Isoconversional kinetic analysis of ring-opening polymerization of ε-caprolactone: Steric influence of titanium(IV) alkoxides as initiators

Four titanium(IV) alkoxides, namely: Ti(IV) n-propoxide (1), Ti(IV) n-butoxide (2), Ti(IV) tert-butoxide (3), and Ti(IV) 2-ethylhexoxide (4), have been used as initiators in the bulk ring-opening polymerization (ROP) of ε-caprolactone (ε-CL). The influence of the alkoxide group on the course of the ROP of ε-CL was investigated by means of ¹H-NMR and differential scanning calorimetry (DSC). The ¹H-NMR spectra confirmed that the ROP reaction of ε-CL proceeded via the widely accepted coordination-insertion mechanism for each of the four initiators. Isoconversional methods have been used to evaluate non-isothermal DSC data via the equations of Friedman, Kissinger-Akahira-Sunose (KAS) and Ozawa-Flynn-Wall (OFW). The kinetic studies showed that the polymerization rate for the four initiators (1-4) was in the order of 1 > 2 ≈ 4 > 3. The lowest activation energies (40–47, 42–44, and 49–52 kJ/mol for the Friedman, KAS and OFW methods respectively) were found in the polymerizations using Ti(IV) n-propoxide (1), while the highest activation energies (84–107, 77–87, and 80–91 kJ/mol for the Friedman, KAS and OFW methods respectively) were obtained using Ti(IV) tert-butoxide (3). Differences in the rates of polymerization and the activation energies amongst the four initiators appeared to be governed mainly by the different degrees of steric hindrance in the initiator structure. These results represent important findings regarding the steric influence of the alkoxide groups on the kinetics of the ROP of ε-CL initiated by titanium(IV) alkoxides.     

An explorative study on the cell wall polysaccharides in the pulp and peel of dragon fruits (Hylocereus spp.)

The pectic and hemicellulosic cell wall polysaccharides from the pulp and the peel of white-flesh and red-flesh dragon fruits (Hylocereus spp.) were isolated and compared in terms of degree of methoxylation (DM), solubility properties (relative content of uronic acids and neutral sugars in different fractions), neutral sugar composition, molar mass distribution, and affinity toward some specific anti-pectin antibodies. Hereto, the alcohol-insoluble residues were extracted and sequentially fractionated using hot water, a chelating agent, sodium carbonate, and potassium hydroxide solutions to obtain different pectin fractions and a hemicellulose fraction. Chemical analyses were used to characterize these polysaccharide fractions. The results show that cell wall polysaccharides of the pulp and especially of the peel from white-flesh and red-flesh dragon fruits contain significant amounts of pectic substances that are lowly methyl-esterified. The cell wall polysaccharides of the peel as well as those of the pulp contain high amounts (38–47 %) of loosely bound (water-soluble) pectic substances. In the water-soluble fraction (WSF) of the peel samples, uronic acids are the predominant monomers. On the contrary, rhamnogalacturonan-I type neutral sugars, and especially arabinose and galactose, contribute equally, as compared to uronic acid, to the WSF of the pulp samples. Despite the low average DM value of pulp and peel pectin, pectic substances in both samples showed affinity for antibodies with different specificities indicating that a wide range of epitopes, including long blocks of unesterified galacturonic acids (GalA) residues as well as (short) blocks of esterified GalA residues, is present. No large differences between the pectic substances among the different dragon fruit varieties were observed.     

Dragon Fruit (Hylocereus spp.) Seed Oils: Their Characterization and Stability Under Storage Conditions

Oil was extracted from the seeds of white-flesh and red-flesh dragon fruits (Hylocereus spp.) using a cold extraction process with petroleum ether. The seeds contained significant amounts of oil (32–34 %). The main fatty acids were linoleic acid (C18:2, 45–55 %), oleic acid (C18:1, 19–24 %), palmitic acid (C16:0, 15–18 %) and stearic acid (C18:0, 7–8 %). The seed oils are interesting from a nutritional point of view as they contain a large amount of essential fatty acids, amounting to up to 56 %. In both dragon fruit seed oils, tri-unsaturated triacylglycerol (TAG) was mainly found while their TAG composition and relative percentage however varied considerably. Therefore, they showed a different melting profile. A significant amount of total tocopherols was observed (407–657 mg/kg) in which the α-tocopherol was the most abundant (~72 % of total tocopherol content). The impact of storage conditions, cold and room temperatures, on the oxidative stability and behavior of tocopherols was monitored over a 3-month storage period. During storage, the oxidative profile changed with a favorably low oxidation rate (~1 mequiv O₂/week) whilst tocopherols decreased the most at room temperature. After 12 weeks, the total tocopherol content, however, still remained high (65–84 % compared to the initial oils). Hereto, the dragon fruit seed oils can be considered as a potential source of essential fatty acids and tocopherols, with a good oxidative resistance.     

Impact of Thermal Treatment on Physicochemical, Antioxidative and Rheological Properties of White-Flesh and Red-Flesh Dragon Fruit (Hylocereus spp.) Purees

White-flesh (Hylocereus undatus; WF) and red-flesh (Hylocereus polyrhizus; RF) dragon fruit purees were subjected to heat treatment for 0 to 60 min at temperatures between 50 and 90 °C. The influence of the different heat treatments on the physicochemical properties, colour, betacyanins content, microbial destruction, antioxidative properties and rheological parameters were investigated. The physicochemical values and antioxidative properties of the unheated RF were significantly higher than that of the unheated WF (p?<?0.05). The betacyanins content of RF after 90 °C for 60 min decreased to 32.35%, based on the initial puree. Total colour change (TCC) and betacyanins degradation followed the second-order kinetic. The L* and b* values of the purees can be recommended as an online quality control (R ²?≥?0.7733) and TCC of RF can be used to predict the betacyanins content (R ²?=?0.9442). The antioxidative properties of the heated WF and RF increased with heating treatment. The linear correlation among the antioxidative properties was strong (R ²?≥?0.8587). WF and RF showed shear thinning behaviour. After heating, the apparent viscosity of WF and RF increased and all cases fitted very well with the power law model (R ²?≥?0.9988). Thus, the heated dragon fruit purees, particularly the RF, offer possibilities to be applied in foodstuffs due to their interesting physicochemical properties and nutritional attributes after thermal treatment.