Smart advanced solvents for bioactive compounds recovery from agri-food by-products: A review

https://doi.org/10.1016/j.tifs.2020.05.007Get rights and content

Highlights

  • This review includes all the aspects of extraction of bioactives from agri-food wastes using smart solvents.

  • Toxicity and recyclability of DESs and NaDESs are exhaustively reviewed.

  • DESs and NaDESs are sustainable and safe solvents in the extraction of biomolecules.

  • More research about the use of smart solvents to exploit of agri-food residues is necessary.

  • The combination of DESs and NaDESs with intensive techniques improves extraction yields.

Abstract

Background

Worldwide, huge amounts of by-products and wastes are generated in agri-food sector annually. This biomass is usually discarded provoking serious environmental problems. However, these residues represent an excellent source of bioactive compounds so that their exploitation can be considered as a promising possibility from an economic and environmental perspective. Conventional extraction technologies using organic solvents have been employed to recover high-value molecules showing several drawbacks such as toxicity, high volatility and non-renewability. Therefore, the search of alternative green solvents for the extraction of bioactives and in order to reduce the environmental impact and to achieve a widespread consumer acceptance is mandatory. Recently, deep eutectic solvents (DESs) and natural deep eutectic solvents (NaDESs) have received great attention for their physicochemical features for bioactive compounds extraction.

Scope and approach

This review describes the state of the art of the applications of DESs and NaDESs in the field of the revalorization of agri-food by-products to obtain and isolate bioactive compounds. The synthesis and properties of these avant-garde solvents are described. In particular, the main bioactives extracted using DESs and NaDESs from several residues from citrus, winemaking, olive oil production, onion, seaweeds, animal and fish industries were systematically reviewed and collected.

Key findings and conclusions

DESs and NaDESs combined with emerging technologies to recover biomolecules from agri-food by-products show promising results in comparison with traditional methods of extraction using conventional solvents. These emerging solvents present advantages which make them good candidates for being implemented by the industry, considering their low toxicity, recyclability, tunable properties and environmentally friendly. Therefore, this new generation of solvents opens new options in the field of recovering bioactive compounds from agri-food by-products.

Introduction

The agri-food industry generates a vast amount of by-products which are considered as an important problem worldwide due to its damaging environmental impacts. This biomass is usually under valorized (Dedousi, Mamoudaki, Grigorakis, & Makris, 2017) despite several studies have suggested that it could be a remarkable source of a wide range of bioactive compounds (such as polyphenols, polysaccharides, pectin, anthocyanins, chitin, keratin, peptides, among others), which have been extensively studied for their health benefits, and anti-inflammatory, antimicrobial, antioxidant, and anticarcinogenic properties (Al Khawli et al., 2019; Borrajo et al., 2019; Echegaray et al., 2018; Grassino et al., 2018; Roselló-Soto et al., 2018, 2019; Gullón et al., 2017).

Taking into account the concerns about the improvement of the sustainability of the food industry and environmental problems involved in the management of these residues, there is a current growing interest in the valorization of these agri-food by-products to obtain valuable compounds (Barba et al., 2017; Gullón, Eibes, Moreira., Herrera, Labidi, & Gullón, 2018; Gullón, Gullón, et al., 2018). Nowadays, the revalorization of residual biomass from agri-food sector as a raw material for the production of novel commodities and biocompounds through biorefinery processes is considered pivotal for a sustainable growth based on a circular economy and as driving force for the implementation of “zero waste policies” (Athanasiadis, Grigorakis, Lalas, & Makris, 2017; Dedousi et al., 2017; Gullón et al., 2020). This type of processing introduces the concept of “grey” biorefinery and utilizes the food waste until its exhaustion to produce bioactive compounds in a similar way to how the fossil resources are processed in petroleum based refineries (Benvenutti, Zielinski, & Ferreira, 2019; Kamani et al., 2019).

In recent years, considerable efforts have been made to develop extraction methods for biomolecules recovery from agri-food wastes (Pal & Jadeja, 2019a; 2019b). These valuable compounds are usually obtained via conventional extraction processes using organic solvents such as acetone, hexane, methanol, ethanol, or ethyl acetate. However, the conventional solvents present several drawbacks such as toxicity, volatility and flammability limiting their application in the extraction of natural compounds (Benvenutti et al., 2019; Liu et al., 2018). In this framework, the agri-food industries must face the great challenge to adopt sustainable process strategies through the employment of emerging green technologies, decreasing at the same time the environmental deterioration and improving the process performance for transforming agri-food wastes into products with marketable value (Jiang et al., 2018; Putnik et al., 2017).

In this context, a new generation of solvents known as Deep Eutectic Solvents (DESs) including Natural Deep Eutectic Solvents (NaDESs) have been delineated as sustainable and safe solvents to replace conventional organic solvents in the extraction of bioactive compounds due to their excellent biocompatibility and low toxicity that make them suitable for pharmaceutical, cosmetic, agrochemical, and food applications. Furthermore, these solvents possess the stabilizing capacity of the extracted solutes possibly due to the formation of hydrogen bonds between solutes and DESs/NaDESs (Fernández, Espino, Gomez, & Silva, 2018), a clear advantage over those conventional solvents.

Moreover, the DESs and NaDESs have also been displayed to have high potential as solvents in combination with innovative and alternative technologies of extraction namely: ultrasounds, microwaves, pressurized liquid extraction (PLE) and homogenate-assisted extraction (HAE) (Benvenutti et al., 2019). These innovative extraction technologies present competitive advantages over the conventionals such as the reduction of operation time, decrease the volume of used solvent, saving the operation cost, and keeping the quality of the target molecules. For these reasons, they are considered as green extraction technologies. The combination of these avant-garde solvents with intensive extraction techniques also allows the improvement of extraction yields, which is attributed to the heat generated by ultrasounds and microwaves decreasing the solvent viscosity and enhancing the penetration of DESs and NaDESs into the biomass matrix (Mišan et al., 2019). However, despite the advantages of the combination of these emerging technologies with smart solvents, until date scarce data have been reported about its use to extract natural products from agri-food by-products.

Despite the literature collects several works about the use of DESs and NaDESs as solvents to recover biomolecules from natural sources, studies using these cutting-edge solvents for the exploitation of agri-food industry derived-residues is limited and this topic still has not been compiled in a review. Therefore, recent researches about the valorization of several agri-food wastes including those generated in citrus processing, winemaking, olive oil production, onion, seaweeds, animal and fish industries using DESs or NaDESs are approached in the present review. Their properties, synthesis, toxicity and recyclability are described focusing on the target compounds, as well as the main factors involved in the extraction process. In addition, the main agri-food industries that generate interesting sources of bioactive compounds are identified and the main results are described. Final remarks and a schematic overview related to bioactive compounds extraction by DESs or NaDESs (Fig. 1) are also included.

Section snippets

Deep eutectic solvents: historical aspects, advantages and synthesis

Novel extraction technologies using emerging solvents have arisen as greener alternative to conventional processes based on organic solvents to improve and increase the yield and selectivity of bioactive compounds derived from agri-food residues and to decrease the energy consumption of extraction processes. Particularly, the growing interest for deep eutectic solvents has emerged as a more biodegradable solution than imidazolium-based ionic liquid and as alternative solvents with applicability

Influencing factors on the assisted extraction by DESs and NaDESs of added value biomolecules from agri food wastes

There are a set of factors that affect the extraction capacity of DESs and NaDESs such as their molecular structure and composition, water content, and physicochemical properties, namely, viscosity, polarity, pH and solubility (Huang et al., 2019). These properties can be fine-tuned in order to design a tailored-made system for target compound extraction. Besides of these inherent characteristics to the type of solvent, there are other parameters related to the extraction process including

Application of DESs and NaDESs for extraction of value-added compounds from agri-food by-products

The use of DESs and NaDESs to extract bioactives from natural sources has been reported in several studies (Zhang & Wang, 2017; Zhao et al., 2015). However, the information about their application to revalorize agri-food industry wastes and by-products is still scarce. Therefore, in this section, the most relevant agri-food industries have been selected based on their huge amounts of residues generated that could be used for obtaining of valuable compounds. Some works reported in the literature

Emerging studies on the toxicity of NaDESs and DESs

The first studies about the use of DESs and NaDESs for obtaining phytochemicals from agro-industrial wastes date from 2004; however, the works on toxicity and cytotoxicity of this new generation of designer solvents started in 2013 conducted by Hayyan et al. (2013). Concerning this topic, only 19 researches were found after a search in the Scopus database (search made on November 12, 2019).

The scarce research about the deleterious effects of these avant-garde solvents can be attributed to the

Solvent recovery and recycling

For an industrial application of these tunable solvents, their recycling and re-using after the extraction methods is one of the main challenges to attain a cost-efficient process (Benvenutti et al., 2019). For the re-use of DESs and NaDESs, these can be easily regenerated from water by the addition of anti-solvent such as acetone (Chen & Mu, 2019). Nevertheless, the low vapor pressure of eutectic mixtures is considered a drawback for its recovery after extraction process, since it is not

Conclusion remarks

Current interest in industrial processes based on green chemistry has encouraged the search of more efficient solvents as DES and NaDES. Their use for bioactive compounds extraction from agri-food residues matrix has notably improved the extraction processes. These solvents present advantages over the conventional solvents such as the possibility to design them for specific purposes, higher extraction efficiency, higher stability of the biocompounds and enhanced bioactivities, low volatility

Acknowledgements

Thanks to GAIN (Axencia Galega de Innovación) for supporting this review (grant number IN607A2019/01). Jose M. Lorenzo is member of the HealthyMeat network, funded by CYTED (ref. 119RT0568). B. Gullón would like to express their gratitude to the Spanish Ministry of Economy and Competitiveness for financial support (Grant reference RYC2018-026177-I).

References (109)

  • Y.H. Choi et al.

    Green solvents for the extraction of bioactive compounds from natural products using ionic liquids and deep eutectic solvents

    Current Opinion in Food Science

    (2019)
  • S.C. Cunha et al.

    Extraction techniques with deep eutectic solvents

    TRAC Trends in Analytical Chemistry

    (2018)
  • Y. Dai et al.

    Natural deep eutectic solvents as new potential media for green technology

    Analytica Chimica Acta

    (2013)
  • Y. Dai et al.

    Tailoring properties of natural deep eutectic solvents with water to facilitate their applications

    Food Chemistry

    (2015)
  • A.K. Das et al.

    Deep eutectic solvents as efficient solvent system for the extraction of κ-carrageenan from Kappaphycus alvarezii

    Carbohydrate Polymers

    (2016)
  • N. Echegaray et al.

    Chestnuts and by-products as source of natural antioxidants in meat and meat products: A review

    Trends in Food Science & Technology

    (2018)
  • S. El Kantar et al.

    Green extraction of polyphenols from grapefruit peels using high voltage electrical discharges, deep eutectic solvents and aqueous glycerol

    Food Chemistry

    (2019)
  • M. de los A. Fernández et al.

    Novel approaches mediated by tailor-made green solvents for the extraction of phenolic compounds from agro-food industrial by-products

    Food Chemistry

    (2018)
  • C. Florindo et al.

    Deep eutectic solvents: Overcoming 21st century challenges

    Current Opinion in Green and Sustainable Chemistry

    (2019)
  • A. García et al.

    Extraction of phenolic compounds from virgin olive oil by deep eutectic solvents (DESs)

    Food Chemistry

    (2016)
  • M. Gavahian et al.

    Health benefits of olive oil and its components: Impacts on gut microbiota antioxidant activities, and prevention of noncommunicable diseases

    Trends in Food Science & Technology

    (2019)
  • A.N. Grassino et al.

    Analytical tools used for the identification and quantification of pectin extracted from plant food matrices, wastes and by-products: A review

    Food Chemistry

    (2018)
  • B Gullón et al.

    Optimization of solvent extraction of antioxidants from Eucalyptus globulus leaves by response surface methodology: Characterization and assessment of their bioactive properties

    Industrial Crops and Products

    (2017)
  • P. Gullón et al.

    Green sustainable process to revalorize purple corn cobs within a biorefinery frame: Co-production of bioactive extracts

    The Science of the Total Environment

    (2020)
  • B. Gullón et al.

    Yerba mate waste: A sustainable resource of antioxidant compounds

    Industrial Crops and Products

    (2018)
  • B. Gullón et al.

    Valorisation of olive agro-industrial by-products as a source of bioactive compounds

    The Science of the Total Environment

    (2018)
  • N. Guo et al.

    Natural deep eutectic solvents couple with integrative extraction technique as an effective approach for mulberry anthocyanin extraction

    Food Chemistry

    (2019)
  • M. Hayyan et al.

    Are deep eutectic solvents benign or toxic?

    Chemosphere

    (2013)
  • J. Huang et al.

    Ionic deep eutectic solvents for the extraction and separation of natural products

    Journal of Chromatography A

    (2019)
  • Y Huang et al.

    Green and efficient extraction of rutin from tartary buckwheat hull by using natural deep eutectic solvents

    Food Chemistry

    (2017)
  • M. Jablonský et al.

    Extraction of value-added components from food industry based and agro-forest biowastes by deep eutectic solvents

    Journal of Biotechnology

    (2018)
  • K.M. Jeong et al.

    Tailoring and recycling of deep eutectic solvents as sustainable and efficient extraction media

    Journal of Chromatography A

    (2015)
  • S.Q. Liew et al.

    Acid and deep eutectic solvent (DES) extraction of pectin from pomelo (citrus grandis (L.) Osbeck) peels

    Biocatalysis and Agricultural Biotechnology

    (2018)
  • Y. Liu et al.

    Enhanced extraction of natural pigments from Curcuma longa L. using natural deep eutectic solvents

    Industrial Crops and Products

    (2019)
  • H.G. Morrison et al.

    Characterization of thermal behavior of deep eutectic solvents and their potential as drug solubilization vehicles

    International Journal of Pharmaceutics

    (2009)
  • B. Ozturk et al.

    Extraction of polyphenolic antioxidants from orange peel waste using deep eutectic solvents

    Separation and Purification Technology

    (2018)
  • I. Pacheco-Fernández et al.

    Green solvents in analytical chemistry

    Current Opinion in Green and Sustainable Chemistry

    (2019)
  • M. Panić et al.

    Enabling technologies for the extraction of grape-pomace anthocyanins using natural deep eutectic solvents in up-to-half-litre batches extraction of grape-pomace anthocyanins using NADES

    Food Chemistry

    (2019)
  • X. Peng et al.

    Green extraction of five target phenolic acids from Lonicerae japonicae Flos with deep eutectic solvent

    Separation and Purification Technology

    (2016)
  • K. Radošević et al.

    Evaluation of toxicity and biodegradability of choline chloride based deep eutectic solvents

    Ecotoxicology and Environmental Safety

    (2015)
  • K. Radošević et al.

    Natural deep eutectic solvents as beneficial extractants for enhancement of plant extracts bioactivity

    LWT - Food Science and Technology

    (2016)
  • E. Roselló-Soto et al.

    Evaluating the impact of supercritical-CO 2 pressure on the recovery and quality of oil from “horchata” by-products: Fatty acid profile, α-tocopherol, phenolic compounds, and lipid oxidation parameters

    Food Research International

    (2019)
  • E. Roselló-Soto et al.

    Tiger nut and its by-products valorization: From extraction of oil and valuable compounds to development of new healthy products

    Innovative Food Science & Emerging Technologies

    (2018)
  • S. Şahin

    Tailor-designed deep eutectic liquids as a sustainable extraction media: An alternative to ionic liquids

    Journal of Pharmaceutical and Biomedical Analysis

    (2019)
  • P.S. Saravana et al.

    Green and efficient extraction of polysaccharides from brown seaweed by adding deep eutectic solvent in subcritical water hydrolysis

    Journal of Cleaner Production

    (2018)
  • K. Sharma et al.

    Converting citrus wastes into value-added products: Economic and environmently friendly approaches

    Nutrition

    (2017)
  • Q. Wen et al.

    Assessing the toxicity and biodegradability of deep eutectic solvents

    Chemosphere

    (2015)
  • A.P. Abbott et al.

    Deep Eutectic Solvents formed between choline chloride and carboxylic acids: Versatile alternatives to ionic liquids

    Journal of the American Chemical Society

    (2004)
  • A.P. Abbott et al.

    Novel solvent properties of choline chloride/urea mixtures

    Chemical Communications

    (2003)
  • F. Al Khawli et al.

    Innovative green technologies of intensification for valorization of seafood and their by-products

    Marine Drugs

    (2019)
  • Cited by (105)

    View all citing articles on Scopus
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