L. Pisonis Nut Oil Extraction

L. Pisonis Nut Oil Extraction The search for new crops to provide vegetable oils for use in the industry and also for human consumption is growing increasingly over the past two decades. A rapid search on Web of Science„ ¢ platform present more than 19200 results related to nuts, more than 7600 documents are related to edible oils, and more than 22000 results associated with vegetable oil. Additionally, the published items regarding vegetable oil increased from 282 in 1996, to more than 1930 in 2016 proving the growing interest by the scientific community in such field of study [1]. Several Brazilian seeds/nuts species, especially from the Amazonian area have been studied during the last years and most of them were shown to present bioactive compounds and also potential as functional foods [2]-[7]. Nevertheless, some other species are not well-known or were not summited to any further study to elucidate other characteristics. Lecythis pisonis Camb., a Lecythydaceae tree that grows in Brazil, Colombia, Venezuela and in the Guyanas, commonly known as sapucaia provide nuts particularly similar with that of Brazil nut (Bertholletia excelsa). The delicious edible kernels of sapucaia present a characteristic sweet flavor, being considered more digestible than Brazil nut [8]. In addition to the economic and ecological importance of sapucaia, often used to shade cocoa plantations in Brazilian agroforestry systems [9], the nuts from L. pisonis are a valuable source of macro and micronutrients, essential amino acids, minerals such as P, K, S, Mg, Ca, Mn, Ba, Zn, Fe, Sr, Cu, B, Al, and Cl [3], [10], and also fibers [11]. Furthermore, the sapucaia nuts constitute a relevant source of lipids, about 51-64% [5], [8], [10], [11], in which there is a predominance of the linoleic acid (essential fatty acid). Although sapucaia can be considered a potential crop to provide raw material for the production of vegetable oil, the available papers that studied the nuts have mostly focused on the mineral and fatty acid profile [3], [5], [10], [12], [13], and the latest reports are limited to some agronomic, microbial and pharmacological aspects [9], [14]-[17]. Vegetable oils are widely utilized in many applications such as food, cosmetic, pharmaceutics, and biofuel industries. Consequently, stability tests, rheological essays, phase transitions and other properties of the oils should be well characterized to optimize processing conditions and energy inputs [18], [19]. No reference has been found regarding the total phenolic compounds, antioxidant activity, thermal and rheological characterization of sapucaia nut oil. Therefore, the aim of this work was to study the sapucaia nut oils extracted by Soxhlet and Bligh Dyer means and evaluated for their fatty acid composition, rheological behavior, and thermal properties by using DSC and TG/TGA analysis, total phenolic content, antioxidant properties and oxidative stability by Rancimat in addition to Attenuated Total Reflectance-Fourier transform infrared spectroscopy (ATR-FTIR). 2.1 Chemicals Other reagents used in the experiments were of analytical grade. The aqueous solutions were prepared using ultrapure water. 2.2 Samples Lecythis pisonis nuts were harvest from a crop area located in the city of Araguanà £, Maranhà £o State, Brazil. The nuts (Fig. 1) were dried in an air-circulating oven (Soc. Fabbe, Brazil) at 40  °C for 24 h. Nutshells were removed manually using a stainless steel knife and then submitted to freeze-drying (Liotop L101, Liobras, Brazil) to remove the residual moisture. Prior to the oil extraction, the nut samples were crushed for 30 s with the aid of a stainless steel knife grinder (MA630/1 Marconi Ltda., Brazil). 2.3 Extraction of nuts oils The oil content of L. pisonis nut samples was extracted by the Bligh Dyer method described in AOCS Ba 3-38 method, and also using n-hexane with Soxhlet apparatus (Vidrolabor ®, Labor Quimi, Brazil) according to American Oil and Chemical Society Official Method (1997). Oils were named LP1 and LP2, respectively. After the oil extraction, solvents were removed at 43  °C under reduced pressure using a rotary evaporator (Model 801, Fisatom Ltda., Brazil). Samples were dried at 45  °C in an air circulating oven (Solab, Brazil) and then flushed with gaseous N2 before storage. The oils were kept in an amber glass and stored at -10  °C until further analysis. 2.4 Analytical determinations 2.4.1 Water content and apparent pH Water content was measured by volumetric Karl Fischer titration using a titration system (V30 Mettler-Toledo, Switzerland) [21]. The determination of the pH was performed according to Pena Muniz et al. (2015), as recommended by the Brazilian National Agency for Sanitary Surveillance without previous dilution of the oil, with the aid of a digital pH meter (Model PG1800 Gehaka) at 25  ± 2  °C. The results represent the mean of three measurements. 2.4.2 Measurement of fatty acid composition Fatty acid composition of fresh L. pisonis oils was investigated according to AOCS Official Method Ce 1a-13 [20] by using a GC-MS system (GC-2010) coupled to a mass spectrometer (GCMS-TQ8030) and automatic injection system by headspace (Shimadzu, Japan). Oil samples solubilized with hexane were methylated as described by AOCS Ce 2-66 and then injected into a capillary HP88 column (60 m ÃÆ'- 0.250 mm i.d., 0.2 ÃŽÂ ¼m film thickness, Agilent Technologies) using helium as carrier gas (0.64 mL/min). Oven temperature was programmed to be 175  °C (isothermal) and the detector was held at 250  °C. An aliquot of 1 ÃŽÂ ¼L of the sample was injected using the split injection mode (1:100). Fatty acid composition was expressed as the percentage of the total peak area of all the fatty acids in the oil sample. 2.4.3 Rheological studies Rheological measurements of oils were performed according to Teixeira et al. (2016), by using a Haake Mars II (Thermo Electron GmbH, Germany) rheometer connected to a thermostatic bath (Haake K15), a thermo-circulator water unit (Haake DC5B3) and a Peltier temperature control (Haake UTM Controller). A sensor cone-plate (C60/2  °Ti L) with a diameter of 60 mm and a cone angle of 2  ° was used. Samples remained in the rheometer for 5 min prior to analysis, and sampling was carried out in duplicate. The following measurements were performed: i) flow curve ( = 0.01-500 s-1, t = 300 s); ii) dynamic stress sweep (à Ã¢â‚¬Å¾ = 0.01-100 Pa, à Ã¢â‚¬ ° = 1 Hz) and subsequent dynamic frequency sweep (à Ã¢â‚¬ ° = 0.1-100 Hz, à Ã¢â‚¬Å¾ = 1.0 Pa); and iii) temperature sweep (T = 10-60  °C, t = 1440 s, 2  °C/min and 60-10  °C, t = 600 s, 5  °C/min; à Ã¢â‚¬ ° = 1 Hz, à Ã¢â‚¬Å¾ = 1.0 Pa). Temperature sweeps were performed at a constant tension of 0.5% in the Linear Viscoelastic Region (LVR). The samples were covered by using a sample hood in order to avoid interference of the ambient temperature. The coefficient of determination (R2) and chi-square (à Ã¢â‚¬ ¡2) were chosen to evaluate the fit of the Ostwald-de Waele (Eq. (1)) and Herschel-Bulkley (Eq. (2)) models to the experimentally obtained flow curves: Ostwald-de Waele (OW) (1) à Ã¢â‚¬Å¾ = + ()nH Herschel-Bulkley (HB) (2) where à Ã¢â‚¬Å¾ is the shear stress (Pa), is the shear rate (s-1), à Ã¢â‚¬Å¾0H is the HB yield stress (Pa), K and KH are the consistency index (Pa ·sn), and n and nH are the flow behavior indexes (dimensionless). The effect of the temperature on apparent viscosity was evaluated according to an Arrhenius type equation (Eq. (3)), using a shear rate of 53.4 s-1. (3) where is the apparent viscosity at a specific shear rate, is the preexponential factor, is the activation energy (J.mol-1), is the gas constant (8.31 J. K-1 . mol-1) and is the absolute temperature (K). 2.4.4 Oxidative Stability Index The oxidative stability index (OSI) was estimated in a Metrohm Rancimat model 743 (Herisau, Switzerland), following the American Oil Chemists Society Official Method Cd 12b-92 [20]. Briefly, increasing water conductivities were continually measured while air (20 L/h) was bubbled into the oil (3  ± 0.1 g) heated to 110  °C and their volatile compounds were collected in water. The time taken to reach the conductivity inflection time was recorded. IP was registered by Rancimat 743 PC Software 1.1. 2.4.5 Infrared spectroscopy Fourier transform infrared spectroscopy (FTIR) analyses were determined by using a Vertex-70 spectrometer (Bruker, USA) with an attenuated total reflectance (ATR) accessory, at 25  °C. The oil samples were placed uniformly in the ATR crystal (1.5 mm active area). The FTIR spectra were recorded in the wavenumber range of 4000 to 600 cmˆ’1 with a spectral resolution of 4 cmˆ’1 [23]. 2.4.6 TG-TGA Thermal decomposition TGA analyses were performed in TGA 4000 equipment (PerkinElmer Inc. Waltham, USA). Oil sample (~10 mg) was placed into the platinum pan and then placed in a furnace. The sample was heated from 30 to 750  °C (10  °C/min) in the air atmosphere (70 mL/min flow rate) or under a nitrogen atmosphere. Data on the weight changes of oil samples were obtained from the Pyris„ ¢ software. TG and derivative thermogravimetric (DTG) curves were further analyzed by using Origin 8.6 software (OriginLab, Massachusetts, USA). The thermal stability was measured from the extrapolated onset temperature of the first step of thermal decomposition from respective TG curves, by using the beginning and the peak temperature of the respective DTG peak, as the temperature limits of the data analysis software of the instrument. 2.4.7 DSC Analysis For DSC analysis, a DSC 8500 (PerkinElmer Inc. Waltham, USA) equipped with Pyris„ ¢ software was used. Nitrogen (99.99% purity, White Martins, Brazil) was the purge gas (20 mL/min). The DSC instrument was previously calibrated with Indium (m.p. 156.6  °C, ΆH = 28.45 J/g). The sample was weighed into an aluminum pan and sealed. An empty hermetically sealed aluminum sample pan was used as the reference. In order to reduce temperature gradients, the sample mass was kept small (~ 9.0 mg). The methodology applied was adapted from Zhang et al. (2013). For cooling and melting curves, the samples were first rapidly heated to 80  °C (30  °C/min) from room temperature and held for 10 min. Then, the samples were cooled to ˆ’80  °C (10  °C /min) and held for 10 min to make them fully crystallized, then heated to 80  °C (5  °C /min). To study the effect of the cooling rate on crystallization, samples were rapidly heated to 80  °C (30  °C/min) from room temperature to erase the crystallization memory, and held for 5 min, then the samples were cooled to ˆ’80  °C at the cooling rates of 2  °C/min, 5  °C/min and 10  °C/min, respectively. The cooling thermogram was recorded. For investigating melting profile of L. pisonis oils under isothermal crystallization, the samples were heated at 80  °C (30  °C/min) for 5 min and then cooled (100  °C/min) to a preset temperature (ˆ’10  °C, 0  °C, 10  °C, 20  °C), and hold at that temperature for 10 min for crystallization, then heated to 80  °C (5  °C/min). The melting thermogram was recorded. Pyris„ ¢ manager software was used to calculate the parameters of crystallization and melting, enthalpies, and the solid fat content (SFC) which was estimated based on the integrated area under the melting curve [25]. To measure the cloud point of the oils, the cooling curves at the rate of 2  °C/min were used. The cloud point was the onset temperature of the initial small exothermic peak on these cooling curves [26]. 2.4.8 Total phenolic compounds Contents of the total phenolic compounds (TPC) were determined using the Folin-Ciocalteu reagent assay in methanolic extracts of vegetable oils [27]using microplates technique [28],with gallic acid as a standard for the calibration curve. The absorbance at 720 nm was measured using a spectrophotometer (Tecan Nanoquant Infinite ® M200, Tecan Trading AG, Switzerland) after reaction with the Folin-Ciocalteu reagent in the alkaline medium stand in the dark for 1 h. Contents of the TPC were expressed in mg of gallic acid equivalents (GAE)/100 g of oil. 2.4.9 Antioxidant essays of the oil extracts The free radical scavenging evaluated by the DPPH assay was determined in triplicate using the method proposed byBrand-Williams et al., (1995). The absorbance at a wavelength of 517 nm was measured using a spectrophotometer (Tecan Nanoquant Infinite ® M200, Tecan Trading AG, Switzerland). ABTS scavenging activity of oil extracts was determined in triplicate using the method described by Re et al., (1999). The absorbance at 734 nm was measured. The total antioxidant potential of the oil extracts was performed using the ferric reducing antioxidant power (FRAP) assay [31]. Measurements were performed using the spectrophotometer at 593 nm. The absorbance of the samples was compared to a standard curve (100-1000  µmol/L) and results expressed in mmoL Trolox equivalent per g of oil [mmol TE/g]. All the essays had minor changes as proposed by Zielinski et al., (2016). The determinations were performed in triplicate. 2.5 Data analysis Origin 8.6 software (OriginLab, Massachusetts, USA) was employed to data treatment and graphs. Statistica 10.0 (Statsoft, Brazil) was used for statistical analysis, including means and standard deviations (SD). The experiments were carried out in triplicate. 3.1 Water content and apparent pH As expected for this type of raw material, sapucaia (Lecythis pisonis) oil (SO) samples presented very low water content, to be specific 0.077  ± 0.006 %, and 0.097  ± 0.006 % for LP1 and LP2, respectively. Regarding the apparent pH of SO, LP1 presented 5.720  ± 0.036 and LP2 showed a pH value of 5.353  ± 0.040. 3.2 Phenolic compounds and antioxidant properties Concerning the content of phenolic compounds in SO, LP1 presented higher TPC content than LP2(Table 1). In this regard, SO present greater TPC content (1.418 mg GAE/100 g, average value) than almond oil (0.95 mg GAE/100 g), however, Brazil nut has twice the content of TPC (3.64 mg GAE/100 g) than sapucaia, and macadamia presents fifteen times more TPC (22.5 mg GAE/100 g) [33]. In general terms, the sample LP1 obtained by a cold extraction process showed better antioxidant characteristics than LP2. Natural antioxidants that might prevent biological systems from reactive oxygen species are generally present in vegetable oils as phenolic compounds, phytosterols, tocopherols (Vitamin E) and carotenoid compounds [34]. The results found by in vitro antioxidant assays present some variations that might be assigned to the different mechanisms in the analysis (Table 1). These assays are grouped in the electron-transfer category and there is some specificity among them. DPPH and ABTS radical cations have the same mechanism and present characteristic color which can be monitored by a spectrophotometer when the oil extract is mixed with a reactant solution and the reduced form of the radical shows a loss of color as a result of the donation of a hydrogen atom. Similarly, in the presence of antioxidants compounds, FRAP is characterized by electron transfer ability, tha t results in the reduction of iron ions [35] 3.3 Fatty acids profile Fourteen different fatty acids (FA) were identified in the studied SO (Table 2). The oils were composed predominantly of unsaturated fatty acids (UFA) (61-73%), in which 39.08-45.66% were monounsaturated (MUFA), and 21.95-27.63% were comprised of polyunsaturated (PUFA), such as linoleic and ÃŽÂ ±-linolenic acids, which have been proved to effectively reduce the risk of cancer, osteoporosis, cardiovascular diseases, and diabetes [36]. Such FA profile is rather common for Brazilian edible nuts [5], [37], which reinforces the idea of consuming more nuts rich in fatty acids beneficial to human health, since the main commercial source of PUFA, such as à Ã¢â‚¬ °-3 and à Ã¢â‚¬ °-6 has been fish and fish fat [36]. Among the MUFAs, oleic was the major FA found in SO, ranging from 35.54-44.28% for LP2, and LP1, respectively. Important to note that oleic acid is the primary à Ã¢â‚¬ °-9 FA in the human diet, and it is the predominant MUFA in many oil nuts, totalizing, for example 38.50% in Brazil nut (Bertholletia excelsa) [22], 65.59% in garampara (Dipteryx lacunifera) [5], 67.62% in tucumà £ (Astrocaryum vulgare Mart.) and 39.04% in cutia nut (Couepia edulis) [37]. Besides, the SO presented 21.65-27.19% of linoleic acid, an essential FA which presence in reasonable amounts is important for human health [38]. SO also contains two important cis-MUFA, the cis-Vaccenic and cis-11-Eicosenoic in amounts higher than 1.0%. With regard to the saturated fatty acids (SFA), it is noticed that they represented 25.01-37.25% of total FA, mainly palmitic (14.70-21.38%) and stearic (9.63-11.09%); likewise, other SFA such as myristic, heptadecanoic, and behenic were identified in smaller amounts. Arachidic acid, which is usually present in peanut oil was also found in SO in small quantities and the result is in agreement with Costa and Jorge (2012) who found about 0.22% C20:0 for L. pisonis oil. A similar pattern occurs for Brazil nut, which shows 0.36% arachidic acid, and 14.26% palmitic acid [22]. A good factor to evaluate the quality and digestibility of a vegetable oil can be obtained by the amount and composition of UFA and SFA. A high amount of linoleic acid in comparison to oleic acid (à Ã¢â‚¬ °-9) represents a better quality of the vegetable oil [5]. In this regard, the relationship between linoleic/oleic acids should be considered. The oils can present diverse values for this relationship depending on the extraction method. According to Table 3, the UFA/SFA ratio, as well as the linoleic/oleic ratio for sapucaia oils are lower to those found by [5] and [10], once their oils showed higher content of linoleic acid (Table 2). When compared to other Brazilian oleaginous nuts such as Brazil nut, garampara [5], and cutia nut [37] the unsaturation relationship values between linoleic and oleic acid were also quite different. 3.4 Oxidative Stability Index The oxidative stability index (OSI) is considered an important step in evaluating oil quality. The OSI was evaluated during Rancimat analysis until the end point of stability for SO samples and was expressed in hours. Experimental results confirmed that Bligh Dyer (13.28  ± 0.22 h), which is a cold extraction process, is a technique that causes less damage to the oil in comparison to Soxhlet (7.18  ± 0.50 h) which provided almost one-half of the OSI. The high oleic acid content in SO tends to protect the oil against thermo-oxidation. Costa and Jorge (2012) found 24.89 h of OSI (evaluation at 100  °C) for L. pisonis oil extracted by cold pressing. At the same Rancimat conditions used in this study, similar results were found for Brazil nut oil (8.24 h), hazelnut (8.88 h) and macadamia (7.38 h) [33]. 3.5 Thermal decomposition Thermogravimetric curve (TG) shows the mass loss, and the derivative thermogravimetric curve (DTG) shows the rate of mass loss of SO during thermal decomposition from 30 to 750  °C by TGA (Fig. 2). The values of mass loss are indicated in Table 4. The TG curves indicated that SO were thermally stable up to 303  °C with a mass loss of ~5%. This can be explained by the loss of moisture and volatile compounds in the oils. The oxidative process in vegetable oils is characterized initially by the oxidation forming secondary products (peroxides). The following phase corresponds to the decomposition of MUFA, mainly oleic acid and the polymerization of the substances remaining from the previous phase [39]. Dynamic and inert atmospheres cause different pattern in the TG/DTG profiles. The decomposition and carbonization processes in the air atmosphere occurred in three phases of the curve starting at around 130  °C, achieving about 53-58% mass loss at 405-440  °C, and ending at a temperature range of 611-625  °C, while for nitrogen atmosphere, the process showed two steps, initiating at ~160  °C, reaching 62-75 % mass loss at 426-435  °C, and finishing at 500  °C. DTG curves (Fig. 2) shows more clearly the steps of thermal decomposition. At the higher above-mentioned temperatures, the mass loss reached 100% (no residue remaining). The high UFA content in SO, mainly oleic and linoleic acid are related to be responsible for the occurrence of oxidative degradation reactions [22]. The high values of Ti (onset temperature) showed that SO have high thermal stability, being that the higher is the Ti of decomposition of the oil, the higher is the thermal stability. The results are similar to that of Brazil nut, which is thermally stable up to 209-220  °C and reaches a maximum mass loss of 97% at 580-602  °C [22], [39]. Differences between the thermal behaviors of SO can be related to the FA compositional differences, and also because of the presence of natural antioxidants which tends to protect the oils against oxidation, thus retarding the degradation [40]. 3.6 Thermal behavior for crystallization and melting 3.6.1 Temperature for crystallization and the influence of scanning rate In order to investigate the melting profile of SO under isothermal crystallization, previous tests were done. In one hand, the melting thermogram (Fig. 3 a, b) revealed that when frozen at -10  °C the oil samples showed endothermic peaks at -6.81  °C (LP1) and at -6.16  °C (LP2), with a enthalpy of 9.28 J/g for LP1 and 7.26 for LP2. On the other hand, it was demonstrated that there was no event afterward 0  °C, revealing that no crystallization occurs after that temperature. Such a feature may confirm the liquid state of the SO at room temperature (25  °C). During cooling, the oils exhibited two transitions. The thermograms showed that the position of the exotherms is dependent on the cooling rate, while the amount of the exotherms is independent on the cooling rate. In addition, increasing the cooling rate causes the crystallization peak temperature to shift to lower temperatures, the peak height and area increase (Fig. 3 c, d). This behavior may correspond to the differential crystallization of higher melting triacylglycerols (TAGs) firstly and lower melting TAGs secondly. Similar results are described for palm oil fractions [24]. The scanning rate of 2  °C/min reduces the lag in output response from the DSC instrument as well as preserves the minor peaks and reduces the smoothing tendencies, which occurred at a higher scanning rate; however, the first peak is too small when compared to the rate of 5  °C/min, which provided better resolution for the peak analysis in the Pyris„ ¢ software. 3.6.2 Cooling curve During cooling (Fig. 4a), SO presented a similar pattern of crystallization showing two distinct peaks (exothermic) in the crystallization behavior, namely peak 1 (PC1) and peak 2 (PC2). PC1 which indicates the change from liquid to solid was found in the temperature of -11.56 (LP1) and -12.51 (LP2), while the PC2 was observed in the temperature range of -59.80 to -73.93  °C, both related to the crystallization of TAGs. The crystallization onset temperature occurs at around -8.0  °C and this process extends over a range of 15-23  °C. The sum of the crystallization enthalpy of the two peaks for the two oils were -22.17 and -32.56 J/g for LP1 and LP2, respectively (Table 5). Heat is released during the phase transition of oil from liquid form to solid form; for this reason, values for crystallization enthalpy were negative [41]. Different endothermic and exothermic peaks are exhibited according to different contents of saturated or unsaturated TAG and FA present in the oils [42]. Smaller or shoulder peak are also correlated to the differing type of TAG. In addition, an inseparable shoulder peak which melts at the same temperature range comes from the complex nature of the TAG [43]. 3.6.3 Heating curve During melting, SO were found to be completely melted at 8.28  °C and 6.29  °C (LP1 and LP2, respectively) when heated at 5  °C/min (Fig. 4b). Moreover, LP1 showed a single major shoulder before the maximum melting peaks (PM) at -18.42  °C, while LP2 showed a major shoulder before PM (-21.47  °C) and an additional one, after the major peak at -6.61  °C. The melting curve of SO began at -25.77  °C (LP1), and -29.87  °C (LP2) and the major peak was observed in a temperature region varying between -7.99 to -10.13  °C, ending the events around -1.09 to -1.68  °C. The process comprises a melting range of 24-28  °C, with a melting enthalpy of 59.34 (LP1) and 64.76J/g (LP2) (Table 5). During heating treatment of oil, multiple endothermic regions are correlated to the separate melting events of the TAG. Furthermore, the composition and polymorphism of the oils can cause some overlapping effects, resulting in different shapes of the endothermic peaks [18]. The phase transitions are principally determined by the degree of heterogeneity in the composition of the oils, and include breaking/formation of hydrogen bonds, being a result of structural rearrangements in the chains of glycerides. [44]. 3.6.4 Cloud point The cloud point is referred as the temperature at which oil begins to cloud as a result as a result of the first stage of crystallization under controlled cooling, and it is related to the oils degree of unsaturation. The higher is the unsaturation of the oil, the lower the cloud point [26]. The cooling curves of sapucaia oils showed an initial small exothermic peak at -6.87  °C (LP1) and -7.00  °C (LP2). This peak corresponded to the first stage of crystallization and cloud point corresponded to the onset of crystallization. A second large exothermic peak at ˆ’49.95  °C (LP1) and -49.96  °C (LP2) with further cooling indicated the oil underwent an additional crystallization step. The same behavior was found for hazelnut oils, which presented the first small exothermic peak at -12.4  °C and a large one at -31.5  °C [26]. The lower cloud point of sapucaia oils was also a result of the lower content of SFA compared to the UFA. 3.6.5 Solid Fat Content The solid fat content (SFC) is considered an important physical property of lipids because it expresses their physical, sensorial, technological and protecting/release properties, and it affects physical properties such as consistency, spreadability, and stability [45]. According to the melting thermograms (Fig. 4b), SO presented no changes in SFC previously to -40  °C, so then the data analysis was performed in the range of -40 to 20  °C (melting peak region). The SFC showed less than 2.5% decrease between -40 to -30  °C for the two oils, and started to drop rapidly at around -20 up to 0  °C; then slowed down from 6 to 10  °C until there was no solid fat remaining (Fig. 5). The SFC is associated with the FA profile. Oils with higher content of UFA are easier to melt compared to ones with higher SFA [41], [45]. 3.7 Rheology properties 3.7.1 Steady state rheology The results for rheological behavior of SO shows that the apparent viscosity (ÃŽÂ ·) tends to decrease with increasing temperature (T) and also with increasing the shear rate (ÃŽÂ ³), indicating that the flow of the sapucaia oils is pseudoplastic (n > 1) (Table 6, 7 and Fig. 6). On the one hand, it is usual for oils to exhibit a dependency of T; on the other hand, a non-dependency of higher ÃŽÂ ³ is observed. At 50  °C, the ÃŽÂ · is almost constant throughout the entire range tested, with minimum influence of the ÃŽÂ ³. Furthermore, 2.0 s-1wasthe maximum value of ÃŽÂ ³ which induced major changes in ÃŽÂ · (see detail in Fig. 6, b and c). According to Gila et al. (2015), a greater amount of FAs such as C18:1 and C18:2 as the major components of the oils appear to make a great contribution to the flow behavior of oils. The experimental data fitted by Ostwald-de Waele (OW) and Herschel-Bulkley (HB) models (Fig. 6a, Table 6) showed a good fit (R2 > 0.999; à Ã¢â‚¬ ¡2 KH values decrease (Fig. 6e and Table 6). Similar observation for many edible oils such as coconut, sunflower, canola, corn [47] and olive oils [48] was reported. The OW model showed that the oils were non-Newtonian (n nH > 1) at 30 and 40  °C (Fig. 6f). The HB model is able to determine yield stress (à Ã¢â‚¬Å¾0H), at which a material begins to deform plastically without returning to its original shape when the applied stress is removed. SO have small values for à Ã¢â‚¬Å¾0H which also tends to decrease with the increase of T. Fig. 7 shows the non

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In this, and subsequent descriptions of the trenches, I may lay myself open to the charge of exaggeration. But it must be remembered that I am describing trench life in the early days of 1914, and I feel sure that those who had experience of them will acquit me of any such charge. To give a recipe for getting a rough idea, in case you want to, I recommend the following procedure. Select a flat ten-acre ploughed field, so sited that all the surface water of the surrounding country drains into it.Now cut a zig-zag slot about four feet deep and three feet wide diagonally across, dam off as much water as you can so as o leave about one hundred yards of squelchy mud; delve out a hole at one side of the slot, then endeavour to live there for a month on bully beef and damp biscuits, whilst a friend has instructions to fire at you with his Winchester every time you put your head above the surface. Well, here I was anyway, and the next thing was to make the bets of it.As I have before said, t hese were the days of the earliest trenches in this war; days when we had none of those â€Å"props† such as corrugated iron, floorboards, and sand bags. When you made a dug-out in those days you made it out of anything you could find, and generally had to make it yourself. Some British soldiers found that captured German trenches were better built than British ones – as H S Clapham wrote after a successful attack

“Click” by John Barth Essay

Barth insight on the worlds technological advancement with computers gave him a good start on an interesting story. By incorporating today’s living with literature he turn out Click. â€Å"Click† some hated it, but some liked it. I think the lack of understanding of this story is what caused those people to dislike the story; the fact that the story was very long also had something to do with it. I will present the in-depth thought that made me understand and really like the story. Also I will put some points from the elements of fiction. I really like the concepts â€Å"Click† presented when I read it. There were some thoughts that the writer expressed, then there were some that was more in-depth and you had to think about. So lets begin the argument. One explicit theme to ‘Click’ is told best by Barth, â€Å"The Hypertextuality of Everyday Life†(73). Where each word can take you further and further into a maze of choices. The choices can go deeper which defines the terms of what you read. Those terms travels along side the paths of day by day activities. Until you get to an endless sea of terms, â€Å"given time and clicks enough, you will have ‘accessed’ virtually the sum of language, the entire expressible world. That’s ‘hypertext,'(75). I understood the combination of these words that are expressed to the fullest extent to be part of this story. The author gave so many side notes in parentheses or any other expressible notation that it could have drove the reader to throw the book against the wall. So, as Barth does so when he goes to express himself with the following â€Å"(because all these digressions, suspensions, parentheses, and brackets are setting the Narrator’s t eeth on edge†¦.)†(77). The text will be to long to show an example from the story. Lets try it anyway â€Å"(Parenthesized elements in this case = amplification that might indeed be cut, but might instead well be ‘hypertexted’ behind the bare-bones description, to accessed on demand, just as further amplifications [not given, but perhaps hypertexted] might lie behind {any highlighted/underlined words})† (76). With this quote you can click on the word that you want to get the information on. If you haven’t figured it out yet hypertext is usually used on a computer thus comes the title â€Å"Click†. Where the computer is the gateway to many passages to more information than any one human brain can handle. Where someone well rehearsed can crack the  highest of security codes with the whelms of their thought; all the way through to the illiterate who use two fingers instead of ten. Wait I’m getting sidetracked, which brings me to my next point of the story. Where â€Å"the flashy home page of their Web-server program, actually encouraging her (the character) to sidetrack here and there in the What’s new? And What’s Cool? Departments† .(78) Where the web give you so many options to go down. I don’t know if any one person can honestly navigate through the entanglement of â€Å"the World Wide Web (WWW), [without] the deployment of ‘bookmarks’ as shortcuts through that electronic labyrinth, the black hole of leisure and very antidote to spare time.† (77) It would have been to frustrating and so over whelming to be focus on one particular thing. Although once you start the journey that’s all one has is time when getting on the internet. Clicking is an action with a choice in a computer’s world. You can get lost with that massive instrument. You can also get lost with the twists of everyday life too. If you assume â€Å"everybody knows, after all (or believes that he or she know,) what ‘everyday life’ is, different as may be the everyday lives of , say, Kuwaiti oil sheikhs and American felons serving life sentences in maximum-security prisons without possibility of parole†.(74) You just deal with all the little conflicts and dilemmas. Where some one’s life can be painstakingly slow. While another’s is speed right through. The point of view of life will always be held by that individual. Where the authors point of view in this story varies. It goes from the third to the first then to the audience. The story is letting’s us experience the everyday life of each character. It is how their lives intertwine that make the story. A good story is drawn on many basis. Barth bring ups the point if a story has â€Å"this constant sidetracking, this what’s-the-rush digression, can take the edge off the main event by the time one gets to it, the way some restaurants lay on so many introductory courses and side dishes that one has no appetite for the entrà ©e†. (82) This concept with drain the life out the story or overly stuff them with tedious details. The audience will lose interest which will distract them from what the author wants to get through to them. If the story holds the â€Å"full agenda [which] was a single item, [the] top  priority always and only the bottom line, [the] eternal (and infernal) Let’s get on with the story in fact a Let’s get done with the story, for the reason†, (83) of a means to an end. The story will be so short that you won’t have much to go on to understanding the story in the first place. These two concepts alone causes a story to tarnish and be a waste of paper in some since. It is the combination of the two that makes a great story. â€Å"Its between fundamentally opposite views of and modes of dealing with the infinitely complex nature of reality† (87). The center of narrative gravity pulls us to the perception of reality on this story. Without the ying there is no yang that holds the boundaries of a story. â€Å"Their tendencies represent contrary narrative impulses of equal validity and importance.† (90) The opposites of each other that counterbalance themselves. Give us â€Å"[a] satisfyingly told story requires enough [Ying]—that is, enough detail amplification, and analysis— to give it clarity, texture, solidity, verisimilitude, and empathetic effect.† (90) The detail terms that can be taken out of the parenthesis sometime with give that require information (that hypertexted). â€Å"It [also] requires equally enough [Yang]—that is, efficiently directed forward motion, ‘profluence,’ on-with-the-storyness– for coherence, anti-tedium, and dramatic effect.† (90). The story has to keep to a single track, because if you split it up to much you have multiple stories with no ending. Where â€Å"CNG’s interactive E-fiction serendipitously supply the terms ‘Expediter’ and ‘Enhancer’ to shorthand the characterological differences that erupted†,(87) expediter being Mark and the enhancer being Valerie. Valerie the ying of the story. The one who you need to fill the story in with enough details to help the reader understand what it is all about. Where Valerie validates what Marks role have to do with the story by saying his concept is â€Å"who gave a damn?–[Mark’s] idea of living life was the same, Let’s get done with it, [an example of her situation] every time she saw him ready and fidgeting in the car a full ten minutes earlier than he knew as well as she they needed to leave for work, she was tempted to suggest that they drive straight to the funeral parlor and get done with it.† (83) That is what the expediter can’t help but do. Val’s statement † ‘I thought you  were the big moving-onner and I was the over-dwelling-on-things.’ â€Å"(88) The author gave us a foreshadowing uncharacteristic of, the intrapersonal relationship with Mark, Valerie where â€Å"(Val ‘s better than Mark, we remember, at shrugging of f their infrequent blowups)†. (87) Although by the end of the story you have â€Å"Val (who, decidedly herself even after deciding to be more Marklike)†, (91) Which we will confront of Marks behave. Then there is Mark the yang of the story. You need him to get to the point of the story and not to lead you to different paths that are available to access in the story. Where his thoughts were â€Å"having no timetable or deadlines doesn’t mean having no agenda or priorities†, (82) to give and example â€Å"Expediter and enhancer in the Supermarket, he with grocery list in one hand, pencil in other, and eye on watch, she already examining the (unlisted) radicchio and improvising new menu plans down the line†¦Ã¢â‚¬ , (79). Where that is the Enhancer for you, the person who comes up with more of the story and gives you a better â€Å"taste† variety. Where his uncharacteristic foreshadowing is shown with, â€Å"He’s less ready to take offense, but slower to put their occasional tiffs behind him.† (81). Also â€Å"(Val’s better than Mark, we remember, he tends to forget that and to project from his own distress [of dwelling on their argu ment longer ])†, (87). When toward the end â€Å"Mark (inescapably himself even when determined to be more Valish)† (91). The contradictory of the two characters gave the story its base. The â€Å"anonymous oddball whose homepage [was] http://www.epiphs.art† (78) alias CNG â€Å"who happened just then to be passing by and sympathetically so saw and heard them [at that horrible Saturday quarrel], or a couple not unlike them, toe-to-toeing it, and who then subsequently was inspired to imagine.† (84) Created and gave us the fictional story of Irma and Fred, who are the replacement to Valerie and Mark. They where part of the beginning (of the end) of the story. They along with millions of other names in the world are made up identities in order for its users to surf the web freely. It could also represent the wants of that individual to be someone else other than themselves. Although we are not going to get into that ordeal. The setup of the story begins with the near ending which in Marks case is â€Å"Lets be done with it† morality. CNG who is the supposedly author/narrator of the â€Å"Click†Ã‚  story. Kind of at first threw me off, because I thought the story was going to be a third person point of view. Well once the ideal of the end of the Irma and Fred story here comes the bulk of the actual story, where the Val morality is used. When the end of the end came it left me wanting more. â€Å"Valerie lifts one [long] [lithe] [cinnamon-tan] leg up and with her [left] [great] toe gives the Mac’ master switch a† (92). WHAT? I would have yell if I wasn’t in a crowded area when I read that last page. It leaves you with the daunting of the hypertexts of choices. Since this is a book you wouldn’t be able click on any of the above words to get the ending. You left tittering on the edge of a cliff that drops for days on ends. The taunting the author leaves you by not using the Mark in any good story. Yet that was his aim even for the ending to turn out to be happy and open to imagination.

Essay on Sexual Harassment Case Study - 1211 Words

Individual Case Study #1 1. Is there a case of sexual harassment in this situation or is it only fun? This is a case of sexual harassment because; the words and actions of fellow employees ultimately made Rosetta quit her job. The technical definition of harassment is when members of an organization treat an employee in a different manner due to that person’s sex, race, religion, age, and etc. Harassment also includes unwelcomed remarks or jokes which make the employee feel uncomfortable. These guys that Rosetta had been working with, as she mentioned were making remarks and asking uncomfortable questions regarding her personal relationships (asking about her boyfriend, asking intimate details and asking if she prefers Canadian men†¦show more content†¦This applies to this situation because Rosetta let the guys knows that she did not like the remarks by sayings â€Å"leave me alone† and â€Å"mind your own business† and they still continue to make remarks which leads to the second characteristic; conduct must continue despite the complainant protests, fi nally the third characteristic is complainants cooperation must be due to employment related threats. Rosetta suffered and took the harassment for so long from the fear of the manager, and being fired from her job. 2. If you were Eva, what would-and could-you do? What are the options? What is the probability of success of each option? 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