Complexation of Danube common nase (Chondrostoma nasus L.) oil by β-cyclodextrin and 2-hydroxypropyl-β-cyclodextrin
Introduction
Omega-3 based fish oils are mostly consumed for preventing and ameliorating cardio-vascular and neuronal diseases. They belong to polyunsaturated fatty acids (PUFAs) and the main fish oil PUFAs are EPA and DHA ((all-Z)-5,8,11,14,17-eicosapentaenoic acid and (all-Z)-4,7,10,13,16,19-docosahexaenoic acid, respectively) (Rubio-Rodríguez, Beltrán, Jaime, de-Diego, Sanz, & Carballido, 2010). Moreover, the omega-3/omega-6 ratio must be higher than 0.2 in order to be valuable for human health (Rubio-Rodríguez et al., 2010). A disadvantage of fish oils are the presence of the toxic compounds (e.g., heavy metals, pesticides and related by-products) in some fish species and the weak stability of PUFAs in the presence of air/oxygen and light. It is well known and studied the influence of the environmental pollution on the quality of fish oils. Heavy metals (cadmium, copper, lead, or mercury) and hydrophobic pesticides or by-products (polychlorinated diphenyls, hexachlorocyclohexane or dioxins) significantly influence the quality of such food products (Davodi et al., 2011, Erdogrul et al., 2005, Jirsa et al., 2008, Jürgens et al., 2013, Visnjic-Jeftic et al., 2010). Mostly, oily fish species from oceans are subjected to such contamination. It is the case of sardines, herring, anchovies, salmon, tuna, swordfish and mackerel (Hădărugă et al., 2017, Hădărugă et al., 2016, Ünlüsayin et al., 2016). On the other hand, the presence of a high number of non-conjugated double bonds into the PUFA structures (free or as triglycerides, mainly contained by fish oils) provide less stable products. The degradation of PUFAs to harmful free radicals is favored by number and geometry of double bonds (cis configuration is less stable), the FA content, oxygen concentration, temperature, contact surface and moisture content (a water activity less than 0.1 or higher than 0.55 is the most favorable for FA degradation) (Belitz, Grosch, & Schieberle, 2009). The energy requirement for scavenging of a H-atom from a methylene group bound to other two ethylene groups (CHCHCH2CHCH), such as the case of EPA and DHA, is almost at a half in comparison with the case of terminal methyl group. The presence of di- or trivalent metal ions (Fe, Cu, Ni, Co, Mn) can accelerate the decomposition of the FA hydroperoxides (Belitz et al., 2009).
Common nase (Chondrostoma nasus L.) is a common fish species growing in European rivers. It belongs to Cyprinidae family and is classified by IUCN (International Union for Conservation of Nature) as “Least concern (LC) fish species” (Freyhof, 2011). Common nase is a migratory, shoaling and schooling fish. It can reach up to 40 cm length and over 1 kg weight. There are some studies regarding the living, reproduction, management, contaminants content and diseases of common nase living in Danube River (Devaux et al., 2015, Djikanović et al., 2016, Hauer et al., 2008, Jirsa et al., 2008, Lechner et al., 2018). FA profile of common nase lipids were evaluated by Aggelousis and Lazos for fish caught from Evros River, Greece (Aggelousis & Lazos, 1991). The total omega-3 FA was 2.3 g/kg, the main compounds being EPA and DHA (0.8 and 1.2 g/kg, which represented 6 (±1) % and 9 (±3.5) % from the total FAs). To our knowledge, no other studies regarding the chemical composition of Danube common nase have been performed. Moreover, the presence of an important content of PUFAs in the common nase oil (CNO) made this omega-3 source less stable under processing, storage and consumption conditions.
Fish oils can be protected against degradation by various methods including micro- and nanoencapsulation. Various matrices such as oligo- and polysaccharides, or protein hydrolysates were investigated. Chitosan and derivatives have been successfully used for fish oil encapsulation. Thus, N-lauroyl- or N-stearoyl-O-butyl-glyceryl chitosan have been obtained and applied for encapsulation of fish oil samples using membrane and ultrasonic emulsification processes. The fish oil microcapsules of mean diameter of ~1 μm presented enhanced colloidal stability, loading capacity, encapsulation efficiency, release profile and gastrointestinal stability (Chatterjee and Judeh, 2015, Chatterjee and Judeh, 2016). Microencapsulated fish oil powder based on maltodextrin, Arabic gum, methylcellulose or fish protein hydrolysates with enhanced overall stability have been obtained using spray-drying technique (Morales-Medina, Tamm, Guadix, Guadix, & Drusch, 2016). There are some studies on nanoencapsulation of fish oils using cyclic oligosaccharides. The most valuable and GRAS-FDA recognized as food additives are natural α-, β- and γ-cyclodextrin (α-, β- and γ-CD) (Kurkov and Loftsson, 2013, Mortensen et al., 2016). They are cyclic oligosaccharides with truncated cone shapes and hydrophobic cavities that can completely or partially nanoencapsulates geometrically compatible hydrophobic compounds (Crini, 2014, Szente & Fenyvesi, 2017, Zhang and Ma, 2013). The access of oxygen and light to the reactive sites of the guest compounds is much lowered. Consequently, the oxidative stability of the nanoencapsulated labile compounds is enhanced. Moreover, the high number of the hydroxyl groups of the CD structure (comprise of 6–8 glucopyranose units for α-, β- and γ-CD) allows significant enhancement of the apparent water solubility of hydrophobic compounds entrapped into the CD cavity. This also determines enhanced bioavailability and controlled release properties (Kfoury et al., 2015, Lopez-Nicolas and Garcia-Carmona, 2008). FA triglycerides are appropriate guest compounds for CD nanoencapsulation due to the size, flexibility and high hydrophobicity of FA moieties. Both single FA compound and triglyceride mixture have been used as guests for CD complexation. It was proved the enhanced thermal and oxidative stability of linoleic acid by α- and β-CD nanoencapsulation (Hădărugă et al., 2006) as well as the enhanced properties of various fish oils complexed with CDs (Choi et al., 2010, Choi et al., 2009, Hădărugă et al., 2017, Hădărugă et al., 2016, Lee et al., 2013, Ünlüsayin et al., 2016, Vestland et al., 2015).
The goal of the study was to evaluate the influence of the fatty acid profile of Danube common nase (Chondrostoma nasus L.) on the β-CD and 2-hydroxypropyl-β-CD (HP-β-CD) complexation for valorization as omega-3 food supplements. The complex formation and the moisture content were evaluated through thermal and spectroscopic techniques.
Section snippets
Materials and CNO separation
Common nase (Chondrostoma nasus L.) samples were fished out from the Romanian sector 2 of the Danube River (Mehedinţi County, Romania, 44°13′33″ N, 22°42′33″ E) on April 2016. They were transported, handled, and slaughtered according to EU regulations (“Council Regulation (EC) No 1099/2009 of 24 September 2009 on the protection of animals at the time of killing”, “Directive 2010/63/EU of the European Parliament and of the Council of 22 September 2010 on the protection of animals used for
Fatty acid profile of Danube common nase oil
Common nase muscle have a moderate content of lipids, the separation yield being less than 5%. However, this CNO can also be extracted from other fish parts (e.g., liver), where the lipid content is higher, but this aspect is subjected to another study. The FA profile differ for this fish parts. In the case of CNO separated from muscle by heating-pressing technique, the derivatization to the more volatile FAMEs was needed in order to analyze by GC–MS (see “Supplementary Material” file for GC
Conclusion
Danube common nase (Chondrostoma nasus L.) oil have been separated from the fish muscle, characterized from the FA profile point of view and complexed by β-CD and HP-β-CD for the first time. The most important ω-3 FAs (especially as triglycerides), named EPA and DHA, have been identified in the raw CNO at high relative concentrations of 6.7–10.6%, EPA being four times more concentrated. The higher hydrophobicity of these less stable PUFA triglycerides make such compounds almost ideal for CD
Ethical statement
European Directives and Regulations on catching, transportation, handling and slaughtering of Danube common nase samples (“Council Regulation (EC) No 1099/2009 of 24 September 2009 on the protection of animals at the time of killing”, “Directive 2010/63/EU of the European Parliament and of the Council of 22 September 2010 on the protection of animals used for scientific purposes”, “Regulations (EC) No 853/2004 and No 854/2004 of the European Parliament and of the Council of 29 April 2004 laying
Declaration of Competing Interest
The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.
Acknowledgments
Authors want to thank to PNCDI III 2015-2020 – ID 368 institutional development project “Ensuring excellence in R&D within USAMVBT” from the institutional performance subprogram 1.2, development of the R&D national system program 1, Ministry of Research and Innovation of Romania, Executive Unit for Financing Higher Education, Research, Development and Innovation (UEFISCDI).
References (40)
- et al.
Fatty acid composition of the lipids from eight freshwater fish species from Greece
Journal of Food Composition and Analysis
(1991) - et al.
Encapsulation of fish oil with N-stearoyl O-butylglyceryl chitosan using membrane and ultrasonic emulsification processes
Carbohydrate Polymers
(2015) - et al.
Impact of encapsulation on the physicochemical properties and gastrointestinal stability of fish oil
LWT – Food Science and Technology
(2016) - et al.
Physical characteristics of fish oil encapsulated by beta-cyclodextrin using an aggregation method or polycaprolactone using an emulsion–diffusion method
Food Chemistry
(2010) - et al.
Morphological characterization of encapsulated fish oil with beta-cyclodextrin and polycaprolactone
Food Research International
(2009) - et al.
Concentration of polychlorinated biphenyls and organochlorine pesticides in some edible fish species from the Shadegan Marshes (Iran)
Ecotoxicology and Environmental Safety
(2011) - et al.
Field evidence of reproduction impairment through sperm DNA damage in the fish nase (Chondrostoma nasus) in anthropized hydrosystems
Aquatic Toxicology
(2015) - et al.
Age-specific metal and accumulation patterns in different tissues of nase (Chodrostoma nasus) from the Medjuvršje Reservoir
Science of the Total Environment
(2016) - et al.
Levels of organochlorine pesticides, polychlorinated biphenyls and polybrominated diphenyl ethers in fish species from Kahramanmaras, Turkey
Environment International
(2005) - et al.
Moisture evaluation of β-cyclodextrin/fish oils complexes by thermal analyses: A data review on common barbel (Barbus barbus L.), Pontic shad (Alosa immaculata Bennett), European wels catfish (Silurus glanis L.), and common bleak (Alburnus alburnus L.) living in Danube river
Food Chemistry
(2017)
Differentiation of rye and wheat flour as well as mixtures by using the kinetics of Karl Fischer water titration
Food Chemistry
Water content of flavonoid/cyclodextrin nanoparticles: Relationship with the structural descriptors of biologically active compounds
Food Chemistry
Water content of natural cyclodextrins and their essential oil complexes: A comparative study between Karl Fischer titration and thermal methods
Food Chemistry
Thermal stability of the linoleic acid/alpha- and beta-cyclodextrin complexes
Food Chemistry
The presence of EU priority substances mercury, hexachlorobenzene, hexachlorobutadiene and PBDEs in wild fish from four English rivers
Science of the Total Environment
Promising applications of cyclodextrins in food: Improvement of essential oils retention, controlled release and antiradical activity
Carbohydrate Polymers
Cyclodextrins
International Journal of Pharmaceutics
Rapid, simple and sensitive determination of the apparent formation constants of trans-resveratrol complexes with natural cyclodextrins in aqueous medium using HPLC
Food Chemistry
Functional and antioxidant properties of hydrolysates of sardine (S. pilchardus) and horse mackerel (T. mediterraneus) for the microencapsulation of fish oil by spray-drying
Food Chemistry
Production of omega-3 polyunsaturated fatty acid concentrates: A review
Innovative Food Science and Emerging Technologies
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