Shape stability and bundling of ultrathin nanowires

Ultrathin nanowires are promising nanoscale materials. They can reach length-to-diameter aspect ratios exceeding 1000, making them suitable building blocks for optoelectronic devices such as transparent conducting films. An organic ligand shell surrounds their inorganic core, provides colloidal stability, and guides their one-dimensional growth. Two unresolved issues limit their application. Nanowires can agglomerate into elongated bundles, but efficient use of this superstructure is difficult since we do not yet understand the bundling mechanisms. Furthermore, nanowires are prone to the Plateau-Rayleigh instability: thin wires tend to fragment into discrete spheroidal particles to reduce their surface energy, limiting their lifetime and reliability. This thesis investigates superstructure formation and nanowire stability and the link between both topics. Bundles are shown to emerge in non-polar solvents for entropic reasons. Solvent or unbound ligand molecules align in proximity to the ligand shell, thus losing entropy. Bundling decreases this loss in entropy by reducing contact with the bulk solvent. The structural stability of nanowires is enhanced or degraded by the ligand shell, depending on the relationship between free energy and local surface curvature. Kinetic barriers in ad- and desorbing ligands and rearrangement of surface atoms slow down the break-up. Bundling further stabilizes the wires by confining the space available to them.Ultradünne Nanodrähte, bestehend aus einem anorganischen Kern und einer organischen Ligandenhülle, können Aspektverhältnisse von über 1:1000 erreichen und sind potenzielle Materialien für optoelektronische Technologien wie transparente Elektroden. Einer breiteren Anwendung stehen zwei Herausforderungen entgegen. Nanodrähte können zu Bündeln agglomerieren, aber eine effiziente Nutzung dieser Superstruktur ist schwierig, da unser Verständnis der zugrundeliegenden Bündelungsmechanismen unvollständig ist. Zudem sind Nanodrähte instabil: gemäß der Plateau-Rayleigh-Instabilität zerbrechen sie zur Reduktion ihrer Oberflächenenergie in kleinere Nanopartikel, was ihre Langzeit-Anwendung verhindert. Sowohl Formstabilität und Superstruktur als auch der Zusammenhang zwischen beiden Themen wurden in dieser Dissertation untersucht. Bündel entstehen in unpolaren Lösemitteln, weil sich Lösemittelmoleküle oder freie Liganden parallel zur Ligandenhülle ausrichten und dabei Entropie verlieren. Durch die Anordnung in Bündeln wird der Kontakt zum Lösemittel reduziert, sodass der Entropieverlust geringer ausfällt. Die Formstabilität von Nanodrähten wird von der Ligandenhülle verbessert oder verschlechtert, je nach Zusammenhang zwischen freier Energie und Oberflächenkrümmung. Kinetische Barrieren in der Ad- und Desorption von Liganden und der Reorganisation der Oberfläche verlangsamen den Zerfall. Bündel verbessern die Formstabilität, indem sie den für die Nanodrähte verfügbaren Raum begrenzen

Low Friction and High Solid-Solid Contact Ratio—A Contradiction for Laser-Patterned Surfaces?

Recording of Stribeck-like curves is a common way to study the effect of laser-patterned surfaces on the frictional efficiency. However, solely relying on the coefficient of friction when identifying the lubrication regime and the underlying working principles can be misleading. Consequently, a ball-on-disc tribometer was combined with an electrical resistivity circuit to simultaneously measure Stribeck-like curves and solid-solid contact ratios for polished and laser-patterned samples. Line-like surface patterns with different periodicities were produced by direct laser interference patterning on steel substrates (AISI304). The reference shows a Stribeck-like behavior well correlating with the contact ratios. The behavior deviates for high sliding velocities (high contact ratios) due to a loss of lubricant induced by centrifugal forces pulling the lubricant out of the contact zone. In contrast, the solid–solid contact ratio of the laser-patterned samples is around 80% for all sliding velocities. Those values can be explained by higher contact pressures and the structural depth induced by the surface topography which make a full separation of the surfaces unlikely. Despite those high values for the contact ratio, laser-patterning significantly reduces friction, which can be traced back to a reduced real contact area and the ability to store oil in the contact zone

On the geometric stability of an inorganic nanowire and an organic ligand shell

The break-up of a nanowire with an organic ligand shell into discrete droplets is analysed in terms of the Rayleigh-Plateau instability. Explicit account is taken of the effect of the organic ligand shell upon the energetics and kinetics of surface diffusion in the wire. Both an initial perturbation analysis and a full numerical analysis of the evolution in wire morphology are conducted, and the governing non-dimensional groups are identified. The perturbation analysis is remarkably accurate in obtaining the main features of the instability, including the pinch-off time and the resulting diameter of the droplets. It is conjectured that the surface energy of the wire and surrounding organic shell depends upon both the mean and deviatoric invariants of the curvature tensor. Such a behaviour allows for the possibility of a stable nanowire such that the Rayleigh-Plateau instability is not energetically favourable. A stability map illustrates this. Maps are also constructed for the final droplet size and pinch-off time as a function of two non-dimensional groups that characterise the energetics and kinetics of diffusion in the presence of the organic shell. These maps can guide future experimental activity on the stabilisation of nanowires by organic ligand shells

Low friction and high solid-solid contact ratio—A contradiction for laser-patterned surfaces?

Recording of Stribeck-like curves is a common way to study the effect of laser-patterned surfaces on the frictional efficiency. However, solely relying on the coefficient of friction when identifying the lubrication regime and the underlying working principles can be misleading. Consequently, a ball-on-disc tribometer was combined with an electrical resistivity circuit to simultaneously measure Stribeck-like curves and solid-solid contact ratios for polished and laser-patterned samples. Line-like surface patterns with different periodicities were produced by direct laser interference patterning on steel substrates (AISI304). The reference shows a Stribeck-like behavior well correlating with the contact ratios. The behavior deviates for high sliding velocities (high contact ratios) due to a loss of lubricant induced by centrifugal forces pulling the lubricant out of the contact zone. In contrast, the solid–solid contact ratio of the laser-patterned samples is around 80% for all sliding velocities. Those values can be explained by higher contact pressures and the structural depth induced by the surface topography which make a full separation of the surfaces unlikely. Despite those high values for the contact ratio, laser-patterning significantly reduces friction, which can be traced back to a reduced real contact area and the ability to store oil in the contact zone

Simultaneous DNA and RNA isolation from brain punches for epigenetics

BACKGROUND: Epigenetic modifications such as DNA methylation play an important role for gene expression and are regulated by developmental and environmental signals. DNA methylation typically occurs in a highly tissue- and cell-specific manner. This raises a severe challenge when studying discrete, small regions of the brain where cellular heterogeneity is high and tissue quantity limited. Because gene expression and methylation are often tightly linked it appears of interest to compare both parameters in the same sample. FINDINGS: We present a refined method for the simultaneous extraction of DNA for bisulfite sequencing and RNA for expression analysis from small mouse brain tissue punches. This method can also be easily adapted for other small tissues or cell populations. CONCLUSIONS: The method described herein results in DNA and RNA of a quantity and quality permitting highly reliable bisulfite analysis and quantitative RT-PCR measurements, respectively

Breakdown of continuum models for spherical probe adhesion tests on micropatterned surfaces

Funding Information: SB, DY, EA, and RH acknowledge funding from the European Research Council (ERC) under the European Union's Seventh Framework Program (FP/2007–2013)/ERC Advanced Grant No. 340929 . RMM acknowledges the Alexander von Humboldt Foundation for awarding the “Virtual Humboldt Cluster on the Mechanics and Physics of Adhesion and Grip”.Peer reviewedPublisher PD

IMHOTEP: cross-professional evaluation of a three-dimensional virtual reality system for interactive surgical operation planning, tumor board discussion and immersive training for complex liver surgery in a head-mounted display

Background Virtual reality (VR) with head-mounted displays (HMD) may improve medical training and patient care by improving display and integration of different types of information. The aim of this study was to evaluate among different healthcare professions the potential of an interactive and immersive VR environment for liver surgery that integrates all relevant patient data from different sources needed for planning and training of procedures. Methods 3D-models of the liver, other abdominal organs, vessels, and tumors of a sample patient with multiple hepatic masses were created. 3D-models, clinical patient data, and other imaging data were visualized in a dedicated VR environment with an HMD (IMHOTEP). Users could interact with the data using head movements and a computer mouse. Structures of interest could be selected and viewed individually or grouped. IMHOTEP was evaluated in the context of preoperative planning and training of liver surgery and for the potential of broader surgical application. A standardized questionnaire was voluntarily answered by four groups (students, nurses, resident and attending surgeons). Results In the evaluation by 158 participants (57 medical students, 35 resident surgeons, 13 attending surgeons and 53 nurses), 89.9% found the VR system agreeable to work with. Participants generally agreed that complex cases in particular could be assessed better (94.3%) and faster (84.8%) with VR than with traditional 2D display methods. The highest potential was seen in student training (87.3%), resident training (84.6%), and clinical routine use (80.3%). Least potential was seen in nursing training (54.8%). Conclusions The present study demonstrates that using VR with HMD to integrate all available patient data for the preoperative planning of hepatic resections is a viable concept. VR with HMD promises great potential to improve medical training and operation planning and thereby to achieve improvement in patient care

Polycomb Binding Precedes Early-Life Stress Responsive DNA Methylation at the Avp Enhancer

Early-life stress (ELS) in mice causes sustained hypomethylation at the downstream Avp enhancer, subsequent overexpression of hypothalamic Avp and increased stress responsivity. The sequence of events leading to Avp enhancer methylation is presently unknown. Here, we used an embryonic stem cell-derived model of hypothalamic-like differentiation together with in vivo experiments to show that binding of polycomb complexes (PcG) preceded the emergence of ELS-responsive DNA methylation and correlated with gene silencing. At the same time, PcG occupancy associated with the presence of Tet proteins preventing DNA methylation. Early hypothalamic-like differentiation triggered PcG eviction, DNA-methyltransferase recruitment and enhancer methylation. Concurrently, binding of the Methyl-CpG-binding and repressor protein MeCP2 increased at the enhancer although Avp expression during later stages of differentiation and the perinatal period continued to increase. Overall, we provide evidence of a new role of PcG proteins in priming ELS-responsive DNA methylation at the Avp enhancer prior to epigenetic programming consistent with the idea that PcG proteins are part of a flexible silencing system during neuronal development

Intergenerational accumulation of impairments in maternal behavior following postnatal social stress

Early adversity such as depressed maternal care can have long-term physiological and behavioral effects on offspring and future generations. Exposure to chronic social stress (CSS), an ethologically model of postpartum depression and anxiety, during lactation impairs maternal care and exerts similar effects on the F1 dam offspring of the stressed F0 dams. These changes associate with increased corticosterone and neuroendocrine alterations. CSS F2 offspring further display decreased social behavior as juveniles and adults and decreased basal levels of corticosterone. This current study investigates the intergenerational inheritance of alterations in maternal behavior in F2 CSS dams together with neuroendocrine and immune markers to explore whether aspects of maternal behavior are intergenerationally inherited through immune and neuroendocrine mechanisms. We find that defects in maternal care behavior persist into the F2 generation with F2 dams exhibiting a pervasively depressed maternal care and increased restlessness throughout lactation. This occurs together with reduced basal cortisol (in contrast to an increase in F1 dams), a lack of changes in neuroendocrine gene expression, and reduced serum ICAM-1 (intercellular adhesion molecule-1) levels - a marker for inflammation and blood–brain barrier integrity. The data support the hypothesis that the effects of chronic social stress can accumulate across multiple generations to depress maternal care, increase restlessness and alter basal functioning of the immune system and hypothalamic pituitary adrenal axis