detail in batch experiments. The archaea and the bacterium showed different association mechanisms with uranium. Brachybacterium sp. G1 cells sorbed uranium within a short time, whereas a much longer and a multi-stage bioassociation process, dependent on the uranium concentration, occurred with the archaea. Furthermore, a multi-spectroscopic (time-resolved laser-induced fluorescence spectroscopy and X-ray absorption spectroscopy) and -microscopic (scanning electron microscopy coupled with energy-dispersive X-ray analysis for elemental mapping) approach was used to elucidate the U(VI) bioassociation behavior. By using these spectroscopic and microscopic tools, the formation of a U(VI) phosphate mineral, such as meta-autunite, by the Halobacterium species was demonstrated. These findings offer new insights into the microbe-actinide interactions at highly saline conditions relevant to the disposal of nuclear waste. [ABSTRACT FROM AUTHOR]