Metal‐containing Polymers via Electropolymerization

Electropolymerization represents a suitable and well‐established approach for the assembly of polymer structures, in particular with regard to the formation of thin, insoluble films. Utilization of monomers that are functionalized with metal complex units allows the combination of structural and functional benefits of polymers and metal moieties. Since a broad range of both electropolymerizable monomers and metal complexes are available, various structures and, thus, applications are possible. Recent developments in the field of synthesis and potential applications of metal‐functionalized polymers obtained via electropolymerization are presented, highlighting the significant advances in this field of research.     

The Role of Polymorphisms at the Interleukin-1, Interleukin-4, GATA-3 and Cyclooxygenase-2 Genes in Non-Surgical Periodontal Therapy

Periodontitis is a multifactorial disease. The aim of this explorative study was to investigate the role of Interleukin-(IL)-1, IL-4, GATA-3 and Cyclooxygenase-(COX)-2 polymorphisms after non-surgical periodontal therapy with adjunctive systemic antibiotics (amoxicillin/metronidazole) and subsequent maintenance in a Caucasian population. Analyses were performed using blood samples from periodontitis patients of a multi-center trial (ClinicalTrials.gov {"type":"clinical-trial","attrs":{"text":"NCT00707369","term_id":"NCT00707369"}}NCT00707369=ABPARO-study). Polymorphisms were analyzed using quantitative real-time PCR. Clinical attachment levels (CAL), percentage of sites showing further attachment loss (PSAL) ≥1.3 mm, bleeding on probing (BOP) and plaque score were assessed. Exploratory statistical analysis was performed. A total of 209 samples were genotyped. Patients carrying heterozygous genotypes and single-nucleotide-polymorphisms (SNP) on the GATA-3-IVS4 +1468 gene locus showed less CAL loss than patients carrying wild type. Heterozygous genotypes and SNPs on the IL-1A-889, IL-1B +3954, IL-4-34, IL-4-590, GATA-3-IVS4 +1468 and COX-2-1195 gene loci did not influence CAL. In multivariate analysis, CAL was lower in patients carrying GATA-3 heterozygous genotypes and SNPs than those carrying wild-types. For the first time, effects of different genotypes were analyzed in periodontitis progression after periodontal therapy and during supportive treatment using systemic antibiotics demonstrating a slight association of GATA-3 gene locus with CAL. This result suggests that GATA-3 genotypes are a contributory but non-essential risk factor for periodontal disease progression.     

Intramyocardial Inflammation after COVID-19 Vaccination: An Endomyocardial Biopsy-Proven Case Series

Myocarditis in response to COVID-19 vaccination has been reported since early 2021. In particular, young male individuals have been identified to exhibit an increased risk of myocardial inflammation following the administration of mRNA-based vaccines. Even though the first epidemiological analyses and numerous case reports investigated potential relationships, endomyocardial biopsy (EMB)-proven cases are limited. Here, we present a comprehensive histopathological analysis of EMBs from 15 patients with reduced ejection fraction (LVEF = 30 (14–39)%) and the clinical suspicion of myocarditis following vaccination with Comirnaty^® (Pfizer-BioNTech) (n = 11), Vaxzevria^® (AstraZenica) (n = 2) and Janssen^® (Johnson & Johnson) (n = 2). Immunohistochemical EMB analyses reveal myocardial inflammation in 14 of 15 patients, with the histopathological diagnosis of active myocarditis according the Dallas criteria (n = 2), severe giant cell myocarditis (n = 2) and inflammatory cardiomyopathy (n = 10). Importantly, infectious causes have been excluded in all patients. The SARS-CoV-2 spike protein has been detected sparsely on cardiomyocytes of nine patients, and differential analysis of inflammatory markers such as CD4⁺ and CD8⁺ T cells suggests that the inflammatory response triggered by the vaccine may be of autoimmunological origin. Although a definitive causal relationship between COVID-19 vaccination and the occurrence of myocardial inflammation cannot be demonstrated in this study, data suggest a temporal connection. The expression of SARS-CoV-2 spike protein within the heart and the dominance of CD4⁺ lymphocytic infiltrates indicate an autoimmunological response to the vaccination.     

Consensus reaching in multi-agent packet-switched networks with non-linear coupling

An important task for multi-agent systems (MAS) is to reach a consensus, e.g. to align their velocity vectors. Recent results propose appropriate consensus protocols to achieve such tasks, but most of them do not consider the effect of communication constraints such as the presence of time-delays in the exchange of information between the agents. In this article, we provide conditions for a non-linear, locally passive MAS of arbitrary size to reach a consensus, when the agents communicate over a packet-switched network that is characterised by a given topology. Both the cases of constant and switching topologies are considered. The nature of the communication channel imposes constraints that are modelled using stochastic delays of arbitrary distribution. We first embed this model in another, distributed but deterministic delay model and provide conditions for the error introduced by this simplification. In our main result, we provide conditions for the locally passive MAS with distributed delays to reach a consensus. In the case of a fixed topology, the underlying directed graph has to contain a spanning tree. In the case of a switching topology, only the union graph of all graphs that persist over time is required to contain a spanning tree. These conditions are independent of the distribution and the size of the packet delays. To show attractivity of the consensus set, we use an invariance principle for systems described by functional differential equations based on an appropriate Lyapunov–Razumikhin function. This methodological approach is the main contribution of this work and can also be applied to other consensus problems with delays. We illustrate our results by numerical simulations showing synchronisation of non-linear Kuramoto oscillators over a digital network.     

Evaluating experience sampling of stress in a single-subject research design

How can we measure subjective experiences or internal states? The rise of happiness as a variable of interest in policy decisions, for instance, necessitates appropriate methods for valid and practical measurements. This self-experimental work contributes to scientific development by analysing and evaluating three methods for recording stress: the experience sampling method with a smartphone, an adapted version of the day reconstruction method (DRM, a diary method) and an ubiquitous biophysical measure of the heart rate. All three methods yield significant treatment effects for eight “natural experiments” as stressors. Surprisingly, the DRM outperforms the other two methods in a simple factor analysis and appears to have no recall bias. Also reactivity has no substantial impact, and an applied researcher should minimise the complexity of the input (amount and type of questions, interface and integration) rather than reduce the number of prompts. Some evidence suggests a Likert-type scale should be preferred over a continuous one. This work also reflects upon the nature of single-subject research and the role of the experimenter.     

Materials Surgery – Reactivity Differences of Organic Groups in Hybrids

Synergistic properties in hybrid materials can emerge if the inorganic matrix has an electronic influence on the organic constituents and vice versa. This paper describes the drastic effect of SiO₂ in periodically ordered mesoporous organosilica materials (PMOs) on ethylene groups. A sophisticated, in situ solid‐state NMR spectroscopy study showed that the ozonolysis of ethylene groups follows an entirely different mechanism than is normal for organic, molecular groups. Ultimately, this leads to the topotactic transformation of the PMO material. Only if silicon is not in the alpha position to the double bond does it became possible to establish a new method to functionalize PMOs materials: the targeted scission of the ethylene group and the creation of functionalized pockets inside the pore walls of the mesoporous solid.     

Solving the trade-off between fairness and throughput: Token bucket and leaky bucket-based weighted fair queueing schedulers

In this article, we present two efficient weighted fair queueing (WFQ) scheduling algorithms leaned on the well-known token bucket and leaky bucket shaping/policing algorithms. The performance of the presented algorithms is compared to those of the state-of-the-art WFQ approximations such as weighted round robin (WRR) and the recently proposed bin sort fair queueing (BSFQ). Our simulation results show that the proposed algorithms provide a better fairness at a lower implementation complexity while simultaneously achieving a comparable network utilization.     

Superconducting Quantum Metamaterials from High Pressure Melt Infiltration of Metals into Block Copolymer Double Gyroid Derived Ceramic Templates

Mesoscale order can lead to emergent properties including phononic bandgaps or topologically protected states. Block copolymers offer a route to mesoscale periodic architectures, but their use as structure directing agents for metallic materials has not been fully realized. A versatile approach to mesostructured metals via bulk block copolymer self-assembly derived ceramic templates, is demonstrated. Molten indium is infiltrated into mesoporous, double gyroidal silicon nitride templates under high pressure to yield bulk, 3D periodic nanocomposites as free-standing monoliths which exhibit emergent quantum-scale phenomena. Vortices are artificially introduced when double gyroidal indium metal behaves as a type II superconductor, with evidence of strong pinning centers arrayed on the order of the double gyroid lattice size. Sample behavior is reproducible over months, showing high stability. High pressure infiltration of bulk block copolymer self-assembly based ceramic templates is an enabling tool for studying high-quality metals with previously inaccessible architectures, and paves the way for the emerging field of block-copolymer derived quantum metamaterials.