Influence of chemical interesterification on thermal behavior, microstructure, polymorphism and crystallization properties of canola oil and fully hydrogenated cottonseed oil blends

This work evaluated chemical interesterification of canola oil (CaO) and fully hydrogenated cottonseed oil (FHCSO) blends, with 20%, 25%, 30%, 35% and 40%(w/w) FHCSO content. Interesterification produced reduction of trisaturated and increase in monounsaturated and diunsaturated triacylglycerols contents, which caused important changes in temperatures and enthalpies associated with the crystallization and melting thermograms. It was verified reduction in medium crystal diameter in all blends, in addition crystal morphology modification. Crystallization kinetics revealed that crystal formation induction period and maximum solid fat content were altered according to FHCSO content in original blends and as a result of random rearrangement. Changes in Avrami constant (k) and exponent (n) indicated, respectively, that interesterification decreased crystallization rates and altered crystalline morphology. However, X-ray diffraction analyses showed randomization did not change the original crystalline polymorphism. The original and interesterified blends had significant predominance of beta` polymorph, which is interesting for several food applications. (C) 2009 Elsevier Ltd. All rights reserved.

Syntheses of two new 1D and 3D networks of Cu(II) and Co(II) using malonate and urotropine as bridging ligands: Crystal structures and magnetic studies

Two new metal-organic based polymeric complexes, [Cu-4(O2CCH2CO2)(4)(L)].7H(2)O (1) and [CO2(O2CCH2CO2)(2)(L)].2H(2)O (2) [L = hexamethylenetetramine (urotropine)], have been synthesized and characterized by X-ray crystal structure determination and magnetic studies. Complex 1 is a 1D coordination polymer comprising a carboxylato, bridged Cu-4 moiety linked by a tetradentate bridging urotropine. Complex 2 is a 3D coordination polymer made of pseudo-two-dimensional layers of Co(II) ions linked by malonate anions in syn-anticonformation which are bridged by bidentate urotropine in trans fashion, Complex 1 crystallizes in the orthothombic system, space group Pmmn, with a = 14,80(2) Angstrom, b = 14.54(2) Angstrom, c = 7.325(10) Angstrom, beta = 90degrees, and Z = 4. Complex 2 crystallizes in the orthorhombic system, space group Imm2, a = 7.584(11) Angstrom, b = 15.80(2) Angstrom, c = 6.939(13) Angstrom, beta = 90.10degrees(1), and Z = 4. Variable temperature (300-2 K) magnetic behavior reveals the existence of ferro- and antiferromagnetic interactions in 1 and only antiferromagnetic interactions in 2. The best fitted parameters for complex 1 are J = 13.5 cm(-1), J = -18.1 cm(-1), and g = 2.14 considering only intra-Cu-4 interactions through carboxylate and urotropine pathways. In case of complex 2, the fit of the magnetic data considering intralayer interaction through carboxylate pathway as well as interlayer interaction via urotropine pathway gave no satisfactory result at this moment using any model known due to considerable orbital contribution of Co(II) ions to the magnetic moment and its complicated structure. Assuming isolated Co(II) ions (without any coupling, J = 0) the shape of the chi(M)T curve fits well with experimental data except at very low temperatures.

Syntheses, crystal structures and magnetic properties of carboxylato-bridged polymeric networks of Mn-II

Three new carboxylato-bridged polymeric networks of Mn-II having molecular formula [Mn(ox)(dpyo)](n) (1), {[Mn-2(mal)(2)(bpee)(H2O)(2)]center dot 0.5(bpee)center dot 0.5(CH3OH)}n, (2) and {[Mn-3(btc)(2)(2,2'-bipy)(2)(H2O)(6)]center dot 4H(2)O}(n) (3) [dpyo, 4,4'-bipyridine N,N'dioxide; bpee, trans-1,2 bis(4-pyridyl) ethylene; 2,2'-bipy, 2,2'-bipyridine; ox = oxalate dianion; mal = malonate dianion; btc = 1,3,5-benzenetricarboxylate trianion] have been synthesized and characterized by single-crystal X-ray diffraction studies and low temperature magnetic measurements. Structure determination of complex I reveals a covalent bonded 2D network containing bischelating oxalate and bridging dpyo; complex 2 is a covalent,bonded 3D polymeric architecture, formed by bridging malonate and bpee ligands, resulting in an open framework with channels filled by uncoordinated disordered bpee and methanol molecules. Whereas complex 3, comprising btc anions bound to three metal centers, is a 1D chain which further extends its dimensionality to 3D via pi-pi and H-bonding interactions. Low temperature magnetic measurements reveal the existence of weak antiferromagnetic interaction in all these complexes. ((c) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006).

Morphology of polymer networks formed in the chiral and non chiral phases of an anti-ferroelectric liquid crystal

We introduced photo-polymer networks into the various liquid crystalline phases of the antiferroelectric liquid crystal AS612 and studied the effects of these networks by measuring the temperature dependence of the Bragg wavelengths selectively reflected. After polymerization, the decrease in Bragg wavelengths with respect to the original values is consistent with a shorter helical pitch due to polymer network shrinkage. Also, by removing the liquid crystalline material, we are able to image the residual polymer network using scanning electron microscopy and polarized light microscopy. The polymer strands are a few microns thick and the networks show both chiral and non-chiral features.

Terbium(III) and dysprosium(III) 8-connected 3D networks containing 2,5-thiophenedicarboxylate anion: Crystal structures and photoluminescence studies

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Terbium(III) and dysprosium(III) 8-connected 3D networks containing 2,5-thiophenedicarboxylate anion: Crystal structures and photoluminescence studies

Two novel coordination polymers with the formula {[Ln(2)(2,5-tdc)(3)(dmso)(2)].H2O}(n) (Ln = Tb(III) for (1) and Dy(III) for (2)), (2,5-tdc(2-) = 2,5-thiophenedicarboxylate and dmso = dimethylsulfoxide) have been synthesized by the diffusion method and characterized by thermal analysis, vibrational spectroscopy and single crystal X-ray diffraction analysis. Structure analysis reveals that 2,5-tdc(2-) play a versatile role toward different lanthanide ions to form three-dimensional metal-organic frameworks (MOFs) in which the lanthanides ions are heptacoordinated. Photophysical properties were studied using excitation and emission spectra, where the photoluminescence data show the high emission intensity of the characteristic transitions D-5(4 ->) F-7(J) (J= 6, 5, 4 and 3) for (1) and (F9/2 -> HJ)-F-4-H-6 (J = 15/2, 13/2 and 11/2) for (2), indicating that 2,5-tdc(2-) is a good sensitizer. (C) 2012 Elsevier Ltd. All rights reserved.

A cellulose liquid crystal motor: a steam engine of the second kind

The salient feature of liquid crystal elastomers and networks is strong coupling between orientational order and mechanical strain. Orientational order can be changed by a wide variety of stimuli, including the presence of moisture. Changes in the orientation of constituents give rise to stresses and strains, which result in changes in sample shape. We have utilized this effect to build soft cellulose-based motor driven by humidity. The motor consists of a circular loop of cellulose film, which passes over two wheels. When humid air is present near one of the wheels on one side of the film, with drier air elsewhere, rotation of the wheels results. As the wheels rotate, the humid film dries. The motor runs so long as the difference in humidity is maintained. Our cellulose liquid crystal motor thus extracts mechanical work from a difference in humidity.

A cellulosic liquid crystal pool for cellulose nanocrystals: structure and molecular dynamics at high shear rates

Cellulose and its derivatives, such as hydroxypropylcellulose (HPC) have been studied for a long time but they are still not well understood particularly in liquid crystalline solutions. These systems can be at the origin of networks with properties similar to liquid crystalline (LC) elastomers. The films produced from LC solutions can be manipulated by the action of moisture allowing for instance the development of a soft motor (Geng et al., 2013) driven by humidity. Cellulose nanocrystals (CNC), which combine cellulose properties with the specific characteristics of nanoscale materials, have been mainly studied for their potential as a reinforcing agent. Suspensions of CNC can also self-order originating a liquid-crystalline chiral nematic phases. Considering the liquid crystalline features that both LC-HPC and CNC can acquire, we prepared LC-HPC/CNC solutions with different CNC contents (1,2 and 5 wt.%). The effect of the CNC into the LC-HPC matrix was determined by coupling rheology and NMR spectroscopy - Rheo-NMR a technique tailored to analyse orientational order in sheared systems. (C) 2015 Elsevier Ltd. All rights reserved.

Carbon nanotubes as reinforcement of cellulose liquid crystalline responsive networks

The incorporation of small amount of highly anisotropic nanoparticles into liquid crystalline hydroxypropylcellulose (LC-HPC) matrix improves its response when is exposed to humidity gradients due to an anisotropic increment of order in the structure. Dispersed nanoparticles give rise to faster order/disorder transitions when exposed to moisture as it is qualitatively observed and quantified by stress-time measurements. The presence of carbon nanotubes derives in a improvement of the mechanical properties of LC-HPC thin films.

Old cellulose for new multifunctional networks

Dissertação para obtenção do Grau de Doutor em Ciência e Engenharia de Materiais

Balanceo distribuido del encaminamiento para topologías fat-tree sobre redes Infiniband

Las redes de interconexión juegan un papel importante en el rendimiento de los sistemas de altas prestaciones. Actualmente la gestión del encaminamiento de los mensajes es un factor determinante para mantener las prestaciones de la red. Nuestra propuesta es trabajar sobre un algoritmo de encaminamiento adaptativo, que distribuye el encaminamiento de los mensajes para evitar los problemas de congestión en las redes de interconexión, que aparecen por el gran volumen de comunicaciones de aplicaciones científicas ó comerciales. El objetivo es ajustar el algoritmo a una topología muy utilizada en los sistemas actuales como lo es el fat‐tree, e implementarlo en una tecnología Infiniband. En la experimentación realizada comparamos el método de control de congestión de la arquitectura Infiniband, con nuestro algoritmo. Los resultados obtenidos muestran que mejoramos los niveles de latencia por encima de un 50% y de throughput entre un 38% y un 81%.

Artificial neural networks (ANN): prediction of sensory measurements from instrumental data

The objective of this study was to predict by means of Artificial Neural Network (ANN), multilayer perceptrons, the texture attributes of light cheesecurds perceived by trained judges based on instrumental texture measurements. Inputs to the network were the instrumental texture measurements of light cheesecurd (imitative and fundamental parameters). Output variables were the sensory attributes consistency and spreadability. Nine light cheesecurd formulations composed of different combinations of fat and water were evaluated. The measurements obtained by the instrumental and sensory analyses of these formulations constituted the data set used for training and validation of the network. Network training was performed using a back-propagation algorithm. The network architecture selected was composed of 8-3-9-2 neurons in its layers, which quickly and accurately predicted the sensory texture attributes studied, showing a high correlation between the predicted and experimental values for the validation data set and excellent generalization ability, with a validation RMSE of 0.0506.

Molecular Networks Created by Charge-Assisted Hydrogen Bonds Between Bis(aminidinium) Cations and Carboxylates, Sulfonates, Phosphonates and Phosphates

L'objectif de cette étude est d'apprendre à créer de nouveaux matériaux moléculaires par design. À l'heure actuelle, il n'existe aucune méthode générale pour la prédiction des structures et des propriétés, mais des progrès importants ont été accomplis, en particulier dans la fabrication de matériaux moléculaires ordonnés tels que des cristaux. En ces matériaux, l'organisation peut être contrôlée efficacement par la stratégie de la tectonique moléculaire. Cette approche utilise des molécules appelées “tectons”, qui peuvent s’associer de manière dirigée par des interactions non covalentes prévisibles. De cette façon, la position de chaque molécule par rapport à ses voisins peut être programmée avec un degré élevé de fiabilité pour créer des cristaux et d'autres matériaux organisés avec des caractéristiques et des propriétés structurelles souhaitables. Le travail que nous allons décrire est axé sur l'utilisation de l'association des cations bis(aminidinium) avec des carboxylates, sulfonates, phosphonates et phosphates, afin de créer des réseaux moléculaires prévisibles. Ces réseaux promettent d'être particulièrement robuste, car ils sont maintenus ensemble par de multiples liaisons hydrogène assistées par des interactions électrostatiques.

Development of thermo-analytical prediction and classification models for food in thermal devices using a multi sensor system and artificial neural networks

Die thermische Verarbeitung von Lebensmitteln beeinflusst deren Qualität und ernährungsphysiologischen Eigenschaften. Im Haushalt ist die Überwachung der Temperatur innerhalb des Lebensmittels sehr schwierig. Zudem ist das Wissen über optimale Temperatur- und Zeitparameter für die verschiedenen Speisen oft unzureichend. Die optimale Steuerung der thermischen Zubereitung ist maßgeblich abhängig von der Art des Lebensmittels und der äußeren und inneren Temperatureinwirkung während des Garvorgangs. Das Ziel der Arbeiten war die Entwicklung eines automatischen Backofens, der in der Lage ist, die Art des Lebensmittels zu erkennen und die Temperatur im Inneren des Lebensmittels während des Backens zu errechnen. Die für die Temperaturberechnung benötigten Daten wurden mit mehreren Sensoren erfasst. Hierzu kam ein Infrarotthermometer, ein Infrarotabstandssensor, eine Kamera, ein Temperatursensor und ein Lambdasonde innerhalb des Ofens zum Einsatz. Ferner wurden eine Wägezelle, ein Strom- sowie Spannungs-Sensor und ein Temperatursensor außerhalb des Ofens genutzt. Die während der Aufheizphase aufgenommen Datensätze ermöglichten das Training mehrerer künstlicher neuronaler Netze, die die verschiedenen Lebensmittel in die entsprechenden Kategorien einordnen konnten, um so das optimale Backprogram auszuwählen. Zur Abschätzung der thermische Diffusivität der Nahrung, die von der Zusammensetzung (Kohlenhydrate, Fett, Protein, Wasser) abhängt, wurden mehrere künstliche neuronale Netze trainiert. Mit Ausnahme des Fettanteils der Lebensmittel konnten alle Komponenten durch verschiedene KNNs mit einem Maximum von 8 versteckten Neuronen ausreichend genau abgeschätzt werden um auf deren Grundlage die Temperatur im inneren des Lebensmittels zu berechnen. Die durchgeführte Arbeit zeigt, dass mit Hilfe verschiedenster Sensoren zur direkten beziehungsweise indirekten Messung der äußeren Eigenschaften der Lebensmittel sowie KNNs für die Kategorisierung und Abschätzung der Lebensmittelzusammensetzung die automatische Erkennung und Berechnung der inneren Temperatur von verschiedensten Lebensmitteln möglich ist.

Fat-Tree Routing for Transit

The Transit network provides high-speed, low-latency, fault-tolerant interconnect for high-performance, multiprocessor computers. The basic connection scheme for Transit uses bidelta style, multistage networks to support up to 256 processors. Scaling to larger machines by simply extending the bidelta network topology will result in a uniform degradation of network latency between all processors. By employing a fat-tree network structure in larger systems, the network provides locality and universality properties which can help minimize the impact of scaling on network latency. This report details the topology and construction issues associated with integrating Transit routing technology into fat-tree interconnect topologies.