Search Results
Low-energy constraints on photoelectron spectra measured from liquid water and aqueous solutions
We report on the effects of electron collision and indirect ionization processes, occurring at photoexcitation and electron kinetic energies well below 30 eV, on the photoemission spectra of liquid water. We show that the nascent photoelectron spectrum and, hence, the inferred electron binding energy can only be accurately determined if electron energies are large enough that cross sections for quasi-elastic scattering processes, such as vibrational excitation, are negligible. Otherwise, quasi-elastic scattering leads to strong, down-to-few-meV kinetic energy scattering losses from the direct photoelectron features, which manifest in severely distorted intrinsic photoelectron peak shapes. The associated cross-over point from predominant (known) electronically inelastic to quasi-elastic scattering seems to arise at surprisingly large electron kinetic energies, of approximately 10–14 eV. Concomitantly, we present evidence for the onset of indirect, autoionization phenomena (occurring via superexcited states) within a few eV of the primary and secondary ionization thresholds. These processes are inferred to compete with the direct ionization channels and primarily produce low-energy photoelectrons at photon and electron impact excitation energies below ∼15 eV. Our results highlight that vibrational inelastic electron scattering processes and neutral photoexcitation and autoionization channels become increasingly important when photon and electron kinetic energies are decreased towards the ionization threshold. Correspondingly, we show that for neat water and aqueous solutions, great care must be taken when quantitatively analyzing photoelectron spectra measured too close to the ionization threshold. Such care is essential for the accurate determination of solvent and solute ionization energies as well as photoelectron branching ratios and peak magnitudes.
Multifunctional coatings combining bioactive peptides and affinity-based cytokine delivery for enhanced integration of degradable vascular grafts
Insufficient endothelialization of cardiovascular devices is a high-risk factor for implant failure. Presentation of extracellular matrix (ECM)-derived coatings is a well-known strategy to improve implant integration. However, the complexity of the system is challenging and strategies for applying multifunctionality are required. Here, we engineered mussel-derived surface-binding peptides equipped with integrin (c[RGDfK]) and proteoglycan binding sites (FHRRIKA) for enhanced endothelialization. Surface-binding properties of the platform containing l-3,4-dihydroxyphenylalanine (DOPA) residues were confirmed for hydrophilized polycaprolactone-co-lactide scaffolds as well as for glass and polystyrene. Further, heparin and the heparin-binding angiogenic factors VEGF, FGF-2 and CXCL12 were immobilized onto the peptide in a modular assembly. Presentation of bioactive peptides greatly enhanced human umbilical vein endothelial cell (HUVEC) adhesion and survival under static and fluidic conditions. In subsequent investigations, peptide-heparin-complexes loaded with CXCL12 or VEGF had an additional increasing effect on cell viability, differentiation and migration. Finally, hemocompatibility of the coatings was ensured. This study demonstrates that coatings combining adhesion peptides, glycosaminoglycans and modulators are a versatile tool to convey ECM-inspired multifunctionality to biomaterials and efficiently promote their integration. © 2020 The Royal Society of Chemistry.
Multiscale simulations of the electronic structure of III-nitride quantum wells with varied indium content: Connecting atomistic and continuum-based models
Carrier localization effects in III-N heterostructures are often studied in the frame of modified continuum-based models utilizing a single-band effective mass approximation. However, there exists no comparison between the results of a modified continuum model and atomistic calculations on the same underlying disordered energy landscape. We present a theoretical framework that establishes a connection between atomistic tight-binding theory and continuum-based electronic structure models, here a single-band effective mass approximation, and provide such a comparison for the electronic structure of (In,Ga)N quantum wells. In our approach, in principle, the effective masses are the only adjustable parameters since the confinement energy landscape is directly obtained from tight-binding theory. We find that the electronic structure calculated within effective mass approximation and the tight-binding model differ noticeably. However, at least in terms of energy eigenvalues, an improved agreement between the two methods can be achieved by adjusting the band offsets in the continuum model, enabling, therefore, a recipe for constructing a modified continuum model that gives a reasonable approximation of the tight-binding energies. Carrier localization characteristics for energetically low lying, strongly localized states differ, however, significantly from those obtained using the tight-binding model. For energetically higher lying, more delocalized states, good agreement may be achieved. Therefore, the atomistically motivated continuum-based single-band effective mass model established provides a good, computationally efficient alternative to fully atomistic investigations, at least at when targeting questions related to higher temperatures and carrier densities in (In,Ga)N systems.
Photon-electron coincidence experiments at synchrotron radiation facilities with arbitrary bunch modes
We report the adaptation of an electron–photon coincidence detection scheme to the multibunch hybrid mode of the synchrotron radiation source BESSY II (Helmholtz-Zentrum Berlin). Single-event-based data acquisition and evaluation, combined with the use of relative detection times between the coincident particles, enable the acquisition of proper coincidence signals from a quasi-continuous excitation pattern. The background signal produced by accidental coincidences in the time difference representation is modeled using the non-coincident electron and photon spectra. We validate the method by reproducing previously published results, which were obtained in the single bunch mode, and illustrate its usability for the multibunch hybrid mode by investigating the photoionization of CO2 into CO+2 B satellite states, followed by subsequent photon emission. The radiative lifetime obtained and the electron binding energy are in good agreement with earlier publications. We expect this method to be a useful tool to extend the versatility of coincident particle detection to arbitrary operation modes of synchrotron radiation facilities and other excitation sources without the need for additional experimental adjustments.
Pinning and trapped field in MgB2- and MT-YBaCuO bulk superconductors manufactured under pressure
The relevant pinning centers of Abrikosov vortices in MgB2-based materials are oxygen-enriched Mg-B-O inclusions or nanolayers and inclusions of MgBx (x>4) phases. The high critical current densities, jc, of 106 and 103A/cm2 at 1 and 8.5 T, respectively, at 20 K can be achieved in polycrystalline materials (prepared at 2 GPa) containing a large amount of admixed oxygen. Besides, oxygen can be incorporated into the MgB2 structure in small amounts (MgB1.5O0.5), which is supported by Auger studies and calculations of the DOS and the binding energy. The jc of melt textured YBa2Cu3O7-δ (or Y123)-based superconductors (MT-YBaCuO) depends not only on the perfectness of texture and the amount of oxygen in the Y123 structure, but also on the density of twins and micro-cracks formed during the oxygenation (due to shrinking of the c-lattice parameter). The density of twins and microcracks increases with the reduction of the distance between Y2BaCuO5 (Y211) inclusions in Y123. At 77 K jc=8·104 A/cm2 in self-field and jc=103 A/cm2 at 10 T were found in materials oxygenated at 16 MPa for 3 days with a density of twins of 22–35 per µm (thickness of the lamellae: 45-30 nm) and a density of micro-cracks of 200–280 per mm. Pinning can occur at the points of intersection between the Y123 twin planes and the Y211 inclusions. MTYBaCuO at 77 K can trap 1.4 T (38×38×17 mm, oxygenated at 0.1 MPa for 20 days) and 0.8 T (16 mm in diameter and 10 mm thick with 0.45 mm holes oxygenated at 10 MPa for 53 h). The sensitivity of MgB2 to magnetic field variations (flux jumps) complicates estimates of the trapped field. At 20 K 1.8 T was found for a block of 30 mm in diameter and a thickness of 7.5 mm and 1.5 T (if the magnetic field was increased at a rate of 0.1 T) for a ring with dimensions 24×18 mm and a thickness of 8 mm.