An Approach to a Bislactone Skeleton: A Scalable Total Synthesis of (+/-)-Penifulvin A

An efficient and scalable total synthesis of the architecturally challenging sesquiterpenoid (+/-)-penifulvin A has been accomplished via a 12-step sequence with an overall yield of 16%. For the construction of this structurally complex tetracyclic molecule, the key steps used included 1,4-conjugate addition, a Pd(0) catalyzed cross-coupling reaction between an enol phosphate and trimethyl aluminum, Claisen rearrangement using the Johnson orthoester protocol, Ti(III)-mediated reductive epoxide opening-cyclization, Lewis acid catalyzed epoxy-aldehyde rearrangement, and finally a substrate controlled oxidative cascade lactonization process.

Total internal reflection Raman spectroscopy of poly(alpha-olefin) oils in a lubricated contact

The rheology of a poly(alpha-olefin) base oil (PAO) in a sliding point contact has been investigated by total internal reflection (TIR) Raman spectroscopy. TIR Raman has the sensitivity to analyse nanometer-thick lubricant films in a tribological contact. The Raman signal generated from the sliding contact was used to determine the lubricant film thickness. The experimentally obtained film thicknesses were compared with theoretical calculations and a transition from Newtonian to non-Newtonian behaviour was observed at high shear rates. The Raman spectra showed no significant changes in the conformation of the PAO chains under the applied conditions of pressure and shear, but the polarisation dependence of the spectra revealed a preferred orientation of the hydrocarbon side chains in the shear-thinned region. Monolayers formed by a boundary lubricant, arachidic acid, dissolved in the PAO could be detected on the surfaces in the elastohydrodynamic regime.

Total synthesis of the indole alkaloids henrycinol A and B

The total synthesis of new indole alkaloids henrycinol A and B were accomplished starting from L-tryptophan methyl ester. The key step is a stereochemically flexible Pictet-Spengler reaction governed by the presence or absence of an N-allyl group in the tryptophan precursor. The natural products henrycinol A and B were synthesized in good overall yield in eight and nine steps, respectively. (C) 2014 Elsevier Ltd. All rights reserved.

Total synthesis of (+)-anamarine

An enantiospecific total synthesis of polyhydroxy delta-pyrone natural product (+)-anamarine is accomplished. The main features of the synthesis include the stereoselective reduction of the ketone obtained by the desymmetrization of the bis-dimethyl amide of tartaric acid and further elaboration involving asymmetric Brown's allylation and ring closing metathesis. (C) 2014 Elsevier Ltd. All rights reserved.

Toward the total synthesis of a lagunamide B analogue

Lagunamides, isolated from a marine cyanobacterium Lyngbya majuscule found in Singapore, showed very potent activities against Plasmodium falciparum and murine leukemia cell line (P388). Herein, a concise synthetic approach toward the total synthesis of a lagunamide B analogue is discussed. Macrolactonization, HWE-olefination, and modified Crimmin's aldol are some of the key reactions featured in this synthesis. (C) 2014 Elsevier Ltd. All rights reserved.

Enantiospecific Total Synthesis of Macrolactone Sch 725674

The enantiospecific total synthesis of 14-membered macrolactone Sch 725674 was accomplished from tartaric acid. Key reactions in the synthesis include the Ley's dithiaketalization of an alkynone derived from the bis-Weinreb amide of tartaric acid, Boord olefination, and ring-closing metathesis of an acrylate ester.

Hydrogen bonding, halogen bonding and lithium bonding: an atoms in molecules and natural bond orbital perspective towards conservation of total bond order, inter- and intra-molecular bonding

One hundred complexes have been investigated exhibiting D-X center dot center dot center dot A interactions, where X = H, Cl or Li and DX is the `X bond' donor and A is the acceptor. The optimized structures of all these complexes have been used to propose a generalized `Legon-Millen rule' for the angular geometry in all these interactions. A detailed Atoms in Molecules (AIM) theoretical analysis confirms an important conclusion, known in the literature: there is a strong correlation between the electron density at the X center dot center dot center dot A bond critical point (BCP) and the interaction energy for all these interactions. In addition, we show that extrapolation of the fitted line leads to the ionic bond for Li-bonding (electrostatic) while for hydrogen and chlorine bonding, it leads to the covalent bond. Further, we observe a strong correlation between the change in electron density at the D-X BCP and that at the X center dot center dot center dot A BCP, suggesting conservation of the bond order. The correlation found between penetration and electron density at BCP can be very useful for crystal structure analysis, which relies on arbitrary van der Waals radii for estimating penetration. Various criteria proposed for shared-and closed-shell interactions based on electron density topology have been tested for H/Cl/Li bonded complexes. Finally, using the natural bond orbital (NBO) analysis it is shown that the D-X bond weakens upon X bond formation, whether it is ionic (DLi) or covalent (DH/DCl) and the respective indices such as ionicity or covalent bond order decrease. Clearly, one can think of conservation of bond order that includes ionic and covalent contributions to both D-X and X center dot center dot center dot A bonds, for not only X = H/Cl/Li investigated here but also any atom involved in intermolecular bonding.

Enantiospecific Formal Total Synthesis of Iriomoteolide 3a

A formal total synthesis of the marine macrolide iriomoteolide3a is described. Salient features of the synthesis include the elaboration of a -keto phosphonate derived from D-(-)-tartaric acid and the extension of a chiral butyrolactone derived from L-glutamic acid. Ring-closing metathesis is employed to construct the macrolactone core of the natural product.

Investigations on Optimal Pulse-Width Modulation to Minimize Total Harmonic Distortion in the Line Current

PWM waveforms with positive voltage transition at the positive zero crossing of the fundamental voltage (type-A) are generally considered for PWM waveform with even number of switching angles per quarter whereas, waveforms with negative voltage transition at the positive zero crossing (type-B) are considered for odd number of switching angles per quarter. Optimal PWM, for minimization of total harmonic distortion of line to line (VWTHD), is generally solved with the aforementioned criteria. This paper establishes that a combination of both types of waveforms gives better performance than any individual type in terms of minimum VWTHD for complete range of modulation index (M). Optimal PWM for minimum VWTHD is solved for PWM waveforms with pulse numbers (P) of 5 and 7. Both type-A and type-B waveforms are found to be better in different ranges of M. The theoretical findings are confirmed through simulation and experimental results on a 3.7 kW squirrel cage induction motor in an open-loop V/f drive. Further, the optimal PWM is analysed from a space vector point of view.

Biosensor with Total Internal reflection Imaging Ellipsometry

In order to monitor multiple protein reaction processes simultaneously, a biosensor based on imaging ellipsometry operated in the total internal reflection mode is proposed. It could be realised as an automatic analysis for protein interaction processes with real-time label-free method. Its principle and methodology as well as a demonstration for its applications are presented.

Evaluación de la sustitucion parcial o total de aceite de palma (Elaeis guinensis) por aceite de fritura como fuente de energía en la ración alimenticia de pollos de engorde

La presente investigación estuvo dirigida a determinar la viabilidad, que sobre el desempeño productivo del pollo de engorde, podía ejercer la sustitución parcial o total del porcentaje de aceite de palma (Elaeís guínensis, Jacq) por aceite de fritura como fuente de energía en la ración alimenticia. La sustitución parcial o total se hizo con base en el 6% de aceite que se incluye en la fórmula alimenticia, ajustada a los requerimientos de los pollos de engorde. El ensayo experimental fue realizado en la granja avícola "La Trinidad", propiedad de la empresa TIP-TOP INDUSTRIAL S.A. Se utilizaron 700 pollos de engorde para producción comercial, del híbrido Peterson-Hubbard, de un día de edad y mantenidos en evaluación durante un periodo de 42 días. Estos fueron distribuidos aleatoriamente en cuatro tratamientos, conformados cada uno de cinco unidades experimentales, y éstas a su vez con 35 pollos cada una, quedando de la forma siguiente: Tratamiento T1 (testigo): 6% aceite de palma; tratamiento T2 : 2% aceite de palma y 4% aceite de fritura; tratamiento T3: 1% aceite de palma y 5% aceite de fritura; tratamiento T4 : 6% aceite de fritura. El resto de los ingredientes que conformó la dieta alimenticia fue igual para todos los tratamientos; así como también el manejo de los pollos se realizó al igual que lo hace la Empresa para toda su producción. Las variables estudiadas fueron consumo de alimento, peso vivo final y conversión de alimento. Los resultados obtenidos a partir de estas variables fueron analizados a través de un Diseño Completamente Aleatorio y sometidos a la Prueba de Tukey, el que proporcionó la superioridad existente entre tratamientos. Se encontraron diferencias significativas (p<0.05) entre tratamientos para la variable conversión alimenticia, con índices de conversión para el final de período experimental, de 1.8050, 1.7829, 1.7550 y 1.7310 para los tratamientos T1, T2, T3 y T4, respectivamente. Las variables consumo acumulado de alimento y peso vivo final no presentaron diferencias estadísticas a un nivel de significancia de p<0.05. El análisis financiero demostró que el tratamiento T4 tiene un menor costo de alimentación, siendo este de C$3.35/kg peso vivo. Encontrándose los tratamientos T1.T2 y T3 con costos de C$3.8210, C$3.5624; y C$3.4527/kg peso vivo, respectivamente. El mayor beneficio neto por kilogramo de peso vivo lo obtuvo el tratamiento T4, con C$0.47. Siendo el beneficio neto para los tratamientos T2 y T3 de C$0.26 y C$ 0.37, respectivamente. La mortalidad presentada por los tratamientos T1, T2, T3, y T4 para el final del período experimental fue de 5.13, 3.99, 2.85 y 3.99 (%), respectivamente.

Efecto de distintos intervalos de mediciones de leche sobre la estimación de producción de leche total, repetibilidad y la forma de la curva de lactancia en un hato reyna

El presente trabajo se realizó con el objetivo de estudiar el efecto de cuatro intervalos de medición de leche (diario, cada 7, 14 y 28 días) sobre la producción de leche total, la repetibilidad y la forma de la curva de lactancia. Para lo cual se utilizaron los registros productivos y reproductivos del hato criollo Reyna de la Finca San José ubicada en Masatepe, Nicaragua. Se estudiaron 105 lactancia provenientes de 28 vacas durante el periodo de 1982 - 1990. Las características estudiadas fueron PLTOT, repetibilidad y la forma de la curva de lactancia. Todos los análisis estadísticos fueron realizados con el procedimiento de mínimos cuadrados y máxima verosimilitud establecido en el paquete estadístico LSMLMW total, obteniéndose las siguientes medias de mínimos cuadrados: 1,655.23±77.79 para el tratamiento 1 total. Los valores encontrados para los indices de Repetibilidad para cada uno de los tratamientos fueron de: 0.46±0.11, 0.50±0.11, 0.48±0.11 y 0.50±0.11 para los tratamientos 1, 2, 3, 4 respectivamente Los valores para los parámetros y variables estudias en la curva de la lactancia fueron 3.2±2.5, 0.47±0.32, 0.01± 0.06, 51.81±29.10, 9.45±3.49 y 6.97±1.02 para a, b, c, Tp, Rp y S respectivamente Al estudiar el efecto de los tratamiento sobre las variables y parámetros de la curva de lactancia se determino que solamente la variable (S) que determina la persistencia fue afectada significativamente

Revelation of a Functional Dependence of the Sum of Two Uniaxial Strengths/Hardness on Elastic Work/Total Work of Indentation

Dimensional and finite element analyses were used to analyze the relationship between the mechanical properties and instrumented indentation response of materials. Results revealed the existence of a functional dependence of (engineering yield strength sigma(E,y) + engineering tensile strength sigma(E,b))/Oliver & Pharr hardness on the ratio of reversible elastic work to total work obtained from an indentation test. The relationship links up the Oliver & Pharr hardness with the material strengths, although the Oliver & Pharr hardness may deviate from the true hardness when sinking in or piling up occurs. The functional relationship can further be used to estimate the SUM sigma(E,y) + sigma(E,b) according to the data of an instrumented indentation test. The sigma(E,y) + sigma(E,b) value better reflects the strength of a material compared to the hardness value alone. The method was shown to be effective when applied to aluminum alloys. The relationship can further be used to estimate the fatigue limits, which are usually obtained from macroscopic fatigue tests in different modes.

Efectos de la combinación de abonos orgánicos y fertilizante químico sobre la densidad aparente y el espacio poroso total de un suelo volcánico Nicaragüense

Se realizó un muestreo de suelos en parcelas experimentales de un ensayo de campo, con el fin de evaluar los efectos de la aplicación de tres dosis de Abonos Orgáníeos (AO), combinadas con fertilizante químico, sobre la densidad aparente (á) y el espacio poroso total (FPT) de un suelo volcánico nicaragüense. El ensayo se realizó durante la época de Postrera (Septiembre -Diciembre) de 1989, en la Finca Experimental La Compañía, Carazo, Nicaragua; sobre un suelo franco - arenoso derivado de cenizas volcánicas (Typic Durandepts). Se utilizó un experimento Bifactorial en diseño de parcelas divididas en Bloques completos al azar, con cuatro réplicas. Los AO empleados fueron Gallinaza, Compost y Pulpa de café, siendo las dosis ensayadas de 5, 10 y 15 ton.ha 1 de cada uno, combinadas con Fosfato Díamónico a razón de 64.8 kg.ba· 1• Se observó una disminoción de la d y un aumento del EPT con la aplícacion de los AO, siendo este efecto influido por las dosis incorporadas. Las parcelas que presentaron la menor d y el mayor EPT, fueron aquellas donde se incorporó el Compost.