Some physical properties of castor oil esters and hydrogenated castor oil esters

Esters of castor oil and hydrogenated castor oil were prepared with C₆, C₁₂, C₁₆, C₁₈ fatty acids, using tetra‐n‐butyl titanate as a catalyst and n‐butyl benzene as a water entrainer. Physical properties such as melting point, refractive index, viscosity, and specific gravity of these esters were measured. Slip melting points of the esters were very low in both cases. These esters did not crystallize even at low temperature. The highest slip melting point obtained was 21 °C with stearoyl hydrogenated castor oil ester and lowest slip melting point obtained was —6 °C with hexanoyl castor oil ester.     

A New Type of Sulfobetaine Surfactant with Double Alkyl Polyoxyethylene Ether Chains for Enhanced Oil Recovery

A new type of sulfobetaine with double alkyl polyoxyethylene (n) ether chains, dicoconut oil alcohol polyoxethylene (n) ether methylhydroxylpropyl sulfobetaine (diC_12–14E _n HSB) was synthesized using a commercial nonionic surfactant, coconut oil alcohol polyoxethylene (n) ether, as raw material and its properties as a surfactant for enhanced oil recovery (EOR) in the absence of alkali was studied. The purified product is a mixture of homologues with mainly C₁₂/C₁₂, C₁₂/C₁₄ and C₁₄/C₁₄ alkyl chains and widely distributed EO chains (n = 2.2 on average) with an average molar mass of 742.6 g/mol. The diC_12–14E_2.2HSB has an improved aqueous solubility at 25 °C compared with didodecylmethylhydroxylpropyl sulfobetaine (diC₁₂HSB), a homologue without an EO chain, and is highly surface active as reflected by its low CMC (4.6 × 10^?6 mol/L), high saturated adsorption (6.8 × 10^?10 mol/cm²) and small cross sectional area (0.24 nm²/molec.) at the air/water interface. With a hydrophile–lipophile balance well matched with Daqing crude oil/connate water system, the sulfobetaine can reduce Daqing crude oil/connate water interfacial tension to ultra-low values at 45 °C in the absence of alkali, and displays a low saturated adsorption at the sandstone/water interface (0.0024 mmol/g), reduced by 69 and 92 % respectively in comparison with that of the corresponding carboxyl betaine, diC_12–14E_2.2B and its homologue without an EO chain, didodecylmethylcarboxyl betaine (diC₁₂B). With these excellent properties diC_12–14E_2.2HSB gives a high tertiary recovery, 18.4 % original oil in place, when mixed with other hydrophobic and hydrophilic sulfobetaines in surfactant-polymer (SP) flooding free of alkali. The insertion of EO chains in combination with the replacement of carboxyl betaine by sulfobetaine is therefore very efficient for improving the properties of the double chain hydrophobic carboxyl betaines as surfactants for SP flooding free of alkali.     

Aggregation Behavior of Surface Active Dialkylimidazolium Ionic Liquids [C12C n im]Br (n = 1–4) in Aqueous Solutions

Four diakylimidazolium ionic liquids, namely 1-alkyl-3-dodecylimidazolium bromides ([C₁₂C _n im]Br) with the same dodecyl long-chain tail (C₁₂) and the short alkyl side chain (C _n , n = 1–4), were synthesized, and their molecule structures were confirmed by ESI–MS, ¹H-NMR and elemental analysis. The physicochemical properties of [C₁₂C _n im]Br (n = 1–4) were determined by means of surface tension and fluorescence probe methods, respectively. It was found that elongation of the side chain length will bring about an enhancement of surface activity. Along with the side chain length increasing, the critical micelle concentration (CMC), surface tension at CMC (γ _CMC), the maximum surface excess (Γ_m), micellar aggregation number (N _m) and micellar microenvironment polarity of [C₁₂C _n im]Br decrease, while adsorption efficiency (pC ₂₀), surface pressure at CMC (Π_CMC), the minimum molecular cross-sectional area (A _min) at air-solution interfaces and CMC/C ₂₀ ratio increase.     

Wax Ester Variation in Olive Oils Produced in Calabria (Southern Italy) During Olive Ripening

The wax ester composition of pressed olive oil and its variation during olive ripening were investigated by column chromatography/GC-on column technique. Six compounds were identified: C₃₆, C₃₈, C₄₀, C₄₂, C₄₄ and C₄₆ wax esters, which were grouped as total detected wax esters (TDWEs). The European Union (EU) includes C₄₀, C₄₂, C₄₄ and C₄₆ waxes (TEWEs) as a distinctive characteristic between different categories, with a maximum total content ≤250 mg/kg for an extra virgin olive oil. The International Olive Council (IOC) includes C₄₂, C₄₄ and C₄₆ waxes (TIOCWEs) as a purity parameter, with a maximum total content ≤150 mg/kg for an extra virgin olive oil. The analytical technique proposed by EU and IOC do not separate the wax esters from fatty acids esters with diterpenic alcohols (phytol and geranylgeraniol) that interfere with detected peaks. Although the examined cultivars were grown in the same geographical area and the same agricultural practices were applied to the trees, ANOVA analysis found significant differences among the oils extracted with the same machinery. The oil produced from the Itrana cultivar showed the lowest content in TEWEs (25.00–39.00 mg/kg) and in TIOCWEs (5.67–9.00 mg/kg). Wax content in Leccino and Pendolino cultivars showed a significant tendency to decrease during olive maturation, and a tendency to increase in all other cultivars from the first to the last harvest date when olive pigmentation changed from green to black.     

Waxes and volatile oils inHypericum ericoides (Guttiferae)

A wax isolated from an hexane extract ofHypericum ericoides L. was shown to contain only an, aldehydic and an alcoholic fraction. The aldehydic fraction was found to be largelyn-octacosanal (≈77%), with minor amounts of other linear homologous aldehydes, whereas the alcoholic fraction was almost puren-octacosanol. From the same hexane extract, a volatile oil was also isolated and studied by combined gas chromatography-mass spectrometry (GC-MS). Monoterpene, sesquiterpene and aliphatic straight chain (C₈–C₁₁) hydrocarbons, sesquiterpene alcohols and aliphatic long-chain acids (C₈, C₉, C₁₀, C₁₁, C₁₂, C₁₄, C₁₆ and C₁₈) were found. Biogenetic relationships are discussed.     

Geochemical characterization of solid residues, bitumen and expelled oil based on steam pyrolysis experiments from Irati oil shale, Brazil: A preliminary study

Steam pyrolysis experiments were performed on immature samples from the Irati oil shale, Paraná Basin, Brazil, using a maximum temperature of 350 °C with up to 98 h exposure time at that temperature. The objectives were to study geochemical and petrographical changes in the source material during stepwise increase in maturity, in steam conditions, comparing the properties of expelled oil with the bitumen retained in the solid residue after experimentation.Petrographical and geochemical parameters such as vitrinite reflectance and T_max, indicated an increase in maturity related to the exposure time of the organic matter to the maximum temperature. However, biomarker ratios such as 22S/(22S + 22R) C₃₁ and C₃₂ homohopanes, 20S/(20S + 20R) and αββ/(αββ + ααα) C₂₉ sterane, which are considered to be indicators of organic matter maturity levels, did not reach their equilibrium values. Some biomarkers frequently used as indicators of specific sources and/or paleoenvironments of deposition such as hopane/sterane ratio, and the concentrations of C₂₇ and C₂₉ steranes showed significant variations related to the stage of maturity. Based on the evaluation of Rock-Eval parameters, the transformation ratios in steam pyrolysis conditions reached levels higher than 80% in samples having 9 and more hours of exposure time to maximum temperature. Bitumen was found to be enriched in components of heavier molecular weight (resins and asphaltenes), whereas the expelled oils contained higher quantities of aliphatic and aromatic components. At relatively low maturity levels the n-alkane distribution of expelled oils indicate a somewhat higher maturity level when compared to the n-alkane distribution of the bitumen retained in the source rock, whereas at higher maturity levels the n-alkane distribution for the expelled oil and for the bitumen is very similar.     

Synthesis and Surface Tension Study of the Spacer Chain Length Effect on the Adsorption and Micellization Properties of a New Kind of Carboxylate Gemini Surfactant

A series of carboxylate gemini surfactants, which contain two hydrocarbon chains linked by amide groups, two carboxylate groups, a flexible alkane spacer were synthesized by three-step reactions and named alkylidene–bis-(N,N′-dodecyl-carboxypropylamides) (2C₁₂H₂₅CnAm; n = 2, 3, 4, 6, 8 is the number of methylene groups of the spacer), their structures were confirmed by FTIR,¹H NMR, and LC–MS/TOF, and their purity checked by HPLC. The micellar properties with increasing spacer chain length of these gemini surfactants were determined by surface tension methods. The critical micelle concentration (CMC) varies slightly with spacer chain length; surface tension at CMC(γ_CMC), the tendency of micellization versus adsorption, CMC/C₂₀, the minimum area per surfactant molecule at the air/solution interface (A_CMC), all decrease with increasing spacer chain length; surface reduction efficiency, pC₂₀, the surface excess at the air/solution interface (Г_CMC) increase with increasing spacer chain length. The results probably indicate that increasing spacer chain length of these carboxylate gemini surfactants will increase spacer incorporation into the double hydrophobic chain.     

Effect of Polyoxyethylene Chain Length on the Physicochemical Properties of N,N‐Dimethyl‐N‐dodecyl Polyoxyethylene Amine Oxide Hybrid Surfactants (C12EOnAO,with n = 1–4)

In order to determine the structure‐performance relationship of nonionic‐zwitterionic hybrid surfactants, N,N‐dimethyl‐N‐dodecyl polyoxyethylene (n) amine oxides (C₁₂EO_nAO) with different polyoxyethylene lengths (EO_n, n = 1–4) were synthesized. For homologous C₁₂EO_nAO, it was observed that the critical micelle concentration (CMC), the maximum surface excess (Γ_m), CMC/C₂₀, and the critical micelle aggregation number (N_m,c) decreased on going from 1 to 4 in EO_n. However, there were concomitant increases in surface tension at the CMC (γ_CMC), minimum molecular cross‐sectional area (A_min), adsorption efficiency (pC₂₀), and the polarity ([I₁/I₃]_m) based on the locus of solubilization for pyrene. The values of log CMC and N_m,c decreased linearly with EO_n lengthening from 1 to 4, although the impact of each EO unit on the CMC of C₁₂EO_nAO (n = 1–4) was much smaller than that typically seen for methylene units in the hydrophobic main chains of traditional surfactants. Compared to the structurally related conventional surfactant N,N‐dimethyl‐N‐dodecyl amine oxide (C₁₂AO), C₁₂EO_nAO (n = 1–4) have smaller CMC, A_min, and CMC/C₂₀, but larger pC₂₀, Γ_m, and N_m,c with a higher [I₁/I₃]_m. This may be attributed to the moderately amphiphilic EO_n (n = 1–4) between the hydrophobic C₁₂ tail and the hydrophilic AO head group.     

A Comprehensive Study on the Synthesis and Micellization of Disymmetric Gemini Imidazolium Surfactants

Two groups of disymmetric Gemini imidazolium surfactants, [C₁₄C₄C _m im]Br₂ (m = 10, 12, 14) and [C _m C₄C _n im]Br₂ (m + n = 24, m = 12, 14, 16, 18) surfactants, were synthesized and their structures were confirmed by ¹H NMR and ESI–MS spectroscopy. Their adsorption at the air/water interface, thermodynamic parameters and aggregation behavior were explored by means of surface tension, electrical conductivity and steady-state fluorescence. A series of surface activity parameters, including cmc, γ _cmc, π _cmc, pC ₂₀, cmc/C ₂₀, Γ _max and A _min, were obtained from surface tension measurements. The results revealed that the overall hydrophobic chain length (N _c) for [C₁₄C₄C _m im]Br₂ and the disymmetry (m/n) for [C _m C₄C _n im]Br₂ had a significant effect on the surface activity. The cmc values decreased with an increase of N _c or m/n. The thermodynamic parameters of micellization (ΔG _m ^θ , ΔH _m ^θ , ΔS _m ^θ ) derived from the electrical conductivity indicated that the micellization process of [C₁₄C₄C _m im]Br₂ and [C _m C₄C _n im]Br₂ was entropy-driven at different temperatures, but the contribution of ΔH _m ^θ to ΔG _m ^θ was enhanced by increasing N _c or m/n. The micropolarity and micellar aggregation number (N _agg) were estimated by steady-state fluorescence measurements. The results showed that the surfactant with higher N _c or m/n can form larger micelles, due to a tighter micellar structure.     

Effects of Olive Trees Age on the Minor Components of Oueslati Virgin Olive Oils Produced from Olives Harvested at Different Ripening Degrees

Phenolics, volatiles, squalene, tocopherols, and fatty acids of virgin olive oils (VOO) from adult and young olive trees of the Oueslati variety, typically cultivated in the Center of Tunisia, were analyzed at three different harvesting periods. Significant differences in contents of saturated fatty acids (p < 0.05), squalene (p < 0.05), alpha-tocopherol and total tocopherol (p < 0.02) and oxidized form of decarboxymethyl oleuropein aglycon (p < 0.05) were seen between VOO from adult and young trees during maturation. Moreover, the volatile profiles of VOO from adult and young trees showed significant differences in the amounts of hexanal, 1-penten-3-ol (p < 0.05), (Z)-3-hexenal and (Z)-2-penten-1-ol (p < 0.01). Principal component analysis showed that olives from adult trees should be harvested at the cherry stage of maturation to obtain a satisfactory level of oil quality, while olives from young trees should be harvested at the black maturation stage.     

Purification,Surface Tensions,and Miscibility Gaps of Alkyldimethyl and Alkyldiethylphosphine Oxides

Alkyldimethyl (C _n DMPO) with chain lengths of n = 8 (octyl), 10 (decyl), 12 (dodecyl), and 14 (tetradecyl) as well as alkyldiethyl (C _n DEPO) phosphine oxides with chain lengths of n = 10, 12, and 14 were synthesized and purified to study how the adsorption properties and the location of the miscibility gap of these surfactants depend on the size of the head group and on the length of the alkyl chain. After surfactant purification, the surface tension isotherms were determined from which the cmc, the minimum surface tension σ_cmc, the maximum surface concentration Γ_max, and the minimum surface area A _min were obtained. As expected, for one homologous series, a decrease in the cmc and an increase in Γ_max was observed with increasing alkyl chain length. For two surfactants of the same alkyl chain length, the cmc values of the C _n DEPO surfactants are approximately two times lower than those of the C _n DMPO surfactants. However, the Γ_max values of C _n DEPO are lower than those of C _n DMPO as two ethyl chains are sterically more demanding than two methyl chains. In addition to the adsorption properties, the location of the miscibility gap as a function of the alkyl chain length and the head group size was studied. Its location depends on the total number of carbon atoms and not primarily on the length of the main alkyl chain. This observation reflects the decreasing water solubility which can be tuned by increasing the length of either the main alkyl chain or of the shorter head group chains.     

Partition of <Emphasis Type="Italic">n</Emphasis>-Butanol Among Phases and Solubilization Ability of Winsor type III Microemulsions

The partition of n-butanol in Winsor type III (W-III) microemulsions was investigated in this work. Three kinds of anionic surfactants (sodium dodecyl sulfate (SDS), sodium dodecyl sulfonate (DSS), and sodium dodecyl benzene sulfonate (SDBS)) and two kinds of anionic/cationic surfactant mixtures (SDS/octadecyl trimethyl ammonium chloride (OTAC) mixtures and DSS/OTAC mixtures) were studied. Internal standard gas chromatography was employed in n-butanol content analysis. The results showed that no water exists in the excess oil (EO) phase and no oil exists in the excess water (EW) phase. For the W-III microemulsions obtained by salinity scanning, relatively constant n-butanol content in the EO (11–12 v%) and EW (1–4 v%) was found under different salinities. Accurate measurement of n-butanol content in each phase is important for those systems having low solubilization ability. For the W-III microemulsions prepared using SDS/OTAC surfactant mixture, the percentage of n-butanol distributed into the interfacial layer decreased while the fraction of n-butanol in the interfacial layer first increased sharply and then tended to be stable with the addition of n-butanol. For the different optimum W-III microemulsion systems tested, most of the surfactant-to-alcohol molar ratio data are near 1:3, but obvious deviation could be observed for some data. On the basis of the accurate measurement of n-butanol content in the EO and EW phases, the standard free energy, ΔG _o→in ^* (T = 298.15 K) of n-butanol transferring from the EO phase to the interfacial region was calculated. The results show negative ΔG _o→in ^* values. For microemulsions with the same components, n-butanol content is an important factor influencing the ΔG _o→in ^* value, and a high absolute value of ΔG _o→in ^* leads to high solubilization ability.     

Organic geochemistry of Cretaceous Lamza and Chikila coals, upper Benue trough, Nigeria

Some biomarkers and other compounds in the aliphatic and aromatic fractions of the Lamza and the Chikila coals were characterized and used in assessing the source input, maturity, hence the hydrocarbon generative potentials of the coals. The samples exhibit a slight n-alkanes odd carbon preference (CPI ∼ 1), high pristane/phytane ratios and a dominance of 20S epimer of C₂₉ sterane. The ratio of C₃₀ αβ/(αβ + βα) sterane and 22S/(22S + 22R) C₃₁-homohopane gave values of 0.77-0.83 and 0.58-0.60, respectively. The low Ts/Tm ratios are in agreement with the calculated vitrinite reflectance, R_c (0.60-0.70%). The methylphananthrenes maturity derived parameters (1-MP/9-MP; MPR; MPI-1; R_c) revealed a very slight variation and a consistent order of samples maturity with the exception of the R_c values. All these together with some other hopanoid ratios, show that the organic matter is terrestrially derived, deposited in an oxic environment and at marginal maturity for hydrocarbon generation.     

Synthesis,Surface Activities and Toluene Solubilization by Amine-oxide Gemini Surfactants

A series of amine-oxide gemini surfactants featuring amide groups [N, N’-dimethyl-N, N’-bis(2-alkylamideethyl)-ethylenediamine oxide (alkyl = C₁₁H₂₃, C₁₃H₂₇, C₁₅H₃₁, C₁₇H₃₅)] have been synthesized via a three-step synthetic route, and their chemical structures were confirmed by mass spectra, FTIR and ¹H-NMR spectra. The surface activities of these compounds have been measured. The results show that these synthesized amine-oxide gemini surfactants reduced the surface tension of water to a minimum value of approximately 26.91 mN m^?1 at a concentration of 2.92 × 10^?5mol L^?1. Furthermore, their critical micelle concentration (CMC) values and solubilization of toluene decrease with an increase of the hydrophobic chain length from 12 to 18. Isoelectric point measurements revealed that their pI values range from 4.0 to 10.5.     

Analysis of coal-derived liquid obtained by mild hydrogenation: 1. Neutral oil distilling at 186–343 °C

Taiheiyo coal (77% C) was hydrogenated under mild conditions to preserve the unit structure of the parent coal as far as possible. The n-hexane-solubles (yield, 49.8 wt% daf coal) were washed with acid and base and the neutral material separated into 7 fractions by vacuum distillation. The three lower boiling fractions, DS01 (7.3 wt% neutral oil), DS02 (3.6 wt%) and DS03 (4.8 wt%), were further separated by liquid chromatography into hydrocarbon subfractions which were analysed by g.c. and g.c.-m.s. Saturates are most abundant, especially the n-alkanes which comprise ≈9–13 wt% of each fraction. The saturates also contain isoprenoids (C₁₅, C₁₆, C₁₈, C₁₉ and C₂₀), branched alkanes, n-alkyl cyclohexanes, terpanes and others. With increasing boiling point, smaller amounts of monoaromatic ring hydrocarbons and more di- or triaromatic ring hydrocarbons are found. The alkyl side-chains of aromatic nuclei have a large carbon number, especially in the smaller rings. The existence of phenyltetralin or phenylnaphthalene shows a feature of bonding between aromatic nuclei.     

Synthesis and Structural Characterization of Triorganotin(IV) Derivatives with 2,2′-Thiodiglycolic Acid and 3,3′-Thiodipropionic Acid

The synthesis and structural characterization of four novel triorganotin(IV) complexes, {(R₃Sn)₂[C₂H₄S(COO)₂]} _n (R = Me: 1), {(R₃Sn)₄[C₂H₄S(COO)₂]₂} _n (R = nBu: 2), {(R₃Sn)₂[C₄H₈S(COO)₂]} _n (R = Me: 3; nBu: 4) were obtained by the reaction of 2,2′-thiodiglycolic acid, 3,3′-thiodipropionic acid and the corresponding R₃SnCl (R = Me, nBu) with potassium hydroxide in methanol. All the complexes were characterized by elemental analysis, Fourier transform infrared and nuclear magnetic resonance (¹H, ¹³C, ¹¹⁹Sn) spectroscopies, X-ray crystallography and thermogravimetric analyses. The crystal structures show that 1 has 2D network structure in which 2,2′-thiodiglycolic acid acts as a tetradentate ligand coordinating to the trimethyltin(IV) ions. Complexes 2, 3, and 4 are 3D metal-organic framework structures in which the deprotoned acids act as a tetradentate ligand afforded by four oxygen atoms.     

Microwave Assisted Crystal Growth of a New Organic—Decavanadate Assembly: [V10O27(OH)] · 2(C6N2H14) · (C6N2H13) · (C6N2H12) · 2H2O

Microwave synthesis was used to grow single crystals of a new organic–inorganic supramolecular assembly, [V₁₀O₂₇(OH)] · 2(C₆N₂H₁₄) · (C₆N₂H₁₃) · (C₆N₂H₁₂) · 2H₂O, in a very short time compared to the conventional solution technique. In order to generate crystals suitable for single crystal experiments, an equimolar mixture of reactants and a few hours of microwave heating are required. Although non-merohedral twinning is an inherent problem, the crystal structure can be solved and refined in the orthorhombic space group Pna2 ₁ with a = 20.972(4) Å, b = 10.3380(14) Å, c = 20.432(3) Å, Z = 4, with an excellent result, R(F²) = 0.0431. The assembly is hydrogen bond-assisted and built up of the monoprotonated decavanadate and 1,4-diazabicyclo[2.2.2]octane of various degrees of protonation. The number and location of protons on both the inorganic and organic motifs govern the formation of the extensive hydrogen bonding network, which in turn regulates the assembly architecture.     

X-ray structure and spectroscopic properties of some lanthanides(III) complexes derived from 2,6-diacetylpyridine-bis(benzoylhydrazone)

A series of trivalent lanthanide complexes of type [Ln(L) NO₃)(S)_n](NO₃)_m(S^′)_n, have been synthesized by the reaction of 2,6-diacetylpyridine-bis-(benzoylhydrazone) (H₂L) with lanthanide(III) nitrates in ethanol. These complexes have been characterized by analysis, molar conductance, magnetic measurements, infrared spectral studies and X-ray diffraction. The analytical data revealed the formation of 1:1 (metal:ligand) stoichiometry. Molar conductance in dmf gives 2:1 electrolytes in all the complexes. Magnetic moment values are close proximity of the Van Vleck values. IR study suggests the coordination of the ligand through the azomethine and the oxygen of the hydrazonic moiety. The nitrate ion is also found to be bidentate in all the complexes. The crystal structures were determined. 6, C₂₇H₃₁N₆O₇S₂Gd: a=b=8.6821(4) Å, c=84.363(5) Å, tetragonal P4₁2₁2 and Z=8. bf 7, C₂₅H₂₅N₆O₆SDy: a=11.750(3) Å, b=13.250(3) Å, c=36.000(6) Å, β=98.50(2), monoclinic, C2/c, Z=8. 9, C₂₄H₂₅N₆O₇Yb: a=10.750(2) Å, b=17.750(3) Å, c=14.250(4) Å, β=99.00(2), monoclinic, P2₁/n, Z=4. In these complexes the lanthanide ion assumes a nine coordinated geometry for Gd and an eight coordinated geometry for Dy and Yb.     

New Environmentally Friendly Oxidative Scission of Oleic Acid into Azelaic Acid and Pelargonic Acid

Oleic acid (OA) is a renewable monounsaturated fatty acid obtained from high oleic sunflower oil. This work was focused on the oxidative scission of OA, which yields a mono-acid (pelargonic acid, PA) and a di-acid (azelaic acid, AA) through an emulsifying system. The conventional method for producing AA and PA consists of the ozonolysis of oleic acid, a process which presents numerous drawbacks. Therefore, we proposed to study a new alternative process using a green oxidant and a solvent-free system. OA was oxidized in a batch reactor with a biphasic organic-aqueous system consisting of hydrogen peroxide (H₂O₂, 30 %) as an oxidant and a peroxo–tungsten complex Q₃{PO₄[WO(O₂)₂]₄} as a phase-transfer catalyst/co-oxidant. Several phase-transfer catalysts were prepared in situ from tungstophosphoric acid, H₂O₂ and different quaternary ammonium salts (Q⁺, Cl^–). The catalyst [C₅H₅N(n-C₁₆H₃₃)]₃{PO₄[WO(O₂)₂]₄} was found to give the best results and was chosen for the optimization of the other parameters of the process. This optimization led to a complete conversion of OA into AA and PA with high yields (>80 %) using the system OA/H₂O₂/[C₅H₅N(n-C₁₆H₃₃)]₃{PO₄[WO(O₂)₂]₄} (1/5/0.02 molar ratio) at 85 °C for 5 h. In addition, a new treatment was developed in order to recover the catalyst.     

Quality Characteristics and Antioxidant Activity during Fruit Ripening of Three Monovarietal Olive Oils Cultivated in China

Numerous olive cultivars have been planted in China, mainly to reap the health benefits of olive oil. This study characterized the quality and investigated the antioxidant activity of olives harvested at three different maturation stages, defined by the skin color of the olives (black, purple, and green), from three newly introduced olive cultivars (Barnea, Manzanilla and Kadesh) grown in China. The oleic acid content of olives from all three olive cultivars decreased significantly during maturation, whereas the linoleic acid content increased. The highest content of total phenols was recorded in Manzanilla cultivar (284.94 mg kg⁻¹), whereas the lowest was recorded in Kadesh cultivar (134.82 mg kg⁻¹). In addition, a total of 13 individual phenolic compounds were obtained, and their concentrations were significantly influenced by the cultivar and maturity (P < 0.05). Secoiridoids were the main group of phenolic compounds, but their quantity decreased during maturation. The content of secoiridoids in the Manzanilla cultivar was significantly higher than that of the Barnea and Kadesh cultivars. In general, a significant decrease (P < 0.05) in the values of antioxidant activity and the contents of pigments, α-tocopherol, and squalene occurred during maturation. Furthermore, principal component analysis was used to classify the nine olive oil samples according to the cultivar and ripening degree.