INMdok (Leibniz Institute for New Materials)
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Non-Markovian and Collective Search Strategies
Get PDFAgents searching for a target can improve their efficiency by memorizing where they have already been searching or by cooperating with other searchers and using strategies that benefit from collective effects. This chapter reviews such concepts: non-Markovian and collective search strategies. We start with the first passage properties of continuous non-Markovian processes and then proceed to the discrete random walker with 1-step and n-step memory. Next we discuss the auto-chemotactic walker, a random walker that produces a diffusive chemotactic cue from which the walker tries to avoid. Then ensembles of agents searching for a single target are discussed, whence the search efficiency may comprise in addition to the first passage time also metabolic costs. We consider the first passage properties of ensembles of chemotactic random walkers and then the pursuit problem, in which searchers (or hunters / predators) see the mobile target over a certain distance. Evasion strategies of single or many targets are also elucidated. Finally we review collective foraging strategies comprising many searchers and many immobile targets. We finish with an outlook on future research directions comprising yet unexplored search strategies of immune cells and in swarm robotics
In-situ investigation of temperature induced agglomeration in non-polar magnetic nanoparticle dispersions by small angle X-ray scattering
Get PDFNon-polar magnetic nanoparticles agglomerate upon cooling. This process is followed by in-situ small angle X-ray scattering to assess structural properties of the emerging agglomerates. On the length scale of a few particle diameters, no differences are found between the agglomerates of small (d = 12nm) and large (d = 22nm) nanoparticles. Hard-sphere like random packing with a local packing fraction of η = 0.4 is seen. On larger length scales, small particle form compact superstructures, while large particles arrange into agglomerates that resemble chain-like structure in SAXS. This can be explained by directed magnetic dipole interactions that dominate larger particles, while isotropic van der Waals interaction governs the agglomeration of smaller particles
Effects of Periodic Pore Ordering on Photocatalytic Hydrogen Generation with Mesoporous Semiconductor Oxides
Get PDFCrystalline and 3D continuous mesoporous quaternary CsTaWO6 semiconductors are prepared with different degrees of long-range periodic order and local order, respectively, to investigate the influence of periodic pore order on the photocatalytic performance in hydrogen evolution of mesoporous photocatalysts. The degree of long-range order of the mesopores is changed by modifying the ratio between metal precursors and soft polymer template poly(isoprene-b-styrene-b-ethylene oxide) (PI-b-PS-b-PEO; ISO) in the sol–gel synthesis. Long-range periodic order is found to have no appreciable advantage compared with an only locally ordered continuous pore system. On the contrary, nonperiodically ordered mesopores result in higher activity toward photocatalytic hydrogen evolution, even with slightly smaller pore diameter and lower cumulative pore volume. Most importantly, it is shown that pore connectivity and heterogeneous pore systems in mesoporous photocatalysts play a major role for hydrogen evolution when other parameters are confirmed to be not rate limiting
Electroactive nanoinjection platform for intracellular delivery and gene silencing
Get PDFNanoinjection—the process of intracellular delivery using vertically configured nanostructures—is a physical route that efficiently negotiates the plasma membrane, with minimal perturbation and toxicity to the cells. Nanoinjection, as a physical membrane-disruption-mediated approach, overcomes challenges associated with conventional carrier-mediated approaches such as safety issues (with viral carriers), genotoxicity, limited packaging capacity, low levels of endosomal escape, and poor versatility for cell and cargo types. Yet, despite the implementation of nanoinjection tools and their assisted analogues in diverse cellular manipulations, there are still substantial challenges in harnessing these platforms to gain access into cell interiors with much greater precision without damaging the cell’s intricate structure. Here, we propose a non-viral, low-voltage, and reusable electroactive nanoinjection (ENI) platform based on vertically configured conductive nanotubes (NTs) that allows for rapid influx of targeted biomolecular cargos into the intracellular environment, and for successful gene silencing. The localization of electric fields at the tight interface between conductive NTs and the cell membrane drastically lowers the voltage required for cargo delivery into the cells, from kilovolts (for bulk electroporation) to only ≤ 10 V; this enhances the fine control over membrane disruption and mitigates the problem of high cell mortality experienced by conventional electroporation
Consequence of anisotropy on flocking: the discretized Vicsek model [Version 1]
Get PDFWe numerically study a discretized Vicsek model (DVM) with particles orienting in q possible orientations in two dimensions. The study probes the significance of anisotropic orientation and microscopic interaction on the macroscopic behavior. The DVM is an off-lattice flocking model like the active clock model [ACM; EPL {\bf 138}, 41001 (2022)] but the dynamical rules of particle alignment and movement are inspired by the prototypical Vicsek model (VM). The DVM shows qualitatively similar properties as the ACM for intermediate noise strength where a transition from macrophase to microphase separation of the coexistence region is observed as q is increased. But for small q and noise strength, the liquid phase appearing in the ACM at low temperatures is replaced in the DVM by a configuration of multiple clusters with different polarization which does not exhibit any long-range order. We find that the dynamical rules have a profound influence on the overarching features of the flocking phase. We further identify the metastability of the ordered liquid phase subjected to a perturbation
Crystalline Carbosilane-Based Block Copolymers: Synthesis by Anionic Polymerization and Morphology Evaluation in the Bulk State
Get PDFBlock copolymers (BCPs) in the bulk state are known to self-assemble into different morphologies depending on their polymer segment ratio. For polymers with amorphous and crystalline BCP segments, the crystallization process can be influenced significantly by the corresponding bulk morphology. Herein, the synthesis of the amorphous-crystalline BCP poly(dimethyl silacyclobutane)-block-poly(2vinyl pyridine), (PDMSB-b-P2VP), by living anionic polymerization is reported. Polymers with overall molar masses ranging from 17 400 g to 592 200 g mol−1 and PDMSB contents of 4.8–83.9 vol% are synthesized and characterized by size-exclusion chromatography and NMR spectroscopy. The bulk morphology of the obtained polymers is investigated by means of transmission electron microscopy and small angle X-ray scattering, revealing a plethora of self-assembled structures, providing confined and nonconfined conditions. Subsequently, the influence of the previously determined morphologies and their resulting confinement on the crystallinity and crystallization behavior of PDMSB is analyzed via differential scanning calorimetry and powder X-ray diffraction. Here, fractionated crystallization and supercooling effects are observable as well as different diffraction patterns of the PDMSB crystallites for confined and nonconfined domains
Anion and ether group influence in protic guanidinium ionic liquids
Get PDFIonic liquids are attractive liquid materials for many advanced applications. For targeted design, in-depth knowledge about their structure–property-relations is urgently needed. We prepared a set of novel protic ionic liquids (PILs) with a guanidinium cation with either an ether or alkyl side chain and different anions. While being a promising cation class, the available data is insufficient to guide design. We measured thermal and transport properties, nuclear magnetic resonance (NMR) spectra as well as liquid and crystalline structures supported by ab initio computations and were able to obtain a detailed insight into the influence of the anion and the ether substitution on the physical and spectroscopic properties. For the PILs, hydrogen bonding is the main interaction between cation and anion and the H-bond strength is inversely related to the proton affinity of the constituting acid and correlated to the increase of 1H and 15N chemical shifts. Using anions from acids with lower proton affinity leads to proton localization on the cation as evident from NMR spectra and self-diffusion coefficients. In contrast, proton exchange was evident in ionic liquids with triflate and trifluoroacetate anions. Using imide-type anions and ether side groups decreases glass transitions as well as fragility, and accelerated dynamics significantly. In case of the ether guanidinium ionic liquids, the conformation of the side chain adopts a curled structure as the result of dispersion interactions, while the alkyl chains prefer a linear arrangement
Revealing the Meissner Corpuscles in Human Glabrous Skin Using In Vivo Non-Invasive Imaging Techniques
Get PDFThe presence of mechanoreceptors in glabrous skin allows humans to discriminate textures by touch. The amount and distribution of these receptors defines our tactile sensitivity and can be affected by diseases such as diabetes, HIV-related pathologies, and hereditary neuropathies. The quantification of mechanoreceptors as clinical markers by biopsy is an invasive method of diagnosis. We report the localization and quantification of Meissner corpuscles in glabrous skin using in vivo, non-invasive optical microscopy techniques. Our approach is supported by the discovery of epidermal protrusions which are co-localized with Meissner corpuscles. Index fingers, small fingers, and tenar palm regions of ten participants were imaged by optical coherence tomography (OCT) and laser scan microscopy (LSM) to determine the thickness of the stratum corneum and epidermis and to count the Meissner corpuscles. We discovered that regions containing Meissner corpuscles could be easily identified by LSM with an enhanced optical reflectance above the corpuscles, caused by a protrusion of the strongly reflecting epidermis into the stratum corneum with its weak reflectance. We suggest that this local morphology above Meissner corpuscles has a function in tactile perception
Prussian blue and its analogues as functional template materials: control of derived structure compositions and morphologies
Get PDFHexacyanometallates, known as Prussian blue (PB) and its analogues (PBAs), are a class of coordination compounds with a regular and porous open structure. The PBAs are formed by the self-assembly of metallic species and cyanide groups. A uniform distribution of each element makes the PBAs robust templates to prepare hollow and highly porous (hetero)nanostructures of metal oxides, sulfides, carbides, nitrides, phosphides, and (N-doped) carbon, among other compositions. In this review, we examine methods to derive materials from PBAs focusing on the correlation between synthesis steps and derivative morphologies and composition. Insights into catalytic and electrochemical properties resulting from different derivatization strategies are also presented. We discuss challenges in manipulating the derivatives' properties, give perspectives of synthetic approaches for the target applications and present an outlook on less investigated grounds in Prussian blue derivatives
Dynamics, cation conformation and rotamers in guanidinium ionic liquids with ether groups
Get PDFIonic liquids are modern materials with a broad range of applications, including electrochemical devices, the exploitation of sustainable resources and chemical processing. Expanding the chemical space to include novel ion classes allows for the elucidation of novel structure-property relationships and fine tuning for specific applications. We prepared a set of ionic liquids based on the sparsely investigated pentamethyl guanidinium cation with a 2-ethoxy-ethyl side chain in combination with a series of frequently used anions. The resulting properties are compared to a cation with a pentyl side chain lacking ether functionalization. We measured the thermal transitions and transport properties to estimate the performance and trends of this cation class. The samples with imide-type anions form liquids at ambient temperature, and show good transport properties, comparable to imidazolium or ammonium ionic liquids. Despite the dynamics being significantly accelerated, ether functionalization of the cation favors the formation of crystalline solids. Single crystal structure analysis, ab initio calculations and variable temperature nuclear magnetic resonance measurements (VT-NMR) revealed that cation conformations for the ether- and alkyl-chain-substituted are different in both the solid and liquid states. While ether containing cations adopt compact, curled structures, those with pentyl side chains are linear. The Eyring plot revealed that the curled conformation is accompanied by a higher activation energy for rotation around the carbon-nitrogen bonds, due to the coordination of the ether chain as observed by VT-NMR