Enantioselective Nucleophile-Catalyzed Synthesis of Tertiary Alkyl Fluorides via the α‑Fluorination of Ketenes: Synthetic and Mechanistic Studies

The catalytic asymmetric synthesis of alkyl fluorides, particularly α-fluorocarbonyl compounds, has been the focus of substantial effort in recent years. While significant progress has been described in the formation of enantioenriched secondary alkyl fluorides, advances in the generation of tertiary alkyl fluorides have been more limited. Here, we describe a method for the catalytic asymmetric coupling of aryl alkyl ketenes with commercially available N-fluorodibenzenesulfonimide (NFSI) and C_6F_5ONa to furnish tertiary α-fluoroesters. Mechanistic studies are consistent with the hypothesis that the addition of an external nucleophile (C_6F_5ONa) is critical for turnover, releasing the catalyst (PPY*) from an N-acylated intermediate. The available data can be explained by a reaction pathway wherein the enantioselectivity is determined in the turnover-limiting transfer of fluorine from NFSI to a chiral enolate derived from the addition of PPY* to the ketene. The structure and the reactivity of the product of this proposed elementary step, an α-fluoro-N-acylpyridinium salt, have been examined

An investigation into the role of thought suppression in the retrieval of autobiographical memories

This program of research was designed to examine the role of thought suppression in the retrieval of autobiographical memories (ABMs). The principal theory proposed here is that thought suppression is an important mechanism in explaining certain ABM retrieval patterns relevant to trauma and self-harm. Study 1 examined the role of thought suppression as a correlate of ABM retrieval in a nonclinical student sample, and showed that higher levels of thought suppression were significantly correlated with the faster recall of negative episodic ABMs as well as the recall of fewer personal semantic memories. Study 2 used a suppression manipulation procedure designed to examine whether this was a causal relationship, and revealed that induced thought suppression directly led to a significant enhancement in the retrieval of negative episodic ABMs as well as significantly fewer overgeneral first responses to negative cues. Furthermore, the induced thought suppression also resulted in the recall of significantly fewer personal semantic memories. Together these results support the theory that thought suppression is an important factor in ABM recall. The enhanced recall of negative memories could be particularly important in individuals who are self-harming, suicidal and/or suffering from PTSD, as enhanced negative recall has previously been observed in these populations. In order to further examine how thought suppression affects ABM retrieval and whether the enhanced negative recall observed in Study 2 was a result of mood-congruent recall, Study 3 used a similar suppression manipulation paradigm to examine the effects of induced thought suppression on mood. The results suggested that the enhanced negative ABM recall was unlikely to have been a by-product of the suppression manipulation resulting in a more negative mood state. Finally, Study 4 examined the role of thought suppression and ABM recall in a clinical sample of self-harming adolescents (who also reported high levels of post-traumatic stress symptoms). The results showed that levels of thought suppression were significantly higher in the self-harmers than the control group, indicating that thought suppression is an important coping mechanism in self-harmers. Furthermore, in terms of the autobiographical memory retrieval, it was found that the self-harmers were significantly faster in their retrieval of negative episodic ABMs and recalled fewer personal semantic memories than the control group. Multiple regression analysis of the data revealed that thought suppression remained as the most important predictor of variability in negative episodic ABM retrieval and personal semantic memory retrieval, even when variability explained by symptoms of depression and PTSD was considered. This program of research extends current theories of ABM retrieval by identifying thought suppression as a cognitive mechanism that directly affects the retrieval of both episodic as well as personal semantic ABMs. The theoretical importance and clinical relevance of this program of research are discussed

Barriers and drivers to vaccination among healthcare workers in Germany

Vaccine hesitancy is a major threat to global public health. Reasons not to vaccinate are multifaceted. Healthcare workers (HCWs) are key figures in the vaccination system – both as vaccine providers and vaccine recipients. This dissertation project aimed to (i) investigate barriers and drivers to vaccination among HCWs in Germany and (ii) identify vaccination gaps among HCWs. It further aimed to (iii) investigate whether HCWs favor vaccine mandates as an intervention to increase vaccine uptake. Survey data was collected from family physicians (FPs), hospital staff and primary care physicians. HCWs’ vaccination coverage for various vaccines and recommendation behavior were assessed. Further, we assessed psychological determinants of vaccination and additional barriers to vaccination. Lastly, we assessed psychological determinants of physician attitudes towards vaccine mandates. In all studies, associations between outcomes and determinants were examined using linear and logistic regression analysis. The surveys revealed that there are relevant vaccination gaps among FPs and hospital staff. These vary by vaccine (measles, influenza, hepatitis B), by setting (hospital, private practice) and by target group (nurses, physicians). The majority of FPs claimed to actively recommend vaccines to patients. Of the psychological determinants, vaccine confidence was associated with FPs’ own vaccination status and recommendation behavior. Collective responsibility, constraints and complacency were associated with own vaccination status. Among hospitals staff, constraints and lack of confidence were the main reasons not to get vaccinated against influenza. Regarding the newly introduced measles vaccine mandate, 86% of physicians expressed being in favor of it. The attitude towards the mandate was associated with its projected consequences, e.g., believing that it will increase vaccination coverage. The higher physicians scored on confidence and collective responsibility and the lower on complacency and calculation, the stronger they were in favor of vaccine mandates. These findings have several policy implications. In hospital settings access to vaccines should be made more convenient. Private physicians were predominantly in favor of the newly implemented measles vaccine mandate. However, some reservations can be found, e.g., with regards to the effectiveness of such a mandate. The introduction of the mandate should be evaluated with regards to its outcomes. Furthermore, we found that psychological determinants for vaccination behavior and attitude towards vaccine mandates overlap. Hence, interventions addressing confidence, collective responsibility and complacency will both motivate vaccination behavior and foster a friendly reception of a mandate.Eine geringe Impfbereitschaft ist eine relevante Bedrohung für die weltweite Gesundheit. Die Gründe nicht zu impfen sind divers. Beschäftigte im Gesundheitswesen spielen eine zentrale Rolle als impfende Akteure und als Empfänger von Impfungen. Diese Dissertation hatte zum Ziel (i) hemmende und fördernde Faktoren für das Impfen bei Gesundheitspersonal in Deutschland zu untersuchen und (ii) Impflücken bei Gesundheitspersonal zu identifizieren. Weiterhin sollte untersucht werden, (iii) ob das Gesundheitspersonal Impfpflichten als Mittel zur Steigerung von Impfquoten positiv gegenübersteht. Es wurden Befragungsdaten von Hausärzt*innen, Krankenhauspersonal und Ärzt*innen der Primärversorgung erhoben. Die Impfquoten für verschiedene Impfungen und das Impfempfehlungsverhalten bei Gesundheitspersonal wurden erfragt. Weiterhin wurden psychologische Determinanten des Impfverhaltens und weitere Barrieren für das Impfen erfasst. In allen Studien wurden die Zusammenhänge zwischen den Prädiktoren und den Zielvariablen in linearen und logistischen Regressionsanalysen untersucht. Die Befragungsdaten zeigen, dass es relevante Impflücken bei Hausärzt*innen und Krankenhauspersonal gibt. Diese variieren je nach Impfung (Masern, Influenza, Hepatitis B), Umfeld (Krankenhaus, Arztpraxis) und Zielgruppe (Pflege, Ärzteschaft). Der Großteil der Hausärzt*innen empfiehlt den Patient*innen Impfungen aktiv. Von den psychologischen Determinanten des Impfverhaltens war das Vertrauen in die Impfung (Confidence) bei Hausärzt*innen mit dem eigenen Impfstatus und dem Empfehlungsverhalten assoziiert. Gemeinsinn (Collective Responsibility), praktische Barrieren (Constraints) und eine niedrige Risikowahrnehmung (Complacency) waren mit dem eigenen Impfstatus assoziiert. Bei Krankenhauspersonal waren praktische Barrieren und fehlendes Vertrauen die Hauptgründe, sich nicht gegen Influenza impfen zu lassen. 86% der Ärzt*innen befürworteten die neu eingeführte Masernimpfpflicht. Die Einstellung zur Impfpflicht war mit den erwarteten Konsequenzen assoziiert, bspw. der Überzeugung, die Impfquote würde dadurch steigen. Je größer Confidence und Collective Responsibility der Ärzt*innen, je höher die Risikowahrnehmung (niedrige Complacency) und je geringer das Bedürfnis nach Informationen und Abwägung (Calculation), umso mehr befürworteten die Befragten Impfpflichten. Die Ergebnisse haben strategische Implikationen. In Krankenhäusern sollte der Zugang zu Impfungen erleichtert werden. Ärzt*innen befürworten die neue Masernimpfpflicht überwiegend. Dennoch finden sich einige Bedenken, bspw. ob eine solche Impfpflicht ihr Ziel erreicht. Die Einführung der Masernimpfpflicht sollte in Bezug auf das Erreichen der Ziele evaluiert werden. Die psychologischen Determinanten sind sowohl für das Impfverhalten als auch die Einstellung zur Impfpflicht relevant. Daher können Interventionen, die Confidence, Collective Responsibility und Complacency adressieren, sowohl eigenes Impfverhalten motivieren als auch das Wohlwollen gegenüber einer neuen Impfpflicht erhöhen

A New Productivity Strategy for Europe. Bertelsmann Stiftung Inclusive Growth for Europe Policy Paper April 2020.

Europe has a productivity problem. In recent years, pro- ductivity growth in many European economies has sys- tematically slowed down and regional differences have widened. The slowdown is connected to decreasing com- petitiveness, fewer prospects for growth and shrinking opportunities for redistribution. Moreover, diverging changes in productivity within the EU endanger the eco- nomic and, ultimately, political stability of the common economic and monetary area. As a result of the current crisis situation, the productivity problem, which up to now has been of subordinate importance in politics, could pose particular challenges for economic policy. Economic policy measures must have a stimulating effect on the business cycle and at the same time always aim to increase productivity. What policies and instruments can reverse the trend and increase long-term productivity in Europe? This paper proposes nine points for a new productivity strategy in Europe. The main pillars of this strategy are: a substan- tially stronger innovation policy, the targeted promotion of technology diffusion and comprehensive, sustainable investments in the future

Engagement in an e-Health Tool (ORION) predicts opioid-dependent patient likelihood of behavioural change

Background: An eHealth computer-based tool named ORION was constructed to assist patients in the clinic to appreciate the factors responsible for risks of drug overdose. The aim of this study was to investigate the associations between risk perception of overdose, engagement in the ORION tool and willingness to alter overdose risk factors. Methods: 194 opioid dependent patients participated from 4 countries (UK, N=39; Germany, N=99; Italy, N=40 and Denmark, N=16).A structural equation model was fitted (AMOS version 17) to summarise the predicted associations between perceived risk and willingness to change risks of opioid overdose. The degree of engagement with the tool (time spent and number of changes to overdose risk factors) was explored. Results: A variety of models were fitted and the most parsimonious model provided a non-significant difference between the raw data and the specified model: Chi Sq = 16.87, df10, p = .077chi sq/df = 1.688. The fit indices: CFI = .991, RMSEA = .066. Pre and post self-assessments of risk towards known factors linked with overdose were highly correlated. A significant path was found between engagement in the tool and the willingness to change one or more risk factors (stand. coeff. = 0.16, p = .04). In addition, the final assessment of the risk factors was associated with engagement (stand. coeff. = 0.18, p = .02). Conclusion: The encouragement of drug users to engage in exploring changes to their overdose risk when presented on a computer screen appears to increase willingness to change risky behaviour.Publisher PDFPeer reviewe

Determinants of physician attitudes towards the new selective measles vaccine mandate in Germany

Background In Germany, a mandatory policy on measles vaccination came into effect in March 2020. Physicians, as the main vaccine providers, have a crucial role in implementing it. Mandatory vaccination changes the preconditions under which patient-provider communication on vaccines occurs. Physicians might or might not favor vaccine mandates depending on, among other factors, their attitudes towards vaccines and capabilities as vaccine providers. The aim of this study was to investigate in different subgroups of physicians the association between various factors and their attitudes towards a mandatory policy. Methods In total, 2229 physicians participated in a mixed-mode online/paper-pencil survey. Respondents were general practitioners, pediatricians, gynecologists, and internists. Primary determinants were the 5C psychological antecedents of vaccination, communication self-efficacy, patient clientele, projected consequences of the mandate and sociodemographic characteristics. Associations between outcomes and determinants were examined using linear regression analysis. Results Approximately 86% of physicians were in favor of the measles vaccine mandate for children. Regarding the 5C model, physicians were more in favor of vaccine mandates when they scored higher on confidence and collective responsibility, and lower on complacency and calculation. They were more in favor of vaccine mandates when they had higher communication self-efficacy and a more vaccine-positive patient clientele. Pediatricians were less in favor of mandates for children (80.0%) than other physician subgroups (87.1%). They were also less convinced that a mandate would result in more children getting vaccinated (59.3%) than other physician subgroups (78.3%). When controlled for these expected consequences, being a pediatrician no longer lowered the attitude towards the mandate. Conclusions Physicians in Germany are predominantly in favor of a measles vaccine mandate. Whether or not physicians believe the mandate to be effective in increasing vaccine coverage affects their attitude towards the mandate. In pediatricians, this belief explains their less positive attitude towards the mandate. In addition, physicians need adequate support to communicate well with patients, especially those who are hesitant, to booster their communication self-efficacy. To increase acceptance of vaccine mandates, the 5C model can be used, e.g., collective responsibility can be communicated, to avoid anger stemming from a negative attitude to mandates.Peer Reviewe

How a generally well-accepted measles vaccine mandate may lead to inequities and decreased vaccine uptake: a preregistered survey study in Germany

Additional file 1: Supplementary Figure 1. Directed acyclic graph (DAG) on hypothesis 2: Higher reactance to the measles mandate among parents decreases uptake of other vaccines and the intention to vaccinate children against other diseases. Supplementary  Table 1. ANCOVA results for socio-economic status (income) and for knowledge about the measles vaccine mandate and the measles vaccine. Supplementary Table 2. ANCOVA results for socio-economic status (education) and for knowledge about the measles vaccine mandate and the measles vaccine. Supplementary  Table 3. Parental vaccination decisions for vaccines that had just become due or were soon to come. Supplementary  Table 4. Relationship between reactance and vaccination behavior. Results from multiple logistic regression model with hexavalent and pneumococcal vaccination status as outcomes, reactance as predictor and the 5C model, age, gender, region and institutional trust included as covariates. Supplementary  Table 5. Relationship between reactance and vaccination intention. Results from multiple linear regression models with intention to get vaccinated against HPV, Tdap, Men C as outcomes, reactance as predictor and the 5C model, age, gender, region and institutional trust included as covariates. Supplementary  Table 6. Mediation analyses: Effect of institutional trust (X) on attitude towards the mandate (Y) via reactance (M)

Die Masernimpfpflicht – eine Erfolgsgeschichte?

Im November 2024 führte das Robert Koch-Institut (RKI) im Rahmen eines Forschungs¬projekts zur Evaluation der Masernimpfpflicht den Workshop „Die Masernimpfpflicht – eine Erfolgsgeschichte?“ durch. Anlass war die Frage, ob fünf Jahre nach Verabschie¬dung des Masernschutzgesetzes 2019 die Nachweis¬pflicht über die Masernimpfung als erfolgreiche Public-Health-Maßnahme gelten kann. Der Tagungsbericht im Epidemiologischen Bulletin 10/2025 beschreibt, wie gemeinsam mit Akteu¬rinnen und Akteuren aus dem Öffentlichem Gesund¬heitsdienst sowie aus Wissenschaft, Politik und Praxis an zwei Tagen Daten diskutiert, Erfahrungen ausgetauscht und in Gruppen Fragen zur Zukunft der Masernimpfpflicht bearbeitet wurden