Insertion Reactions of Six-Membered Cyclopalladated N,N `,N `'-Triarylguanidine, Pd{kappa(2)(C,N)-C6H3Me-3(NHC(NHAr)(=NAr))-2)(mu-Br)](2) (Ar=2-MeC6H4) with PhCC C-C(O)OR (R = Me and Et): A Gateway to Second Orthopalladation through Novel Rearrangements

The reaction of Pd{kappa(2)(C,N)-C6H3Me-3-(NHC(NHAr)(=NAr))-2}(mu-Br)](2) (Ar = 2-MeC6H4; 1) with 4 equiv of PhC C-C(O)OMe in CH2Cl2 afforded Pd{kappa(2)(C,N)-C(Ph)=C(C(O)OMe)C(Ph)=C(C(O)-OMe)C6H3Me-3(N=C(NH Ar)(2))-2}Br] (Ar = 2-MeC6H4; 2) in 70% yield, and the aforementioned reaction carried out with 10 equiv of PhC C-C(O)OR (R = Me, and Et) afforded an admixture of two regioisomers of Pd{kappa(3)(N,C,O)-O=C(OR)-C5Ph3(C(O)OR)C(C(O)OR)C6H3Me-3(N=C(NHAr)( 2))- 2}Br] (Ar = 2-MeC6H4; R = Me (3a/3b), Et (4a/4b)) in 80 and 87% yields, respectively. In one attempt, the minor regioisomer, 4b, was isolated from the mixture in 6% yield by fractional crystallization. Palladacycles 3a/3b and 4a/4b, upon stirring in CH2Cl2/MeCN (1/1, v/v) mixture at ambient condition for S days, afforded Pd{eta(3)-allyl,(KN)-N-1)-C-5(C(O)OR)(2)Ph3C-(C(O)OR)C6H3Me-3(N=C(NH Ar)(2))(-2)}Br] (Ar = 2-MeC6H4; R = Me (5a/5b), Et (6a/6b)) in 94 and 93% yields, respectively. Palladacycles 3a/3b and 4a/4b, upon reaction with AgOTf in CH2CH2/Me2C(O) (1/1, v/v) mixture at ambient temperature for 15 min, afforded Pd{kappa(3)(N,C,O)-O=C(OR)C5Ph3(C(O)OR)C(C(O)OR)C6H3Me-3(N=C(NHAr)(2 ))-2}(OTf)] (Ar = 2-MeC6H4; R = Me (7a/7b), Et (8a/8b)) in 79 and 77% yields, respectively. Palladacycles 7a/7b and 8a/ 8b, upon reflux in PhC1 separately for 6 h, or palladacycles 5a/5b and 6a/6b, upon treatment with AgOTf in CH2Cl2/Me2C(O) (7/3, v/v) mixture for 15 min, afforded Pd{(eta(2)-Ph)C5Ph2(C(O)OR)kappa(2)(C,N)-C(C(O)OR)C6H3Me-3(N=C(NHAr) (2))-2}(OTf)] (Ar = 2-MeC6H4; R = Me (9a/9h), Et (10a/10b)) in >= 87% yields. Palladacycles 9a/9b, upon stirring in MeCN in the presence of excess NaOAc followed by crystallization of the reaction mixture in the same solvent, afforded Pd{kappa(3)(N,C,C)-(C6H4)C5Ph2(C(O)OMe)(2)C(C(O)OMe)(2)C6H3Me-3(N=C( NHAr)(2))-2}(NCMe)] (Ar = 2-MeC6H4; 11a/11b) in 82% yield. The new palladacycles were characterized by analytical, IR, and NMR (H-1 and C-13) spectroscopic techniques, and the molecular structures of 2, 3a, 4a, 4b, 5a, 6a, 7a, 9a, 10a, and 11a-d(3) were determined by single crystal X-ray diffraction. The frameworks in the aforementioned palladacycles, except that present in 2, are unprecedented. Plausible pathways for the formation of new palladacycles and the influence of the guanidine unit in 1, substituents in alkynes, reaction conditions, and electrophilicity of the bromide and the triflate upon the frameworks of the insertion products have been discussed.

Optical, Electrochemical, and Structural Properties of Spray Coated Dihexyl Substituted Poly (3,4 propylene dioxythiophene) Film for Optoelectronics Devices

The dihexyl substituted poly (3,4-propylenedioxythiophene) (PProDOT-Hx(2)) thin films uniformly deposited by cost effective spray coating technique on transparent conducting oxide coated substrates. The electro-optical properties of PProDOT-Hx(2) films were studied by UV-Vis spectroscopy that shows the color contrast about 45% with coloration efficiency of approximate to 185cm(2)/C. The electrochemical properties of PProDOT-Hx(2) films were studied by cyclic voltammetry and AC impedance techniques. The cyclic voltammogram shows that redox reaction of films are diffusion controlled and ions transportation will be faster on the polymer film at higher scan rate. Impedance spectra indicate that polymer films are showing interface charge transfer process as well as capacitive behavior between the electrode and electrolyte. The XRD of the PProDOT-Hx(2) thin films revealed that the films are in amorphous nature, which accelerates the transportation of ions during redox process.

Performance enhancement of online handwritten Tamil symbol recognition with reevaluation techniques

In this article, we aim at reducing the error rate of the online Tamil symbol recognition system by employing multiple experts to reevaluate certain decisions of the primary support vector machine classifier. Motivated by the relatively high percentage of occurrence of base consonants in the script, a reevaluation technique has been proposed to correct any ambiguities arising in the base consonants. Secondly, a dynamic time-warping method is proposed to automatically extract the discriminative regions for each set of confused characters. Class-specific features derived from these regions aid in reducing the degree of confusion. Thirdly, statistics of specific features are proposed for resolving any confusions in vowel modifiers. The reevaluation approaches are tested on two databases (a) the isolated Tamil symbols in the IWFHR test set, and (b) the symbols segmented from a set of 10,000 Tamil words. The recognition rate of the isolated test symbols of the IWFHR database improves by 1.9 %. For the word database, the incorporation of the reevaluation step improves the symbol recognition rate by 3.5 % (from 88.4 to 91.9 %). This, in turn, boosts the word recognition rate by 11.9 % (from 65.0 to 76.9 %). The reduction in the word error rate has been achieved using a generic approach, without the incorporation of language models.

beta gamma-fused turn structures in sugar amino acid (SAA) containing cyclic tetrapeptides with alpha 3 delta architecture

The current manuscript describes conformational analysis of 15-membered cyclic tetrapeptides (CTPs), with alpha 3 delta architecture, containing sugar amino acids (SAA) having variation in the stereocenter at C5 carbon. Conformational analyses of both the series, in protected and deprotected forms, were carried out in DMSO-d(6) using various NMR techniques, supported by restrained MD calculations. It was intriguing to notice that the alpha 3 delta macrocycles got stabilized by both 10-membered beta-turn as well as a seven-membered gamma-turn, fused within the same macrocycle. The presence of fused sub-structures within a 15-membered macrocycle is rare to see. Also, the stereocenter variation at C5 did not affect the fused turn structures and exhibited similar conformations in both the series. The design becomes highly advantageous as fused reverse turn structures are occurring in the cyclic structure with minimalistic size macrocycle and this can be applied to develop suitable pharmacophores in the drug development process. (C) 2014 Elsevier Ltd. All rights reserved.

Postsynthetic Exterior Decoration of an Organic Cage by Copper(I)-Catalysed A(3)-Coupling and Detection of Nitroaromatics

A new synthetic protocol based on one-pot, copper(I)-catalysed multicomponent reaction of formaldehyde, secondary amine and terminal alkyne has been employed to postsynthetically modify a self-assembled nanoscopic organic cage. By employing this synthetic strategy, three new cages appended with phenyl-, xylyl-and naphthyl-acetylene moieties have been synthesised. The resulting modified cages were characterised by using a range of spectroscopic techniques. The synthesised cages were fluorescent and thus one of them was tested to explore the potential use of such compounds as chemosensors for the detection of nitroaromatics. Experimental findings suggest a high selective quenching of initial fluorescence intensity in the presence of nitroaromatic compounds. Furthermore, it has been observed that among the various nitroaromatics tested, nitrophenolic compounds have better quenching ability.

Learning-Based Fast Iterative Convergence of 3-D MoM via Eigen-AGMRES Method

Three-dimensional (3-D) full-wave electromagnetic simulation using method of moments (MoM) under the framework of fast solver algorithms like fast multipole method (FMM) is often bottlenecked by the speed of convergence of the Krylov-subspace-based iterative process. This is primarily because the electric field integral equation (EFIE) matrix, even with cutting-edge preconditioning techniques, often exhibits bad spectral properties arising from frequency or geometry-based ill-conditioning, which render iterative solvers slow to converge or stagnate occasionally. In this communication, a novel technique to expedite the convergence of MoMmatrix solution at a specific frequency is proposed, by extracting and applying Eigen-vectors from a previously solved neighboring frequency in an augmented generalized minimum residual (AGMRES) iterative framework. This technique can be applied in unison with any preconditioner. Numerical results demonstrate up to 40% speed-up in convergence using the proposed Eigen-AGMRES method.

A Perspective on Computer Assisted Assessment Techniques for Short Free-Text Answers

Computer Assisted Assessment (CAA) has been existing for several years now. While some forms of CAA do not require sophisticated text understanding (e.g., multiple choice questions), there are also student answers that consist of free text and require analysis of text in the answer. Research towards the latter till date has concentrated on two main sub-tasks: (i) grading of essays, which is done mainly by checking the style, correctness of grammar, and coherence of the essay and (ii) assessment of short free-text answers. In this paper, we present a structured view of relevant research in automated assessment techniques for short free-text answers. We review papers spanning the last 15 years of research with emphasis on recent papers. Our main objectives are two folds. First we present the survey in a structured way by segregating information on dataset, problem formulation, techniques, and evaluation measures. Second we present a discussion on some of the potential future directions in this domain which we hope would be helpful for researchers.

Comparison of relative flexoelectric coefficients measured by different techniques

While it is well known that it is possible to determine the effective flexoelectric coefficient of nematic liquid crystals using hybrid cells [1], this technique can be difficult due to the necessity of using a D.C. field. We have used a second method[2], requiring an A.C. field, to determine this parameter and here we compare the two techniques. The A.C. method employs the linear flexoelectrically induced linear electro-optic switching mechanism observed in chiral nematics. In order to use this second technique a chiral nematic phase is induced in an achiral nematic by the addition of a small amount of chiral additive (∼3% concentration w/w) to give helix pitch lengths of typically 0.5-1.0 μm. We note that the two methods can be used interchangeably, since they produce similar results, and we conclude with a discussion of their relative merits.

Evaluacion de la produccion de chilote en el cultivo de maiz (Zea mays L.) variedad HS-5G utilizando sustratos mejorados y determinacion de los coeficientes "Kc" y "Ky", bajo riego, Finca Las Mercedes, Managua 2009

El presente trabajo de investigación se estableció el 20 de Abril al 16 Junio del 2009, en la Unidad Productiva Hacienda Las Mercedes propiedad de la Universidad Nacional Agraria, ubicada en el municipio de Managua Departamento de Managua km 11 carretera Norte, entrada al carnic 2 km al lago, teniendo su ubicación geográfica en las siguientes coordenadas: 12°10’14” a 12°08’05” de latitud Norte y 86°10’22” a 86°09’44” longitud Oeste, a 56 msnm. La temperatura promedio es de 32.7°C, con una precipitación de 1400-1450 mm anuales, humedad relativa de 72% y una velocidad máxima del viento de 25.2Km/h. El propósito del experimento fue Evaluar la producción de chilote en el cultivo de maíz (Zea mays, L. ) variedad HS-5G, con los diferentes tratamientos Compost, Bocashi, Biofertilizante, Químico (Urea 46%) y la obtención de los coeficientes de cultivos “Kc” y el rendimiento “Ky”, bajo el sistema de riego por aspersión en la finca Hacienda Las Mercedes. Las dosis utilizadas fueron calculadas a parti r de los requerimientos del cultivo y un análisis de suelo realizado previo a la siembra, se aplicaron las dosis de 17,857 kg.h-1 de compost, 10,521 kg.h-1 de Bocashi 26,450 gal.h-1 de Biofertilizante todos estos abonos orgánicos fueron elaborados como parte de la investigación haciendo uso de los distintos materiales que se tienen en la finca para su composición, el fertilizante mineral con 214 kg.h- 1 urea 46%. El ensayo se estableció en un diseño de bloque completo al azar (BCA) con cuatro tratamientos y cuatro repeticiones. La dimensión Total del ensayo es de 585m2 (26m x 22.5m), cada parcela era de 14m2 (4m x 3.5m) 1.5 m2 para la parcela útil. La distancia entre bloque fue de 2 m y de 1.5 m entre parcela. Las variables cuantitativas evaluadas fueron Altura de la planta, Número de hojas, Diámetro del tallo y en los componentes del rendimiento: Altura del chilote, Peso con braquia, Peso sin braquia, Longitud del chilote, Diámetro del chilote y Rendimiento por tratamiento. A los datos obtenidos se les sometió a un análisis de varianza (ANDEVA) y separación de medias mediante el uso de la prueba de Diferencias Mínimas Signi ficativas (LSD α=0.05). Utilizando Software estadístico Infostat. Los resultados muestran que la única variable que presentó diferencias significativas fue la altura de planta a los 8 días después de siembra encontrándose alturas mayor de 5.99 cm cuando el cultivo fue fertilizado con Bocashi ya que el bocashi retiene mayor humedad. Serealizo un análisis económico, logrando un beneficio neto de C$517,165 el fertilizante sintético urea 46% obtuvo una tasa de retorno marginal (37.93 %). Con respecto a las variables de riego, tomando en cuenta las etapas fonológicas del cultivo se le aplico mayor volumen de agua en la fase de emergencia y crecimiento vegetativo para todos los tratamientos se obtuvo un coeficiente decultivo uniforme y un coeficiente de rendimiento por lo que el químico fue el que obtuvo una menor pérdida con respecto a los otros tratamientos.

Dynamics of pneumococcal nasopharyngeal carriage in healthy children attending a day care center in northern Spain. Influence of detection techniques on the results

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International Workshop for Management and Trade of Caiman yacare, Gainsville, FL, 3-5 October 2002

A workshop was held 3-5 October 2002 in Gainesville, Florida, USA to discuss management, conservation and trade in Caiman yacare. Twenty five official participants represented the four yacare range states (Argentina, Bolivia, Brazil, Paraguay), Venezuela, USA, the meeting sponsors (US Fish and Wildlife Service, CITES Secretariat, Louisiana Fur and Alligator Council), TRAFFIC Sur America and Crocodile Specialist Group. A series of country reports detailing yacare management in the four range states were distributed in Spanish and English prior to the meeting and presentations on these and on general principles of crocodilian harvest, conservation and management provided the basis for the discussions. Three working groups considered: • Requirements and field techniques for field data collection. • Requirements and techniques for regulation of harvest. • Requirements and processes for regulation of trade and export. Written reports of working groups and a plenary drafting session were finalized during the meeting and distributed, with the country reports, to participants. The workshop drafted a framework for caiman management and regulation that could be used as a template and adapted for use in each range state. The meeting agreed to convene an ad-hoc working group of range state representatives to continue discussions on the harmonization of caiman management into the future.