Interferon alpha-2b (IFN- (Formula presented.) 2b) is an essential cytokine widely used in the treatment of chronic hepatitis C and hairy cell leukemia, and serum albumin is the most abundant plasma protein with numerous physiological functions. Effective single-step aqueous biphasic system (ABS) extraction for the simultaneous purification of IFN- (Formula presented.) 2b and BSA (serum albumin protein) was developed in this work. Effects of the ionic liquid (IL)-based ABS functionalization, fluorinated ILs (FILs; [C (Formula presented.) C (Formula presented.) Im][C (Formula presented.) F (Formula presented.) SO (Formula presented.)] and [N (Formula presented.)][C (Formula presented.) F (Formula presented.) SO (Formula presented.)]) vs. mere fluoro-containing IL ([C (Formula presented.) C (Formula presented.) Im][CF (Formula presented.) SO (Formula presented.)]), in combination with sucrose or [N (Formula presented.)][H (Formula presented.) PO (Formula presented.)] (well-known globular protein stabilizers), or high-charge-density salt K (Formula presented.) PO (Formula presented.) were investigated. The effects of phase pH, phase water content (%wt), phase composition (%wt), and phase volume ratio were investigated. The phase pH was found to have a significant effect on IFN- (Formula presented.) 2b and BSA partition. Experimental results show that simultaneous single-step purification was achieved with a high yield (extraction efficiency up to 100%) for both proteins and a purification factor of IFN- (Formula presented.) 2b high in the enriched IFN- (Formula presented.) 2b phase (up to 23.22) and low in the BSA-enriched phase (down to 0.00). SDS-PAGE analysis confirmed the purity of both recovered proteins. The stability and structure of IFN- (Formula presented.) 2b and BSA were preserved or even improved (FIL-rich phase) during the purification step, as evaluated by CD spectroscopy and DSC. Binding studies of IFN- (Formula presented.) 2b and BSA with the ABS phase-forming components were assessed by MST, showing the strong interaction between FILs aggregates and both proteins. In view of their biocompatibility, customizable properties, and selectivity, FIL-based ABSs are suggested as an improved purification step that could facilitate the development of biologics.

The development of efficient adsorbent materials for the selective capture of greenhouse gases (GHGs) is crucial. The porosity and surface area of the materials are key factors for the GHGs separation. This study demonstrates how waste from coconut shell (CS) biomass can be used to design novel biomaterials (CS-CO2, CS-ZnCl2) with enhanced GHG selectivity. A comparison with activated carbon monoliths (ACM) and a metal-organic framework (Fe-BTC) was carried out to assess the impact of different porous matrices on GHGs capture. The adsorption equilibrium of R-32, R-125, R-134a, R-143a, CO2, and CH4 on these materials was measured between 283.15–323.15 K. The adsorption isotherms obtained were fitted using the dual-site Langmuir model. For R-32, R-125, R-134a and R-143a, the adsorption capacity follows ACM > CS-ZnCl2 > Fe-BTC > CS-CO2 due to the decrease of the surface area. The CO2 adsorption capacity is ACM > Fe-BTC > CS-ZnCl2 > CS-CO2, which is related to the micropore volume. In this case, CS-CO2 has a smaller adsorption capacity but is similar to ACM and outperforms Fe-BTC at P < 0.4 MPa. The selectivity of R-410A, R-407C, R-404A, and CO2/CH4 blends was determined with the Ideal Adsorbed Solution Theory (IAST). CS-ZnCl2 shows a higher selectivity for R-125 over R-32 in R-410A and R-407C separations due to its larger pore volume. CS-CO2 predominantly adsorbs R-134a and R-143a over R-125 in R-404A separation. ACM preferentially adsorbs CO2 over CH4 due to its large, elongated micropores. This study introduces innovative materials that improve GHGs separation and help reduce emissions.

This work unfolds functionalized ABSs composed of FILs ([C2C1Im][C4F9SO3] and [(Formula presented.)][C4F9SO3]), mere fluoro-containing ILs ([C2C1Im][CF3SO3] and [C4C1Im][CF3SO3]), known globular protein stabilizers (sucrose and [(Formula presented.)][C4F9SO3]), low-molecular-weight carbohydrate (glucose), and even high-charge density salt (K3PO4). The ternary phase diagrams were determined, stressing that FILs highly increased the ability for ABS formation. The functionalized ABSs (FILs vs. mere fluoro-containing ILs) were used to extract lysozyme (Lys). The ABSs’ biphasic regions were screened in terms of protein biocompatibility, analyzing the impact of ABS phase-forming components in Lys by UV-VIS spectrophotometry, CD spectroscopy, fluorescence spectroscopy, DSC, and enzyme assay. Lys partition behavior was characterized in terms of extraction efficiency (% EE). The structure, stability, and function of Lys were maintained or improved throughout the extraction step, as evaluated by CD spectroscopy, DSC, enzyme assay, and SDS-PAGE. Overall, FIL-based ABSs are more versatile and amenable to being tuned by the adequate choice of the phase-forming components and selecting the enriched phase. Binding studies between Lys and ABS phase-forming components were attained by MST, demonstrating the strong interaction between Lys and FILs aggregates. Two of the FIL-based ABSs (30 %wt [C2C1Im][C4F9SO3] + 2 %wt K3PO4 and 30 %wt [C2C1Im][C4F9SO3] + 25 %wt sucrose) allowed the simultaneous purification of Lys and BSA in a single ABS extraction step with high yield (extraction efficiency up to 100%) for both proteins. The purity of both recovered proteins was validated by SDS-PAGE analysis. Even with a high-charge density salt, the FIL-based ABSs developed in this work seem more amenable to be tuned. Lys and BSA were purified through selective partition to opposite phases in a single FIL-based ABS extraction step. FIL-based ABSs are proposed as an improved extraction step for proteins, based on their biocompatibility, customizable properties, and selectivity.

Fluorinated ionic liquids (FILs) are defined as molecules having fluorinated tags equal to or longer than 4 carbon atoms in the anion and/or cation structures. They present nanosegregated domains making them 3-in-1 solvents with exceptional properties, including an attractive solubility power. This work is an important contribution towards understanding the current research on the phase behavior of FILs, which may be used as task-specific materials for industrial applications. An overview of the main works published in the last two decades is presented, concerning gas solubility in FILs, the application of membranes to improve the gas absorption in FILs, and the use of modeling approaches to ease the application of FILs in gas capture and separation processes, with emphasis on the relationship between the structural properties and their performance. Contributions concerning the liquid-liquid and solid-liquid equilibria behavior of FILs, including the liquid-liquid equilibria (LLE) of FILs in water and perfluoroalkanes, and the solid-liquid equilibria (SLE) of solid FILs in water and mixtures of FILs are also presented. Regarding the absorption of gases in FILs, a careful analysis of the published works reveals that: (1) an optimal density of fluorine atoms in FILs structure is required to positively impact the absorption of different gases, (2) the functionalization of membranes can be also a useful method to improve the performance in separation processes, and (3) modeling tools can ease the screening of the features that promote the absorption of gases by FILs. The study of FILs LLE showed a rich phase behavior with water and perfluoroalkanes and the enhanced surfactant power of FILs, which is highly dependent on the length of the hydrogenated and fluorinated side chains. Finally, studying the SLE of FILs mixtures allowed the formation of deep eutectic systems that enlarges the applicability of FILs.

The recovery of high purity fluorinated gases from refrigerant blends is vital to promote a circular economy in the field of refrigeration and air conditioning. In this work, we evaluate the performance of a four-step Vacuum Swing Adsorption (VSA) process using activated carbon for the recovery of R-32 (difluoromethane) from a R-410A refrigerant blend: a binary mixture of R-125 (pentafluoroethane) and R-32 (yR−32=0.7; yR−125=0.3). Breakthrough curves were performed using dilute and bulk feed concentrations to determine mass and heat transfer parameters, which were then employed in simulations of fixed-bed adsorber dynamics. The mathematical model employed successfully predicts the experimental results of a four-step VSA cycle (feed, blowdown, purge, pressurization). The VSA performance was evaluated using process simulation. For a cycle time of 800 s (each step taking 200 s) and feed and regeneration pressures of 1.01 and 0.01 bar, respectively, R-32 is obtained with 97.0 mol-% purity and 30.9% recovery, with process productivity of 4.06 mol h−1 per kilogram of adsorbent, and energy consumption of 123.2 kJ/mol. Our results demonstrate the feasibility of using VSA processes for the recovery of R-32 from the near-azeotropic R-410A refrigerant blend.

Compliance with the international agreements and regulations aiming at mitigating emissions of gases with high global warming potential (GWP) requires the involvement of all stakeholders in the value chain of equipment containing refrigeration gases. In particular, the technicians dealing with the installation, maintenance, and dismantling of refrigeration equipment have a relevant role in the prevention of the release of refrigerant gases and their correct management. Besides technical information and training, the awareness of these technicians about the effects of fluorinated gases (F-gases) on global warming is critical for policy, regulations and strategies related to F-gases. This work presents the results of a questionnaire conducted with 586 Portuguese, Spanish, and French technicians to diagnose their behaviours, knowledge, and risk perception face to refrigeration gases and global warming. The results reveal that the repaired equipment mostly contains the pure HFCs R-32 and R-134a, the HFC blends R-410A, R-407C, and R-404A, and the fourth-generation HFC[sbnd]HFO blend R-449A. They also indicate the need to implement more efficient and credible information/awareness campaigns and to improve the training of these professionals in key respects, such as the relation between F-gases and climate change and the importance of their individual responsibility. Several suggestions were provided by the inquired technicians to improve the repair/maintenance process aiming at mitigating the effect of refrigeration gases on climate change, and to improve the awareness of this topic. These suggestions should be taken into consideration to improve legislation and policies.

The development of advanced and innovative biomaterials with porous structural characteristics for the capture of fluorinated gases (F-gases) is important to contribute to the reduction of emissions of these gases with very high global warming potential. In this work, four biocarbons (CC-1:3H3PO4, CC-1:1H3PO4, CC-K2CO3 and CC-CO2) were produced by chemical and physical activation of corn cob biomass (CC). The adsorption equilibria of difluoromethane (R-32), pentafluoroethane (R-125), 1,1,1-tetrafluoroethane (R-125), 1,1,2-tetrafluoroethane (R-134a), sulphur hexafluoride (SF6), and nitrogen (N2) on these biocarbons were determined at 303.15 K. The highest adsorption capacities were obtained for CC-K2CO3 and CC-CO2 and a full characterization was also performed for these biomaterials at 283.15 and 323.15 K. On the other hand, the selectivities of SF6/N2 and the commercial refrigerants R-410A, R-407C, and R-407F were estimated using the Ideal Adsorption Solution theory (IAST). The results obtained for SF6/N2 show that the biocarbon CC-K2CO3 stands out from the other materials. In addition, the CC-CO2 shows a preference for R-32 over R-125 for the separation of the R-410A. Finally, CC-K2CO3 has a greater preference for R-134a over R-32 and R-125 in the R-407C and R-407F blends. Overall, these novel biocarbons improve the separation and purification of the F-gases under study, facilitating their application on a pilot scale.