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- ItemMelt Electrowriting of Graded Porous Scaffolds to Mimic the Matrix Structure of the Human Trabecular Meshwork(Washington, DC : ACS Publ., 2022) Włodarczyk-Biegun, Małgorzata K.; Villiou, Maria; Koch, Marcus; Muth, Christina; Wang, Peixi; Ott, Jenna; del Campo, AranzazuThe permeability of the human trabecular meshwork (HTM) regulates eye pressure via a porosity gradient across its thickness modulated by stacked layers of matrix fibrils and cells. Changes in HTM porosity are associated with increases in intraocular pressure and the progress of diseases such as glaucoma. Engineered HTMs could help to understand the structure-function relation in natural tissues and lead to new regenerative solutions. Here, melt electrowriting (MEW) is explored as a biofabrication technique to produce fibrillar, porous scaffolds that mimic the multilayer, gradient structure of native HTM. Poly(caprolactone) constructs with a height of 125-500 μm and fiber diameters of 10-12 μm are printed. Scaffolds with a tensile modulus between 5.6 and 13 MPa and a static compression modulus in the range of 6-360 kPa are obtained by varying the scaffold design, that is, the density and orientation of the fibers and number of stacked layers. Primary HTM cells attach to the scaffolds, proliferate, and form a confluent layer within 8-14 days, depending on the scaffold design. High cell viability and cell morphology close to that in the native tissue are observed. The present work demonstrates the utility of MEW for reconstructing complex morphological features of natural tissues.
- ItemConductive Gas Plasma Treatment Augments Tumor Toxicity of Ringer’s Lactate Solutions in a Model of Peritoneal Carcinomatosis(Basel : MDPI, 2022) Miebach, Lea; Freund, Eric; Cecchini, Alessandra Lourenço; Bekeschus, SanderReactive species generated by medical gas plasma technology can be enriched in liquids for use in oncology targeting disseminated malignancies, such as metastatic colorectal cancer. Notwithstanding, reactive species quantities depend on the treatment mode, and we recently showed gas plasma exposure in conductive modes to be superior for cancer tissue treatment. However, evidence is lacking that such a conductive mode also equips gas plasma-treated liquids to confer augmented intraperitoneal anticancer activity. To this end, employing atmospheric pressure argon plasma jet kINPen-treated Ringer’s lactate (oxRilac) in a CT26-model of colorectal peritoneal carcinomatosis, we tested repeated intraabdominal injection of such remotely or conductively oxidized liquid for antitumor control and immunomodulation. Enhanced reactive species formation in conductive mode correlated with reduced tumor burden in vivo, emphasizing the advantage of conduction over the free mode for plasma-conditioned liquids. Interestingly, the infiltration of lymphocytes into the tumors was equally enhanced by both treatments. However, significantly lower levels of interleukin (IL)4 and IL13 and increased levels of IL2 argue for a shift in intratumoral T-helper cell subpopulations correlating with disease control. In conclusion, our data argue for using conductively over remotely prepared plasma-treated liquids for anticancer treatment.
- ItemShort-Range Cooperative Slow-down of Water Solvation Dynamics Around SO42--Mg2+ Ion Pairs(Washington, DC : American Chemical Society, 2022) Kundu, Achintya; Mamatkulov, Shavkat I.; Brünig, Florian N.; Bonthuis, Douwe Jan; Netz, Roland R.; Elsaesser, Thomas; Fingerhut, Benjamin P.The presence of ions affects the structure and dynamics of water on a multitude of length and time scales. In this context, pairs of Mg2+ and SO42- ions in water constitute a prototypical system for which conflicting pictures of hydration geometries and dynamics have been reported. Key issues are the molecular pair and solvation shell geometries, the spatial range of electric interactions, and their impact on solvation dynamics. Here, we introduce asymmetric SO42- stretching vibrations as new and most specific local probes of solvation dynamics that allow to access ion hydration dynamics at the dilute concentration (0.2 M) of a native electrolyte environment. Highly sensitive heterodyne 2D-IR spectroscopy in the fingerprint region of the SO42- ions around 1100 cm-1 reveals a specific slow-down of solvation dynamics for hydrated MgSO4 and for Na2SO4 in the presence of Mg2+ ions, which manifests as a retardation of spectral diffusion compared to aqueous Na2SO4 solutions in the absence of Mg2+ ions. Extensive molecular dynamics and density functional theory QM/MM simulations provide a microscopic view of the observed ultrafast dephasing and hydration dynamics. They suggest a molecular picture where the slow-down of hydration dynamics arises from the structural peculiarities of solvent-shared SO42--Mg2+ ion pairs.
- ItemTransient spin injection efficiencies at ferromagnet/metal interfaces(Weinheim : Wiley-VCH, 2022-10-19) Elliott, Peter; Eschenlohr, Andrea; Chen, Jinghao; Shallcross, Sam; Bovensiepen, Uwe; Dewhurst, John Kay; Sharma, SangeetaSpin injection across interfaces driven by ultrashort optical pulses on femtosecond timescales constitutes a new way to design spintronics applications. Targeted utilization of this phenomenon requires knowledge of the efficiency of non-equilibrium spin injection. From a quantitative comparison of ab initio time-dependent density functional theory and interface-sensitive, time-resolved non-linear optical experiment, the spin injection efficiency (SIE) at the Co/Cu(001) interface is determined, and its microscopic origin, i.e., the influence of spin-orbit coupling and the interface electronic structure, is discussed. Moreover, we theoretically predict that the SIE at ferromagnetic–metal interfaces can be optimized through laser pulse and materials parameters, namely the fluence, pulse duration, and substrate material.
- ItemThe Role of Al2O3 ALD Coating on Sn-Based Intermetallic Anodes for Rate Capability and Long-Term Cycling in Lithium-Ion Batteries(Weinheim : Wiley-VCH, 2022) Soltani, Niloofar; Abbas, Syed Muhammad; Hantusch, Martin; Lehmann, Sebastian; Nielsch, Kornelius; Bahrami, Amin; Mikhailova, DariaThe electrochemical performances of CoSn2 and Ni3Sn4 as potential anode materials in lithium-ion batteries (LIBs) are investigated using varying thicknesses of an alumina layer deposited by the atomic layer deposition (ALD) technique. Rate capability results showed that at high current densities, Al2O3-coated CoSn2 and Ni3Sn4 electrodes after 10-ALD cycles outperformed uncoated materials. The charge capacities of coated CoSn2 and Ni3Sn4 electrodes are 571 and 134 mAh g−1, respectively, at a high current density of 5 A g−1, while the capacities of uncoated electrodes are 363 and 11 mAh g−1. When the current density is reduced to 1 A g−1, however, the cycling performances of Al2O3-coated CoSn2 and Ni3Sn4 electrodes fade faster after almost 40 cycles than uncoated electrodes. The explanation is found in the composition of the solid-electrolyte interface (SEI), which strongly depends on the current rate. Thus, X-ray photoelectron spectroscopy analysis of SEI layers on coated samples cycles at a low current density of 0.1 Ag−1, revealed organic carbonates as major products, which probably have a low ionic conductivity. In contrast, the SEI of coated materials cycled at 5 Ag−1 consists mostly of mixed inorganic/organic fluorine-rich Al-F and C-F species facilitating a higher ionic transport, which improves electrochemical performance.
- ItemZwitterionic Dendrimersomes: A Closer Xenobiotic Mimic of Cell Membranes(Weinheim : Wiley-VCH, 2022-10-31) Joseph, Anton; Wagner, Anna M.; Garay-Sarmiento, Manuela; Aleksanyan, Mina; Haraszti, Tamás; Söder, Dominik; Georgiev, Vasil N.; Dimova, Rumiana; Percec, Virgil; Rodriguez-Emmenegger, CesarBuilding functional mimics of cell membranes is an important task toward the development of synthetic cells. So far, lipid and amphiphilic block copolymers are the most widely used amphiphiles with the bilayers by the former lacking stability while membranes by the latter are typically characterized by very slow dynamics. Herein, a new type of Janus dendrimer containing a zwitterionic phosphocholine hydrophilic headgroup (JDPC) and a 3,5-substituted dihydrobenzoate-based hydrophobic dendron is introduced. JDPC self-assembles in water into zwitterionic dendrimersomes (z-DSs) that faithfully recapitulate the cell membrane in thickness, flexibility, and fluidity, while being resilient to harsh conditions and displaying faster pore closing dynamics in the event of membrane rupture. This enables the fabrication of hybrid DSs with components of natural membranes, including pore-forming peptides, structure-directing lipids, and glycans to create raft-like domains or onion vesicles. Moreover, z-DSs can be used to create active synthetic cells with life-like features that mimic vesicle fusion and motility as well as environmental sensing. Despite their fully synthetic nature, z-DSs are minimal cell mimics that can integrate and interact with living matter with the programmability to imitate life-like features and beyond.
- ItemSilane-Mediated Expansion of Domains in Si-Doped κ-Ga2O3 Epitaxy and its Impact on the In-Plane Electronic Conduction(Weinheim : Wiley-VCH, 2022) Mazzolini, Piero; Fogarassy, Zsolt; Parisini, Antonella; Mezzadri, Francesco; Diercks, David; Bosi, Matteo; Seravalli, Luca; Sacchi, Anna; Spaggiari, Giulia; Bersani, Danilo; Bierwagen, Oliver; Janzen, Benjamin Moritz; Marggraf, Marcella Naomi; Wagner, Markus R.; Cora, Ildiko; Pécz, Béla; Tahraoui, Abbes; Bosio, Alessio; Borelli, Carmine; Leone, Stefano; Fornari, RobertoUnintentionally doped (001)-oriented orthorhombic κ-Ga2O3 epitaxial films on c-plane sapphire substrates are characterized by the presence of ≈ 10 nm wide columnar rotational domains that can severely inhibit in-plane electronic conduction. Comparing the in- and out-of-plane resistance on well-defined sample geometries, it is experimentally proved that the in-plane resistivity is at least ten times higher than the out-of-plane one. The introduction of silane during metal-organic vapor phase epitaxial growth not only allows for n-type Si extrinsic doping, but also results in the increase of more than one order of magnitude in the domain size (up to ≈ 300 nm) and mobility (highest µ ≈ 10 cm2V−1s−1, with corresponding lowest ρ ≈ 0.2 Ωcm). To qualitatively compare the mean domain dimension in κ-Ga2O3 epitaxial films, non-destructive experimental procedures are provided based on X-ray diffraction and Raman spectroscopy. The results of this study pave the way to significantly improved in-plane conduction in κ-Ga2O3 and its possible breakthrough in new generation electronics. The set of cross-linked experimental techniques and corresponding interpretation here proposed can apply to a wide range of material systems that suffer/benefit from domain-related functional properties.
- ItemOptical Anisotropy and Momentum-Dependent Excitons in Dibenzopentacene Single Crystals(Washington, DC : ACS Publications, 2022) Graf, Lukas; Liu, Fupin; Naumann, Marco; Roth, Friedrich; Debnath, Bipasha; Büchner, Bernd; Krupskaya, Yulia; Popov, Alexey A.; Knupfer, MartinHigh-quality single crystals of the organic semiconductor (1,2;8,9)-dibenzopentacene were grown via physical vapor transport. The crystal structure─unknown before─was determined by single-crystal X-ray diffraction; polarization-dependent optical absorption measurements display a large anisotropy in the ac plane of the crystals. The overall Davydov splitting is ∼110 meV, which is slightly lower than that in the close relative pentacene (120 meV). Momentum-dependent electron energy-loss spectroscopy measurements show a clear exciton dispersion of the Davydov components. An analysis of the dispersion using a simple 1D model indicates smaller electron- and hole-transfer integrals in dibenzopentacene as compared to pentacene. The spectral weight distribution of the excitation spectra is strongly momentum-dependent and demonstrates a strong momentum-dependent admixture of Frenkel excitons, charge-transfer excitons, and vibrational modes.
- ItemMixed Cu-Fe Sulfides Derived from Polydopamine-Coated Prussian Blue Analogue as a Lithium-Ion Battery Electrode(Washington, DC : ACS Publications, 2022) Bornamehr, Behnoosh; Presser, Volker; Husmann, SamanthaBatteries employing transition-metal sulfides enable high-charge storage capacities, but polysulfide shuttling and volume expansion cause structural disintegration and early capacity fading. The design of heterostructures combining metal sulfides and carbon with an optimized morphology can effectively address these issues. Our work introduces dopamine-coated copper Prussian blue (CuPB) analogue as a template to prepare nanostructured mixed copper-iron sulfide electrodes. The material was prepared by coprecipitation of CuPB with in situ dopamine polymerization, followed by thermal sulfidation. Dopamine controls the particle size and favors K-rich CuPB due to its polymerization mechanism. While the presence of the coating prevents particle agglomeration during thermal sulfidation, its thickness demonstrates a key effect on the electrochemical performance of the derived sulfides. After a two-step activation process during cycling, the C-coated KCuFeS2electrodes showed capacities up to 800 mAh/g at 10 mA/g with nearly 100% capacity recovery after rate handling and a capacity of 380 mAh/g at 250 mA/g after 500 cycles.
- ItemApplication of scanning electrochemical microscopy for topography imaging of supported lipid bilayers(Cambridge : RSC Publ., 2022) Nasri, Zahra; Memari, Seyedali; Striesow, Johanna; Weltmann, Klaus-Dieter; von Woedtke, Thomas; Wende, KristianOxidative stress in cellular environments may cause lipid oxidation and membrane degradation. Therefore, studying the degree of lipid membrane morphological changes by reactive oxygen and nitrogen species will be informative in oxidative stress-based therapies. This study introduces the possibility of using scanning electrochemical microscopy as a powerful imaging technique to follow the topographical changes of a solid-supported lipid bilayer model induced by reactive species produced from gas plasma. The introduced strategy is not limited to investigating the effect of reactive species on the lipid bilayer but could be extended to understand the morphological changes of the lipid bilayer due to the action of membrane proteins or antimicrobial peptides.