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- ItemMagnetically responsive composites: electron beam assisted magnetic nanoparticle arrest in gelatin hydrogels for bioactuation(Cambridge : RSC Publ., 2019) Deuflhard, Marie; Eberbeck, Dietmar; Hietschold, Philine; Wilharm, Nils; Mühlberger, Marina; Friedrich, Ralf P.; Alexiou, Christoph; Mayr, Stefan G.As emerging responsive materials, ferrogels have become highly attractive for biomedical and technical applications in terms of soft actuation, tissue engineering or controlled drug release. In the present study, bioderived ferrogels were fabricated and successfully deformed within moderate, heterogeneous magnetic fields. Synthesis was realized by arresting iron oxide nanoparticles in porcine gelatin by introduction of covalent crosslinks via treatment with energetic electrons for mesh refinement. This approach also allows for tuning thermal and mechanical stability of the gelatin matrix. Operating the bioferrogel in compression, magnetic forces on the nanoparticles are counterbalanced by the stiffness of the hydrogel matrix that is governed by a shift in thermodynamic equilibrium of swelling, as derived in the framework of osmosis. As gelatin and iron oxide nanoparticles are established as biocompatible constituents, these findings promise potential for in vivo use as contactless mechanical transducers.
- ItemLow-energy constraints on photoelectron spectra measured from liquid water and aqueous solutions(Cambridge : RSC Publ., 2021) Malerz, Sebastian; Trinter, Florian; Hergenhahn, Uwe; Ghrist, Aaron; Ali, Hebatallah; Nicolas, Christophe; Saak, Clara-Magdalena; Richter, Clemens; Hartweg, Sebastian; Nahon, Laurent; Lee, Chin; Goy, Claudia; Neumark, Daniel M; Meijer, Gerard; Wilkinson, Iain; Winter, Bernd; Thürmer, StephanWe 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.
- ItemProton dynamics in molecular solvent clusters as an indicator for hydrogen bond network strength in confined geometries(Cambridge : RSC Publ., 2020) Saak, Clara-Magdalena; Richter, Clemens; Unger, Isaak; Mucke, Melanie; Nicolas, Christophe; Hergenhahn, Uwe; Caleman, Carl; Huttula, Marko; Patanen, Minna; Björnholm, OlleHydrogen bonding leads to the formation of strong, extended intermolecular networks in molecular liquids such as water. However, it is less well-known how robust the network is to environments in which surface formation or confinement effects become prominent, such as in clusters or droplets. Such systems provide a useful way to probe the robustness of the network, since the degree of confinement can be tuned by altering the cluster size, changing both the surface-to-volume ratio and the radius of curvature. To explore the formation of hydrogen bond networks in confined geometries, here we present O 1s Auger spectra of small and large clusters of water, methanol, and dimethyl ether, as well as their deuterated equivalents. The Auger spectra of the clusters and the corresponding macroscopic liquids are compared and evaluated for an isotope effect, which is due to proton dynamics within the lifetime of the core hole (proton-transfer-mediated charge-separation, PTM-CS), and can be linked to the formation of a hydrogen bond network in the system. An isotope effect is observed in water and methanol but not for dimethyl ether, which cannot donate a hydrogen bond at its oxygen site. The isotope effect, and therefore the strength of the hydrogen bond network, is more pronounced in water than in methanol. Its value depends on the average size of the cluster, indicating that confinement effects change proton dynamics in the core ionised excited state.
- ItemProperties of gaseous closo-[B6X6]2− dianions (X = Cl, Br, I)(Cambridge : RSC Publ., 2020) Rohdenburg, Markus; Yang, Zheng; Su, Pei; Bernhardt, Eduard; Yuan, Qinqin; Apra, Edoardo; Grabowsky, Simon; Laskin, Julia; Jenne, Carsten; Wang, Xue-Bin; Warneke, JonasElectronic structure, collision-induced dissociation (CID) and bond properties of closo-[B6X6]2− (X = Cl–I) are investigated in direct comparison with their closo-[B12X12]2− analogues. Photoelectron spectroscopy (PES) and theoretical investigations reveal that [B6X6]2− dianions are electronically significantly less stable than the corresponding [B12X12]2− species. Although [B6Cl6]2− is slightly electronically unstable, [B6Br6]2− and [B6I6]2− are intrinsically stable dianions. Consistent with the trend in the electron detachment energy, loss of an electron (e− loss) is observed in CID of [B6X6]2− (X = Cl, Br) but not for [B6I6]2−. Halogenide loss (X− loss) is common for [B6X6]2− (X = Br, I) and [B12X12]2− (X = Cl, Br, I). Meanwhile, X˙ loss is only observed for [B12X12]2− (X = Br, I) species. The calculated reaction enthalpies of the three competing dissociation pathways (e−, X− and X˙ loss) indicated a strong influence of kinetic factors on the observed fragmentation patterns. The repulsive Coulomb barrier (RCB) determines the transition state for the e− and X− losses. A significantly lower RCB for X− loss than for e− loss was found in both experimental and theoretical investigations and can be rationalized by the recently introduced concept of electrophilic anions. The positive reaction enthalpies for X− losses are significantly lower for [B6X6]2− than for [B12X12]2−, while enthalpies for X˙ losses are higher. These observations are consistent with a difference in bond character of the B–X bonds in [B6X6]2− and [B12X12]2−. A complementary bonding analysis using QTAIM, NPA and ELI-D based methods suggests that B–X bonds in [B12X12]2− have a stronger covalent character than in [B6X6]2−, in which X has a stronger halide character.
- ItemPeptides@mica: From affinity to adhesion mechanism(Cambridge : RSC Publ., 2016) Gladytz, A.; John, T.; Gladytz, T.; Hassert, R.; Pagel, M.; Risselada, H.J.; Naumov, S.; Beck-Sickinger, A.G.; Abel, B.Investigating the adsorption of peptides on inorganic surfaces, on the molecular level, is fundamental for medicinal and analytical applications. Peptides can be potent as linkers between surfaces and living cells in biochips or in implantation medicine. Here, we studied the adsorption process of the positively charged pentapeptide RTHRK, a recently identified binding sequence for surface oxidized silicon, and novel analogues thereof to negatively charged mica surfaces. Homogeneous formation of monolayers in the nano- and low micromolar peptide concentration range was observed. We propose an alternative and efficient method to both quantify binding affinity and follow adhesion behavior. This method makes use of the thermodynamic relationship between surface coverage, measured by atomic force microscopy (AFM), and the concomitant free energy of adhesion. A knowledge-based fit to the autocorrelation of the AFM images was used to correct for a biased surface coverage introduced by the finite lateral resolution of the AFM. Binding affinities and mechanisms were further explored by large scale molecular dynamics (MD) simulations. The combination of well validated MD simulations with topological data from AFM revealed a better understanding of peptide adsorption processes on the atomistic scale. We demonstrate that binding affinity is strongly determined by a peptide's ability to form salt bridges and hydrogen bonds with the surface lattice. Consequently, differences in hydrogen bond formation lead to substantial differences in binding affinity despite conservation of the peptide's overall charge. Further, MD simulations give access to relative changes in binding energy of peptide variations in comparison to a lead compound.
- ItemNanoscale patterning of self-assembled monolayer (SAM)-functionalised substrates with single molecule contact printing(Cambridge : RSC Publ., 2017) Sajfutdinow, M.; Uhlig, K.; Prager, A.; Schneider, C.; Abel, B.; Smith, D.M.Defined arrangements of individual molecules are covalenty connected ("printed") onto SAM-functionalised gold substrates with nanometer resolution. Substrates were initially pre-functionlised by coating with 3,3′-dithiodipropionic acid (DTPA) to form a self-assembled monolayer (SAM), which was characterised by atomic force microscopy (AFM), contact angle goniometry, cyclic voltammetry and surface plasmon resonance (SPR) spectroscopy. Pre-defined "ink" patterns displayed on DNA origami-based single-use carriers ("stamp") were covalently conjugated to the SAM using 1-ethyl-3-(3-dimethylamino-propyl)carbodiimide (EDC) and N-hydroxy-succinimide (NHS). These anchor points were used to create nanometer-precise single-molecule arrays, here with complementary DNA and streptavidin. Sequential steps of the printing process were evaluated by AFM and SPR spectroscopy. It was shown that 30% of the detected arrangements closely match the expected length distribution of designed patterns, whereas another 40% exhibit error within the range of only 1 streptavidin molecule. SPR results indicate that imposing a defined separation between molecular anchor points within the pattern through this printing process enhances the efficiency for association of specific binding partners for systems with high sterical hindrance. This study expands upon earlier findings where geometrical information was conserved by the application of DNA nanostructures, by establishing a generalisable strategy which is universally applicable to nearly any type of prefunctionalised substrate such as metals, plastics, silicates, ITO or 2D materials.