Quality of Biodiesel Prepared from Phorbol Ester Extracted <Emphasis Type="Italic">Jatropha curcas</Emphasis> Oil

Jatropha curcas seeds are rich in oil (28–32%), which can be converted to high quality biodiesel. The oil is non-edible due to the presence of toxic compounds, namely, phorbol esters (PEs). PEs have a number of agricultural/medicinal/pharmaceutical applications and hence their recovery generates a value added co-product towards the biodiesel production chain. This study aims to assess the effects of PE extraction on quality of both the residual oil and the biodiesel production from it. Two Approaches (1, use of an Ultra-turrax; and 2, use of a magnetic stirrer) were used with an effective treatment time of 2 and 5 min, resulting in 80 and 78% extraction of PEs, respectively. The phosphorus content was reduced by 70.2 and 75.8%, free fatty acids by 55.3 and 55.6%, and the fatty acid composition did not change in the residual oils. The peroxide value increased from 2.69 (untreated oil) to 3.01 and 3.49 mequiv O₂/kg in the residual oils following Approach 1 and Approach 2, respectively. The biodiesel prepared from both residual oils met European (EN 14214:2008) and American biodiesel standard (ASTM D6751-09) specifications. Oxidative stability indices for both the biodiesels were well within the permitted limit. It is concluded that PEs could be isolated in active forms for various applications by either of the two methods with a high yield and the residual oil can be processed to produce high quality biodiesel.     

TAG Profiles of <Emphasis Type="Italic">Jatropha curcas</Emphasis> L. Seed Oil by Easy Ambient Sonic-Spray Ionization Mass Spectrometry

Easy ambient sonic-spray ionization mass spectrometry (EASI–MS) was used to follow the maturation of Jatropha curcas L. seeds via the monitoring of the triacylglycerides (TAG) profile of the oil. Results show that TAG composition is significantly modified during seed development but remains nearly unchanged during storage. The EASI–MS oil analysis performed herein is simple, requires just a tiny droplet of the oil and is performed without any pre-separation or chemical manipulation. The oil from Jatropha gossypifolia L. was also evaluated, and a very different TAG profile was obtained.     

Phospholipid Composition of <Emphasis Type="Italic">Jatropha curcus</Emphasis> Seed Lipids

Jatropha curcus L. oil has emerged as one of the most important raw materials for biodiesel production. However, no detailed study has been reported on characterizing the lipid constituents of jatropha oil. The present study revealed that the total oil content of jatropha seeds was 32% with a composition of 97.6% neutral lipids, 0.95% glycolipids and 1.45% phospholipids. The fatty acid composition of total lipids, neutral lipids, phospholipids and glycolipids was also determined and found to contain oleic acid (18:1) and linoleic acids (18:2) as major fatty acids. The phospholipids fraction was further characterized and quantified and found to contain phosphatidyl choline (PC) 60.5%, phosphatidyl inositol (PI) 24% and phosphatidyl ethanolamine (PE) 15.5%. The fatty acid composition and the positional distribution of the fatty acids of individual phospholipids were also reported.     

Physicochemical Characteristics of Nigella Seed (<Emphasis Type="Italic">Nigella sativa</Emphasis> L<Emphasis Type="Italic">.</Emphasis>) Oil as Affected by Different Extraction Methods

The physicochemical properties of crude Nigella seed (Nigella sativa L.) oil which was extracted using Soxhlet, Modified Bligh–Dyer and Hexane extraction methods were determined. The effect of different extraction methods which includes different parameters, such as temperature, time and solvent on the extraction yield and the physicochemical properties were investigated. The experimental results showed that temperature, different solvents and extraction time had the most significant effect on the yield of the Nigella oil extracts. The fatty acid (FA) compositions of Nigella seed oil were further analyzed by gas chromatography to compare the extraction methods. The C16:0, C18:1 and C18:2 have been identified to be the dominant fatty acids in the Nigella seed oils. However, the main triacylglycerol (TAG) was LLL followed by OLL and PLL. The FA and TAG content showed that the composition of the Nigella seed oil extracted by different methods was mostly similar, whereas relative concentration of the identified compounds were apparently different according to the extraction methods. The melting and crystallization temperatures of the oil extracted by Soxhlet were −2.54 and −55.76 °C, respectively. The general characteristics of the Nigella seed oil obtained by different extraction methods were further compared. Where the Soxhlet extraction method was considered to be the optimum process for extracting Nigella seed oil with a higher quality with respect to the other two processes.     

Dynamic Analysis of Phorbol Esters in the Manufacturing Process of Fatty Acid Methyl Esters from <Emphasis Type="Italic">Jatropha curcas</Emphasis> Seed Oil

Jatropha curcas seed oil, which is unsuitable as an edible oil but has received attention as a novel vegetable fat and oil resource, contains tumor-promoting phorbol esters. Currently, six types of derivatives of 12-deoxy-16-hydroxyphorbol (DHPEs) in J. curcas oil have been identified, and their toxicological safety for humans is being discussed. However, it is reported that most DHPEs disappear during the transesterification process. We investigated the dynamics of phorbol esters in the manufacturing process of fatty acid methyl esters from J. curcas seed oil. With the assumption that the precursor ion was the fragment ion (m/z = 311) from the frame unit of phorbol esters and their derivatives, we developed an LC–MS method for detecting the product ion (m/z = 165), which was obtained by cleavage of the fragment ion. The derivatives generated from the structural changes of the phorbol esters existed in fractions of glycerine–water in the manufacturing process; however, phorbol esters and their derivatives were not detected in the fatty acid methyl esters that were produced via a high-vacuum distillation process. Investigation into the dynamics of phorbol esters confirmed that the contents of phorbol esters, including DHPEs, in the fatty acid methyl esters were under detection limits.     

Removal and Degradation of Phorbol Esters during Pre-treatment and Transesterification of <Emphasis Type="Italic">Jatropha curcas</Emphasis> Oil

Phorbol esters present in Jatropha curcas oil are toxic when consumed and are co-carcinogens. These could be a potential constraint in the widespread acceptance of Jatropha oil as a source of biodiesel. Phorbol esters were quantified in the fractions obtained at different stages of oil pre-treatment and biodiesel production. During degumming some phorbol esters were removed in the acid gums and wash water. This implies that the use of these acid gums in animal feed is not possible and care should be taken when disposing the wash water into the environment. Silica treatment did not decrease the phorbol esters, while stripping/deodorization at 260 °C at 3 mbar pressure with 1% steam injection completely degraded phorbol esters. Phorbol esters were not detected in stripped oil, fatty acid distillate, transesterified oil (biodiesel) and glycerine. The presence of possibly toxic phorbol ester degradation products in these fractions could not be ruled out.     

Chemical Composition and Nutritional Characteristics of the Seed Oil of Wild <Emphasis Type="Italic">Lathyrus</Emphasis>, <Emphasis Type="Italic">Lens</Emphasis> and <Emphasis Type="Italic">Pisum</Emphasis> Species from Southern Spain

The fatty acid composition of the seed oil of 19 wild legume species from southern Spain was analyzed by gas chromatography. The main seed oil fatty acids ranged from C_14:0 to C_20:0. Among unsaturated fatty acids, the most abundant were linoleic, oleic and linolenic acids, except for Lathyrus angulatus, L. aphaca, L. clymenum, L. sphaericus and L. nigricans where C_18:3 contents were higher than C_18:1 contents. Palmitic acid was the most abundant saturated acid in studied species, ranging from 11.6% in Lathyrus sativus to 19.3% in Lens nigricans. All studied species showed higher amounts of total unsaturated fatty acids than saturated ones. Among studied species, the ω6/ω3 ratio was variable, ranging from 2.0% in L. nigricans to 13.8% in L. sativus, there being eight species in which the ω6/ω3 ratio was below 5. The fatty acids observed in these plants supports the use of these plants as a source of important dietary lipids.     

Formation and Phase Behavior of Winsor Type III <Emphasis Type="Italic">Jatropha curcas</Emphasis>-Based Microemulsion Systems

The formation and phase behavior of Jatropha curcas-based microemulsion systems, which could potentially be used in enhanced oil recovery applications, has been investigated. Winsor type III microemulsions were obtained by adding n-octane to Winsor type I microemulsion systems prepared using various concentrations of alkyl polyglucoside (APG). To optimize the formulation of type III microemulsion systems, five different types of co-surfactants, i.e. normal butyl alcohol (NBA), isobutyl alcohol, isopropyl alcohol, fatty acid alcohol C8 (FAC8) and fatty acid alcohol C8/C10 (FAC8/C10) were used. The microemulsion phase behavior was determined along with particle size distributions by dynamic light scattering measurements. Results show that the optimum Winston type III system can be achieved by mixing 3 wt% of NBA, 1 wt% APG and 3 wt% NaCl. At the optimum formulation, the IFT reached a minimum value (0.016 mN/m) and formed very small emulsion droplets with a narrow particle size distribution.     

<Emphasis Type="Italic">Santalum </Emphasis><Emphasis Type="Italic">insulare</Emphasis> Acetylenic Fatty Acid Seed Oils: Comparison within the <Emphasis Type="Italic">Santalum</Emphasis> Genus

The sandalwood kernels of Santalum insulare (Santalaceae) collected in French Polynesia give seed oils containing significant amounts of ximenynic acid, E-11-octadecen-9-oic acid (64–86%). Fatty acid (FA) identifications were performed by gas chromatography/mass spectrometry (GC/MS) of FA methyl esters. Among the other main eight identified fatty acids, oleic acid was found at a 7–28% level. The content in stearolic acid, octadec-9-ynoic acid, was low (0.7–3.0%). An inverse relationship was demonstrated between ximenynic acid and oleic acid using 20 seed oils. Results obtained have been compared to other previously published data on species belonging to the Santalum genus, using multivariate statistical analysis. The relative FA S. insulare composition, rich in ximenynic acid is in the same order of those given for S. album or S. obtusifolium. The other compared species (S. acuminatum, S. lanceolatum, S. spicatum and S. murrayanum) are richer in oleic acid (40–59%) with some little differences in linolenic content.     

Physicochemical Properties of Garden Cress (<Emphasis Type="Italic">Lepidium sativum</Emphasis> L.) Seed Oil

Garden cress (Lepidium sativum L.) is an edible, underutilised herb, grown mainly for its seeds in India. Physicochemical properties, minor components (unsaponifiable matter, tocopherols, carotenoids), fatty acid composition and storage stability of garden cress seed oil (GCO) were studied. Cold press, solvent and supercritical CO₂ extraction methods were employed to extract the oil. The total oil content of garden cress (GC) seeds was 21.54, 18.15 and 12.60% respectively by solvent, supercritical CO₂ and cold press methods. The physical properties of GCO extracted by the above methods were similar in terms of refractive index, specific gravity and viscosity. However, cold pressed oil showed low PV and FFA compared to the oil extracted by other methods. α-Linolenic acid (34%) was the major fatty acid in GCO followed by oleic (22%), linoleic (11.8%), eicosanoic (12%), palmitic (10.1%) erucic (4.4%), arachidic (3.4%) and stearic acids (2.9%). Oleic acid (39.9%) and α-linolenic acid (42.1%) were the predominant fatty acids at the sn-2 position. The total tocopherol and carotenoid content of GCO was 327.42 and 1.0 μmol/100 g oil, respectively. The oil was stable up to 4 months at 4 °C. Tocopherol and BHT offered the least protection, while ascorbyl palmitate (200 ppm) offered the maximum protection to the oil, when subjected to the accelerated oxidative stability test. Thus GCO can be considered as a fairly stable oil with a high content of α-linolenic acid.     

Potential of <Emphasis Type="Italic">Jatropha curcas</Emphasis> as a Biofuel,Animal Feed and Health Products

Jatropha curcas is a multipurpose plant with numerous attributes. It can potentially become one of the world’s key energy crops. Its seed weighs 0.53–0.86 g and the seed kernel contains 22–27% protein and 57–63% lipid indicating good nutritional value. The seeds can produce crude vegetable oil that can be transformed into high quality biodiesel. Several methods for oil extraction have been developed. In all processes, about 75% of the weight of the seed remains as a press cake containing mainly carbohydrates, protein and residual oil and is a potential source of livestock feed. The highly toxic nature of whole as well as dehulled seed meal due to the presence of high levels of shells, toxic phorbol esters and other antinutrients prevents its use in animal diet. The genetic variation among accessions from different regions of the world and rich diversity among Mexican genotypes in terms of phorbol ester content and distinct molecular profiles indicates the potential for improvement of germplasm of Jatropha through breeding programs. The extracts of Jatropha display potent cytotoxic, antitumor, anti-inflammatory and antimicrobial activities. The possibilities on the exploitation potential of this plant through various applications have been explored.     

Synthesis,Characterization and Properties of <Emphasis Type="Italic">N</Emphasis>-Alkyl-<Emphasis Type="Italic">N</Emphasis>,<Emphasis Type="Italic">N</Emphasis>-di(2-hydroxyethyl) Amine Oxides

N‐Dodecyl‐N,N‐di(2‐hydroxyethyl) amine oxide (C₁₂DHEAO) and N‐stearyl‐N,N‐di(2‐hydroxyethyl) amine oxide (C₁₈DHEAO) were synthesized with N‐alkyl‐diethanolamine and hydrogen peroxide. Their chemical structures were confirmed using ¹H‐NMR spectra, mass spectral fragmentation and FTIR spectroscopic analysis. It was found that C₁₂DHEAO and C₁₈DHEAO reduced the surface tension of water to a minimum value of approximately 28.75 mN m^?1 at concentration of 2.48 × 10^?3 mol L^?1 and 32.45 mN m^?1 at concentration of 5.21 × 10^?5 mol L^?1, respectively. The minimum interfacial tension (IFT_min) and the dynamic interfacial tension (DIT) of oil–water system were measured. When C₁₈DHEAO concentration was in the range of 0.1–0.5%, the IFT_min between liquid paraffin and C₁₈DHEAO solutions all reached the ultra‐low interfacial tension. Furthermore, their foam properties were investigated by Ross‐Miles method, and the height of foam of C₁₂DHEAO was 183 mm. It was also found that they showed strong emulsifying power.     

Preparation and Evaluation of Biodiesel from <Emphasis Type="Italic">Sterculia foetida</Emphasis> Seed Oil

Sterculia foetida oil contains cyclopropene fatty acids namely 8,9-methylene-heptadec-8-enoic acid (malvalic) and 9,10-methylene-octadec-9-enoic acid (sterculic) to an extent of 50–55%. The present study reports the preparation of biodiesel from S. foetida oil using sodium hydroxide as catalyst. The resultant biodiesel was evaluated for physico-chemical properties namely iodine value (72.6), free fatty acids (0.17%), phosphorous content (0 ppm), flash point (179 °C), cloud point (3 °C), pour point (3 °C), viscosity at 40 °C (4.72 cSt), oxidative stability at 110 °C (3.42 h), density (0.850 g/cm³ at 15 °C), and trace metals (Group I metals 0.21 ppm). The properties were compared with that of sunflower, soybean and rapeseed oil-based biodiesels and found to be comparable except for the pour point.     

Electrosynthesis of nitroso compounds from (<Emphasis Type="Italic">1</Emphasis><Emphasis Type="Bold">S</Emphasis>, <Emphasis Type="Italic">2</Emphasis><Emphasis Type="Bold">S</Emphasis>)-2-amino-l-(4-nitrophenyl)-propane-1,3-diol derivatives

Nitroso compounds were electrogenerated from (1S, 2S)-2-amino-1-(4-nitrophenyl)-propane-1,3-diol derivatives (derivatives of p-nitrophenylserinol) in a “redox” flow cell equipped with two consecutive porous electrodes of opposite polarities. In spite. of the relative instability in methanol-acetate buffer of the hydroxylamine intermediates produced at the first porous electrode (cathode), the nitroso derivatives were prepared in good yields at the second one (anode). A coupling reaction between some nitroso derivatives and p-toluenesulphinic acid led to N-sulphonylphenylhydroxylamines.     

Seed oil composition of <Emphasis Type="Italic">Paullinia cupana</Emphasis> var. <Emphasis Type="Italic">sorbilis</Emphasis> (Mart.) Ducke

The chemical composition of the oil extracted from the seeds of Paullinia cupana var. sorbilis (Mart.) Ducke (syn. P. sorbilis) was investigated. Cyanolipids constituted 3% of the total oil from guaraná seeds, whereas acylglycerols accounted for 28%. ¹H and ¹³C NMR analyses indicated that type 1 cyanolipids (1-cyano-2-hydroxymethylprop-2-ene-1-ol diesters) are present in the oil from P. cupana. GC and GC-MS analysis showed that cis-11-octadecenoic (cis-vaccenic acid) and cis-11-eicosenoic acids were the main FA (30.4 and 38.7%) esterified to the nitrile group. Paullinic acid (7.0%) was also an abundant component. Oleic acid (37.4%) was the dominant fatty acyl chain in the acylglycerols.     

Identification of Crepenynic Acid in the Seed Oil of <Emphasis Type="Italic">Atractylodes lancea</Emphasis> and <Emphasis Type="Italic">A. macrocephala</Emphasis>

Atractylodes rhizome is widely used in traditional Chinese herbal medicine. Although the chemical composition of the root has been studied in detail, the oil content and fatty acid composition of the seeds of Atractylodes species have not been reported. Fatty acyl composition of seeds from Atractylodes lancea and A. macrocephala was determined by gas chromatography and mass spectrometry of fatty acid methyl esters and 3-pyridylcarbinol esters. The predominant fatty acid in the seeds of both species was linolenic acid, but the unusual acetylenic fatty acid, crepenynic acid (cis-9-octadecen-12-ynoic acid), was also observed at levels of 18% in A. lancea and 13–15% in A. macrocephala. Fatty acid content was 24% for the samples of A. lancea and 16–17% for samples from A. macrocephala. sn-1,3 regioselective lipase digestion of seed lipids revealed that crepenynic acid was absent from the sn-2 position of the seed triacylglycerol. Crepenynic acid was also found in the seed oil of Jurinea mollis at 24% and was not present in the sn-2 position of the TAG. A contrasting distribution of crepenynic acid was found in the oil of Crepis rubra, suggesting differences in crepenynic acid synthesis or TAG assembly between these species.     

Parameters for optimization of coke quality (<Emphasis Type="Italic">CRI</Emphasis> and <Emphasis Type="Italic">CSR</Emphasis>)

Experimental data illustrate the diversity of ash composition in Russian coal, even within a single rank. Examples show that the ash basicity may be used for effective optimization of the coking-batch composition by basin, rank, and components, in improving the CRI and CSR values of coke.     

Physicochemical Properties of <Emphasis Type="Italic">Acer truncatum</Emphasis> Seed Oil Extracted Using Supercritical Carbon Dioxide

Acer truncatum seed oil rich in nervonic acid was extracted using supercritical carbon dioxide. GC (Gas Chromatography) analysis revealed that the oil contained approximately 6.22% nervonic acid. The sn‐2 compositions were also determined using lipase hydrolysis. A total of 52 triacylglycerides (TAG) were tentatively identified in the oil using an ultra‐performance convergence chromatography (UPC²) coupled with quadrupole time‐of‐flight mass spectrometry (Q‐TOF‐MS) for the first time. In addition, the contents of phytosterols (1961.9–2402.8 μmol/kg) and β‐carotene (2.09–2.35 μmol/kg) were also quantified for the first time, along with tocopherols (2352.0–2654.3 μmol/kg). The γ‐tocopherol (1296.9‐1442.3 μmol/kg) was the primary tocopherol, while β‐sitosterol (1355.2–1631.3 μmol/kg) was the dominant phytosterol. The physicochemical properties of the oil were also investigated. This study indicated that A. truncatum seed oil is rich in nervonic acid and other nutraceutical constituents. It has a high potential in functional foods for improving human health.     

Effects of Root Isoquinoline Alkaloids from <Emphasis Type="Italic">Hydrastis canadensis</Emphasis> on <Emphasis Type="Italic">Fusarium oxysporum</Emphasis> Isolated from <Emphasis Type="Italic">Hydrastis</Emphasis> Root Tissue

Goldenseal (Hydrastis canadensis L.) is a popular medicinal plant distributed widely in North America. The rhizome, rootlets, and root hairs produce medicinally active alkaloids. Berberine, one of the Hydrastis alkaloids, has shown antifungal activity. The influence of a combination of the major Hydrastis alkaloids on the plant rhizosphere fungal ecology has not been investigated. A bioassay was developed to study the effect of goldenseal isoquinoline alkaloids on three Fusarium isolates, including the two species isolated from Hydrastis rhizosphere. The findings suggest that the Hydrastis root extract influences macroconidia germination, but that only the combined alkaloids—berberine, canadine, and hydrastine—appear to synergistically stimulate production of the mycotoxin zearalenone in the Fusarium oxysporum isolate. The Hydrastis root rhizosphere effect provided a selective advantage to the Fusarium isolates closely associated with the root tissue in comparison with the Fusarium isolate that had never been exposed to Hydrastis.     

(1<Emphasis Type="Italic">S</Emphasis>,3<Emphasis Type="Italic">R</Emphasis>)-<Emphasis Type="Italic">cis</Emphasis>-Chrysanthemyl Tiglate: Sex Pheromone of the Striped Mealybug, <Emphasis Type="Italic">Ferrisia virgata</Emphasis>

Derivatives of 2,2-dimethyl-3-(2-methylprop-1-enyl)cyclopropanecarboxylic acid (chrysanthemic acid) are classic natural pyrethroids discovered in pyrethrum plants and show insecticidal activity. Chrysanthemic acid, with two asymmetric carbons, has four possible stereoisomers, and most natural pyrethroids have the (1R,3R)-trans configuration. Interestingly, chrysanthemic acid–related structures are also found in insect sex pheromones; carboxylic esters of (1R,3R)-trans-(2,2-dimethyl-3-(2-methylprop-1-enyl)cyclopropyl)methanol (chrysanthemyl alcohol) have been reported from two mealybug species. In the present study, another ester of chrysanthemyl alcohol was discovered from the striped mealybug, Ferrisia virgata (Cockerell), as its pheromone. By means of gas chromatography–mass spectrometry, nuclear magnetic resonance spectrometry, and high-performance liquid chromatography analyses using a chiral stationary phase column and authentic standards, the pheromone was identified as (1S,3R)-(?)-cis-chrysanthemyl tiglate. The (1S,3R)-enantiomer strongly attracted adult males in a greenhouse trapping bioassay, whereas the other enantiomers showed only weak activity. The cis configuration of the chrysanthemic acid–related structure appears to be relatively scarce in nature, and this is the first example reported from arthropods.