Krogsgaardlott0082

Reversible addition-fragmentation chain transfer (RAFT) dispersion polymerization of benzyl methacrylate is used to prepare a series of well-defined poly(stearyl methacrylate)-poly(benzyl methacrylate) (PSMA-PBzMA) diblock copolymer nanoparticles in mineral oil at 90 °C. A relatively long PSMA54 precursor acts as a steric stabilizer block and also ensures that only kinetically trapped spheres are obtained, regardless of the target degree of polymerization (DP) for the core-forming PBzMA block. This polymerization-induced self-assembly (PISA) formulation provides good control over the particle size distribution over a wide size range (24-459 nm diameter). 1H NMR spectroscopy studies confirm that high monomer conversions (≥96%) are obtained for all PISA syntheses while transmission electron microscopy and dynamic light scattering analyses show well-defined spheres with a power-law relationship between the target PBzMA DP and the mean particle diameter. Gel permeation chromatography studies indicate a gradual loss of control over the molecular weight distribution as higher DPs are targeted, but well-defined morphologies and narrow particle size distributions can be obtained for PBzMA DPs up to 3500, which corresponds to an upper particle size limit of 459 nm. Thus, these are among the largest well-defined spheres with reasonably narrow size distributions (standard deviation ≤20%) produced by any PISA formulation. Such large spheres serve as model sterically stabilized particles for analytical centrifugation studies.Microbial transformations of two tetracyclic beyerane-type diterpenes, ent-16β-oxobeyeran-19-oic acid (1) and its chemical reduction product, ent-16β-hydroxybeyeran-19-oic acid (2), by the filamentous fungus Cunninghamella echinulata ATCC 8688a yielded eight metabolites (3-10). Incubation of the substrate 2 with C. selleckchem echinulata afforded three new hydroxylated ones (3-5) along with two known ones (6-7), while incubation of 1 gave three known ones (8-10). The new compounds were characterized by 1D and 2D NMR as well as HRESIMS analysis, and the stereostructures of 3 and 4 were confirmed by X-ray crystallography. The bio-reactions were involved not only in stereoselective incorporation of hydroxyl groups at inert positions C-7, -9, -12, and -14 of the two beyerane diterpenes but also in glucosidation at C-19 of 2. This is the first report on the biotransformation of the diterpenes by using C. echinulata. All compounds were assayed for their α-glucosidase inhibitory, neurotrophic, anti-inflammatory, and phytotoxic activity, and only in neurotrophic assay compounds 2 and 9 were found to display NGF-mediated neurite-outgrowth promoting effects in PC12 cells; the others were inactive.The hydroazidation of alkynes is the most straightforward way to access vinyl azides-versatile building blocks in organic synthesis. We previously realized such a fundamental reaction of terminal alkynes using Ag2CO3 as a catalyst. However, the high catalyst loading seriously limits its practicality, and moreover, the exact reaction mechanism remains unclear. Here, on the basis of X-ray diffraction studies on the conversion of silver salts, we report the identification of AgN3 as the real catalytic species in this reaction and developed a AgN3-catalyzed hydroazidation of terminal alkynes. AgN3 proved to be a highly robust catalyst, as the loading of AgN3 could be as low as 5 mol %, and such a small proportion of AgN3 is still highly efficient even at a 50 mmol reaction scale. Further, the combination of experimental investigations and theoretical calculations disclosed that the concerted addition mechanism via a six-membered transition state is more favored than the classical silver acetylide mechanism.Nature provides various exquisite photonic structures of antireflection. Here, we investigate the color and structure of the inner surface of the shell edge (ISSE) of blue mussel shells, using a fiber optical spectrometer, scanning electron microscope (SEM), and X-ray diffraction (XRD). We demonstrate that the structurally assisted black color of the ISSE is produced by a pyramidal microstructure. Furthermore, we use the two-step biotemplate (TSBT) method to successfully replicate this microstructure. Particularly, we modify this method by using a poly(vinyl alcohol) (PVA) film as the negative replica and an epoxy resin film as the positive replica both fabricated without vacuum treatment. We show that the natural and replicated structures show a reflectivity of ∼4% and of ∼3% in the visible wavelength. Finally, we hope our investigation can provide basic data for the study of the bioinspired antireflective structures, which have a promising application in smart windows and optical devices.A novel porous organic cage (POC) was prepared via condensation reaction between 1,3,5-triformylbenzene (TFB) and (1R,2R)-4-cyclohexene-1,2-diamine (CHEDA). This POC could pack in either an amorphous structure or a crystalline one. Atomically precise structure determination of POC was achieved through ab initio powder X-ray diffraction (PXRD) structure analysis in the chiral trigonal space group R3. The same atomically precise structure determination of POC from single-crystal X-ray diffraction (SXRD) structure analysis could be obtained independently with a slight difference in cell parameter, indicating that the refinement method through ab initio PXRD structure analysis is reliable and may serve as an essential method for atomically precise structure determination. The cage could adsorb up to 8 mmol/g CO2 at 298 K and 1 bar. Furthermore, 1-thioglycerol and 1-octadecanethiol were chosen to prove that postmodification of this POC was flexible. After post-synthetic modification (PSM) via highly efficient photoinitiated thiol-ene click reaction, the products still kept porous with relatively higher special surface area (337 m2/g of 5T and 156 m2/g of 5O) than mostly reported cages via the reduced-amine approach.Droplet jumping phenomenon widely exists in the fields of self-cleaning, antifrosting, and heat transfer enhancement. Numerous studies have been reported on the static droplet jumping while the rolling droplet jumping still remains unnoticed even though it is very common in practice. Here, we used the volume of fluid (VOF) method to simulate the droplet jumping induced by coalescence of a rolling droplet and a stationary one with corresponding experiments conducted to validate the correctness of the simulation model. The departure velocity of the jumping droplet was the main concerned here. The results show that when the center velocity of the rolling droplet (V0 = ωR, where ω is the angular velocity of the rolling droplet and R is the droplet radius) is fixed, the vertical departure velocity satisfies a power law which can be expressed as Vz,depar = aRb. When the droplet radius is fixed, the vertical departure velocity first decreases and then increases if the center velocity exceeds a critical value. Interestingly, the critical center velocity is demonstrated to be approximately 0.76 times the capillary-inertial velocity, corresponding to a constant Weber number of 0.58. Different from the vertical departure velocity, the horizontal departure velocity is basically proportional to the center velocity of the rolling droplet. These results deepen the understanding of the droplet jumping physics, which shall further promote related applications in engineering fields.Carbon-fiber microelectrodes are instrumental tools in neuroscience used for the electroanalysis of neurochemical dynamics and recordings of neural activity. However, performance is variable and dependent on fabrication strategies, the biological response to implantation, and the physical and chemical composition of the recording environment. This presents an analytical challenge, as electrode performance is difficult to quantitatively assess in situ, especially when electrodes are permanently implanted or cemented in place. We previously reported that electrode impedance directly impacts electrochemical performance for molecular sensing. In this work, we investigate the impacts of individual components of the electrochemical system on impedance. Equivalent circuit models for glass- and silica-insulated carbon-fiber microelectrodes were determined using electrochemical impedance spectroscopy (EIS). The models were validated based on the ability to assign individual circuit elements to physical properties of the electrochemical system. Investigations were performed to evaluate the utility of the models in providing feedback on how changes in ionic strength and carbon fiber material alter impedance properties. Finally, EIS measurements were used to investigate the electrode/solution interface prior to, during, and following implantation in live brain tissue. A significant increase in impedance and decrease in capacitance occur during tissue exposure and persist following implantation. Electrochemical conditioning, which occurs continually during fast-scan cyclic voltammetry recordings, etches and renews the carbon surface, mitigating these effects. Overall, the results establish EIS as a powerful method for characterization of carbon-fiber microelectrodes, providing unprecedented insight into how real-world factors affect the electrode/solution interface.in English, French Contexte Les appels au personnel interne par téléavertisseur, surtout la nuit, perturbent le sommeil et entraînent de la fatigue le lendemain. Même si certains de ces appels sont urgents, d’autres ne nécessitent pas de réponse immédiate. Avec cette étude nous avons voulu identifier les appels par téléavertisseur qui sont injustifiés et trouver des façons d’en réduire le nombre. Méthodes Sur une période 2 mois, nous avons documenté tous les appels par téléavertisseur adressés durant les heures de garde au service d’urologie pédiatrique de l’Hôpital SickKids de Toronto, au Canada, et demandé aux médecins y ayant répondu d’en évaluer le bien-fondé au plan médical. Après avoir analysé les raisons des appels jugés injustifiés, nous avons adopté plusieurs mesures pour en réduire le nombre sans compromettre les soins. Un an plus tard, nous avons de nouveau comptabilisé les appels par téléavertisseur pour mesurer l’efficacité de nos interventions. Résultats Durant la période de mesure initiale, auces soins et la sécurité des patients, les raisons de communiquer avec eux doivent être appropriées. Le rappel des consignes et le recours à d’autres canaux de communication peuvent améliorer les soins aux patients et réduire le nombre d’appels le soir et la nuit.in English, French Contexte Les services de chirurgie dans les unités de soins actifs (CSA) et de chirurgie générale dans les services d’urgence (CGSU) doivent fournir rapidement des soins et des interventions à des patients dont les besoins sont parmi les plus complexes. En effet, les patients pris en charge par les services de CSA sont souvent gravement malades et présentent des comorbidités sur fond de faible réserve physiologique. Même si les services de CSA/CGSU se sont répandus en Amérique du Nord, les taux réels de morbidité postopératoire demeurent pour une bonne part inconnus. Méthodes Dans cette étude prospective, on a suivi pendant 30 jours ou jusqu’à leur congé, les patients hospitalisés pour des interventions chirurgicales dans 8 centres de CSA/CGSU achalandés de divers endroits au Canada. On a également tenu compte des réadmissions dans les 30 jours. Les paramètres pré-, per- et postopératoires ont été enregistrés. Une méthodologie statistique standard a été appliquée. Résultats En tout, 601 patients de CSA/CGSU ont ainsi été suivis pendant une durée allant jusqu’à 30 jours d’hospitalisation ou de réadmission après leur intervention urgente initiale.