Chemical fixation of CO2 is an efficient means for decreasing amount of CO2 in the atmosphere. One of promising technologies is the cycloaddition of CO2 with epoxides to synthesize cyclic carbonates. In this reaction, ionic liquid (IL) catalysts show versatile and unique advantages. However, the reaction mechanism using ILs is not clear. In this work, a detailed theoretical investigation was performed by DFT calculations. The energetic profile shows that the reaction consists of three steps, with the ring-opening step being the rate-determining step. Based on the results, effects of cations, anions and water were calculated. Cations show strong hydrogen bonding interactions with epoxides, which decreases the energy barrier of the ring-opening step, indicating that hydrogen bonds play a positive role in promoting the reaction. The effect of anions was evaluated by nucleophilicity index (NNu ); anions with a larger NNu (stronger nucleophilicity) value show lower energy barriers. The influence of water was investigated by implicit and explicit models. Compared with the solvent-free case, water as an implicit solvent decreases the energy barriers through polarization with epoxides. In the explicit solvent model, the water molecules form new hydrogen bonds with epoxides and cations, which can efficiently reduce the energy barriers. The result indicates that there is a new synergic catalytic mechanism, in which the water acts not only as solvent but also as a catalyst in the reaction. buy BC-2059 Supporting experiments further confirm the calculation results. Transfer time for patients with fractured hips is a significant problem in Australia. Current guidelines support operative management of hip fractures within 48 h with delays to surgery resulting in worse outcomes. The aim of study is to evaluate transfer times and delays and their effect on outcomes. A total of 506 hip fractures undergoing surgical management were reviewed between 2017 and 2018 at a tertiary metropolitan hospital. We examined age, time to surgery, transfer time, delay to surgery, American Society of Anesthesiologists grading and 30-day and 1-year mortality. We directly compared outcomes between patients presenting initially to the tertiary hospital and those who were referred from a peripheral site requiring inter-hospital transfer. The mean time to surgery was 24.4 h. Ninety-five percent of patients received their emergency surgery within 48 h with inter-hospital transfer patients delayed on average only by 12.08 h when compared to primary presenters. Patients who received their surgery in more than 48 h had worse mortality outcomes. Inter-hospital transfer, regardless of time to surgery, was associated with increased mortality. Increased time to surgery was associated with increased mortality rates. Transfer delays from a peripheral hospital had a significant bearing on time to surgery. Transfer, regardless of time to surgery, is associated with increased mortality. Early transfer to a referral hospital or bypass of the peripheral hospital is recommended.Increased time to surgery was associated with increased mortality rates. Transfer delays from a peripheral hospital had a significant bearing on time to surgery. Transfer, regardless of time to surgery, is associated with increased mortality. Early transfer to a referral hospital or bypass of the peripheral hospital is recommended.Surface acoustic waves (SAW) allow to manipulate surfaces with potential applications in catalysis, sensor and nanotechnology. SAWs were shown to cause a strong increase in catalytic activity and selectivity in many oxidation and decomposition reactions on metallic and oxidic catalysts. However, the promotion mechanism has not been unambiguously identified. Using stroboscopic X-ray photoelectron spectro-microscopy, we were able to evidence a sub-nanosecond work function change during propagation of 500 MHz SAWs on a 9 nm thick platinum film. We quantify the work function change to 455 μeV. Such a small variation rules out that electronic effects due to elastic deformation (strain) play a major role in the SAW-induced promotion of catalysis. In a second set of experiments, SAW-induced intermixing of a five monolayers thick Rh film on top of polycrystalline platinum was demonstrated to be due to enhanced thermal diffusion caused by an increase of the surface temperature by about 75 K when SAWs were excited. Reversible surface structural changes are suggested to be a major cause for catalytic promotion.Reaction of an Al-centered anion with toluene proceeded to form C-H cleaved product with a perfect meta-selectivity and a relatively small kinetic isotope effect (KIE, kH /kD =1.51). DFT calculations suggested a two-step reaction mechanism and electronically controlled meta-selectivity arising from the electron-donating methyl group. The reaction with other mono-substituted arenes was also investigated.Supernumerary breast components occur predominantly between the breast and umbilicus. Carcinoma of this ectopic, or accessory breast tissue (ABT), is exceedingly rare, accounting for less then 1% of breast cancer cases. Historically, ectopic breast carcinoma was considered aggressive with poor outcome. In 1995, Evans et al reported 90 cases spanning from 1929 to 1993 with a 9.4% survival beyond 4 years. More contemporary studies reveal improvement in both treatment and survival. There is currently no consensus on whether prophylactic excision of an ipsilateral supernumerary nipple at the time of initial breast cancer diagnosis is necessary. The following describes a patient with an ipsilateral tumor uniquely located within her supernumerary nipple 5 years after mastectomy.We introduce the bioconjugation of polymers synthesized by RAFT polymerization, bearing no specific functional end group, by means of hetero-Diels-Alder cycloaddition through their inherent terminal thiocarbonylthio moiety with a diene-modified model protein. Quantitative conjugation occurs over the course of a few hours, at ambient temperature and neutral pH, and in the absence of any catalyst. Our technology platform affords thermoresponsive bioconjugates, whose aggregation is solely controlled by the polymer chains.

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