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- ItemKelvin probe force microscopy of charged indentation-induced dislocation structures in KBr(Saarbrücken : Leibniz-Institut für neue Materialien, 2009) Egberts, Philip; Bennewitz, RolandThe incipient stages of plasticity in KBr single crystals have been examined in ultrahigh vacuum by means of Atomic Force Microscopy and Kelvin Probe Force Microscopy (KPFM). Conducting diamond-coated tips have been used to both indent the crystals and image the resulting plastic deformation. KPFM reveals that edge dislocations intersecting the surface carry a negative charge similar to kinks in surface steps, while screw dislocations show no contrast. Weak topographic features extending in <110> direction from the indentation are identified by atomic-resolution imaging to be pairs of edge dislocations of opposite sign, separated by a distance similar to the indenter radius. They indicate the glide of two parallel {110} planes perpendicular to the surface, a process that allows for a slice of KBr to be pushed away from the indentation site.
- ItemLighting the Path: Light Delivery Strategies to Activate Photoresponsive Biomaterials In Vivo(Weinheim : Wiley-VCH, 2021) Pearson, Samuel; Feng, Jun; del Campo, AránzazuPhotoresponsive biomaterials are experiencing a transition from in vitro models to in vivo demonstrations that point toward clinical translation. Dynamic hydrogels for cell encapsulation, light-responsive carriers for controlled drug delivery, and nanomaterials containing photosensitizers for photodynamic therapy are relevant examples. Nonetheless, the step to the clinic largely depends on their combination with technologies to bring light into the body. This review highlights the challenge of photoactivation in vivo, and presents strategies for light management that can be adopted for this purpose. The authors’ focus is on technologies that are materials-driven, particularly upconversion nanoparticles that assist in “direct path” light delivery through tissue, and optical waveguides that “clear the path” between external light source and in vivo target. The authors’ intention is to assist the photoresponsive biomaterials community transition toward medical technologies by presenting light delivery concepts that can be integrated with the photoresponsive targets. The authors also aim to stimulate further innovation in materials-based light delivery platforms by highlighting needs and opportunities for in vivo photoactivation of biomaterials. © 2021 The Authors. Advanced Functional Materials published by Wiley-VCH GmbH.
- ItemEpidermal growth factor receptor subunit locations determined in hydrated cells with environmental scanning electron microscopy(London : Nature Publishing Group, 2013) Peckys, Diana B; Baudoin, Jean-Pierre; Eder, Magdalena; Werner, Ulf; de Jonge, NielsImaging single epidermal growth factor receptors (EGFR) in intact cells is presently limited by the available microscopy methods. Environmental scanning electron microscopy (ESEM) of whole cells in hydrated state in combination with specific labeling with gold nanoparticles was used to localize activated EGFRs in the plasma membranes of COS7 and A549 cells. The use of a scanning transmission electron microscopy (STEM) detector yielded a spatial resolution of 3 nm, sufficient to identify the locations of individual EGFR dimer subunits. The sizes and distribution of dimers and higher order clusters of EGFRs were determined. The distance between labels bound to dimers amounted to 19 nm, consistent with a molecular model. A fraction of the EGFRs was found in higher order clusters with sizes ranging from 32–56 nm. ESEM can be used for quantitative whole cell screening studies of membrane receptors, and for the study of nanoparticle-cell interactions in general.
- ItemDense arrays of uniform submicron pores in silicon and their applications(Washington D.C. : American Chemical Society, 2015) Brodoceanu, Daniel; Elnathan, Roey; Prieto-Simón, Beatriz; Delalat, Bahman; Guinan, Taryn M.; Kroner, Elmar Karsten; Voelcker, Nicolas H.; Kraus, TobiasWe report a versatile particle-based route to dense arrays of parallel submicron pores with high aspect ratio in silicon, and explore the application of these arrays in sensors, optics, and polymer micropatterning. Polystyrene (PS) spheres are convectively assembled on gold-coated silicon wafers and sputter-etched, resulting in well-defined gold disc arrays with excellent long-range order. The gold discs act as catalysts in Metal-Assisted Chemical Etching (MACE), yielding uniform pores with straight walls, flat bottoms and high aspect ratio. The resulting pore arrays can be used as robust antireflective surfaces, in biosensing applications, and as templates for polymer replica molding.
- ItemFlexible distributed Bragg reflectors from nanocolumnar templates(Hoboken, NJ : Wiley, 2015) Calvo, Mauricio E.; González-García, Lola; Parra-Barranco, Julián; Barranco, Angel; Jiménez-Solano, Alberto; González-Elipe, Agustín R.; Míguez, HernánA flexible distributed Bragg reflector is made by the infiltration of a nanocolumnar array with polydimethyl siloxane oligomers. The high optical reflectance displayed by the final material is a direct consequence of the high refractive index contrast of the columnar layers whereas the structural stability is due to the polymer properties.
- ItemPerspective on statistical effects in the adhesion of micropatterned surfaces(Melville, NY : American Inst. of Physics, 2021) Booth, Jamie A.; Hensel, RenéBioinspired micropatterned adhesives have attracted extensive research interest in the past two decades. In modeling the performance of these adhesives, the common assumption has been that the adhesive strength of each sub-contact is identical. Recent experiments, however, have shown that interfacial defects of different characters lead to a distribution of the adhesive strength within a fibrillar array. Based on experimental observations of detachment events, a statistical model for the distribution of the local adhesive strength and the resulting performance of a micropatterned adhesive are presented. This approach constitutes a paradigm shift, providing better understanding of micropatterned adhesives under real conditions. Examples presented include the prediction of unstable detachments in compliant systems. Future directions are discussed, including the extension of the statistical approach to non-uniform loading and rate-dependent effects, the contribution of suction to adhesion and aging of contacts over specific time periods, as well as the necessity for a more in-depth understanding of defect formation considering surface roughness and other imperfections in the system.
- ItemExceptionally slow movement of gold nanoparticles at a solid/liquid interface investigated by scanning transmission electron microscopy(Washington D.C. : American Chemical Society, 2015) Verch, Andreas; Pfaff, Marina; de Jong, NielsGold nanoparticles were observed to move at a liquid/solid interface 3 orders of magnitude slower than expected for the movement in a bulk liquid by Brownian motion. The nanoscale movement was studied with scanning transmission electron microscopy (STEM) using a liquid enclosure consisting of microchips with silicon nitride windows. The experiments involved a variation of the electron dose, the coating of the nanoparticles, the surface charge of the enclosing membrane, the viscosity, and the liquid thickness. The observed slow movement was not a result of hydrodynamic hindrance near a wall but instead explained by the presence of a layer of ordered liquid exhibiting a viscosity 5 orders of magnitude larger than a bulk liquid. The increased viscosity presumably led to a dramatic slowdown of the movement. The layer was formed as a result of the surface charge of the silicon nitride windows. The exceptionally slow motion is a crucial aspect of electron microscopy of specimens in liquid, enabling a direct observation of the movement and agglomeration of nanoscale objects in liquid.
- ItemDynamic effects in friction and adhesion through cooperative rupture and formation of supramolecular bonds(Cambridge : Royal Society of Chemistry, 2015) Blass, Johanna; Albrecht, Marcel; Bozna, Bianca L.; Wenz, Gerhard; Bennewitz, RolandWe introduce a molecular toolkit for studying the dynamics in friction and adhesion from the single molecule level to effects of multivalency. As experimental model system we use supramolecular bonds established by the inclusion of ditopic adamantane connector molecules into two surface-bound cyclodextrin molecules, attached to a tip of an atomic force microscope (AFM) and to a flat silicon surface. The rupture force of a single bond does not depend on the pulling rate, indicating that the fast complexation kinetics of adamantane and cyclodextrin are probed in thermal equilibrium. In contrast, the pull-off force for a group of supramolecular bonds depends on the unloading rate revealing a non-equilibrium situation, an effect discussed as the combined action of multivalency and cantilever inertia effects. Friction forces exhibit a stick-slip characteristic which is explained by the cooperative rupture of groups of host-guest bonds and their rebinding. No dependence of friction on the sliding velocity has been observed in the accessible range of velocities due to fast rebinding and the negligible delay of cantilever response in AFM lateral force measurements.
- ItemNiobium carbide nanofibers as a versatile precursor for high power supercapacitor and high energy battery electrodes(London [u.a.] : RSC, 2016) Tolosa, Aura; Krüner, Benjamin; Fleischmann, Simon; Jäckel, Nicolas; Zeiger, Marco; Aslan, Mesut; Grobelsek, Ingrid; Presser, VolkerThis study presents electrospun niobium carbide/carbon (NbC/C) hybrid nanofibers, with an average diameter of 69 ± 30 nm, as a facile precursor to derive either highly nanoporous niobium carbide-derived carbon (NbC–CDC) fibers for supercapacitor applications or niobium pentoxide/carbon (Nb2O5/C) hybrid fibers for battery-like energy storage. In all cases, the electrodes consist of binder-free and free-standing nanofiber mats that can be used without further conductive additives. Chlorine gas treatment conformally transforms NbC nanofiber mats into NbC–CDC fibers with a specific surface area of 1508 m2 g−1. These nanofibers show a maximum specific energy of 19.5 W h kg−1 at low power and 7.6 W h kg−1 at a high specific power of 30 kW kg−1 in an organic electrolyte. CO2 treatment transforms NbC into T-Nb2O5/C hybrid nanofiber mats that provide a maximum capacity of 156 mA h g−1. The presence of graphitic carbon in the hybrid nanofibers enabled high power handling, maintaining 50% of the initial energy storage capacity at a high rate of 10 A g−1 (64 C-rate). When benchmarked for an asymmetric full-cell, a maximum specific energy of 86 W h kg−1 was obtained. The high specific power for both systems, NbC–CDC and T-Nb2O5/C, resulted from the excellent charge propagation in the continuous nanofiber network and the high graphitization of the carbon structure.
- ItemHeat-to-current conversion of low-grade heat from a thermocapacitive cycle by supercapacitors(Cambridge : Royal Society of Chemistry, 2015) Härtel, Andreas; Janssen, Mathijs; Weingarth, Daniel; Presser, Volker; van Roij, ReneThermal energy is abundantly available, and especially low-grade heat is often wasted in industrial processes as a by-product. Tapping into this vast energy reservoir with cost-attractive technologies may become a key element for the transition to an energy-sustainable economy and society. We propose a novel heat-to-current converter which is based on the temperature dependence of the cell voltage of charged supercapacitors. Using a commercially available supercapacitor, we observed a thermal cell-voltage rise of around 0.6 mV K-1 over a temperature window of 0 °C to 65 °C. Within our theoretical model, this can be used to operate a Stirling-like charge-voltage cycle whose efficiency is competitive to the most-efficient thermoelectric (Seebeck) engines. Our proposed heat-to-current converter is built from cheap materials, contains no moving parts, and could operate with a plethora of electrolytes which can be chosen for optimal performance at specific working temperatures. Therefore, this heat-to-current converter is interesting for small-scale, domestic, and industrial applications.