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Time‐Dependent Cation Selectivity of Titanium Carbide MXene in Aqueous Solution

2022, Wang, Lei, Torkamanzadeh, Mohammad, Majed, Ahmad, Zhang, Yuan, Wang, Qingsong, Breitung, Ben, Feng, Guang, Naguib, Michael, Presser, Volker

Electrochemical ion separation is a promising technology to recover valuable ionic species from water. Pseudocapacitive materials, especially 2D materials, are up-and-coming electrodes for electrochemical ion separation. For implementation, it is essential to understand the interplay of the intrinsic preference of a specific ion (by charge/size), kinetic ion preference (by mobility), and crystal structure changes. Ti3C2Tz MXene is chosen here to investigate its selective behavior toward alkali and alkaline earth cations. Utilizing an online inductively coupled plasma system, it is found that Ti3C2Tz shows a time-dependent selectivity feature. In the early stage of charging (up to about 50 min), K+ is preferred, while ultimately Ca2+ and Mg2+ uptake dominate; this unique phenomenon is related to dehydration energy barriers and the ion exchange effect between divalent and monovalent cations. Given the wide variety of MXenes, this work opens the door to a new avenue where selective ion-separation with MXene can be further engineered and optimized.

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DNA and RNA extraction and quantitative real-time PCR-based assays for biogas biocenoses in an interlaboratory comparison

2016, Lebuhn, Michael, Derenkó, Jaqueline, Rademacher, Antje, Helbig, Susanne, Munk, Bernhard, Pechtl, Alexander, Stolze, Yvonne, Prowe, Steffen, Schwarz, Wolfgang H., Schlüter, Andreas, Liebl, Wolfgang, Klocke, Michael

Five institutional partners participated in an interlaboratory comparison of nucleic acid extraction, RNA preservation and quantitative Real-Time PCR (qPCR) based assays for biogas biocenoses derived from different grass silage digesting laboratory and pilot scale fermenters. A kit format DNA extraction system based on physical and chemical lysis with excellent extraction efficiency yielded highly reproducible results among the partners and clearly outperformed a traditional CTAB/chloroform/isoamylalcohol based method. Analytical purpose, sample texture, consistency and upstream pretreatment steps determine the modifications that should be applied to achieve maximum efficiency in the trade-off between extract purity and nucleic acid recovery rate. RNA extraction was much more variable, and the destination of the extract determines the method to be used. RNA stabilization with quaternary ammonium salts was an as satisfactory approach as flash freezing in liquid N2. Due to co-eluted impurities, spectrophotometry proved to be of limited value for nucleic acid qualification and quantification in extracts obtained with the kit, and picoGreen® based quantification was more trustworthy. Absorbance at 230 nm can be extremely high in the presence of certain chaotropic guanidine salts, but guanidinium isothiocyanate does not affect (q)PCR. Absolute quantification by qPCR requires application of a reliable internal standard for which correct PCR efficiency and Y-intercept values are important and must be reported.

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Uncertainty in the measurement of indoor temperature and humidity in naturally ventilated dairy buildings as influenced by measurement technique and data variability

2017, Hempel, Sabrina, König, Marcel, Menz, Christoph, Janke, David, Amon, Barbara, Banhazi, Thomas M., Estellés, Fernando, Amon, Thomas

The microclimatic conditions in dairy buildings affect animal welfare and gaseous emissions. Measurements are highly variable due to the inhomogeneous distribution of heat and humidity sources (related to farm management) and the turbulent inflow (associated with meteorologic boundary conditions). The selection of the measurement strategy (number and position of the sensors) and the analysis methodology adds to the uncertainty of the applied measurement technique. To assess the suitability of different sensor positions, in situations where monitoring in the direct vicinity of the animals is not possible, we collected long-term data in two naturally ventilated dairy barns in Germany between March 2015 and April 2016 (horizontal and vertical profiles with 10 to 5 min temporal resolution). Uncertainties related to the measurement setup were assessed by comparing the device outputs under lab conditions after the on-farm experiments. We found out that the uncertainty in measurements of relative humidity is of particular importance when assessing heat stress risk and resulting economic losses in terms of temperature-humidity index. Measurements at a height of approximately 3 m–3.5 m turned out to be a good approximation for the microclimatic conditions in the animal occupied zone (including the air volume close to the emission active zone). However, further investigation along this cross-section is required to reduce uncertainties related to the inhomogeneous distribution of humidity. In addition, a regular sound cleaning (and if possible recalibration after few months) of the measurement devices is crucial to reduce the instrumentation uncertainty in long-term monitoring of relative humidity in dairy barns. © 2017 The Authors

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Polymer Brush-Functionalized Chitosan Hydrogels as Antifouling Implant Coatings

2017, Buzzacchera, Irene, Vorobii, Mariia, Kostina, Nina Yu, de Los Santos Pereira, Andres, Riedel, Tomáš, Bruns, Michael, Ogieglo, Wojciech, Möller, Martin, Wilson, Christopher J., Rodriguez-Emmenegger, Cesar

Implantable sensor devices require coatings that efficiently interface with the tissue environment to mediate biochemical analysis. In this regard, bioinspired polymer hydrogels offer an attractive and abundant source of coating materials. However, upon implantation these materials generally elicit inflammation and the foreign body reaction as a consequence of protein fouling on their surface and concomitant poor hemocompatibility. In this report we investigate a strategy to endow chitosan hydrogel coatings with antifouling properties by the grafting of polymer brushes in a "grafting-from" approach. Chitosan coatings were functionalized with polymer brushes of oligo(ethylene glycol) methyl ether methacrylate and 2-hydroxyethyl methacrylate using photoinduced single electron transfer living radical polymerization and the surfaces were thoroughly characterized by XPS, AFM, water contact angle goniometry, and in situ ellipsometry. The antifouling properties of these new bioinspired hydrogel-brush coatings were investigated by surface plasmon resonance. The influence of the modifications to the chitosan on hemocompatibility was assessed by contacting the surfaces with platelets and leukocytes. The coatings were hydrophilic and reached a thickness of up to 180 nm within 30 min of polymerization. The functionalization of the surface with polymer brushes significantly reduced the protein fouling and eliminated platelet activation and leukocyte adhesion. This methodology offers a facile route to functionalizing implantable sensor systems with antifouling coatings that improve hemocompatibility and pave the way for enhanced device integration in tissue.

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A hyperbranched dopamine-containing PEG-based polymer for the inhibition of α-synuclein fibrillation

2015, Breydo, Leonid, Newland, Ben, Zhang, Hong, Rosser, Anne, Werner, Carsten, Uversky, Vladimir N., Wang, Wenxin

Aggregation of α-synuclein is believed to play an important role in Parkinson's disease and in other neurodegenerative maladies. Small molecule inhibitors of this process are among the most promising drug candidates for neurodegenerative diseases. Dendrimers have also been studied for anti-fibrillation applications but they can be difficult and expensive to synthetize. Here we show that RAFT polymerization can be used to produce a hyperbranched polyethylene glycol structure via a one-pot reaction. This polymer included a dopamine moiety, a known inhibitor of α-synuclein fibril formation. Dopamine within the polymer structure was capable of aggregation inhibition, although not to the same degree as free dopamine. This result opens up new avenues for the use of controlled radical polymerizations as a means of preparing hyperbranched polymers for anti-fibrillation activity, but shows that the incorporation of functional groups from known small molecules within polymers may alter their biological activity.

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Variable tree rooting strategies are key for modelling the distribution, productivity and evapotranspiration of tropical evergreen forests

2021, Sakschewski, Boris, Bloh, Werner von, Drüke, Markus, Sörensson, Anna Amelia, Ruscica, Romina, Langerwisch, Fanny, Billing, Maik, Bereswill, Sarah, Hirota, Marina, Oliveira, Rafael Silva, Heinke, Jens, Thonicke, Kirsten

A variety of modelling studies have suggested tree rooting depth as a key variable to explain evapotranspiration rates, productivity and the geographical distribution of evergreen forests in tropical South America. However, none of those studies have acknowledged resource investment, timing and physical constraints of tree rooting depth within a competitive environment, undermining the ecological realism of their results. Here, we present an approach of implementing variable rooting strategies and dynamic root growth into the LPJmL4.0 (Lund-Potsdam-Jena managed Land) dynamic global vegetation model (DGVM) and apply it to tropical and sub-tropical South America under contemporary climate conditions. We show how competing rooting strategies which underlie the trade-off between above- and below-ground carbon investment lead to more realistic simulation of intra-annual productivity and evapotranspiration and consequently of forest cover and spatial biomass distribution. We find that climate and soil depth determine a spatially heterogeneous pattern of mean rooting depth and below-ground biomass across the study region. Our findings support the hypothesis that the ability of evergreen trees to adjust their rooting systems to seasonally dry climates is crucial to explaining the current dominance, productivity and evapotranspiration of evergreen forests in tropical South America.

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Switchable Adhesion Surfaces with Enhanced Performance Against Rough Counterfaces

2016, Prieto-López, Lizbeth, Williams, John

In a recent study, we demonstrated that the pressurization of micro-fluidic features introduced in the subsurface of a soft polymer can be used to actively modify the magnitude of the adhesion to a harder counterface by changing its waviness or long wavelength undulations. In that case, both contacting surfaces had very smooth finishes with root-mean-square roughnesses of less than 20 nm. These values are far from those of many engineering surfaces, which usually have a naturally occurring roughness of between ten and a hundred times this value. In this work, we demonstrate that appropriate surface features, specifically relatively slender “fibrils”, can enhance the ability of a such a soft surface to adhere to a hard, but macroscopically rough, counterface, while still maintaining the possibility of switching the adhesion force from one level to another. Conversely, stiffer more conical surface features can suppress adhesion even against a smooth counterface. Examples of each form of topography can be found in the natural world.

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BEXIS2: A FAIR-aligned data management system for biodiversity, ecology and environmental data

2021, Chamanara, Javad, Gaikwad, Jitendra, Gerlach, Roman, Algergawy, Alsayed, Ostrowski, Andreas, König-Ries, Birgitta

Obtaining fit-to-use data associated with diverse aspects of biodiversity, ecology and environment is challenging since often it is fragmented, sub-optimally managed and available in heterogeneous formats. Recently, with the universal acceptance of the FAIR data principles, the requirements and standards of data publications have changed substantially. Researchers are encouraged to manage the data as per the FAIR data principles and ensure that the raw data, metadata, processed data, software, codes and associated material are securely stored and the data be made available with the completion of the research.

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Surface-Enhanced Raman Spectroscopy to Characterize Different Fractions of Extracellular Vesicles from Control and Prostate Cancer Patients

2021, Osei, Eric Boateng, Paniushkina, Liliia, Wilhelm, Konrad, Popp, Jürgen, Nazarenko, Irina, Krafft, Christoph

Extracellular vesicles (EVs) are membrane-enclosed structures ranging in size from about 60 to 800 nm that are released by the cells into the extracellular space; they have attracted interest as easily available biomarkers for cancer diagnostics. In this study, EVs from plasma of control and prostate cancer patients were fractionated by differential centrifugation at 5000× g, 12,000× g and 120,000× g. The remaining supernatants were purified by ultrafiltration to produce EV-depleted free-circulating (fc) fractions. Spontaneous Raman and surface-enhanced Raman spectroscopy (SERS) at 785 nm excitation using silver nanoparticles (AgNPs) were employed as label-free techniques to collect fingerprint spectra and identify the fractions that best discriminate between control and cancer patients. SERS spectra from 10 µL droplets showed an enhanced Raman signature of EV-enriched fractions that were much more intense for cancer patients than controls. The Raman spectra of dehydrated pellets of EV-enriched fractions without AgNPs were dominated by spectral contributions of proteins and showed variations in S-S stretch, tryptophan and protein secondary structure bands between control and cancer fractions. We conclude that the AgNPs-mediated SERS effect strongly enhances Raman bands in EV-enriched fractions, and the fractions, EV12 and EV120 provide the best separation of cancer and control patients by Raman and SERS spectra.

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Quantifying ligand-cell interactions and determination of the surface concentrations of ligands on hydrogel films: The measurement challenge

2015, Beer, Meike V., Hahn, Kathrin, Diederichs, Sylvia, Fabry, Marlies, Singh, Smriti, Spencer, Steve J., Salber, Jochen, Möller, Martin, Shard, Alexander G., Groll, Jürgen

Hydrogels are extensively studied for biomaterials application as they provide water swollen noninteracting matrices in which specific binding motifs and enzyme-sensitive degradation sites can be incorporated to tailor cell adhesion, proliferation, and migration. Hydrogels also serve as excellent basis for surface modification of biomaterials where interfacial characteristics are decisive for implant success or failure. However, the three-dimensional nature of hydrogels makes it hard to distinguish between the bioactive ligand density at the hydrogel-cell interface that is able to interact with cells and the ligands that are immobilized inside the hydrogel and not accessible for cells. Here, the authors compare x-ray photoelectron spectrometry (XPS), time-of-flight secondary ion mass spectroscopy (ToF-SIMS), enzyme linked immunosorbent assay (ELISA), and the correlation with quantitative cell adhesion using primary human dermal fibroblasts (HDF) to gain insight into ligand distribution. The authors show that although XPS provides the most useful quantitative analysis, it lacks the sensitivity to measure biologically meaningful concentrations of ligands. However, ToF-SIMS is able to access this range provided that there are clearly distinguishable secondary ions and a calibration method is found. Detection by ELISA appears to be sensitive to the ligand density on the surface that is necessary to mediate cell adhesion, but the upper limit of detection coincides closely with the minimal ligand spacing required to support cell proliferation. Radioactive measurements and ELISAs were performed on amine reactive well plates as true 2D surfaces to estimate the ligand density necessary to allow cell adhesion onto hydrogel films. Optimal ligand spacing for HDF adhesion and proliferation on ultrathin hydrogel films was determined as 6.5 ± 1.5 nm.