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Since their discovery in 1610 by Galileo Galilei, Saturn's rings continue to fascinate both experts and amateurs. Countless numbers of icy grains in almost Keplerian orbits reveal a wealth of structures such as ringlets, voids and gaps, wakes and waves, and many more. Grains are found to increase in size with increasing radial distance to Saturn. Recently discovered "propeller" structures in the Cassini spacecraft data, provide evidence for the existence of embedded moonlets. In the wake of these findings, the discussion resumes about origin and evolution of planetary rings, and growth processes in tidal environments. In this thesis, a contact model for binary adhesive, viscoelastic collisions is developed that accounts for agglomeration as well as restitution. Collisional outcomes are crucially determined by the impact speed and masses of the collision partners and yield a maximal impact velocity at which agglomeration still occurs. Based on the latter, a self-consistent kinetic concept is proposed. The model considers all possible collisional outcomes as there are coagulation, restitution, and fragmentation. Emphasizing the evolution of the mass spectrum and furthermore concentrating on coagulation alone, a coagulation equation, including a restricted sticking probability is derived. The otherwise phenomenological Smoluchowski equation is reproduced from basic principles and denotes a limit case to the derived coagulation equation. Qualitative and quantitative analysis of the relevance of adhesion to force-free granular gases and to those under the influence of Keplerian shear is investigated. Capture probability, agglomerate stability, and the mass spectrum evolution are investigated in the context of adhesive interactions. A size dependent radial limit distance from the central planet is obtained refining the Roche criterion. Furthermore, capture probability in the presence of adhesion is generally different compared to the case of pure gravitational capture. In contrast to a Smoluchowski-type evolution of the mass spectrum, numerical simulations of the obtained coagulation equation revealed, that a transition from smaller grains to larger bodies cannot occur via a collisional cascade alone. For parameters used in this study, effective growth ceases at an average size of centimeters.
“Chunking” spoken language
(2021)
In this introductory paper to the special issue on “Weak cesuras in talk-in-interaction”, we aim to guide the reader into current work on the “chunking” of naturally occurring talk. It is conducted in the methodological frameworks of Conversation Analysis and Interactional Linguistics – two approaches that consider the interactional aspect of humans talking with each other to be a crucial starting point for its analysis. In doing so, we will (1) lay out the background of this special issue (what is problematic about “chunking” talk-in-interaction, the characteristics of the methodological approach chosen by the contributors, the cesura model), (2) highlight what can be gained from such a revised understanding of “chunking” in talk-in-interaction by referring to previous work with this model as well as the findings of the contributions to this special issue, and (3) indicate further directions such work could take starting from papers in this special issue. We hope to induce a fruitful exchange on the phenomena discussed, across methodological divides.
“Chunking” spoken language
(2021)
In this introductory paper to the special issue on “Weak cesuras in talk-in-interaction”, we aim to guide the reader into current work on the “chunking” of naturally occurring talk. It is conducted in the methodological frameworks of Conversation Analysis and Interactional Linguistics – two approaches that consider the interactional aspect of humans talking with each other to be a crucial starting point for its analysis. In doing so, we will (1) lay out the background of this special issue (what is problematic about “chunking” talk-in-interaction, the characteristics of the methodological approach chosen by the contributors, the cesura model), (2) highlight what can be gained from such a revised understanding of “chunking” in talk-in-interaction by referring to previous work with this model as well as the findings of the contributions to this special issue, and (3) indicate further directions such work could take starting from papers in this special issue. We hope to induce a fruitful exchange on the phenomena discussed, across methodological divides.
The reaction of oxygen-substituted naphthalenes with singlet oxygen (O-1(2)) has been investigated, and labile endoperoxides have been isolated and characterized at -78 degrees C for the first time. Low-temperature kinetics by UV spectroscopy revealed that alkoxy and silyloxy substituents remarkably increase the rate of photooxygenations compared to 1,4-dimethylnaphthalene, whereas acyloxy-substituted acenes are inert towards O-1(2). The reactivities nicely correlate with HOMO energies and free activation energies, which we determined by density functional theory calculations. The lability of the isolated endoperoxides is due to their very fast back reaction to the corresponding naphthalenes even at -20 degrees C under release of O-1(2), making them to superior sources of this reactive species under very mild conditions. Finally, a carbohydrate-substituted naphthalene has been synthesized, which reacts reversibly with O-1(2) and might be applied for enantioselective oxidations in future work.
Experimental and kinetic modelling studies are presented to investigate the mechanism of 3,3 ',5,5 '-tetramethylbenzidine (TMB) oxidation by hydrogen peroxide (H2O2) catalyzed by peroxidase-like Pt nanoparticles immobilized in spherical polyelectrolyte brushes (SPB-Pt). Due to the high stability of SPB-Pt colloidal, this reaction can be monitored precisely in situ by UV/VIS spectroscopy. The time-dependent concentration of the blue-colored oxidation product of TMB expressed by different kinetic models was used to simulate the experimental data by a genetic fitting algorithm. After falsifying the models with abundant experimental data, it is found that both H2O2 and TMB adsorb on the surface of Pt nanoparticles to react, indicating that the reaction follows the Langmuir-Hinshelwood mechanism. A true rate constant k, characterizing the rate-determining step of the reaction and which is independent on the amount of catalysts used, is obtained for the first time. Furthermore, it is found that the product adsorbes strongly on the surface of nanoparticles, thus inhibiting the reaction. The entire analysis provides a new perspective to study the catalytic mechanism and evaluate the catalytic activity of the peroxidase-like nanoparticles.
Background: The prevalence of diabetes worldwide is predicted to increase from 2.8% in 2000 to 4.4% in 2030. Diabetic neuropathy (DN) is associated with damage to nerve glial cells, their axons, and endothelial cells leading to impaired function and mobility.
Objective: We aimed to examine the effects of an endurance-dominated exercise program on maximum oxygen consumption (VO2max), ground reaction forces, and muscle activities during walking in patients with moderate DN.
Methods: Sixty male and female individuals aged 45–65 years with DN were randomly assigned to an intervention (IG, n = 30) or a waiting control (CON, n = 30) group. The research protocol of this study was registered with the Local Clinical Trial Organization (IRCT20200201046326N1). IG conducted an endurance-dominated exercise program including exercises on a bike ergometer and gait therapy. The progressive intervention program lasted 12 weeks with three sessions per week, each 40–55 min. CON received the same treatment as IG after the post-tests. Pre- and post-training, VO2max was tested during a graded exercise test using spiroergometry. In addition, ground reaction forces and lower limbs muscle activities were recorded while walking at a constant speed of ∼1 m/s.
Results: No statistically significant baseline between group differences was observed for all analyzed variables. Significant group-by-time interactions were found for VO2max (p < 0.001; d = 1.22). The post-hoc test revealed a significant increase in IG (p < 0.001; d = 1.88) but not CON. Significant group-by-time interactions were observed for peak lateral and vertical ground reaction forces during heel contact and peak vertical ground reaction force during push-off (p = 0.001–0.037; d = 0.56–1.53). For IG, post-hoc analyses showed decreases in peak lateral (p < 0.001; d = 1.33) and vertical (p = 0.004; d = 0.55) ground reaction forces during heel contact and increases in peak vertical ground reaction force during push-off (p < 0.001; d = 0.92). In terms of muscle activity, significant group-by-time interactions were found for vastus lateralis and gluteus medius during the loading phase and for vastus medialis during the mid-stance phase, and gastrocnemius medialis during the push-off phase (p = 0.001–0.044; d = 0.54–0.81). Post-hoc tests indicated significant intervention-related increases in vastus lateralis (p = 0.001; d = 1.08) and gluteus medius (p = 0.008; d = 0.67) during the loading phase and vastus medialis activity during mid-stance (p = 0.001; d = 0.86). In addition, post-hoc tests showed decreases in gastrocnemius medialis during the push-off phase in IG only (p < 0.001; d = 1.28).
Conclusions: This study demonstrated that an endurance-dominated exercise program has the potential to improve VO2max and diabetes-related abnormal gait in patients with DN. The observed decreases in peak vertical ground reaction force during the heel contact of walking could be due to increased vastus lateralis and gluteus medius activities during the loading phase. Accordingly, we recommend to implement endurance-dominated exercise programs in type 2 diabetic patients because it is feasible, safe and effective by improving aerobic capacity and gait characteristics.
Background: The prevalence of diabetes worldwide is predicted to increase from 2.8% in 2000 to 4.4% in 2030. Diabetic neuropathy (DN) is associated with damage to nerve glial cells, their axons, and endothelial cells leading to impaired function and mobility.
Objective: We aimed to examine the effects of an endurance-dominated exercise program on maximum oxygen consumption (VO2max), ground reaction forces, and muscle activities during walking in patients with moderate DN.
Methods: Sixty male and female individuals aged 45–65 years with DN were randomly assigned to an intervention (IG, n = 30) or a waiting control (CON, n = 30) group. The research protocol of this study was registered with the Local Clinical Trial Organization (IRCT20200201046326N1). IG conducted an endurance-dominated exercise program including exercises on a bike ergometer and gait therapy. The progressive intervention program lasted 12 weeks with three sessions per week, each 40–55 min. CON received the same treatment as IG after the post-tests. Pre- and post-training, VO2max was tested during a graded exercise test using spiroergometry. In addition, ground reaction forces and lower limbs muscle activities were recorded while walking at a constant speed of ∼1 m/s.
Results: No statistically significant baseline between group differences was observed for all analyzed variables. Significant group-by-time interactions were found for VO2max (p < 0.001; d = 1.22). The post-hoc test revealed a significant increase in IG (p < 0.001; d = 1.88) but not CON. Significant group-by-time interactions were observed for peak lateral and vertical ground reaction forces during heel contact and peak vertical ground reaction force during push-off (p = 0.001–0.037; d = 0.56–1.53). For IG, post-hoc analyses showed decreases in peak lateral (p < 0.001; d = 1.33) and vertical (p = 0.004; d = 0.55) ground reaction forces during heel contact and increases in peak vertical ground reaction force during push-off (p < 0.001; d = 0.92). In terms of muscle activity, significant group-by-time interactions were found for vastus lateralis and gluteus medius during the loading phase and for vastus medialis during the mid-stance phase, and gastrocnemius medialis during the push-off phase (p = 0.001–0.044; d = 0.54–0.81). Post-hoc tests indicated significant intervention-related increases in vastus lateralis (p = 0.001; d = 1.08) and gluteus medius (p = 0.008; d = 0.67) during the loading phase and vastus medialis activity during mid-stance (p = 0.001; d = 0.86). In addition, post-hoc tests showed decreases in gastrocnemius medialis during the push-off phase in IG only (p < 0.001; d = 1.28).
Conclusions: This study demonstrated that an endurance-dominated exercise program has the potential to improve VO2max and diabetes-related abnormal gait in patients with DN. The observed decreases in peak vertical ground reaction force during the heel contact of walking could be due to increased vastus lateralis and gluteus medius activities during the loading phase. Accordingly, we recommend to implement endurance-dominated exercise programs in type 2 diabetic patients because it is feasible, safe and effective by improving aerobic capacity and gait characteristics.
Progression or impediment of fundamental motor skills performance (FMSP) in children depends on internal and environmental factors. Shoes as an environmental constraint are believed to affect these movements as children showed to perform qualitatively better with sports shoes than flip-flop sandals. However, locomotor performance assessments based on biomechanical variables are limited. Therefore, the objective of this experiment was to assess the biomechanical effects of wearing shoes while performing fundamental motor skills in children. Barefoot and shod conditions were tested in healthy children between the age of 4 and 7 years. They were asked to perform basic and advanced motor skills including double-leg stance, horizontal jumps, walking as well as counter-movement jumps, single-leg stance and sprinting. Postural control and ground reaction data were measured with two embedded force plates. A 3D motion capture system was used to analyse the spatiotemporal parameters of walking and sprinting. Findings showed that the parameters of single- and double-leg stance, horizontal and counter-movement jump did not differ between barefoot and shod conditions. Most of the spatiotemporal variables including cadence, stride length, stride time, and contact time of walking and sprinting were statistically different between the barefoot and shod conditions. Consequently, tested shoes did not change performance and biomechanics of postural control and jumping tasks; however, the spatiotemporal gait parameters indicate changes in walking and sprinting characteristics with shoes in children.
Im Rahmen der EU-weiten REACH-Verordnung haben Alternativmethoden zum Tierversuch in der Toxikologie an Bedeutung gewonnen. Die Alternativmethoden gliedern sich auf in In-vitro- und In-silico-Methoden. In dieser Dissertation wurden verschiedene Konzepte der In-silico-Toxikologie behandelt.
Die bearbeiteten Themen reichen von quantitativen Strukturaktivitätsbeziehungen (QSAR) über eine neue Herangehensweise an das gängige Konzept zur Festlegung von Grenzwerten bis hin zu computerbasierten Modellierungen zum Alkohol- und Bisphenol-A-Stoffwechsel.
Das Kapitel über QSAR befasst sich im Wesentlichen mit der Erstellung und Analyse einer Datenbank mit 878 Substanzen, die sich aus Tierversuchsstudien aus dem Archiv des Bundesinstituts für Risikobewertung zusammensetzt. Das Design wurde dabei an eine bereits bestehende Datenbank angepasst, um so einen möglichst großen Datenpool zu generieren. In der Analyse konnte u.a. gezeigt werden, dass Stoffe mit niedrigerem Molekulargewicht ein erhöhtes Potential für toxikologische Schäden aufwiesen als größere Moleküle.
Mit Hilfe des sogenannten TTC-Konzepts können Grenzwerte für Stoffe geringer Exposition festgelegt werden, zu denen keine toxikologischen Daten zur Verfügung stehen. In dieser Arbeit wurden für die Stoffe dreier Datenbanken entsprechende Grenzwerte festgelegt. Es erfolgte zunächst eine gängige strukturbasierte Aufteilung der Substanzen in die Kategorien "nicht toxisch", "möglicherweise toxisch" und "eindeutig toxisch". Substanzen, die aufgrund ihrer Struktur in eine der drei Klassen eingeordnet werden, erhalten den entsprechenden Grenzwert. Da in die dritte Klasse auch Stoffe eingeordnet werden, deren Toxizität nicht bestimmbar ist, ist sie sehr groß. Daher wurden in dieser Arbeit die ersten beiden Klassen zusammengelgt, um einen größeren Datenpool zu ermöglichen. Eine weitere Neuerung umfasst die Erstellung eines internen Grenzwerts. Diese Vorgehensweise hat den Vorteil, dass der Expositionsweg herausgerechnet wird und somit beispielsweise Studien mit oraler Verabreichung mit Studien dermaler Verabreichung verglichen werden können.
Mittels physiologisch basiertem kinetischem Modelling ist es möglich, Vorgänge im menschlichen Körper mit Hilfe spezieller Software nachzuvollziehen. Durch diese Vorgehensweise können Expositionen von Chemikalien simuliert werden. In einem Teil der Arbeit wurden Alkoholexpositionen von gestillten Neugeborenen simuliert, deren Mütter unmittelbar zuvor alkoholische Getränke konsumiert hatten. Mit dem Modell konnte gezeigt werden, dass die Expositionen des Kindes durchweg gering waren. Nach einem Glas Wein wurden Spitzenkonzentrationen im Blut von Neugeborenen von 0,0034 Promille ermittelt. Zum Vergleich wurde die Exposition durch ein für Säuglinge zugelassenes alkoholhaltiges pflanzliches Arzneimittel simuliert. Hier wurden Spitzenkonzentrationen von 0,0141 Promille erreicht. Daher scheinen Empfehlungen wie gelegentlicher Konsum ohne schädigende Wirkung auf das Kind wissenschaftlich fundiert zu sein.
Ein weiteres Kinetik-Modell befasste sich mit dem Stoffwechsel von Bisphenol A. Teils widersprüchliche Daten zur Belastung mit BPA in der wissenschaftlichen Literatur führen wiederholt zu Anregungen, den Grenzwert der Chemikalie anzupassen. Die Funktionalität der am Metabolismus beteiligten Enzyme kann je nach Individuum unterschiedlich ausgeprägt sein. Mittels Modellings konnte hier gezeigt werden, dass dies maßgeblich dazu führt, dass sich berechnete Plasmaspiegel von Individuen bis zu 4,7-fach unterscheiden.
Die Arbeit konnte somit einen Beitrag zur Nutzung und Weiterentwicklung von In-silico-Modellen für diverse toxikologische Fragestellungen leisten.
Achilles tendinopathy (AT) is a debilitating injury in athletes, especially for those engaged in repetitive stretch-shortening cycle activities. Clinical risk factors are numerous, but it has been suggested that altered biomechanics might be associated with AT. No systematic review has been conducted investigating these biomechanical alterations in specifically athletic populations. Therefore, the aim of this systematic review was to compare the lower-limb biomechanics of athletes with AT to athletically matched asymptomatic controls. Databases were searched for relevant studies investigating biomechanics during gait activities and other motor tasks such as hopping, isolated strength tasks, and reflex responses. Inclusion criteria for studies were an AT diagnosis in at least one group, cross-sectional or prospective data, at least one outcome comparing biomechanical data between an AT and healthy group, and athletic populations. Studies were excluded if patients had Achilles tendon rupture/surgery, participants reported injuries other than AT, and when only within-subject data was available.. Effect sizes (Cohen's d) with 95% confidence intervals were calculated for relevant outcomes. The initial search yielded 4,442 studies. After screening, twenty studies (775 total participants) were synthesised, reporting on a wide range of biomechanical outcomes. Females were under-represented and patients in the AT group were three years older on average. Biomechanical alterations were identified in some studies during running, hopping, jumping, strength tasks and reflex activity. Equally, several biomechanical variables studied were not associated with AT in included studies, indicating a conflicting picture. Kinematics in AT patients appeared to be altered in the lower limb, potentially indicating a pattern of “medial collapse”. Muscular activity of the calf and hips was different between groups, whereby AT patients exhibited greater calf electromyographic amplitudes despite lower plantar flexor strength. Overall, dynamic maximal strength of the plantar flexors, and isometric strength of the hips might be reduced in the AT group. This systematic review reports on several biomechanical alterations in athletes with AT. With further research, these factors could potentially form treatment targets for clinicians, although clinical approaches should take other contributing health factors into account. The studies included were of low quality, and currently no solid conclusions can be drawn.