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Organocatalytic ring-opening polymerization of cyclic carbonate monomers derivatized with metallocenes is described for the rapid synthesis of high Mn metallopolymers.

The electronic structures and, particularly, the nature of the HOMO in a series of PcFeL2, PcFeL'L″, and [PcFeX2]2- complexes (Pc = phthalocyaninato(2-) ligand; L = NH3, n-BuNH2, imidazole (Im), pyridine (Py), PMe3, PBu3, t-BuNC, P(OBu)3, and DMSO; L' = CO; L″ = NH3 or n-BuNH2; X = NCO-, NCS-, CN-, imidazolate (Im-), or 1,2,4-triazolate(Tz-)) were probed by electrochemical, spectroelectrochemical, and chemical oxidation as well as theoretical (density functional theory, DFT) studies. In general, energies of the metal-centered occupied orbitals in various six-coordinate iron phthalocyanine complexes correlate well with Lever Electrochemical Parameter EL and intercross the phthalocyanine-centered a1u orbital in several compounds with moderate-to-strong π-accepting axial ligands. In these cases, an oxidation of the phthalocyanine macrocycle (Pc(2-)/Pc(1-)) rather than the central metal ion (Fe(II)/Fe(III)) was theoretically predicted and experimentally confirmed.

Resume Les 2 et 3 juin 2021, une panne telephonique nationale affecte le fonctionnement des numeros d’urgence. L’analyse de l’activite des CRRA15 des huit SAMU d’Ile-de-France a montre (par rapport aux periodes de reference) une baisse du nombre d’appels au SAMU centre 15 et une diminution des dossiers de regulation medicale pendant la panne, suivie d’une augmentation 2 heures plus tard. Parallelement, il n’a pas ete observe de variation du nombre de sorties des SMUR, ni du nombre de patients accueillis dans les services d’urgences hospitaliers. Le faible impact observe peut etre explique par la nature partielle de la panne, mais aussi par la mise en place rapide par l’ARSIF et l’AP-HP d’une information destinee au public et d’une solution de contournement de la panne.

Although there has been substantial improvement in ACL reconstructive surgery, graft failure remains a devastating complication for some patients. Revision procedures are inherently more complex and technically challenging. The purpose of this study is to determine the incidence of short-term complications after these procedures and to compare trends in operative length, relative valuation, and reimbursement after primary versus revision ACL reconstruction. Primary and revision arthroscopic ACL reconstruction cases were identified on the American College of Surgeons’ NSQIP database using Current Procedural Terminology (CPT) and International Classification of Diseases (ICD) codes between January 1, 2012 and December 31, 2017. Demographics, patient variables, and surgical variables were compared between primary and revision groups using Chi-squared tests. Logistic regression was used to identify independent risk factors for revision ACL reconstruction. Various 30-day outcome measures were compared between the primary and revision ACL reconstruction groups. Various measures of valuation—including total relative value units (RVU) and reimbursement per minute—were calculated and compared between the two groups. A total of 8292 patients—8135 primary and 157 revision procedures—were included in the final cohort. Higher ASA scores were associated with revision ACL reconstructions. Patients undergoing revision procedures were less likely to have an ASA score of 1 (p

As biocrude exhibits inferior properties for it to be used as a high-value fuel, upgrading is needed. Thermochemical upgrading methods prove to be the most successful in terms of oxygen removal and stabilisation of biocrude; however, heavy organics in biocrude have the tendency to polymerise upon thermal treatment. This results in catalyst deactivation and coking during hydrotreatment of biocrude. Chemical upgrading, such as conventional esterification at mild reaction conditions, is also ineffective as the esterification reaction is incomplete due to the carboxylic acid-water equilibrium reaction. In this study, the enzymatic upgrading route was evaluated by studying the conversion of fatty acids to methyl esters in the biocrude. A fatty acid conversion of 94.6 mass % at 30 ֯C was obtained, showing that moisture and other components present in biocrude do not have a negative effect on fatty acid esterification using lipase catalysis. The difference in oil-to-oil molar ratio between 1:2 and 1:18 is not significant due to the presence of hydroxyl groups in the oil which contributes to the esterification reaction. No heavy fraction formation was observed in the boiling curves which is an indication that no significant coking occurred. Although the fuel value of the produced biodiesel at 34.9 MJ/kg is lower than that of petroleum fuel, the biodiesel in this study can be used in blends for heating, cooking and electricity generation applications.

L’épidémie de COVID 19 a nécessité un renforcement en moyens techniques comme en personnel dans le cadre des activités de régulation médicale mais aussi pour les interventions pré hospitalières non médicalisées ou des SMUR. Ce renforcement a été adapté à l’évolution de l’activité. Au SAMU de Paris, l’activité a imposé le doublement des postes de régulation dès la deuxième semaine de mars afin de répondre à la fois aux appels habituels mais aussi à la demande liée au COVID. Des étudiants en médecine de diplôme de formation approfondie en sciences médicales (DFASM) de 1re, 2e et 3e années volontaires ont été mobilisés pour venir renforcer la régulation médicale et assurer les réponses au sein d’une salle supplémentaire installée pour répondre aux appels COVID. Seuls, les étudiants en médecine du 2ème cycle ont donc été intégrés à cette organisation, ils bénéficiant à leur arrivée d’une formation adaptée à leur niveau d’étude et aux fonctions à accomplir au sein de la régulation médicale et aussi tout au long de leur activité d’un encadrement par un médecin sénior de l’aide médicale d’urgence et /ou de la permanence des soins ambulatoires. Cette activité était donc sécurisée par des médecins séniors comme dans tout stage hospitalier. Cette organisation a contribué notamment à Paris, à la réponse à l’afflux des appels au SAMU. Ce renfort a ensuite été maintenu, aussi bien dans le cadre de la crise que dans l’activité quotidienne et dans le déploiement du Service d’Accès aux Soins (SAS).

Resume L’enseignement RMAT est une initiation courte a la prise en charge des victimes d’attentats terroristes pour les etudiants en medecine. Cet enseignement comporte aussi des notions d’organisation medicale en cas d’accident catastrophique ou de situation sanitaire exceptionnelle. Les auteurs rapportent le contenu, le deroulement et les modalites pratiques de cette formation originale qui a ete apprecie et a repondu aux attentes des etudiants du deuxieme cycle des etudes medicales dans un domaine qui n’est pas classiquement enseigne a ce stade de leurs etudes.

The electronic structures and, particularly, the nature of the HOMO in a series of PcFeL

Introduction Studies have shown that the use of total shoulder arthroplasty is increasing every year in the United Stated at a rate higher than that of total hip or total knee arthroplasty. As the population of the United States continues to age, it is becoming more important for surgeons to understand the true impact of age on outcomes and complications following procedures such a total shoulder arthroplasty. The purpose of this study was to determine if octogenarians have poorer outcomes after total shoulder arthroplasty compared to a younger, matched control group. Methods Data was obtained through the American College of Surgeons National Surgical Quality Improvement Program database (ACS NSQIP). Patients who had undergone total shoulder arthroplasty were identified by Current Procedural Terminology code (23472). Indication for arthroplasty was determined by ICD9/10 code (osteoarthritis, fracture, other). Each octogenarian was matched 1:1 to a non-octogenarian based on sex, BMI, ASA class, medical comorbidities, functional status, and surgical indication for arthroplasty by propensity scoring. A subgroup analysis was performed to compare outcomes between only those patients who underwent TSA for osteoarthritis.Outcomes of interest were assessed between the two groups for statistical significance using a chi-squared test or fisher exact test for expected values of less than 5. Statistical significance was set at p

Biomass from microalgae is a potential feedstock for biofuels production. It poses no threat to food security as it does not compete with agricultural crops for arable land. Scenedesmus acutus was used as feedstock to produce bio-oil in a large liquefaction reactor. The influence of reaction temperature (280–360ºC), reaction atmosphere (N2 or CO2) and solvent on bio-oil yield, C-16 fatty acid yield and oil properties were investigated. Oils were characterised using gas chromatography, Fourier transform infrared (FTIR) spectroscopy and ultimate analysis. Higher bio-oil yields were obtained in a CO2 atmosphere (250 g.kg-1 dry microalgae) than in a N2 atmosphere (210 g.kg-1 dry microalgae) whilst higher C16 fatty acid concentrations (600 g.kg-1 bio-oil) were recorded in N2 atmosphere compared to oil prepared in a CO2 atmosphere (500 g.kg-1 bio-oil). The oil yield increased to a maximum at 320°C, after which there were no significant changes. Highest bio-oil yields (425 g.kg-1 dry microalgae) were obtained in ethanol as solvent. FTIR spectroscopy and ultimate analysis showed that proteins present in the feedstock were degraded by breakage of peptide linkages, and nitrogen present in the oils is peptide fragments from protein degradation. The carbon content of all produced oils was high, but the hydrogen content was low, leading to low hydrogen/carbon ratios. Energy consumption and energy efficiency calculations showed that liquefaction in both reaction atmospheres results in a net energy gain, and a CO2 atmosphere is best for high energy efficiency.

Although there has been substantial improvement in ACL reconstructive surgery, graft failure remains a devastating complication for some patients. Revision procedures are inherently more complex and technically challenging. The purpose of this study is to determine the incidence of short-term complications after these procedures and to compare trends in operative length, relative valuation, and reimbursement after primary versus revision ACL reconstruction.Primary and revision arthroscopic ACL reconstruction cases were identified on the American College of Surgeons' NSQIP database using Current Procedural Terminology (CPT) and International Classification of Diseases (ICD) codes between January 1, 2012 and December 31, 2017. Demographics, patient variables, and surgical variables were compared between primary and revision groups using Chi-squared tests. Logistic regression was used to identify independent risk factors for revision ACL reconstruction. Various 30-day outcome measures were compared between the primary and revision ACL reconstruction groups. Various measures of valuation-including total relative value units (RVU) and reimbursement per minute-were calculated and compared between the two groups.A total of 8292 patients-8135 primary and 157 revision procedures-were included in the final cohort. Higher ASA scores were associated with revision ACL reconstructions. Patients undergoing revision procedures were less likely to have an ASA score of 1 (p 0.001) and more likely to have an ASA score of 2 (p = 0.004) or 3 (p = 0.020). Revision ACL reconstruction was associated with higher rates of poor 30-day outcome measures, including unplanned readmission (p = 0.029), reoperation (p = 0.012), return to the OR (p = 0.012), and surgical complications (p = 0.021). The total RVUs and reimbursement for revision procedures were significantly greater than those for primary procedures (p 0.001). However, when accounting for operative time, the RVU/minute and reimbursement/minute were similar between the two groups (n.s.).Relative to primary ACL reconstruction, revision ACL procedures are associated with worse short-term outcomes-including unplanned readmission, reoperation, return to the OR, and surgical complications. A greater ASA score was independently predictive of revision ACL surgery. The current RVU system undervalues revision ACL procedures, considering the increased operative time and complexity of such procedures.Level III.

Governments and social benefit organizations are expected to consider evidence in decision-making. In development and sustainability, evidence spans disciplines and methodological traditions and is often inconclusive. Graphical models are widely promoted to organize interdisciplinary evidence and improve decision-making by considering mediating variables. However, the reproducibility, objectivity and benefits for decision-making of graphical models have not been studied. We evaluate these considerations in the setting of energy services in the developing world, a contemporary development and sustainability imperative. We develop a database of relevant causal relations (313 concepts, 1337 relationships) asserted in the literature (561 peer-reviewed articles). We demonstrate that high-level relationships of interest to practitioners feature less consistent evidence than the causal relationships that underpin them, supporting increased use of problem decomposition through graphical modeling approaches. However, adding such detail increases complexity exponentially, introducing a hazard of overparameterization if evidence is not available to match the level of mechanistic detail. Published (Publication status)

Spectroscopic studies of aluminum monofluoride (AlF) have revealed its highly favorable properties for direct laser cooling. All $Q$ lines of the strong A$^1\Pi$ $\leftarrow$ X$^1\Sigma^+$ transition around 227~nm are rotationally closed and thereby suitable for the main cooling cycle. The same holds for the narrow, spin-forbidden a$^3\Pi$ $\leftarrow$ X$^1\Sigma^+$ transition around 367 nm which has a recoil limit in the micro Kelvin range. We here report on the spectroscopic characterization of the lowest rotational levels in the a$^3\Pi$ state of AlF for $v=0-8$ using a jet-cooled, pulsed molecular beam. An accidental AC Stark shift is observed on the a$^3\Pi_0, v=4$ $\leftarrow$ X$^1\Sigma^+, v=4$ band. By using time-delayed ionization for state-selective detection of the molecules in the metastable a$^3\Pi$ state at different points along the molecular beam, the radiative lifetime of the a$^3\Pi_1, v=0, J=1$ level is experimentally determined as $\tau=1.89 \pm 0.15$~ms. A laser/radio-frequency multiple resonance ionization scheme is employed to determine the hyperfine splittings in the a$^3\Pi_1, v=5$ level. The experimentally derived hyperfine parameters are compared to the outcome of quantum chemistry calculations. A spectral line with a width of 1.27 kHz is recorded between hyperfine levels in the a$^3\Pi, v=0$ state. These measurements benchmark the electronic potential of the a$^3\Pi$ state and yield accurate values for the photon scattering rate and for the elements of the Franck-Condon matrix of the a$^3\Pi$ $-$ X$^1\Sigma^+$ system., Comment: 16 pages, 9 figures

Applications for surgical staplers continue to grow, due to the increase in minimally invasive surgical approaches, and range from vessel ligation to tissue transection and anastomoses. Complications associated with stapled tissue, such as bleeding or leaks, continue to be a concern for surgeons, as both can be associated with prolonged operative times and can contribute to postoperative morbidity and mortality. The goal of this retrospective study was to evaluate the performance of the da Vinci® Xi EndoWrist® Stapler 45 with SmartClamp™ technology during robotic-assisted right colectomy with intracorporeal anastomosis. We reviewed 113 consecutive cases from four medical centers. Preclinical diagnoses were inflammatory bowel disease (IBD) (n = 5), benign bowel disease (n = 77), and malignant bowel disease (n = 31). No anastomotic leaks occurred; one event of anastomotic bleeding (0.88%) resolved without surgical intervention. Overall, there were 643 clamp attempts (5.7 attempts per case), and 570 fires (5.0 fires per case). SmartClamp™ occurrences happened in approximately one out of three cases, with the highest proportion of occurrences in the IBD group (2.0 occurrences per case). The most commonly fired reload was blue (1.5 mm closed height) with 4.1 blue reloads fired per case overall. No incomplete fires occurred during the procedures. The study data demonstrate the performance of the da Vinci Xi EndoWrist® Stapler 45 as used in right colon resection with intracorporeal anastomosis. The collection and analysis of these data provide surgeons with information related to stapler firings, which were not previously available; as such, this analysis may lead to deductions that are useful for intraoperative decision-making and clinical outcomes.

Residues obtained from hydrothermal liquefaction of municipality waste (MSWR) and coffee waste (CR) were blended with coal and charred at 1000 °C. Co-gasification experiments were conducted on the coal, MSWR, CR, and their respective blended chars using a thermogravimetric analyser. The reactivities of the char samples decreased in the order: MSWR > CR > MSWR-coal blend > CR-coal blend > coal. RPM was found to best predict the reaction profile of the coal, and the blended chars, except for the MSWR and CR chars, which fitted satisfactorily upon the application of the MRPM. The activation energies obtained using the RPM, MRPM, and the different reactivity models showed that the MSWR, CR, and the blend chars have lower activation energies when compared to the feed coal char. Although the MSWR and CR exhibited catalytic influence on the coal char during co-gasification, the synergistic effect was inhibitory with all determined SE

Summary Invasive dental procedures performed in the standing, sedated horse are facilitated by local and regional anaesthesia. The traditional transcutaneous approach to the mental foramen is used to desensitise the incisive region including the mandibular incisors, but is not well tolerated by many sedated patients. In this study, a new, intraoral needle insertion technique for nerve block at the mental foramen was investigated. In 15 equine cadaver heads and two live horses, computed tomography (CT) was used to verify Tuohy needle placement into each mental foramen using an intraoral technique. Varying volumes of contrast medium (3, 6, 10 mL) were injected into the mandibular canal with and without digital occlusion of the mental foramen. The distance of retrograde flow was measured. Additionally, measurements were taken to determine the position of the mental foramen within the interdental space. Correct placement of Tuohy needles and injection of contrast medium into the mandibular canal using an intraoral approach at the mental foramen was achieved in all injections. Retrograde flow of contrast medium was accomplished with all volumes, regardless of occlusion. Although not statistically significant, the 10 mL group appeared to have a greater distance of flow. The needle insertion technique described here appears to be a potential alternative to traditional transcutaneous approaches to mental nerve block for procedures involving the incisive region. In addition, it was found that 79% of the mandibular canals injected with 10 mL of contrast medium had retrograde flow to the position of PM4, suggesting this method may be a useful alternative technique for nerve block for the more rostrally located cheek teeth. The location of the mental foramen was consistently found in the distal third of the interdental space (approximately 60–80% of the distance between the distal aspect of the lateral corner incisor and the mesial aspect of the second premolar).

Urogenital problems are dramatically increasing; especially chronic pelvic pain syndrome (CPPS) poses a major challenge for physicians and therapists. Few forms of therapy have been able to promise relief because the cause of CPPS remains unclear. Functional complaints are increasingly discussed as triggers. Osteopathic treatment has been reported to help many patients in recent years. In this article, the approach and osteopathic point of view of functional complaints are presented. In addition, possible causes for the development of CPPS and important anatomical structures that are directly involved in it are explained. Further interdisciplinary research of functional relationships would be desirable in the future.

Background Access to an Emergency Medical Communication Centre is essential for the population in emergency situations. Handling inbound calls without delay requires managing activity, process and outcome measures of the Emergency Medical Communication Centre to improve the workforce management and the level of service. France is facing political decisions on the evolution of the organisation of Emergency Medical Communication Centres to improve accessibility for the population. First, we aim to describe the variation in activity between Emergency Medical Communication Centres, and second, to explore the correlation between process measures and outcome measures. Methods Using telephone activity data extraction, we conducted an observational multicentre study of six French Emergency Medical Communication Centres from 1 July 2016 to 30 June 2017. We described the activity (number of incoming calls, call rate per 1000 inhabitants), process measure (agent occupation rate), and outcome measure (number of calls answered within 20 s) by hourly range and estimated the correlation between them according to the structural equation methods. Results A total of 52,542 h of activity were analysed, during which 2,544,254 calls were received. The annual Emergency Medical Communication Centre call rate was 285.5 [95% CI: 285.2–285.8] per 1000 inhabitants. The average hourly number of calls ranged from 29 to 61 and the call-handled rate from 75 to 98%. There are variations in activity between Emergency Medical Communication Centres. The mean agent occupation rate was correlated with the quality of service at 20 s (coefficient at − 0.54). The number of incoming calls per agent was correlated with the mean occupation rate (coefficient at 0.67). Correlation coefficients varied according to the centres and existed between different process measures. Conclusions The activity dynamics of the six Emergency Medical Communication Centres are not identical. This variability, illustrating the particularity of each centre, must be accurately assessed and should be taken into account in managerial considerations. The call taker occupation rate is the leverage in the workforce management to improve the population accessibility.

Accurate fault locating on transmission lines is of great value to power transmission asset owners and operators. Fault locating as a discipline dates back to the 1940s. Visual inspection methods evolved from road patrols in the past, to air patrols today, and, more recently, to trials with unmanned aerial vehicles. Fault locating using electrical measurements evolved from simple electromechanical devices to microprocessor-based systems integrated with geospatial data.

Pour faire face a l'attentat terroriste multisite du 13 novembre 2015, une regulation medicale zonale des huit Samu de la region Ile-de-France a ete mise en place au Samu de Paris. Elle a permis, en utilisant une strategie de sectorisation des moyens Smur et des ressources hospitalieres, la medicalisation des sites, la regulation et le transport par des equipes medicales de la majorite des victimes en urgence absolue. Des moyens Smur et des hopitaux ont pu etre gardes en reserve pour faire face a une aggravation de la situation (notamment sur le site du Bataclan) et a d'eventuelles autres attaques. L'analyse de cette experience montre de nombreux points forts mais aussi des pistes d'amelioration utiles pour tous ceux qui seraient confrontes a un tel evenement.

Applications for surgical staplers continue to grow, due to the increase in minimally invasive surgical approaches, and range from vessel ligation to tissue transection and anastomoses. Complications associated with stapled tissue, such as bleeding or leaks, continue to be a concern for surgeons, as both can be associated with prolonged operative times and can contribute to postoperative morbidity and mortality. The goal of this retrospective study was to evaluate the performance of the da Vinci

La Presse Medicale - In Press.Proof corrected by the author Available online since vendredi 8 mai 2015

Self-monitoring of food intake is a core strategy in cognitive–behavioral therapy (CBT) for weight management, but some concerns have been raised about the use of food monitoring (FM), particularly with youth. Appetite monitoring (AM), a form of self-monitoring in which participants track their appetite cues, has shown promise as a potentially acceptable and equally useful alternative. This pilot study implemented AM at a residential camp for overweight and obese youth (ages 9–14) that promotes family based healthy lifestyle habits. Campers and their families were taught to rate their appetite (using a form called the “Hunger Scale”) at family weekends in the spring, and were encouraged to use the scale at home. During the children’s 5-day summertime overnight camp, they were prompted to attend to their appetite cues before all meals. At the end of the camp week, counselor and camper ratings indicated that the AM intervention was feasible, acceptable, helpful, and utilized. At the fall reunion weekends, campers and parents reported remembering the Hunger Scale and continued to rate the intervention positively. On average, campers reported improved awareness of their appetite cues at the end of camper week, which was maintained at the fall reunion weekend. The most improvement was reported by campers identified by parents at baseline as having objective overeating episodes (i.e., eating clearly large amounts). These results are preliminary and warrant further investigation, but suggest that AM could be a promising alternative or additional self-monitoring strategy within camps and other interventions for overweight and obese youth.

The Sources of Discomfort Scale (SODS) assesses discomfort manifestations based on source of discomfort, thus making it both distinct from and complementary to pain assessments for persons with dementia. Sources were categorized as pertaining to physical discomfort, to body position, and to environmental sources. Body position sources of discomfort were related to poor functional status and to pain. The SODS scores were not related to cognitive functioning, and sources of discomfort other than those pertaining to body position were not correlated with pain. This paper demonstrates a direct and enhanced method to detect the manifestations of discomfort separately from pain indicators in a population with advanced dementia. The determination of the source of discomfort has direct implications for intervention.

OBJECTIVE: X-linked adrenoleukodystrophy (ALD) is a neurodegenerative disorder due to mutations in the peroxisomal very long-chain fatty acyl-CoA transporter, ABCD1, with limited therapeutic options. ALD may manifest in a slowly progressive adrenomyeloneuropathy (AMN) phenotype, or switch to rapid inflammatory demyelinating cerebral disease (cALD), in which microglia have been shown to play a pathophysiological role. The aim of this study was to determine the role of patient phenotype in the immune response of ex vivo monophagocytic cells to stimulation, and to evaluate the efficacy of polyamidoamine dendrimer conjugated to the antioxidant precursor N-acetyl-cysteine (NAC) in modulating this immune response. METHODS: Human monophagocytic cells were derived from fresh whole blood, from healthy (n = 4), heterozygote carrier (n = 4), AMN (n = 7), and cALD (n = 4) patients. Cells were exposed to very long-chain fatty acids (VLCFAs; C24:0 and C26:0) and treated with dendrimer-NAC (D-NAC). RESULTS: Ex vivo exposure to VLCFAs significantly increased tumor necrosis factor α (TNFα) and glutamate secretion from cALD patient macrophages. Additionally, a significant reduction in total intracellular glutathione was observed in cALD patient cells. D-NAC treatment dose-dependently reduced TNFα and glutamate secretion and replenished total intracellular glutathione levels in cALD patient macrophages, more efficiently than NAC. Similarly, D-NAC treatment decreased glutamate secretion in AMN patient cells. INTERPRETATION: ALD phenotypes display unique inflammatory profiles in response to VLCFA stimulation, and therefore ex vivo monophagocytic cells may provide a novel test bed for therapeutic agents. Based on our findings, D-NAC may be a viable therapeutic strategy for the treatment of cALD.

Urogenital problems are dramatically increasing; especially chronic pelvic pain syndrome (CPPS) poses a major challenge for physicians and therapists. Few forms of therapy have been able to promise relief because the cause of CPPS remains unclear. Functional complaints are increasingly discussed as triggers. Osteopathic treatment has been reported to help many patients in recent years. In this article, the approach and osteopathic point of view of functional complaints are presented. In addition, possible causes for the development of CPPS and important anatomical structures that are directly involved in it are explained. Further interdisciplinary research of functional relationships would be desirable in the future.