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Leveraging large-deviation statistics to decipher the stochastic properties of measured trajectories
(2021)
Extensive time-series encoding the position of particles such as viruses, vesicles, or individualproteins are routinely garnered insingle-particle tracking experiments or supercomputing studies.They contain vital clues on how viruses spread or drugs may be delivered in biological cells.Similar time-series are being recorded of stock values in financial markets and of climate data.Such time-series are most typically evaluated in terms of time-averaged mean-squareddisplacements (TAMSDs), which remain random variables for finite measurement times. Theirstatistical properties are different for differentphysical stochastic processes, thus allowing us toextract valuable information on the stochastic process itself. To exploit the full potential of thestatistical information encoded in measured time-series we here propose an easy-to-implementand computationally inexpensive new methodology, based on deviations of the TAMSD from itsensemble average counterpart. Specifically, we use the upper bound of these deviations forBrownian motion (BM) to check the applicability of this approach to simulated and real data sets.By comparing the probability of deviations fordifferent data sets, we demonstrate how thetheoretical bound for BM reveals additional information about observed stochastic processes. Weapply the large-deviation method to data sets of tracer beads tracked in aqueous solution, tracerbeads measured in mucin hydrogels, and of geographic surface temperature anomalies. Ouranalysis shows how the large-deviation properties can be efficiently used as a simple yet effectiveroutine test to reject the BM hypothesis and unveil relevant information on statistical propertiessuch as ergodicity breaking and short-time correlations.
Stereoselective [4+2] Cycloaddition of Singlet Oxygen to Naphthalenes Controlled by Carbohydrates
(2021)
Stereoselective reactions of singlet oxygen are of current interest. Since enantioselective photooxygenations have not been realized efficiently, auxiliary control is an attractive alternative. However, the obtained peroxides are often too labile for isolation or further transformations into enantiomerically pure products. Herein, we describe the oxidation of naphthalenes by singlet oxygen, where the face selectivity is controlled by carbohydrates for the first time. The synthesis of the precursors is easily achieved starting from naphthoquinone and a protected glucose derivative in only two steps. Photooxygenations proceed smoothly at low temperature, and we detected the corresponding endoperoxides as sole products by NMR. They are labile and can thermally react back to the parent naphthalenes and singlet oxygen. However, we could isolate and characterize two enantiomerically pure peroxides, which are sufficiently stable at room temperature. An interesting influence of substituents on the stereoselectivities of the photooxygenations has been found, ranging from 51:49 to up to 91:9 dr (diastereomeric ratio). We explain this by a hindered rotation of the carbohydrate substituents, substantiated by a combination of NOESY measurements and theoretical calculations. Finally, we could transfer the chiral information from a pure endoperoxide to an epoxide, which was isolated after cleavage of the sugar chiral auxiliary in enantiomerically pure form.
Nicht im Trüben fischen
(2021)
Mehr Schein als Sein
(2021)
In this paper I am concerned with the idiomatic constructions fr. avoir l'air (de) and sp. tener el aire (de). I describe these form-function pairs from a constructionist perspective and analyze them as cases of evidential strategies in French and Spanish.
Die ersten 40 Rechtsprofessoren der Viadrina immatrikulierten sich von 1506 bis 1571 in Frankfurt an der Oder. Sie lassen sich in zwei Gruppen einteilen, die von der Gründung der Universität 1506 bis 1539 Immatrikulierten und die nach Einführung der Reformation im Kurfürstentum Brandenburg 1539/40 bis zum Regierungsantritt des Kurfürsten Johann Georg von Brandenburg 1571 an der Viadrina eingeschriebenen Juristen. Die Profile der vorreformatorischen und der nachreformatorischen Rechtsexperten weisen Gemeinsamkeiten, z.B. die Eheschließung, aber auch Unterschiede auf. Am besten illustriert das Beispiel der Rechtsprofessorendynastien Zoch und Köppen die "Familienuniversität" Viadrina.
The present study aims to identify the optimal body-size/shape and maturity characteristics associated with superior fitness test performances having controlled for body-size, sex, and chronological-age differences. The sample consisted of 597 Tunisian children (396 boys and 201 girls) aged 8 to 15 years. Three sprint speeds recorded at 10, 20 and 30 m; two vertical and two horizontal jump tests; a change-of-direction and a handgrip-strength tests, were assessed during physical-education classes. Allometric modelling was used to identify the benefit of being an early or late maturer. Findings showed that being tall and light is the ideal shape to be successful at most physical fitness tests, but the height-to-weight “shape” ratio seems to be test-dependent. Having controlled for body-size/shape, sex, and chronological age, the model identified maturity-offset as an additional predictor. Boys who go earlier/younger through peak-height-velocity (PHV) outperform those who go at a later/older age. However, most of the girls’ physical-fitness tests peaked at the age at PHV and decline thereafter. Girls whose age at PHV was near the middle of the age range would appear to have an advantage compared to early or late maturers. These findings have important implications for talent scouts and coaches wishing to recruit children into their sports/athletic clubs.
This study aimed to compare the training load of a professional under-19 soccer team (U-19) to that of an elite adult team (EAT), from the same club, during the in-season period. Thirty-nine healthy soccer players were involved (EAT [n = 20]; U-19 [n = 19]) in the study which spanned four weeks. Training load (TL) was monitored as external TL, using a global positioning system (GPS), and internal TL, using a rating of perceived exertion (RPE). TL data were recorded after each training session. During soccer matches, players’ RPEs were recorded. The internal TL was quantified daily by means of the session rating of perceived exertion (session-RPE) using Borg’s 0–10 scale. For GPS data, the selected running speed intensities (over 0.5 s time intervals) were 12–15.9 km/h; 16–19.9 km/h; 20–24.9 km/h; >25 km/h (sprint). Distances covered between 16 and 19.9 km/h, > 20 km/h and >25 km/h were significantly higher in U-19 compared to EAT over the course of the study (p = 0.023, d = 0.243, small; p = 0.016, d = 0.298, small; and p = 0.001, d = 0.564, small, respectively). EAT players performed significantly fewer sprints per week compared to U-19 players (p = 0.002, d = 0.526, small). RPE was significantly higher in U-19 compared to EAT (p = 0.001, d = 0.188, trivial). The external and internal measures of TL were significantly higher in the U-19 group compared to the EAT soccer players. In conclusion, the results obtained show that the training load is greater in U19 compared to EAT.
New cryogels for selective dye removal from aqueous solution were prepared by free radical polymerization from the highly water-soluble crosslinker N,N,N’,N’-tetramethyl-N,N’-bis(2-ethylmethacrylate)-propyl-1,3-diammonium dibromide and the sulfobetaine monomer 2-(N-3-sulfopropyl-N,N-dimethyl ammonium)ethyl methacrylate. The resulting white and opaque cryogels have micrometer sized pores with a smaller substructure. They adsorb methyl orange (MO) but not methylene blue (MB) from aqueous solution. Mixtures of MO and MB can be separated through selective adsorption of the MO to the cryogels while the MB remains in solution. The resulting cryogels are thus candidates for the removal of hazardous organic substances, as exemplified by MO and MB, from water. Clearly, it is possible that the cryogels are also potentially interesting for removal of other compounds such as pharmaceuticals or pesticides, but this must be investigated further.
Background/objective
Dry land-training (e.g., plyometric jump training) can be a useful mean to improve swimming performance. This study examined the effects of an 8-week plyometric jump training (PJT) program on jump and sport-specific performances in prepubertal female swimmers.
Methods
Twenty-two girls were randomly assigned to either a plyometric jump training group (PJTG; n = 12, age: 10.01 ± 0.57 years, maturity-offset = -1.50 ± 0.50, body mass = 36.39 ± 6.32 kg, body height = 146.90 ± 7.62 cm, body mass index = 16.50 ± 1.73 kg/m2) or an active control (CG; n = 10, age: 10.50 ± 0.28 years, maturity-offset = -1.34 ± 0.51, body mass = 38.41 ± 9.42 kg, body height = 143.60 ± 5.05 cm, body mass index = 18.48 ± 3.77 kg/m2). Pre- and post-training, tests were conducted for the assessment of muscle power (e.g., countermovement-jump [CMJ], standing-long-jump [SLJ]). Sport-specific-performances were tested using the timed 25 and 50-m front crawl with a diving-start, timed 25-m front crawl without push-off from the wall (25-m WP), and a timed 25-m kick without push-off from the wall (25-m KWP).
Results
Findings showed a significant main effect of time for the CMJ (d = 0.78), the SLJ (d = 0.91), 25-m front crawl test (d = 2.5), and the 25-m-KWP (d = 1.38) test. Significant group × time interactions were found for CMJ, SLJ, 25-m front crawl, 50-m front crawl, 25-m KWP, and 25-m WP test (d = 0.29–1.63) in favor of PJTG (d = 1.34–3.50). No significant pre-post changes were found for CG (p > 0.05).
Conclusion
In sum, PJT is effective in improving muscle power and sport-specific performances in prepubertal swimmers. Therefore, PJT should be included from an early start into the regular training program of swimmers.