Feasibility of Hemp Seed Oil Oleogels Structured with Natural Wax as Solid Fat Replacement in Margarine

Cold-pressed hempseed oil (HSO) is known to have many health benefits due to many phytochemicals and high polyunsaturated fatty acids content. In this study, HSO oleogels were prepared with 3, 5, and 7% natural waxes including sunflower wax (SW), rice bran wax (RBW), beeswax, and candelilla wax to evaluate their potential as solid fat replacements in margarines and spreads. Firmness, crystal structures, and melting properties of these oleogels were evaluated. In general, wax-based HSO oleogels except for RBW-HSO oleogels had lower firmness and weaker crystal network than the corresponding soybean oil (SBO) oleogels. In contrast, RBW-HSO oleogels had similar firmness, comparable or stronger crystal network, and higher melting and crystallization enthalpies compared to those of SBO oleogels. After removing polar compounds from HSO, waxes except for RBW provided oleogels with greater firmness, higher melting and crystallization enthalpies, and stronger crystal network. Therefore, it was concluded that polar compounds negatively affected the physical properties of wax-HSO oleogels but not those of RBW-HSO oleogels. Margarine samples were prepared with SW- and RBW-HSO oleogels, and their firmness and melting properties were examined. The firmness of these margarines indicated that wax-HSO oleogels may achieve the firmness of commercial spreads with less than 3% wax while the firmness of stick margarines cannot be achieved even with 7% wax. Although the properties of wax-HSO oleogels should be further improved, they showed potential as solid fat replacements in margarines and spreads.

Bioprospecting of Less-Polar Fractions of Ericaria crinita and Ericaria amentacea: Developmental Toxicity and Antioxidant Activity

Ericaria crinita and Ericaria amentacea from the Adriatic Sea (Croatia) were investigated with respect to the presence of less-polar compounds for the first time after fractionation by solid-phase extraction (SPE). The composition of less-polar fractions of freeze-dried E. crinita (FdEc) and E. amentacea (FdEa) were analyzed by high-performance liquid chromatography–high-resolution mass spectrometry with electrospray ionization (UHPLC-ESI-HRMS). The major identified compounds were: amides of higher aliphatic acids (palmitoleamide, linoleamide, palmitamide, oleamide and erucamide) and related compounds, carotenoid (fucoxanthin), chlorophyll derivatives (pheophytin a and b and their derivatives) and higher terpenes (loliolide, isoamijiol with its oxidation product), β-stigmasterol and (3β,6α)-14-methylergosta-8,24(28)-diene-3,6-diol). The toxic effects observed on the less-polar fractions obtained from Ericaria species on zebrafish Danio rerio embryos could be associated with the high abundance of all five detected amides. The antioxidant activity of the fractions was evaluated by means of five independent assays, including the reduction of the radical cation (ABTS), the oxygen radical absorbance capacity (ORAC), ferric-reducing antioxidant power (FRAP), the 2,2-diphenyl-1-picryl-hydrazyl (DPPH) assay and the Folin–Ciocalteu method. A higher antioxidant activity of E. amentacea in comparison to that of the E. crinita fractions was found with IC50 concentrations of 0.072 and 1.177 mg/mL, respectively. The correlation between the activity and the chemical composition revealed that the synergistic effect of different compounds impacted their antioxidant response.

Influence of rutin-ammonium complex on the physiological condition of pine seedlings

In the plant body, phenolic compounds nonspecifically affect the processes of morphogenesis and perform a wide range of regulatory and protective functions. Of particular interest are the processes involved in the complexation of flavonoids as a result of their interaction with ammonium forms of nitrogen. Polar compounds, which are formed in tissues as a result of chemical transformation, are quite mobile in soil solutions and show high biological activity. The properties of phenol-ammonium complexes are of considerable interest in terms of morphogenesis, physiology of stability, as well as in the system of interaction of plants with soil microorganisms. Studies of the effect of phenol-ammonium complex were performed on seeds and seedlings of Scots pine. Quantitative indicators of germination energy and germination were determined by seed germination. Biochemical profiling of seedling tissue extracts was performed by high-performance thin layer chromatography. It has been experimentally confirmed that rutin (quercetin-3-O-rutinoside) after interaction with 10% aqueous ammonia solution forms a complex of substances, among which the chromatography revealed polar products that potentially affect the regulation of growth. At a total concentration of 15 mg/l, these substances significantly increased germination energy and seed germination. In pine seedlings, they stimulated the growth of roots and shoots. The effect of the complex of organic compounds on seedlings depended on the concentration, duration of seed treatment and had a prolonged effect. The obtained phenol-ammonium complex at a concentration of 10-15 mg/l contributed to an increase in the amount of chlorophylls, carotenoids in the tissues of seedlings, and at 20-40 mg/l increased the content of phenolic synthesis products.

Performance of Olive-Pomace Oils in Discontinuous and Continuous Frying. Comparative Behavior with Sunflower Oils and High-Oleic Sunflower Oils

Frying performance of olive-pomace oils (OPOs) as compared to sunflower oils (SOs) and high-oleic sunflower oils (HOSOs) was studied in discontinuous frying (DF) and continuous frying (CF) for the first time. DF is used in household, restaurants and frying outlets, while CF is used in the food industry. Oil alteration during frying was determined by measurements of polar compounds (PC) and polymers. Fried potatoes were analyzed for oil absorption and alteration, color, and evaluated in an acceptability test. Results for DF showed that all SOs reached 25% PC at the 9th frying operation (FO), whereas HOSOs did between the 17–18th FO and variable results were found for OPOs since initial levels of diacylglycerols were different. Rates of formation of PC or polymers were the lowest for OPOs, thus showing the best performance in DF. Specifically for PC, relative rates of formation were 1.00–1.11, 2.46–2.71 and 1.37–1.41 for OPOs, SOs and HOSOs respectively. In CF, OPOs and HOSOs behaved similarly and better than SOs, although none reached 25% PC after 40 FO. The good performance of OPOs can be attributed to the high monounsaturated-to-polyunsaturated ratio, in common with HOSOs, and the additional positive effect of minor compounds, especially β-sitosterol and squalene.

Polarity Dependence of Transport of Pharmaceuticals and Personal Care Products Through Birnessite-Coated Porous Media

Pharmaceuticals and personal care products (PPCPs) have drawn increasing concern of environmental health as they are continuously released into the environment. This study examined the effects of birnessite (δ-MnO2) on the transport and retention of five PPCPs in porous media under steady saturated flow conditions. Considering that natural birnessite occurs as discrete particles and small nodules, birnessite-coated sand was used to mimic the natural regime of birnessite in the environment. Batch isotherm experiments were conducted using uncoated and birnessite-coated sand; results showed that the difference in the affinity of the five PPCPs was correlated to their polarity characteristics. Column experiments were conducted by mixing 0, 10, and 20% birnessite-coated sands with the uncoated sands. These three percentages are equivalent to three contents of manganese (Mn) in the experimental columns (0, 55, and 109 μg Mn g−1 sand). Results suggested that polar compounds (such as bisphenol-A, tetracycline, and ciprofloxacin) had a higher affinity to birnessite-coated sands than the weak polar compounds (such as ibuprofen and carbamazepine) because the polarity was favorable to electrostatic attraction and oxidative reaction. Overall, birnessite decreased the mobility of polar PPCPs but exerted no significant effect on the mobility of weak polar PPCPs under continuous flow conditions. The polarity-based correlation extended traditional electrostatic theory while well interpreting the complicated effects of birnessite on the adsorption and transport of PPCPs, especially neutral or non-dissociated compounds like carbamazepine.

MULTICHARME: A modified Chernin-type multi-pass cell designed for IR and THz long-path absorption measurements in the CHARME atmospheric simulation chamber

We have developed MULTICHARME, a modified Chernin-type multi-pass cell especially designed for IR and THz long-path absorption measurements in the CHamber for Atmospheric Reactivity and Metrology of the Environment (CHARME). By measuring the output power using a near-IR diode-laser and a THz amplified multiplication chain, we have established that the effective reflectivity of MULTICHARME is better than 94 % over approximately three decades of frequency. Absorption measurements of N2O have been performed by probing highly excited rovibrational transitions in the near-IR and ground state rotational transitions at submillimetre wavelengths. In each case the linearity of the absorbance with the pathlengths was verified. Finally, we demonstrate that THz spectroscopy is able to study the isotopic composition of greenhouse polar gases such as N2O and to absolutely quantify stable (N2O) and reactive (O3) species at trace levels. Moreover, a THz monitoring at low pressure of the ozone decay in the chamber has been performed. The deduced ozone lifetime of 3.4 ± 0.1 h is shorter compared with previous measurements performed in CHARME at atmospheric pressure. For the first time, the ability of THz rotational spectroscopy to monitor, with a very high degree of selectivity, stable and reactive polar compounds at trace level in an atmospheric simulation chamber is demonstrated. However, the sensitivity of the THz monitoring needs to be improved to reach the atmospheric trace levels. For this purpose, it is necessary to figure out the baseline variations as well as possible induced by the multiple standing waves present in MULTICHARME.

Separation of Polar Compounds using Poly(Ethylene Oxide) Bonded Stationary Capillary Liquid Chromatography

Poly(ethylene oxide) (PEO) bonded stationary phase has been synthesized by a single and simple step reaction. Poly(ethylene glycol monomethyl ether p-toluene sulfonate) (tosylated-PEO, molecular weight 900, n ≈ 18) was chemically bonded to 3-aminopropyl silica (TSKgel NH2-60, 5 µm particle size, and 60 Å mean pore diameter). The prepared stationary phase was able to separate polar compounds such as phenolics and nucleobases in capillary liquid chromatography. The retention and separation of phenolics and nucleobases could be achieved under isocratic elution condition. Nucleobases such as thymine, adenine, uracil, uridine, cytidine and toluene and phenolics (phenol, pyrocatechol, pyrogallol) were baseline separated in less than 6 min using 98% acetonitrile and less than 7 minutes using 80% acetonitrile, respectively. We demonstrated that the retention of nucleobases as analyte decreased with decreasing eluent concentration. The retention of these polar compounds was believed to be based on dipole-dipole and/or hydrogen-bonding interactions.

Determination of the Chemical Composition of Eucalyptus spp. for Cellulosic Pulp Production

The chemical composition of wood is important to assess the quality of this raw material for the industry of cellulosic pulp production. The purpose of this work was to determine the chemical composition of Eucalyptus spp. grown for cellulosic pulp production. Ten Eucalyptus spp. clones with six years of age, located in the municipality of Itamarandiba, Minas Gerais, Brazil, were used. Quantification was obtained for extractives, monosaccharides, uronic acids, acetates, lignin, ash and the phenolic composition of the extracts. In average, clones showed around 2.7% extractives, with a predominance of polar compounds soluble in ethanol and water; 27.7% lignin and 0.3% ash. Glucose was the main sugar detected (64.2%), followed by xylose (19.3%). The main components of the extractives were steroids, fatty acids and aromatic acids, followed by smaller amounts of substituted alkanoic acids, fatty alcohols, glycerol derivatives and triterpenes. The ethanol–water extracts presented total phenol contents ranging from 321.4 to 586.6 mg EAG/g of extract, tannins from 28.1 to 65.1 mg catechin/g of extract and flavonoids from 73.6 to 256.9 mg catechin/g of extract. Clones with a higher holocellulose amount and a lower lignin content showed a higher potential for cellulosic pulp production. These findings are important for the development of high-quality wood based on important traits for the pulp and paper sector.

Volatiles Emission by Crotalaria nitens after Insect Attack

Plants are known to increase the emission of volatile organic compounds upon the damage of phytophagous insects. However, very little is known about the composition and temporal dynamics of volatiles released by wild plants of the genus Crotalaria (Fabaceae) attacked with the specialist lepidopteran caterpillar Utetheisa ornatrix (Linnaeus) (Erebidae). In this work, the herbivore-induced plant volatiles (HIPV) emitted by Crotalaria nitens Kunth plants were isolated with solid phase micro-extraction and the conventional purge and trap technique, and their identification was carried out by GC/MS. The poly-dimethylsiloxane/divinylbenzene fiber showed higher affinity for the extraction of apolar compounds (e.g., trans-β-caryophyllene) compared to the Porapak™-Q adsorbent from the purge & trap method that extracted more polar compounds (e.g., trans-nerolidol and indole). The compounds emitted by C. nitens were mainly green leaf volatile substances, terpenoids, aromatics, and aldoximes (isobutyraldoxime and 2-methylbutyraldoxime), whose maximum emission was six hours after the attack. The attack by caterpillars significantly increased the volatile compounds emission in the C. nitens leaves compared to those subjected to mechanical damage. This result indicated that the U. ornatrix caterpillar is responsible for generating a specific response in C. nitens plants. It was demonstrated that HIPVs repelled conspecific moths from attacked plants and favored oviposition in those without damage. The results showed the importance of volatiles in plant–insect interactions, as well as the choice of appropriate extraction and analytical methods for their study.

Use of an In Vitro Skin Parallel Artificial Membrane Assay (Skin-PAMPA) as a Screening Tool to Compare Transdermal Permeability of Model Compound 4-Phenylethyl-Resorcinol Dissolved in Different Solvents

Absorption through the skin of topically applied chemicals is relevant for both formulation development and safety assessment, especially in the early stages of development. However, the supply of human skin is limited, and the traditional in vitro methods are of low throughput. As an alternative, an artificial membrane-based Skin Parallel Artificial Membrane Permeability Assay (Skin-PAMPA) has been developed to mimic the permeability through the stratum corneum. In this study, this assay was used to measure the permeability of a model compound, 4-phenylethyl-resorcinol (PER), dissolved in 13 different solvents that are commonly used in cosmetic formulation development. The study was performed at concentrations close to the saturated solution of PER in each solvent to investigate the maximum thermodynamic potential of the solvents. The permeability of PER in selected solvents was also measured on ex vivo pig skin for comparison. Pig ear skin is an accepted alternative model of human skin. The permeability coefficient, which is independent of the concentration of the applied solution, showed a good correlation (R2 = 0.844) between the Skin-PAMPA and the pig skin permeation data. Our results support the use of the Skin-PAMPA to screen the suitability of different solvents for non-polar compounds at an early stage of formulation development.