Search results for "Supercritical"
showing 10 items of 236 documents
Comparative effect of supercritical carbon dioxide and high pressure processing on structural changes and activity loss of oxidoreductive enzymes
2019
Abstract Due to the CO2 specific characteristics, it has been used as supercritical (Sc) fluid for several applications, including enzyme inactivation. The influence of Sc-CO2 (10–65 MPa/10–30 min/35–65 °C) on mushroom polyphenol oxidase (PPO) and horseradish peroxidase (POD) was evaluated and the results were compared with those found using high pressure processing (HPP) (200–900 MPa/5–45 °C/1–15 min). The free ion concentration was also studied to compare the enzymatic activity and changes in electrical conductivity. Additionally both enzymes, untreated or treated using either Sc-CO2 or HPP, were used as additives in the CuCl2 crystallization method. The resulting additive-specific CuCl2 …
Oxidation of alcohols to carbonyl compounds with CrO3.SiO2 in supercritical carbon dioxide.
2006
Supercritical carbon dioxide (scCO2) is an effective reaction medium to perform the oxidation of primary and secondary aliphatic alcohols to the corresponding carbonyl compounds with chromium trioxide supported on silica. These reactions were performed by flowing a solution of the alcohol in scCO2 through a column containing the supported reagent and recovering the product by depressurization. This method avoids the use of organic solvents and the contamination of the products with chromium species.
QENS from polymeric micelles in supercritical CO[sub 2]
2000
We report QENS measurements from PS-b-PFOA aggregates in supercritical CO2. These consist of dense cores of CO2-insoluble polystyrene surrounded by a ‘corona’ of PFOA surfactant molecules whose CO2-philic groups interface with supercritical CO2. Lineshapes are dominated by localized diffusive modes and segmental dynamics of the anchored, finite-length PFOA chains. For Q∼0.6 A−1, we obtain effective diffusion coefficients of ≈0.8×10−6 cm2/sec. At higher Q, a single component is not sufficient as shown by excess intensity on the flanks. For Q>1.5 A−1, the wings reflect contributions due to a distribution of faster, more localized chain modes.
Critical micellization density: A small-angle-scattering structural study of the monomer-aggregate transition of block copolymers in supercriticalCO2
2000
In this paper we report a small-angle neutron-scattering investigation of micelle formation by the fluorocarbon-hydrocarbon block copolymer, polyvinyl acetate-b-poly (1,1,2,2-tetrahydroperfluoro-octyl acrylate) in supercritical CO{sub 2} (scCO{sub 2}) at 313 K. At high pressure the copolymer is in a monomeric state with a random coil structure, while at low pressure the polymer forms spherical aggregates stable in a wide range of thermodynamic conditions. By profiling pressure, a sharp monomer-micelle transition is obtained due to the tuning of the solvating ability of scCO{sub 2}. We confirm the previous finding that this aggregate-monomer transition is driven by the gradual penetration of…
Green Solvents for Analytical Separation and Analyses
2010
The alternatives to the use of organic solvents that have been offered by the scientific literature reviewed. In order to look at the best solvents from both analytical and sustainable view points, the use of water under superheated conditions, supercritical fluids, renewable organics, ionic liquids, and aqueous solutions of amphiphillic compounds, have been evaluated. As a general conclusion, it can be seen that, at present, green alternatives to the traditional organic solvents employed in analytical separations and analysis that are being well explored are the capabilities of the use of alcohols, supercritical fluids, and superheated water; and remain unexplored tremendous possibilities …
ChemInform Abstract: Continuous Hydrothermal Synthesis of Nanometric BaZrO3in Supercritical Water.
2008
Abstract Nanocrystalline barium zirconate (BaZrO 3 ) was synthesized using a hydrothermal synthesis process working in supercritical conditions and in a continuous way. By this method, we succeeded in the continuous and rapid production of nanopowders. As a preliminary work three barium precursors have been investigated: barium hydroxide (Ba(OH) 2 ), barium acetate (Ba(CH 3 COO) 2 ) and barium nitrate (Ba(NO 3 ) 2 ). Two of them (Ba(CH 3 COO) 2 and Ba(NO 3 ) 2 ) led to the pure perovskite phase. Then an experimental design has been conducted in order to determine the influence of the experimental parameters on the crystallinity and the grain size of the final product.
ChemInform Abstract: Homogeneous Metal-Based Catalysis in Supercritical Carbon Dioxide as Reaction Medium
2016
Above 31.1 °C and 73.8 bar, carbon dioxide reaches the supercritical state, being transformed into a fluid (scCO2) that has attracted interest in the last few decades as reaction medium for several transition-metal-catalyzed organic transformations. The main feature of this fluid rests on its capability to dissolve large amounts of other gases such as hydrogen, carbon monoxide, ethylene, or even methane and light alkanes. In this manner, very high concentrations of these reactants are available for catalysis. In this contribution a review of the main achievements of the use of transition-metal complexes as catalysts in scCO2 is presented.
CO2 as a C1-Building Block for Dialkyl Carbonate Synthesis
2002
Carbon dioxide, one of the major man-made greenhouse gas, is a renewable resource of carbon which can be viewed as a C1 synthon to build valuable chemicals. The development of new applications is of major interest considering CO2 conversion and environmentally friendly reactions. As chemical catalysis offers interesting options, we are studying the molecular design of catalysts for the formation of dialkyl carbonates from alcohols and CO2. This paper reports results on the mechanistic approach for dialkyl carbonate formation with alkoxybutyl tin(IV) compounds. The insertion of CO2 into Sn-OR bonds (R = Me, 1Pr) occurs at atmospheric pressure and room temperature leading to alkylcarbonato ti…
ChemInform Abstract: Baeyer-Villiger Oxidation of Ketones with a Silica-Supported Peracid in Supercritical Carbon Dioxide under Flow Conditions.
2009
[2-Percarboxyethyl]-functionalized silica reacts with ketones in supercritical carbon dioxide at 250 bar and 40 °C under flow conditions to yield the corresponding esters and lactones. The solid reagent can be easily recycled through treatment with 70% hydrogen peroxide in the presence of an acid at 0 °C. This procedure not only simplifies the isolation of the reaction products, but has the advantage of using only water and carbon dioxide as solvents under mild conditions.
Copolymerization of Vinylidene Fluoride and Acrylic Acid in Supercritical Carbon Dioxide
2010
The free-radical copolymerization of vinylidene fluoride (VDF) and acrylic acid (AA) was carried out in supercritical carbon dioxide using both precipitation and dispersion techniques in the presence of an ammonium carboxylate perfluoropolyether compound. Formation of a copolymer was confirmed by variable contact time CP MAS NMR spectroscopy. Macromolecular matrices were significantly enriched in AA with respect to the initial feed composition and we found that the nonfluorinated monomer has a much higher reactivity ratio with respect to VDF. The cumulative concentration, crystallinity, and water affinity of the synthesized copolymers could be modified changing the initial feed composition,…