Enzymatic Lipophilization Research Articles

Enzymatic Modification of Pomace Olive Oil with Natural Antioxidants: Effect on Oxidative Stability.

Enzymatic lipophilization has been proposed as a cost-effective strategy to produce new liposoluble antioxidant compounds. In this study, modified oils rich in structured phenolipids were prepared via one-pot enzymatic acylation of hydroxytyrosol (HTYR), vanillyl alcohol (VA) and homovanillyl alcohol (HVA) with pomace olive oil (POO) in solvent-free conditions using immobilized lipase on biogenic nanoparticles. The effect of temperature (30-70 °C) and enzyme concentration (0.1-1%, w/w) on the efficiency of the bioprocess as well as the reusability of the nanobiocatalyst were thoroughly investigated. The modified oils exhibited increased antioxidant activity compared to the control oil according to DPPH and CUPRAC assays (p < 0.05). The oxidative stability of pomace olive oil was also significantly enhanced after modification, as depicted by the K232 values and TBARS contents under accelerated oxidation at 60 °C (p < 0.05). Moreover, a fortified mayonnaise containing modified oil with HTYR was prepared that was noticeably stable compared to the control mayonnaise at 28 °C for 5 months (p < 0.05). Enzymatically modified oils have great potential for application in the nutraceutical and food industry, encouraging the exploitation of immobilized lipases as effective and green catalytic tools.

Phenolipids, Amphipilic Phenolic Antioxidants with Modified Properties and Their Spectrum of Applications in Development: A Review.

Polyphenols, as secondary metabolites from plants, possess a natural antioxidant capacity and biological activities attributed to their chemical and structural characteristics. Due to their mostly polar character, polyphenols present a low solubility in less polar environments or hydrophobic matrices. However, in order to make polyphenols able to incorporate in oils and fats, a transformation strategy is necessary. For the above, the functionalization of polyphenols through chemical or enzymatic lipophilization has allowed the synthesis of phenolipids. These are amphipilic molecules that preserve the natural phenolic core to which an aliphatic motif is attached by esterification or transesterification reactions. The length of the aliphatic chain in phenolipids allows them to interact with different systems (such as emulsions, oily molecules, micelles and cellular membranes), which would favor their use in processed foods, as vehicles for drugs, antimicrobial agents, antioxidants in the cosmetic industry and even in the treatment of degenerative diseases related to oxidative stress.

Mini-Review on the Enzymatic Lipophilization of Phenolics Present in Plant Extracts with the Special Emphasis on Anthocyanins.

Different plant extracts have the potential to be important sources of phenolic compounds. Their antibacterial, antifungal and antioxidant properties are of interest to researchers due to various possibilities for use in the pharmacy, cosmetic and food industries. Unfortunately, the direct application of phenolics in food is limited because of their hydrophilic nature and low solubility. The review is devoted to the recent advances in the methods of lipophilization of phenolic extracts along with the use of enzymes. The concept of extract modification instead of single compound modification is based on the expected synergistic effect of many phenolic compounds. The main focus is on the phenolic compounds found in fruits, flowers and leaves of different common and underutilized as well as medicinal, folk-medicinal or endemic plants. The compiled papers point to the great interest in the modification of anthocyanins, highly active but often unstable phenolics. Some examples of other flavonoids are also outlined. The possible applications of the lipophilized plant extracts are presented for improving the stability of edible oils, decreasing the content of acrylamide, exhibiting higher color stability in thermal processing and increasing the nutritional value.

Biological Properties, Health Benefits and Enzymatic Modifications of Dietary Methoxylated Derivatives of Cinnamic Acid.

Methoxylated derivatives of cinnamic acid play an important role in the formation of the pro-health potential of food products. Numerous reports present them as molecules with strong antimicrobial, antidiabetic, anticancer as well as hepato-, cardio-, and neuroprotective activities. In the last three decades, many research groups have tried to extend the practical application of these molecules as therapeutic and antioxidant agents extensively studying the methods of their lipophilization as the solution of problems of their low oral bioavailability and rapid metabolism. This article summarizes the latest data of natural sources of occurrence, biological potential and bioavailability of methoxy derivatives of cinnamic acids. Metabolism and pharmacokinetics of this group of dietary compounds are also extensively discussed as well as reviewing the methods of their chemical and enzymatic lipophilization in the aspect of their use in food and pharmaceutical industries.

Enzymatic lipophilization of d-borneol extracted from Cinnamomum camphora chvar. Borneol seed

Borneol esters have attracted increasing interest due to their potential application in the food industry. In this study, the extraction of d-borneol from Cinnamomum camphora chvar. borneol seed was carried out via steam distillation to gain highly purified d-borneol (99.66%). The lipase-catalyzed lipophilization of extracted d-borneol with oleic acid was performed in a solvent-free system. The influences of lipase type, substrate molar ratio, lipase loading, reaction temperature and reaction time on d-bornyl oleate yield were evaluated. Among four kinds of commercial lipases screened for their esterification efficiency, CRL (lipase from Candida rugose) displayed the highest catalytic activity in the synthesis of d-bornyl oleate. The yield of more than 95% was obtained under the optimal conditions: substrate molar ratio 1:2 (d-borneol/oleic acid), lipase loading 8%, reaction temperature 45 °C, reaction time 48 h. The structural identification of d-borneol and product d-bornyl oleate was performed by gas chromatography mass spectrometry (GC-MS) and proton nuclear magnetic resonance spectroscopy (1H NMR). The results showed that the product was confirmed to be d-bornyl oleate and the purity of which was 97.51%. This study will pave the way for d-borneol and its esters application in food industry.

Disaccharide anthocyanin delphinidin 3-O-sambubioside from Hibiscus sabdariffa L.: Candida antarctica lipase B-catalyzed fatty acid acylation and study of its color properties

Enzymatic lipophilization is an important process to extend the use of anthocyanins in lipidic media. In this work delphinidin 3-O-sambubioside (Dp3sam) isolated from Hibiscus sabdariffa L. flower was esterified with octanoic acid using Candida antarctica lipase B. The physical-chemical properties of the new lipophilic pigment were studied by UV–vis spectroscopy. Dp3sam with chloride, acetate and formate as counter ions were employed to study the lipophilization reaction. The hydrolysis of the reagent was avoided with a formate counter ion and the expected product was achieved with a noteworthy change of solubility. 1D and 2D NMR characterization of Dp3sam-C8 confirmed that the lipophilization took place at the primary alcohol of the glucoside moiety. Overall, the Dp3sam-C8 ester presents a stabilization of the quinoidal base (blue color) at neutral or moderate alkaline pH, which foresees a potential use of this pigment as a broad kind of industries on lipo-soluble formulations.

Microwave-Assisted Synthesis and Ionic Liquids: Green and Sustainable Alternatives toward Enzymatic Lipophilization of Anthocyanin Monoglucosides.

Anthocyanins recycling and transformations into novel compounds have been of great interest of the scientific community to improve the circular economy and enhance their technological applications. The enzymatic acylation of anthocyanins into lipophilic derivatives by conjugation with fatty acids emerged as one of the approaches; however, the literature describes only the use of organic solvents and conventional heating. In this work, the production of cyanidin-3-glucoside-octanoic acid conjugate combining ionic liquids (ILs), microwave (MW) irradiation, and Candida antarctica lipase B as a biocatalyst was attempted for the first time. Overall, the use of MW irradiation could reduce drastically the reaction time, allowing the formation of an acylated product with similar concentrations to the conventional method. On the other hand, the study of the lipophilic conjugate synthesis using different ILs showed that their composition is crucial to achieve the desired enzymatic reaction, and in this case, the combination of an imidazolium derivative as the cation with the triflate as the anion was suitable for the production of this derivative. These promising results achieved through the combination of greener alternatives to those reported in the literature are a starting point for further developments to produce this kind of anthocyanin derivatives exploring such sustainable and ecofriendly conditions.

Selective enzymatic lipophilization of anthocyanin glucosides from blackcurrant (Ribes nigrum L.) skin extract and characterization of esterified anthocyanins

Anthocyanins (ANC) are hydrophilic and water-soluble polyphenolic plant pigments. The current barriers to successful application of ANC in the food, cosmetic and pharmaceutical industries are predominantly related to performance, stability, formulation properties, and color. Enzymatic acylation of ANC could increase their stability without compromising bioactivity and chromatic features. Lipophilization of ANC-rich blackcurrant skin extract with Candida antarctica lipase B and octanoic acid was selective to cyanidin and delphinidin glucosides, but not the corresponding rutinosides. The reaction was chemo- and regioselective for acylation at the primary alcohol of the glucose moieties, greatly facilitating separation of the different glycoside derivatives.

EFFECTO DE LA LIPOFILIZACIÓN ENZIMÁTICA SOBRE LAS PROPIEDADES FUNCIONALES DE LA α-LACTOALBÚMINA BOVINA

Bovine α-lactalbumin (α-LA) was enzymatically modified with a lipase from Rhizopus orizae in an organic environment which catalyzed the covalent bonding of different length chain fatty acids, at reaction times of 3 and 7 days. Structural changes and functional properties of native and enzymatically modified α-LA in a pH range from 3 to 10 were analyzed. The degree of modification was higher than 40 %. The enzymatic lipophilization modified the functionality of the α-LA due to the increase in the surface hydrophobicity. In general, the surface properties were improved by the lipophilization specially at alkaline pH values, increasing the emulsifying activity more than 60 % and showing higher foam stability.

Antioxidative capacity of crude camellia seed oil: Impact of lipophilization products of blueberry anthocyanin

ABSTRACTNatural antioxidants have received considerable research interest nowadays, especially their usage in oil products. Blueberry anthocyanin extracts were added to crude camellia seed oil and lipophilized with free fatty acids in the oil through enzymatic process. The results showed that lipophilized anthocyanin derivates were synthesized, the oxidative stability of the oil under high temperature was improved, and the content of free fatty acids of the crude camellia seed oil was decreased. In conclusion, enzymatic lipophilization of blueberry extracts with free fatty acids in crude camellia seed oil could improve the quality of oil, especially the performance under high temperature.

High yielding and direct enzymatic lipophilization of ferulic acid using lipase from Rhizomucor miehei

Ferulic acid is an abundant phenolic acid and a good antioxidant that occurs naturally in free form or esterified. The structure of this hydroxycinnamic acid, with a hydroxyl group in para-position, makes enzymatic esterification with lipases challenging. Adjusted lipophilicity of the ferulic acid as an antioxidant is crucial for complex food matrices, calling for a simple esterification method. Esterification of ferulic acid with ethanol and decanol in n-hexane using immobilized lipase from Rhizomucor miehei was optimized using surface response methodology. After 72h, the yields were 76% and 88% for ethyl ferulate and decyl ferulate, respectively. Furthermore, ferulate esters of primary alcohols with varying chain lengths from C-2 to C-18 were also synthesized, with yields ranging from 76% to 92%. Finally, ferulic acid was preferably esterified to short chain alcohols in a mixture of primary alcohols. This study provides simple and efficient methods for the enzymatic esterification of ferulic acid.

Enzymatic lipophilization of phenolic extract from rowanberry (Sorbus aucuparia) and evaluation of antioxidative activity in edible oil

Phenolic extracts from Sorbus aucuparia (L.) were lipophilized in the presence of Candida antarctica lipase using octadecanol as the alkyl donor. The antioxidant activity of the lipophilized extract was assessed in refined, bleached and deodorized rapeseed oil during accelerated storage at 65 °C and frying at 180 °C. Rapeseed oil fortified with lipophilized extract showed significantly higher storage stability with 43% decrease in peroxide value at the end of the 7-day storage compared to rapeseed control sample without extract; however, no significant difference was observed in the performance of lipophilized extract and the native extract. On the contrary, the lipophilized extract exhibited markedly better protection against thermo-oxidative degradation during frying, inhibiting polar component formation and polymerization of triacylglycerol by up to 48%, compared to 30% by the native extract. At the end of the frying, French fries prepared in the presence of lipophilized extract had 7 times more phenolic compounds compared to fries prepared in the native extract indicating better solubilization of the phenolic compounds in the frying medium. Thus, lipophilization of phenolic compounds enhanced their protective activity in frying oil and improved the functionality of the prepared food.

Lipophilization of flavonoids for their food, therapeutic and cosmetic applications

Lipophilization of flavonoids for their food, therapeutic and cosmetic applicationsFlavonoids represent large group of plant pigments. These polyphenolic compounds may be found in the nature as active components of fruits, vegetables and other plants and derived products. Due to established biological effects they are attractive substances for many areas of human life. Many flavonoids are nowadays used in pharmaceutical, cosmetic and food preparations. Their practical applications are in most cases limited by low solubility and stability in lipophilic media. Chemical or enzymatic lipophilization of flavonoid skeleton may not only increase their solubility and stability in lipophilic environment but also their biological properties. This review summarizes current knowledge in this field.

Lipophilisation de composés phénoliques par voie enzymatique et propriétés antioxydantes des molécules lipophilisées

The oxidative modification of lipids in foods and cosmetics may lead to alteration of their qualities and can have physiopathological repercussion on consumer. To counteract these inauspicious effects, phenolic compounds, derived from plants, such as phenolic acids and flavonoids seem to be particularly promising. However, their relatively low solubility in apolar media limits their application in oil-based products. In emulsion, thanks to their water-solubility, these compounds are located in aqueous compartment, whereas lipid peroxidation occurs at the oil-water interface. Therefore, there is an interest in trying to enhance the amphiphilic character of phenolic antioxidants by enzymatic lipophilization which corresponds to the grafting of an aliphatic chain (fatty alcohol, acid or amine) through lipase-catalysed esterification or amidation reactions. Due to its amphiphilic nature, the resulting functionalized antioxidant would accumulate at the oil-water interface, increasing protection of target-lipids from oxidation. Various operational conditions and strategies can be adopted to perform lipase-mediated hydrophobation with high yields. This paper firstly presents a panorama of the advances in this field. Finally, the antioxidant capacity of lipophilized compounds is reviewed and compared with that of the native molecule.

Lipophilisation de composés phénoliques par voie enzymatique et propriétés antioxydantes des molécules lipophilisées

The oxidative modification of lipids in foods and cosmetics may lead to alteration of their qualities and can have physiopathological repercussion on consumer. To counteract these inauspicious effects, phenolic compounds, derived from plants, such as phenolic acids and flavonoids seem to be particularly promising. However, their relatively low solubility in apolar media limits their application in oil-based products. In emulsion, thanks to their water-solubility, these compounds are located in aqueous compartment, whereas lipid peroxidation occurs at the oil-water interface. Therefore, there is an interest in trying to enhance the amphiphilic character of phenolic antioxidants by enzymatic lipophilization which corresponds to the grafting of an aliphatic chain (fatty alcohol, acid or amine) through lipase-catalysed esterification or amidation reactions. Due to its amphiphilic nature, the resulting functionalized antioxidant would accumulate at the oil-water interface, increasing protection of target-lipids from oxidation. Various operational conditions and strategies can be adopted to perform lipase-mediated hydrophobation with high yields. This paper firstly presents a panorama of the advances in this field. Finally, the antioxidant capacity of lipophilized compounds is reviewed and compared with that of the native molecule.

Phenolic Acids Enzymatic Lipophilization

Lipophilization is the esterification of a lipophilic moiety (fatty acid or fatty alcohol) on different substrates (phenolic acid, sugar, protein, ...), resulting in new molecules with modified hydrophilic/lipophilic balance. This reaction can be obtained chemically or enzymatically using different enzymes. Phenolic acids possess interesting biological properties (antioxidant, chelator, free radical scavenger, UV filter, antimicrobial, ...), but because of their relatively low solubility in aprotic media, their application in oil-based products is limited. Therefore, the esterification of their carboxylic acid function with a fatty alcohol enhances their hydrophobicity and results in a multifunctional amphiphilic molecule. Enzymatic lipophilization of phenolic acids is nowadays studied for potential industrial applications. Different systems have been proposed to perform the reaction yield [free or immobilized enzymes (lipase, feruloyl esterase, tannase, etc.), free or added organic solvent, addition of surfactant, microemulsion system, etc.]. Some of the functional properties of these esters have been demonstrated. This review presents a panorama of the advances in this field.