The Kinetics of Epoxidation of A,B-Unsaturated Esters by Dimethyldioxirane: A Mechanistic Study

The epoxidation of a series of α,β-unsaturated esters by dimethyldioxirane was studied. Second order rate constants were determined under pseudo first order conditions. The epoxide of each ester upon full conversion was found to be the only isolable product. Second order rate constants for the cis-like ethyl tiglate showed a 4 fold increase over that of trans-like angelic methyl ester. The ester substituent was found to have little effect on overall rate constants. A comparison of a relatively strained cyclopentene carboxylate to the cyclohexene carboxylate showed a 2 fold increase in selectivity for the former. Ethyl methacrylate displayed unexpected reactivity toward dioxirane; undergoing reaction faster than more substituted electron rich alkenes. Computer modeling studies using the AM-1 and density functional approaches were carried out to gain insights into the mechanistic aspects of the reaction. The esters in general favored the S-cis conformation or were evenly distributed among S-cis and S-trans except for the ethyl methacrylate case. The AM-1 approach did not predict the reactivity of open chain esters. The density functional approach predicted the relative reactivity of seven of the nine esters but could not predict the reactivity when the R1 group was substituted. One possible explanation is that the computer model predicts the methyl groups of the dioxirane to be positioned over the R1 group in the lowest energy of all other esters, but steric clash prevents this for angelic methyl ester and ethyl 3,3 dimethyl acrylate

Supersolid phase with cold polar molecules on a triangular lattice

We study a system of heteronuclear molecules on a triangular lattice and analyze the potential of this system for the experimental realization of a supersolid phase. The ground state phase diagram contains superfluid, solid and supersolid phases. At finite temperatures and strong interactions there is an additional emulsion region, in contrast to similar models with short-range interactions. We derive the maximal critical temperature $T_c$ and the corresponding entropy $S/N = 0.04(1)$ for supersolidity and find feasible experimental conditions for its realization.Comment: 4 pages, 4 figure

Sport, doping and male fertility

It is universally accepted that lifestyle interventions are the first step towards a good overall, reproductive and sexual health. Cessation of unhealthy habits, such as tobacco, alcohol and drug use, poor nutrition and sedentary behavior, is suggested in order to preserve/improve fertility in humans. However, the possible risks of physical exercise per se or sports on male fertility are less known. Being fit does not only improve the sense of well-being, but also has beneficial effects on general health: in fact physical exercise is by all means a low-cost, high-efficacy method for preventing or treating several conditions, ranging from purely physical (diabetes and obesity) to psychological (depression and anxiety), highly influencing male reproduction. If male sexual and reproductive health could be positively affected by a proper physical activity, inadequate bouts of strength - both excessive intensity and duration of exercise training - are more likely to have detrimental effects. In addition, the illicit use of prohibited drugs (i.e. doping) has reached pandemic proportions, and their actions, unfortunately very often underestimated by both amateur and professional athletes, are known to disrupt at different levels and throughout various mechanisms the male hypothalamic-pituitary-gonadal axis, resulting in hypogonadism and infertility

Quasi-Lie schemes and Emden--Fowler equations

The recently developed theory of quasi-Lie schemes is studied and applied to investigate several equations of Emden type and a scheme to deal with them and some of their generalisations is given. As a first result we obtain t-dependent constants of the motion for particular instances of Emden equations by means of some of their particular solutions. Previously known results are recovered from this new perspective. Finally some t-dependent constants of the motion for equations of Emden type satisfying certain conditions are recovered

Changing the paradigm in postherpetic neuralgia treatment: lidocaine 700 mg medicated plaster

OBJECTIVE: Chronic pain is currently considered a disease state with biopsychosocial consequences and a negative impact on patients' quality of life (QoL). Pain from postherpetic neuralgia (PHN) can persist for months or years and is a prototypical example of chronic pain. We analyzed PHN as a model of chronic pain. including its effects on QoL and clinical aspects. We explored treatment options, focusing on the topical treatment with lidocaine 700 mg medicated plaster (LMP) and how this impacts PHN management.MATERIALS AND METHODS: This article is a narrative review of published studies. Preclinical and clinical studies were retrieved from literature through a search performed in PubMed/MEDLINE.RESULTS: To choose the appropriate treatment for chronic pains, such as PHN, not only efficacy but also tolerability, manageability, practicality, and compliance are important factors. especially in the long term. It is also important to set treatment expectations with the patients as total suppression of pain may be unrealistic. and a balance needs to be found between pain control and the minimization of adverse events. In this respect, LMP may be the best currently available treatment: it is easy to use, has low systemic absorption and thus a low risk for pharmacological interactions. Therefore, treatments can be personalized, and concomitant medications can be added, if needed. Recent data from a real-world study support this view by showing that LMP has superior effectiveness in reducing pain and improving the QoL compared to other commonly used systemic treatments and confirming its good tolerability profile that is mainly characterized by localized skin reactions.CONCLUSIONS: LMP is one of the best currently available treatment options for PHN patients balancing good efficacy with an excellent tolerability profile and can therefore be considered for use as a first-line treatment for PHN

Intraoperative Monitoring of the Obese Patient Undergoing Surgery: A Narrative Review

With the increasing prevalence of obesity in the population, anaesthetists must confidently manage both the pathophysiological and technical challenges presented in bariatric and non-bariatric surgery. The intraoperative period represents an important opportunity to optimise and mitigate risk. However, there is little formal guidance on what intraoperative monitoring techniques should be used in this population. This narrative review collates the existing evidence for intraoperative monitoring devices in the obese patients. Although a number of non-invasive blood pressure monitors have been tested, an invasive arterial line remains the most reliable monitor if accurate, continuous monitoring is required. Goal-directed fluid therapy is recommended by clinical practice guidelines, but the methods tested to assess this had guarded applicability to the obese population. Transcutaneous carbon dioxide (CO2) monitoring may offer additional benefit to standard capnography in this population. Individually titrated positive end expiratory pressure (PEEP) and recruitment manoeuvres improved intraoperative mechanics but yielded no benefit in the immediate postoperative period. Depth of anaesthesia monitoring appears to be beneficial in the perioperative period regarding recovery times and complications. Objective confirmation of reversal of neuromuscular blockade continues to be a central tenet of anaesthesia practice, particularly relevant to this group who have been characterised as an "at risk" extubation group. Where deep neuromuscular blockade is used, continuous neuromuscular blockade is suggested. Both obesity and the intraoperative context represent somewhat unstable search terms, as the clinical implications of the obesity phenotype are not uniform, and the type and urgency of surgery have significant impact on the intraoperative setting. This renders the generation of summary conclusions around what intraoperative monitoring techniques are suitable in this population highly challenging

Effectiveness of extracorporeal shock wave therapy in bone marrow edema syndrome of the hip

There is no gold standard for treatment of bone marrow edema syndrome of the hip (BMESH). Usually, treatment is conservative, owing to the favorable and self-limiting prognosis. In musculoskeletal disorders, the effectiveness of extracorporeal shock wave therapy (ESWT) has been widely recognized and recent research supports its use in the treatment of the first stages of avascular osteonecrosis of the proximal femur and in other conditions where bone marrow edema is present. On this basis, we performed a prospective study to evaluate the effectiveness of ESWT in normalizing the symptoms and imaging features of BMESH. Twenty consecutive symptomatic patients underwent two treatments of high-energy ESWT and were followed-up at 2, 3 and 6 months, with a final clinical follow-up at mean 15.52 +/- A 1.91 months. Patients underwent magnetic resonance imaging of the hip and were evaluated according to the Harris hip score. The mean improvement in HHS over the course of the study was of 58.5 +/- A 14.9 points (p < 0.0001), and the mean edema area reduced from 981.9 +/- A 453.2 mm(2) pre-treatment to 107.8 +/- A 248.1 mm(2) at 6 months. ESWT seems to be a powerful, non-pharmacological tool that produces rapid pain relief and functional improvement and aids the normalization of the vascular and metabolic impairments which characterize BMESH

Wave packet retrieval by multi-photon quantum beat spectroscopy in helium

We show that we can probe the components of an attosecond bound electron wave packet by mapping the quantum beat signal produced by a synchronized delayed few-cycle infrared pulse into the continuum. In addition, spectrally overlapping peaks that result from one-, two- or three-photon processes from more or less deeply bound states can in principle be interferometrically resolved with high resolution

Generating socially appropriate tutorial dialog

Analysis of student-tutor coaching dialogs suggest that good human tutors attend to and attempt to influence the motivational state of learners. Moreover, they are sensitive to the social face of the learner, and seek to mitigate the potential face threat of their comments. This paper describes a dialog generator for pedagogical agents that takes motivation and face threat factors into account. This enables the agent to interact with learners in a socially appropriate fashion, and foster intrinsic motivation on the part of the learner, which in turn may lead to more positive learner affective states