Showing papers on "Acetone published in 2012"

Metabolic Engineering of Clostridium acetobutylicum ATCC 824 for Isopropanol-Butanol-Ethanol Fermentation

Abstract: Clostridium acetobutylicum naturally produces acetone as well as butanol and ethanol. Since acetone cannot be used as a biofuel, its production needs to be minimized or suppressed by cell or bioreactor engineering. Thus, there have been attempts to disrupt or inactivate the acetone formation pathway. Here we present another approach, namely, converting acetone to isopropanol by metabolic engineering. Since isopropanol can be used as a fuel additive, the mixture of isopropanol, butanol, and ethanol (IBE) produced by engineered C. acetobutylicum can be directly used as a biofuel. IBE production is achieved by the expression of a primary/secondary alcohol dehydrogenase gene from Clostridium beijerinckii NRRL B-593 (i.e., adhB-593) in C. acetobutylicum ATCC 824. To increase the total alcohol titer, a synthetic acetone operon (act operon; adc-ctfA-ctfB) was constructed and expressed to increase the flux toward isopropanol formation. When this engineering strategy was applied to the PJC4BK strain lacking in the buk gene (encoding butyrate kinase), a significantly higher titer and yield of IBE could be achieved. The resulting PJC4BK(pIPA3-Cm2) strain produced 20.4 g/liter of total alcohol. Fermentation could be prolonged by in situ removal of solvents by gas stripping, and 35.6 g/liter of the IBE mixture could be produced in 45 h.

Aqueous-phase furfural-acetone aldol condensation over basic mixed oxides

Abstract: Catalytic aqueous-phase aldol-condensation of acetone and furfural has been studied in this work. Three different mixed-oxides catalysts (Mg–Zr, Mg–Al and Ca–Zr, with different basic sites distribution) were studied, their activity and selectivity being correlated with their physico-chemical properties. Catalysts with the highest concentration of basic sites (especially medium-strength basic sites) are the most active and selective for the C13 fraction, whereas molar ratios of 1:1 yield the highest selectivities for C13 fraction (more than 60% atomic yield for the Mg–Zr mixed oxide). Concerning to reaction mechanism, cis isomers are the first ones formed, whereas trans isomers are the most abundant at higher reaction times. The main causes of catalysts deactivation are the modification of the physico-chemical properties of catalysts – because of the interaction with water – and in minor extent, the leaching effect; although homogeneous catalytic effects are discarded at studied conditions. The products formed, and the kinetic dependence on reactant concentration, are consistent with a catalytic mechanism in which the rate-determining step is the formation of the enolate species. The model considers consecutive reversible reactions yielding C8, in the first step, and C13, in the second step; with a first-order dependence on the species with α-hydrogen (acetone and C8), and zero-th order on those species without it (furfural and C13).

Reutilization of Mango Byproducts: Study of the Effect of Extraction Solvent and Temperature on Their Antioxidant Properties

Abstract: Mango biowastes, obtained after processing, contain large amounts of compounds with antioxidant activity that can be reused to reduce their environmental impact. The present study evaluates the effect of solvent (methanol, ethanol, acetone, water, methanol:water (1:1), ethanol:water (1:1), and acetone:water (1:1)), and temperature (25, 50, and 75 ◦ C) on the efficiency of the extraction of antioxidants from mango peel and seed. Among the factors optimized, extraction solvent was the most important. The solvents that best obtained extracts with high antioxidant capacity were methanol, methanol:water, ethanol:water, and acetone:water (β-carotene test, antioxidant activity coefficient 173 to 926; thiobarbituric acid reactive substances test, inhibition ratio 15% to 89%; 2,2 � -azino-bis-(3-ethylbenzothiazoline)-6- sulfonic acid ABTS + ; and 2,2-diphenyl-1-picrylhydrazyl DPPH scavenging, 7 to 22 and 8 to 28 g trolox equivalent antioxidant capacity (TE) per 100 g mango biowaste on a dry matter basis (DW)). Similarly, the flavonoid (0.21 to 1.4 g (+)-catechin equivalents per 100 g DW), tannin (3.8 to 14 g tannic acid equivalents per 100 g DW), and proanthocyanidin (0.23 to 7.8 g leucoanthocyanidin equivalents per 100 g DW) content was highest in the peel extracts obtainedwithmethanol,ethanol:water,oracetone:waterandintheseedextractsobtainedwithmethanoloracetone:water. From the perspective of food security, it is advisable to choose ethanol (which also has a notable antioxidant content), ethanol:water, or acetone:water, as they are all solvents that can be used in compliance with good manufacturing practice. In general, increasing temperature improves the capacity of the extracts obtained from mango peel and seed to inhibit lipid peroxidation; however, its effect on the extraction of phytochemical compounds or on the capacity of the extracts to scavenge free radicals was negligible in comparison to that of the solvent.

Ultrahigh sensitivity of Au/1D α-Fe2O3 to acetone and the sensing mechanism.

Abstract: Hematite (α-Fe(2)O(3)) is a nontoxic, stable, versatile material that is widely used in catalysis and sensors. Its functionality in sensing organic molecules such as acetone is of great interest because it can result in potential medical applications. In this report, microwave irradiation is applied in the preparation of one-dimensional (1D) α-FeOOH, thereby simplifying our previous hydrothermal method and reducing the reaction time to just a few minutes. Upon calcination, the sample was converted to porous α-Fe(2)O(3) nanorods, which were then decorated homogeneously by fine Au particles, yielding Au/1D α-Fe(2)O(3) at nominally 3 wt % Au. After calcination, the sample was tested as a potential sensor for acetone in the parts per million range and compared to a similarly loaded Pt sample and the pure 1D α-Fe(2)O(3) support. Gold addition results in a much enhanced response whereas Pt confers little or no improvement. From tests on acetone in the 1-100 ppm range in humid air, Au/1D α-Fe(2)O(3) has a fast response, short recovery time, and an almost linear response to the acetone concentration. The optimum working temperature was found to be 270 °C, which was judged to be a compromise between the thermal activation of lattice oxygen in hematite and the propensity for acetone adsorption. The surface reaction was investigated by diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), and a possible sensing mechanism is proposed. The presence of Au nanoparticles is believed to promote the dissociation of molecular oxygen better in replenishing O vacancies, thereby increasing the instantaneous supply of lattice oxygen to the oxidation of acetone (to H(2)O and CO(2)), which proceeds through an adsorbed acetate intermediate. This work contributes to the development of next-generation sensors, which offer ultrahigh detection capabilities for organic molecules.

Electrospinning cellulosic nanofibers for biomedical applications: structure and in vitro biocompatibility

Abstract: Electrospinning of cellulose acetate (CA) was studied in relation to factors of solvent composition, polymer concentration, and flow rate to elucidate how the processing parameters impact electrospun CA structure. Fibrous cellulose-based mats were produced from electrospinning cellulose acetate (CA, Mn = 30,000, DS = 2.45) in acetone, acetone/isopropanol (2:1), and acetone/dimethylacetamide (DMAc) (2:1) solutions. The effect of CA concentration and flow rate was evaluated in acetone/DMAc (2:1) solution. The morphology of electrospun CA mats was impacted by solvent system, polymer concentration, and solution flow rate. Fibers produced from acetone and the mixture of acetone/isopropanol (2:1) exhibited a ribbon structure, while acetone/DMAc (2:1) system produced the common cylindrical fiber shape. It was determined that the electrospinning of 17 % CA solution in acetone/DMAc (2:1, w/w) produced fibers with an average fiber diameter in the submicron range and the lowest size distribution among the solvents tested. The solution flow rate had a power law relationship of 0.26 with the CA fiber size for 17 % CA in acetone/DMAc (2:1). Solvent composition and flow rate also impacted the stability of the network structure of the electrospun fibers. Only samples from acetone/DMAc (2:1) at solution flow rates equal or higher than 1 mL/h produced fibrous meshes that were able to preserve their original network structure after deacetylation. These samples after regeneration showed no residual DMAc and exhibited no cytotoxic effects on mammalian cells.

Organosolvent pretreatment and enzymatic hydrolysis of rice straw for the production of bioethanol

Abstract: The present study investigates the operational conditions for organosolvent pretreatment and hydrolysis of rice straw. Among the different organic acids and organic solvents tested, acetone was found to be most effective based on the fermentable sugar yield. Optimization of process parameters for acetone pretreatment were carried out. The structural changes before and after pretreatment were investigated by scanning electron microscopy, X-ray diffraction and Fourier transform infrared (FTIR) analysis. The X-ray diffraction profile showed that the degree of crystallinity was higher for acetone pretreated biomass than that of the native. FTIR spectrum also exhibited significant difference between the native and pretreated samples. Under optimum pretreatment conditions 0.458 g of reducing sugar was produced per gram of pretreated biomass with a fermentation efficiency of 39%. Optimization of process parameters for hydrolysis such as biomass loading, enzyme loading, surfactant concentration and incubation time was done using Box–Benhken design. The results indicate that acetone pretreated rice straw can be used as a good feed stock for bioethanol production.

Continuous bio-catalytic conversion of sugar mixture to acetone–butanol–ethanol by immobilized Clostridium acetobutylicum DSM 792

Abstract: Continuous production of acetone, n-butanol, and ethanol (ABE) was carried out using immobilized cells of Clostridium acetobutylicum DSM 792 using glucose and sugar mixture as a substrate. Among various lignocellulosic materials screened as a support matrix, coconut fibers and wood pulp fibers were found to be promising in batch experiments. With a motive of promoting wood-based bio-refinery concept, wood pulp was used as a cell holding material. Glucose and sugar mixture (glucose, mannose, galactose, arabinose, and xylose) comparable to lignocellulose hydrolysate was used as a substrate for continuous production of ABE. We report the best solvent productivity among wild-type strains using column reactor. The maximum total solvent concentration of 14.32 g L(-1) was obtained at a dilution rate of 0.22 h(-1) with glucose as a substrate compared to 12.64 g L(-1) at 0.5 h(-1) dilution rate with sugar mixture. The maximum solvent productivity (13.66 g L(-1) h(-1)) was obtained at a dilution rate of 1.9 h(-1) with glucose as a substrate whereas solvent productivity (12.14 g L(-1) h(-1)) was obtained at a dilution rate of 1.5 h(-1) with sugar mixture. The immobilized column reactor with wood pulp can become an efficient technology to be integrated with existing pulp mills to convert them into wood-based bio-refineries.

The Effect of Solvents, Acetone, Water, and Ethanol, on the Morphological and Optical Properties of ZnO Nanoparticles Prepared by Microwave

Abstract: HDA-capped ZnO nanoparticles were prepared by solvothermal method using solvents of different polarities. A number of parameters were kept constant such as temperature, pressure, time, and pH while solvents were varied, that is, water, ethanol, and acetone. The TEM was used for the structural properties and morphologies such as spheres, mixture of rods, and spheres and stars were obtained in ethanol, acetone, and water, respectively, in a given reaction time of 15 minutes. Both ethanol and acetone gave rods with high aspect ratio primarily because of the lengths of the rods. Water and ethanol have the hydroxyl groups which interact with nanoparticles from nucleation, growth, and termination giving rise to nonspherical shapes. The hydroxyl group promotes growth in a nonuniform way resulting in stars and rods. The optical features were typical of ZnO nanoparticles with excitonic peaks in the range 368 to 374 nm from their absorption spectra. The XRD patterns of the particles gave the most stable form of ZnO which is the hexagonal phase, with high degree of crystallinity and with the 101 plane predominant in all solvents.

Optimization of soy isoflavone extraction with different solvents using the simplex-centroid mixture design.

Abstract: The objective of this study was to optimize the extraction of different isoflavone forms (glycosidic, malonyl-glycosidic, aglycone and total) from defatted cotyledon soy flour using the simplex-centroid experimental design with four solvents of varying polarity (water, acetone, ethanol and acetonitrile). The obtained extracts were then analysed by high-performance liquid chromatography. The profile of the different soy isoflavones forms varied with different extractions solvents. Varying the solvent or mixture used, the extraction of different isoflavones was optimized using the centroid-simplex mixture design. The special cubic model best fitted to the four solvents and its combination for soy isoflavones extraction. For glycosidic isoflavones extraction, the polar ternary mixture (water, acetone and acetonitrile) achieved the best extraction; malonyl-glycosidic forms were better extracted with mixtures of water, acetone and ethanol. Aglycone isoflavones, water and acetone mixture were best extracted and total isoflavones, the best solvents were ternary mixture of water, acetone and ethanol.

Stable gold nanoparticles obtained in pure acetone by laser ablation with different wavelengths

Abstract: We prepared gold nanoparticles (NPs) by ps laser ablation in pure acetone and water with 532 and 1,064 nm wavelengths The NPs obtained in pure acetone are stable for years and, depending on the fabrication conditions, they can be very small, quasi monodisperse and fluorescent These properties are not lost when they are transferred from acetone to water Post-irradiation tests of the colloids with 532 nm pulses, before and after phase transfer to water, and surface enhanced Raman spectroscopy (SERS), either on liquid and on dried samples, suggest that the stabilization mechanism in acetone is related to the light-induced formation on the gold surface of enolate which, in some cases, can undergo degradation with formation of amorphous carbon Micro-SERS tests were also used to demonstrate that functionalization of the particles with 1,10-phenanthroline or adenine is possible after transfer to the water phase, which opens the way to the use of such structures for biological and medical applications, such as biocompatible fluorescent or Raman markers

The Peculiar Nature of Molecular Interactions between an Imidazolium Ionic Liquid and Acetone

Abstract: We present novel insights into the molecular interactions between polar solvents and imidazolium ionic liquids using the example of 1-ethyl-3-methylimidazolium ethyl sulfate and acetone. Recently published volumetric property data of this particular system have revealed peculiarities which could not be fully explained by steric effects. In order to shed light on the behavior at a molecular level, we apply IR spectroscopy and analyze solvent-induced line shifts as well as the excess IR spectra. From the spectroscopic results a conclusive picture of the site-specific molecular interactions is developed and our explanation is in concert with the volumetric effects. The data suggest the initial formation of trimers in which acetone interacts with existing ion pairs through interactions of the acetone oxygen atom with the imidazolium ring rather than forming directed hydrogen bonds at the CH moieties. With further addition of acetone, tetramers are formed which significantly weaken the interionic interactions and eventually initiate ion pair dissociation. Once the ions are released, the anion is rapidly saturated with acetone while the cation solvation proceeds more slowly with acetone addition.

Electrocatalytic Reduction of Acetone in a Proton‐Exchange‐Membrane Reactor: A Model Reaction for the Electrocatalytic Reduction of Biomass

Abstract: Acetone was electrocatalytically reduced to isopropanol in a proton-exchange-membrane (PEM) reactor on an unsupported platinum cathode. Protons needed for the reduction were produced on the unsupported Pt-Ru anode from either hydrogen gas or electrolysis of water. The current efficiency (the ratio of current contributing to the desired chemical reaction to the overall current) and reaction rate for acetone conversion increased with increasing temperature or applied voltage for the electrocatalytic acetone/water system. The reaction rate and current efficiency went through a maximum with respect to acetone concentration. The reaction rate for acetone conversion increased with increasing temperature for the electrocatalytic acetone/hydrogen system. Increasing the applied voltage for the electrocatalytic acetone/hydrogen system decreased the current efficiency due to production of hydrogen gas. Results from this study demonstrate the commercial feasibility of using PEM reactors to electrocatalytically reduce biomass-derived oxygenates into renewable fuels and chemicals.

Dual-layer PBI/P84 hollow fibers for pervaporation dehydration of acetone

Abstract: Acetone dehydration via pervaporation is challenging, because acetone and water have close molecular sizes, and acetone has a much higher vapor pressure than water. Acetone is also a powerful solvent, which dissolves or swells most polymers. We have developed novel polybenzimidazole/BTDA-TDI/MDI (PBI/P84) dual-layer hollow fibers for pervaporation dehydration of acetone for industrial and biofuel separations. Both thermal and chemical crosslinking modifications were applied to the membranes to investigate their effectiveness to overcome acetone-induced swelling. Thermal treatment can effectively enhance separation performance, but performance stability can only be achieved through the crosslinking modification of PBI. Crosslinking by p-xylene dichloride followed by a thermal treatment above 250°C show significant effectiveness to improve and stabilize pervaporation performance. The fractional free volume of the PBI selective layer reduces from 3.27 to 1.98% and 1.33%, respectively, after thermal treatment and a combination of chemical/thermal crosslinking modifications characterized by positron annihilation spectroscopy. © 2011 American Institute of Chemical Engineers AIChE J, 2012

Metal-Exchanged β Zeolites as Catalysts for the Conversion of Acetone to Hydrocarbons

Abstract: Various metal-β zeolites have been synthesized under similar ion-exchange conditions. During the exchange process, the nature and acid strength of the used cations modified the composition and textural properties as well as the Bronsted and Lewis acidity of the final materials. Zeolites exchanged with divalent cations showed a clear decrease of their surface Bronsted acidity and an increase of their Lewis acidity. All materials were active as catalysts for the transformation of acetone into hydrocarbons. Although the protonic zeolite was the most active in the acetone conversion (96.8% conversion), the metal-exchanged zeolites showed varied selectivities towards different products of the reaction. In particular, we found the Cu-β to have a considerable selectivity towards the production of isobutene from acetone (over 31% yield compared to 7.5% of the protonic zeolite). We propose different reactions mechanisms in order to explain the final product distributions.

1-Ethyl-3-methylimidazolium Dicyanamide as a Very Efficient Entrainer for the Extractive Distillation of the Acetone + Methanol System

Abstract: Isobaric vapor–liquid equilibria (VLE) for the ternary system acetone + methanol +1-ethyl-3-methylimidazolium dicyanamide ([emim][DCA]) as well as the two solvent + IL binary systems have been obtained at 100 kPa using a recirculating still. The addition of [emim][DCA] to the solvent mixture produced a salting-out effect greater than that produced by other ionic liquids, showing that this ionic liquid is, until now, the best IL tested as an entrainer for the extractive distillation of the acetone + methanol mixtures, causing the azeotrope to disappear for an ionic liquid mole fraction as low as 0.031, at 100 kPa. This behavior can be explained on the basis of the influence of the IL concentration on the activity coefficient of each solvent in the binary mixtures. The electrolyte nonrandom two-liquid (NRTL) model was used for fitting successfully the experimental data.

Dewetting of Stable Thin Polymer Films Induced by a Poor Solvent: Role of Polar Interactions

Abstract: We investigate the room temperature instability and dewetting of ultrathin (<100 nm) stable polystyrene (PS) films induced by a poor solvent, such as acetone, on a higher energy silicon substrate without an oxide layer. Instability behavior is contrasted for thermal annealing and acetone-vapor annealing and by immersion under liquid acetone. The PS films that are stable under thermal annealing are rendered unstable to dewetting when contacted by acetone, notwithstanding the stabilizing apolar van der Waals interactions in all the three systems. Relatively high molecular weight films dewet only in the liquid acetone, but low molecular weight films dewet on contact with both vapor and liquid acetone. These findings indicate the role of polar interactions engendered by acetone in the film instability modified possibly by nanophase separation aided by the substrate and nucleative mechanisms. Liquid acetone greatly enhances the instability so that the number density of holes produced in liquid acetone is about...

Selective production of acetone during continuous synthesis gas fermentation by engineered biocatalyst Clostridium sp. MAceT113

Abstract: Aims: To engineer acetogen biocatalyst capable of fermenting synthesis gas blend to acetone as the only liquid carbonaceous product. Methods and Results: The metabolic engineering comprised inactivation of phosphotransacetylase via integration of a cassette comprising synthetic genes erm(B), thiolase and HMG-CoA synthase. Acetaldehyde dehydrogenase was inactivated via integration of a cassette consisting of synthetic genes cat, HMG-CoA lyase and acetoacetate decarboxylase. The engineered biocatalyst Clostridum sp. MAceT113 lost production of 253 mmol l−1 ethanol and 296 mmol l−1 acetate and started producing 1·8 mol l−1 acetone in single-stage continuous syngas fermentation. Conclusions: The acetone concentration in culture broth is economical for bulk manufacture because it is about twenty times of that achieved with known acetone–butanol–ethanol fermentation of sugars. Significance and Impact of the Study: The process shows the opportunity to produce acetone from synthesis gas at concentrations comparable with production of acetone from products of petroleum cracking. This is the first report on elimination of acetate and acetaldehyde production and directing carbon flux from Acetyl-CoA to acetone via a non-naturally occurring in acetogen acetone biosynthesis pathway identified in eukaryotic organisms.

Solvent elimination from polymer nanoparticle suspensions by continuous supercritical extraction

Abstract: Nanoprecipitation is a simple and effective process for the production of nanoparticle suspensions However, until now only a marginal attention has been given to the problem of the solvents elimination from the prepared suspensions; this part of the process is very important in pharmaceutical/medical applications In this work, a new approach to the problem of acetone and acetone/ethanol mixtures removal, from the suspension of nanoparticles has been proposed, using supercritical CO 2 continuous solvent elimination technique The process parameters: pressure, temperature and liquid to gas ratios have been optimized and it has been tested on two polymers: polylactic-co-glycolic acid (PLGA) and polycaprolactone (PCL) The supercritical assisted post processing allowed to eliminate almost all the solvent residues until few ppm The suspensions produced were stable and no modifications in the nanoparticles suspension were induced

Effect of air-drying on the solvent evaporation, degree of conversion and water sorption/solubility of dental adhesive models

Abstract: This study evaluated protocols to eliminate acetone from dental adhesives and their effect on the kinetic of water sorption and percent of conversion of these adhesives. Experimental methacrylate-based adhesives with increasing hydrophilicity (R2, R3, R5) were used as reference materials. Primer-like solutions were prepared by addition of 50 wt% acetone. Acetone elimination was measured gravimetrically before and after: a spontaneous evaporation, an application of air-drying at room temperature or application of 40°C air-drying. Protocols were performed from 15 to 60 s. Specimens of adhesive/acetone mixtures were photo-activated and tested for degree of conversion, water sorption and solubility. Data were analyzed by ANOVA and Bonferroni’s tests (α = 0.05). Complete acetone elimination was never achieved, but it was significantly greater after the 40°C air-drying application. Higher acetone elimination was observed for the least hydrophilic adhesive. Longer periods for acetone evaporation and heated air-stream can optimize polymerization and reduce the water sorption/solubility of adhesive system models.

Optimal Conditions for Continuous Immobilization of Pseudozyma hubeiensis (Strain HB85A) Lipase by Adsorption in a Packed-Bed Reactor by Response Surface Methodology

Abstract: This study aimed to develop an optimal continuous process for lipase immobilization in a bed reactor in order to investigate the possibility of large-scale production. An extracellular lipase of Pseudozyma hubeiensis (strain HB85A) was immobilized by adsorption onto a polystyrene-divinylbenzene support. Furthermore, response surface methodology (RSM) was employed to optimize enzyme immobilization and evaluate the optimum temperature and pH for free and immobilized enzyme. The optimal immobilization conditions observed were 150 min incubation time, pH 4.76, and an enzyme/support ratio of 1282 U/g support. Optimal activity temperature for free and immobilized enzyme was found to be 68°C and 52°C, respectively. Optimal activity pH for free and immobilized lipase was pH 4.6 and 6.0, respectively. Lipase immobilization resulted in improved enzyme stability in the presence of nonionic detergents, at high temperatures, at acidic and neutral pH, and at high concentrations of organic solvents such as 2-propanol, methanol, and acetone.

Bifunctionalized hollow nanospheres for the one-pot synthesis of methyl isobutyl ketone from acetone.

Abstract: Pd-doped propyl sulfonic acid-functionalized hollow nanospheres proved to be efficient bifunctionalized catalysts for the one-pot synthesis of methyl isobutyl ketone (MIBK) from acetone and hydrogen in liquid phase. These hollow nanospheres exhibited a higher activity than their bulk mesoporous counterparts (SBA-15 or FDU-12), mainly due to the short diffusion resistance of hollow nanospheres. Hollow nanospheres with silica frameworks showed higher activity and selectivity for MIBK than those with ethane-bridged frameworks, suggesting that hollow nanospheres with hydrophilic surface properties favor the formation of MIBK. This is probably due to the increased affinity of the hydrophilic surface towards acetone and its decreased affinity towards MIBK, which precludes deep condensation of MIBK with acetone. Under optimal conditions, up to 90 % selectivity for MIBK can be obtained with conversions of acetone as high as 43 %. This result is among the best reported so far for mesoporous silica-based catalysts. The control/fine-tuning of morphology and surface properties provides an efficient strategy for improving the catalytic performance of solid catalysts.