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- ItemSolvent effects on catalytic activity and selectivity in amine-catalyzed D-fructose isomerization(Amsterdam [u.a.] : Elsevier, 2022) Drabo, Peter; Fischer, Matthias; Emondts, Meike; Hamm, Jegor; Engelke, Mats; Simonis, Marc; Qi, Long; Scott, Susannah L.; Palkovits, Regina; Delidovich, IrinaRational catalyst design and optimal solvent selection are key to advancing biorefining. Here, we explored the organocatalytic isomerization of D-fructose to a valuable rare monosaccharide, D-allulose, as a function of solvent. The isomerization of D-fructose to D-allulose competes with its isomerization to D-glucose and sugar degradation. In both water and DMF, the catalytic activity of amines towards D-fructose is correlated with their basicity. Solvents impact the selectivity significantly by altering the tautomeric distribution of D-fructose. Our results suggest that the furanose tautomer of D-fructose is isomerized to D-allulose, and the fractional abundance of this tautomer increases as follows: water < MeOH < DMF ≈ DMSO. Reaction rates are also higher in aprotic than in protic solvents. The best D-allulose yield, 14 %, was obtained in DMF with 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD) as the catalyst. The reaction kinetics and mechanism were explored using operando NMR spectroscopy.
- ItemSize, concentration, and origin of human exhaled particles and their dependence on human factors with implications on infection transmission(Amsterdam [u.a.] : Elsevier, 2022) Bagheri, Gholamhossein; Schlenczek, Oliver; Turco, Laura; Thiede, Birte; Stieger, Katja; Kosub, Jana M.; Clauberg, Sigrid; Pöhlker, Mira L.; Pöhlker, Christopher; Moláček, Jan; Scheithauer, Simone; Bodenschatz, EberhardUnderstanding infection transmission between individuals, as well as evaluating the efficacy of protective measures, are key issues in pandemics driven by human respiratory particles. The key is a quantitative understanding of the size and concentration of particles exhaled and their variability across the size range for a representative population of all ages, genders, and different activities. Here we present data from 132 healthy volunteers aged 5 to 80 years, measured over the entire particle size range for each individual. Conventional particle spectrometry was combined with in-line holography under well-controlled conditions for common activities such as breathing, speaking, singing, and shouting. We find age to be the most important parameter for the concentration of small exhale particles <5 µm (PM5), which doubles over a 7-year period in adolescents and over a 30-year period in adults. Gender, body mass index, smoking or exercise habits have no discernible effect. We provide evidence that particles with a diameter of <5 µm originate from the lower respiratory tract, 5–15 µm from the larynx/pharynx, and >15 µm from the oral cavity. PM5 concentration can vary by one order of magnitude within a person, while inter-person variability can span two orders of magnitude, largely explained by difference in age. We found no discernible inter-person variability for particles larger than 5 µm. Our results show that cumulative volume of PM5 is 2–8 times higher in adults than in children. In contrast, number and volume concentration of larger particles, which are produced predominantly in the upper respiratory tract, is largely independent of age. Finally, we examined different types of airborne-transmissible respiratory diseases and provided insights into possible modes of infection transmission with and without several types/fits of face masks.
- ItemEndothelial cell spreading on lipid bilayers with combined integrin and cadherin binding ligands(Amsterdam [u.a.] : Elsevier, 2022) Koçer, Gülistan; Albino, Inês M.C.; Verheijden, Mark L.; Jonkheijm, PascalEndothelial cells play a central role in the vascular system, where their function is tightly regulated by both cell-extracellular matrix (e.g., via integrins) and cell–cell interactions (e.g., via cadherins). In this study, we incorporated cholesterol-modified integrin and N-cadherin peptide binding ligands in fluid supported lipid bilayers. Human umbilical vein endothelial cell adhesion, spreading and vinculin localization in these cells were dependent on ligand density. One composition led to observe a higher extent of cell spreading, where cells exhibited extensive lamellipodia formation and a qualitatively more distinct N-cadherin localization at the cell periphery, which is indicative of N-cadherin clustering and a mimic of cell–cell contact formation. The results can be used to reconstitute the endothelial-pericyte interface on biomedical devices and materials.
- ItemTowards hybrid one-pot/one-electrode Pd-NPs-based nanoreactors for modular biocatalysis(Amsterdam [u.a.] : Elsevier, 2021) Koch, M.; Apushkinskaya, N.; Zolotukhina, E.V.; Silina, Y.E.Here, fundamental aspects affecting template-assisted engineering of oxidase-associated peroxide oxidation co-catalysis of the modeled microanalytical system based on the hybrid palladium nanoparticles (Pd-NPs) with tailored functional properties were studied. By an accurate tuning and validation of the experimental setup, a modular Pd-NPs-doped one-pot/one-electrode amperometric nanobiosensor for advanced multiplex analyte detection was constructed. The specific operational conditions (electrochemical read-out mode, pH, regeneration procedure) of the modular one-pot/one-electrode nanobiosensor allowed a reliable sensing of L-lactate (with linear dynamic range, LDR = 500 µM – 2 mM, R2 = 0.977), D-glucose (with LDR = 200 µM – 50 mM, R2 = 0.987), hydrogen peroxide (with LDR = 20 µM – 100 mM, R2 = 0.998) and glutaraldehyde (with LDR = 1 – 100 mM, R2 = 0.971). In addition, mechanistic aspects influencing the performance of Pd-NPs-doped one-pot/one-electrode for multiplex analyte sensing were studied in detail. The designed one-pot/one-electrode amperometric nanobiosensor showed a thin layer electrochemical behavior that greatly enhanced electron transfer between the functional hybrid layer and the electrode. Finally, a specific regeneration procedure of the hybrid one-pot/one-electrode and algorithm towards its usage for modular biocatalysis were developed. The reported strategy can readily be considered as a guideline towards the fabrication of commercialized nanobiosensors with tailored properties for advanced modular biocatalysis.
- ItemRhodium-catalyzed borylative carbon monoxide reduction to gem-diborylmethane(Amsterdam [u.a.] : Elsevier, 2021) Xua, Jian-Xing; Wu, Fu-Peng; Wu, Xiao-FengHerein, we developed a rhodium-catalyzed reduction of CO with bis(pinacolato)diboron (B2pin2) under atmospheric pressure of CO with silane as the hydride source, gem-diborylmethane [H2C(Bpin)2] as a versatile and fundamental C1 compound can be formed. Notably, this is the first example on transition metal-catalyzed borylation of CO. © 2020 The Author(s)
- ItemExperimental evaluation and application of genetic programming to develop predictive correlations for hydrochar higher heating value and yield to optimize the energy content(Amsterdam [u.a.] : Elsevier, 2022) Marzban, Nader; Libra, Judy A.; Hosseini, Seyyed Hossein; Fischer, Marcus G.; Rotter, Vera SusanneThe hydrothermal carbonization (HTC) process has been found to consistently improve biomass fuel characteristics by raising the higher heating value (HHV) of the hydrochar as process severity is increased. However, this is usually associated with a decrease in the solid yield (SY) of hydrochar, making it difficult to determine the optimal operating conditions to obtain the highest energy yield (EY), which combines the two parameters. In this study, a graph-based genetic programming (GP) method was used for developing correlations to predict HHV, SY, and EY for hydrochars based on published values from 42 biomasses and a broad range of HTC experimental systems and operating conditions, i.e., 5 ≤ holding time (min) ≤ 2208, 120 ≤ temperature (°C) ≤ 300, and 0. 0096 ≤ biomass to water ratio ≤ 0.5. In addition, experiments were carried out with 5 pomaces at 4 temperatures and two reactor scales, 1 L and 18.75 L. The correlations were evaluated using this experimental data set in order to estimate prediction errors in similar experimental systems. The use of the correlations to predict HTC conditions to achieve the maximum EY is demonstrated for three common feedstocks, wheat straw, sewage sludge, and a fruit pomace. The prediction was confirmed experimentally with pomace at the optimized HTC conditions; we observed 6.9 % error between the measured and predicted EY %. The results show that the correlations can be used to predict the optimal operating conditions to produce hydrochar with the desired fuel characteristics with a minimum of actual HTC runs.
- ItemSilica/gold nanoplatform combined with a thermosensitive gel for imaging-guided interventional therapy in PDX of pancreatic cancer(Amsterdam [u.a.] : Elsevier, 2020) Xinga, Lingxi; Lib, Xin; Xingd, Zehua; Lie, Fan; Shenb, Mingwu; Wanga, Hong; Shib, Xiangyang; Du, LianfangImaging-guided interventional therapy is a promising means of minimally invasive and targeted drug delivery for patients with advanced pancreatic cancer. The effectiveness of the method depends on clear imaging and complete removal of cancer cells, especially peripheral infiltration and distant metastasis, to prevent recurrence. We synthesized hollow mesoporous silica-based nanoparticles, Gem-PFH-Au star-HMS-IGF1, with gemcitabine (Gem) and perfluorohexane (PFH) encapsulated internally, gold nanostars (Au NSs) and insulin-like growth factor-1 (IGF1) modified outwardly, to enhance multimode ultrasound (US)/computed tomography (CT)/photoacoustic (PA)/thermal imaging, guide photothermal therapy, and evaluate the effect in real time. We also prepared a type of thermosensitive gel that solidified at body temperature to facilitate the controlled release of Gem and achieve a single-administration interventional therapy. A patient-derived xenograft (PDX) mouse model was established in this study. The PDX was precisely ablated by photothermal therapy under the guidance of US/CT/PA imaging, and the residual pancreatic cancer cells were completely inhibited by Gem to prevent recurrence. This strategy ingeniously simulated the approach of surgical resection and postoperative chemotherapy in clinical procedures to treat malignancy and paves the way for interventional therapy. © 2019 The Authors
- ItemAcoustic resonance effects and cavitation in SAW aerosol generation(Amsterdam [u.a.] : Elsevier, 2023) Roudini, Mehrzad; Manuel Rosselló, Juan; Manor, Ofer; Ohl, Claus-Dieter; Winkler, AndreasThe interaction of surface acoustic waves (SAWs) with liquids enables the production of aerosols with adjustable droplet sizes in the micrometer range expelled from a very compact source. Understanding the nonlinear acousto-hydrodynamics of SAWs with a regulated micro-scale liquid film is essential for acousto-microfluidics platforms, particularly aerosol generators. In this study, we demonstrate the presence of micro-cavitation in a MHz-frequency SAW aerosol generation platform, which is touted as a leap in aerosol technology with versatile application fields including biomolecule inhalation therapy, micro-chromatography and spectroscopy, olfactory displays, and material deposition. Using analysis methods with high temporal and spatial resolution, we demonstrate that SAWs stabilize spatially arranged liquid micro-domes atop the generator's surface. Our experiments show that these liquid domes become acoustic resonators with highly fluctuating pressure amplitudes that can even nucleate cavitation bubbles, as supported by analytical modeling. The observed fragmentation of liquid domes indicates the participation of three droplet generation mechanisms, including cavitation and capillary-wave instabilities. During aerosol generation, the cavitation bubbles contribute to the ejection of droplets from the liquid domes and also explain observed microstructural damage patterns on the chip surface eventually caused by cavitation-based erosion.