Refine
Has Fulltext
- yes (94) (remove)
Year of publication
- 2022 (94) (remove)
Document Type
- Article (39)
- Doctoral Thesis (26)
- Working Paper (16)
- Monograph/Edited Volume (4)
- Postprint (3)
- Other (2)
- Report (2)
- Master's Thesis (1)
- Review (1)
Keywords
- COVID-19 (2)
- gender (2)
- hydraulic fracturing (2)
- machine learning (2)
- numerical modelling (2)
- numerische Modellierung (2)
- self-employment (2)
- 2D Numerical Modelling (1)
- ARMS (1)
- ASPECT (1)
Institute
- Extern (94) (remove)
Inverted perovskite solar cells still suffer from significant non-radiative recombination losses at the perovskite surface and across the perovskite/C₆₀ interface, limiting the future development of perovskite-based single- and multi-junction photovoltaics. Therefore, more effective inter- or transport layers are urgently required. To tackle these recombination losses, we introduce ortho-carborane as an interlayer material that has a spherical molecular structure and a three-dimensional aromaticity. Based on a variety of experimental techniques, we show that ortho-carborane decorated with phenylamino groups effectively passivates the perovskite surface and essentially eliminates the non-radiative recombination loss across the perovskite/C₆₀ interface with high thermal stability. We further demonstrate the potential of carborane as an electron transport material, facilitating electron extraction while blocking holes from the interface. The resulting inverted perovskite solar cells deliver a power conversion efficiency of over 23% with a low non-radiative voltage loss of 110 mV, and retain >97% of the initial efficiency after 400 h of maximum power point tracking. Overall, the designed carborane based interlayer simultaneously enables passivation, electron-transport and hole-blocking and paves the way toward more efficient and stable perovskite solar cells.
Intuitively, strongly constraining contexts should lead to stronger probabilistic representations of sentences in memory. Encountering unexpected words could therefore be expected to trigger costlier shifts in these representations than expected words. However, psycholinguistic measures commonly used to study probabilistic processing, such as the N400 event-related potential (ERP) component, are sensitive to word predictability but not to contextual constraint. Some research suggests that constraint-related processing cost may be measurable via an ERP positivity following the N400, known as the anterior post-N400 positivity (PNP). The PNP is argued to reflect update of a sentence representation and to be distinct from the posterior P600, which reflects conflict detection and reanalysis. However, constraint-related PNP findings are inconsistent. We sought to conceptually replicate Federmeier et al. (2007) and Kuperberg et al. (2020), who observed that the PNP, but not the N400 or the P600, was affected by constraint at unexpected but plausible words. Using a pre-registered design and statistical approach maximising power, we demonstrated a dissociated effect of predictability and constraint: strong evidence for predictability but not constraint in the N400 window, and strong evidence for constraint but not predictability in the later window. However, the constraint effect was consistent with a P600 and not a PNP, suggesting increased conflict between a strong representation and unexpected input rather than greater update of the representation. We conclude that either a simple strong/weak constraint design is not always sufficient to elicit the PNP, or that previous PNP constraint findings could be an artifact of smaller sample size.
This dissertation aimed to determine differential expressed miRNAs in the context of chronic pain in polyneuropathy. For this purpose, patients with chronic painful polyneuropathy were compared with age matched healthy patients. Taken together, all miRNA pre library preparation quality controls were successful and none of the samples was identified as an outlier or excluded for library preparation. Pre sequencing quality control showed that library preparation worked for all samples as well as that all samples were free of adapter dimers after BluePippin size selection and reached the minimum molarity for further processing. Thus, all samples were subjected to sequencing. The sequencing control parameters were in their optimal range and resulted in valid sequencing results with strong sample to sample correlation for all samples. The resulting FASTQ file of each miRNA library was analyzed and used to perform a differential expression analysis. The differentially expressed and filtered miRNAs were subjected to miRDB to perform a target prediction. Three of those four miRNAs were downregulated: hsa-miR-3135b, hsa-miR-584-5p and hsa-miR-12136, while one was upregulated: hsa-miR-550a-3p. miRNA target prediction showed that chronic pain in polyneuropathy might be the result of a combination of miRNA mediated high blood flow/pressure and neural activity dysregulations/disbalances. Thus, leading to the promising conclusion that these four miRNAs could serve as potential biomarkers for the diagnosis of chronic pain in polyneuropathy.
Since TRPV1 seems to be one of the major contributors of nociception and is associated with neuropathic pain, the influence of PKA phosphorylated ARMS on the sensitivity of TRPV1 as well as the part of AKAP79 during PKA phosphorylation of ARMS was characterized. Therefore, possible PKA-sites in the sequence of ARMS were identified. This revealed five canonical PKA-sites: S882, T903, S1251/52, S1439/40 and S1526/27. The single PKA-site mutants of ARMS revealed that PKA-mediated ARMS phosphorylation seems not to influence the interaction rate of TRPV1/ARMS. While phosphorylation of ARMST903 does not increase the interaction rate with TRPV1, ARMSS1526/27 is probably not phosphorylated and leads to an increased interaction rate. The calcium flux measurements indicated that the higher the interaction rate of TRPV1/ARMS, the lower the EC50 for capsaicin of TRPV1, independent of the PKA phosphorylation status of ARMS. In addition, the western blot analysis confirmed the previously observed TRPV1/ARMS interaction. More importantly, AKAP79 seems to be involved in the TRPV1/ARMS/PKA signaling complex. To overcome the problem of ARMS-mediated TRPV1 sensitization by interaction, ARMS was silenced by shRNA. ARMS silencing resulted in a restored TRPV1 desensitization without affecting the TRPV1 expression and therefore could be used as new topical therapeutic analgesic alternative to stop ARMS mediated TRPV1 sensitization.
„Europäische Bildung beginnt in der Schule.“ Gerade in Zeiten einer Renaissance von Nationalismen und einem spürbaren Rechtsruck in Europa scheint diese Maxime wichtiger denn je zu sein. Die umfassendste Möglichkeit, mittel- und langfristig eine europäische Dimension in den Schulen der EU-Mitgliedsstaaten zu verankern, stellt eine binationale oder sogar internationale Lehramtsausbildung dar. Die Einrichtung derartiger Ausbildungen ist jedoch mit hohen Hürden verbunden. Ihre Anzahl ist überschaubar und allein im deutsch-französischen Kontext vorhanden. Hintergrund hierfür sind erstens die nur schwer zu überwindbaren Hindernisse, die sich aus den stark divergierenden Studien-, Rekrutierungs- und Ausbildungssystemen ergeben. Zweitens ist der Lehramtsbereich besonders stark durch Reformen geprägt. Eine Nutzen-Kosten-Analyse der häufig benötigten und ressourcenintensiven Anpassungen von Programmen auf der einen Seite und der geringen Anzahl der Absolventinnen und Absolventen auf der anderen Seite fällt demnach an vielen Universitäten negativ aus. Ein Rückblick auf die seit 2000 bestehenden Bemühungen der Kooperation Mainz-Dijon hinterlässt eine durchmischte Bilanz. Die Gelegenheit, die lehramtsbezogene binationale Ausbildung dieser Kooperation integrierter zu gestalten, bietet die sich derzeit auf französischer Seite vollziehende Neustrukturierung der französischen Lehramtsausbildung. Die Loi Blanquer vom 26. Juli 2019 führt zu einer Annäherung der beiden Systeme und ermöglicht – auch dank bereits bestehender juristischer Instrumente – eine Verkürzung der Ausbildungszeit sowie eine verbesserte Anerkennungspraxis.
Das Modell Friedland
(2022)
Mit dem Band 14 „Das Modell Friedland: Vom Zusammenleben deutscher, jüdischer und wendischer Bewohner in einer Niederlausitzer Kleinstadt“ haben die Herausgeber den Autoren Alfred Roggan und Tobias Preßler die Erweiterung ihrer Forschungen ermöglicht: Widmete sich deren Band 12 „Sorbische/Wendische Spuren in der nördlichen Niederlausitz“ (2019) noch Befunden einer binationalen, weil deutsch-wendischen Geschichte, so wird mit dem Band 14 erstmalig für Ostdeutschland die Dokumentation einer ‚trinationalen‘, also deutsch-jüdisch-wendischen Lebenswelt vorgenommen.
Die Untersuchungen verdeutlichen, wie sich drei, im 18. Jahrhundert annähernd gleich große Einwohner-Gruppen, mit ihren Gotteshäusern, ihren Sprachen und einem differenzierten Einwohnerstatus etablierten bzw. arrangiert haben. Es zeigten sich Alleinstellungsmerkmale in Lebens- sowie Kultorganisation, Wirtschaftstätigkeiten und der Kommunikation zwischen den Beheimateten. Mit der Amts-Verwaltung des Johanniter-Ritterordens und dem Stadtrat befanden sie sich in berechenbaren (deutschdominierten) Strukturen. Aus diesem Gefüge und der territorialen Grenzlage zum Kurfürstentum Brandenburg begründeten sich Bedingungen, ohne die es wohl zu keinem „Modell Friedland“ gekommen wäre.
Die Autoren sind dankbar, dass sich mit Friedland die gnädige Chance bot, einen Bereich zu untersuchen, in dem Prozesse der wendisch-deutschen Assimilierung in einer eigenen Stetigkeit abliefen, jedoch das Ende jüdischen Lebens auf die Abwanderungen infolge der preußischen Emanzipations-Gesetze des 19. Jahrhunderts und nicht auf die Demütigungen, Verfolgungen sowie dem Völkermord des faschistischen deutschen Staates, zurückzuführen sind.
Background
Animal personality has emerged as a key concept in behavioral ecology. While many studies have demonstrated the influence of personality traits on behavioral patterns, its quantification, especially in wild animal populations, remains a challenge. Only a few studies have established a link between personality and recurring movements within home ranges, although these small-scale movements are of key importance for identifying ecological interactions and forming individual niches. In this regard, differences in space use among individuals might reflect different exploration styles between behavioral types along the shy-bold continuum.
Methods
We assessed among-individual differences in behavior in the European hare (Lepus europaeus), a characteristic mammalian herbivore in agricultural landscapes using a standardized box emergence test for captive and wild hares. We determined an individuals’ degree of boldness by measuring the latencies of behavioral responses in repeated emergence tests in captivity. During capture events of wild hares, we conducted a single emergence test and recorded behavioral responses proven to be stable over time in captive hares. Applying repeated novel environment tests in a near-natural enclosure, we further quantified aspects of exploration and activity in captive hares. Finally, we investigated whether and how this among-individual behavioral variation is related to general activity and space use in a wild hare population. Wild and captive hares were treated similarly and GPS-collared with internal accelerometers prior to release to the wild or the outdoor enclosure, respectively. General activity was quantified as overall dynamic body acceleration (ODBA) obtained from accelerometers. Finally, we tested whether boldness explained variation in (i) ODBA in both settings and (ii) variation in home ranges and core areas across different time scales of GPS-collared hares in a wild population.
Results
We found three behavioral responses to be consistent over time in captive hares. ODBA was positively related to boldness (i.e., short latencies to make first contact with the new environment) in both captive and wild hares. Space use in wild hares also varied with boldness, with shy individuals having smaller core areas and larger home ranges than bold conspecifics (yet in some of the parameter space, this association was just marginally significant).
Conclusions
Against our prediction, shy individuals occupied relatively large home ranges but with small core areas. We suggest that this space use pattern is due to them avoiding risky, and energy-demanding competition for valuable resources. Carefully validated, activity measurements (ODBA) from accelerometers provide a valuable tool to quantify aspects of animal personality along the shy-bold continuum remotely. Without directly observing—and possibly disturbing—focal individuals, this approach allows measuring variability in animal personality, especially in species that are difficult to assess with experiments. Considering that accelerometers are often already built into GPS units, we recommend activating them at least during the initial days of tracking to estimate individual variation in general activity and, if possible, match them with a simple novelty experiment. Furthermore, information on individual behavioral types will help to facilitate mechanistic understanding of processes that drive spatial and ecological dynamics in heterogeneous landscapes.
Among the multitude of geomorphological processes, aeolian shaping processes are of special character, Pedogenic dust is one of the most important sources of atmospheric aerosols and therefore regarded as a key player for atmospheric processes. Soil dust emissions, being complex in composition and properties, influence atmospheric processes and air quality and has impacts on other ecosystems. In this because even though their immediate impact can be considered low (exceptions exist), their constant and large-scale force makes them a powerful player in the earth system. dissertation, we unravel a novel scientific understanding of this complex system based on a holistic dataset acquired during a series of field experiments on arable land in La Pampa, Argentina. The field experiments as well as the generated data provide information about topography, various soil parameters, the atmospheric dynamics in the very lower atmosphere (4m height) as well as measurements regarding aeolian particle movement across a wide range of particle size classes between 0.2μm up to the coarse sand.
The investigations focus on three topics: (a) the effects of low-scale landscape structures on aeolian transport processes of the coarse particle fraction, (b) the horizontal and vertical fluxes of the very fine particles and (c) the impact of wind gusts on particle emissions.
Among other considerations presented in this thesis, it could in particular be shown, that even though the small-scale topology does have a clear impact on erosion and deposition patterns, also physical soil parameters need to be taken into account for a robust statistical modelling of the latter. Furthermore, specifically the vertical fluxes of particulate matter have different characteristics for the particle size classes. Finally, a novel statistical measure was introduced to quantify the impact of wind gusts on the particle uptake and its application on the provided data set. The aforementioned measure shows significantly increased particle concentrations during points in time defined as gust event.
With its holistic approach, this thesis further contributes to the fundamental understanding of how atmosphere and pedosphere are intertwined and affect each other.
The increasing demand for energy in the current technological era and the recent political decisions about giving up on nuclear energy diverted humanity to focus on alternative environmentally friendly energy sources like solar energy. Although silicon solar cells are the product of a matured technology, the search for highly efficient and easily applicable materials is still ongoing. These properties made the efficiency of halide perovskites comparable with silicon solar cells for single junctions within a decade of research. However, the downside of halide perovskites are poor stability and lead toxicity for the most stable ones.
On the other hand, chalcogenide perovskites are one of the most promising absorber materials for the photovoltaic market, due to their elemental abundance and chemical stability against moisture and oxygen. In the search of the ultimate solar absorber material, combining the good optoelectronic properties of halide perovskites with the stability of chalcogenides could be the promising candidate.
Thus, this work investigates new techniques for the synthesis and design of these novel chalcogenide perovskites, that contain transition metals as cations, e.g., BaZrS3, BaHfS3, EuZrS3, EuHfS3 and SrHfS3. There are two stages in the deposition techniques of this study: In the first stage, the binary compounds are deposited via a solution processing method. In the second stage, the deposited materials are annealed in a chalcogenide atmosphere to form the perovskite structure by using solid-state reactions.
The research also focuses on the optimization of a generalized recipe for a molecular ink to deposit precursors of chalcogenide perovskites with different binaries. The implementation of the precursor sulfurization resulted in either binaries without perovskite formation or distorted perovskite structures, whereas some of these materials are reported in the literature as they are more favorable in the needle-like non-perovskite configuration.
Lastly, there are two categories for the evaluation of the produced materials: The first category is about the determination of the physical properties of the deposited layer, e.g., crystal structure, secondary phase formation, impurities, etc. For the second category, optoelectronic properties are measured and compared to an ideal absorber layer, e.g., band gap, conductivity, surface photovoltage, etc.
Abzug unter Beobachtung
(2022)
Mehr als vier Jahrzehnte lang beobachteten die Streitkräfte und Militärnachrichtendienste der NATO-Staaten die sowjetischen Truppen in der DDR. Hierfür übernahm in der Bundesrepublik Deutschland der Bundesnachrichtendienst (BND) die militärische Auslandsaufklärung unter Anwendung nachrichtendienstlicher Mittel und Methoden. Die Bundeswehr betrieb dagegen taktische Fernmelde- und elektronische Aufklärung und hörte vor allem den Funkverkehr der „Gruppe der sowjetischen Streitkräfte in Deutschland“ (GSSD) ab. Mit der Aufstellung einer zentralen Dienststelle für das militärische Nachrichtenwesen, dem Amt für Nachrichtenwesen der Bundeswehr, bündelte und erweiterte zugleich das Bundesministerium für Verteidigung in den 1980er Jahren seine analytischen Kapazitäten. Das Monopol des BND in der militärischen Auslandsaufklärung wurde von der Bundeswehr dadurch zunehmend infrage gestellt.
Nach der deutschen Wiedervereinigung am 3. Oktober 1990 befanden sich immer noch mehr als 300.000 sowjetische Soldaten auf deutschem Territorium. Die 1989 in Westgruppe der Truppen (WGT) umbenannte GSSD sollte – so der Zwei-plus-Vier-Vertrag – bis 1994 vollständig abziehen. Der Vertrag verbot auch den drei Westmächten, in den neuen Bundesländern militärisch tätig zu sein. Die für die Militäraufklärung bis dahin unverzichtbaren Militärverbindungsmissionen der Westmächte mussten ihre Dienste einstellen. Doch was geschah mit diesem „alliierten Erbe“? Wer übernahm auf deutscher Seite die Aufklärung der sowjetischen Truppen und wer kontrollierte den Truppenabzug?
Die Studie untersucht die Rolle von Bundeswehr und BND beim Abzug der WGT zwischen 1990 und 1994 und fragt dabei nach Kooperation und Konkurrenz zwischen Streitkräften und Nachrichtendiensten. Welche militärischen und nachrichtendienstlichen Mittel und Fähigkeiten stellte die Bundesregierung zur Bewältigung des Truppenabzugs zur Verfügung, nachdem die westlichen Militärverbindungsmissionen aufgelöst wurden? Wie veränderten sich die Anforderungen an die militärische Auslandsaufklärung des BND? Inwieweit setzten sich Konkurrenz und Kooperation von Bundeswehr und BNDbeim Truppenabzug fort? Welche Rolle spielten dabei die einstigen Westmächte? Die Arbeit versteht sich nicht nur als Beitrag zur Militärgeschichte, sondern auch zur deutschen Nachrichtendienstgeschichte.
Gruppierung von Daten
(2022)
Dieser Beitrag beinhaltet einen Vergleich zwischen den Methoden der Topologischen Datenanalyse (TDA) und statistischen Clusterverfahren bei der Gruppierung von Daten. Es werden Gemeinsamkeiten und Unterschiede bei der Bildung der Cluster und Zuordnung der statistischen Einheiten identifiziert. Hierzu werden zwei empirische Datensätze aus der Biologie und Medizin herangezogen.
Zusammengefasst haben sich die Verfahren der TDA als ein praktikables Werkzeug bei der Gruppierung von Objekten erwiesen. Vor allem mit dem Mapper-Algorithmus konnten adäquate Cluster erkannt werden. Beim Iris Flower-Datensatz hat die TDA ähnliche Ergebnisse wie die Clusteranalyse erzielt. Der Heart Disease-Datensatz war schwieriger zu behandeln. Die genutzten clusteranalytischen Verfahren waren nicht geeignet, die beiden Gruppen von Patienten korrekt zu identifizieren. Im Vergleich zu den Standardverfahren der Clusteranalyse zeigte sich eine leichte Überlegenheit der topologischen Verfahren.
Untersucht werden die von BulwienGesa erhobenen und aufbereiteten jahresdurchschnittlichen Mieten von Wohnungen und die Relation des Wiederverkaufswertes von Eigentumswohnungen zu den Wohnungsmieten (Preis-Miet-Relation) in 401 kreisfreien Städten und Landkreisen für die Jahre 2004–2017. Dabei zeigt sich bei den Wohnungsmieten eine Zunahme der regionalen Streuung im Zeitverlauf vor allem in der auf die Finanzkrise 2007–2009 folgenden Zeit. Bei der Preis-Miet-Relation nimmt die Streuung im Zeitverlauf ab 2010 ebenfalls zu. Im Durchschnitt der Regionen (Landkreise und kreisfreie Städte) steigen über den gesamten Zeitabschnitt die Mieten und in der überwiegenden Zahl der Regionen auch die Preis-Miet-Relation (allerdings erst ab 2010); sie entwickeln sich aber regional stark unterschiedlich. Dies führt auch zur Zunahme der Variationskoeffizienten, also der relativen Streuung der regionalen Mieten und – ab 2010 – auch der regionalen Preis-Miet-Relationen.
Dies deutet auf eine Zunahme der regionalen Disparitäten in der Bundesrepublik Deutschland hin. Besondere Divergenzen zeigen sich zwischen den alten und den neuen Bundesländern, wie auch zwischen prosperierenden kreisfreien Städten und deren Umland und ökonomisch schwächeren Städten und Landkreisen.
»Ich hab eine Idee!«
(2022)
Stimuli-promoted in situ formation of hydrogels with thiol/thioester containing peptide precursors
(2022)
Hydrogels are potential synthetic ECM-like substitutes since they provide functional and structural similarities compared to soft tissues. They can be prepared by crosslinking of macromolecules or by polymerizing suitable precursors. The crosslinks are not necessarily covalent bonds, but could also be formed by physical interactions such as π-π interactions, hydrophobic interactions, or H-bonding. On demand in situ forming hydrogels have garnered increased interest especially for biomedical applications over preformed gels due to the relative ease of in vivo delivery and filling of cavities. The thiol-Michael addition reaction provides a straightforward and robust strategy for in situ gel formation with its fast reaction kinetics and ability to proceed under physiological conditions. The incorporation of a trigger function into a crosslinking system becomes even more interesting since gelling can be controlled with stimulus of choice. The use of small molar mass crosslinker precursors with active groups orthogonal to thiol-Michael reaction type electrophile provides the opportunity to implement an on-demand in situ crosslinking without compromising the fast reaction kinetics.
It was postulated that short peptide sequences due to the broad range structural-function relations available with the different constituent amino acids, can be exploited for the realisation of stimuli-promoted in situ covalent crosslinking and gelation applications. The advantages of this system over conventional polymer-polymer hydrogel systems are the ability tune and predict material property at the molecular level.
The main aim of this work was to develop a simplified and biologically-friendly stimuli-promoted in situ crosslinking and hydrogelation system using peptide mimetics as latent crosslinkers. The approach aims at using a single thiodepsipeptide sequence to achieve separate pH- and enzyme-promoted gelation systems with little modification to the thiodepsipeptide sequence. The realization of this aim required the completion of three milestones.
In the first place, after deciding on the thiol-Michael reaction as an effective in situ crosslinking strategy, a thiodepsipeptide, Ac-Pro-Leu-Gly-SLeu-Leu-Gly-NEtSH (TDP) with expected propensity towards pH-dependent thiol-thioester exchange (TTE) activation, was proposed as a suitable crosslinker precursor for pH-promoted gelation system. Prior to the synthesis of the proposed peptide-mimetic, knowledge of the thiol-Michael reactivity of the would-be activated thiol moiety SH-Leu, which is internally embedded in the thiodepsipeptide was required. In line with pKa requirements for a successful TTE, the reactivity of a more acidic thiol, SH-Phe was also investigated to aid the selection of the best thiol to be incorporated in the thioester bearing peptide based crosslinker precursor. Using ‘pseudo’ 2D-NMR investigations, it was found that only reactions involving SH-Leu yielded the expected thiol-Michael product, an observation that was attributed to the steric hindrance of the bulkier nature of SH-Phe. The fast reaction rates and complete acrylate/maleimide conversion obtained with SH-Leu at pH 7.2 and higher aided the direct elimination of SH-Phe as a potential thiol for the synthesis of the peptide mimetic.
Based on the initial studies, for the pH-promoted gelation system, the proposed Ac-Pro-Leu-Gly-SLeu-Leu-Gly-NEtSH was kept unmodified. The subtle difference in pKa values between SH-Leu (thioester thiol) and the terminal cysteamine thiol from theoretical conditions should be enough to effect a ‘pseudo’ intramolecular TTE. In polar protic solvents and under basic aqueous conditions, TDP successfully undergoes a ‘pseudo’ intramolecular TTE reaction to yield an α,ω-dithiol tripeptide, HSLeu-Leu-Gly-NEtSH. The pH dependence of thiolate ion generation by the cysteamine thiol aided the incorporation of the needed stimulus (pH) for the overall success of TTE (activation step) – thiol-Michael addition (crosslinking) strategy.
Secondly, with potential biomedical applications in focus, the susceptibility of TDP, like other thioesters, to intermolecular TTE reaction was probed with a group of thiols of varying thiol pKa values, since biological milieu characteristically contain peptide/protein thiols. L-cysteine, which is a biologically relevant thiol, and a small molecular weight thiol, methylthioglycolate both with relatively similar thiol pKa, values, led to an increase concentration of the dithiol crosslinker when reacted with TDP. In the presence of acidic thiols (p-NTP and 4MBA), a decrease in the dithiol concentration was observed, an observation that can be attributed to the inability of the TTE tetrahedral intermediate to dissociate into exchange products and is in line with pKa requirements for successful TTE reaction. These results additionally makes TDP more attractive and the potentially the first crosslinker precursor for applications in biologically relevant media.
Finally, the ability of TDP to promote pH-sensitive in situ gel formation was probed with maleimide functionalized 4-arm polyethylene glycol polymers in tris-buffered media of varying pHs. When a 1:1 thiol: maleimide molar ratio was used, TDP-PEG4MAL hydrogels formed within 3, 12 and 24 hours at pH values of 8.5, 8.0 and 7.5 respectively. However, gelation times of 3, 5 and 30 mins were observed for the same pH trend when the thiol: maleimide molar was increased to 2:1.
A direct correlation of thiol content with G’ of the gels at each pH could also be drawn by comparing gels with thiol: maleimide ratios of 1:1 to those with 2:1 thiol: maleimide mole ratios. This is supported by the fact that the storage modulus (G') is linearly dependent on the crosslinking density of the polymer. The values of initial G′ for all gels ranged between (200 – 5000 Pa), which falls in the range of elasticities of certain tissue microenvironments for example brain tissue 200 – 1000 Pa and adipose tissue (2500 – 3500 Pa).
Knowledge so far gained from the study on the ability to design and tune the exchange reaction of thioester containing peptide mimetic will give those working in the field further insight into the development of new sequences tailored towards specific applications.
TTE substrate design using peptide mimetic as presented in this work has revealed interesting new insights considering the state-of-the-art. Using the results obtained as reference, the strategy provides a possibility to extend the concept to the controlled delivery of active molecules needed for other robust and high yielding crosslinking reactions for biomedical applications. Application for this sequentially coupled functional system could be seen e.g. in the treatment of inflamed tissues associated with urinary tract like bladder infections for which pH levels above 7 were reported. By the inclusion of cell adhesion peptide motifs, the hydrogel network formed at this pH could act as a new support layer for the healing of damage epithelium as shown in interfacial gel formation experiments using TDP and PEG4MAL droplets.
The versatility of the thiodepsipeptide sequence, Ac-Pro-Leu-Gly-SLeu-Leu-Gly-(TDPo) was extended for the design and synthesis of a MMP-sensitive 4-arm PEG-TDPo conjugate. The purported cleavage of TDPo at the Gly-SLeu bond yields active thiol units for subsequent reaction of orthogonal Michael acceptor moieties. One of the advantages of stimuli-promoted in situ crosslinking systems using short peptides should be the ease of design of required peptide molecules due to the predictability of peptide functions their sequence structure. Consequently the functionalisation of a 4-arm PEG core with the collagenase active TDPo sequence yielded an MMP-sensitive 4-arm thiodepsipeptide-PEG conjugate (PEG4TDPo) substrate.
Cleavage studies using thiol flourometric assay in the presence of MMPs -2 and -9 confirmed the susceptibility of PEG4TDPo towards these enzymes. The resulting time-dependent increase in fluorescence intensity in the presence of thiol assay signifies the successful cleavage of TDPo at the Gly-SLeu bond as expected. It was observed that the cleavage studies with thiol flourometric assay introduces a sigmoid non-Michaelis-Menten type kinetic profile, hence making it difficult to accurately determine the enzyme cycling parameters, kcat and KM .
Gelation studies with PEG4MAL at 10 % wt. concentrations revealed faster gelation with MMP-2 than MMP-9 with 28 and 40 min gelation times respectively. Possible contributions by hydrolytic cleavage of PEG4TDPo has resulted in the gelation of PEG4MAL blank samples but only after 60 minutes of reaction. From theoretical considerations, the simultaneous gelation reaction would be expected to more negatively impact the enzymatic than hydrolytic cleavage. The exact contributions from hydrolytic cleavage of PEG4TDPo would however require additional studies.
In summary this new and simplified in situ crosslinking system using peptide-based crosslinker precursors with tuneable properties exhibited in situ crosslinking gelation kinetics on similar levels with already active dithiols reported. The advantageous on-demand functionality associated with its pH-sensitivity and physiological compatibility makes it a strong candidate worth further research as biomedical applications in general and on-demand material synthesis is concerned.
Results from MMP-promoted gelation system unveils a simple but unexplored approach for in situ synthesis of covalently crosslinked soft materials, that could lead to the development of an alternative pathway in addressing cancer metastasis by making use of MMP overexpression as a trigger. This goal has so far not being reach with MMP inhibitors despite the extensive work this regard.
Urban pollution
(2022)
We use worldwide satellite data to analyse how population size and density affect urban pollution. We find that density significantly increases pollution exposure. Looking only at urban areas, we find that population size affects exposure more than density. Moreover, the effect is driven mostly by population commuting to core cities rather than the core city population itself. We analyse heterogeneity by geography and income levels. By and large, the influence of population on pollution is greatest in Asia and middle-income countries. A counterfactual simulation shows that PM2.5 exposure would fall by up to 36% and NO2 exposure up to 53% if within countries population size were equalized across all cities.
Indigene Rechte und COVID-19 (Brasilien) – indigenes Land und Gesundheit unter ernster Bedrohung
(2022)
Kollektiv zum Recht
(2022)
The Greenland Ice Sheet is the second-largest mass of ice on Earth. Being almost 2000 km long, more than 700 km wide, and more than 3 km thick at the summit, it holds enough ice to raise global sea levels by 7m if melted completely. Despite its massive size, it is particularly vulnerable to anthropogenic climate change: temperatures over the Greenland Ice Sheet have increased by more than 2.7◦C in the past 30 years, twice as much as the global mean temperature. Consequently, the ice sheet has been significantly losing mass since the 1980s and the rate of loss has increased sixfold since then. Moreover, it is one of the potential tipping elements of the Earth System, which might undergo irreversible change once a warming threshold is exceeded. This thesis aims at extending the understanding of the resilience of the Greenland Ice Sheet against global warming by analyzing processes and feedbacks relevant to its centennial to multi-millennial stability using ice sheet modeling.
One of these feedbacks, the melt-elevation-feedback is driven by the temperature rise with decreasing altitudes: As the ice sheet melts, its thickness and surface elevation decrease, exposing the ice surface to warmer air and thus increasing the melt rates even further. The glacial isostatic adjustment (GIA) can partly mitigate this melt-elevation feedback as the bedrock lifts in response to an ice load decrease, forming the negative GIA feedback. In my thesis, I show that the interaction between these two competing feedbacks can lead to qualitatively different dynamical responses of the Greenland Ice Sheet to warming – from permanent loss to incomplete recovery, depending on the feedback parameters. My research shows that the interaction of those feedbacks can initiate self-sustained oscillations of the ice volume while the climate forcing remains constant.
Furthermore, the increased surface melt changes the optical properties of the snow or ice surface, e.g. by lowering their albedo, which in turn enhances melt rates – a process known as the melt-albedo feedback. Process-based ice sheet models often neglect this melt-albedo feedback. To close this gap, I implemented a simplified version of the diurnal Energy Balance Model, a computationally efficient approach that can capture the first-order effects of the melt-albedo feedback, into the Parallel Ice Sheet Model (PISM). Using the coupled model, I show in warming experiments that the melt-albedo feedback almost doubles the ice loss until the year 2300 under the low greenhouse gas emission scenario RCP2.6, compared to simulations where the melt-albedo feedback is neglected,
and adds up to 58% additional ice loss under the high emission scenario RCP8.5. Moreover, I find that the melt-albedo feedback dominates the ice loss until 2300, compared to the melt-elevation feedback.
Another process that could influence the resilience of the Greenland Ice Sheet is the warming induced softening of the ice and the resulting increase in flow. In my thesis, I show with PISM how the uncertainty in Glen’s flow law impacts the simulated response to warming. In a flow line setup at fixed climatic mass balance, the uncertainty in flow parameters leads to a range of ice loss comparable to the range caused by different warming levels.
While I focus on fundamental processes, feedbacks, and their interactions in the first three projects of my thesis, I also explore the impact of specific climate scenarios on the sea level rise contribution of the Greenland Ice Sheet. To increase the carbon budget flexibility, some warming scenarios – while still staying within the limits of the Paris Agreement – include a temporal overshoot of global warming. I show that an overshoot by 0.4◦C increases the short-term and long-term ice loss from Greenland by several centimeters. The long-term increase is driven by the warming at high latitudes, which persists even when global warming is reversed. This leads to a substantial long-term commitment of the sea level rise contribution from the Greenland Ice Sheet.
Overall, in my thesis I show that the melt-albedo feedback is most relevant for the ice loss of the Greenland Ice Sheet on centennial timescales. In contrast, the melt-elevation feedback and its interplay with the GIA feedback become increasingly relevant on millennial timescales. All of these influence the resilience of the Greenland Ice Sheet against global warming, in the near future and on the long term.
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, expansion and innovation activities for up to 40 months after business formation. Using 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.
Das Praxissemester stellt eine zentrale Lerngelegenheit für Studierende dar. Im Rahmen dieser Studie wurden 6 Personen mit einem Zeitabstand von einem bis drei Jahren zu ihrem Praxissemester interviewt. Schwerpunkte der Befragung waren die wahrgenommenen Lerngelegenheiten und Lernzuwächse während des Praxissemesters und dessen retrospektive Beurteilung. Im Einklang mit anderen Studien nahmen die Befragten ihren eigenen Unterricht als wichtigste Lerngelegenheit wahr, da sie dort ihre Berufswahlentscheidung bestätigt sahen, sich im Unterrichten ausprobieren konnten und vom Feedback ihrer Schülerinnen und Schüler sowie Ausbildungslehrkräfte profitierten. Mit einem zeitlichen Abstand von einem bis drei Jahren nahmen sie das Praxissemester noch immer positiv wahr. Der Teil der Befragten, die sich zum Zeitpunkt der Befragung im Referendariat befanden, beschrieben das Praxissemester als Möglichkeit, erste Eindrücke aus dem Schulalltag zu sammeln und sich auf das Referendariat vorzubereiten.
Überzeugungen zum Lehren und Lernen sind als Teil der professionellen Kompetenz von Lehrkräften bereits im Lehramtsstudium relevant und haben insbesondere in längeren Praxisphasen Entwicklungspotenzial. Welche Faktoren für die Entwicklung von Überzeugungen in Praxisphasen von Bedeutung sind, ist bislang aber nur unzureichend erforscht. In Interviews haben wir N = 16 Studierende befragt, welche Lerngelegenheiten für die Entwicklung ihrer Überzeugungen im Praxissemester eine Rolle spielten. Dabei konnten wir mittels Inhaltsanalyse vier übergeordnete Faktoren identifizieren: die universitäre Lernbegleitung, die Mentorinnen und Mentoren, die Schülerinnen und Schüler und die Reflexion eigener Unterrichtserfahrungen. Den Faktoren wurden untergeordnete Faktoren (z. B. Hospitationen durch Universitätsdozierende) zugeordnet und es wird dargestellt, warum und unter welchen Umständen diese Lerngelegenheiten für die Entwicklung der Überzeugungen aus Studierendensicht relevant sind.
Das Praxissemester, in dem die Studierenden mehrere Monate am Schulleben teilhaben, ist ein wichtiger Bestandteil schulpraktischer Ausbildung geworden. Die vielfältigen Ziele schließen den Kompetenzerwerb entsprechend den KMK-Vorgaben sowie die Berufswahlüberprüfung ein. Forschungsbefunde deuten jedoch darauf hin, dass nicht alle erhoff ten Ziele in Schulpraktika auch tatsächlich erreicht werden. Die konkreten Lernsituationen im Praxissemester standen hingegen bisher wenig im Fokus. Um dies aufzugreifen, interviewten wir für die vorliegende Studie N = 7 Lehramtsstudierende unmittelbar nach Abschluss ihres Praxissemesters zu den von Ihnen wahrgenommenen Lernerfolgen und den Lerngelegenheiten, in denen sie diese erzielten. Die Ergebnisse zeigen, dass die Studierenden glauben, vor allem ihre Unterrichts-Kompetenzen weiterentwickelt und sich als Lehrkraft sowie ihre Lehrer:innenpersönlichkeit kennengelernt zu haben. Als zentrale Lerngelegenheit benennen sie insbesondere den Austausch mit den Mentorinnen und Mentoren.
Die Fähigkeit zu beraten gilt als ein wichtiger Aspekt professioneller Kompetenz von Lehrkräften. Lehrveranstaltungskonzepte, die theoretisches Beratungswissen vermitteln und gleichzeitig praktische Erfahrungen im Beraten ermöglichen, sind daher hochrelevant für die Entwicklung berufsspezifischer Fähigkeiten. Angelehnt an ein vierdimensionales Modell der Beratungskompetenz wurde an der Universität Potsdam ein Seminarkonzept für angehende Lehrkräfte entwickelt. Es bietet Lerngelegenheiten, um Beratungswissen zu Kommunikations-, Diagnostik-, Problemlöse- und Bewältigungs-Skills zu erwerben und dieses Wissen in konstruierten Beratungssituationen im Seminar anzuwenden, die klassisch für die berufliche Schulpraxis sind. Darüber hinaus wurden die Lehramtsstudierenden motiviert, spezifische Beratungskompetenzen – konkret das aktive Zuhören – im Rahmen der Schulpraktischen Übungen anzuwenden. Erste Erkenntnisse der Analyse der durchgeführten Unterrichtsstunden werden dargestellt.
Im Potsdamer Modell der Lehrerbildung stellt das Praktikum in pädagogisch-psychologischen Handlungsfeldern (PppH) die zweite der fünf vorgesehenen Praxisphasen dar. Die Ziele des PppH sind (1) Sensibilisierung für Heterogenität und Inklusion, (2) Unterstützung bei der Entwicklung einer forschenden Haltung und (3) Förderung von (Selbst-)Reflexion. Konkret wird das außerunterrichtliche Praktikum durch wöchentliche Seminarsitzungen vor- und anschließende Blockveranstaltung nachbereitet. Alle PppH-Veranstaltungen wurden vom WS 15/16 bis WS 17/18 in einer Begleitforschung mit jeweils mehreren Messzeitpunkten eingerahmt. Für die vorliegende Arbeit wurden zwei kontinuierlich korrespondierenden Messzeitpunkte ausgewählt und über vier Semesterkohorten aggregiert. In einem quasi-experimentellen Prä-Post-Design zeigen die empirischen Ergebnisse insgesamt positive Einstellungen und relative hohe Selbstwirksamkeit sowie einige positive Prä-Post-Entwicklungen von kleiner Effektstärke.
Digitale Musikmedien und -technologien in der Musiklehrer*innenausbildung an der Universität Potsdam
(2022)
This chapter takes the ongoing conflict in South Sudan as a starting point for assessing the concept of transitional justice as such and its implementation in the country in particular. Following a brief description of the conflict and the peace processes, the author sheds light on the shortcomings of the established concept of transitional justice in the situation at hand. Then, the author outlines the alternate concept of transformational justice und takes a closer look at its implications on the situation in South Sudan. The author highlights existing initiatives of transformative justice and is very much in favour of their victim-centered approach.
At different times and places, civic engagement in nonviolent resistance (NVR) has repeatedly shown to be an effective tool in times of conflict to initiate societal change from below. History teaches us that there have been successes (Mahatma Gandhi in India) and failures (the Tiananmen Square protests in China).
Along with the recognition of the duality between transformative potential and stark consequences, the historical development of NVR was accompanied by the emergence of scholarly debate, fractured along disputes around purpose, character and effectivity of nonviolent actions taken by civil society stakeholders engaged in making their voices heard. One of the field’s current points of interest is the examination of the long-term effects of NVR movements resulting in societal transformation on the stability and adequacy of a subsequently altered or emerging democracy, suggesting that NVR contributes positively to the sustainable and representative design of an egalitarian governing system.
The conclusion of the Nepalese civil war in 2006 should pose as an unambiguous example for the illustration of this phenomenon, but simultaneously raises the question why there was no successful implementation of a transitional process focusing on the needs of the victims.
Transitional justice is conventionally theorized as how a society deals with past injustices after regime change and alongside democratization. Nonetheless, scholars have not reached a consensus on what is to be included or excluded. Recent ideas of transformative justice seek to expand the understanding of transitional justice to include systemic restructuring and socioeconomic considerations. In the context of Nicaragua — where two transitions occurred within an 11-year span — very little transitional justice took place, in terms of the conventional concept of top-down legalistic mechanisms; however, distinct structural changes and socioeconomic policies can be found with each regime change. By analyzing the transformative justice elements of Nicaragua’s dual transition, this chapter seeks to expand the understanding of transitional justice to include how these factors influence goals of transitions such as sustainable peace and reconciliation for past injustices. The results argue for increased attention to transformative justice theories and a more nuanced conception of justice.
While the concept of transitional justice and its range of measures have gained importance on an international level to come to terms with major crimes of the past, colonial crimes and mass violence committed by Western actors have not been addressed by transitional justice so far. In this chapter, the Herero’s and Nama’s struggle for justice for the genocide on their ancestors by Germany from 1904 – 1908 and the arising challenges are set in relation to conceptual debates in the field of transitional justice. Building on current debates in the field, suggesting more structural and transformative conceptualizations of transitional justice and an approach ‘from below’, it is argued that decolonial activism of formerly colonized communities and transitional justice debates can inform each other in a dialogic and fruitful form to formulate suggestions for a process towards post-colonial justice.
This paper aims to contribute a different approach to transitional justice, one in which political decisions are rocketed to the forefront of the research. Theory asserts that, after a transition to democracy, it is the constituency who defines the direction a country will take. Therefore, pleasing them should be at the fore of the responses taken by those in power. However, reality distances itself from theory. History provides us with many examples of the contrary, which indicates that the politicization of transitional justice is an ever-present event. The first section will outline current definitions and obstacles faced by transitional justice, focusing on the implicit ties between them and the aforementioned politicization. An original categorization of Transitional Justice as a method of analysis will also be introduced, which I denominate Political Opportunism. The case of Argentina, a country that is usually described as a model to export but that after 35 years is still dealing with the consequences brought by the contradictions of using several methods of justice, will then be reinterpreted through this perspective. At the end of the paper, the inevitable question will be posed: can this new angle be exported and implemented in every transition?