Emulation des thermischen Verhaltens eines Gebäudes

In der heutzutage effizienten Welt spielt die Heizquelle eine grosse Rolle. Es ist das Kernstück für Wärme und den Konform in einem Gebäude. Um diese Heizung optimal einem Gebäude anzupassen, werden numerische Software verwendet welche den Gebäudeverbrauch simulieren. Jedoch gilt dies nur für einen Richtwert um eine Vorstellung vom Gebäude zu erhalten. Um dies nun in realen Bedingungen zu testen, wird ein Emulator erstellt, der das thermische Verhalten von Gebäuden simulieren kann. An diesen kann eine Vielzahl von Wärmepumpen angeschlossen und getestet werden. So können Heizsysteme auf das Gebäude abgestimmt bzw. angepasst werden. Diese Diplomarbeit wird in der HES-SO in Sitten erstellt und erarbeitet

The PAS-domain kinase PASKIN: a new sensor in energy homeostasis

Abstract.: The PAS domain kinase PASKIN, also termed PAS kinase or PASK, is an evolutionarily conserved potential sensor kinase related to the heme-based oxygen sensors of nitrogen-fixing bacteria. In yeast, the two PASKIN homologs link energy flux and protein synthesis following specific stress conditions. In mammals, PASKIN may regulate glycogen synthesis and protein translation. Paskin knock-out mice do not show any phenotype under standard animal husbandry conditions. Interestingly, these mice seem to be protected from the symptoms of the metabolic syndrome when fed a high-fat diet. Energy turnover might be increased in specific PASKIN-deficient cell types under distinct environmental conditions. According to the current model, binding of a putative ligand to the PAS domain disinhibits the kinase domain and activates PASKIN auto- and target phosphorylation. Future research needs to be conducted to elucidate the nature of the putative ligand and the molecular mechanisms of downstream signalling by PASKI

The Aid Effectiveness Architecture in Africa: An Analysis of Aid Structures in Kenya’s Agriculture Sector

This study examines in detail the development aid architecture in Kenya’s agriculture sector. The focus is on the mechanisms in place within the Kenyan government (and ministry of agriculture in particular), mechanisms among and within donor agencies, and overall coordination mechanisms that bring together the donors and the government. Findings show that coordination and harmonization activities among donors are yet to yield the desired outcomes such as the division of labor protocol and joint programming. Weaknesses are also observed on the government side where it appears authorities are yet to internalize PD concepts and interpret them to suit the country\u27s needs. The author argues for the need to strengthen mechanisms of citizen participation and oversight over aid effectiveness architecture thereby ensure greater accountability from lead agencies involved in the development cooperation processes including government bureaucrats

Femtosecond spectroscopy of charge-transfer dynamics in self-assembled Pd(II) based donor-acceptor/host-guest cages and heterobinuclear alkyne-bridged W(II)-Ru(II) and W(II)-Ir(III) complexes

Mit Hilfe von femtosekunden UV/vis-pump-UV/vis-probe und -midIR-probe Absorptionspektroskopie wurden die Ladungsübertragungsdynamiken von selbstorganisierenden Donor-Akzeptor Pd(II) Koordinationskäfigen und heterobinuklearen Alkin-überbrückten W(II)-Ru(II)- und W(II)-Ir(III)-Komplexen untersucht. Die Käfige bestanden aus Liganden mit den folgenden Chromophoren als Rückgrat: - Phenothiazin (PTZ)-Donor und Fluorenon (FLO)-Akzeptor - Triphenylamin (TPA)-Donor and Fluorenon (FLO)-Akzeptor - Phenothiazin (PTZ)-Donor/Gastgeber and Anthrachinon (ANQ)-Akzeptor/Gast Die ersten beiden Komplexe bestanden beide aus Donor- und Akzeptor-Liganden, die ein Käfigmolekül formten, der dritte Komplex war ein blanker Donor-Käfig um den Akzeptor herum als Gastgeber-Gast-Verbindung. Ein allgemeines Muster wurde für sie alle erkannt: spezifische Fotoanregung des Donors erzeugte den Donor-S1-Zustand, von dem aus Ladungsübertragungsprozesse zur Erzeugung eines kurzlebigen Donor-Radikal-Kations D•+ führten, was aus zeitaufgelösten UV/vis-Spektren abgeleitet wurde, in denen Banden ähnlich denen eines chemisch oxidierten Donor-Käfigs [Pd2D4]4+ beobachtet wurden. Diese Banden fallen mit mindestens 2 verschiedenen Zeitkonstanten ab, was auf mehrere Ladungsübertragungspartner hindeutet. Für die Donor-Akzeptor-Käfige wurden 3 Zeitkonstanten mit ����1 ≈ 1 ps, ����2 ≈ 100 ps und ����3 > 1 ns gefunden, die einer Ligand-zu-Metall Ladungsübertragung (LMCT) vom Donor zum Pd(II) und zwei Donor-Akzeptor Ladungsübertragungen (DACT) vom Donor zum Akzeptor zugeordnet wurden. Die zwei DACT wurden einer Übertragung zum Akzeptor in cis- bzw. trans-Stellung zum angeregten Donor zugesprochen. Das Akzeptor-Radikal-Anion A•− wurde via zeitaufgelöster midIR-Spektroskopie identifiziert, wo trotz der praktisch ausschließlicher Anregung des Donors sowohl Donor- als auch Akzeptor-Grundzustandsausbleichen als auch Peaks von angeregten Zuständen, die mit Hilfe von DFT-Berechnungen und Spektren der chemisch oxidierten/reduzierten Analoga D•+ and A•− zugeordnet wurden, gleichzeitig erschienen sind. Für den Gastgeber/Gast-Käfig wurde auch eine Ladungsübertragung zwischen Donor und Akzeptor beobachtet, allerdings wurde das A•− nur in den zeitaufgelösten UV/vis-Spektren identifiziert, da zeitaufgelöste midIR-Messungen wegen der schlechten Löslichkeit der Verbindung in Lösungsmitteln mit ausreichender Transparenz im IR nicht möglich waren. Das Verhältnis von LMCT und DACT war 60:40 für den PTZ-FLO-Käfig, 50:50 für den TPA-FLO-Käfig und für den PTZ-ANQ-Gastgeber-Gast-Käfig 56:44. Die heterobinuklearen Wolfram-Komplexe zeigten beide die ultraschnelle Bildung eines Triplett-Metall-zu-Ligand-Ladungsübertragungszustandes (3MLCT) nach Fotoanregung, der nicht in einen Metall-zu-Metall Ladungsübertragungszustand konvertiert ist, was an Hand der kleinen Blauverschiebung in den zeitaufgelösten midIR-Spektren im Vergleich zur großen Blauverschiebung in den FTIR-Spektren nach Oxidation hergeleitet werden kann, sondern wahrscheinlich zu einer leichten Reduktion der Elektronendichte am W(II) führte. Nachfolgende Relaxation in den elektronischen Grundzustand innerhalb von 60 ps resultierte in der Anregung der anharmonischen Carbonyl-Streckschwingung, die im mononuklearen Wolfram-Komplex dank der ultraschnellen inneren Umwandlung sofort erreicht wird. Zusätzlich wurde im W(II)-Ru(II)-Komplex ein stark rotverschobener Peak beobachtet, der nicht sicher zugeordnet werden konnte, aber vermutlich von einer side-on-Koordination des Carbonyls an das W(II) stammt.Using femtosecond UV/vis-pump-UV/vis-probe and -midIR-probe absorption spectroscopy the charge-transfer dynamics of self-assembling donor-acceptor Pd(II) coordination cages and heterobinuclear alkyne-bridged W(II)-Ru(II) and W(II)-Ir(III) complexes were investigated. The cages consisted of ligands with the following chromophore backbones: - Phenothiazine (PTZ)-donor and fluorenone (FLO)-acceptor - Triphenylamine (TPA)-donor and fluorenone (FLO)-acceptor - Phenothiazine (PTZ)-donor/host and anthraquinone (ANQ)-acceptor/guest The first two complexes both consisted of donor and acceptor ligands forming a cage molecule, the third complex was a bare donor cage built around the acceptor as a host-guest compound. A general pattern was discovered for all of them: photoexcitation of specifically the donor created the donor S1 state, from which charge-transfer processes lead to the generation of a short-lived donor radical cation D•+ as was deduced from the time-resolved UV/vis spectra, where bands similar to a chemically oxidized donor cage [Pd2D4]4+ were observed. Those bands decay with at least two different time constants indicating multiple charge-transfer partners. For the donoracceptor cages three time constants with 1 ≈ 1 ps, 2 ≈ 100 ps and 3 > 1 ns were attributed to a ligand-to-metal charge-transfer (LMCT) from donor to Pd(II) and two donor-acceptor chargetransfers (DACT) from donor to acceptor that were assigned to a CT towards an acceptor in cis, the other in trans position to the excited donor. The acceptor radical anion A•− was identified via time-resolved midIR spectroscopy, where, despite practically pure donor excitation, both donor and acceptor bleaches as well as excited state peaks, that were assigned to D•+ and A•− via DFT calculations and spectra of the chemically oxidized/reduced analogues, appeared simultaneously. For the host-guest cage a CT between donor and acceptor was observed as well, however, the A•− was only identified in the time-resolved UV/vis spectra and time-resolved midIR measurements were not possible because the compound was not soluble in any solvent with sufficient IR transparency. The ratio of LMCT to DACT was 60:40 for the PTZ-FLO cage, 50:50 for the TPAFLO cage and for the PTZ-ANQ-host-guest cage 56:44. The heterobinuclear tungsten complexes both showed ultrafast generation of a triplet metal-toligand charge-transfer state (3MLCT) upon photoexcitation that was not converted into a metal-tometal charge-transfer (MMCT) given the small blue-shift in the time-resolved midIR spectra compared to the large shift in the FTIR spectra upon oxidation, but most likely led to a slight reduction of electron density at the W(II). Subsequent relaxation to the electronic ground state within about 60 ps resulted in the vibrational excitation of the anharmonic carbonyl stretching vibration, which was immediately achieved in the mononuclear tungsten complex due to ultrafast internal conversion. Additionally, in the W(II)-Ru(II) complex a far red shifted peak was observed that could not be safely identified, but is assumed to stem from a side-on coordinated carbonyl.2024-04-1

How Speededness of a Reasoning Test and the Complexity of Mental Speed Tasks Influence the Relation between Mental Speed and Reasoning Ability.

Although previous research has consistently reported a positive association between mental speed and reasoning ability, it remains unclear whether the magnitude of this association depends on whether the reasoning test is administered with or without a time limit. In addition, it is unknown how mental speed task complexity affects the mental speed-reasoning association when the effects of time limitations in the reasoning test (labeled "speededness") are controlled for. The present study examined these questions in a sample of 200 participants who completed the time-limited Culture Fair Test (CFT) and a Hick task with three levels of complexity to measure mental speed. Results showed that the latent correlation between mental speed and reasoning was slightly lower when the effect of speededness in reasoning was statistically controlled for. However, for both controlled and uncontrolled reasoning, the correlation with mental speed was of medium size and statistically significant. When reasoning was controlled for the effects of speededness, only complexity-related mental speed aspects were correlated with reasoning, whereas basic mental speed aspects were correlated with the speededness factor and unrelated to reasoning. These findings demonstrate that time limitations in reasoning tests and complexity in mental speed tasks affect the magnitude of the mental speed-reasoning association

Photoinduced host-to-guest electron transfer in a self-assembled coordination cage

A [Pd2L4] coordination cage, assembled from electron-rich phenothiazine-based ligands and encapsulating an electron-deficient anthraquinone-based disulfonate guest, is reported. Upon excitation at 400 nm, transient absorption spectroscopy unveils photoinduced electron transfer from the host's chromophores to the guest, as indicated by characteristic spectral features assigned to the oxidized donor and reduced acceptor. The structure of the host–guest complex was characterized by NMR spectroscopy, mass spectrometry and single-crystal X-ray analysis. Spectroelectrochemical experiments and DFT calculations both agree with the proposed light-induced charge separation. A kinetic analysis of the involved charge transfer channels reveals, besides a guest-independent LMCT path, 44% efficiency for the host–guest charge transfer (HGCT)

The effectiveness of the Wim Hof method on cardiac autonomic function, blood pressure, arterial compliance, and different psychological parameters.

The Wim Hof method (WHM) is a multi-disciplinary approach to physical and mental well-being combining cold exposure, breathing exercises, and meditation. This study evaluated the effects of a 15 days WHM intervention on cardiovascular parameters at rest and during a cold pressor test (CPT), as well as on various psychological parameters. Forty two participants were randomized into an intervention (IG) and a control group. Throughout the 15 days intervention, the IG performed the WHM daily. Before and after the intervention, systolic (SBP) and diastolic blood pressure (DBP), pulse wave velocity (PWV), heart rate (HR), root mean sum of squared distance (RMSSD), and standard deviation of RR-intervals (SDNN) were assessed at rest and during a CPT. Furthermore, perceived stress (PSS), positive affect (PANAS+), negative affect (PANAS-), and subjective vitality (trait (SVSt) and state (SVSs)) was determined. No significant time × group interactions could be detected in HR (p = 0.709); RMSSD (p = 0.820), SDNN (p = 0.186), SBP (p = 0.839), DBP (p = 0.318), PWV (p = 0.983), PANAS+ (p = 0.427), PANAS- (p = 0.614), SVSt (p = 0.760), SVSs (p = 0.366), and PSS (p = 0.364). No significant time × group effects could be detected during the CPT (ΔHR: p = 0.596; ΔSBP: p = 0.366; ΔDBP: p = 0.999; ΔPWV: p = 0.635; perceived pain: p = 0.231). Performing the WHM daily did not exert positive effects on cardiovascular and psychological parameters