Core Precession and Global Modes in Granular Bulk Flow

A transition from local to global shear zones is reported for granular flows in a modified Couette cell. The experimental geometry is a slowly rotating drum which has a stationary disc of radius R_s fixed at its bottom. Granular material, which fills this cell up to height H, forms a wide shear zone which emanates from the discontinuity at the stationary discs edge. For shallow layers (H/R_s < 0.55), the shear zone reaches the free surface, with the core of the material resting on the disc and remaining stationary. In contrast, for deep layers (H/R_s > 0.55), the shear zones meet below the surface and the core starts to precess. A change in the symmetry of the surface velocities reveals that this behavior is associated with a transition from a local to a global shear mode.Comment: 4 pages, 7 figures, submitte

Low-dimensional hybrid perovskites containing an organic cation with an extended conjugated system : tuning the excitonic absorption features

Low-dimensional hybrid perovskites are receiving increased attention. One of the advantages of the low-dimensional hybrids over their 3D counterparts is their greater structural flexibility towards the incorporation of bigger, more complex, organic cations. In this communication, we introduce a pyrene derivative as an organic cation containing an extended pi-system for use in a variety of low-dimensional hybrids. We show that materials with different excitonic absorption features can be obtained by tuning the iodide/lead ratio in the precursor solutions, using the same pyrene cation. In this way, hybrids with optical characteristics corresponding to 2D, 1D and 0D hybrid perovskites are obtained. The formation and thermal stability of the different hybrids is analysed and compared

The elusive seven-membered cyclic imino ether tetrahydrooxazepine

Cyclic imino ether heterocycles are used as ligands in transition metal catalysis, in various drugs and as reactive monomers in living cationic ring-opening polymerization (CROP). While five- and six-membered cyclic imino ethers, i.e. 2-oxazolines and 4,S-dihydro-1,3-oxazines, have extensively been studied in these areas, their seven-membered ring counterparts have remained unexplored. Herein, we report the synthesis of 2-phenyl-4,5,6,7-tetrahydro-1,3-oxazepine allowing reassignment of the earlier, incorrectly reported 4,5,6,7-tetrahydro-1,3-oxazepines as their N-acylated pyrrolidine isomers. Finally, we also report a comparison of the CROP reactivity of a homologous series of cyclic imino ethers with a 2-carbon, 3-carbon, and 4-carbon methylene bridge, revealing a remarkable ring size effect

Direct regio- and diastereoselective diphosphonylation of cyclic enamines : one-pot synthesis of α,α′-bis(diphenylphosphoryl)- and α,α′-bis(diphenylphosphorothioyl)cycloalkanones

A straightforward regio- and diastereoselective process has been developed for the synthesis of unprecedented symmetrical trans-alpha,alpha '-bis(diphenylphosphoryl)- and alpha,alpha '-bis(diphenylphosphorothioyl)cycloalkanones, through the reaction of cyclic enamines with excess P-chlorodiphenylphosphine in the presence of triethylamine, followed by oxidation or sulfurization and hydrolytic workup

Universal and wide shear zones in granular bulk flow

We present experiments on slow granular flows in a modified (split-bottomed) Couette geometry in which wide and tunable shear zones are created away from the sidewalls. For increasing layer heights, the zones grow wider (apparently without bound) and evolve towards the inner cylinder according to a simple, particle-independent scaling law. After rescaling, the velocity profiles across the zones fall onto a universal master curve given by an error function. We study the shear zones also inside the material as function of both their local height and the total layer height.Comment: Minor corrections, accepted for PRL (4 pages, 6 figures

Preparation of 4 '-spirocyclobutyl nucleoside analogues as novel and versatile adenosine scaffolds

Despite the large variety of modified nucleosides that have been reported, the preparation of constrained 4 '-spirocyclic adenosine analogues has received very little attention. We discovered that the [2+2]-cycloaddition of dichloroketene on readily available 4 '-exo-methylene furanose sugars efficiently results in the diastereoselective formation of novel 4 '-spirocyclobutanones. The reaction mechanism was investigated via density functional theory (DFT) and found to proceed either via a non-synchronous or stepwise reaction sequence, controlled by the stereochemistry at the 3 '-position of the sugar substrate. The obtained dichlorocyclobutanones were converted into nucleoside analogues, providing access to a novel class of chiral 4 '-spirocyclobutyl adenosine mimetics in eight steps from commercially available sugars. Assessment of the biological activity of designed 4 '-spirocyclic adenosine analogues identified potent inhibitors for protein methyltransferase target PRMT5

The working alliance with people experiencing suicidal ideation : a qualitative study of nurses’ perspectives

Aims: This study aimed to enhance the conceptual understanding of the working alliance in the context of nursing care for people experiencing suicidal ideation. Design: A qualitative study based on grounded theory was conducted. Methods: Two authors conducted individual semi-structured interviews from September 2017-January 2019. Twenty-eight nurses in 13 wards of four psychiatric hospitals participated. The Qualitative Analysis Guide of Leuven was used to support constant data comparisons and the cyclic processes of data collection and data analysis. Findings: The nurses' perspectives revealed that the working alliance can be understood as an interpersonal and collaborative relational process. This relational process highlighted the core variable 'seeking connectedness and attunement with the person at risk of suicide'. The core variable underpinned three clusters: investing in the foundations of the working alliance, nourishing the clinical dimension of the working alliance and realizing an impact with the working alliance. Conclusion: This study highlights the importance for nurses to assess, evaluate and respond to persons' suicidal ideation in harmony with a commitment to connect with them and attune to their perspective. Impact: The relational process uncovered through this study offers valuable insights to support advanced nursing practice, where nurses meaningfully integrate relational elements of care with their contributions to suicide prevention and treatment

The evaluation of equine allogeneic tenogenic primed mesenchymal stem cells in a surgically induced superficial digital flexor tendon lesion model

Background: Tendon injuries are very common in horses and jeopardize the athletic performance, and due to the high risk of reinjury may lead to early retirement. The use of mesenchymal stem cells for the treatment of equine tendon disease is widely investigated because of their regenerative potential. The objective of this study is to investigate the safety and efficacy of equine allogeneic tenogenic primed mesenchymal stem cells (tpMSCs) for the management of tendinitis in horses. Methods: A core lesion was surgically induced in the superficial digital flexor tendon of both forelimbs of eight horses. After 7 days, one forelimb was treated with tpMSCs, while the contralateral forelimb served as an intra-individual control and was treated with saline. A prescribed exercise program was started. All horses underwent a daily clinical evaluation throughout the entire study period of 112 days. Blood samples were taken at different time points for hematological and biochemical analysis. Tendon assessment, lameness examination, ultrasound assessment and ultrasound tissue characterization (UTC) were performed at regular time intervals. At the end of the study period, the superficial digital flexor tendons were evaluated macroscopically and histologically. Results: No suspected or serious adverse events occurred during the entire study period. There was no difference in local effects including heat and pain to pressure between a single intralesional injection of allogeneic tpMSCs and a single intralesional injection with saline. A transient moderate local swelling was noted in the tpMSC treated limbs, which dissipated by day 11. Starting at a different time point depending on the parameter, a significant improvement was observed in the tpMSC treated limbs compared to the placebo for echogenicity score, fiber alignment score, anterior-posterior thickness of the tendon and echo type by UTC assessment. Immunohistochemistry 112 days post-injection revealed that the amount of collagen type I and Von Willebrand factor were significantly higher in the tendon tissue of the tpMSC group, while the amount of collagen type III and smooth muscle actin was significantly lower. Conclusion: Equine allogeneic tenogenic primed mesenchymal stem cells were shown to be well-tolerated and may be effective for the management of tendon injuries

A feasibility study on the use of equine chondrogenic induced mesenchymal stem cells as a treatment for natural occurring osteoarthritis in dogs

Conventional treatments of osteoarthritis (OA) reduce pain and the inflammatory response but do not repair the damaged cartilage. Xenogeneic peripheral blood-derived equine chondrogenically induced mesenchymal stem cells (ciMSC) could thus provide an interesting alternative. Six client-owned dogs with confirmed elbow OA were subjected to a baseline orthopedic examination, pressure plate analysis, general clinical examination, hematological analysis, synovial fluid sampling, and radiographic examination, and their owners completed two surveys. After all examinations, a 0.9% saline solution (placebo control product=CP) was administered intra-articularly. After 6 weeks, all examinations were repeated, owners again completed two surveys, and equine ciMSCs were administered in the same joint. After another 6 weeks, dogs were returned for a final follow-up. No serious adverse events or suspected adverse drug reactions were present during this study. No significant differences in blood analysis were noted between the CP and ciMSC treatment. Two adverse events were observed, both in the same dog, one after CP treatment and one after ciMSC treatment. The owner surveys revealed significantly less pain and lameness after ciMSC treatment compared to after CP treatment. There was no significant difference in the orthopedic examination parameters, the radiographic examination, synovial fluid sampling, and pressure plate analysis between CP treatment and ciMSC treatment. A single intra-articular administration of equine ciMSCs proved to be a well-tolerated treatment, which reduced lameness and pain according to the owner's evaluations compared to a placebo treatment