A closer look at how the dispersive liquid-liquid microextraction method works. Investigation of the effect of solvent mixture composition on the quality and stability of the cloudy state.

The dispersive liquid-liquid microextraction (DLLME) is one of the most popular miniaturized extraction procedures. In this paper, the degree of dispersion and dispersion stability were studied with the aim to assess the correlations of these parameters with efficiency for the selected analytical application. The dependence between the degree of dispersion (cloudy state quality) and its stability obtained by various emulsification procedures, such as solvent-assisted emulsification (using various dispersive solvents) and mechanical emulsification (using auxiliary energies), is investigated and discussed. It was found out that the degree of dispersion depends on the type of emulsification procedure and decreases in the series: solvent-assisted (SA-) = ultrasound-assisted (UA-) > air-assisted (AA-) > vortex-assisted (VA-) emulsification. The emulsion stability depends on the degree of dispersion and there were 1810 and 2070 s for the most effective emulsification procedures, such us solvent-assisted and ultrasound-assisted emulsification, respectively. A comparison between the sensitivity of the analytical methods (using spectrophotometric determination of the anionic surfactants) and the degree of dispersion have been made. The sensitivity of the methods was ranked as follows: DLLME > UA-LLME > VA-LLME > AA-LLME.

Agri-food waste biosorbents for volatile organic compounds removal from air and industrial gases - A review.

Approximately 1.3 billion metric tons of agricultural and food waste is produced annually, highlighting the need for appropriate processing and management strategies. This paper provides an exhaustive overview of the utilization of agri-food waste as a biosorbents for the elimination of volatile organic compounds (VOCs) from gaseous streams. The review paper underscores the critical role of waste management in the context of a circular economy, wherein waste is not viewed as a final product, but rather as a valuable resource for innovative processes. This perspective is consistent with the principles of resource efficiency and sustainability. Various types of waste have been described as effective biosorbents, and methods for biosorbents preparation have been discussed, including thermal treatment, surface activation, and doping with nitrogen, phosphorus, and sulfur atoms. This review further investigates the applications of these biosorbents in adsorbing VOCs from gaseous streams and elucidates the primary mechanisms governing the adsorption process. Additionally, this study sheds light on methods of biosorbents regeneration, which is a key aspect of practical applications. The paper concludes with a critical commentary and discussion of future perspectives in this field, emphasizing the need for more research and innovation in waste management to fully realize the potential of a circular economy. This review serves as a valuable resource for researchers and practitioners interested in the potential use of agri-food waste biosorbents for VOCs removal, marking a significant first step toward considering these aspects together.

Deep eutectic solvent-based shaking-assisted extraction for determination of bioactive compounds from Norway spruce roots.

Polyphenolic compounds play an essential role in plant growth, reproduction, and defense mechanisms against pathogens and environmental stresses. Extracting these compounds is the initial step in assessing phytochemical changes, where the choice of extraction method significantly influences the extracted analytes. However, due to environmental factors, analyzing numerous samples is necessary for statistically significant results, often leading to the use of harmful organic solvents for extraction. Therefore, in this study, a novel DES-based shaking-assisted extraction procedure for the separation of polyphenolic compounds from plant samples followed by LC-ESI-QTOF-MS analysis was developed. The DES was prepared from choline chloride (ChCl) as the hydrogen bond acceptor (HBA) and fructose (Fru) as the hydrogen bond donor (HBD) at various molar ratios with the addition of 30% water to reduce viscosity. Several experimental variables affecting extraction efficiency were studied and optimized using one-variable-at-a-time (OVAT) and confirmed by response surface design (RS). Nearly the same experimental conditions were obtained using both optimization methods and were set as follows: 30 mg of sample, 300 mg of ChCl:Fru 1:2 DES containing 30% w/w of water, 500 rpm shaking speed, 30 min extraction time, 10°C extraction temperature. The results were compared with those obtained using conventional solvents, such as ethanol, methanol and water, whereby the DES-based shaking-assisted extraction method showed a higher efficiency than the classical procedures. The greenness of the developed method was compared with the greenness of existing procedures for the extraction of polyphenolic substances from solid plant samples using the complementary green analytical procedure index (ComplexGAPI) approach, while the results for the developed method were better or comparable to the existing ones. In addition, the practicability of the developed procedure was evaluated by application of the blue applicability grade index (BAGI) metric. The developed procedure was applied to the determination of spruce root samples with satisfactory results and has the potential for use in the analysis of similar plant samples.

Magnetic superhydrophobic melamine sponges for crude oil removal from water.

This paper proposes the preparation of a new sorbent material based on melamine sponges (MS) with superhydrophobic, superoleophilic, and magnetic properties. This study involved impregnating the surface of commercially available MS with eco-friendly deep eutectic solvents (DES) and Fe3O4 nanoparticles. The DES selection was based on the screening of 105 eutectic mixtures using COSMO-RS modeling. Other parameters affecting the efficiency and selectivity of oil removal from water were optimized using the Box-Bhenken model. Menthol:Thymol (1:1)@Fe3O4-MS exhibited the highest sorption capacity for real crude oils (101.7-127.3 g/g). This new sponge demonstrated paramagnetic behavior (31.06 emu/g), superhydrophobicity (151°), superoleophobicity (0°), low density (15.6 mg/cm3), high porosity (99 %), and excellent mechanical stability. Furthermore, it allows multiple regeneration processes without losing its sorption capacity. Based on these benefits, Menthol:Thymol (1:1)@Fe3O4-MS shows promise as an efficient, cost-effective, and eco-friendly substitute for the existing sorbents.

Plant-based meat substitute analysis using microextraction with deep eutectic solvent followed by LC-MS/MS to determine acrylamide, 5-hydroxymethylfurfural and furaneol.

For the analysis of plant-based meat substitutes and the determination of Maillard reaction products such as acrylamide, 5-hydroxymethylfurfural and furaneol, a novel and effective procedure based on hydrophobic natural deep eutectic solvent and liquid chromatography coupled with tandem mass spectrometry was developed for the first time. The 49 compositions of the deep eutectic solvents were designed and screened to select the most suitable option. The terpenoids eugenol and thymol in a molar ratio of 2:1 were selected as precursors for solvent formation, allowing effective extraction of the target analytes. The developed procedure comprised two main steps: extraction - in which the analytes are isolated from the solid sample due to the salting-out effect and pre-concentrated in the deep eutectic solvent, and back-extraction - in which the analytes are re-extracted into the formic acid solution for subsequent mass spectrometric detection. As the density of the aqueous phases changed during the extraction and back-extraction steps, the phenomenon of inversion of the coalesced organic phase was observed, which simplified the withdrawing of the phases. The linear range was 1-50 ng/mL for acrylamide, 10-1000 ng/mL for 5-hydroxymethylfurfural and 200-1000 ng/mL for furaneol with coefficients of determination above 0.9952. The developed method was fully validated and found recoveries were in the range 83-120%, with CVs not exceeding 4.9%. The method was applied to real sample analysis of pea-based meat substitutes.

VOCs absorption from gas streams using deep eutectic solvents - A review.

Volatile organic compounds (VOCs) are one of the most severe atmospheric pollutants. They are mainly emitted into the atmosphere from anthropogenic sources such as automobile exhaust, incomplete fuel combustion, and various industrial processes. VOCs not only cause hazards to human health or the environment but also adversely affect industrial installation components due to their specific properties, i.e., corrosive and reactivity. Therefore, much attention is being paid to developing new methods for capturing VOCs from gaseous streams, i.e., air, process streams, waste streams, or gaseous fuels. Among the available technologies, absorption based on deep eutectic solvents (DES) is widely studied as a green alternative to other commercial processes. This literature review presents a critical summary of the achievements in capturing individual VOCs using DES. The types of used DES and their physicochemical properties affecting absorption efficiency, available methods for evaluating the effectiveness of new technologies, and the possibility of regeneration of DES are described. In addition, critical comments on the new gas purification methods and future perspectives are included.

Deep Eutectic Solvents or Eutectic Mixtures? Characterization of Tetrabutylammonium Bromide and Nonanoic Acid Mixtures.

Deep eutectic solvents have quickly attracted the attention of researchers because they better meet the requirements of green chemistry and thus have the potential to replace conventional hazardous organic solvents in some areas. To better understand the nature of these mixtures, as well as expand the possibilities of their use in different industries, a detailed examination of their physical properties, such as density, viscosity, the nature of the interactions between their constituents, the phase diagrams, depression of their melting point, and interpretation of these results is necessary. In this work, the mixtures of tetrabutylammonium bromide (TBAB) and nonanoic acid (NA) in different molar ratios are theoretically and experimentally investigated by applying a phase diagram constructed on the basis of differential scanning calorimetry measurements and COSMO-RS model. Spectral properties are investigated based on Fourier transform infrared spectroscopy and density functional theory. The observed eutectic point indicates the formation of a DES in the TBAB-NA system in a 1:2 molar ratio. This is due to the presence of hydrogen bonds between the carboxyl group from the NA molecule and the bromine atom from the TBAB molecule. Other eutectic mixtures are most likely the solutions of TBAB in NA, in which hydrogen bonds predominate between acid molecules.

End-of-life management of single-use baby diapers: Analysis of technical, health and environment aspects.

Single-use baby diapers belongs to an important group of products used in the parenting journey because of their high performance and convenience. Single-use baby diapers are normally thrown away after one-time use, resulting in a waste management problem. The goal of this paper was to better understand main environmental concerns of different types of diapers and address how to reduce them, with a special consideration of waste management strategies and user behaviour practices. Furthermore, health and environmental hazards potentially associated with materials included in diapers, or substances formed from diapers during the waste treatment stage, are also analysed (e.g., phthalates, pesticides, dioxins, pesticides). Three main types of baby diapers have been analysed: single-use baby diapers, reusable baby diapers, and biodegradable single-use diapers. Each type of diaper comes with technical characteristics and environmental concerns and challenges, which are discussed in this paper to support the development of measures for the safe(r) and sustainable design, use and end of life management of baby diapers.

Superhydrophobic sponges based on green deep eutectic solvents for spill oil removal from water.

The paper described a new method for crude oil-water separation by means of superhydrophobic melamine sponges impregnated by deep eutectic solvents (MS-DES). Due to the numerous potential of two-component DES formation, simple and quick screening of 156 non-ionic deep eutectic solvents using COSMO-RS (Conductor-like Screening Model for Real Solvents) computational model was used. DES which were characterized by high solubility of hydrocarbons and the lowest water solubility were synthesized and embedded on melamine sponges. The new sponges were characterized by Fourier transform infrared spectroscopy (FT-IR), scanning electron microscopy (SEM), X-ray diffraction (XRD), and goniometer. Several parameters affecting the crude oil-water separation (i.e. type and amount of DES, density and porosity of sponges, water contact eagle) were thoroughly studied. In order to studies of MS-DES affinity to the selected groups of crude oil i.e. Saturated, Aromatic, Resins, Asphaltenes (SARA) the thin layer liquid chromatography-flame ionization detection (TLC-FID) was used. The obtained results indicate that the melamine sponges impregnated by DES composed of eucalyptol and menthol in 1:5 molar ratio have high real crude oil absorption capacity in the range of 96.1 - 132.2 g/g and slightly depends on crude oil compositions, superhydrophobic properties (water contact angle 152°), low density of 9.23 mg/cm3, high porosity of 99.39%, and excellent reusability which was almost not changing even after 80 cycles. The outcomes indicate that new MS-DES materials could be excellent alternatives as absorbents for the cleanup of crude oil-polluted water.

New Carvone-Based Deep Eutectic Solvents for Siloxanes Capture from Biogas.

During biogas combustion, siloxanes form deposits of SiO2 on engine components, thus shortening the lifespan of the installation. Therefore, the development of new methods for the purification of biogas is receiving increasing attention. One of the most effective methods is physical absorption with the use of appropriate solvents. According to the principles of green engineering, solvents should be biodegradable, non-toxic, and have a high absorption capacity. Deep eutectic solvents (DES) possess such characteristics. In the literature, due to the very large number of DES combinations, conductor-like screening models for real solvents (COSMO-RS), based on the comparison of siloxane activity coefficient of 90 DESs of various types, were studied. DESs, which have the highest affinity to siloxanes, were synthesized. The most important physicochemical properties of DESs were carefully studied. In order to explain of the mechanism of DES formation, and the interaction between DES and siloxanes, the theoretical studies based on σ-profiles, and experimental studies including the 1H NMR, 13C NMR, and FT-IR spectra, were applied. The obtained results indicated that the new DESs, which were composed of carvone and carboxylic acids, were characterized by the highest affinity to siloxanes. It was shown that the hydrogen bonds between the active ketone group (=O) and the carboxyl group (-COOH) determined the formation of stable DESs with a melting point much lower than those of the individual components. On the other hand, non-bonded interactions mainly determined the effective capture of siloxanes with DES.

Removal of Siloxanes from Model Biogas by Means of Deep Eutectic Solvents in Absorption Process.

The paper presents the screening of 20 deep eutectic solvents (DESs) composed of tetrapropylammonium bromide (TPABr) and glycols in various molar ratios, and 6 conventional solvents as absorbents for removal of siloxanes from model biogas stream. The screening was achieved using the conductor-like screening model for real solvents (COSMO-RS) based on the comparison of siloxane solubility in DESs. For the DES which was characterized by the highest solubility of siloxanes, studies of physicochemical properties, i.e., viscosity, density, and melting point, were performed. DES composed of tetrapropylammonium bromide (TPABr) and tetraethylene glycol (TEG) in a 1:3 molar ratio was used as an absorbent in experimental studies in which several parameters were optimized, i.e., the temperature, absorbent volume, and model biogas flow rate. The mechanism of siloxanes removal was evaluated by means of an experimental FT-IR analysis as well as by theoretical studies based on σ-profile and σ-potential. On the basis of the obtained results, it can be concluded that TPABr:TEG (1:3) is a very effective absorption solvent for the removal of siloxanes from model biogas, and the main driving force of the absorption process is the formation of the hydrogen bonds between DES and siloxanes.

Efficient Extraction of Fermentation Inhibitors by Means of Green Hydrophobic Deep Eutectic Solvents.

The methods for hydrogen yield efficiency improvements, the gaseous stream purification in gaseous biofuels generation, and the biomass pretreatment are considered as the main trends in research devoted to gaseous biofuel production. The environmental aspect related to the liquid stream purification arises. Moreover, the management of post-fermentation broth with the application of various biorefining techniques gains importance. Chemical compounds occurring in the exhausted liquid phase after biomass pretreatment and subsequent dark and photo fermentation processes are considered as value-added by products. The most valuable are furfural (FF), 5-hydroxymethylfurfural (HMF), and levulinic acid (LA). Enriching their solutions can be carried with the application of liquid-liquid extraction with the use of a suitable solvent. In these studies, hydrophobic deep eutectic solvents (DESs) were tested as extractants. The screening of 56 DESs was carried out using the Conductor-like Screening Model for Real Solvents (COSMO-RS). DESs which exposed the highest inhibitory effect on fermentation and negligible water solubility were prepared. The LA, FF, and HMF were analyzed using FT-IR and NMR spectroscopy. In addition, the basic physicochemical properties of DES were carefully studied. In the second part of the paper, deep eutectic solvents were used for the extraction of FF, LA, and HMF from post-fermentation broth (PFB). The main extraction parameters, i.e., temperature, pH, and DES: PFB volume ratio (VDES:VPFB), were optimized by means of a Box-Behnken design model. Two approaches have been proposed for extraction process. In the first approach, DES was used as a solvent. In the second, one of the DES components was added to the sample, and DES was generated in situ. To enhance the post-fermentation broth management, optimization of the parameters promoting HMF, FF, and LA extraction was carried under real conditions. Moreover, the antimicrobial effect of the extraction of FF, HMF, and LA was investigated to define the possibility of simultaneous separation of microbial parts and denatured peptides via precipitation.