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Hidden semi-Markov models generalise hidden Markov models by explicitly modelling the time spent in a given state, the so-called dwell time, using some distribution defined on the natural numbers. While the (shifted) Poisson and negative binomial distribution provide natural choices for such distributions, in practice, parametric distributions can lack the flexibility to adequately model the dwell times. To overcome this problem, a penalised maximum likelihood approach is proposed that allows for a flexible and data-driven estimation of the dwell-time distributions without the need to make any distributional assumption. This approach is suitable for direct modelling purposes or as an exploratory tool to investigate the latent state dynamics. The feasibility and potential of the suggested approach is illustrated in a simulation study and by modelling muskox movements in northeast Greenland using GPS tracking data. The proposed method is implemented in the R-package PHSMM which is available on CRAN.
Predicting entrepreneurial development based on individual and business-related characteristics is a key objective of entrepreneurship research. In this context, we investigate whether the motives of becoming an entrepreneur influence the subsequent entrepreneurial development. In our analysis, we examine a broad range of business outcomes including survival and income, as well as job creation, and expansion and innovation activities for up to 40 months after business formation. Using the self-determination theory as conceptual background, we aggregate the start-up motives into a continuous motivational index. We show – based on a unique dataset of German start-ups from unemployment and non-unemployment – that the later business performance is better, the higher they score on this index. Effects are particularly strong for growth-oriented outcomes like innovation and expansion activities. In a next step, we examine three underlying motivational categories that we term opportunity, career ambition, and necessity. We show that individuals driven by opportunity motives perform better in terms of innovation and business expansion activities, while career ambition is positively associated with survival, income, and the probability of hiring employees. All effects are robust to the inclusion of a large battery of covariates that are proven to be important determinants of entrepreneurial performance.
Seed dispersal plays an important role in population dynamics in agricultural ecosystems, but the effects of surrounding vegetation height on seed dispersal and population connectivity on the landscape scale have rarely been studied. Understanding the effects of surrounding vegetation height on seed dispersal will provide important information for land-use management in agricultural landscapes to prevent the spread of undesired weeds or enhance functional connectivity. We used two model species, Phragmites australis and Typha latifolia, growing in small natural ponds known as kettle holes, in an agricultural landscape to evaluate the effects of surrounding vegetation height on wind dispersal and population connectivity between kettle holes. Seed dispersal distance and the probability of long-distance dispersal (LDD) were simulated with the mechanistic WALD model under three scenarios of "low", "dynamic" and "high" surrounding vegetation height. Connectivity between the origin and target kettle holes was quantified with a connectivity index adapted from Hanski and Thomas (1994). Our results show that mean seed dispersal distance decreases with the height of surrounding matrix vegetation, but the probability of long-distance dispersal (LDD) increases with vegetation height. This indicates an important vegetation-based trade-off between mean dispersal distance and LDD, which has an impact on connectivity. Matrix vegetation height has a negative effect on mean seed dispersal distance but a positive effect on the probability of LDD. This positive effect and its impact on connectivity provide novel insights into landscape level (meta-)population and community dynamics - a change in matrix vegetation height by land-use or climatic changes could strongly affect the spread and connectivity of wind-dispersed plants. The opposite effect of vegetation height on mean seed dispersal distance and the probability of LDD should therefore be considered in management and analyses of future land-use and climate change effects.
Ranking local climate policy
(2021)
Climate mitigation and climate adaptation are crucial tasks for urban areas and can involve synergies as well as trade-offs. However, few studies have examined how mitigation and adaptation efforts relate to each other in a large number of differently sized cities, and therefore we know little about whether forerunners in mitigation are also leading in adaptation or if cities tend to focus on just one policy field. This article develops an internationally applicable approach to rank cities on climate policy that incorporates multiple indicators related to (1) local commitments on mitigation and adaptation, (2) urban mitigation and adaptation plans and (3) climate adaptation and mitigation ambitions. We apply this method to rank 104 differently sized German cities and identify six clusters: climate policy leaders, climate adaptation leaders, climate mitigation leaders, climate policy followers, climate policy latecomers and climate policy laggards. The article seeks explanations for particular cities' positions and shows that coping with climate change in a balanced way on a high level depends on structural factors, in particular city size, the pathways of local climate policies since the 1990s and funding programmes for both climate mitigation and adaptation.
Die Beschaffung von Leistungen zur medizinischen Rehabilitation wurde durch den neuen § 15 SGB VI zum 1. Juli 2023 grundlegend reformiert. Seither gilt ein mehrstufiges System aus Zulassung der Rehabilitationskliniken, Belegungsvertrag, Belegungsentscheidung und Vergütung. Sämtliche Beschaffungsstufen werden von der DRV Bund durch verbindliche Entscheidungen gesteuert.
Dieses neue Beschaffungssystem verstößt gegen das Wettbewerbsrecht der Europäischen Union und ist deshalb unwirksam. Das Unionsrecht (Art. 106 Abs. 1 AEUV), aber auch das nationale Kartellrecht (§ 19 Abs. 2 Nr. 1 GWB) und das Verfassungsrecht (Art. 12 Abs. 1 GG) verlangen eine Trennung von hoheitlichen Befugnissen und unternehmerischen Funktionen der Rentenversicherungsträger. Anderenfalls ist die gebotene Gleichbehandlung (Nichtdiskriminierung) der Rehabilitationskliniken freigemeinnütziger und privater Träger mit den Rehabilitationskliniken der Rentenversicherungsträger bei der Erbringung von Leistungen zur medizinischen Rehabilitation nicht gewährleistet.
Dieses Trennungsprinzip ist verletzt. Denn die Rentenversicherungsträger nehmen hoheitliche Zulassungs-, Belegungs- und Vergütungsaufgaben wahr und sind gleichzeitig unternehmerisch mit eigenen Rehabilitationseinrichtungen auf dem Markt der Erbringung von Leistungen zur medizinischen Rehabilitation tätig. Freigemeinnützige und private Rehabilitationskliniken werden auf allen Stufen der Beschaffung gegenüber den Kliniken der Rentenversicherungsträger diskriminiert. Das gilt insbesondere für die Belegungsentscheidungen der Rentenversicherungsträger, weil hierdurch systematisch eigene Kliniken gegenüber freigemeinnützigen und privaten Kliniken begünstigt werden.
Objective:
Following a life course perspective, this study examines the link between partnership trajectories and three dimensions of psychological well-being: psychological health, overall sense of self-worth and quality of life.
Background:
Assuming that life outcomes are the result of prior decisions, experiences and events, partnership histories can be seen as a resource for psychological well-being. Furthermore, advantages or disadvantages from living with or without a partner should accumulate over time. While previous cross-sectional research has mainly focused on the influence of partnership status or a status change on well-being, prior longitudinal studies could not control for reverse causality of well-being and partnership trajectories. This research addresses the question of how different patterns of partnership biographies are related to a person's well-being in middle adulthood. Selection effects of pre-trajectory well-being as well as current life conditions are also taken into account.
Method:
Using data from the German LifE Study, the partnership trajectories between ages of 16 and 45 are classified by sequence and cluster analysis. OLS regression is then used to examine the link between types of partnership trajectories and depression, self-esteem and overall life satisfaction at age 45.
Results:
For women, well-being declined when experiencing unstable non-cohabitational union trajectories or divorce followed by unpartnered post-marital trajectories. Men suffered most from being long-term single. The results could not be explained by selection effects of pre-trajectory well-being.
Conclusion:
While women seem to 'recover' from most of the negative effects of unstable partnership trajectories through a new partnership, for men it was shown that being mainly unpartnered has long-lasting effects on their psychological well-being.
Carbon nitride semiconductors: properties and application as photocatalysts in organic synthesis
(2023)
Graphitic carbon nitrides (g-CNs) are represented by melon-type g-CN, poly(heptazine imides) (PHIs), triazine-based g-CN and poly(triazine imide) with intercalated LiCl (PTI/Li+Cl‒). These materials are composed of sp2-hybridized carbon and nitrogen atoms; C:N ratio is close to 3:4; the building unit is 1,3,5-triazine or tri-s-triazine; the building units are interconnected covalently via sp2-hybridized nitrogen atoms or NH-moieties; the layers are assembled into a stack via weak van der Waals forces as in graphite. Due to medium band gap (~2.7 eV) g-CNs, such as melon-type g-CN and PHIs, are excited by photons with wavelength ≤ 460 nm. Since 2009 g-CNs have been actively studied as photocatalysts in evolution of hydrogen and oxygen – two half-reactions of full water splitting, by employing corresponding sacrificial agents. At the same time application of g-CNs as photocatalysts in organic synthesis has been remaining limited to few reactions only. Cumulative Habilitation summarizes research work conducted by the group ‘Innovative Heterogeneous Photocatalysis’ between 2017-2023 in the field of carbon nitride organic photocatalysis, which is led by Dr. Oleksandr Savatieiev.
g-CN photocatalysts activate molecules, i.e. generate their more reactive open-shell intermediates, via three modes: i) Photoinduced electron transfer (PET); ii) Excited state proton-coupled electron transfer (ES-PCET) or direct hydrogen atom transfer (dHAT); iii) Energy transfer (EnT). The scope of reactions that proceed via oxidative PET, i.e. one-electron oxidation of a substrate to the corresponding radical cation, are represented by synthesis of sulfonylchlorides from S-acetylthiophenols. The scope of reactions that proceed via reductive PET, i.e. one-electron reduction of a substrate to the corresponding radical anion, are represented by synthesis of γ,γ-dichloroketones from the enones and chloroform.
Due to abundance of sp2-hybridized nitrogen atoms in the structure of g-CN materials, they are able to cleave X-H bonds in organic molecules and store temporary hydrogen atom. ES-PCET or dHAT mode of organic molecules activation to the corresponding radicals is implemented for substrates featuring relatively acidic X-H bonds and those that are characterized by low bond dissociation energy, such as C-H bond next to the heteroelements. On the other hand, reductively quenched g-CN carrying hydrogen atom reduces a carbonyl compound to the ketyl radical via PCET that is thermodynamically more favorable pathway compared to the electron transfer. The scope of these reactions is represented by cyclodimerization of α,β-unsaturated ketones to cyclopentanoles.
g-CN excited state demonstrates complex dynamics with the initial formation of singlet excited state, which upon intersystem crossing produces triplet excited state that is characterized by the lifetime > 2 μs. Due to long lifetime, g-CN activate organic molecules via EnT. For example, g-CN sensitizes singlet oxygen, which is the key intermediate in the dehydrogenation of aldoximes to nitrileoxides. The transient nitrileoxide undergoes [3+2]-cycloaddition to nitriles and gives oxadiazoles-1,2,4.
PET, ES-PCET and EnT are fundamental phenomena that are applied beyond organic photocatalysis. Hybrid composite is formed by combining conductive polymers, such as poly(3,4-ethylenedioxythiophene) polystyrene sulfonate (PEDOT:PSS) with potassium poly(heptazine imide) (K-PHI). Upon PET, K-PHI modulated population of polarons and therefore conductivity of PEDOT:PSS. The initial state of PEDOT:PSS is recovered upon material exposure to O2. K-PHI:PEDOT:PSS may be applied in O2 sensing.
In the presence of electron donors, such as tertiary amines and alcohols, and irradiation with light, K-PHI undergoes photocharging – the g-CN material accumulates electrons and charge-compensating cations. Such photocharged state is stable under anaerobic conditions for weeks, but at the same time it is a strong reductant. This feature allows decoupling in time light harvesting and energy storage in the form of electron-proton couples from utilization in organic synthesis. The photocharged state of K-PHI reduces nitrobenzene to aniline, and enables dimerization of α,β-unsaturated ketones to hexadienones in dark.
This eye-tracking study establishes basic benchmarks of eye movements during reading in heritage language (HL) by Russian-speaking adults and adolescents of high (n = 21) and low proficiency (n = 27). Heritage speakers (HSs) read sentences in Cyrillic, and their eye movements were compared to those of Russian monolingual skilled adult readers, 8-year-old children and L2 learners. Reading patterns of HSs revealed longer mean fixation durations, lower skipping probabilities, and higher regressive saccade rates than in monolingual adults. High-proficient HSs were more similar to monolingual children, while low-proficient HSs performed on par with L2 learners. Low-proficient HSs differed from high-proficient HSs in exhibiting lower skipping probabilities, higher fixation counts, and larger frequency effects. Taken together, our findings are consistent with the weaker links account of bilingual language processing as well as the divergent attainment theory of HL.
Deutsche Bürger
(2021)
This study examined the effect of 6 weeks of progressed and nonprogressed volume-based overload plyometric training (PT) on components of physical fitness and body composition measures in young male basketball players, compared with an active control group. Subjects were randomly assigned to a progressed PT (PPT, n = 7; age = 14.6 +/- 1.1 years), a non-PPT (NPPT, n = 8, age = 13.8 +/- 2.0 years), or a control group (CG, n = 7, age = 14.0 +/- 2.0 years). Before and after training, body composition measures (muscle mass and fat mass), countermovement jump with arms (CMJA) and countermovement jump without arms (CMJ), horizontal bilateral (HCMJ) and unilateral jump with right leg (RJ) and left leg (LJ), 20-cm drop jump (DJ20), sprint speed (10 m sprint), and change of direction speed (CODS [i.e., T-test]) were tested. Significant effects of time were observed for muscle and fat mass, all jump measures, and CODS (all p < 0.01; d = 0.37-0.83). Significant training group x time interactions were observed for all jump measures (all p < 0.05; d = 0.24-0.41). Post hoc analyses revealed significant pre-post performance improvements for the PPT (RJ and LJ: increment 18.6%, d = 0.8 and increment 22.7%, d = 0.9, respectively; HCMJ: increment 16.4%, d = 0.8; CMJ: increment 22.4%, d = 0.7; CMJA: increment 23.3%, d = 0.7; and DJ20: increment 39.7%, d = 1.1) and for the NPPT group (LJ: increment 14.1%, d = 0.4; DJ20: increment 32.9%, d = 0.8) with greater changes after PPT compared with NPPT for all jump measures (all p < 0.05; d = 0.21-0.81). The training efficiency was greater (p < 0.05; d = 0.22) after PPT (0.015% per jump) compared with NPPT (0.0053% per-jump). The PPT induced larger performance improvements on measures of physical fitness as compared to NPPT. Therefore, in-season progressive volume-based overload PT in young male basketball players is recommended.