Synthesis of Trilaurin by Developing Pisa Seeds (Actinodaphne hookeri)

The developing seeds of Actinodaphne hookeri were investigated to delineate their ability to synthesize large amounts of trilaurin. Until 88 days after flowering the embryos contained 71% neutral lipids (NL) and 29% phospholipids (PL) and both these components contained C-16:0, C-18:0, C-18:2, and C-18:3 as the major fatty acids (FA). At 102 days after flowering the seeds began to accumulate triacylglycerols (TAG) and to synthesize lauric acid (C-12:0). By 165 days after flowering, when the seeds were mature, they contained about 99% NL and 1% FL. At this stage the TAG contained exclusively C-12:0, while the PL consisted of long-chain fatty acids (LCFA) only. Leaf lipids in contrast did not contain any C-12:0. Experiments on [1-C-14]acetate incorporation into developing seed slices showed that at 88 days after flowering only 4% of the label was in TAG, 1% in diacylglycerols (DAG), and 87% in FL. One hundred two days after flowering seeds incorporated only 2% of the label into TAG, 30% into DAG, and 64% into FL. In contrast at 114 days after flowering 71% of the label was incorporated into TAG, 25% into DAG, and only 2% into FL. Analysis of labeled FA revealed that up to 102 days after flowering it was incorporated only into LCFA, whereas at 114 days after flowering it was incorporated exclusively into C-12:0. Furthermore, 67% of the label in PL at 114 days after flowering was found to be dilaurylglycerophosphate. Analysis of the label in DAG at this stage showed that it was essentially in dilaurin species. These observations indicate the induction of enzymes of Kennedy pathway for the specific synthesis of trilaurin at about 114 days after flowering, Homogenates of seeds (114 days after flowering) incubated with labeled FA in the presence of glycerol-3-phosphate and coenzymes A and ATP incorporated 84% of C-12:0 and 61% of C-14:0, but not C-16:0, C-18:2, and C-18:3, into TAG. In contrast the LCFA were incorporated preferentially into FL. It is concluded that, between 102 and 114 days after flowering, a switch occurs in A. hookeri for the synthesis of C-12:0 and trilaurin which is tissue specific. Since the seed synthesizes exclusively C-12:0 at 114 days after flowering onwards and incorporates specifically into TAG, this system appears to be ideal for identifying the enzymes responsible for medium-chain fatty acid as well as trilaurin synthesis and for exploiting them for genetic engineering. (C) 1994 Academic Press, Inc.

Synthesis, properties and crystal structures of diastereomeric areneruthenium(II) chiral Schiff-base complexes

Diastereomers (SRu,Sc)-1a and (RRu,Sc)-1b, in a ratio of 85: 15 and formulated as [Ru(η-MeC6H4Pri-p)Cl(L*)], have been prepared by treating [{Ru(η-MeC6H4Pri-p)Cl2}2] with the sodium salt of (S)-α-methylbenzylsalicylaldimine (HL*) in tetrahydrofuran at –70 °C. The reaction of 1(1a+1b) with AgClO4 in acetone followed by an addition of PPh3 or 4-methylpyridine (4Me-py) leads to the formation of adducts [Ru(η-MeC6H4Pri-p)(PPh3)(L*)]ClO42[(SRu,Sc)2a, (FRu,Sc)2b] and [Ru(η-MeC6H4Pri-p)(4Me-py)(L*)]ClO43[(SRu,Sc)3a, (RRu,Sc)3b] in the diastereomeric ratios (SRu,Sc) : (RRu,Sc) of 2 : 98 and 76 : 24, respectively. Complex 1 crystallises with equal numbers of 1a and 1b molecules in an asymmetric unit of monoclinic space group P21 with a= 10.854(1), b= 17.090(1), c= 12.808(4)Å, β= 110.51(1)°, and Z= 4. The structure was refined to R= 0.0552 and R′= 0.0530 with 2893 reflections having I[gt-or-equal] 1.5σ(I). The absolute configurations of the chiral centres in the optically pure single crystal of the PPh3 adduct have been obtained from an X-ray study. Crystals of formulation [Ru(η-MeC6H4Pri-p)-(PPh3)(L*)]2[ClO4][PF6]·1.5 CHCl3, obtained in presence of both ClO4 and PF6 anions, belong to the non-centric triclinic space group P1 with a= 10.852(2), b= 14.028(1), c= 15.950(2)Å, α= 91.51(1), β= 105.97(1), γ= 106.11(1)°, and Z= 2. The final residuals were R= 0.0713, R′= 0.0752 with 7283 reflections having I[gt-or-equal] 2.5σ(I). The crystal structures of 1a,1b, and the PPh3 adduct (2b,2b′) consist of a ruthenium(II) centre bonded to a η-p-cymene, a bidentate chelating Schiff base, and a unidentate ligand (Cl or PPh3). The chirooptical properties of the complexes have been studied using 1H NMR and CD spectral data. The presence of a low-energy barrier for the intermediate involved in these reactions, showing both retention as well as inversion of the metal configuration, is discussed.

Carbon recombination lines between 34.5 and 770 MHz toward Cassiopeia A

We present observations of low-frequency recombination lines of carbon toward Cas A near 34.5 MHz (n similar to 575) using the Gauribidanur radio telescope and near 560 MHz (n similar to 225) and 770 MHz (n similar to 205) using the NRAO 140 foot (43 m) telescope in Greenbank. We also present high angular resolution (1') observations of the C270 alpha line near 332 MHz using the Very Large Array in B-configuration. A high signal-to-noise ratio spectrum is obtained at 34.5 MHz, which clearly shows a Voigt profile with distinct Lorentzian wings, resulting from significant pressure and radiation broadening at such high quantum numbers. The emission lines detected near 332, 550, and 770 MHz, on the other hand, are narrow and essentially Doppler-broadened. The measured Lorentzian width at 34.5 MHz constrains the allowed combinations of radiation temperature, electron density, and electron temperature in the line-forming region. Radiation broadening at 34.5 MHz places a lower limit of 115 pc on the separation between Cas A and the line-forming clouds. Modeling the variation in the integrated line-to-continuum ratio with frequency indicates that the region is likely to be associated with the cold atomic hydrogen component of the interstellar medium, and the physical properties of this region are likely to be T-e = 75 K, n(e) = 0.02 cm(-3), T-R100 = 3200 K, and n(H) T-e = 10,000 cm(-3) K. Comparison of the distribution of the C270 alpha recombination line emission across Cas A with that of (CO)-C-12 and H I also supports the above conclusion.

Synthesis and cation binding properties of new bile acid-based crown ethers

A series of bile acid-based crown ethers (7a-c,12 and 13) were easily constructed from readily available precursors. Measurement of association constants (K-a) with alkali metal picrates in CHCl3 showed that azacrown ethers 7a-c and Chola-Cuowns 12 and 13 show greater binding towards Rb+ and K+. The presence of the aromatic moieties showed subtle changes in the binding properties. Insight II minimized structures show very different conformations of aromatic units in 7a-b and 13.

Structural characterization of folded pentapeptides containing centrally positioned beta(R)Val, gamma(R)Val and gamma(S)Val residues

A cylindrical pore of similar to 7.5 angstrom diameter containing a one-dimensional water wire, within the confines of a hydrophobic channel lined with the valine side chain, has been observed in crystals of the peptide Boc-D-Pro-Aib-Val-Aib-Val-OMe (1) (Raghavender et al., 2009, 2010). The synthesis and structural characterization in crystals of three backbone homologated analogues Boc-D-Pro-Aib-beta(3)(R) Val-Aib-Val-OMe (2), Boc-D-Pro-Aib-gamma(4)(R)Val-Aib-Val-OMe (3), Boc-D-Pro-Aib-gamma(4)(S)Val-Aib-Val-OMe (4) are described. Crystal structures of peptides 2, 3 and 4 reveal close-packed arrangements in which no pore was formed. In peptides 2 and 3 the N-terminus D-Pro-Aib segment adopted conformations closely related to Type II' beta-turns, while residues 2-4 form one turn of an alpha beta right-handed C-11 helix in 2 and an alpha gamma C-12 helix in 3. In peptide 4, a continuous left-handed helical structure was observed with the D-Pro-Aib segment forming a Type III' beta-turn, followed by one turn of a left-handed alpha gamma C-12 helix. (C) 2012 Elsevier Ltd. All rights reserved.

Structural characterization of backbone-expanded helices in hybrid peptides: (αγ) n and (αβ) n sequences with unconstrained β and γ homologues of L-Val

Learning your αβγ's: The diversity of hydrogen-bonding patterns in backbone-expanded hybrid helices is shown by crystal-structure determination of several oligomeric peptides (see scheme; C=gray; H=white; O=red; N=blue). C 12 helices were observed in the αγ peptide series for n=2-8. In comparison, the αα peptide and αβ peptide sequences show C 10 and mixed C 14/C 15 helices, respectively. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Synthesis, structural analysis and solvatochromic behaviour of 4,6-bis (4-butoxyphenyl)-2-methoxynicotinonitrile mesogen

In this communication, we report the synthesis and characterisation of a new luminescent liquid crystalline material, 4,6-bis (4-butoxyphenyl)-2-methoxynicotinonitrile (3). We have confirmed its structure by Fourier transform infrared and 1H nuclear magnetic resonance spectroscopy, elemental analysis and X-ray single crystal diffraction studies. The newly synthesised compound crystallises in a monoclinic system with the space group C2/c and its cell parameters are found to be a?=?25.181(4) angstrom, b?=?15.651(4)angstrom, c?=?12.703(19) angstrom, V?=?4880.4 (16) angstrom, Z?=?8. The results indicate that the presence of weak CH center dot center dot center dot O and CH center dot center dot center dot N hydrogen bonding as short-range intermolecular interactions are responsible for the formation of its crystal assembly. The measured torsion angle shows the existence of a distorted structure for the molecule wherein 4-butoxyphenylene ring substituent at the fourth position of the central pyridine ring forms a torsion angle chiC(4), C(3), C(10), C(19)] of 40.55 degrees. Its liquid crystalline behaviour was investigated with the aid of polarised optical microscopy and differential scanning calorimetry. The study reveals that the compound displays a broad nematic phase in the range of 78112 degrees C. Further, solution phase optical studies indicate that it is a blue light emitter in different non-polar and polar organic solvents at a concentration of 10-5M.

Solution of Time Dependent Joule Heat Equation for a Graphene Sheet Under Thomson Effect

We address a physics-based solution of joule heating phenomenon in a single-layer graphene (SLG) sheet under the presence of Thomson effect. We demonstrate that the temperature in an isotopically pure (containing only C-12) SLG sheet attains its saturation level quicker than when doped with its isotopes (C-13). From the solution of the joule heating equation, we find that the thermal time constant of the SLG sheet is in the order of tenths of a nanosecond for SLG dimensions of a few micrometers. These results have been formulated using the electron interactions with the inplane and flexural phonons to demonstrate a field-dependent Landauer transmission coefficient. We further develop an analytical model of the SLG specific heat using the quadratic (out of plane) phonon band structure over the room temperature. Additionally, we show that a cooling effect in the SLG sheet can be substantially enhanced with the addition of C-13. The methodologies as discussed in this paper can be put forward to analyze the graphene heat spreader theory.

A fast NMR method for resonance assignments: application to metabolomics

We present a new method for rapid NMR data acquisition and assignments applicable to unlabeled (C-12) or C-13-labeled biomolecules/organic molecules in general and metabolomics in particular. The method involves the acquisition of three two dimensional (2D) NMR spectra simultaneously using a dual receiver system. The three spectra, namely: (1) G-matrix Fourier transform (GFT) (3,2)D C-13, H-1] HSQC-TOCSY, (2) 2D H-1-H-1 TOCSY and (3) 2D C-13-H-1 HETCOR are acquired in a single experiment and provide mutually complementary information to completely assign individual metabolites in a mixture. The GFT (3,2)D C-13, H-1] HSQC-TOCSY provides 3D correlations in a reduced dimensionality manner facilitating high resolution and unambiguous assignments. The experiments were applied for complete H-1 and C-13 assignments of a mixture of 21 unlabeled metabolites corresponding to a medium used in assisted reproductive technology. Taken together, the experiments provide time gain of order of magnitudes compared to the conventional data acquisition methods and can be combined with other fast NMR techniques such as non-uniform sampling and covariance spectroscopy. This provides new avenues for using multiple receivers and projection NMR techniques for high-throughput approaches in metabolomics.

Structural characterization of folded and extended conformations in peptides containing gamma amino acids with proteinogenic side chains: crystal structures of gamma(n), (alpha gamma)(n) and gamma gamma delta gamma sequences

The crystal structures of nine peptides containing gamma(4)Val and gamma(4)Leu are described. The short sequences Boc-gamma(4)(R)Val](2)-OMe 1, Boc-gamma(4)(R)Val](3)-NHMe 2 and Boc-gamma(4)(S)Val-gamma(4)(R)Val-OMe 3 adopt extended apolar, sheet like structures. The tetrapeptide Boc-gamma(4)(R)Val](4)-OMe 4 adopts an extended conformation, in contrast to the folded C-14 helical structure determined previously for Boc-gamma(4)(R)Leu](4)-OMe. The hybrid alpha gamma sequence Boc-Ala-gamma(4)(R)Leu](2)-OMe 5 adopts an S-shaped structure devoid of intramolecular hydrogen bonds, with both alpha residues adopting local helical conformations. In sharp contrast, the tetrapeptides Boc-Aib-gamma(4)(S)Leu](2)-OMe 6 and Boc-Leu-gamma(4)(R)Leu](2)-OMe 7 adopt folded structures stabilized by two successive C-12 hydrogen bonds. gamma(4)Val residues have also been incorporated into the strand segments of a crystalline octapeptide, Boc-Leu-gamma(4)(R)Val-Val-(D)Pro-Gly-Leu-gamma(4)(R)Val-Val-OMe 8. The gamma gamma delta gamma tetrapeptide containing gamma(4)Val and delta(5)Leu residues adopts an extended sheet like structure. The hydrogen bonding pattern at gamma residues corresponds to an apolar sheet, while a polar sheet is observed at the lone delta residue. The transition between folded and extended structures at gamma residues involves a change of the torsion angle from the gauche to the trans conformation about the C-beta-C-alpha bond.

Efecto de la inclusión de saccharina sobre el comportamiento productivo de cerdos de engorde

El presente trabajo experimental se realizó con el objetivo de evaluar el efecto de inclusión de dos niveles de Saccharina sobre los rendimientos productivos: Ganancia Media Diaria (GMD.); Consumo de Alimento Promedio (CAP); Conversión Alimenticia (CA) en cerdos de engorde, evaluándose la utilidad económica de los tratamientos. Se utilizaron tres tratamientos. T1: testigo; T2: 7.38 % de Saccharina y T3 : 14.76 % de Saccharina, los que estaban conformados por grupos de siete cerdos cada uno, con edades y pesos promedios de 120 días y 34.55 Kg. El análisis estadístico empleado fué un Diseño Completamente Aleatorio (DCA), para las variables GMD/Tratamiento y C.A/Tratamiento. Se obtuvieron ganancias medias diarias de T1: 750.48; T2 : 893.34; T3 : 774.29 gr/días/cerdos respectivamente. Resultando no significativa al Pr≤ O.05 para los tres tratamientos. Con la realización del análisis de costo de alimento por Kg de ganancia de peso se obtuvieron los valores de C$ 5.13 (T1); C$ 4.62 (T2); C$ 4.48 (T3) respectivamente. Al realizarse el presupuesto parcial se determinó que el tratamiento que obtuvo la mayor utilidad fue el tratamiento dos (T2) resultando de C$ 57.77 siendo para el tratamiento tres (T3 ) la utilidad de C$ 12.27 ambos tratamientos con respecto al tratamiento uno (T1). Por tanto, el tratamiento T2 es el que genera las beneficios económicos.

Diagnóstico sobre la producción y comercialización de los productos lacteos en el municipio de San Pedro de Lóvago, Chontales, Nicaragua

El trabajo fue realizado en la época de verano en el municipio de San pedro de Lóvago, Chontales donde se encuestó el 10% de los productores. La población total del municipio es de 7,125 habitantes, donde la mayoría viven en zonas rurales; la principal base de subsistencia es la ganadería siendo su principal fuente de trabajo.Es un municipio con alto potencial en su producción de leche y ocupando el segundo lugar en el departamento de chontales, cuenta con 46269 cabezas de ganado en todo el municipio con un rendimiento promedio de cuatro litros de leche por vaca y su explotación es de doble propósito, pastoreo directo y extensivo. Las prácticas de manejo, sanidad, alimentación y reproducción siguen siendo las mismas de manera tradicional. Aun no existe en la mayoría de los productores interés al cambio, los resultados muestran que la producción total de leche diaria en el municipio durante el verano es de 10,393.25 galones a diario y en invierno es de 12,000 galones aproximados. Los productores que mas elaboran en el municipio son: queso mosarela, queso moralique, cuajadas, crema, queso palmito y quesillos. El precio de la leche varia según la épocas del año siendo en verano el mejor precio pagado (C$ 14.00 por galón) debido a que existe una poca producción de leche en caso contrario en invierno que es cuando se produce el "golpe de leche" y el precio llega alcanzar hasta (C$ 4.00 por galón). La parmalat es la única empresa que recolecta leche en las cooperativas: Manantial con 1,400 galones a diario y la cooperativa San pedro con 1,104.25 galones a diario para un total de 2,504.25 en verano y 5,008.5 galones en invierno, la cual mantiene durante todo el año el precio estable por galón de C$ 12.00. La comercialización se empieza desde el productor hasta el consumidor final a través de una cadena de intermediarios. La mayor pate de los productos van destinados a la capital (80%) y otra parte se exportan a El Salvador (20%) de manera directa. La producción anual de carne en el municipio es alrededor de 3,000 kilogramos siendo los principales acopiadores o centro de venta de. novíllo de modalidad canal caliente y en pie. El matadero MASESA con un 30% de la producción total, el matadero Nandaime con 20%, el matadero CARNIC con un 10%, los corrales de tipitapa 30% y los matarifes con el 10% restante de cabezas d ganado bovino.

Estudio de seis tratamientos nitrogenados bajo riego por goteo de 3.6 litros de agua por metro lineal por día en la producción de chilote en el cultivo del maíz (Zea mays L.), variedad NB-S, a una densidad de 62 500 ptas/ha

El presente trabajo de investigación se estableció entre los meses de febrero–mayo del año 2012, bajo sistema de riego por goteo en los terrenos propiedad de la Universidad Nacional Agraria (UNA), ubicada en el km 12 1/2 carretera norte, municipio de Managua con las coordenadas 12°08 ́36” latitud norte y 86°09 ́49” longitud oeste a una alturade 56 msnm. Con el objetivo de estudiar seis tratamientos nitrogenados (A=50 kg ha-1 de N aplicada 100% a los 21 ddg; B = 50 kg ha-1 de N; Aplicada 50% a los 21dds y 50 % a los 42 ddg; C=50 kg ha-1 de N aplicada 100% a los 42 ddg; D= 100 kg ha-1 de N; Aplicada 100% a los 21 ddg; E= 100 kg ha-1 de N; Aplicada 50% a los 21 ddg y 50 % a los 42 ddg; F=100 kg ha-1 de N; Aplicado 100% a los 42 ddg) ) se estableció un experimento unifactorial en bloques completos al azar, para evaluar el efecto de los mismos sobre el crecimiento del maíz y rendimiento del chilote. Las variables evaluadas fueron durante el desarrollo de la planta: altura de planta, diámetro de tallo, número de hojas. A la cosecha: Altura de la 1era y 2da inserción del chilote (cm),peso del chilote con brácteas y sin brácteas (kg),longitud del chilote con brácteas y sin brácteas (cm), diámetro del chilote con brácteas y sin brácteas (cm) y rendimiento del chilote (kg/ha). La evaluación estadística a los datos de estas variables, se realizó por medio del Análisis de Varianza y separación de medias por Duncan al 5 % de confiabilidad. De los seis tratamientos evaluados, el tratamiento. E indujo al mayor rendimiento de chilote con una producción de 2,265.63 kg ha-1,con un beneficio neto de C$ 12,493.03 córdobas ha-1 y una tasa de retorno marginal del 201.49%

Efecto de suplementación de miel urea al 10 % versus concentrado El Ranchero al 16% en novillos de finalización en comarca Coyanchigue, Camoapa, Boaco

El presente estudio, se realizó con el objetivo de evaluar el comportamiento productivo y económico de novillos de finalización sometidos a dos suplementos nutricionales como parte de la dieta alimenticia que utiliza la Asociación de Ganaderos de Camoapa. Los suplementos correspondieron a suministro por animal de miel-urea al 10 % (180 g de urea-0.6 kg de melaza-120 g de sal común y mineral) y 2.7kg de concentrado comercial El Ranchero al 16 %, este suplemento se suministró durante 50 días a dos grupos conformados por 9 novillos correspondientemente, con pesos inicial es de entre 304-309 kg. Después de realizar análisis de muestras pareadas de t-student a los promedios de peso final y ganancia media diaria (GMD), se encontró diferencia significativa (Pr=0.03; gle=17) para los tratamientos: El Ranchero 16% tuvo un peso final promedio de 382.5 ± 10.7 kg y 366.9 ± 20.1 kg con suplementado con miel-urea 10 %. La GMD tuvo el promedio de 1.46 kg para El Ranchero 16% y 1.25 kg para miel-urea 10%. Los costos de suplemento miel-urea 10% fue de C$12.30 y de C$27.6 para El Ranchero 16%. La relación beneficio-costo para miel-urea reflejó que por cada córdoba invertido se generan C$ 2.82 y para concentrado el Ranchero al 16% se generan C$1.43.

A exposição a fumaça de cigarro altera distribuição de tecido adiposo branco de camundongos fêmeas jovens

O tabagismo e a obesidade são as principais causas de morbidade e mortalidade no mundo. Estudos populacionais relatam que fumantes, principalmente do sexo feminino, apresentam baixo índice de massa corporal. Porém, são escassos os estudos que avaliem a composição corporal de humanos e animais expostos a fumaça de cigarro, em especial nos adolescentes. Aos 35 d de idade, camundongos fêmeas foram expostos à fumaça de cigarros 3R4F (médio teor de nicotina), 8 h/dia, por 15 dias (F, n=12), paralelamente foi avaliado animais não expostos (C, n=12). Imediatamente após a exposição, metade dos animais de cada grupo foi sacrificada e a outra metade permaneceu em observação por 30dias. Durante todo o período experimental, a massa e comprimento corporal e ingestão alimentar foram avaliados. Ao final de cada período, os animais foram avaliados por DXA (Dual Energy X-ray Absorptiometry) e sacrificados por exsanguinação. Para avaliação e comprovação da exposição ao fumo foi utilizado a cotinina e morfologia do pulmão. No plasma foram avaliados colesterol, triglicerídeos, glicose, cotinina e insulina. Amostras de tecido adiposo intra-abdominal (IA) e subcutâneo (SC) foram coletadas e processadas por técnica histológica de rotina para análise morfológica. As expressões de PPAR, UCP2 e CPT1 foram avaliadas no tecido IA por western blotting. Durante a exposição, a massa, o comprimento corporal, a ingestão alimentar, a massa magra e a massa de tecido IA, bem como a glicose e o colesterol e a expressão de PPAR permaneceram inalterados. A expressão de UCP2 e CPT1, assim como a insulina circulante diminuiram. A gordura corporal total e do tronco, triglicerídeos e cotinina aumentaram. A análise morfológica não evidenciou alteração no tecido IA, mas, houve aumento do número e diminuição da área dos adipócitos no tecido SC. Após trinta de dias de abstinência a massa corporal, a massa e o número de adipócitos do tecido IA e a glicose aumentaram no grupo F, enquanto houve diminuição do colesterol, da área do adipócito IA e SC e do número do SC. Porém, sem alteração da ingestão, do comprimento corporal, da massa magra, da massa de gordura total e do tronco, da insulina e dos triglicerídeos e também da expressão de PPAR, UCP2 e CPT1 no IA. A exposição à fumaça de cigarro, em camundongos fêmeas jovens, desencadeou mudanças na adiposidade, que repercutiram de forma prejudicial e precoce sobre o metabolismo. Mesmo com a cessação do hábito de fumar os distúrbios metabólicos permanecem expressivos