Netzwerkheterogenität und kooperative Bewegung: Untersuchung von Netzwerken unterschiedlicher Vernetzungsmechanismen mit dynamischer Lichtstreuung

Die Struktur von Netzwerken wird durch die Wahl der Netzwerkaufbaureaktion, der Ausgangsmoleküle und der Reaktionsbedingungen bestimmt. Es ist schwierig, wenn nicht gar unmöglich, geeignete Reaktionsparameter zu finden, die zum Aufbau homogener Netzwerkstrukturen führen. Die unterschiedliche Reaktivität der Ausgangsmoleküle resultiert in Unregelmäßigkeiten innerhalb der Netzwerkstruktur, z. B. durch inhomogene Verteilung der Vernetzungspunkte. Als Maß für die Heterogenität eines Netzwerkes kann die Streuintensität herangezogen werden. Diese besteht bei Netzwerken aus einem dynamischen und einem statischen Teil. In stark heterogenen Netzwerken überwiegt die statische Komponente der Streuintensität, die dynamischen Beiträge sind gering. Bei homogeneren Strukturen überwiegt die dynamische Komponente. Deshalb kann der Beitrag dynamischer Konzentrationsfluktuationen zur Gesamtstreuintensität als Maß für den Grad der Heterogenität dienen. Die meisten Netzwerke werden durch radikalische Copolymerisation von Monomeren und Vernetzern synthetisiert. Aufgrund der unterschiedlichen Reaktivitäten sind die entstehenden Strukturen stark heterogen. Die Verwendung anderer Mechanismen zum Netzwerkaufbau bietet eine Möglichkeit, homogenere Netzwerke zu erhalten. Vor allem die Vernetzung polymerer Ketten, ausgehend von einer homogenen halbverdünnten Lösung, ist eine strategisch interessante Variante. Ziel dieser Arbeit war die systematische Untersuchung des Einflusses der chemischen Zusammensetzung, der Netzwerkaufbaureaktion, der Polymerkonzentration und der Netzwerkdichte auf die thermodynamischen Eigenschaften (kooperative Diffusionskoeffizienten Dcoop) und die Netzwerkstruktur (Heterogenität) unterschiedlicher Netzwerksysteme. Am Beispiel von Polyacrylsäure (PAS) Netzwerken (radikalische Vernetzung) und Poly(styrol-co-maleinsäureanhydrid) (PScoMSA) Netzwerken (Vernetzung polymerer Lösungen) wurden zwei Netzwerksysteme untersucht, die sich hinsichtlich ihrer Aufbaureaktion unterscheiden. Mittels klassischer Netzwerkanalyse können diese Systeme sehr gut charakterisiert werden. Die kooperativen Diffusionskoeffizienten sowie die Netzwerkheterogenität wurden durch dynamische Lichtstreuung bestimmt

Certified Training: Small Boxes are All You Need

We propose the novel certified training method, SABR, which outperforms existing methods across perturbation magnitudes on MNIST, CIFAR-10, and TinyImageNet, in terms of both standard and certifiable accuracies. The key insight behind SABR is that propagating interval bounds for a small but carefully selected subset of the adversarial input region is sufficient to approximate the worst-case loss over the whole region while significantly reducing approximation errors. SABR does not only establish a new state-of-the-art in all commonly used benchmarks but more importantly, points to a new class of certified training methods promising to overcome the robustness-accuracy trade-off

A Novel Modelling Process in Chemistry: Merging Biological and Mathematical Perspectives to Develop Modelling Competences

Models are essential in science and therefore in scientific literacy. Therefore, pupils need to attain competency in the appropriate use of models. This so-called model–methodical competence distinguishes between model competence (the conceptual part) and modelling competence (the procedural part), wherefrom a definition follows a general overview of the concept of models in this article. Based on this, modelling processes enable the promotion of the modelling competence. In this context, two established approaches mainly applied in other disciplines (biology and mathematics) and a survey among chemistry teachers and employees of chemistry education departments (N = 98) form the starting point for developing a chemistry modelling process. The article concludes with a description of the developed modelling process, which by its design, provides an opportunity to develop students’ modelling competence

Influencing the coupling between network building blocks in CdSe/CdS dot/rod aerogels by partial cation exchange

The assembly of CdSe/CdS dot/rod nanocrystals (NCs) with variable length of ZnS tips into aerogel networks is presented. To this end, a partial region selective cation exchange procedure is performed replacing Cd by Zn starting at the NC tip. The produced aerogel networks are investigated structurally and optically. The networks of tip-to-tip connected NCs have an intricate band structure with holes confined to the CdSe cores while electrons are delocalized within the CdS also within connected building blocks. However, the ZnS tips act as a barrier of variable length and strength between the NC building blocks partly confining the electrons. This results in NC based aerogel networks with tunable strength of coupling between building blocks

On the electrolyte convection around a hydrogen bubble evolving at a microelectrode under the influence of a magnetic field

Water electrolysis was carried out in a 1 M H2SO4 solution under different potentiostatic conditions in the presence of a magnetic field oriented normal to the horizontal microelectrode (100 μm in diameter). The imposed magnetohydrodynamic (MHD) electrolyte flow around the evolving hydrogen bubble was studied to clarify the effect on the detachment of the bubble from the electrode and the mass transfer toward the electrode. Different particle imaging and tracking techniques were applied to measure the three-dimensional flow in the bulk of the cell as well as in close vicinity of the evolving bubble. The periodic bubble growth cycle was analyzed by measurements of the current oscillations and microscopic high-speed imaging. In addition, a numerical study of the flow was conducted to support the experimental results. The results demonstrate that the MHD flow imposes only a small stabilizing force on the bubble. However, the observed secondary flow enhances the mass transfer toward the electrode and may reduce the local supersaturation of dissolved hydrogen

High-Gradient Magnetic Separation of Compact Fluorescent Lamp Phosphors: Elucidation of the Removal Dynamics in a Rotary Permanent Magnet Separator

In an ongoing effort towards a more sustainable rare-earth element market, there is a high potential for an efficient recycling of rare-earth elements from end-of-life compact fluorescent lamps by physical separation of the individual phosphors. In this study, we investigate the separation of five fluorescent lamp particles by high-gradient magnetic separation in a rotary permanent magnet separator. We thoroughly characterize the phosphors by ICP-MS, laser diffraction analysis, gas displacement pycnometry, surface area analysis, SQUID-VSM, and Time-Resolved Laser-Induced Fluorescence Spectroscopy. We present a fast and reliable quantification method for mixtures of the investigated phosphors, based on a combination of Time-Resolved Laser-Induced Fluorescence Spectroscopy and parallel factor analysis. With this method, we were able to monitor each phosphors’ removal dynamics in the high-gradient magnetic separator and we estimate that the particles’ removal efficiencies are proportional to (d$^{2}$·χ)$^{1/3}$. Finally, we have found that the removed phosphors can readily be recovered easily from the separation cell by backwashing with an intermittent air–water flow. This work should contribute to a better understanding of the phosphors’ separability by high-gradient magnetic separation and can simultaneously be considered to be an important preparation for an upscalable separation process with (bio)functionalized superparamagnetic carriers

Luminescence encoding of polymer microbeads with organic dyes and semiconductor quantum dots during polymerization

Luminescence-encoded microbeads are important tools for many applications in the life and material sciences that utilize luminescence detection as well as multiplexing and barcoding strategies. The preparation of such beads often involves the staining of premanufactured beads with molecular luminophores using simple swelling procedures or surface functionalization with layer-by-layer (LbL) techniques. Alternatively, these luminophores are sterically incorporated during the polymerization reaction yielding the polymer beads. The favorable optical properties of semiconductor quantum dots (QDs), which present broadly excitable, size-tunable, narrow emission bands and low photobleaching sensitivity, triggered the preparation of beads stained with QDs. However, the colloidal nature and the surface chemistry of these QDs, which largely controls their luminescence properties, introduce new challenges to bead encoding that have been barely systematically assessed. To establish a straightforward approach for the bead encoding with QDs with minimized loss in luminescence, we systematically assessed the incorporation of oleic acid/oleylamine-stabilized CdSe/CdS-core/shell-QDs into 0.5–2.5 µm-sized polystyrene (PS) microspheres by a simple dispersion polymerization synthesis that was first optimized with the organic dye Nile Red. Parameters addressed for the preparation of luminophore-encoded beads include the use of a polymer-compatible ligand such as benzyldimethyloctadecylammonium chloride (OBDAC) for the QDs, and crosslinking to prevent luminophore leakage. The physico-chemical and optical properties of the resulting beads were investigated with electron microscopy, dynamic light scattering, optical spectroscopy, and fluorescence microscopy. Particle size distribution, fluorescence quantum yield of the encapsulated QDs, and QD leaking stability were used as measures for bead quality. The derived optimized bead encoding procedure enables the reproducible preparation of bright PS microbeads encoded with organic dyes as well as with CdSe/CdS-QDs. Although these beads show a reduced photoluminescence quantum yield compared to the initially very strongly luminescent QDs, with values of about 35%, their photoluminescence quantum yield is nevertheless still moderate

Rationale for Combining Radiotherapy and Immune Checkpoint Inhibition for Patients With Hypoxic Tumors

In order to compensate for the increased oxygen consumption in growing tumors, tumors need angiogenesis and vasculogenesis to increase the supply. Insufficiency in this process or in the microcirculation leads to hypoxic tumor areas with a significantly reduced pO2, which in turn leads to alterations in the biology of cancer cells as well as in the tumor microenvironment. Cancer cells develop more aggressive phenotypes, stem cell features and are more prone to metastasis formation and migration. In addition, intratumoral hypoxia confers therapy resistance, specifically radioresistance. Reactive oxygen species are crucial in fixing DNA breaks after ionizing radiation. Thus, hypoxic tumor cells show a two- to threefold increase in radioresistance. The microenvironment is enriched with chemokines (e.g., SDF-1) and growth factors (e.g., TGFβ) additionally reducing radiosensitivity. During recent years hypoxia has also been identified as a major factor for immune suppression in the tumor microenvironment. Hypoxic tumors show increased numbers of myeloid derived suppressor cells (MDSCs) as well as regulatory T cells (Tregs) and decreased infiltration and activation of cytotoxic T cells. The combination of radiotherapy with immune checkpoint inhibition is on the rise in the treatment of metastatic cancer patients, but is also tested in multiple curative treatment settings. There is a strong rationale for synergistic effects, such as increased T cell infiltration in irradiated tumors and mitigation of radiation-induced immunosuppressive mechanisms such as PD-L1 upregulation by immune checkpoint inhibition. Given the worse prognosis of patients with hypoxic tumors due to local therapy resistance but also increased rate of distant metastases and the strong immune suppression induced by hypoxia, we hypothesize that the subgroup of patients with hypoxic tumors might be of special interest for combining immune checkpoint inhibition with radiotherapy

Exploring larval phenology as predictor for range expansion in an invasive species

Predicting range expansion of invasive species is one of the key challenges in ecology. We modelled the phenological window for successful larval release and development (WLR) in order to predict poleward expansion of the invasive crab Hemigrapsus sanguineus along the Atlantic coast of North America and north Europe. WLR quantifies the number of opportunities (in days) when larval release leads to a successful completion of the larval phase; WLR depends on the effects of temperature on the duration of larval development and survival. Successful larval development is a necessary requirement for the establishment of self‐persistent local populations. WLR was computed from a mechanistic model, based on in situ temperature time series and a laboratory–calibrated curve predicting duration of larval development from temperature. As a validation step, we checked that model predictions of the time of larval settlement matched observations from the field for our local population (Helgoland, North Sea). We then applied our model to the North American shores because larvae from our European population showed, in the laboratory, similar responses to temperature to those of a North American population. WLR correctly predicted the northern distribution limit in North American shores, where the poleward expansion of H. sanguineus appear to have stalled (as of 2015). For north Europe, where H. sanguineus is a recent invader, WLR predicted ample room for poleward expansion towards NE England and S Norway. We also explored the importance of year‐to‐year variation in temperature for WLR and potential expansion: variations in WLR highlighted the role of heat waves as likely promoters of recruitment subsidising sink populations located at the distribution limits. Overall, phenological windows may be used as a part of a warning system enabling more targeted programs for monitoring