• Epstein Alexander opublikował 1 rok, 8 miesięcy temu

    Metal sub-nanoclusters (SNCs) have shown great promise for a variety of catalytic reactions. However, the fabrication of stable metal SNCs simultaneously with high dispersion and high metal contents remains a challenge. Herein, we report a novel and versatile strategy for the synthesis of various bimetal SNCs stabilized within hierarchical porous carbons (HPC). This facile synthesis only involves the self-assembly of a metal-organic framework (MOF) as the precursor, a molten salt assisted pyrolysis process and the final metal replacement. The metal SNCs (mostly less than 0.8 nm) derived from the metal nodes of the MOF are exclusively confined and homogeneously dispersed throughout the organic ligands derived HPC at high loadings (up to 11.2 wt %). The obtained Cu-Pd@HPC composite exhibits superior catalytic activity and recycling durability in the selective transformation of furfural to maleic acid, achieving 97.8 % yield of maleic acid with a TOF value as high as 20.1 h-1 under mild conditions. DFT calculations reveal that the introduction of Pd shifts the partial density of states of Cu toward the Fermi level, leading to stronger chemisorption of furfural to enhance the catalytic activity.High-surface-area gold catalysts are promising catalysts for a number of selective oxidation and reduction reactions but typically suffer catalyst deactivation at higher temperatures. The major reason for catalyst deactivation is sintering, which can be triggered via two mechanisms particle migration and coalescence, and Ostwald ripening. Herein, a direct method to synthesize Au25 clusters stabilized with 3-mercaptopropyltrimethoxysilane (MPTS) ligands is discussed. The sintering of Au25 (MPTS)18 clusters on mesoporous silica (SBA-15) is monitored by using an environmental in situ transmission electron microscopy (TEM) technique. Results show that agglomeration of smaller particles is accelerated by increased mobility of particles during heat treatment, while growth of immobile particles occurs via diffusion of atomic species from smaller particles. The mobility of the Au clusters can be alleviated by fabricating overlayers of silica around the clusters. The resulting materials show tremendous sinter-resistance at temperatures up to 650 °C as shown by in situ TEM and extended X-ray absorption fine structure analysis.

    The purpose was to assess the effect of bilateral subthalamic nucleus deep brain stimulation (STN DBS) on diphasic dyskinesia in patients with Parkinson disease (PD) and to assess the factors associated with the remission of diphasic dyskinesia.

    Medical records for PD patients who underwent bilateral STN DBS at the Movement Disorder Center of Seoul National University Hospital from March 2005 to November 2016 were reviewed. Patients were evaluated preoperatively and at 3, 6 and 12months after surgery, and annually thereafter. The presence of peak-dose dyskinesia and diphasic dyskinesia is based on the interview and examination of patients at baseline and at each follow-up.

    Amongst 202 patients who underwent STN DBS, 66 patients who had diphasic dyskinesia preoperatively were included in the analysis. Diphasic dyskinesia disappeared in 49 (74%) after surgery. In 27 (55.1%) patients whose diphasic dyskinesia disappeared after DBS, peak-dose and diphasic dyskinesia disappeared persistently from as early as 3months postoperatively. Age at onset was younger and disease duration at surgery was longer in patients whose diphasic dyskinesia persisted compared with patients whose diphasic dyskinesia disappeared. Multivariate Cox regression analysis demonstrated that patients with greater postoperative decrease of dopaminergic medications were more likely to have remission of diphasic dyskinesia.

    This study showed that bilateral STN DBS is effective in controlling diphasic dyskinesia and should be considered in PD patients with diphasic dyskinesia.

    This study showed that bilateral STN DBS is effective in controlling diphasic dyskinesia and should be considered in PD patients with diphasic dyskinesia.

    To understand the lived experience of mothers surrounding the time of being informed of neonatal deaths in intensive care units.

    A phenomenological qualitative approach was employed.

    Twelve mothers (age 24-41 years) were identified from the neonatal mortality records of two large neonatal intensive care units with high neonate turnover rates in Amman, Jordan. Data were collected using semistructured interviews with the participants. Interpretive phenomenology was used to generate themes regarding the essence of the mother’s experience.

    Critical analyses of mothers’ accounts revealed three major themes (a) Minimize the hurt, which described how mothers intuited overprotection by their families while the news was conveyed indirectly to them; (b) The striking reality of death, which captured mothers’ distressing experiences while realizing the loss of their neonates; and (c) Farwell my baby, which accentuated mothers’ needs and experiences while neonates’ bodies were honored and prepared for burial per the cultural norms in Jordan.

    Our findings highlighted the complex dynamics of familial interactions and cultural influences on mothers’ bereavement experiences at the time of neonatal death. The grieving mothers expressed unfulfilled needs of receiving professional bereavement support at the time of neonatal death. Strategies are needed to optimize the supportive role of specialized nurses in providing family-centered bereavement care to mothers and their families who experience neonatal death.

    Our findings highlighted the complex dynamics of familial interactions and cultural influences on mothers’ bereavement experiences at the time of neonatal death. The grieving mothers expressed unfulfilled needs of receiving professional bereavement support at the time of neonatal death. Strategies are needed to optimize the supportive role of specialized nurses in providing family-centered bereavement care to mothers and their families who experience neonatal death.Multidimensional fabrication of metal-organic frameworks (MOFs) into multilevel channel integrated devices are in high demanded for Li-S separators. Such separators have advantages in pore-engineering that might fulfill requirements such as intercepting the diffusing polysulfides and improving the Li+ /electrolyte transfer in Li-S batteries. However, most reported works focus on the roles of MOFs as ionic sieves for polysulfides while offering limited investigation on the tuning of Li+ transfer across the separators. A photoinduced heat-assisted processing strategy is proposed to fabricate MOFs into multidimensional devices (e.g., hollow/Janus fibers, double-or triple-layer membranes). For the first time, a triple-layer separator with stepped-channels has been designed and demonstrated as a powerful separator with outstanding specific capacity (1365.0 mAh g-1 ) and cycling performance (0.03 % fading per cycle from 100th to 700th cycle), which is superior to single/double-layer and commercial separators. The findings may expedite the development of MOF-based membranes and extend the scope of MOFs in energy-storage technologies.Clioquinol has been reported to act as a potential therapy for neurodegenerative diseases and cancer. However, the underlying mechanism is unclear. We have previously reported that clioquinol induces S-phase cell cycle arrest through the elevation of calcium levels in human neurotypic SH-SY5Y cells. In this study, different types of cells were observed to detect if the effect of clioquinol on intracellular calcium levels is cell type-specific. The Cell Counting Kit-8 assay showed that clioquinol exhibited varying degrees of concentration-dependent cytotoxicity in different cell lines, and that the growth inhibition caused by it was not related to cell source or carcinogenesis. In addition, the inhibition of cell growth by clioquinol was positively associated with its effect on intracellular calcium content ([Ca2+ ]i ). Furthermore, the elevation of [Ca2+ ]i induced by clioquinol led to S-phase cell cycle arrest. Similar to our previous studies, the increase in [Ca2+ ]i was attributed to changes in the expression levels of the calcium pump SERCA2. Comparison of expression levels of SERCA2 between cell lines showed that cells with high levels of SERCA2 were more sensitive to clioquinol. In addition, analysis using UALCAN and the Human Protein Atlas also showed that the expression of SERCA2 in the corresponding human tissues was similar to that of the cells tested in this study, suggesting potential in the application of clioquinol in the future. In summary, our results expand the understanding of the molecular mechanism of clioquinol and provide an important strategy for the rational use of clioquinol.Silver nanoclusters (NCs) are of significant interest owing to their interesting structural, electronic, and catalytic properties. Among these NCs, Ag25 (SR)18 is particularly attractive due to its identical geometry as its Au counterpart, Au25 (SR)18 . Herein, the site-specific electronic properties of Ag25 (SR)18 and Au25 (SR)18 using X-ray spectroscopy experiments and quantum simulations are presented. To overcome the final state effect observed in X-ray photoelectron spectroscopy (XPS), a unique method is developed to reliably analyze the charge transfer behavior of the NCs. Density functional theory calculations are combined with XPS to provide more insight into the electronic properties of the NCs. The differences in the XPS valence bands of these two NCs are further compared and interpreted using the relativistic effect. The first derivative of the X-ray absorption near-edge structure (XANES) spectrum is further used as a tool to sensitively probe the bonding properties of Ag25 (SR)18 . By combining the experimental XANES data and their site-specific quantum simulations, the large impact of the staple motif on the bonding properties of the NC is demonstrated. These findings highlight the unique electronic properties of each atomic site in Ag25 (SR)18 ; the effective X-ray analysis techniques developed here can offer new opportunities for the site-specific study of other NCs.

    Career paths leading to department chair positions are elusive. Women represent only 11% of academic emergency department (ED) chairs. It is unclear whether the pathway to chair is different for men and women; the characteristics, achievements, and qualifications among those who become ED chairs is unknown.

    This study is a cross-sectional analysis of curriculum vitae (CV) of current ED chairs in departments with Accreditation Council for Graduate Medical Education (ACGME)-accredited residency programs. Former women chairs were included due to paucity of current women chairs. Statistics were calculated using bivariate and multivariate analysis.

    Of 163 eligible chairs, 88 CV (54%) were obtained, including six former women chairs. A majority (86.4%) self-identified as White/Caucasian, 21.5% were women, 46% were chief residents, 28.4% completed additional postgraduate degrees, and 21.8% were fellowship trained. At time of chair appointment, 58% were professor rank, 53.5% held ED operations roles, and 32% served as vice chair.

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