Photoreduction of carbon dioxide on zinc sulfide to give four-carbon and two-carbon acids

Aqueous solutions of CO₂ containing tetramethylammonium chloride were photolysed with visible light in the presence of colloidal ZnS to yield tartaric acid, glyoxylic acid, oxalic acid, formic acid and formaldehyde.

High-pressure phase equilibrium in the {carbon dioxide (1) + 1-chloropropane (2)} binary system

Abstract The current study reports original vapour-liquid equilibrium (VLE) for the system {CO2 (1) + 1-chloropropane (2)}. The measurements have been performed over the entire pressure-composition range for the (303.15, 313.15 and 328.15) K isotherms. The values obtained have been used for comparison of four predictive approaches, namely the equation of state (EoS) of Peng and Robinson (PR), the Soave modification of Benedict–Webb–Rubin (SBWR) EoS, the Critical Point-based Revised Perturbed-Chain Association Fluid Theory (CP-PC-SAFT) EoS, and the Conductor-like Screening Model for Real Solvents (COSMO-RS). It has been demonstrated that the three EoS under consideration yield similar and qualitatively accurate predictions of VLE, which is not the case for the COSMO-RS model examined. Although CP-PC-SAFT EoS exhibits only minor superiority in comparison with PR and SBWR EoS in predicting VLE in the system under consideration, its relative complexity can be justified when taking into account the entire thermodynamic phase space and, in particular, considering the liquid densities and sound velocities over a wider pressure-volume-temperature range.

Novel Supercritical Carbon Dioxide Impregnation Technique for the Production of Amorphous Solid Drug Dispersions: A Comparison to Hot Melt Extrusion

The formulation of BCS Class II drugs as amorphous solid dispersions has been shown to provide advantages with respect to improving the aqueous solubility of these compounds. While hot melt extrusion (HME) and spray drying (SD) are among the most common methods for the production of amorphous solid dispersions (ASDs), the high temperatures often required for HME can restrict the processing of thermally labile drugs, while the use of toxic organic solvents during SD can impact on end-product toxicity. In this study, we investigated the potential of supercritical fluid impregnation (SFI) using carbon dioxide as an alternative process for ASD production of a model poorly water-soluble drug, indomethacin (INM). In doing so, we produced ASDs without the use of organic solvents and at temperatures considerably lower than those required for HME. Previous studies have concentrated on the characterization of ASDs produced using HME or SFI but have not considered both processes together. Dispersions were manufactured using two different polymers, Soluplus and polyvinylpyrrolidone K15 using both SFI and HME and characterized for drug morphology, homogeneity, presence of drug-polymer interactions, glass transition temperature, amorphous stability of the drug within the formulation, and nonsink drug release to measure the ability of each formulation to create a supersaturated drug solution. Fully amorphous dispersions were successfully produced at 50% w/w drug loading using HME and 30% w/w drug loading using SFI. For both polymers, formulations containing 50% w/w INM, manufactured via SFI, contained the drug in the γ-crystalline form. Interestingly, there were lower levels of crystallinity in PVP dispersions relative to SOL. FTIR was used to probe for the presence of drug-polymer interactions within both polymer systems. For PVP systems, the nature of these interactions depended upon processing method; however, for Soluplus formulations this was not the case. The area under the dissolution curve (AUC) was used as a measure of the time during which a supersaturated concentration could be maintained, and for all systems, SFI formulations performed better than similar HME formulations.

The Use of High Surface Area Silica and Supercritical Carbon Dioxide to Enhance Solubility of Poorly Water-Soluble Drugs

Purpose Poor water-solubility of BCS class II drugs can limit their commercialization because of reduced oral bioavailability. It has been reported that loading of drug by adsorption onto porous silica would enhance drug solubility due to the increased surface area available for solvent diffusion. In this work, solid dispersions are formed using supercritical carbon dioxide (scCO2). The aim of this research was to characterise the solid-state properties of scCO2 dispersion and to investigate the impact of altering scCO2 processing conditions on final amorphous product performance that could lead to enhancement of drug dissolution rate for BCS class II drugs. Methods Indomethacin (IND) was purchased from Sigma-Aldrich (Dorset, UK) and was used as a model drug with two grades of high surface area silica (average particle sizes 3&[micro] and 7&[micro]), which were obtained directly from Grace-Davison (Germany). Material crystallinity was evaluated using powder X-ray diffraction (PXRD, Rigaku™, miniflex II, Japan) and high-speed differential scanning calorimetry (Hyper-DSC 8000, Perkin Elmer, USA). Materials were placed in a high-pressure vessel consisting of a CO2 cylinder, a Thar™ Technologies P50 high-pressure pump and a 750 ml high-pressure vessel (Thar, USA). Physical mixtures were exposed to CO2 gas above its critical conditions. SEM imaging and elemental analysis were conducted using a Jeol 6500 FEGSEM (Advanced MicroBeam Inc., Austria). Drug release was examined using USP type II dissolution tester (Caleva™, UK). Results The two grades of silica were found to be amorphous using PXRD and Hyper-DSC. Using PXRD, it was shown that an increase in incubation time and pressure resulted in a decrease in the crystalline content. Drug release profiles from the two different silica formulations prepared under the same conditions are shown in Figure 1. It was found that there was a significant enhancement in drug release, which was influenced, by silica type and other experiment conditions such as temperature, pressure and exposure time. SEM imaging and elemental analysis showed drug deposited inside silica pores as well as on the outer surface. Conclusion This project has shown that silica carrier platforms may be used as an alternative approach to generating polymeric solid dispersions of amorphous drugs exhibiting enhanced solubility.

Reduction of Carbon Dioxide to Formate at Low Overpotential using a Superbase Ionic Liquid

A new low-energy pathway is reported for the electrochemical reduction of CO2 to formate and syngas at low overpotentials, utilizing a reactive ionic liquid as the solvent. The superbasic tetraalkyl phosphonium ionic liquid [P66614][124Triz] is able to chemisorb CO2 through equimolar binding of CO2 with the 1,2,4-triazole anion. This chemisorbed CO2 can be reduced at silver electrodes at overpotentials as low as 0.17 V, forming formate. In contrast, physically absorbed CO2 within the same ionic liquid or in ionic liquids where chemisorption is impossible (such as [P66614][NTf2]) undergoes reduction at significantly increased overpotentials, producing only CO as the product.