Vegetable Oils Deacidification by Solvent Extraction: Liquid-Liquid Equilibrium Data for Systems Containing Sunflower Seed Oil at 298.2 K

Liquid-liquid equilibrium experimental data for refined sunflower seed oil, artificially acidified with commercial oleic acid or commercial linoleic acid and a solvent (ethanol + water), were determined at 298.2 K. This set of experimental data and the experimental data from Cuevas et al.,(1) which were obtained from (283.2 to 333.2) K, for degummed sunflower seed oil-containing systems were correlated using NRTL and UNIQUAC models with temperature-dependent binary parameters. The deviation between experimental and calculated compositions presented average values of (1.13 and 1.41) % for NRTL and UNIQUAC equations, respectively, indicating that the models were able to correctly describe the behavior of compounds under different temperature and solvent hydration.

Densities and Viscosities of vegetable oils of nutritional value

Densities and viscosities of five vegetable oils (Babassu oil, Buriti oil, Brazil nut oil, macadamia oil, and grape seed oil) and of three blends of Buriti oil and soybean oil were measured as a function of temperature and correlated by empirical equations. The estimation capability of two types of predictive methodologies was tested using the measured data. The first group of methods was based on the fatty acid composition of the oils, while the other was based on their triacylglycerol composition, as a multicomponent system. In general, the six models tested presented a good representation of the physical properties considered in this work. A simple method of calculation is also proposed to predict the dynamic viscosity of methyl and ethyl ester biodiesels, based on the fatty acid composition of the original oil. Data presented in this work and the developed model can be valuable for designing processes and equipment for the edible oil industry and for biodiesel production.

Underutilized Annona Species from the Brazilian Cerrado and Amazon Rainforest: A Study on Fatty Acids Profile and Yield of Seed Oils

Annona (Annonaceae) is an important source of fruits in the Brazilian Cerrado and the Amazon Rainforest. Some Annona species are widely commercialized as fresh fruit or as frozen pulp. Seeds are accustomedly discarded. Our main goal was to analyze fatty acids profile from seeds of A. crassiflora and A. coriacea from Cerrado, A. montana from Amazon Forest, and three cultivars (A. cherimola cv. Madeira, A. cherimola x A. squamosa cv. Pink`s Mammonth and A. cherimola x A. squamosa cv. Gefner). The total oil yield ranged between 20 and 42% by weight of dry mass. The A cherimola x A. squamosa cv. Gefner has significantly higher total lipid yield than all other samples. 100 g of fruit of this species present 6-8 g of seeds. Considering the fruit production of Chile (over 221 ton of fruits/year), more than 1300 ton of seed/year could be obtained, which could provide at least 200 ton of seed oil. Oleic acid was predominant for most samples, but for A. montana linoleic acid was the most abundant FA. Phenotypic variation on FAME profile was observed. These new data are an urgent requirement for supporting conservation programs, mainly for Cerrado areas in Brazil.

Chemical Composition, Seasonal Variation and Evaluation of Antimicrobial Activity of Essential Oils of Talauma ovata A. St. Hil. (Magnoliaceae)

The essential oils isolated by hydrodistillation from trunk bark and leaves of Talauma ovata A. St. Hil. (Magnoliaceae), collected in four seasons, were analyzed by capillary GC and GC/MS. Altogether 52 components were identified, The oils were characterized by predominance of cyclic sesquiterpenes. The main components were linalool, trans-beta-guaiene, germaerene D, germacrene B, spathulenol, caryophyllene oxide, viridiflorol and alpha-endesmol. The content of individual components was variable during the year. All oils were screened against several strains of bacteria and yeasts, using the agar well-diffusion technique. The antimicrobial activity of oils showed strong dependence with the season. Significant activity was found for oils obtained in the spring and summer.

Stability and interface properties of thin cellulose ester films adsorbed from acetone and ethyl acetate solutions

Stability and interface properties of cellulose acetate propionate (CAP) and cellulose acetate butyrate (CAB) films adsorbed from acetone or ethyl acetate onto Si wafers have been investigated by means of contact angle measurements and atomic force microscopy (AFM). Surface energy (gamma(total)(S)) values determined for CAP adsorbed from acetone are larger than those from ethyl acetate. In the case of CAB films adsorbed from ethyl acetate and acetone were similar. Dewetting was observed by AFM only for CAP films prepared from ethyl acetate. Positive values of effective Hamaker constant (A(eff)) were found only for CAP prepared from ethyl acetate, corroborating with dewetting phenomena observed by AFM. Oil the contrary, negative values of A(eff) were determined for CAP and CAB prepared from acetone and for CAB prepared from ethyl acetate, Corroborating with experimental observations. Sum frequency generation (SFG) vibrational spectra indicated that CAP and CAB films prepared from ethyl acetate present more alkyl groups oriented perpendicularly to the polymer-air interface than those films prepared from acetone. Such preferential orientation corroborates with macroscopic contact angle measurements. Moreover, SFG spectra showed that acetone hinds strongly to Si wafers, creating a new surface for CAP and CAB films. (C) 2008 Elsevier Inc. All rights reserved.

A Morphological View of the Sodium 4,4 `-Distyrylbiphenyl Sulfonate Fluorescent Brightness Distribution on Regenerated Cellulose Fibers

Evidence of the sorption of the whitening agent sodium 4,4`-distyrylbiphenyl sulfonate in the presence of the anionic surfactant sodium dodecylsulfate or the cationic surfactant dodecyl trimethyl ammonium chloride on regenerated cellulose fibers is given by several microscopy techniques. Scanning electron microscopy provided images of the cylindrical fibers with dimensions of 3.5 cm (length) and 13.3 mu m (thickness), with empty cores of 1 mu m diameter and a smooth surface. Atomic force microscopy showed a fiber surface with disoriented nanometric domains using both tapping-mode height and phase image modes. Atomic force microscopy also showed that the whitening agent and surfactant molecules were sorbed onto the fiber surface, in agreement with the adsolubilization sorption model. Transmission electron microscopy showed fibers with nanometric parallel cylinders, surrounded by holes where the fluorescent whitening molecules accumulated. On the basis of these techniques, we conclude that the sorption process occurs preferentially on the fiber surface in contact with the water solution, and under saturated conditions, the whitening agent penetrates into the pores and are simultaneously sorbed on the pore walls bulk, forming molecular aggregates. (C) 2010 Wiley Periodicals, Inc. J Appl Polym Sci 2321-2327, 2010

Highly Stable, Edible Cellulose Films Incorporating Chitosan Nanoparticles

The need for biodegradable polymers for packaging has fostered the development of novel, biodegradable polymeric materials from natural sources, as an alternative to reduce amount of waste and environmental impacts. The present investigation involves the synthesis of chitosan nanoparticles-carboxymethylcellulose films, in view of their increasing areas of application in packaging industry. The entire process consists of 2-steps including chitosan nanoparticles preparation and their incorporation in carboxymethylcellulose films. Uniform and stable particles were obtained with 3 different chitosan concentrations. The morphology of chitosan nanoparticles was tested by transmission electron microscopy, revealing the nanoparticles size in the range of 80 to 110 nm. The developed film chitosan nanoparticles-carboxymethylcellulose films were characterized by Fourier transform infrared spectroscopy (FT-IR), thermogravimetric analysis, solubility tests, and mechanical analysis. Improvement of thermal and mechanical properties were observed in films containing nanoparticles, with the best results occurring upon addition of nanoparticles with 110 nm size in carboxymethylcellulose films. Practical Application Carboxymethylcellulose films containing chitosan nanoparticles synthesized and characterized in this article could be a potential material for food and beverage packaging applications products due to the increase mechanical properties and high stability. The potential application of the nanocomposites prepared would be in packaging industry to extend the shelf life of products.

Composition and antifungal activity against Candida albicans, Candida parapsilosis, Candida krusei and Cryptococcus neoformans of essential oils from leaves of Piper and Peperomia species

This study was addressed to investigate the composition and antifungal activity of essential oils from leaves of Piperaceae species (Piper aduncum, Piper amalago, Piper cernuum, Piper diospyrifolium, Piper crassinervium, Piper gaudichaudianum, Piper solmsianum, Piper regnellii, Piper tuberculatum, Piper umbelata and Peperomia obtusifolia) against Candida albicans, C. parapsilosis, C. krusei and Cryptococcus neoformans. The essential oils from P. aduncum, P. gaudichaudianum and P. solmsianum showed the highest antifungal activity against Cryptococcus neoformans with the MIC of 62.5, 62.5 and 3.9 mg.mL-1, respectively. The oil from P. gaudichaudianum showed activity against C. krusei with MIC of 31.25 mg.mL-1.

Differential Acetyl Cholinesterase Inhibition by Volatile Oils from two Specimens of Marlierea racemosa (Myrtaceae) Collected from Different Areas of the Atlantic Rain Forest

The volatile oil composition and anti-acetyl cholinesterase activity were analyzed in two specimens of Marlierea racemosa growing in different areas of the Atlantic Rain Forest (Cananeia and Caraguatatuba, SP, Brazil). Component identifications were performed by GUMS and their acetyl cholinesterase inhibitory activity was measured through colorimetric analysis. The major constituent in both specimens was spathulenol (25.1 % in Cananeia and 31.9% in Caraguatatuba). However, the first one also presented monoterpenes (41.2%), while in the Carguatatuba plants, this class was not detected. The oils from the plants collected in Cananeia were able to inhibit the acetyl cholinesterase activity by LIP to 75%, but for oils from the other locality the maximal inhibition achieved was 35%. These results suggested that the monoterpenes are more effective in the inhibition of acetyl cholinesterase activity than sesquiterpenes as these compounds are present in higher amounts in the M. racemosa plants collected in Cananeia.

Characteristics of thin cellulose ester films spin-coated from acetone and ethyl acetate solutions

Spin-coated films of cellulose acetate (CA), cellulose acetate propionate (CAP), cellulose acetate butyrate (CAB) and carboxymethylcellulose acetate butyrate (CMCAB) have been characterized by ellipsometry, atomic force microscopy (AFM) and contact angle measurements. The films were spin-coated onto silicon wafers, a polar surface. Mean thickness values were determined by means of ellipsometry and AFM as a function of polymer concentration in solutions prepared either in acetone or in ethyl acetate (EA), both are good solvents for the cellulose esters. The results were discussed in the light of solvent evaporation rate and interaction energy between substrate and solvent. The effects of annealing and type of cellulose ester on film thickness, film morphology, surface roughness and surface wettability were also investigated.

Application of solid sampling device for direct determination of chromium and nickel in lubricating oils by graphite furnace atomic absorption spectrometry

One method using a solid sampling device for the direct determination of Cr and Ni in fresh and used lubricating oils by graphite furnace atomic absorption spectrometry are proposed. The high organic content in the samples was minimized using a digestion step at 400 degrees C in combination with an oxidant mixture 1.0% (v v(-1)) HNO3+15% (v v(-1)) H2O2+0.1% (m v(-1)) Triton X-100 for the in situ digestion. The 3-field mode Zeeman-effect allowed the spectrometer calibration up to 5 ng of Cr and Ni. The quantification limits were 0.86 mu g g(-1) for Cr and 0.82 mg g(-1) for Ni, respectively. The analysis of reference materials showed no statistically significant difference between the recommended values and those obtained by the proposed methods.

Microwave-Assisted Derivatization of Cellulose in an Ionic Liquid: An Efficient, Expedient Synthesis of Simple and Mixed Carboxylic Esters

Microwave (MW)-assisted cellulose dissolution in ionic liquids (ILs) has routinely led either to incomplete biopolymer solubilization, or its degradation. We show that these problems can be avoided by use of low-energy MW heating, coupled with efficient stirring. Dissolution of microcrystalline cellulose in the IL 1-allyl-3-methylimidazolium chloride has been achieved without changing its degree of polymerization; regenerated cellulose showed pronounced changes in its index of crystallinity, surface area, and morphology. MW-assisted functionalization of MCC by ethanoic, propanoic, butanoic, pentanoic, and hexanoic anhydrides has been studied. Compared with conventional heating, MW irradiation has resulted in considerable decrease in dissolution and reaction times. The value of the degree of substitution (DS) was found to be DS(ethanoate) > DS(propanoate) > DS(butanoate). The values of DS(pentanoate) and DS(hexanoate) were found to be slightly higher than DS(ethanoate). This surprising dependence on the chain length of the acylating agent has been reported before, but not rationalized. On the basis of the rate constants and activation parameters of the hydrolysis of ethanoic, butanoic, and hexanoic anhydrides in aqueous acetonitrile (a model acyl transfer reaction), we suggest that this result may be attributed to the balance between two opposing effects, namely, steric crowding and (cooperative) hydrophobic interactions between the anhydride and the cellulosic surface, whose lipophilicity has increased, due to its partial acylation. Four ethanoate-based mixed esters were synthesized by the reaction with a mixture of the two anhydrides; the ethanoate moiety predominated in all products. The DS is reproducible and the IL is easily recycled. (C) 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 134-143, 2010

Application of 1-Allyl-3-(1-butyl)imidazolium Chloride in the Synthesis of Cellulose Esters: Properties of the Ionic Liquid, and Comparison with Other Solvents

The ionic liquid (IL), 1-allyl-3-(1-butyl)imidazolium chloride (AlBuImCl), has been synthesized and its properties determined. Increase in the temperature increased its conductivity and decreased its density, polarity, and viscosity. Microcrystalline cellulose (MCC), dissolves in thisIL by heating at 80 degrees C; this did not affect its degree of polymerization, decreased its index of crystallinity (Ic), and changed in morphology after regeneration. Convenient acylation of MCC was achieved by using 50% excess anhydride at 80 degrees C, for 24 or 48 h for acetic and butyric anhydride, respectively. The composition of the mixed esters depended on the initial ratio of the anhydrides, and their order of addition.

Cellulose swelling by aprotic and protic solvents: What are the similarities and differences?

The swelling of microcrystalline, native and mercerized cotton and eucalyptus celluloses by 16 aprotic solvents was investigated. The number of moles of solvent/anhydroglucose unit, nSw, correlates well with solvent molar volume, basicity and dipolarity/polarizability. Swelling is sensitive to cellulose crystallite size, surface area and the presence of its chains in parallel or anti-parallel arrangements. Use of solvatochromic parameters is a superior alternative to the use of other descriptors, such as Hildebrand`s solubility parameters and Gutmann`s donor numbers. The calculated nSw for 28 protic and aprotic solvents correlated well with their experimental counterparts, although hydrogen bond donation by the solvent was not included.

Cellulose swelling by protic solvents: which properties of the biopolymer and the solvent matter?

The question posed in the title has been addressed by studying the swelling of celluloses at 20 C by twenty protic solvents, including water; linear- and branched-chain aliphatic alcohols; unsaturated aliphatic alcohols, and alkoxyalcohols. The biopolymers investigated included microcrystalline cellulose, MC, native and never-dried mercerized cotton cellulose, cotton and M-cotton, and native and never-dried mercerized eucalyptus cellulose, eucalyptus and M-eucalyptus, respectively. In most cases, better correlations with the physico-chemical properties of the solvents were obtained when the swelling was expressed as number of moles of solvent/anhydroglucose unit, nSw, rather than as % increase in sample weight. The descriptors employed in these correlations included, where available, Hildebrand`s solubility parameters, Gutmann`s acceptor and donor numbers, solvent molar volume, V(S), as well as solvatochromic parameters. The latter, employed for the first time for correlating the swelling of biopolymers, included empirical solvent polarity, E(T)(30), solvent ""acidity"", alpha(S), ""basicity"", beta(S), and dipolarity/polarizability, pi(S)*, respectively. Small regression coefficients and large sums of the squares of the residues were obtained when values of nSw were correlated with two solvent parameters. Much better correlations were obtained with three solvent parameters. The most statistically significant descriptor in the correlation equation depends on the cellulose, being pi(S)* for MC, cotton, and eucalyptus, and V(S) for M-cotton and M-eucalyptus. The best correlations were obtained with the same set of four parameters for all celluloses, namely, solvent pKa (or alpha(S)) beta(S), pi(S)*, and V(S), respectively. These results indicate that the supra-molecular structure of the biopolymer, in particular the average sizes of crystallites and micro-pores, and the presence of its chains in parallel (cellulose I) or anti-parallel (cellulose II) arrangements control its swelling. At least for the present biopolymer/solvent systems, use of solvatochromic parameters is a superior alternative to Hildebrand`s solubility parameters and/or Gutmann`s acceptor and donor numbers. The relevance of these results to the accessibility of the hydroxyl groups of cellulose, hence to its reactivity, is briefly discussed.