Modular Palladium Bipyrazoles for the Isomerization of Allylbenzenes - Mechanistic Considerations and Insights into Catalyst Design and Activity, Role of Solvent, and Additive Effects

The catalytic activity of novel bidentate N,N-chelated palladium complexes derived from electron excessive, backbone fused 3,3′-bipyrazoles in the selective isomerization of terminal arylpropenoids and 1-alkenes is described. The catalysts are easily modified by appropriate wing tip substitution, while maintaining the same bulky, rigid unreactive aliphatic backbone. Eleven novel palladium complexes with different electronic and steric properties were investigated. Their performance in the palladium(II)-catalyzed isomerization of a series of substituted allylbenzenes was evaluated in terms of electronic as well as steric effects. Besides the clear finding of a general trend towards higher catalyst activity with more electron-donating properties of the coordinated N,N-bidentate ligands, we found that the catalytic process strongly depends on the choice of solvents and additives. Extensive solvent screening revealed that reactions run best in a 2:1 toluene-methanol mixture, with the alcohol employed being a crucial factor in terms of electronic and steric factors. A reaction mechanism involving a hydride addition–elimination mechanism starting with a palladium hydride species generated in situ in alcoholic solutions, as corroborated by experiments using deuterium labeled allylbenzene, seems to be most likely. The proposed mechanism is also supported by the observed reaction rate orders of κobs[cat.]≈1 (0.94), κobs [substrate]=0.20→1.0 (t→∞) and κobs [methanol]=−0.51 for the isomerization of allylbenzene. Furthermore, the influence of acid and base, as well as the role of the halide coordinated to the catalyst, are discussed. The system catalyzes the isomerization of allylbenzenes very efficiently yielding high E:Z selectivities under very mild conditions (room temperature) and at low catalyst loadings of 1 mol% palladium even in unpurified solvents. The integrity and stability of the catalyst system were confirmed by multiple addition reaction cycles, successive filtration and isolation experiments, and the lack of palladium black formation

Association of regional socioeconomic deprivation and rurality with global developmental delay in early childhood: Data from mandatory school entry examinations in Germany

Background: From birth to young adulthood, health and development of young people are strongly linked to their living situation, including their family’s socioeconomic position (SEP) and living environment. The impact of regional characteristics on development in early childhood beyond family SEP has been rarely investigated. This study aimed to identify regional predictors of global developmental delay at school entry taking family SEP into consideration. Method: We used representative, population-based data from mandatory school entry examinations of the German federal state of Brandenburg in 2018/2019 with n=22,801 preschool children. By applying binary multilevel models, we hierarchically analyzed the effect of regional deprivation defined by the German Index of Socioeconomic Deprivation (GISD) and rurality operationalized as inverted population density of the children’s school district on global developmental delay (GDD) while adjusting for family SEP (low, medium and high). Results: Family SEP was significantly and strongly linked to GDD. Children with the highest family SEP showed a lower odds for GDD compared to a medium SEP (female: OR=4.26, male: OR=3.46) and low SEP (female: OR=16.58, male: OR=12.79). Furthermore, we discovered a smaller, but additional and independent effect of regional socioeconomic deprivation on GDD, with a higher odds for children from a more deprived school district (female: OR=1.35, male: OR=1.20). However, rurality did not show a significant link to GDD in preschool children beyond family SEP and regional deprivation. Conclusion: Family SEP and regional deprivation are risk factors for child development and of particular interest to promote health of children in early childhood and over the life course.Peer Reviewe

Health inequalities among young workers: the mediating role of working conditions and company characteristics

Objective Few studies have investigated health inequalities among young workers. The objectives of this study are to assess the extent of health inequalities in a sample of job starters and to explore the contribution of job demands and organisational factors. Methods We analyze data from the BIBB/BAuA Youth Employment Survey 2012. The cross-sectional survey includes a representative sample of 3214 German employees, apprentices, and trainees aged 15–24 years. Individuals were grouped by their years of schooling into low (< 12 years) and high levels of education (≥ 12 years). Regression analysis estimated the link between education and four health outcomes: self-rated health, number of health events, musculoskeletal symptoms, and mental health problems over the last 12 months. Counterfactual mediation analysis tested for indirect effects of educa- tion via working conditions (i.e., physical and psychosocial job demands) and company characteristics (i.e., company size, health prevention measures, financial situation, downsizing). All analyses were adjusted for age, sex, nationality, region, working hours, job tenure, employment relationship, and economic sector. Results Highly educated workers reported better self-rated health (b = 0.24, 95% CI 0.18–0.31) and lower numbers of health events (Rate Ratio (RR) = 0.74, 95% CI 0.67–0.82), musculoskeletal symptoms (RR = 0.73, 95% CI 0.66–0.80) and mental health problems (RR = 0.84, 95% CI 0.76–0.93). Total job demands explained between 21.6% and 87.2% of the educational differences (depending on health outcome). Unfavourable company characteristics were associated with worse health, but showed no or only small mediation effects. Conclusions Health inequalities are already present at the early working career due to socio-economically stratified working hazards. To enhance prevention measures that aim at reducing inequalities in workplace health, we propose shifting attention towards earlier stages of life.Peer Reviewe

Bulky and Modular 3,3′-Bipyrazoles as Ligands: Synthesis, Characterization, and Catalytic Activity of Pd Complexes

In the present study, the properties of a new bidentate N,N′-chelating ligand class that bears an electron-excessive 3,3′-bipyrazole core have been investigated. The ligands are easily accessible in a three-step procedure by condensation with diethyl oxalate followed by tandem condensation with hydrazine hydrate and finally by aryl- or alkylation exclusively at the N-1,1′-pyrazole positions to furnish overall eleven new ligands with different electronic properties. After structural analysis of the ligands, their coordination to palladium, copper, and cobalt has been studied. These ligands coordinate the 2,2′-pyrazolyl nitrogen atoms in a bidentate fashion to the metals to realize complexes with an (L)MX2 motif. We present two crystal structures of Pd and Cu complexes, which to the best of our knowledge represent the first d8 and d9 2,2′-bipyrazole compounds coordinated through bidentate complexation. Initial catalytic experiments have been performed with palladium complexes with three bipyrazole ligands of this new class; the palladium-catalyzed copper-free Wacker oxidation of different alkenes showed superior activity compared to 2,2′-bipyridines. We attribute this to a higher redox potential of the 3,3′-bipyrazoles, which are ― besides electronic effects ― also strongly influenced by steric effects. These might be enforced by the extended ligand backbone, the choice of the wingtip substitution, and the smaller coordination cavity within the N2,N2′ atoms compared to 2,2′-bipyridine ligands

Nova estratègia diagnòstica per la Tuberculosi : sí, però amb matisos

La realització de nous tests per diagnosticar la Infecció Latent per M.tuberculosi (ITBL), els TIGRAs, basats en la detecció d'una citosina relacionada amb la Resposta Immunològica Cel·lular que es desencadena contra el bacil tuberculós, sembla aportar noves llums al tractament de la infecció: són més sensibles i específics que el tractament estàndard de la Tuberculina (TST). Tot i així, encara es desconeix si la seva utilització posterior a un TST influeix en els resultats finals. Per això, i per ampliar aquesta línia d'investigació, un estudi de seguiment immunològic, dut a terme a la Unitat de Tuberculosi Experimental de l'hospital "Germans Trias i Pujol", ha obtingut uns resultats que demostren la necessitat d'aprofundir sobre aquest tema, malgrat alguns països valoren la possibilitat d'utilitzar-los seqüencialment

Moderating or mediating effects of family characteristics on socioeconomic inequalities in child health in high-income countries – a scoping review

Background: By explaining the development of health inequalities, eco-social theories highlight the importance of social environments that children are embedded in. The most important environment during early childhood is the family, as it profoundly influences children’s health through various characteristics. These include family processes, family structure/size, and living conditions, and are closely linked to the socioeconomic position (SEP) of the family. Although it is known that the SEP contributes to health inequalities in early childhood, the effects of family characteristics on health inequalities remain unclear. The objective of this scoping review is to synthesise existing research on the mediating and moderating effects of family characteristics on socioeconomic health inequalities (HI) during early childhood in high-income countries. Methods: This review followed the methodology of “Preferred Reporting Items for Systematic reviews and Meta-Analyses extension for Scoping Reviews”. To identify German and English scientific peer-reviewed literature published from January 1st, 2000, to December 19th, 2019, the following search term blocks were linked with the logical operator “AND”: (1) family structure/size, processes, living conditions, (2) inequalities, disparities, diversities, (3) income, education, occupation, (4) health and (5) young children. The search covered the electronic databases PubMed, PsycINFO, and Scopus. Results: The search yielded 7,089 records. After title/abstract and full-text screening, only ten peer-reviewed articles were included in the synthesis, which analysed the effects of family characteristics on HI in early childhood. Family processes (i.e., rules /descriptive norms, stress, parental screen time, parent–child conflicts) are identified to have mediating or moderating effects. While families’ living conditions (i.e., TVs in children’s bedrooms) are suggested as mediating factors, family structure/size (i.e., single parenthood, number of children in the household) appear to moderate health inequalities. Conclusion: Family characteristics contribute to health inequalities in early childhood. The results provide overall support of models of family stress and family investment. However, knowledge gaps remain regarding the role of family health literacy, regarding a wide range of children’s health outcomes (e.g., oral health, inflammation parameters, weight, and height), and the development of health inequalities over the life course starting at birth.Peer Reviewe

Self-rated health of university students in Germany–The importance of material, psychosocial, and behavioral factors and the parental socio-economic status

Introduction Health inequalities start early in life. The time of young adulthood, between late teens and early twenties, is especially interesting in this regard. This time of emerging adulthood, the transition from being a child to becoming an adult, is characterized by the detachment from parents and establishing of an own independent life. From a health inequality perspective, the question about the importance of the socio-economic background of parents is important. University students are an especially interesting group. Many students come from a privileged background and the question of health inequality among university students has not yet been properly studied. Methods Based on the National Educational Panel Study (NEPS), we analyzed health inequalities among 9,000 students in Germany (∅ 20 years in the first year of their studies) over a period of 8 years. Results We found that most university students (92%) in Germany reported a good and very good health. Yet, we still found substantial health inequalities. Students whose parents had a higher occupational status reported less health problems. Additionally, we observed that health inequalities had indirect impact on health via health behavior, psychosocial resources, and material conditions. Discussion We believe our study is an important contribution to the understudied subject of students' health. We see the impact of social inequality on health among such a privileged group like university students as an important sign of the importance of health inequality

Stillbirth differences according to regions of origin: an analysis of the German perinatal database, 2004-2007

Reeske A, Kutschmann M, Razum O, Spallek J. Stillbirth differences according to regions of origin: an analysis of the German perinatal database, 2004-2007. BMC Pregnancy and Childbirth. 2011;11(1): 63.Background: Stillbirth is a sensitive indicator for access to, and quality of health care and social services in a society. If a particular population group e. g. migrants experiences higher rates of stillbirth, this might be an indication of social deprivation or barriers to health care. This study examines differences in risk of stillbirth for women of different regions of origin compared to women from Germany in order to identify high risk groups/target groups for prevention strategies. Methods: We used the BQS dataset routinely compiled to examine perinatal outcomes in Germany nationwide. Participation of hospitals and completeness of data has been about 98% in recent years. Data on all live births and stillbirths were obtained for the period 2004 to 2007 (N = 2,670,048). We calculated crude and stratified mortality rates as well as corresponding relative mortality risks. Results: A significantly elevated stillbirth rate was found for women from the Middle East and North Africa (incl. Turkey) (RR 1.34, CI 1.22-1.55). The risk was slightly attenuated for low SES. An elevated risk was also found for women from Asia (RR 1.18, CI 1.02-1.65) and from Mediterranean countries (RR 1.14, CI 0.93-1.28). No considerable differences either in use and timing of antenatal care or preterm birth and low birthweight were observed between migrant and non-migrant women. After stratification for light for gestational age, the relative risk of stillbirth for women from the Middle East/North Africa increased to 1.63 (95% CI 1.25-2.13). When adjusted for preterm births with low birthweight, women from Eastern Europe and the Middle East/North Africa experienced a 26% (43%) higher risk compared with women from Germany. Conclusions: We found differences in risk of stillbirth among women from Middle East/North Africa, especially in association with low SES and low birthweight for gestational age. Our findings suggest a need for developing and evaluating socially and culturally sensitive health promotion and prevention programmes for this group. The findings should also stimulate discussion about the quality and appropriateness of antenatal and perinatal care of pregnant women and newborns with migrant backgrounds