Synthesis of Carbon Nanomaterials through Up-Cycling Agricultural and Municipal Solid Wastes

This work addresses the synthesis of carbon nanomaterials (CNMs) by up-cycling common solid wastes. These feedstocks could supersede the use of costly and often toxic or highly flammable chemicals, such as hydrocarbon gases, carbon monoxide, and hydrogen, which are commonly used as feedstocks in current nanomanufacturing processes for CNMs. Agricultural sugar cane bagasse and corn residues, scrap tire chips, and postconsumer polyethylene (PE) and polyethylene terephthalate (PET) bottle shreddings were either thermally treated by sole pyrolysis or by sequential pyrolysis and partial oxidation. The resulting gaseous carbon-bearing effluents were then channeled into a heated reactor. CNMs, including carbon nanotubes, were catalytically synthesized therein on stainless steel meshes. This work revealed that the structure of the resulting CNMs is determined by the feedstock type, through the disparate mixtures of carbon-bearing gases generated when different feedstocks are pyrolyzed. CNM characterization was conducted by scanning and transmission electron microscopy as well as by Raman spectroscopy and by thermogravimetric analysis. Gas chromatography was used to characterize the gases in the synthesis chamber. This work demonstrated an alternative method for efficient manufacturing of CNMs using both biodegradable and nonbiodegradable agricultural and municipal carbonaceous wastes.

Duodenal stenting for malignant gastric outlet obstruction: Prospective study

AIM: To evaluate the results of duodenal stenting for palliation of gastroduodenal malignant obstruction by using a gastric outlet obstruction score (GOOS). METHODS: A prospective, non-randomized study was performed at a tertiary center between August 2005 and April 2010. Patients were eligible if they had malignant gastric outlet obstruction (GOO) and were not candidates for surgical treatment. Medical history and patient demographics were collected at baseline. Scheduled interviews were made on the day of the procedure and 15, 30, 90 and 180 d later or unscheduled as necessary. RESULTS: Fifteen patients (6 male, 9 female; median age 61 years) with GOO who had undergone duodenal stenting were evaluated. Ten patients had metastasis at baseline (66.6%) and 14 were unable to accept oral intake (93.33%), including 7 patients who were using a feeding tube. Laboratory data showed biliary obstruction in eight cases (53.33%); all were submitted to biliary drainage. Two patients developed obstructive symptoms due to tumor ingrowth after 30 d and another due to tumor overgrowth after 180 d. Two cases of stent migration occurred. A good response to treatment was observed, with a mean time of approximately 1 d (19 h) until toleration of a liquid diet and slightly more than 2 d for both soft solids (51 h) and a solid food/normal diet (55 h). The mean time to first failure to maintain liquid intake (GODS >= 1) was 93 d. During follow-up, the mean time to first failure to maintain the previously achieved GODS of 2-3 (solid/semi-solid food), considered technical failure, was 71 d. On the basis of oral intake a GODS is defined: 0 for no oral intake; 1 for liquids only; 2 for soft solids only; 3 for low-residue or full diet. CONCLUSION: Enteral stenting to alleviate gastroduodenal malignant obstruction improves quality of life in patients with limited life expectancy, which can be evaluated by using a GOO scoring system. (C) 2012 Baishideng. All rights reserved.

Interactions between 1-butyl-3-methylimidazolium tetrafluoroborate ionic liquid and gamma-Al2O3 (100) surface calculated by density functional theory

The main aim of this work is to investigate the 1-butyl-3-methylimidazolium tetrafluoroborate ([C4C1Im]+[BF4]-) ionic liquid (IL) adsorption on the gamma-Al2O3 (100) by density functional theory calculations to try to rationalize the adsorption as an electrostatic phenomenon. Optimized geometries and interaction energies of IL one-monolayer on the gamma-Al2O3 were obtained on high surface coverage (one cationanion pair per 94.96 nm2). A study of dispersion force was made to estimate its contribution to the adsorption. Overall, the process is ruled by electrostatic interaction between ions and surface. Adsorption of the anion [BF4]- and cation [C4C1Im]+ was also studied by Bader charge analysis and charge density difference for supported and unsupported situations. It is suggested that the IL ions have their charges maintained with significant anion cloud polarization inward to the acid aluminum sites. (c) 2012 Wiley Periodicals, Inc.

Recent Advances in the Development of Magnetically Recoverable Metal Nanoparticle Catalysts

The aim of this Account is to provide an overview of our current research activities on the design and modification of superparamagnetic nanomaterials for application in the field of magnetic separation and catalysis. First, an introduction of magnetism and magnetic separation is done. Then, the synthetic strategies that have been developed for generating superparamagnetic nanoparticles spherically coated by silica and other oxides, with a focus on well characterized systems prepared by methods that generate samples of high quality and easy to scale- up, are discussed. A set of magnetically recoverable catalysts prepared in our research group by the unique combination of superparamagnetic supports and metal nanoparticles is highlighted. This Account is concluded with personal remarks and perspectives on this research field.

Ultrasonic sensor for the presence of oily contaminants in water

The determination of the complex reflection coefficient of ultrasonic shear-waves at the solid-liquid interface is a technique employed for the measurement of the viscoelastic properties of liquids. An interesting property of the measurement technique is the very small penetration depth of the shear-waves into the liquid sample, which permits measurements with liquid films of some micrometers thick. This property, along with the adhesion of oily substances to surfaces, can be used for the detection of oily contaminants in water. In this work, the employment of the ultrasonic shear-wave reflection technique to the detection of oily contaminants in water is proposed and the theoretical and experimental concepts involved are discussed. Preliminary experimental results show the measurement technique can detect SAE 40 automotive oil in water in volume proportions less than 0.5%.

Characterization of flexible DNA films

Polymer electrolytes (PEs) are currently the focus of much attention as potential electrolytes in electrochemical devices such as batteries, display devices and sensors. Deoxyribonucleic acid (DNA) as an important biological macromolecule has electric conducting electrochemical properties and unique three dimensional structures. With the goal of developing a new family of environmentally friendly multifunctional biohybrid materials displaying simultaneously high ionic conductivity we have produced in the present work, flexible films based on DNA, incorporating ionic liquids (ILs). Over the last decade ILs have been employed as a new media in electrochemistry and electroanalysis. The materials studied here have been characterized by means of Differential Scanning Calorimetry, Complex Impedance Spectroscopy and Cyclic Voltammetry. (C) 2012 Elsevier B.V. All rights reserved.

Evidence of the participation of electronic excited states in the mechanism of positronium formation in substitutional Tb1-xEux(dpm)(3) solid solutions studied by optical and positron annihilation spectroscopies

Positronium formation in the bimary molecular solid solutions Tb1-xEux (dpm)(3) (dpm = dipivaloylmethanate) has been investigated. A strong linear correlation between the D-5(4) Tb(III) energy level excited state lifetime and the positronium formation probability has been observed. This correlation indicates that the ligand-to-metal charge transfer LMCT states act in both luminescence quenching and positronium formation inhibition, as previously proposed. A kinetic mechanism is proposed to explain this correlation and shows that excited electronic states have a very important role in the positronium formation mechanism.

CHEMICAL COMPOSITION OF SUGAR CANE SPIRITS FERMENTED BY DIFFERENT Saccharomyces cerevisiae YEAST STRAINS

CHEMICAL COMPOSITION OF SUGAR CANE SPIRITS FERMENTED BY DIFFERENT Saccharomyces cerevisiae YEAST STRAINS. The aim of this study was to evaluate the chemical composition of sugar cane spirits, fermented by different commercial Saccharomyces cerevisiae yeast strains and double distilled by pot still. Sugar cane juices were separately fermented by yeasts CA-11, Y-904, BG-1, PE-2, SA-1 and CAT-1 and distilled by pot still according to the methodology used for whisky production. The alcoholic liquids from first and second distillations were analyzed for concentrations of ethanol, volatile acidity, aldehydes, esters, furfural, higher alcohols and methanol. The sugar cane spirits derived from fermentation by the different yeast strains presented distinct chemical compositions.

Computational and experimental characterization of a low-cost piezoelectric valveless diaphragm pump

Flow pumps act as important devices in areas such as Bioengineering, Medicine, and Pharmacy, among other areas of Engineering, mainly for delivering liquids or gases at small-scale and precision flow rate quantities. Principles for pumping fluids based on piezoelectric actuators have been widely studied, since they allow the construction of pump systems for displacement of small fluid volumes with low power consumption. This work studies valveless piezoelectric diaphragm pumps for flow generation, which uses a piezoelectric ceramic (PZT) as actuator to move a membrane (diaphragm) up and down as a piston. The direction of the flow is guaranteed by valveless configuration based on a nozzle-diffuser system that privileges the flow in just one pumping direction. Most research efforts on development of valveless flow pump deal either with computational simulations based on simplified models or with simplified physical approaches based on analytical models. The main objective of this work is the study of a methodology to develop a low-cost valveless piezoelectric diaphragm flow pump using computational simulations, parametric study, prototype manufacturing, and experimental characterization. The parametric study has shown that the eccentricity of PZT layer and metal layer plays a key role in the performance of the pump.

Water-assisted Flow of Heavy Oil in a Vertical Pipe: Pilot-scale Experiments

The use of the core-annular flow pattern, where a thin fluid surrounds a very viscous one, has been suggested as an attractive artificial-lift method for heavy oils in the current Brazilian ultra-deepwater production scenario. This paper reports the pressure drop measurements and the core-annular flow observed in a 2 7/8-inch and 300 meter deep pilot-scale well conveying a mixture of heavy crude oil (2000 mPa.s and 950 kg/m3 at 35 C) and water at several combinations of the individual flow rates. The two-phase pressure drop data are compared with those of single-phase oil flow to assess the gains due to water injection. Another issue is the handling of the core-annular flow once it has been established. High-frequency pressure-gradient signals were collected and a treatment based on the Gabor transform together with neural networks is proposed as a promising solution for monitoring and control. The preliminary results are encouraging. The pilot-scale tests, including long-term experiments, were conducted in order to investigate the applicability of using water to transport heavy oils in actual wells. It represents an important step towards the full scale application of the proposed artificial-lift technology. The registered improvements in terms of oil production rate and pressure drop reductions are remarkable.

Thermal Analysis and Raman Spectra of Different Phases of the Ionic Liquid Butyltrimethylammonium Bis(trifluoromethylsulfonyl)imide

The ionic liquid butyltrimethylammonium bis(trifluoromethylsulfonyl)imide, [C4C1C1C1N][Tf2N], is a glass-forming liquid that exhibits partial crystallization depending on the cooling rate. Differential scanning calorimetry (DSC) indicates crystallization at T-c = 227 K, melting at T-m = 258 K, glass transition at T-g similar to 191 K, and also cold crystallization at T-cc similar to 219 K. Raman spectroscopy shows that the crystalline structure obtained by slow cooling is formed with [Tf2N](-) in cisoid conformation, whereas [Tf2N](-) in transoid conformation results from fast cooling. No preferred conformation of the butyl chain of the [C4C1C1C1N](+) cation is favored by slow or fast cooling of [C4C1C1C1N][Tf2N]. Low-frequency Raman spectroscopy shows that crystalline domains developing in the supercooled liquid result in a glacial state made of a mixture of crystallites and amorphous phase. However, these crystalline structures obtained by slow cooling or cold crystallization are not the same because anion-cation interactions promote local structures with distinct conformations of the [Tf2N](-) anion.

Catalyst Recovery and Recycling Facilitated by Magnetic Separation: Iridium and Other Metal Nanoparticles

The immobilization of metal nanoparticles in magnetic responsive solids allows the easy, fast, and clean separation of catalysts; however, the efficiency of this separation process depends on a strong metalsupport interaction. This interaction can be enhanced by functionalizing the support surface with amino groups. Our catalyst support contains an inner core of magnetite that enables the magnetic separation from liquid systems and an external surface of silica suitable for further modification with organosilanes. We report herein that a magnetically recoverable amino-functionalized support captured iridium species from liquid solutions and produced a highly active hydrogenation catalyst with negligible metal leaching. An analogous Ir0 catalyst prepared with use of a nonfunctionalized support shows a higher degree of metal leaching into the liquid products. The catalytic performance in the hydrogenation of alkenes is compared with that of Rh and Pt catalysts.

Synthesis and Characterization of the Europium(III) Pentakis(picrate) Complexes with Imidazolium Countercations: Structural and Photoluminescence Study

Six new lanthanide complexes of stoichiometric formula (C)(2)[Ln(Pic)(5)]-where (C) is a imidazolium cation coming from the ionic liquids 1-butyl-3-methylimidazolium picrate (BMIm-Pic), 1-butyl-3-ethylimidazolium picrate (BEIm-Pic), and 1,3-dibutylimidazolium picrate (BBIm-Pic), and Ln is Eu(III) or Gd(III) ions-have been prepared and characterized. To the best of our knowledge, these are the first cases of Ln(III) pentakis(picrate) complexes. The crystal structures of (BEIm)(2)[Eu(Pic)(5)] and (BBIm)(2)[Eu(Pic)(5)] compounds were determined by single-crystal X-ray diffraction. The [Eu(Pic)(5)](2-) polyhedra have nine oxygen atoms coordinated to the Eu(III) ion, four oxygen atoms from bidentate picrate, and one oxygen atom from monodentate picrate. The structures of the Eu complexes were also calculated using the sparkle model for lanthanide complexes, allowing an analysis of intramolecular energy transfer processes in the coordination compounds. The photoluminescence properties of the Eu(III) complexes were then studied experimentally and theoretically, leading to a rationalization of their emission quantum yields.

Enzyme Microheterogeneous Hydration and Stabilization in Supercritical Carbon Dioxide

Supercritical carbon dioxide is a promising green-chemistry solvent for many enzyme-catalyzed chemical reactions, yet the striking stability of some enzymes in such unconventional environments is not well understood. Here, we investigate the stabilization of the Candida antarctica Lipase B (CALB) in supercritical carbon dioxide-water biphasic systems using molecular dynamics simulations. The preservation of the enzyme structure and optimal activity depend on the presence of small amounts of water in the supercritical dispersing medium. When the protein is at least partially hydrated, water molecules bind to specific sites on the enzyme surface and prevent carbon dioxide from penetrating its catalytic core. Strikingly, water and supercritical carbon dioxide cover the protein surface quite heterogeneously. In the first solvation layer, the hydrophilic residues at the surface of the protein are able to pin down patches of water, whereas carbon dioxide solvates preferentially hydrophobic surface residues. In the outer solvation shells, water molecules tend to cluster predominantly on top of the larger water patches of the first solvation layer instead of spreading evenly around the remainder of the protein surface. For CALB, this exposes the substrate-binding region of the enzyme to carbon dioxide, possibly facilitating diffusion of nonpolar substrates into the catalytic funnel. Therefore, by means of microheterogeneous solvation, enhanced accessibility of hydrophobic substrates to the active site can be achieved, while preserving the functional structure of the enzyme. Our results provide a molecular picture on the nature of the stability of proteins in nonaqueous media.

Stereoselective synthesis of novel diels-alder adducts of p-substituted Methyl Thiocinnamates and Cyclopentadiene

This article describes the Diels-Alder reaction between methyl thiocinnamates, substituted at the para position by electron-donating and electron-withdrawing groups, with cyclopentadiene in the presence of catechol boron bromide (CBB) as a Lewis acid catalyst. The adduct configuration was confirmed by H-1 NMR coupling constants and single-crystal x-ray diffraction. Total endo stereoselectivity was observed in all reactions and was attributed to the effective secondary interaction between the boron atom and the incipient double bond in the norbonene resulting from the planar geometry of the catalyst. C-13 NMR chemical shifts of the coordinated dienophile carbonyl carbons with CBB compared to those of the non coordinated thiocinammates suggest a strong complexation with the catalyst.