Synthetic covalent monolayer sheets and their subclass, two-dimensional polymers are of particular interest in materials science because of their special dimensionality which renders them very ...different from any bulk matter. However, structural analysis of such entities is rather challenging, and there is a clear need for additional analytical methods. The present study shows how tip-enhanced Raman spectroscopy (TERS) can be performed on monomer monolayers and the covalent sheets prepared from them by 4 + 4-cycloaddition to explore rather complex structural and mechanistic issues. TERS is a surface analytical method that combines the high lateral resolution of scanning probe microscopy (SPM) with a greatly enhanced Raman scattering intensity. The high spatial resolution (<60 nm) and the significantly improved sensitivity (contrast factor of >4000) compared to confocal Raman microscopy provides new insights into the formation of this new and exciting material, namely significant consumption of the reactive units (anthracenes) and exclusion of the alternative 4 + 2-cycloaddition. Moreover, due to the high lateral resolution, it was possible to find a first spectroscopic hint for step growth as the dominant mechanism in the formation of these novel monolayer sheets. In addition, TERS was used to get first insights into the phase behavior of a comonomer mixture.
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IJS, KILJ, NUK, PNG, UL, UM
By using structurally similar amphiphilic monomers, it is shown that compressed monolayers of varying amounts of such monomers at the air/water interface can be converted by photoirradiation into ...the corresponding covalently connected monolayer sheets. Since one of the monomers carries three anthracene units and the other three 1,8‐diaza‐anthracene units, the growth reaction is proposed to take place through photochemically achieved 4+4‐cycloaddition between pairs of these units that are co‐facially (face‐to‐face) arranged, to furnish the corresponding covalent dimers. While evidence for both homodimers is amply available, the existence of the heterodimer needs to be established with the help of a model reaction to support the conceptual aspect of this work, copolymerization in two dimensions. The sheet copolymers exhibit substantial robustness in that they can be spanned over 20 × 20 μm2‐sized holes without rupturing under their own weight. X‐ray photoelectron spectroscopy (XPS) studies reveal that the monomers are incorporated into the sheet copolymers according to feed. These results establish existence of the first covalent sheet copolymer, which is considered a step ahead towards novel 2D materials.
Copolymerization in flatland: the first step toward 2D copolymers. Based on X‐ray photoelectron spectroscopy (XPS) analysis, the monomer feed applied to an air/water interface directly translates into copolymer composition of a covalent monolayer sheet.
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BFBNIB, FZAB, GIS, IJS, KILJ, NLZOH, NUK, OILJ, SAZU, SBCE, SBMB, UL, UM, UPUK
This study aimed to quantify the elongation patterns of the collateral ligaments following TKA during functional activities of daily living. Using mobile video-fluoroscopy to capture radiographic ...images of the knee in a group of six patients, each with an ultra-congruent knee implant, tibiofemoral kinematics were reconstructed throughout complete cycles of level gait, downhill walking, stair descent, and squat activities. Kinematic data were then used to drive subject-specific multibody knee models to estimate length-change patterns of the LCL as well as three bundles of the MCL. In addition, a sensitivity analysis examined the role of the attachment site in the elongation patterns. Our data indicate a slackening of the LCL but non-uniform length-change patterns across the MCL bundles (ranging from lengthening of the anterior fibers to shortening of the posterior fibers) with increasing knee flexion angle. Near-isometric behavior of the intermediate fibers was observed throughout the entire cycle of the studied activities. These length-change patterns were found to be largely consistent across different activities. Importantly, length-change patterns were critically sensitive to the location of the femoral attachment points relative to the femoral component. Thus, in TKA with ultra-congruent implants, implantation of the femoral component may critically govern post-operative ligament function.
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EMUNI, FIS, FZAB, GEOZS, GIS, IJS, IMTLJ, KILJ, KISLJ, MFDPS, NLZOH, NUK, OBVAL, OILJ, PNG, SAZU, SBCE, SBJE, SBMB, SBNM, UKNU, UL, UM, UPUK, VKSCE, ZAGLJ
A comprehensive database was obtained for stationary upward air–water flows in a vertical pipe with an inner diameter of 195.3 mm using the wire-mesh sensor technology. During the experiments the ...sensor was always mounted on the top of the test section while the distance between gas injection and measuring plane was varied to up to 18 different
L/
D by using gas injection chambers at different vertical positions. The gas was injected via holes in the pipe wall. The pressure was kept at 0.25 MPa (absolute) at the location of the active gas injection while the temperature was constant at 30 °C ± 1 K. This procedure exactly represents the evolution of the flow along the pipe, as it would be observed for an injection at a constant height position and a shifting of the measurement plane. The experiments were done for 48 combinations of air and water superficial velocities varying from 0.04 m/s to 1.6 m/s for water and 0.0025 m/s to 3.2 m/s for air. From the raw data time-averaged data as: radial gas volume fraction profiles, bubble size distributions, radial volume fraction profiles decomposed according to the bubble size and the radial profiles of the gas velocity were calculated. Due to the combination of the new experimental procedure with the high spatial and temporal resolution of the wire-mesh sensor technology the data have new quality especially regarding their consistency in the evolution with increasing
L/
D. This closes a gap for data suitable for CFD code development and validation for two-phase flows, especially for models on bubble coalescence and break-up.
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GEOZS, IJS, IMTLJ, KILJ, KISLJ, NUK, OILJ, PNG, SAZU, SBCE, SBJE, UL, UM, UPCLJ, UPUK
Extensive efforts have been made to understand joint kinematics and kinetics in total knee arthroplasty (TKA) in subjects with satisfactory outcomes during daily functional activities and clinical ...tests, but it remains unclear whether such movement characteristics hold the potential to indicate the underlying aetiology of unsatisfactory or bad TKA outcomes.
To investigate which kinematic and kinetic parameters assessed during passive clinical tests and functional activities of daily living are associated with poor functionality and underlying deficits after total knee replacement.
We focused on studies characterizing the kinematic or kinetic parameters of the knee joint that are associated with poor clinical outcome after TKA. Seventeen articles were included for the review, and kinematic and kinetic data from 719 patients with minimal follow up of 6 months were extracted and analyzed.
Passive posterior translation at 90°flexionexhibited good potential for differentiating stable and unstable TKAs. Anterior-posterior (A-P) translation of the medial condyle at 0–30° and 30–60° flexion, A-P translation of the lateral condyle at 60–90°during closed chain exercises, as well asknee extension moment during stair ascent and descent, knee abduction moment during stair descent, knee internal rotation moment and plantar flexion moment during walking, 2ndpeak ground reaction force during stair ascent and walkingshowed the greatest promise as functional biomarkers for a dissatisfied/poor outcome knee after TKA.
In this study, we systematically reviewed the state-of-the-art knowledge of kinematics and kinetics associated with functional deficits, and found 11 biomechanical parameters that showed promise for supportingdecision making in TKA.
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GEOZS, IJS, IMTLJ, KILJ, KISLJ, NLZOH, NUK, OILJ, PNG, SAZU, SBCE, SBJE, UILJ, UL, UM, UPCLJ, UPUK, ZAGLJ, ZRSKP
More than a decade after the discovery of the two-dimensional electron system (2DES) at the interface between the band insulators LaAlO3 (LAO) and SrTiO3 (STO) its microscopic origin is still under ...debate. Several explanations have been proposed, the main contenders being electron doping by oxygen vacancies and electronic reconstruction, i.e., the redistribution of electrons to the interface to minimize the electrostatic energy in the polar LAO film. However, no experiment thus far could provide unambiguous information on the microscopic origin of the interfacial charge carriers. Here we utilize a novel experimental approach combining photoelectron spectroscopy (PES) with highly brilliant synchrotron radiation and apply it to a set of samples with varying key parameters that are thought to be crucial for the emergence of interfacial conductivity. Based on microscopic insight into the electronic structure, we obtain results tipping the scales in favor of polar discontinuity as a generic, robust driving force for the 2DES formation. Likewise, other functionalities such as magnetism or superconductivity might be switched in all-oxide devices by polarity-driven charge transfer.
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CMK, CTK, FMFMET, IJS, NUK, PNG, UM
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