This paper reports the physicochemical (density, dynamic viscosity, electrical conductivity and refractive index) and the thermodynamic (thermal expansion coefficient, molecular volume, lattice energy and heat capacity) properties of several choline chloride (ChCl) based deep eutectic solvents (DESs), with 1:2 mole ratio, respectively: ChCl:propylene glycol, ChCl:1,3-dimethylurea and ChCl:thiourea, at atmospheric pressure as a function of temperature over the range of 293.15?363.15 K. Their properties were also compared with those of some already characterized ChCl-based DESs, namely ChCl:ethylene glycol, ChCl:glycerol and ChCl:urea (1:2 mole ratio). Density, viscosity and refractive index of all DESs decrease with the increasing temperature while the electrical conductivity increases. Viscosity and conductivity of the tested DESs were fitted by both Arrhenius-type and Vogel?Tamman?Fulcher equations. The changes of molar enthalpy, entropy and Gibbs energy of activation, determined using the Eyring theory, demonstrated the interactional factor as predominant over the structural factor for all DES systems. The fractional Walden rule, used to correlate molar conductivity and viscosity, showed an excellent linear behaviour. It was shown that ChCl:propylene glycol DES had properties similar to ChCl:ethylene glycol and ChCl:glycerol DESs. However, the properties (density, viscosity and electrical conductivity) of ChCl:1,3-dimethylurea and ChCl: :thiourea DESs were inferior to those of the ChCl:urea DES. [Project of the Serbian Ministry of Education, Science and Technological Development, Grant no. III 45001]
Many factors can influence antioxidative and antimicrobial characteristics of plant materials. The quality of cocoa as functional food ingredient is influenced through its processing. The main aim of this study was to test if there is difference in polyphenol content, antioxidant capacity, and antimicrobial activity between nonalkalized and alkalized cocoa powders. To estimate polyphenol and flavonoid content in cocoa samples the spectrophotometric microassays were used. Flavan-3ols were determined with reversed-phase high-performance liquid chromatography (RP-HPLC). Antimicrobial activity against 3 Gram positive bacteria, 4 Gram negative bacteria and 1 strain of yeast was determined using broth microdilution method. Total polyphenol content was 1.8 times lower in alkalized cocoa samples than in natural ones. Epicatechin/catechin ratio was changed due to the process of alkalization in favor of catechin (2.21 in natural and 1.45 in alkalized cocoa powders). Combined results of 3 antioxidative tests (DPPH, FRAP, ABTS) were used for calculation of RACI (Relative Antioxidant Capacity Index) and GAS (Global Antioxidant Score) values that were consistently higher in natural than in alkalized cocoa extracts. Obtained results have shown significant correlations between these values and phenolic content (0.929 ≤ r ≤ 0.957, P < 0.01). Antimicrobial activity varied from 5.0 to 25.0 mg/ml (MICs), while Candida albicans was the most sensitive tested microorganism. Cocoa powders subjected to alkalization had significantly reduced content of total and specific phenolic compounds and reduced antioxidant capacity (P < 0.05), but their antimicrobial activity was equal for Gram-positive bacteria or even significantly enhanced for Gram-negative bacteria.
In the past few years, research efforts have focused on plant exploitation for deriving some valuable compounds. Extraction has been usually performed using petrochemical and volatile organic solvents, but nowadays, increased recognition of environmental pollution has prompted the utilization of green solvents as alternatives. Therefore, the aim of the present study was to exploit deep eutectic solvents (DES) (choline chloride: citric acid and choline chloride: glucose) as solvents for extracting valuable phenolic antioxidants from grapes. Investigation was conducted on ten grape varieties, observing seeds and skin as different matrix. Total polyphenol content (TPC) was determined by Folin-Ciocalteu spectrophotometric microassay. Antioxidant activity was investigated using four different tests and results were combined in a unique Antioxidant Composite Index (ACI) to reveal comprehensive information about this biological activity. Polyphenol compounds were identified and quantified with the aim of HPLC-diode array detector (DAD). Overall results support that DES (particularly choline chloride: citric acid) were comparable to conventional solvent, and in most cases even outperformed acidified aqueous ethanol (concerning extraction efficiency and antioxidant activity). Regardless of varietal distinctions, grape seeds have higher antioxidant capacity compared to grape skin, and such findings are according to their phenol compound concentrations.
The amount of organic pomace, left behind agricultural processes, is continuously rising in accordance with industrial progress. Grape pomace, generated in the wine industry all over the world, represents a raw material for obtaining valuable products. Grape seeds are especially rich in oil containing bioactive compounds that can have various health-related effects. The aim of the study is to compare the quality of seed oils obtained from six white grapes, including two Serbian autochthonous varieties. Linoleic acid, associated with numerous health benefits, is the major fatty acid in all samples (≈66% of total); -tocopherol is the main tocopherol homologue. Total polyphenol content ranges from 73.4 to 104.3 mg of gallic acid equivalents per 100 g. In order to provide comprehensive information about antioxidant capacity of grape seed oil (GSO), three tests are performed (ferric ion reducing antioxidant power; 2,2'-diphenyl-1-picrylhydrazyl, and 2,2'-azino-bis(3-ethylbenzthiazoline-6-sulphonic acid) radical scavenging). Antimicrobial activity is investigated against different strains; however, GSO inhibits the growth of Staphylococcus aureus and Candida albicans. Obtained results are used to develop a novel approach for oil quality assessment. Calculated oil quality scores (OQS) reveal no significant difference between international and autochthonous varieties, although Smederevka stands out as the most potent one.Practical applications: Considering the progressive waste increase in the wine industry and keeping in mind all health-promoting effects of grape seed oil (GSO), it is clearly observed that oil production represents a profitable and sustainable utilization of grape seeds. The results of the present study show that GSO is a rich source of compounds with antioxidant and antimicrobial properties. In addition, this work provides deeper insight into a quality of Serbian autochthonous grape varieties that are still insufficiently explored. Furthermore, the proposed oil quality score could be used as a comprehensive and unbiased method that enables quality assessment of oils. This tool can find practical application in comparing different plant oils regarding their compositional and functional properties. Finally, it would contribute to making some general oil intake recommendations.
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