203 research outputs found

    Eocene maar sediments record warming of up to 3.5 °C during a hyperthermal event 47.2 million years ago

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    Eocene hyperthermal events reflect profound perturbations of the global carbon cycle. Most of our knowledge about their onset, timing, and rates originates from marine records. Hence, the pacing and magnitude of hyperthermal continental warming remains largely unaccounted for due to a lack of high-resolution climate records. Here we use terrestrial biomarkers and carbon isotopes retrieved from varved lake deposits of the UNESCO World Heritage site ‘Messel Fossil Pit’ (Germany) to quantify sub-millennial to millennial-scale temperature and carbon isotope changes across hyperthermal event C21n-H1 (47.2 million years ago). Our results show maximum warming of ca. 3.5 °C during C21n-H1. We propose that two components are responsible for the warming pattern across the hyperthermal: (1) the massive release of greenhouse gases into the atmosphere-ocean system and (2) half-precession orbital forcing indicated by ~12.000-year temperature cycles. The carbon isotope record of bulk organic matter indicates a sharp, 7‰ decrease at the peak of the hyperthermal, corresponding to increased organic carbon content and a shift in the lake algal community. Collectively, our proxy data reveal the structure of continental temperature response during the hyperthermal event that is characterized by overall warming with a superimposed pattern of sub-orbital scale temperature fluctuations

    (13)C or Not (13)C: Selective Synthesis of Asymmetric Carbon-13-Labeled Platinum(II) cis-Acetylides.

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    Asymmetric isotopic labeling of parallel and identical electron- or energy-transfer pathways in symmetrical molecular assemblies is an extremely challenging task owing to the inherent lack of isotopic selectivity in conventional synthetic methods. Yet, it would be a highly valuable tool in the study and control of complex light-matter interactions in molecular systems by exclusively and nonintrusively labeling one of otherwise identical reaction pathways, potentially directing charge and energy transport along a chosen path. Here we describe the first selective synthetic route to asymmetrically labeled organometallic compounds, on the example of charge-transfer platinum(II) cis-acetylide complexes. We demonstrate the selective (13)C labeling of one of two acetylide groups. We further show that such isotopic labeling successfully decouples the two ν(C≡C) in the mid-IR region, permitting independent spectroscopic monitoring of two otherwise identical electron-transfer pathways, along the (12)C≡(12)C and (13)C≡(13)C coordinates. Quantum-mechanical mixing leads to intriguing complex features in the vibrational spectra of such species, which we successfully model by full-dimensional anharmonically corrected DFT calculations, despite the large size of these systems. The synthetic route developed and demonstrated herein should lead to a great diversity of asymmetric organometallic complexes inaccessible otherwise, opening up a plethora of opportunities to advance the fundamental understanding and control of light-matter interactions in molecular systems

    Considering medical students’ perception, concerns and needs for e-exam during COVID-19: a promising approach to improve subject specific e-exams

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    The COVID-19 pandemic forced a rapid shift to digital strategies including e-exams in medical schools. However, there are significant concerns, predominately from student perspectives, and further data is required to successfully establish e-assessment in the medical curricula. The objective of the study was to examine medical students’ perceptions, concerns, and needs regarding e-assessment to establish a comprehensive e-exam based on these and previous findings and to evaluate its effectiveness in terms of examinee perceptions and further needs. During the 2021 summer term, a cross-sectional study using qualitative and quantitative methods was conducted among all 1077 students at the School of Medicine, Technical University of Munich. They were asked to provide information regarding their characteristics, preferred exam format, e-assessment perception, concerns, and needs in an online questionnaire. Based on these findings, a pilot e-exam including an e-exam preparation for the students were established and subsequently evaluated among 125 pilot e-exam examinees under study consideration via an online-questionnaire. Of the 317 pre-exam participants (73.2% female), 70.3% preferred in-person exams and showed concerns about the technological framework, privacy, and examination requirements. Qualitative analysis showed that these concerns lead to additional exam stress and fear of failure. The 34 (79.4% female) participants who participated in the evaluation survey showed a significantly more positive e-exam perception. The fairness of the platform, the independence from an internet connection, the organization including the e-exam preparation, and the consideration of participant needs were discussed as particularly positive in the open-ended comments. In both surveys, participants requested uniform platforms and processes for all subjects. This study provides evidence for a positive, complementary role of student participation in a successful e-exam implementation. Furthermore, when establishing an e-exam format in the medical curricula, e-exam training, equal accessibility, availability offline, and all-round fairness should be considered

    Nanoscale detection of a single fundamental charge in ambient conditions using the NV - Center in diamond

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    Single charge nanoscale detection in ambient conditions is a current frontier in metrology that has diverse interdisciplinary applications. Here, such single charge detection is demonstrated using two nitrogen-vacancy (NV) centers in diamond. One NV center is employed as a sensitive electrometer to detect the change in electric field created by the displacement of a single electron resulting from the optical switching of the other NV center between its neutral (NV0) and negative (NV-) charge states. As a consequence, our measurements also provide direct insight into the charge dynamics inside the material

    Microwave Control of the Tin-Vacancy Spin Qubit in Diamond with a Superconducting Waveguide

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    Group-IV color centers in diamond are promising candidates for quantum networks due to their dominant zero-phonon line and symmetry-protected optical transitions that connect to coherent spin levels. The negatively charged tin-vacancy (SnV) center possesses long electron spin lifetimes due to its large spin-orbit splitting. However, the magnetic dipole transitions required for microwave spin control are suppressed, and strain is necessary to enable these transitions. Recent work has shown spin control of strained emitters using microwave lines that suffer from Ohmic losses, restricting coherence through heating. We utilize a superconducting coplanar waveguide to measure SnV centers subjected to strain, observing substantial improvement. A detailed analysis of the SnV center electron spin Hamiltonian based on the angle-dependent splitting of the ground and excited states is performed. We demonstrate coherent spin manipulation and obtain a Hahn echo coherence time of up to T2=430 μT_2 = 430\,\mus. With dynamical decoupling, we can prolong coherence to T2=10 T_2 = 10\,ms, about six-fold improved compared to earlier works. We also observe a nearby coupling 13C^{13}\mathrm{C} spin which may serve as a quantum memory. This substantiates the potential of SnV centers in diamond and demonstrates the benefit of superconducting microwave structures.Comment: Main: 9 pages, 5 figures, 1 tables; Supplement: 15 pages, 10 figures, 1 tabl

    A dinuclear ruthenium(II) phototherapeutic that targets duplex and quadruplex DNA

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    With the aim of developing a sensitizer for photodynamic therapy, a previously reported luminescent dinuclear complex that functions as a DNA probe in live cells was modified to produce a new isostructural derivative containing RuII(TAP)2 fragments (TAP = 1,4,5,8- tetraazaphenanthrene). The structure of the new complex has been confirmed by a variety of techniques including single crystal X-ray analysis. Unlike its parent, the new complex displays RuL-based 3MLCT emission in both MeCN and water. Results from electrochemical studies and emission quenching experiments involving guanosine monophosphate are consistent with an excited state located on a TAP moiety. This hypothesis is further supported by detailed DFT calculations, which take into account solvent effects on excited state dynamics. Cell-free steady-state and time-resolved optical studies on the interaction of the new complex with duplex and quadruplex DNA show that the complex binds with high affinity to both structures and indicate that its photoexcited state is also quenched by DNA, a process that is accompanied by the generation of the guanine radical cation sites as photo-oxidization products. Like the parent complex, this new compound is taken up by live cells where it primarily localizes within the nucleus and displays low cytotoxicity in the absence of light. However, in complete contrast to [{RuII(phen)2}2(tpphz)]4+, the new complex is therapeutically activated by light to become highly phototoxic toward malignant human melanoma cell line showing that it is a promising lead for the treatment of this recalcitrant cancer.EPSRC grant EP/M015572/1 Unviersity of Sheffield/EPSRC Doctoral Fellowship Prize EPSRC Capital Equipment Award ERASMUS

    Political innovation as ideal and strategy: the case of aleatoric democracy in the City of Utrecht

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    Political innovations aim to strengthen democracy but few connect well to the institutionalized democratic context. This paper explores how political innovations can be successfully embedded in existing democratic systems. It builds upon both the literature on political innovation and on new democratic arrangements and studies a practice of aleatoric democracy – using the lottery instead of elections to select representatives – in the Dutch City of Utrecht. The case study shows how the idealist logic of improving democracy and the realist logic of realizing specific political goals intertwine to get the political innovation accepted by the institutionalized democratic system
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