Model-based design of MADIX under bulk and solution conditions

Macromolecular design by interchange of xanthates (MADIX) is a less studied controlled radical polymerization technique from a mechanistic and modeling point of view. In this contribution, MADIX of styrene and chain extension toward the synthesis of block copolymers is investigated, with azobisisobutyronitrile as conventional radical initiator and O-ethylxanthyl ethyl propionate as initial RAFT agent (R0X). Degenerative transfer coefficients for both the exchange with R0X and macro-RAFT agent are reported and their difference is highlighted to be relevant for the kinetic description. The model validity is supported by measurement of end-group functionality (EGF) data considering elemental analysis. Novel mechanistic insights are that in contrast to typical reversible addition fragmentation chain transfer (RAFT) polymerizations the macroradical CLD follows a Schulz-Flory distribution and that both during the homopolymerization and the chain extensions an exchange, so with monomer incorporation, only takes place once [1]. [1] D.J.G. Devlaminck, P.H.M. Van Steenberge, M.-F. Reyniers, D.R. D’hooge, Polym Chem. 2017, 8, 694

The interface penny-shaped crack reconsidered

The penny-shaped crack at the interface between two bonded dissimilar media is reconsidered on the basis of recent developments on the elimination of oscillatory singularities. This is accomplished by assuming an annular frictionless contact zone at the crack circumference and reducing the problem to a Fredholm integral equation. Expressions for the strain energy, crack opening force and bond stresses are obtained and numerical results given for specific material combinations.Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/22767/1/0000322.pd

Biomarkers to assess right heart pressures in recipients of a heart transplant: a proof-of-concept study

Background: This proof-of-concept study investigated the feasibility of using biomarkers to monitor right heart pressures (RHP) in heart transplanted (HTx) patients. Methods: In 298 patients, we measured 7.6 years post-HTx mean pressures in the right atrium (mRAP) and pulmonary artery (mPAP) and capillaries (mPCWP) along with plasma high-sensitivity troponin T (hsTnT), a marker of cardiomyocyte injury, and the multidimensional urinary classifiers HF1 and HF2, mainly consisting of dysregulated collagen fragments. Results: In multivariable models, mRAP and mPAP increased with hsTnT (per 1-SD, +0.91 and +1.26 mm Hg; P < 0.0001) and with HF2 (+0.42 and +0.62 mm Hg; P ≤ 0.035), but not with HF1. mPCWP increased with hsTnT (+1.16 mm Hg; P < 0.0001), but not with HF1 or HF2. The adjusted odds ratios for having elevated RHP (mRAP, mPAP or mPCWP ≥10, ≥24, ≥17 mm Hg, respectively) were 1.99 for hsTnT and 1.56 for HF2 (P ≤ 0.005). In detecting elevated RHPs, areas under the curve were similar for hsTnT and HF2 (0.63 vs 0.65; P = 0.66). Adding hsTnT continuous or per threshold or HF2 continuous to a basic model including all covariables did not increase diagnostic accuracy (P ≥ 0.11), whereas adding HF2 per optimized threshold increased both the integrated discrimination (+1.92%; P = 0.023) and net reclassification (+30.3%; P = 0.010) improvement. Conclusions: Correlating RHPs with noninvasive biomarkers in HTx patients is feasible. However, further refinement and validation of such biomarkers is required before their clinical application can be considered

God\u27s Church Is Just: A Specific Discussion Of Some Cases of Church Discipline

https://digitalcommons.acu.edu/crs_books/1364/thumbnail.jp

The influence of distributed leadership on teachers' organizational commitment: a multilevel approach

In the present study the effects of a cooperative leadership team, distributed leadership, participative decision-making, and context variables on teachers' organizational commitment are investigated. Multilevel analyses on data from 1522 teachers indicated that 9% of the variance in teachers' organizational commitment is attributable to differences between schools. The analyses revealed that especially the presence of a cooperative leadership team and the amount of leadership support played a significantly positive key role in predicting teachers' organizational commitment. Also, participative decision-making and distribution of the supportive leadership function had a significant positive impact on teachers' organizational commitment. In contrast, distribution of the supervisory leadership function and teachers' job experience had a significant negative impact

Influence of subunit structure on the oligomerization state of light harvesting complexes: a free energy calculation study

Light harvesting complexes 2 (LH2) from Rhodospirillum (Rs.) molischianum and Rhodopseudomonas (Rps.) acidophila form ring complexes out of eight or nine identical subunits, respectively. Here, we investigate computationally what factors govern the different ring sizes. Starting from the crystal structure geometries, we embed two subunits of each species into their native lipid-bilayer/water environment. Using molecular dynamics simulations with umbrella sampling and steered molecular dynamics, we probe the free energy profiles along two reaction coordinates, the angle and the distance between two subunits. We find that two subunits prefer to arrange at distinctly different angles, depending on the species, at about 42.5 deg for Rs. molischianum and at about 38.5 deg for Rps. acidophila, which is likely to be an important factor contributing to the assembly into different ring sizes. Our calculations suggest a key role of surface contacts within the transmembrane domain in constraining these angles, whereas the strongest interactions stabilizing the subunit dimers are found in the C-, and to a lesser extent, N-terminal domains. The presented computational approach provides a promising starting point to investigate the factors contributing to the assembly of protein complexes, in particular if combined with modeling of genetic variants.Comment: 28 pages, 7 figures, LaTeX2e - requires elsart.cls (included), submitted to Chemical Physic

The relation between school leadership from a distributed perspective and teachers' organizational commitment: examining the source of the leadership function

Purpose: In this study the relationship between school leadership and teachers’ organizational commitment is examined by taking into account a distributed leadership perspective. The relation between teachers’ organizational commitment and contextual variables of teachers’ perceptions of the quality and the source of the supportive and supervisory leadership function, participative decision making, and cooperation within the leadership team are examined. Research Design: A survey was set up involving 1,522 teachers from 46 large secondary schools in Flanders (Belgium). Because the data in the present study have an inherent hierarchical structure, that is, teachers are nested into schools, hierarchical linear modeling techniques are applied. Findings: The analyses reveal that 9% of the variance in teachers’ organizational commitment is attributable to differences between schools. Teachers’ organizational commitment is mainly related to quality of the supportive leadership, cooperation within the leadership team, and participative decision making. Who performed the supportive leadership function plays only a marginally significant positive role. The quality of the supervisory leadership function and the role of the leadership team members in this function were not significantly related to teachers’ organizational commitment. Conclusions: The implications of the findings are that to promote teachers’ organizational commitment teachers should feel supported by their leadership team and that this leadership team should be characterized by group cohesion, role clarity, and goal orientedness. Recommendations for further research are provided