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Link between a prospective follow-up research following type Any aortic dissection repair: a high rate of distal aneurysmal advancement and reinterventions.
While the presence of sulfur⋅⋅⋅π bonding interaction is a general phenomenon in the biological systems, the exploitation of this noncovalent force in a chemical process yet remains elusive. Herein, we describe the concept of chalcogen⋅⋅⋅π bonding catalysis that activates molecules of π systems through the interaction between chalcogen and π-electron cloud. The proof-of-concept studies using a vinylindole-based Diels-Alder benchmark reaction demonstrate that S⋅⋅⋅π and Se⋅⋅⋅π bonding interaction can drive the cycloaddition reaction efficiently. Experimental results suggest that a simultaneously double Se⋅⋅⋅π bonding interaction directs the stereoselectivity in this cycloaddition process.In Germany, most care dependent people are looked after by family members at home. Professional support can help ease the burden of caring relatives and stabilise home care. Ideally, care then is provided through the co-production of formal and informal caregivers. This article analyses how care dependent people and their family caregivers integrate professional support into their care arrangements. An analysis was conducted using data collected for a qualitative study evaluating integrated local care centres in North-Rhine-Westphalia, Germany. The study is based on episodic interviews with users of these care centres and their family caregivers (N = 26). During the analysis, three interpretive and practice patterns relating to co-production of care were identified. These patterns reveal how the interviewees deal with (increasing) needs for assistance and care while incorporating professional care into their lives. The patterns help differentiate whether the interviewees (a) use developed care skills to contribute actively to the co-production with their layman knowledge, or (b) seek relief of their care responsibilities and withdraw temporarily from the direct sphere of care applying freed capacities to organise family daily life, or (c) use the services of the care centres to meet with other older people and to develop spaces for mutual help and co-production. The interpretive and practice patterns thus differ in the extent to which care users and family caregivers continue to play an 'active role' in the care process and contribute their own knowledge, ideas, expectations and particular care activities. In order to achieve a functioning co-production, professionals face the challenge of understanding these patterns that have been established over many years and of taking them into account appropriately.We present time-dependent density functional theory (TDDFT) calculations of the electronic optical rotation (ORP) for seven oxirane and two aziridine derivatives in the gas phase and in solution and compare the results with the available experimental values. For seven of the studied molecules it is the first time that their optical rotation was studied theoretically and we have therefore investigated the influence of several settings in the TDDFT calculations on the results. This includes the choice of the one-electron basis set, the exchange-correlation functional or the particular polarizable continuum model (PCM). We can confirm that polarized quadruple zeta basis sets augmented with diffuse functions are necessary for converged results and find that the aug-pc-3 basis set is a viable alternative to the frequently employed aug-cc-pVQZ basis set. Based on our study, we cannot recommend the generalized gradient functional KT3 for calculations of the ORP in these compounds, whereas the hybrid functional PBE0 gives results quite similar to the long-range correct CAM-B3LYP functional. Finally, we observe large differences in the solvent effects predicted by the integral equation formalism of PCM and the SMD variant of PCM. For the majority of solute/solvent combinations in this study, we find that the SMD model in combination with the PBE0 functional and the aug-pc-3 basis set gives the best agreement with the experimental values.Determining the temperature sensitivity of terrestrial carbon (C) stores is an urgent priority for predicting future climate feedbacks. A key aspect to solve this long-standing research gap is to determine whether warmer temperatures will increase autotrophic activities leading to greater C storage or promote heterotrophic activities that will drive these systems to become C sources. We experimentally addressed this critical question by subjecting intact plant-soil systems in a UK upland ecosystem to simulated climate warming under natural field conditions. Vadimezan We report the results of a 13-year field-based climate manipulation experiment combining in situ respiration measurements with radiocarbon (14 C) analyses of respired CO2 , dissolved organic carbon (DOC), soil and the tissue contents of the dominant soil fauna (enchytraeids). We found that warming during the growing season produced the largely expected increases in ecosystem respiration (63%) and leaching of DOC (19%) with no evidence for thermal acclimation or substrate exhaustion over the whole 13-year experimental period. Contrary to expectations, we found no evidence to support an increased release of old soil C after more than a decade of simulated climatic change, and indeed, 14 C analyses indicated that warming caused a significant shift towards mineralisation of more recent plant-derived C inputs. Further support came from the radiocarbon analyses of the enchytraeid tissues, which showed a greater assimilation of the more recent (plant-derived) C sources following warming. Therefore, in contrast to subarctic ecosystems, our results suggest that changes in C storage in this UK upland soil are strongly coupled to plant activities and that increasing temperatures will drive the turnover of organic material fixed only within recent years, without resulting in the loss of existing old carbon stores.Maternal internalizing symptoms have been linked with child internalizing symptoms, but paternal internalizing difficulties have received little attention. Our aims were to prospectively analyse the simultaneous effect of maternal and paternal internalizing symptoms on child internalizing difficulties, examining gender differences, and to verify the mediating effect of parenting practices and child irritability. The sample included 470 families assessed at child ages 3, 6, 8, and 11. Multi-group structural equation modelling was performed with Mplus8.2. Complete equivalence was found between boys and girls for all paths. Maternal internalizing symptoms at age 3 had an indirect effect on child internalizing symptoms at age 11, via irritability at age 8. Paternal internalizing symptoms at age 3 were not associated with any of the variables under study. Maternal internalizing symptoms and child irritability are targets for intervention in order to prevent child internalizing difficulties.
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