Chitosan is a cationic natural polysaccharide, which has emerged as an increasingly interesting biomaterialover the past few years. It constitutes a novel perspective in drug delivery systems and nanocarriers’ formulations due to its beneficial properties, including biocompatibility, biodegradability and low toxicity. The potentiality of chemical or enzymatic modifications of the biopolymer, as well as its complementary use with other polymers, further attract the scientific community, offering improved and combined properties in the final materials. As a result, chitosan has been extensively used as a matrix for the encapsulation of several valuable compounds. In this review article, the advantageous character of chitosan as a matrix for nanosystemsis presented, focusing on the encapsulation of natural products. A five-year literature review is attempted covering the use of chitosan and modified chitosan as matrices and coatings for the encapsulation of natural extracts, essential oils or pure naturally occurring bioactive compounds are discussed.

The effect of different extraction methods of rosemary leaves on the total phenolic content (TPC), and the antioxidant activity of the extracts was herein investigated. Firstly, the solid-liquid conventional extraction (CEM) and microwave-assisted extraction (MAE) were implemented in an effort to identify the effect of the solvent and of microwave irradiation on the extract quality. The extract obtained from CEM at room temperature, using ethanol/water 95:5 v/v, showed the highest antioxidant activity (IC₅₀ = 12.1 μg/mL). MAE using ethanol/water 50:50 v/v provided an extract with TPC and DPPH radical scavenging ability in a significantly shorter extraction time (1 h for MAE and 24 h for CEM). Enzyme-assisted extraction (EAE) using five commercial enzyme formulations was implemented, and the kinetic equation was calculated. Finally, the effect of EAE as a pretreatment method to CEM was examined. Pretreatment of the plant material with pectinolytic enzymes for 1 h prior to a 24 h CEM with 50% hydroethanolic solvent was found to be the optimum conditions for the extraction of rosemary leaves, providing an extract with higher DPPH radical scavenging ability (IC₅₀ 14.3 ± 0.8 μg/mL) and TPC (15.2 ± 0.3 mg_GAE/g_rosemary) than the corresponding extract without the enzyme pretreatment.

The extraction of valuable phytochemicals from natural sources is an important and constantly evolving research area. Zingiber officinale Roscoe (ginger) contains high amounts of bioactive phytochemicals, which are desirable due to their significant properties. In this work, the ability of different natural deep eutectic solvents (NaDESs) to serve as green solvents for the preparation of high added value extracts from ginger is explored, in combination with ultrasound assisted extraction. The method was optimized by applying a response surface methodology using the NaDES Bet/La/W (1:2:2.5). Three independent variables, namely the extraction time, ultrasound power and NaDES-to-dry-ginger ratio, were investigated by employing a 17-run three-level Box–Behnken Design (BBD) in order to study the correlation between the extraction conditions and the quality of the obtained extracts. The optimum conditions (in order to achieve simultaneously maximum total phenolic content and antioxidant activity), were found to be 23.8 min extraction time, 60 Watt and NaDES/ginger 25:1 w/w. In the optimum conditions the DPPH radical scavenging ability of the extracts was found to reach IC₅₀ = 18.16 mg/mL after 120 min, whereas the TPC was 20.10 ± 0.26 mg GAE/g of dry ginger. The green methodology was also compared with the extraction using conventional solvents. All the obtained extracts were evaluated for their antioxidant activity and their total phenolic content, while the extract derived by the optimum extraction conditions was further investigated for its ability to bind to calf thymus DNA (ctDNA).

The encapsulation of clove essential oil (CEO) in hydroxypropyl-β-cyclodextrin (HP-β-CD) and the subsequent incorporation of the inclusion complex in an elastic chitosan film in order to achieve a controlled release profile of the volatile CEO are herein presented. Freshly distilled CEO was found to contain eugenol in concentrations higher than 70%. The kneading method was implemented for the preparation of a CEO-HP-β-CD inclusion complex, resulting in a 50% inclusion efficiency of the essential oil in particles sized 214.40 nm with ζ-potential −27.5 mV. Free CEO and CEO-HP-β-CD inclusion complex were tested for their ability to scavenge the 2,2-Diphenyl-1-picrylhydrazyl (DPPH) radical, and it was found that the CEO-HP-β-CD complex presented enhanced antioxidant activity (88%) compared to the free CEO (71%). Choline chloride-containing chitosan (CS) films were prepared, incorporating either the pure CEO or the CEO-HP-β-CD inclusion complex, and their mechanical properties were determined. The study of the release profile in different pH values demonstrated the capacity of the CS-HP-β-CD system to provide sustained release of CEO, noting its potential use in food processing as smart packaging.

Tyrosol, a natural product present in olive oil and white wine, possesses a wide range of bioactivity. The aim of this study was to optimize the preparation of nanosystems encapsulating tyrosol in carbohydrate matrices and the investigation of their ability to bind with DNA. The first encapsulation matrix of choice was chitosan using the ionic gelation method. The second matrix was β-cyclodextrin (βCD) using the kneading method. Coating of the tyrosol-βCD ICs with chitosan resulted in a third nanosystem with very interesting properties. Optimal preparation parameters of each nanosystem were obtained through two three-factor, three-level Box-Behnken experimental designs and statistical analysis of the results. Thereafter, the nanoparticles were evaluated for their physical and thermal characteristics using several techniques (DLS, NMR, FT-IR, DSC, TGA). The study was completed with the investigation of the impact of the encapsulation on the ability of tyrosol to bind to calf thymus DNA. The results revealed that tyrosol and all the studied systems bind to the minor groove of ctDNA. Tyrosol interacts with ctDNA via hydrogen bond formation, as predicted via molecular modeling studies and corroborated by the experiments. The tyrosol-chitosan nanosystem does not show any binding to ctDNA whereas the βCD inclusion complex shows analogous interaction with that of free tyrosol.