Search results for: isomerization

Authors: Sirada Sripinun

Abstract:

This work studied the isomerization of 1-butene over hydrotalcite catalyst. The experiments were conducted at various gas hourly space velocity (GHSV), reaction temperature, and feed concentration. No catalyst deactivation was observed over the reaction time of 16 hours. Two major reaction products were trans-2-butene and cis-2-butene. The reaction temperature played an important role on the reaction selectivity. At high operating temperatures, the selectivity of trans-2-butene was higher than the selectivity of cis-2-butene while it was opposite at a lower reaction temperature. In the range of operating conditions, the maximum conversion of 1-butene was found at 74% when T = 673 K and GHSV = 4 m3/h/kg-cat with trans- and cis-2-butene selectivities of 54% and 46% respectively. Finally, the kinetic parameters of the reaction were determined.

Keywords: hydrotalcite, isomerization, kinetic, 1-butene

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Authors: M. Miriam Hernández-Arroyo, Ivonne Caro-Gonzales, Miguel Ángel Plascencia-Espinosa, Sergio R. Trejo-Estrada

Abstract:

A large biodiversity of Lactobacillus strains has been detected in traditional foods and beverages from Mexico. A selected strain of Lactobacillus sp - PODI-20, used for the obtained from an artisanal fermented beverage was cultivated in different carbon sources in a complex medium, in order to define which carbon sourced induced more effectively the isomerization of arabinose by cell fractions obtained by fermentation. Four different carbon sources were tested in a medium containing peptone and yeast extract and mineral salts. Glucose, galactose, arabinose, and lactose were tested individually at three different concentrations: 3.5, 6, and 10% w/v. The biomass yield ranged from 1.72 to 17.6 g/L. The cell pellet was processed by mechanical homogenization. Both fractions, the cellular debris, and the lysis supernatant were tested for their ability to isomerize arabinose into ribulose. The highest yield of isomer was 12 % of isomerization in the supernatant fractions; whereas up to 9.3% was obtained by the use of cell debris. The isomerization of arabinose has great significance in the production of lactic acid by fermentation of complex carbohydrate hydrolysates.

Keywords: isomerase, tagatose, aguamiel, isomerization

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Authors: Przemyslaw Nogly, Tobias Weinert, Daniel James, Sergio Carbajo, Dmitry Ozerov, Antonia Furrer, Dardan Gashi, Veniamin Borin, Petr Skopintsev, Kathrin Jaeger, Karol Nass, Petra Bath, Robert Bosman, Jason Koglin, Matthew Seaberg, Thomas Lane, Demet Kekilli, Steffen Brünle, Tomoyuki Tanaka, Wenting Wu, Christopher Milne, Thomas A. White, Anton Barty, Uwe Weierstall, Valerie Panneels, Eriko Nango, So Iwata, Mark Hunter, Igor Schapiro, Gebhard Schertler, Richard Neutze, Jörg Standfuss

Abstract:

Ultrafast isomerization of retinal is the primary step in a range of photoresponsive biological functions including vision in humans and ion-transport across bacterial membranes. We studied the sub-picosecond structural dynamics of retinal isomerization in the light-driven proton pump bacteriorhodopsin using an X-ray laser. Twenty snapshots with near-atomic spatial and temporal resolution in the femtosecond regime show how the excited all-trans retinal samples conformational states within the protein binding pocket prior to passing through a highly-twisted geometry and emerging in the 13-cis conformation. The aspartic acid residues and functional water molecules in proximity of the retinal Schiff base respond collectively to formation and decay of the initial excited state and retinal isomerization. These observations reveal how the protein scaffold guides this remarkably efficient photochemical reaction.

Keywords: bacteriorhodopsin, free-electron laser, retinal isomerization mechanism, time-resolved crystallography

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Authors: Thidaya Thitiapichart

Abstract:

The effect of additional magnesium oxide (MgO) was investigated by using the tungsten oxide supported on silica catalyst (WOx/SiO2) physically mixed with MgO in a weight ratio 1:1. The both fresh and spent catalysts were characterized by FT-Raman spectrometer, UV-Vis spectrometer, X-Ray diffraction (XRD), and temperature programmed oxidation (TPO). The results indicated that the additional MgO could enhance the conversion of trans-2-butene due to isomerization reaction. However, adding MgO would increase the amount of coke deposit on the WOx/SiO2 catalyst. The TPO profile presents two peaks when the WOx/SiO2 catalyst was physically mixed with MgO. The further peak was suggested to be coming from the coke precursor that could be produced by isomerization reaction of the undesired product. Then, the occurred coke precursor could deposit and form coke on the acid catalyst.

Keywords: coke formation, metathesis, magnesium oxide, physically mix

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Authors: Natan C. G. Silva, Carlos A. C. Girao Neto, Marcele M. S. Vasconcelos, Luciana R. B. Goncalves, Maria Valderez P. Rocha

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Galactooligosaccharides (GOS) are sugars with prebiotic function that can be synthesized chemically or enzymatically, and this last one can be promoted by the action of β-galactosidases. In addition to favoring the transgalactosylation reaction to form GOS, these enzymes can also catalyze the hydrolysis of lactose. A highly studied type of GOS is lactulose because it presents therapeutic properties and is a health promoter. Among the different raw materials that can be used to produce lactulose, whey stands out as the main by-product of cheese manufacturing, and its discarded is harmful to the environment due to the residual lactose present. Therefore, its use is a promising alternative to solve this environmental problem. Thus, lactose from whey is hydrolyzed into glucose and galactose by β-galactosidases. However, in order to favor the transgalactosylation reaction, the medium must contain fructose, due this sugar reacts with galactose to produce lactulose. Then, the glucose-isomerase enzyme can be used for this purpose, since it promotes the isomerization of glucose into fructose. In this scenario, the aim of the present work was first to develop β-galactosidase biocatalysts of Kluyveromyces lactis and to apply it in the integrated reactions of hydrolysis, isomerization (with the glucose-isomerase from Streptomyces murinus) and transgalactosylation reaction, using whey as a substrate. The immobilization of β-galactosidase in chitosan previously functionalized with 0.8% glutaraldehyde was evaluated using different enzymatic loads (2, 5, 7, 10, and 12 mg/g). Subsequently, the hydrolysis and transgalactosylation reactions were studied and conducted at 50°C, 120 RPM for 20 minutes. In parallel, the isomerization of glucose into fructose was evaluated under conditions of 70°C, 750 RPM for 90 min. After, the integration of the three processes for the production of lactulose was investigated. Among the evaluated loads, 7 mg/g was chosen because the best activity of the derivative (44.3 U/g) was obtained, being this parameter determinant for the reaction stages. The other parameters of immobilization yield (87.58%) and recovered activity (46.47%) were also satisfactory compared to the other conditions. Regarding the integrated process, 94.96% of lactose was converted, achieving 37.56 g/L and 37.97 g/L of glucose and galactose, respectively. In the isomerization step, conversion of 38.40% of glucose was observed, obtaining a concentration of 12.47 g/L fructose. In the transgalactosylation reaction was produced 13.15 g/L lactulose after 5 min. However, in the integrated process, there was no formation of lactulose, but it was produced other GOS at the same time. The high galactose concentration in the medium probably favored the reaction of synthesis of these other GOS. Therefore, the integrated process proved feasible for possible production of prebiotics. In addition, this process can be economically viable due to the use of an industrial residue as a substrate, but it is necessary a more detailed investigation of the transgalactosilation reaction.

Keywords: beta-galactosidase, glucose-isomerase, galactooligosaccharides, lactulose, whey

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Authors: Vaclav Heral

Abstract:

Ideas about the mechanism of heterogeneous catalytic hydrogenation are diverse. The Horiuti-Polanyi mechanism is most often referred to, based on the idea of a semi-hydrogenated state. In our opinion, it does not represent a satisfactory explanation of the hydrogenation mechanism, because, for example: (1) It neglects the fact that the bond of atomic hydrogen to the metal surface is strongly polarized, (2) It does not explain why a surface deprived of atomic hydrogen (by thermal desorption or by alkyne) loses isomerization capabilities, but hydrogenation capabilities remain preserved, (3) It was observed that during the hydrogenation of 1-alkenes, the reaction can be of the 0th order to hydrogen and to the alkene at the same time, which is excluded during the competitive adsorption of both reactants on the catalyst surface. We offer an alternative mechanism that satisfactorily explains many of the ambiguities: It is the idea of an independent course of olefin isomerization, catalyzed by acidic atomic hydrogen bonded on the surface of the catalyst, in addition to the hydrogenation itself, in which a two-layer complex appears on the surface of the catalyst: olefin bound to the surface and molecular hydrogen bound to it in the second layer. The rate-determining step of hydrogenation is the conversion of this complex into the final product. We believe that the Horiuti-Polanyi mechanism is flawed and we naturally think that our two-layer theory better describes the experimental findings.

Keywords: acidity of hydrogenation catalyst, Horiuti-Polanyi, hydrogenation, two-layer hydrogenation

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Authors: Rukshani Wickrama-Arachchi, Tanner Metz, James M. Takacs

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Amines bearing γ-stereocenters are important structural motifs found in many biologically active compounds. Regioselective Rh-catalyzed asymmetric hydroboration of acyclic allylamines is used to synthesize amines bearing chiral β- and γ-boronic esters yields up to 70% with 98:2 enantioselectivity. The major enantiomeric outcome can be independent of starting alkene geometry, revealing that cis/trans-isomerization of alkene can occur before hydroboration. Stereospecific transformations of the newly generated C-B bond illustrates the utility of these chiral synthons.

Keywords: allylamines, borylated amines, chiral amines, hydroboration, rhodium-catalysis

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Authors: Kritsada Pipitthapan

Abstract:

WO3/SiO2 catalysts were modified by an ion exchange method with sodium hydroxide or potassium hydroxide solution. The performance of the modified catalysts was tested in the metathesis of ethylene and trans-2-butene to propylene. During ion exchange, sodium and potassium ions played different roles. Sodium modified catalysts revealed constant trans-2-butene conversion and propylene selectivity when the concentrations of sodium in the solution were varied. In contrast, potassium modified catalysts showed reduction of the conversion and increase of the selectivity. From these results, potassium hydroxide may affect the transformation of tungsten oxide active species, resulting in the decrease in conversion whereas sodium hydroxide did not. Moreover, the modification of catalysts by this method improved the catalyst stability by lowering the amount of coke deposited on the catalyst surface.

Keywords: acid sites, alkali metal, isomerization, metathesis

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Authors: Rajinder Kaur, Atul Khanna

Abstract:

Transparent glass-ceramic and crystalline samples of the system: xSrO-(100-x)TeO2; x = 7.5 and 8.5 mol% were prepared by quenching the melts in the temperature range of 700 to 950oC. A very interesting effect of the temperature on the glass-forming ability (GFA) of strontium tellurite melts is observed,and it is found that the melts produce transparent glass-ceramics when it is solidified from lower temperatures in the range of 700-750oC, however, when the melts are cooled from higher temperatures in the range of 850-950oC, the GFA is significantly reduced andanti-glass and/or crystalline phases are produced on solidification.The effect of temperature on GFA of strontium tellurite melts is attributed to short-range structural transformations: TeO₄TeO₃ which procceds towards the right side with an increrase in temperature. This isomerization reaction lowers the melt viscosity and enhances the crystallization tedendency. It is concluded that the high-temperature strontium tellurite meltsfreeze faster into crystalline phases as compared to the melts at a lower temperature; the latter supercooland solidify into glassy phases.

Keywords: anti-glasss, ceramic, supercool liquid, raman spectroscopy

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Authors: N. Zanganeh, M. Zabet

Abstract:

Lactulose is a synthetic disaccharide which has remarkable applications in food and pharmaceutical fields. Lactulose is not found in nature and it is produced by isomerization reaction of lactose in an alkaline environment. It should be noted that this reaction has a very low yield since significant amount of lactose stays un-reacted in the system. Basically, purification of lactulose is difficult and costly. Previous studies have revealed that solubility of lactose and lactulose are significantly different in ethanol. Considering the fact that solubility is also affected by temperature itself, we investigated the effect of ethanol and temperature on separation process of lactose from the syrup containing lactose and lactulose. For this purpose, a saturated solution containing lactulose and lactose was made at three different temperatures; 25⁰C (room temperature), 31⁰C, and 37⁰C first.  Five samples containing 2g saturated solution was taken and then 2g, 3g, 4g, 5g, and 6g ethanol separately was added to the sampling tubes. Sampling tubes were kept at respective temperatures afterward. The concentration of lactose and lactulose after separation process measured and analyzed by High Performance Liquid Chromatography (HPLC). Results showed that ethanol has such a greater impact than operating temperature on purification process. Also, it was observed that the maximum rate of separation occurred at initial amount of added ethanol.

Keywords: lactulose, lactose, purification, solubility

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