RESUMO
The use of potassium hydroxide activated Starbons® derived from starch and alginic acid as adsorbents for 29 volatile organic compounds (VOCs) was investigated. In every case, the alginic acid derived Starbon (A800K2) was found to be the optimal adsorbent, significantly outperforming both commercial activated carbon and starch derived, activated Starbon (S800K2). The saturated adsorption capacity of A800K2 depends on both the size of the VOC and the functional groups it contains. The highest saturated adsorption capacities were obtained with small VOCs. For VOC's of similar size, the presence of polarizable electrons in lone pairs or π-bonds within non-polar VOCs was beneficial. Analysis of porosimetry data suggests that the VOC's are being adsorbed within the pore structure of A800K2 rather than just on its surface. The adsorption was completely reversible by thermal treatment of the saturated Starbon under vacuum.
RESUMO
Dichloromethane (DCM) is a useful and advantageous solvent used in pharmaceutical development due to its low cost, miscibility with other organic solvents, high volatility, and ability to solubilize drug molecules of variable polarities and functionalities. Despite this favourable behaviour, efforts to identify safer and more sustainable alternatives to hazardous, halogenated solvents is imperative to the expansion of green chemistry. In this work, bio-derived esters tert-butyl acetate, sec-butyl acetate, ethyl isobutyrate, and methyl pivalate are experimentally identified as safe and sustainable alternatives to directly replace DCM within thin-layer chromatography (TLC) in the analysis of small, common drug molecules. To elucidate the intermolecular interactions influencing retardation factors (Rf) a statistical thermodynamic framework, which quantifies the driving molecular interactions that yield empirical TLC measurements, is presented. Within this framework, we are able to deduce Rf dependence on polar eluent concentration, in the presence of a low-polar mediating solvent, between the stationary and mobile phases. The strength of competitive analyte-eluent (and analyte-solvent interactions) are quantified through Kirkwood-Buff integrals (KBIs); resulting KBI terms at the dilute eluent limit provide a theoretical foundation for the observed suitability of alternative green solvents for the replacement of dichloromethane in TLC.
RESUMO
Dihydrolevoglucosenone (Cyrene) is a bio-based molecule, derived in two simple steps from cellulose, which demonstrates significant promise as a dipolar aprotic solvent. The dipolarity of dihydrolevoglucosenone is similar to NMP, DMF and sulpholane. Dihydrolevoglucosenone demonstrates similar performance to NMP in a fluorination reaction and the Menschutkin reaction.
