Non-innocent Role of the Halide Ligand in the Copper-Catalyzed Olefin Aziridination Reaction.

In the context of copper-catalyzed nitrene transfer to olefins, many systems operate upon mixing a CuX salt (X = halide, OTf) and a polydentate N-based ligand, assuming that the X ligand is displaced from the coordination sphere toward a counterion position. Herein, we demonstrated that such general assumption should be in doubt since studies carried out with the well-defined copper(I) complexes (TTM)CuCl and [(TTM)Cu(NCMe)]PF6 (TTM = tris(triazolyl)methane ligand) demonstrate a dual behavior from a catalytic and mechanistic point of view that exclusively depends on the presence or absence of the chloride ligand bonded to the metal center. When coordinated, the turnover-limiting step corresponds to the formation of the carbon-nitrene bond, whereas in its absence, the highest barrier corresponds to the formation of the copper-nitrene intermediate.

Modelling of Animal Activity, Illuminance, and Noise on a Weaned Piglet Farm.

Measuring animal activity and its evolution in real time is useful for animal welfare assessment. In addition, illuminance and noise level are two factors that can improve our understanding of animal activity. This study aims to establish relationships between animal activity as measured by passive infrared sensors, and both illuminance and noise level on a conventional weaned piglet farm. First, regression models were applied, and then cosine models with three harmonics were developed using least squares with a Generalized Reduced Gradient Nonlinear method. Finally, all the models were validated. Linear models showed positive correlations, with values between 0.40 and 0.56. Cosine models drew clear patterns of daily animal activity, illuminance and noise level with two peaks, one in the morning and one in the afternoon, coinciding with human activity inside the building, with a preference for inactivity at night-time and around midday. Cosine model fitting revealed strong correlations, both in the measurement and validation periods, for animal activity (R = 0.97 and 0.92), illuminance (R = 0.95 and 0.91) and noise level (R = 0.99 and 0.92). The developed models could be easily implemented in animal welfare monitoring systems and could provide useful information about animal activity through continuous monitoring of illuminance or noise levels.

Evolution and Neural Network Prediction of CO2 Emissions in Weaned Piglet Farms.

This paper aims to study the evolution of CO2 concentrations and emissions on a conventional farm with weaned piglets between 6.9 and 17.0 kg live weight based on setpoint temperature, outdoor temperature, and ventilation flow. The experimental trial was conducted during one transition cycle. Generally, the ventilation flow increased with the reduction in setpoint temperature throughout the cycle, which caused a reduction in CO2 concentration and an increase in emissions. The mean CO2 concentration was 3.12 g m-3. Emissions of CO2 had a mean value of 2.21 mg s-1 per animal, which is equivalent to 0.195 mg s-1 kg-1. A potential function was used to describe the interaction between 10 min values of ventilation flow and CO2 concentrations, whereas a linear function was used to describe the interaction between 10 min values of ventilation flow and CO2 emissions, with r values of 0.82 and 0.85, respectively. Using such equations allowed for simple and direct quantification of emissions. Furthermore, two prediction models for CO2 emissions were developed using two neural networks (for 10 min and 60 min predictions), which reached r values of 0.63 and 0.56. These results are limited mainly by the size of the training period, as well as by the differences between the behavior of the series in the training stage and the testing stage.

Long-Term Measurement of Piglet Activity Using Passive Infrared Detectors.

Measuring animal activity is useful for monitoring animal welfare in real time. In this regard, passive infrared detectors have been used in recent years to quantify piglet activity because of their robustness and ease of use. This study was conducted on a commercial farm in Northwest Spain during six complete breeding cycles. The hourly average activity of weaned piglets with a body mass of 6-20 kg was recorded and further analyzed by using a multiplicative decomposition of the series followed by a wavelet analysis. Finally, the real series were compared to the theoretical models of activity. Results showed a high level of movement immediately after weaning and a sustained level of activity throughout the cycles. The daily behavior of the piglets followed a clear circadian pattern with several peaks of activity. No differences in behavior were observed between spring-summer cycles and autumn-winter cycles. Single-peak models achieved the best predictive results. In addition, the installed sensors were found to underestimate mild activity.

Predictors of mediastinal staging and usefulness of pet in patients with stage IIIA (N2) or IIIB (N3) lung cancer.

OBJECTIVE: To analyze which factors predict mediastinal N2/N3 lymph node staging and diagnostic accuracy of PET and CT to determine it. PATIENTS AND METHODS: We analyzed data collected prospectively in a database that included patients with non-small cell lung cancer (NSCLC) who underwent EBUS-TBNA. Prior to EBUS-TBNA, CT and PET were used to define the radiographic N stage and lymph nodes with short axis ≥ 1 cm by CT or with ratio between maximum standardized uptake value (maxSUV), by PET, of lymph node and primary tumor greater than 0.56, were considered pathological. Definitive lymph node staging was established through EBUS-TBNA, mediastinoscopy or surgical lymph node dissection. RESULTS: One hundred and thirty four patients were included, in 88 of whom (65.6%), definitive lymph node staging was N2 or N3. Primary tumor of central location, lymph node size, maxSUV of lymph node and radiographic N stage by CT or PET were associated with N2/N3 in univariate analysis, but in logistic regression model it was only independently related with N stage by CT or PET. Negative predictive value and positive predictive value of CT were 0.81 and 0.74, respectively, and for PET 0.78 and 0.68. CONCLUSION: In NSCLC, in locoregional disease radiographic staging by CT or PET predict the existence of N2/N3 mediastinal disease, but negative and positive predictive values of both imaging techniques are not adequate, so EBUS-TBNA samples should be taken in all lymph nodes with a diameter greater than 5 mm, regardless of PET findings.

Intermolecular Allene Functionalization by Silver-Nitrene Catalysis.

Under silver catalysis conditions, using [Tp*,BrAg]2 as the catalyst precursor, allenes react with PhI═NTs in the first example of efficient metal-mediated intermolecular nitrene transfer to such substrates. The nature of the substituent at the allene seems crucial for the reaction outcome since arylallenes are converted into azetidine derivatives, whereas methylene aziridines are the products resulting from alkylallenes. Mechanistic studies allow proposing that azetidines are formed through unstable cyclopropylimine intermediates, which further incorporate a second nitrene group, both processes being silver-mediated. Methylene aziridines from alkylallenes derive from catalytic nitrene addition to the allene double bonds. Both routes have resulted to be productive for further synthetic transformations affording aminocyclopropanes.

Trispyrazolylborate Ligands Supported on Vinyl Addition Polynorbornenes and Their Copper Derivatives as Recyclable Catalysts.

Polynorbornenes prepared by vinyl addition polymerization and bearing pendant alkenyl groups serve as skeletons to support trispyrazolylborate ligands (Tpx ) built at those alkenyl sites. Reaction with CuI in acetonitrile led to VA-PNB-Tpx Cu(NCMe) (VA-PBN=vinyl addition polynorbornene) with a 0.8-1.4 mmol incorporation of Cu per gram of polymer. The presence of tetracoordinated copper(I) ions was been assessed by FTIR studies on the corresponding VA-PNB-Tpx Cu(CO) adducts, in agreement with those on discrete Tpx Cu(CO). The new materials were employed as heterogeneous catalysts in several carbene- and nitrene-transfer reactions, showing a behavior similar to that of the homogeneous counterparts but also being recycled several times maintaining a high degree of activity and selectivity. This is the first example of supported Tpx ligands onto polymeric supports with catalytic applications.

Catalytic Nitrene Transfer To Alkynes: A Novel and Versatile Route for the Synthesis of Sulfinamides and Isothiazoles.

A novel transformation is reported for the reaction of terminal or internal alkynes with the nitrene precursor PhI=NTs (Ts=p-toluenesulfonyl) in the presence of catalytic amounts of TpBr3 Cu(NCMe) (TpBr3 =hydrotris(3,4,5-tribromo-pyrazolylborate). Two products containing an imine functionality have been isolated from the reaction mixtures, identified as sulfinamides and isothiazoles. The former correspond to the formal reduction of the sulfone group into sulfoxide, whereas the latter involves the insertion of an alkyne carbon atom into the aromatic ring of the N-tosyl moiety.

Neurotoxoplasmosis y adherencia al tratamiento antirretroviral en pacientes con VIH/sida. Presentación de un caso / Neurotoxoplasmosis and adherence to the anti-retroviral treatment in HIV/AIDS patients. Case presentation

Fundamento: alrededor de un tercio de los pacientes con VIH/sida presentan complicaciones nerviosas con considerable morbilidad y mortalidad. Una de ellas, la neurotoxoplasmosis, puede tener una alta incidencia en estos pacientes. Han sido pocos los casos descritos en la literatura cubana. Presentación de caso: se reporta un paciente con un cuadro de neurotoxoplasmosis y estado de inmunodepresión grave, con mala adherencia al tratamiento antirretroviral. A pesar de indicársele el tratamiento adecuado evoluciona fatalmente. Conclusiones: la aparición de la neurotoxoplasmosis en el caso reportado se debió a un fracaso terapéutico determinado por la mala adherencia al tratamiento antirretroviral. Uno de los objetivos principales del equipo de atención integral es garantizar el cumplimiento del tratamiento antirretroviral para evitar infecciones oportunistas letales como la neurotoxoplasmosis(AU)

Background: about one third of the HIV/AIDS patients show nervous complications with a significant morbidity and mortality. One of them neurotoxoplasmosis may have a high incidence in these patients. Only a few cases have been described in the Cuban literature. Case presentation: one patient was reported with a neurotoxoplasmosis condition with bad adherence to the anti-retroviral treatment. In spite of prescribing the correct treatment, the patient had a fatal evolution.Conclusions: the onset of the neurotoxoplasmosis in this case was due to a therapeutical mistake determined by the improper adherence to the antiretroviral treatment. One of the main objectives of the integral care team is to guarantee the fulfilment of the antiretroviral treatment to prevent lethal opportunistic infections such as neurotoxoplasmosis(AU)

Neurotoxoplasmosis y adherencia al tratamiento antirretroviral en pacientes con VIH/sida. Presentación de un caso

Fundamento: alrededor de un tercio de los pacientes con VIH/sida presentan complicaciones nerviosas con considerable morbilidad y mortalidad. Una de ellas, la neurotoxoplasmosis, puede tener una alta incidencia en estos pacientes. Han sido pocos los casos descritos en la literatura cubana. Presentación de caso: se reporta un paciente con un cuadro de neurotoxoplasmosis y estado de inmunodepresión grave, con mala adherencia al tratamiento antirretroviral. A pesar de indicársele el tratamiento adecuado evoluciona fatalmente. Conclusiones: la aparición de la neurotoxoplasmosis en el caso reportado se debió a un fracaso terapéutico determinado por la mala adherencia al tratamiento antirretroviral. Uno de los objetivos principales del equipo de atención integral es garantizar el cumplimiento del tratamiento antirretroviral para evitar infecciones oportunistas letales como la neurotoxoplasmosis(AU)

Debut clínico de SIDA: presentación de dos casos / Clinical onset of AIDS: presentation of two cases

Introducción: El debut clínico es un fenómeno particular dentro de la epidemia de VIH/SIDA que se viene observando en todo el mundo. Los cuadros diarreicos son una de las formas de su presentación. Presentación de casos: Se reportan dos pacientes con Virus de Inmunodeficiencia Humana que su debut clínico fueron las diarreas y en los cuales su diagnóstico serológico fue tardío presentándose con estado de inmunodepresión grave. Conclusiones: Luego de ponérseles tratamiento antirretroviral las diarreas desparecieron y hubo una recuperación inmunológica evidente (AU)

Introduction: A clinical onset is a particular phenomenon in HIV / AIDS that has been observed worldwide. Acute diarrhea is one form of their presentation. Case Presentation: We report two patients with Human Immunodeficiency Virus with a clinical onset of diarrhea who had a delayed serological diagnosis and severe immunosuppression. Conclusions: After antiretroviral treatment was begun diarrhea disappeared and there was a clear immunological recovery (AU)