Ionic liquids (ILs) have been proposed as promising media for the extraction and separation of bioactive compounds from the most diverse origins. This critical review offers a compilation on the main ...results achieved by the use of ionic-liquid-based processes in the extraction and separation/purification of a large range of bioactive compounds (including small organic extractable compounds from biomass, lipids, and other hydrophobic compounds, proteins, amino acids, nucleic acids, and pharmaceuticals). ILs have been studied as solvents, cosolvents, cosurfactants, electrolytes, and adjuvants, as well as used in the creation of IL-supported materials for separation purposes. The IL-based processes hitherto reported, such as IL-based solid–liquid extractions, IL-based liquid–liquid extractions, IL-modified materials, and IL-based crystallization approaches, are here reviewed and compared in terms of extraction and separation performance. The key accomplishments and future challenges to the field are discussed, with particular emphasis on the major lacunas found within the IL community dedicated to separation processes and by suggesting some steps to overcome the current limitations.
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Ionic liquids (ILs) are a novel class of solvents with interesting physicochemical properties. Many different applications have been reported for ILs as alternatives to organic solvents in chemical ...and bioprocesses. Despite the argued advantage of having low vapor pressure, even the most hydrophobic ILs show some degree of solubility in water, allowing their dispersion into aquatic systems and raising concerns on its pollutant potential. Moreover, nowadays most widespread notion concerning the ILs toxicity is that there is a direct relationship with their hydrophobicity/lipophilicity. This work aims at enlarging the currently limited knowledge on ILs toxicity by addressing negative impacts in aquatic ecosystems and investigating the possibility of designing hydrophobic ILs of low ecotoxicity, by the manipulation of their chemical structures. The impact of aromaticity on the toxicity of different cations (pyridinium, piperidinium, pyrrolidinium and imidazolium) and hydrophobic anions (bis(trifluoromethylsulfonyl)imide NTf
2
and hexafluorophosphate PF
6
) was analysed. Concomitantly, several imidazolium-based ILs of the type C
n
C
m
C
j
imNTf
2
were also studied to evaluate the effects of the position of the alkyl chain on the ILs’ toxicity. For that purpose, standard assays were performed using organisms of different trophic levels,
Vibrio fischeri
,
Pseudokirchneriella subcapitata
and
Daphnia magna
, allowing to evaluate the consistency of the structure–activity relationships across different biological targets. The results here reported suggest the possibility of designing ILs with an enhanced hydrophobic character and lower toxicity, by elimination of their aromatic nature.
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EMUNI, FIS, FZAB, GEOZS, GIS, IJS, IMTLJ, KILJ, KISLJ, MFDPS, NLZOH, NUK, OILJ, PNG, SAZU, SBCE, SBJE, SBMB, SBNM, UKNU, UL, UM, UPUK, VKSCE, ZAGLJ
Separation and purification of biomacromolecules either in biopharmaceuticals and fine chemicals manufacturing, or in diagnostics and biological characterization, can substantially benefit from ...application of microfluidic devices. Small volumes of equipment, very efficient mass and heat transfer together with high process control result in process intensification, high throughputs, low energy consumption and reduced waste production as compared to conventional processing. This review highlights microfluidics-based separation and purification of proteins and nucleic acids with the focus on liquid-liquid extractions, particularly with biocompatible aqueous two-phase systems, which represent a cost-effective and green alternative. A variety of microflow set-ups are shown to enable sustainable and efficient isolation of target biomolecules both for preparative, as well as for analytical purposes.
Separation and purification of biomacromolecules either in biopharmaceuticals and fine chemicals manufacturing, or in diagnostics and biological characterization, can substantially benefit from application of microfluidic devices.
The increasing interest on the application of ionic liquids (ILs) to a wide range of processes and products has been hampered by a lack of toxicological data, mainly in what concerns novel cations, ...such as guanidinium, phosphonium, and functionalized and non-functionalized imidazolium-based ILs. The present study reports the toxicity of five guanidinium-, six phosphonium, and six imidazolium-based ILs, towards the luminescent marine bacteria
Vibrio fischeri. These new results clearly show that guanidinium-, unlike the imidazolium- and phosphonium-based ILs, do not follow the trend of increasing toxicity with the increase in the alkyl chain length. Moreover, the introduction of oxygenated groups on the alkyl chains, such as ether and ester, leads to a decrease of the toxicity of guanidinium and also imidazolium compounds. In what respects the effect of the different cations, it is possible to recognize that the phosphonium-based ILs seem to be more toxic when compared to the analog imidazolium-based ILs (with the same anion and alkyl chains).
► Toxicological profile of ILs towards
Vibrio fischeri. ► Various ILs families guanidinium, phosphonium, and imidazolium tested. ► Two different established trends: “side chain effect” and “cut-off” effect. ► Decrease in toxicity with the oxygenation of the side chains. ► Affect of anion related with the elongation of the alkyl chains conjugated.
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GEOZS, IJS, IMTLJ, KILJ, KISLJ, NUK, OILJ, PNG, SAZU, SBCE, SBJE, UL, UM, UPCLJ, UPUK
Biopolymers are very favorable materials produced by living organisms, with interesting properties such as biodegradability, renewability, and biocompatibility. Biopolymers have been recently ...considered to compete with fossil-based polymeric materials, which rase several environmental concerns. Biobased plastics are receiving growing interest for many applications including electronics, medical devices, food packaging, and energy. Biopolymers can be produced from biological sources such as plants, animals, agricultural wastes, and microbes. Studies suggest that microalgae and cyanobacteria are two of the promising sources of polyhydroxyalkanoates (PHAs), cellulose, carbohydrates (particularly starch), and proteins, as the major components of microalgae (and of certain cyanobacteria) for producing bioplastics. This review aims to summarize the potential of microalgal PHAs, polysaccharides, and proteins for bioplastic production. The findings of this review give insight into current knowledge and future direction in microalgal-based bioplastic production considering a circular economy approach. The current review is divided into three main topics, namely (i) the analysis of the main types and properties of bioplastic monomers, blends, and composites; (ii) the cultivation process to optimize the microalgae growth and accumulation of important biobased compounds to produce bioplastics; and (iii) a critical analysis of the future perspectives on the field.
Antibodies obtained from egg yolk of immunized hens, immunoglobulin Y (IgY), are an alternative to the most focused mammal antibodies, because they can be obtained in higher titers by less invasive ...approaches. However, the production cost of high‐quality IgY for large‐scale applications remains higher than that of other drug therapies due to the lack of efficient purification methods. The search for new purification platforms is thus vital. The solution could be liquid–liquid extraction by using aqueous biphasic systems (ABS). Herein, we report the extraction and attempted purification of IgY from chicken egg yolk by using a new ABS composed of polymers and Good’s buffer ionic liquids (GB‐ILs). New self‐buffering and biocompatible ILs based on the cholinium cation and anions derived from Good’s buffers were synthesized and the self‐buffering characteristics and toxicity were characterized. Moreover, when these GB‐ILs are combined with PPG 400 (poly(propylene) glycol with a molecular weight of 400 g mol‐1) to form ABS, extraction efficiencies, of the water‐soluble fraction of proteins, ranging between 79 and 94 % were achieved in a single step. Based on computational investigations, we also demonstrate that the preferential partitioning of IgY for the GB‐IL‐rich phase is dominated by hydrogen‐bonding and van der Waals interactions.
Egg extraction: Biocompatible and self‐buffering ionic liquids are shown to be adequate candidates for the extraction/purification of immunoglobulin Y from egg yolk through the formation of aqueous biphasic systems.
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Cholinium-based ionic liquids are quaternary ammonium salts with a wide range of potential industrial applications. Based on the fact that the cholinium is a complex B vitamin and widely used as food ...additive, the cholinium-based ionic liquids are generically regarded as environmentally “harmless” and thus, accepted as “non-toxic”, although their ecotoxicological profile is poorly known. This work provides new ecotoxicological data for ten cholinium-based salts and ionic liquids, aiming to extend the surprisingly restricted body of knowledge about the ecotoxicity of this particular family and to gain insight on the toxicity mechanism of these compounds. The results reported here show that not all the cholinium tested can be considered harmless towards the test organism adopted. Moreover, the results suggest that the cholinium family exhibits a different mechanism of toxicity as compared to the imidazolium ionic liquids previously described in the literature.
•The role of different anions in the ecotoxicity of the cholinium family was studied.•The toxicity of these ILs is higher than some common organic solvents.•Most cholinium-based ILs can be classified as “practically harmless”.•Permeation through the cell membrane plays an important role in the toxicity of these ILs.•The mechanism of toxicity of some cholinium-based ILs seems to be different than anticipated.
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GEOZS, IJS, IMTLJ, KILJ, KISLJ, NUK, OILJ, PNG, SAZU, SBCE, SBJE, UL, UM, UPCLJ, UPUK
Pressurized techniques are straightforward for high-scale applications and highly controllable, which seems an excellent strategy for recovering unstable natural compounds. In this work, the main ...advance was the development of a platform based on the pressurized liquid extraction coupled in-line with a solid-phase extraction step (PLE-SPE) combined with the use of eutectic mixtures as solvents to promote an efficient extraction and purification of natural pigments from food wastes. Eutectic mixtures, conventionally known as (deep) eutectic solvents - (D)ES, are combinations of two or more substances with a lower melting point than any of their components. (D)ES are often referred as "green solvents" because they can potentially be more environmentally friendly than other solvents, especially volatile organic solvents (VOSs). Overall, (D)ES have the potential to contribute to the achievement of several of the SDGs (especially 3, 13, and 14) through their positive impacts on health, environment, and sustainable production and consumption practices. Thus, in this work, (D)ES were used as solvents to valorize Brazilian berry waste (
Plinia cauliflora
). Anthocyanins are the biomass's main compounds of commercial interest, mainly for food and cosmetic applications. However, there are several technological issues regarding color control due to their high sensitivity to light, heat, oxygen, and pH variations. Thus, the data achieved in this work highlighted the high efficiency and low environmental footprint of the PLE-SPE-(D)ES platform developed. The success of the downstream process here developed was proved by the high extraction efficiency and the purity level of the anthocyanins obtained. Besides, thermal stability analysis was evaluated, demonstrating that (D)ES are not only solvents but also stabilizing agents, improving the shelf-life of the extracted colorants.
A PLE-SPE extraction process for the anthocyanins from Jabuticaba wastes was developed using an eutectic mixture, this acting simultaneously as solvent and stabilizing agent.
Zwitterionic compounds (ZIs) have been attracting much attention due to their properties. Unlike ionic liquids - constituted by separated ions - the ZI structures with their cations and anions ...covalently bonded exhibit added complexity and diversity, suggesting that their ecotoxicological behavior should probably not be extrapolated from those of ionic liquids. This study addresses the aquatic toxicity of ZIs towards the bacterium
Allivibrio fischeri
and the microalga
Raphidocelis subcapitata
. Sixteen ZIs comprising five different cationic groups (ammonium, imidazolium, pyridinium, pyrrolidinium and piperidinium) and two anionic groups (sulfonate and carboxylate) were studied, and the relationships between their structure and toxicity are reported. All studied ZIs are harmless or practically harmless for both microalga and bacterium (median effective concentration, EC
50
>100 mg L
−1
), presenting a significantly lower hazardous potential to aquatic species than their ionic liquid counterparts. The results also show that the increased hydrophobicity of ZIs, owing to the increase of the cation alkyl chain or the spacer length, has a significant influence on EC
50
values for microalga, which in turn causes higher toxicity. However, no significant differences were observed when considering the various cationic groups of the ZIs studied, unlike what is known for ecotoxicity of the ionic liquids. Also, no relationships were found between the chemical structure of ZIs and EC
50
values determined for the bacterium
A. fischeri
. The structural differences between ZIs and ionic liquids result in different mechanisms of interactions with microalgae and bacteria membranes, which may explain why the ecotoxicity heuristic rules previously reported for ionic liquids do not seem to apply to ZIs.
Zwitterionic compounds are less ecotoxic than their analogous ionic liquids.
Extractive fermentation using aqueous biphasic systems (ABS) is a promising separation process since it provides a nondenaturing environment for biomolecules and improves the stability of cells. Due ...to environmental concerns and toxicity issues related with common volatile organic solvents, ionic liquids (ILs), a new class of nonvolatile alternative solvents, are being currently investigated for extraction purposes. In this work, a wide range of imidazolium-based ILs was studied aiming at obtaining new insights regarding their ability toward the formation of ABS and their capacity to the extraction of biomolecules. On the basis of the IL cations 1-ethyl-3-methylimidazolium and 1-butyl-3-methylimidazolium, the IL anion influence on ABS formation was assessed through their combination with chloride, bromide, acetate, hydrogensulfate, methanesulfonate, methylsulfate, ethylsulfate, trifluomethanesulfonate, trifluoroacetate, and dicyanamide. Ternary phase diagrams (and respective tie-lines) formed by these hydrophilic ILs, water, and the inorganic salt K3PO4, were measured and are reported. The results indicate that the ability of an IL to induce ABS closely follows the decrease in the hydrogen bond accepting strength or the increase in the hydrogen bond acidity of the IL anion. In addition, the extraction capacity of the studied ABS was evaluated through their application to the extraction of an essential amino acid, L-tryptophan. It is shown that the partition coefficients obtained between the IL and the K3PO4-aqueous rich phases were substantially larger than those typically obtained with polymers−inorganic salts or polymers−polysaccharides aqueous systems.
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