Janus graphene nanoribbons with localized states on a single zigzag edge

Topological design of π electrons in zigzag-edged graphene nanoribbons (ZGNRs) leads to a wealth of magnetic quantum phenomena and exotic quantum phases1,2,3,4,5,6,7,8,9,10. Symmetric ZGNRs typically show antiferromagnetically coupled spin-ordered edge states1,2. Eliminating cross-edge magnetic coupling in ZGNRs not only enables the realization of a class of ferromagnetic quantum spin chains11, enabling the exploration of quantum spin physics and entanglement of multiple qubits in the one-dimensional limit3,12, but also establishes a long-sought-after carbon-based ferromagnetic transport channel, pivotal for ultimate scaling of GNR-based quantum electronics1,2,3,9,13. Here we report a general approach for designing and fabricating such ferromagnetic GNRs in the form of Janus GNRs (JGNRs) with two distinct edge configurations. Guided by Lieb’s theorem and topological classification theory14,15,16, we devised two JGNRs by asymmetrically introducing a topological defect array of benzene motifs to one zigzag edge, while keeping the opposing zigzag edge unchanged. This breaks the structural symmetry and creates a sublattice imbalance within each unit cell, initiating a spin-symmetry breaking. Three Z-shaped precursors are designed to fabricate one parent ZGNR and two JGNRs with an optimal lattice spacing of the defect array for a complete quench of the magnetic edge states at the ‘defective’ edge. Characterization by scanning probe microscopy and spectroscopy and first-principles density functional theory confirms the successful fabrication of JGNRs with a ferromagnetic ground-state localized along the pristine zigzag edge

Elevated plasma soluble lectin-like oxidised low-density lipoprotein receptor 1 as an independent prognostic biomarker in sepsis

Background Soluble lectin-like oxidised low-density lipoprotein receptor 1 (sLOX-1) is overproduced during inflammation, with its expression and release triggered by C-reactive protein (CRP). As CRP levels are typically elevated in sepsis, this study aimed to investigate whether sLOX-1 levels increase in parallel. Methods Plasma sLOX-1 levels of 52 patients with systemic inflammatory response syndrome (SIRS), 45 patients with sepsis, 88 patients with septic shock and 37 controls were measured by ELISA. Associations with CRP, underlying diseases, severe acute respiratory syndrome coronavirus type 2 (SARS-CoV-2) and bacterial infections were analysed. Results Plasma sLOX-1 levels were similarly elevated in patients with SIRS, sepsis, or septic shock compared to controls. Plasma sLOX-1 levels did not differ between male and female controls or patients. Plasma sLOX-1 levels were comparable in patients infected with SARS-CoV-2, Gram-negative bacteria, or Gram-positive bacteria. No association was observed between sLOX-1 levels and underlying liver cirrhosis or pancreatitis. Notably, plasma sLOX-1 levels correlated positively with leukocyte and basophil counts but showed no correlation with CRP or procalcitonin. Of clinical relevance, positive correlations were also found with aspartate aminotransferase (AST) and bilirubin levels. Among the 41 patients who did not survive, sLOX-1, AST, and bilirubin levels were significantly higher compared to those of survivors. Conclusions Plasma levels of sLOX-1 are elevated in patients with SIRS or sepsis and are significantly higher in non-survivors. Of note, they do not correlate with classical inflammatory markers, suggesting that sLOX-1 may function as an independent prognostic biomarker for predicting poor outcomes in patients with SIRS or sepsis

Time course of hospitalizations in patients with heart failure and chronic obstructive pulmonary disease around sleep-disordered-breathing diagnosis

Purpose In heart failure (HF) and chronic obstructive pulmonary disease (COPD) populations, sleep-disordered breathing (SDB) is associated with impaired health outcomes. We evaluated whether in patients with HF, concomitant HF and COPD or COPD, the number of hospitalizations would be reduced in the year after testing for SDB with and without treatment initiation compared to the year before. Methods We performed a multicentre retrospective study of 390 consecutive sleep-clinic patients who had a primary diagnosis of chronic HF, HF and COPD or COPD and a secondary diagnosis of SDB. The date of SDB-testing was defined as the index date. Data on healthcare utilization was extracted for the 12-month period prior to and after this date. Results The initiation of adaptive servoventilation (ASV) and non-invasive ventilation (NIV) treatment resulted in a statistically significant reduction in the number of hospitalisations. While continuous positive airway pressure (CPAP) treatment also demonstrated a reduction in hospitalisations, the observed effect did not reach the level of statistical significance. After accounting for demographics and comorbidities in multivariable regression analyses, only NIV was significantly associated with a reduction in hospitalizations, while CPAP or ASV were not. NIV appears to be underutilized in COPD. Conclusions Our data indicate, that patients with HF or COPD and concomitant SDB may benefit from the initiation of appropriate PAP-therapy. Whether treating SDB in HF- and COPD-patients influences healthcare utilization merits further investigation

Diurnal timing of physical activity in relation to obesity and diabetes in the German National Cohort (NAKO)

Background Physical activity supports weight regulation and metabolic health, but its timing in relation to obesity and diabetes remains unclear. We aimed to assess the diurnal timing of physical activity and its association with obesity and diabetes. Methods We cross-sectionally analyzed hip-worn accelerometry data from 61,116 participants aged 20–75 in the German National Cohort between 2015 and 2019. We divided physical activity into sex- and age-standardized quartiles of total morning (06:00–11:59), afternoon (12:00–17:59), evening (18:00–23:59), and nighttime (00:00–06:00) physical activity. Using multivariable logistic regression, we estimated associations of physical activity timing with obesity (BMI ≥ 30.0 kg/m2) and diabetes (self-reported or HbA1c ≥ 6.5%). We accounted for sex, age, study region, education, employment, risky alcohol use, smoking, night shift work, and sleep duration. Results High afternoon (top vs. bottom quartile, OR: 0.36, 95% CI: 0.33–0.38) and evening physical activity (OR: 0.45, 95% CI: 0.42–0.48) showed lower obesity odds than high morning activity (OR: 0.71, 95% CI: 0.66–0.76), whereas nighttime activity increased obesity odds (OR: 1.58, 95% CI: 1.48–1.68). Associations were similar for diabetes, with the lowest odds for afternoon (OR: 0.47, 95% CI: 0.42–0.53), followed by evening (OR: 0.56, 95% CI: 0.50–0.62) and morning activity (OR: 0.80, 95% CI: 0.71–0.89), and higher odds for nighttime activity (OR: 1.43, 95% CI: 1.29–1.58). Findings were not modified by employment status, night shift work, and sleep duration. Conclusions Our cross-sectional findings require longitudinal corroboration but suggest afternoon and evening activity provide greater metabolic health benefits than morning activity, while nighttime activity is discouraged

Performancevergleich von Luxusuhren, Oldtimern und Wein

Ergänzend zu den Studien Köstlmeier/Röder in CF 2022, CF 2023 und CF 2024 werden die Preisentwicklungen des globalen Markts für Oldtimer von Dez. 2003 bis März 2024 analysiert. Mit einer Rendite von 7,75% p.a. und einem geringen Maximum Drawdown von -3,94% schneiden Oldtimer im Vergleich zu einem Weltmarktportfolio (6,06%, -38,55%) und Aktien (DAX: 7,90%, -52,35%) solide ab. In einer zweiten Zeitreihe von Dez. 2010 bis Dez. 2021 wird die Performance des bereits bekannten Watch30-Index (7,98% p.a.) mit der Wertentwicklung von Oldtimern (7,25%) und Wein (1,60%) verglichen. Eine Korrelationsanalyse deutet potenzielle Diversifikationsvorteile an. In Zusammenhang mit positiver Schiefe und geringem Maximum-Drawdown könnten sich somit für Luxusuhren und Oldtimer attraktive Renditechancen für Investoren bei nur begrenztem Verlustrisiko bei diversifizierten Anlagen zeigen

Small Inorganic Ring Systems: Understanding Cyclization and Bond Activation Processes

Within this work, the modification of the substituents at silicon of heterocyclic four-membered silyl phosphonium ions was investigated. In chapter 1 a general overview of the current state of research, and the design principles, to which the structure of the four-membered phosphonium ions adhere, are presented. The focus of chapter 3 is the modification of previously known silyl phosphine chalcogenides with different substituents and Lewis basic chalcogenides. New synthesis routes towards these novel compounds were developed, the structures synthesized and thoroughly investigated by means of single-crystal X-ray diffraction analysis, NMR analysis and DFT calculations. Through this procedure a deep understanding of the governing principles of steric and electronic effects within these four-membered silyl phosphonium chalcogenides was obtained. When all substituents are replaced by sterically demanding tert-butyl substituents, the choice of chalcogen used as a Lewis base becomes crucial for successful ring formation. The angular strain within the four-membered rings was found to be well balanced in all four-membered CPChSi rings investigated. Thermochemical investigations showed that the substituents on the silicon and phosphorus atoms play an important role for the strength of the intramolecular Ch–Si coordination. In the absence of large steric repulsions through bulky substituents (methyl groups on silicon, tert-butyl groups on phosphorus), a stability sequence depending on the chalcogen atom in the direction Se ≤ S < O can be observed. However, the order is reversed (O < S < Se) in case of strong repulsions between sterically demanding substituents (tert-butyl groups on both silicon and phosphorus atoms). Due to the shorter Si–O bond length compared to the Si–S and Si–Se bond lengths, the substituents of the phosphorus and silicon atom are forced in closer proximity in the four-membered cations. In the case of all-tert-butyl substituted compound I this leads to a significant increase in steric repulsion in this cation, therefore hampering its synthesis. Building upon this knowledge, another second-row element, nitrogen, was investigated as a donor in chapter 4. The nitrogen atom was introduced as a phosphinimine moiety into the systems. In contrast to phosphine chalcogenides, phosphinimine donor moieties allow for further modification of donor strength by the influence of steric or electronic parameters. The introduction of either a trimethylsilyl or a bis(3,5-trifluoromethylphenyl)boryl moiety allows for additional ring strain in these systems. Furthermore, an electronic destabilization of the Si–N bond was expected to be achieved by either resonance stabilization by the bis(3,5-trifluoromethylphenyl)boryl moiety or by hyperconjugative n(N)→σ*(SiMe) interactions from the –SiMe3 moiety. Taken together, these effects are expected to facilitate ring opening and enable small molecule activation or even catalytic transformations. The rational synthesis of these systems, the influence of steric and electronic factors, and the reactivity in terms of catalytic applications and FLP-like behavior were investigated. The silylated phosphinimines can be easily obtained in moderate to good yields. The ring-closure reactions of the methyl- and iso-propyl-substituted silanes (X, XI) proceeded smoothly, however the case of the all tert-butyl substituted silyl phosphinimine IX no ring closure was possible. Like the P–O bond length [1.4958(8) Å] in compound I the P–N bond length [1.538(2) Å] in compound IX is also very short, therefore the same effects hampering the ring formation in compound I were found to also affect the ring formation in compound IX. The Si–N bonds in the SiMe3-substituted four-membered phosphonium ions XII[B(C6F5)4] and XIII[B(C6F5)4] were found to be covalent in nature, and did not possess the ability to reversibly open as anticipated. Nevertheless, we were able to gain valuable insights from these results and therefore we set out to design a new system with a maximum of steric hinderance, while also preserving the desired ability to remove the hydride from the Si¬–H moiety. Therefore, an electrophilic boryl moiety was introduced to study the effect of electron-withdrawing groups on the reversible opening ability of these ring systems. With the zwitterionic compound XIV reversibility was finally achieved which was evidenced by the ability of compound XIV to catalyze the hydrosilylation of nitriles. This validated our approach of combining steric and electronic factors to weaken the Si¬–N bond in compound XIV. Upon receiving preliminary confirmation through this experiment, that reversibility is in principle possible within these systems our attention shifted away from the strongly Lewis acidic silylium-based Lewis acids towards neutral silicon-based Lewis acids. The rational was, that neutral silicon-based Lewis acids are of lower Lewis acidity compared to silylium ions, and therefore reversibility within these systems can be easier achieved. The question whether this really is the case was addressed in chapter 5. Several novel neutral Lewis acidic silanes were prepared and incorporated within the previously described CPSSi cycles (chapter 3). By varying the electron-withdrawing groups from pentafluorophenyl [-C6F5] over pentafluorophenoxy [-OC6F5] to tetrafluorocatecholato [-O2C6F4] moieties, a discernible difference in Lewis acidity at the silicon center was observed (Scheme 8.3). While the pentafluorophenyl [-C6F5] substituted compound showed no Lewis acidity, the tetrafluorocatecholato [-O2C6F4] substituted silane was strongly prone towards formation of the pentacoordinate state making the desired Si–H substituted tetravalent silane inaccessible. A good balance between Lewis acidity and stability of the tetravalent state was found with the pentafluorophenoxy [-OC6F5] substituted compound XV. Through in depth NMR spectroscopic experiments a equilibrium between compounds XV and XVI could be observed. Compound XV represents an intriguing structure as it combines a highly reducing anionic Si–H function, aswell as a protic cationic N–H function in close proximity to each other. To the best of our knowledge this is the only example were both motifs can be found within one molecule. Through additional time resolved NMR experiments it was also found that compound XV is not stable over a prolonged amount of time and slowly reacts with the loss of dihydrogen towards compound XVII. In conclusion the introduction of neutral Lewis acidic silanes indeed proved to ease the ability of the silicon Lewis acids to reversibly attach to Lewis bases. In a second part of this doctoral project, chiral silanethiols were synthesized and investigated as enantioselective hydrogen-atom transfer (HAT) catalysts together with the group of Prof. König. The deracemization was achieved by a sequence of photocatalytic hydrogen-atom transfer, reductive radical-polar crossover (RRPCO), and protonation. Our goal was to design silanethiols which were able to act as potent and enantioselective HAT-catalysts. To achieve this goal, different strategies were employed. The first attempt was made with a silanethiol which was equipped with chiral substituents. Therefore the (–)-menthol substituted silanethiol XVIII was prepared and tested, and while compound XVIII performed well as a HAT-catalysts no enantioselectivity was observed. Next, the Si-chiral silanethiol XIX was prepared and tested. The idea was to bring the chiral information closer to the reactive Si¬–S– function, and therefore enhance enantioselectivity. This approach was successful and compound XIX performed well as a HAT catalyst and gave an enantiomeric excess of 16 % in the final product. While this finding served as proof that chiral silanethiols can indeed be used as enantioselective HAT-catalysts, the enantiomeric excess obtained was not good enough for practical use. In order to increase the enantioselectivity even further, the successful concept of using Si-chiral silanethiols was combined with a chiral backbone. A suitable motif, which combined both desired features was found in a class of silanthiols with a ferrocene backbone [(SSi,SP)-XX and (SSi,SP)-XXI]. While both compounds are Si-stereogenic, they also exhibit planar chirality in the ferrocenyl backbone. However, when employing compounds (SSi,SP)-XX and (SSi,SP)-XXI in the RRPCO-HAT-protonation sequence, decomposition was observed. No catalytic activity nor enantioselectivity was observed for both compounds, therefore concluding that the ferrocene backbone is not suitable for this application. In summary, this lays the foundation for the design of silanethiol HAT catalysts based on the general structure of compound XIX

Nucleophilic Functionalization of a Cationic Pentaphosphole Complex–A Systematic Study of Reactivity

The systematic nucleophilic functionalization of the cationic pentaphosphole ligand complex [Cp*Fe(η4-P5Me)][OTf] (A) with group 16/17 nucleophiles is reported. This method represents a highly reliable and versatile strategy for the design of novel transition-metal complexes featuring twofold substituted end-deck cyclo-P5 ligands, bearing unprecedented hetero-element substituents. By the reaction of A with classical group 16 nucleophiles, complexes of the type [Cp*Fe(η4-P5MeE)] (E=OEt (1), OtBu (2), SPh (3), SePh (4)) are obtained. By transferring this protocol to group 17 nucleophiles, the highly sensitive complexes [Cp*FeP5(η4-P5MeX)] (X=F (5), Cl (6), Br (7), I (8)) could be isolated. All products show exclusively 1,1'-substitution at the cyclo-P5 ring. Interestingly, further studies on the reactivity of the halogenated species revealed their ability to undergo ring-opening reactions with cyclic ethers such as THF and ethylene oxide yielding [Cp*FeP5(η4-P5MeOC4H8X)] (X=Br (9), I (10)) or [Cp*FeP5(η4-P5MeOC2H4X)] (X=Br (11), I (12)), respectively. Furthermore, the use of acyclic ethers such as dimethoxyethane led to the formation of [Cp*FeP5(η4-P5MeOC2H4OCH3)] (13) mediated by C−O bond cleavage, followed by subsequent P−O bond formation, as further enlightened by DFT calculations

The Rapid Adaptation of a Pest Species, The Coffee Berry Borer (Hypothenemus hampei Ferrari): Phenotypic Variation or Local Adaptation?

The Coffee Berry Borer (CBB) has plagued the coffee industry for over a century, causing significant economic losses worldwide. The CBBs’ behaviour inside the coffee berry, chemistry, and genetics are not well studied, even with hundreds of publications to date. This thesis focuses on three distinct aspects of the CBB’s biology; its behavior in cases of double infestation; possible differences in cuticular chemical composition; and genetic variation among different beetle localities. We mainly focus on CBBs in Jamaica, where different regions across the island produce three different classifications of coffee; Lowland, Highland, and the reputable Jamaica Blue Mountain Coffee. We explored the CBB’s biology using a lab population of CBBs and field samples, combined with GC-MS (CBB Chemistry), artificial diet habitats (Behaviour), a new CBB reference genome, and pools of whole-genome sequenced individuals (Genetics). In terms of behaviour, we discovered that double infestation has a negative effect on productivity, and that CBB behaviour is independent of relatedness. We further confirmed the solitary status of the CBB, the presence of parental care and lack of delayed dispersal in daughters. Regarding CBB chemistry, females have a very simple profile that is shared among all CBB localities, despite differences in macroenvironmental conditions. Concerning the CBB’s genome, we assembled and annotated an improved version to serve future studies. Further, sequencing CBBs from different localities showed two introduction events and general low genetic diversity, presumably caused by passing through a genetic bottleneck, and a recent surge in transposable element activity. Together, this thesis focusing on local and basic CBB biology provides insights that could be beneficial in developing future CBB mitigation strategies, as the biology and the management of the pest are interconnected

Bundesweiter Vergleich zu heilkundlichen Maßnahmen durch Notfallsanitäterinnen und Notfallsanitäter

Hintergrund Die heilkundliche Tätigkeit durch Notfallsanitäterinnen und Notfallsanitäter ohne notärztliche Anwesenheit basiert v. a. 1.) auf einer Delegation durch z. B. die Ärztliche Leitung Rettungsdienst oder 2.) auf eigenverantwortlicher Heilkundeausübung nach § 2a Notfallsanitätergesetz. Beide Möglichkeiten unterscheiden sich u. a. hinsichtlich der Verantwortung für die Indikationsstellung. Diese Arbeit gibt erstmals einen bundesweiten Überblick, wer welche Verantwortung im Rahmen der Behandlungsvorgaben für Notfallsanitäterinnen und Notfallsanitäter trägt. Material und Methoden Die Behandlungsalgorithmen zu 5 Krankheitsbildern wurden für alle Bundesländer hinsichtlich ihrer geografischen Gültigkeit, der Deklaration sowie des objektiven Charakters als Delegation der Ärztlichen Leitung Rettungsdienst oder entsprechend verantwortlicher Ärztinnen oder Ärzte (ÄLRD-Delegation) oder Heilkundeausübung (§ 2a NotSanG) und der Erstreckung auf Betäubungsmittel ausgewertet. Die Datenerhebung fand im Zeitraum von Dezember 2020 bis Juni 2022 statt. Ergebnisse Es wurden 112 Algorithmen mit 403 Einzelmaßnahmen analysiert. Für 11 Bundesländer wurden landesweit gültige, in 5 Ländern regional abweichende Behandlungsvorgaben gefunden. Der ÄLRD-Delegations- oder § 2a NotSanG-Status war in lediglich 40 % der einzelnen Maßnahmen explizit deklariert. Diese Deklaration zeigte in 93 % eine Übereinstimmung mit dem objektiven Charakter der Maßnahme. Eine eigenständige oder eigenverantwortliche Betäubungsmittelgabe durch NotSan ist in 6 Ländern vorgesehen. Diskussion In der Mehrheit der für NotSan vorgesehenen Maßnahmen ist nicht ersichtlich, ob diese in ÄLRD-Delegation oder nach § 2a NotSanG angewendet werden sollen. Eine entsprechende Deklaration durch die Ersteller könnte hier für mehr Klarheit bezüglich der Verantwortlichkeiten sorgen. Sowohl eine ÄLRD-Delegation als auch eine Betäubungsmittelgabe ohne Arztanwesenheit ist nicht in allen Bundesländern etabliert. Aufgrund der sich stetig weiterentwickelnden Rechtslage stellen sich die untersuchten Endpunkte in einzelnen Regionen mittlerweile anders dar