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- ItemSuperelasticity of Plasma- and Synthetic Membranes Resulting from Coupling of Membrane Asymmetry, Curvature, and Lipid Sorting(Weinheim : Wiley-VCH, 2021) Steinkühler, Jan; Fonda, Piermarco; Bhatia, Tripta; Zhao, Ziliang; Leomil, Fernanda S. C.; Lipowsky, Reinhard; Dimova, RumianaBiological cells are contained by a fluid lipid bilayer (plasma membrane, PM) that allows for large deformations, often exceeding 50% of the apparent initial PM area. Isolated lipids self-organize into membranes, but are prone to rupture at small (<2–4%) area strains, which limits progress for synthetic reconstitution of cellular features. Here, it is shown that by preserving PM structure and composition during isolation from cells, vesicles with cell-like elasticity can be obtained. It is found that these plasma membrane vesicles store significant area in the form of nanotubes in their lumen. These act as lipid reservoirs and are recruited by mechanical tension applied to the outer vesicle membrane. Both in experiment and theory, it is shown that a “superelastic” response emerges from the interplay of lipid domains and membrane curvature. This finding allows for bottom-up engineering of synthetic biomaterials that appear one magnitude softer and with threefold larger deformability than conventional lipid vesicles. These results open a path toward designing superelastic synthetic cells possessing the inherent mechanics of biological cells.
- ItemPhotophysics of Anionic Bis(4H-imidazolato)CuI Complexes(Weinheim : Wiley-VCH, 2022) Seidler, Bianca; Tran, Jens H.; Hniopek, Julian; Traber, Philipp; Görls, Helmar; Gräfe, Stefanie; Schmitt, Michael; Popp, Jürgen; Schulz, Martin; Dietzek‐Ivanšić, BenjaminIn this paper, the photophysical behavior of four panchromatically absorbing, homoleptic bis(4H-imidazolato)CuI complexes, with a systematic variation in the electron-withdrawing properties of the imidazolate ligand, were studied by wavelength-dependent time-resolved femtosecond transient absorption spectroscopy. Excitation at 400, 480, and 630 nm populates metal-to-ligand charge transfer, intraligand charge transfer, and mixed-character singlet states. The pump wavelength-dependent transient absorption data were analyzed by a recently established 2D correlation approach. Data analysis revealed that all excitation conditions yield similar excited-state dynamics. Key to the excited-state relaxation is fast, sub-picosecond pseudo-Jahn-Teller distortion, which is accompanied by the relocalization of electron density onto a single ligand from the initially delocalized state at Franck-Condon geometry. Subsequent intersystem crossing to the triplet manifold is followed by a sub-100 ps decay to the ground state. The fast, nonradiative decay is rationalized by the low triplet-state energy as found by DFT calculations, which suggest perspective treatment at the strong coupling limit of the energy gap law.
- ItemExcited-State Dynamics in Borylated Arylisoquinoline Complexes in Solution and in cellulo(Weinheim : Wiley-VCH, 2023) Yang, Tingxiang; Valavalkar, Abha; Romero‐Arenas, Antonio; Dasgupta, Anindita; Then, Patrick; Chettri, Avinash; Eggeling, Christian; Ros, Abel; Pischel, Uwe; Dietzek‐Ivanšić, BenjaminTwo four-coordinate organoboron N,C-chelate complexes with different functional terminals on the PEG chains are studied with respect to their photophysical properties within human MCF-7 cells. Their excited-state properties are characterized by time-resolved pump-probe spectroscopy and fluorescence lifetime microscopy. The excited-state relaxation dynamics of the two complexes are similar when studied in DMSO. Aggregation of the complexes with the carboxylate terminal group is observed in water. When studying the light-driven excited-state dynamics of both complexes in cellulo, i. e., after being taken up into human MCF-7 cells, both complexes show different features depending on the nature of the anchoring PEG chains. The lifetime of a characteristic intramolecular charge-transfer state is significantly shorter when studied in cellulo (360±170 ps) as compared to in DMSO (∼960 ps) at 600 nm for the complexes with an amino group. However, the kinetics of the complexes with the carboxylate group are in line with those recorded in DMSO. On the other hand, the lifetimes of the fluorescent state are almost identical for both complexes in cellulo. These findings underline the importance to evaluate the excited-state properties of fluorophores in a complex biological environment in order to fully account for intra- and intermolecular effects governing the light-induced processes in functional dyes.
- ItemSpectromicroscopy Studies of Silicon Nanowires Array Covered by Tin Oxide Layers(Weinheim : Wiley-VCH, 2023) Turishchev, Sergey; Schleusener, Alexander; Chuvenkova, Olga; Parinova, Elena; Liu, Poting; Manyakin, Maxim; Kurganskii, Sergei; Sivakov, VladimirThe composition and atomic and electronic structure of a silicon nanowire (SiNW) array coated with tin oxide are studied at the spectromicroscopic level. SiNWs are covered from top to down with a wide bandgap tin oxide layer using a metal–organic chemical vapor deposition technique. Results obtained via scanning electron microscopy and X-ray diffraction showed that tin-oxide nanocrystals, 20 nm in size, form a continuous and highly developed surface with a complex phase composition responsible for the observed electronic structure transformation. The “one spot” combination, containing a chemically sensitive morphology and spectroscopic data, is examined via photoemission electron microscopy in the X-ray absorption near-edge structure spectroscopy (XANES) mode. The observed spectromicroscopy results showed that the entire SiNW surface is covered with a tin(IV) oxide layer and traces of tin(II) oxide and metallic tin phases. The deviation from stoichiometric SnO2 leads to the formation of the density of states sub-band in the atop tin oxide layer bandgap close to the bottom of the SnO2 conduction band. These observations open up the possibility of the precise surface electronic structures estimation using photo-electron microscopy in XANES mode.
- ItemNanostructured Silicon Matrix for Materials Engineering(Weinheim : Wiley-VCH, 2023) Liu, Poting; Schleusener, Alexander; Zieger, Gabriel; Bochmann, Arne; van Spronsen, Matthijs A.; Sivakov, VladimirTin-containing layers with different degrees of oxidation are uniformly distributed along the length of silicon nanowires formed by a top-down method by applying metalorganic chemical vapor deposition. The electronic and atomic structure of the obtained layers is investigated by applying nondestructive surface-sensitive X-ray absorption near edge spectroscopy using synchrotron radiation. The results demonstrated, for the first time, a distribution effect of the tin-containing phases in the nanostructured silicon matrix compared to the results obtained for planar structures at the same deposition temperatures. The amount and distribution of tin-containing phases can be effectively varied and controlled by adjusting the geometric parameters (pore diameter and length) of the initial matrix of nanostructured silicon. Due to the occurrence of intense interactions between precursor molecules and decomposition by-products in the nanocapillary, as a consequence of random thermal motion of molecules in the nanocapillary, which leads to additional kinetic energy and formation of reducing agents, resulting in effective reduction of tin-based compounds to a metallic tin state for molecules with the highest penetration depth in the nanostructured silicon matrix. This effect will enable clear control of the phase distributions of functional materials in 3D matrices for a wide range of applications.