Solubility measurement of α-asarone in supercritical carbon dioxide

The solubility of α-asarone in supercritical CO₂ (sc-CO₂) has been measured using the dynamic method. The measurement was conducted in the pressure range from 9.0 to 18.0 MPa at temperature 35–49 °C. The experimental data were correlated using the Chrastil model. The results show that the solubility increases as the pressure rises and decreases as the temperature rises, which is well correlated with the Chrastil model.     

Selective hydrogenation of phenol in supercritical carbon dioxide

Liquid phase hydrogenation of phenol over Pt/C catalysts was investigated under conventional conditions and supercritical carbon dioxide (scCO2). The equivalent ration of hydrogen to phenol shows a significant effect on the product selectivity. Hydrogenation of phenol in different solvents was also studied, the experimental results show that polarity of solvents influences the yield of cyclohexanone remarkably, scCO2 has the highest one. Catalytic hydrogenation of phenol in scCO2 or sub-sc…     

Solubility of β-diketonate complexes for cobalt(III) and chromium(III) in supercritical carbon dioxide

The solubilities of tris(2,2,6,6-tetramethyl-3,5-heptanedionate) cobalt(III) (Co(thd)₃) and chromium(III) (Cr(thd)₃) in supercritical carbon dioxide (scCO₂) were measured at temperatures ranging from 313 to 343 K. The measurements were carried out using a circulation-type apparatus with a UV–vis spectrometer. The solubilities of both Co(thd)₃ and Cr(thd)₃ increased as both the density of scCO₂ and the temperature increased, which has the same tendency as cobalt(III) acetylacetonate (Co(acac)₃) and chromium(III) acetylacetonate (Cr(acac)₃) had in our previous work. The solubilities of Cr(thd)₃ were higher than that of Co(thd)₃, and the solubilities of Co(thd)₃ and Cr(thd)₃ were about 50- and 70-fold higher than those of Co(acac)₃ and Cr(acac)₃, respectively. The measured solubilities of the metal complexes were correlated with the equation based on Chrastil's equation. The parameters were determined by correlating the experimental data for each metal complex, and the correlated results well reproduced the experimental data, especially Co(thd)₃. Moreover, the charge density distributions on the molecular surface of CO₂ and the metal complexes used in the measurement were estimated by the quantum chemical calculation and the COSMO-RS to clear the effect of the molecular structure of the metal complexes on the affinity for CO₂.     

Palladium-catalyzed homo-coupling of boronic acids with supported reagents in supercritical carbon dioxide

Palladium-catalyzed homo-coupling of arylboronic acids could proceed smoothly with a commercially available resin functionlised by phosphino or amino group as the ligand in supercritical carbon dioxide thereby offering a simple and efficient protocol for the synthesis of symmetrical bi-aryl molecules and their higher homologues.     

Continuous styrene – methyl methacrylate – glycidyl methacrylate terpolymerizations in homogeneous mixtures with supercritical carbon dioxide

Free-radical terpolymerizations of styrene, methyl methacrylate, and glycidyl methacrylate were carried out in a tubular reactor in the presence of 20 wt.% CO₂ at temperatures between 120 and 180°C and pressures of 300 and 350 bar. The number average molecular weights, M_N, were mostly between 2000 and 3000 g·mol⁻¹ and polydispersity indices around 2. In part of the experiments molecular weights were controlled by n-dodecyl mercaptan serving as the chain-transfer agent. PREDICI modeling indicates that the targeted molecular weights of M_N∼2500 g·mol⁻¹ and polydispersities around 2 may also be reached by using an initiator cocktail, a mixture of two initiators with significantly different decomposition rate coefficients. The predictions are confirmed experimentally.     

Solubility of anthracene in binary alkane + ethanol solvent mixtures at 298.15 K

Experimental solubilities are reported for anthracene in six binary alkane?+?ethanol solvent mixtures at 298.15?K. The alkane solvents studied were hexane, heptane, octane, cyclohexane, methylcyclohexane and 2,2,4-trimethylpentane. Results of these measurements were used to test a mathematical representation based on the combined nearly ideal binary solvent (NIBS)/Redlich–Kister equation. For the six systems studied, the combined NIBS/Redlich–Kister equation was found to accurately describe the experimental data, with an average absolute deviation between measured and back-calculated values being approximately ±0.5%.     

Diiodination of Alkynes in supercritical Carbon dioxide

A general,green and efficient method for the synthesis of transdiiodoalkenes in CO2(sc) has been developed.Trans-diiodoalkenes were obtained stereospecifically in quantitative yields via diiodination of both electron-rich and electron-deficient alkynes in the presence of KI,Ce(SO4)2 and water in supercritical carbon dioxide [CO2(sc)]at 40℃.     

Complex between modified β-cyclodextrins and three components of traditional Chinese medicine in supercritical carbon dioxide medium

In this work, the complex between three hydrophobic efficacious components of plants (anisole, asarone, curcumin) and modified cyclodextrin (2-hydroxypropyl-β-cyclodextrin, methyl-β-cyclodextrin) was investigated in supercritical carbon dioxide medium; and compared with the corresponding complex in air circumstance. The effect of the substitute group in the drug molecule on the complex reaction was also discussed.     

Reduction of carbon dioxide by hydrogen on metal–carbon catalysts under supercritical conditions

The reduction of carbon dioxide with hydrogen on metal–carbon (Ru, Rh, Ir) catalysts is investigated under supercritical conditions for the first time. High selectivity (close to 100%) toward methanation with good stability of catalytic activity is observed for Ru- and Rh-containing catalyst, while the preferred reduction to CO is observed for Ir/C catalyst.     

An experimental study of three- and four-phase equilibria for isopropanol—water—carbon dioxide mixtures at elevated pressures

Compositions and molar volumes of the three phases in liquid—liquid—gas equilibrium are reported for ternary mixtures of isopropanol, water and CO₂ at elevated pressures and at temperatures of 50 and 60°C. Phase compositions and molar volumes were also obtained for three-phase, liquid—liquid—liquid equilibrium and four-phase, liquid—liquid—liquid—gas equilibrium at 40°C. Gas—liquid and liquid—liquid critical endpoints, which represent pressure bounds on the liquid—liquid—gas region at 60°C, were determined from observations of critical opalescence.The phase behavior exhibited by the isopropanol—water—CO₂ system is quite complex, particularly at conditions near the critical point of CO₂. These conditions are well within the range of operating conditions proposed for supercritical-fluid extraction of organic compounds from water using CO₂. Therefore, the existence of multiple coexisting phases can be an important factor in designing and operating such extraction processes.     

Addition of carbon dioxide to epoxides catalyzed by the mixtures of α-amino acids and iodine

Russian Chemical Bulletin - We found a group of available and efficient catalysts for the addition reaction of CO2 to epoxides, which was formed by simple mixing of molecular iodine with...     

Characteristic profiles of the inclusion complex of omeprazole/peracylated-β-cyclodextrin formed in supercritical carbon dioxide

Inclusion properties of the drug omeprazole (OMP) with peracetylated-beta-cyclodextrin (PAc-β-CD) prepared by green method, following supercritical carbon-dioxide (scCO₂), were characterized through thermal (TGA and DSC), crystalline (XRD), NMR spectroscopic and dissolution studies. Comparison amongst PAc-β-CD, OMP, physical binary mixture (equimolar ratio of OMP: PAc-β-CD) and the solid inclusion complex (OMP/PAc-β-CD) revealed scCO₂ as a successful technique for inclusion complex formation as well, identified characteristics performances of PAc-β-CD/OMP interactions. For instance, absence of characteristic DSC or XRD peaks of either chemical in the complex was quite noticeable with the shift of proton peaks in ¹H NMR spectra. The formed inclusion complex also showed an important dissolution performance of OMP for controlled release applications partly due to the hydrophobic nature of PAc-β-CD.     

Solvation behaviour of silver(I) iodate in methanol—acetonitrile and ethanol—acetonitrile mixtures

The solvation behaviour of silver(I) iodate in methanol—acetonitrile (AN) and ethanol—acetonitrile mixtures has been studied at 30°C by solubility and emf measurements. The solubility of the salt increases with the addition of AN and passes through a maximum at X_AN = 0.3 and 0.6 in the case of MeOH-AN and EtOH-AN mixtures, respectively, and then decreases with further addition of AN. The transfer free energy of silver ion decreases while that of iodate ion increases with the addition of AN in both the solvent mixtures. The solvent transport number, Δ of AN is positive with a maximum at X_AN = 0.45 (Δ = 0.45 (Δ = 5.4) and at X_AN = 0.55 (Δ = 2.4) in the case of MeOH-AN and EtOH-AN mixtures, respectively. These results have been interpreted in terms of the heteroselective solvation of the salt, the silver ion being preferentially solvated by AN and the iodate ion by the amphiprotic solvent component in these mixtures.     

Application of the perturbed Lennard–Jones chain equation of state to solute solubility in supercritical carbon dioxide

The perturbed Lennard–Jones chain (PLJC) equation of state is a thermodynamic model based on the perturbation theory of liquid state. This equation has been shown in the past to be a successful model for phase equilibria calculations of binary and ternary fluid mixtures and polymer solutions. In this work, we employed for the first time the PLJC equation to model the solubility of 39 solids in supercritical carbon dioxide. It was shown that the model achieves good correlation with three temperature independent parameters. A comparison of the PLJC with the commonly used Peng–Robinson equation reveals the PLJC equation gives better correlation to the solubility data than the Peng–Robinson model that utilizes temperature dependent parameters.     

Complex formation of cinnamaldehyde-methyl-β-cyclodextrin and muscone-methyl-β-cyclodextrin by supercritical carbon dioxide processing and sealed heating method

Firstly, the interaction between cinnamaldehyde (CIN) and methyl-β- cyclodextrin (MBCD) was studied in aqueous solution. 1:1 inclusion complex was formed and the association constant was 187 ± 9 M^?1. Then the complex of CIN–MBCD and muscone–MBCD was prepared both by sealed heating method and by supercritical carbon dioxide (sc CO₂) approach. Complete complex was obtained by both methods for CIN–MBCD. Some CIN molecules was weakly associated with MBCD molecules in products by sealed heating method, all CIN molecules was strongly associated with MBCD molecules in products by sc CO₂ processing. Complete complex between muscone and MBCD was not obtained. The choice for the size of guest molecule still existed for MBCD cavity in sealed heating method and sc CO₂ processing.     

Effect of supercritical carbon dioxide treatment on structure and mechanical properties of β-nucleated polypropylene processed at different temperatures

Polypropylene (PP) was compounded with β-nucleating agent and injection-molded at 180 °C or 220 °C. The samples were subsequently treated by supercritical carbon dioxide (scCO₂) at different temperatures. Results show that processing temperature and scCO₂ treatment could strongly influence the tensile and impact properties of β-nucleated PP. In particular, the sample processed at 220 °C and treated at 120 °C exhibit much enhanced impact strength (4.8 times that of its untreated counterpart). FTIR, WAXD, SEM and DMA were performed to explore the effects of processing temperature and scCO₂ treatment on structure of the samples. Deformation-induced plastic flow and micro-voids were also evaluated to construct structure-property relations. It was found that the influence of processing temperature on mechanical properties is mainly associated with the β-form content and β-crystalline morphology, while the structural changes in the crystalline lamellar scale may be responsible for the toughening effect of scCO₂ treatment.     

Effects of several inter-molecular interactions on the inclusion between methyl substituted β-cyclodextrin and some linear macromolecule in supercritical carbon dioxide medium

In this work, the inclusion between methyl substitute β-cyclodextrin and some linear macromolecule in supercritical carbon dioxide medium was investigated. The contributions from several factors were studied; such as the hydrogen bonding interaction between the host and guest, the hydrogen bonding interaction between the neighborhood cyclodextrin rims threaded on the polymer chain, and the matching between the host cavity and the size of the polymer axis.     

Can block copolymers be synthesized by a single-step chemoenzymatic route in supercritical carbon dioxide?

We demonstrate the single-step one-pot synthesis of block copolymers by simultaneous enzymatic ring-opening polymerization and chemically catalyzed atom transfer radical polymerization in supercritical carbon dioxide. Both catalyst systems function simultaneously under these conditions, providing a simple route to the formation of block copolymers of dissimilar monomers.