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Mit dem Klima wandelt sich auch notwendig die offene Gesellschaft. Und mit ihr wandelt sich wiederum auch die Verfassung(-sinterpretation). Periodisch wiederkehrende Gesundheits- und Sicherheitskrisen fordern eine dynamische Reaktion des Grundgesetzes auf mit ihnen einhergehende Probleme. In andauernden Krisen wie der Umweltkrise muss die Verfassung gleichzeitig in vielerlei Hinsicht nachhaltig sein. Dabei muss das, was wir unter Freiheit, Klima‑, Umwelt- oder Tierschutz verstehen, immer im Wandel bleiben.
The synthesis and the crystal structure of the double cluster compound [Nb6Cl14(MeCN)(4)][Nb6Cl14(pyz)(4)]middot6CH(3)CN are described. The synthesis is based on a partial ligand exchange reaction, which proceeds upon dissolving [Nb6Cl14(pyz)(4)]middot2CH(2)Cl(2) in acetonitrile. The compound is built up of two discrete neutral cluster units, which consist of octahedra of Nb-6 atoms coordinated by 12 edge-bridging chlorido and two terminal chlorido ligands, and four acetonitrile ligands on one and four pyrazine ligands on the other cluster unit. Co-crystallized acetonitrile molecules are also present. The single-crystal structure determination has revealed a cluster arrangement in which the [Nb6Cl14(pyz)(4)] units are connected by (halogen) lone-pair-(pyrazine) pi interactions. These lead to chains of [Nb6Cl14(pyz)(4)] clusters. These chains are further connected to cluster layers by (nitrile-halogen) dipole-dipole interactions, in which the [Nb6Cl14(MeCN)(4)] and co-crystallized MeCN molecules are also involved. These cluster layers are arranged parallel to the crystallographic {011} plane.
Design thinking is a well-established practical and educational approach to fostering high-level creativity and innovation, which has been refined since the 1950s with the participation of experts like Joy Paul Guilford and Abraham Maslow. Through real-world projects, trainees learn to optimize their creative outcomes by developing and practicing creative cognition and metacognition. This paper provides a holistic perspective on creativity, enabling the formulation of a comprehensive theoretical framework of creative metacognition. It focuses on the design thinking approach to creativity and explores the role of metacognition in four areas of creativity expertise: Products, Processes, People, and Places. The analysis includes task-outcome relationships (product metacognition), the monitoring of strategy effectiveness (process metacognition), an understanding of individual or group strengths and weaknesses (people metacognition), and an examination of the mutual impact between environments and creativity (place metacognition). It also reviews measures taken in design thinking education, including a distribution of cognition and metacognition, to support students in their development of creative mastery. On these grounds, we propose extended methods for measuring creative metacognition with the goal of enhancing comprehensive assessments of the phenomenon. Proposed methodological advancements include accuracy sub-scales, experimental tasks where examinees explore problem and solution spaces, combinations of naturalistic observations with capability testing, as well as physiological assessments as indirect measures of creative metacognition.
Case report
(2023)
The increasing prevalence of Long COVID is an imminent public health disaster, and established approaches have not provided adequate diagnostics or treatments. Recently, anesthetic blockade of the stellate ganglion was reported to improve Long COVID symptoms in a small case series, purportedly by "rebooting" the autonomic nervous system. Here, we present a novel diagnostic approach based on the Adaptive Force (AF), and report sustained positive outcome for one severely affected Long COVID patient using individualized pulsed electromagnetic field (PEMF) at the area C7/T1. AF reflects the capacity of the neuromuscular system to adapt adequately to external forces in an isometric holding manner. In case, maximal isometric AF (AFiso(max)) is exceeded, the muscle merges into eccentric muscle action. Thereby, the force usually increases further until maximal AF (AFmax) is reached. In case adaptation is optimal, AFiso(max) is similar to 99-100% of AFmax. This holding capacity (AFiso(max)) was found to be vulnerable to disruption by unpleasant stimulus and, hence, was regarded as functional parameter. AF was assessed by an objectified manual muscle test using a handheld device. Prior to treatment, AFiso(max) was considerably lower than AFmax for hip flexors (62 N = similar to 28% AFmax) and elbow flexors (71 N = similar to 44% AFmax); i.e., maximal holding capacity was significantly reduced, indicating dysfunctional motor control. We tested PEMF at C7/T1, identified a frequency that improved neuromuscular function, and applied it for similar to 15 min. Immediately post-treatment, AFiso(max) increased to similar to 210 N (similar to 100% AFmax) at hip and 184 N (similar to 100% AFmax) at elbow. Subjective Long COVID symptoms resolved the following day. At 4 weeks post-treatment, maximal holding capacity was still on a similarly high level as for immediately post-treatment (similar to 100% AFmax) and patient was symptom-free. At 6 months the patient's Long COVID symptoms have not returned. This case report suggests (1) AF could be a promising diagnostic for post-infectious illness, (2) AF can be used to test effective treatments for post-infectious illness, and (3) individualized PEMF may resolve post-infectious symptoms.
Raub mit Luftpumpe
(2023)
We conduct a laboratory experiment to study how locus of control operates through people's preferences and beliefs to influence their decisions. Using the principal-agent setting of the delegation game, we test four key channels that conceptually link locus of control to decision-making: (i) preference for agency; (ii) optimism and (iii) confidence regarding the return to effort; and (iv) illusion of control. Knowing the return and cost of stated effort, principals either retain or delegate the right to make an investment decision that generates payoffs for themselves and their agents. Extending the game to the context in which the return to stated effort is unknown allows us to explicitly study the relationship between locus of control and beliefs about the return to effort. We find that internal locus of control is linked to the preference for agency, an effect that is driven by women. We find no evidence that locus of control influences optimism and confidence about the return to stated effort, or that it operates through an illusion of control.
Paid parental leave schemes have been shown to increase women’s employment rates but to decrease their wages in case of extended leave duration. In view of these potential trade-offs, many countries are discussing the optimal design of parental leave policies. We analyze the impact of a major parental leave reform on mothers’ long-term earnings. The 2007 German parental leave reform replaced a means-tested benefit with a more generous earnings-related benefit that is granted for a shorter period of time. Additionally, a ”daddy quota” of two months was introduced. To identify the causal effect of this policy mix on long-run earnings of mothers, we use a difference-in-differences approach that compares labor market outcomes of mothers who gave birth just before and right after the reform and nets out seasonal effects by including the year before. Using administrative social security data, we confirm previous findings and show that the average duration of employment interruptions increased for mothers with high pre-birth earnings. Nevertheless, we find a positive long-run effect on earnings for mothers in this group. This effect cannot be explained by changes in the selection of working mothers, working hours or changes in employer stability. Descriptive evidence suggests that the stronger involvement of fathers, incentivized by the ”daddy months”, could have facilitated mothers’ re-entry into the labor market and thereby increased earnings. For mothers with low pre-birth earnings, however, we do not find beneficial long-run effects of this parental leave reform.
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.
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.