Acetylene as a Dicarbene Equivalent for Gold(I) Catalysis: Total Synthesis of Waitziacuminone in One Step.

The gold(I)-catalyzed reaction of acetylene gas with alkenes leads to (Z,Z)-1,4-disubstituted 1,3-butadienes and biscyclopropanes depending on the donor ligand on gold(I). Acetylene was generated in situ from calcium carbide and water in a user-friendly procedure. Reaction of acetylene with 1,5-dienes gives rise stereoselectively to tricyclo[5.1.0.02,4 ]octanes. This novel double cyclopropanation has been applied to the one step total synthesis of the natural product waitziacuminone from acetylene and geranyl acetone.

Broad-Scope Rh-Catalyzed Inverse-Sonogashira Reaction Directed by Weakly Coordinating Groups.

We report the alkynylation of C(sp2)-H bonds with bromoalkynes (inverse-Sonogashira reaction) directed by synthetically useful ester, ketone, and ether groups under rhodium catalysis. Other less common directing groups such as amine, thioether, sulfoxide, sulfone, phenol ester, and carbamate are also suitable directing groups. Mechanistic studies indicate that the reaction proceeds by a turnover-limiting C-H activation step via an electrophilic-type substitution.

Cyclobutene vs 1,3-Diene Formation in the Gold-Catalyzed Reaction of Alkynes with Alkenes: The Complete Mechanistic Picture.

The intermolecular gold(I)-catalyzed reaction between arylalkynes and alkenes leads to cyclobutenes by a [2 + 2] cycloaddition, which takes place stepwise, first by formation of cyclopropyl gold(I) carbenes, followed by a ring expansion. However, 1,3-butadienes are also formed in the case of ortho-substituted arylalkynes by a metathesis-type process. The corresponding reaction of alkenes with aryl-1,3-butadiynes, ethynylogous to arylalkynes, leads exclusively to cyclobutenes. A comprehensive mechanism for the gold(I)-catalyzed reaction of alkynes with alkenes is proposed on the basis of density functional theory calculations, which shows that the two pathways leading to cyclobutenes or dienes are very close in energy. The key intermediates are cyclopropyl gold(I) carbenes, which have been independently generated by retro-Buchner reaction from stereodefined 1a,7b-dihydro-1H-cyclopropa[a]naphthalenes.

Robust and Accurate Modeling Approaches for Migraine Per-Patient Prediction from Ambulatory Data.

Migraine is one of the most wide-spread neurological disorders, and its medical treatment represents a high percentage of the costs of health systems. In some patients, characteristic symptoms that precede the headache appear. However, they are nonspecific, and their prediction horizon is unknown and pretty variable; hence, these symptoms are almost useless for prediction, and they are not useful to advance the intake of drugs to be effective and neutralize the pain. To solve this problem, this paper sets up a realistic monitoring scenario where hemodynamic variables from real patients are monitored in ambulatory conditions with a wireless body sensor network (WBSN). The acquired data are used to evaluate the predictive capabilities and robustness against noise and failures in sensors of several modeling approaches. The obtained results encourage the development of per-patient models based on state-space models (N4SID) that are capable of providing average forecast windows of 47 min and a low rate of false positives.

Gallium-catalyzed domino arylation/oxycyclization of allenes with phenols.

The synthesis of dihydrobenzofuran-appended oxindoles has been accomplished taking advantage of an unprecedented reaction between allenols and phenols under metal catalysis.

Gastroplastía con banda sueca ajustable para el tratamiento de la obesidad severa-mórbida. Resultados de tres años de experiencia / Nissen Gastroplastía with adjustable Swedish band for the treatment of the severe-mo'rbida obesity. Results of three years of experience

La terapia quirúrgica para el tratamiento de la obesidad mórbida y severa, tiene casi 20 años de historia y ha mostrado ser el método más efectivo para la prevención y control de sus potenciales comorbilidades. La obesidad es un problema de salud ligado a la historia del ser humano, sin embargo en la última década en donde se la reconoce como un verdaero problema social, con alta demanda de costos al igual que limitaciones funcionales en la población expuesta, en especial en los países occidentales. Resumimos en este trabajo nuestra experiencia de 3 años con el uso de la banda gástrica sueca ajustable, colocada por vía laparoscópica, en los primeros 100 pacientes. Las indicaciones fueron IMC sobre 35 con comorbilidades...

Hernias inguinales: tratamiento con el doble sistema de malla / Hernias inguinales: treatment with the double system of mesh

Probablemente la cirugía sobre la región inguinal sea la más frecuente en los hospitales y la que más variantes técnicas haya desarrollado para su tratamiento. Cada una de las cuales presenta innovaciones y novedades que de acuerdo a la época ha sido preferidas. Sin embargo la colocación de prótesis ha sido la que más ha perdurado y sobre la que se han desarrollado nuevas opciones. Presentamos los resultados obtenidos en el tratamiento de hernias inguinales utilizando el sistema de doble malla y plug sobre un universo de 20 pacientes en el Hospital Metropolitano. La mayoría de los pacientes tuvieron un diagnóstico de hernia inguinal primaria. Fueron recidivantes en el 20 por ciento de los casos. Los hallazgos transoperatorios reportaron la presencia de hernia directa en el 85 por ciento...

Networking, coping, and communicating about a medical crisis: a phenomenological inquiry of transplant recipient communication.

Through a phenomenological framework, the authors attempt to shed light on the communication processes of organ transplant recipients when discussing transplantation and related topics. Eight essential themes (awareness, support, commitment, pride, education, mentoring, comparison, and community) emerged from 37 participants as central to the communicative experiences of transplant recipients and their families. Additional insight was generated through a 2nd tier of focus group discussions resulting in a proposed model of transplant recipient communication. An interpretation of the model, implications for future research, and implications for praxis are presented.

Negotiating the tension between policy and reality: exploring nurses' communication about organizational wrongdoing.

This article explores the ways in which registered nurses communicate about organizational wrongdoing. Critical incidents were gathered from over 200 registered nurses. Through the phenomenological process of description, reduction, and interpretation, 5 themes emerged as central to responses of policy violations and personal ethics in the workplace: (a) perceptions of wrongdoing, (b) upholding the ideals of the profession, (c) clarity and evidence of wrongdoing, (d) consequences of reporting, and (e) workplace dynamics. The interpretative findings focus on how these themes are united by a tension that nurses face in terms of adhering to policy while attempting to manage the realities of their everyday professional lives. A discussion of these findings, including how they relate to existing and future research and practice, is offered.

Evaluación de la deficiencia de hierro y anemia ferropriva en poblacion de alto Riesgo

La evaluación de la deficiencia de hierro en población de alto riesgo puede lograrse a través de la selección cuidadosa de diversos indicadores bioquímicos, y hematológicos, que traduzcan adecuadamente los diferentes estadíos de su evolución: 1) deficiencia de las reservas corporales o IDS a travéz de la ferritina sérica 2) aporte medular de hierro deficiente o IDE mediante la dosificación de protoporfirina eritrocitaria, porcentaje de saturación de la trasnferina y receptores de la transferrina, y 3) anemia ferropriva, estimada por la cuantificación de la hemoglobina o el hematocrito. El objetivo que se proponga en la evaluación, permitirá seleccionar adecuadamente el o los indicadores para estimar el status de hierro de la población blanco. La sensibilidad y especificidad de estos es un aspecto importante a considerar, al igual que la magnitud de la carencia marcial y la concurrencia simultánea de otros factores de confusión como; hemoglobinopatías, malaria, infección, etc.

Synthesis of C-(beta-D-glycosyl) analogues of 3-deoxy-D-manno-2-octulosonic acid (Kdo) as potential inhibitors of CMP-Kdo synthetase.

Eight C-(beta-D-glycosyl) analogues (14-21) of Kdo (3-deoxy-D-manno-2-octulosonic acid) were obtained from isopropylidene-protected ester precursors and tested in vitro for their inhibitory activity on CMP-Kdo synthetase. None had more than minor inhibitory activity.

[Omphalopagus conjoined twins with successful surgical separation (author's transl)]. / Separación quirúrgica con supervivencia de dos gemelas siamesas onfalópagos.

The authors present an observation of omphalopagus conjoined twins with successful separation. They comment on the etiopathogenic factors, obstetrical problems, investigation of the extent of the union and operative timing.