Alessandra Lopes de Oliveira

Extraction of bixin from annatto seeds using supercritical carbon dioxide

The solubility of 93% pure bixin in supercritical carbon dioxide (SC-CO2) and of the bixin present in annatto seeds (Bixa orellana L.) was measured. For the seeds, the measurements were made in a temperature range from 30 to 50 o C and pressure between 10 and 35 MPa and for the pure bixin, at 40 o C from 10 to 35 MPa. The main pigments of annatto seeds are bixin and norbixin, but the extracts only showed the presence of cis and trans-bixin, indicating that norbixin is not soluble in SC-CO2. The annatto seeds used in the experiments contained about 2.7% bixin and 3.1% oil. In the seeds, the crossover point of solubility was at about 28 MPa and values for solubility were about ten times higher than those of the pure bixin, giving evidence that the oil acted as a co-solvent with the CO2. Keywords: Supercritical carbon dioxide; Annatto; Bixa orellana L.; Bixin; Solubility.

Isolation by pressurised fluid extraction (PFE) and identification using CPC and HPLC/ESI/MS of phenolic compounds from Brazilian cherry seeds (Eugenia uniflora L.)

Brazilian cherry seeds are a waste product from juice and frozen pulp production and, the seeds composition was investigated to valorize this by-product. Compounds separation was performed with ethanol by pressurised fluid extraction (PFE). Here we determine the effect of temperature (T), static time (ST), number of cycles (C), and flush volume (VF) on the yield, composition and total phenolic content (TPC) of the seed extracts. T, ST and their interaction positively influenced yield and TPC. Extracts were fractionated by high performance liquid chromatography (HPLC) and centrifugal partition chromatography (CPC). The collected fractions characterizations were made by electrospray ionisation mass spectrometry (ESI/MS) and high resolution mass spectrometry (HRMS) indicated the presence of ellagic acid pentoside and deoxyhexose, quercitrin and kaempferol pentoside. All of these compounds have antioxidant properties and normally are found in plant extracts. These results confirm that Brazilian cherry seed extract is a potentially valuable source of antioxidants.

Brazilian roasted coffee oil obtained by mechanical expelling: compositional analysis by GC-MS

oC por 10 min. Diferentes metodologias de preparo de amostra como “headspace”, adsorcao por succao em armadilha com polimero e esterificacao foram usadas. Foi possivel identificar pirazinas, piridinas, derivados de furanos e outros componentes ainda nao apresentados na literatura. Palavras-chave: oleo de cafe, aroma de cafe, acidos graxos, extracao por prensagem. SUMMARY A preliminary analysis by GC-MS comparing the mass spectrum of the compounds with the Wiley 275 L mass spectral data base was used to identify the fatty acids and mainly, some volatile compounds responsible for the flavor of the roasted coffee oil. The oil was obtained by mechanical expelling of Brazilian beans (Coffea arabica) roasted at 238 o C for 10 minutes. Different sample

Sensory evaluation of black instant coffee beverage with some volatile compounds present in aromatic oil from roasted coffee

The oil obtained from Brazilian roasted coffee by supercritical CO2 extraction shows considerable aromatic properties, mainly composed by five aromatic compounds, 2-methylpyrazine; 2-furfurylalcohol, 2,5-dimethylpyrazine; γ-butyrolactone and 2-furfurylacetate. Sensory analyses were used to verify the influence of a mixture of these important classes of aromatic coffee compounds (pyrazines, furans and lactones) and of the roasted coffee aromatic oil on the coffee aroma and flavour of black instant freeze and spray-dried coffee beverages. In the acceptance evaluation of the aroma, the samples prepared with freeze-dried instant coffee without the mixture of volatile compounds (sample 4) were not significantly different from the freeze-dried instant coffee in which the aromatic coffee oil was added (sample 5) and from the sample prepared with freeze-dried coffee in which the mixture of the five volatile was added (sample 3), coincidentally from the same drying process. Therefore, sample (3) did not differ from samples prepared with spray dried instant coffee without (sample 1) and to which (sample 2) the mixture of volatile was added. Therefore, with respect to this attribute, the addition of this mixture did not interfere in this drink acceptance. Taking into consideration the flavor, samples prepared with freeze-dried instant coffee in which the aromatic coffee oil was added (5) and the samples with (3) and without (4) the mixture of the five volatile was added did not differ significantly, however sample (4) did not differ from samples (1) and (2). Regarding this attribute, the addition of the aromatic oil of roasted coffee or a mixture of volatile in samples of freeze-dried instant coffee had a better acceptance than those dried by spray dryer (1) and (2). Thus, the enrichment of drinks with the aromatic oil of roasted coffee, or even with the mixture of the five components did not influence the consumer acceptance with respect to the aroma, but exerts influence with respect to flavour.

Optimization of the isolation and quantitation of kahweol and cafestol in green coffee oil

Kahweol and cafestol are two diterpenes that exist mainly as esters of fatty acids in green coffee oil. To recover them under their free form they have to be either saponified or trans-esterified. These two compounds are well known to be sensitive to heat, and reagents, therefore experimental conditions used in the transesterification reaction are critical. In this paper, a Doehlert experimental design plan is used to optimize the transesterification conditions using some key variables such as the temperature of the reaction, the reagent base concentration and the duration of the reaction. Therefore, the optimal parameters determined from the Doehlert design are equal to 70 °C, temperature of the reaction; 1.25 mol L(-1) concentration of the reagent base; and 60 min reaction time. The contour plots show that the extracted quantity of kahweol and cafestol can depend greatly from the experimental conditions. After transesterification, the free form of the diterpernes is extracted from the lipid fraction using liquid-liquid extraction and analyzed using GC-FID without prior derivatization. The amount of kahweol and cafestol obtained from green coffee oil obtained by cold mechanical press of Catuai coffee bean is equal to 33.2±2.2 and 24.3±2.4 g kg(-1)oil, respectively. In an attempt to streamline the process, the transesterification reaction is performed in an in-flow chemistry reactor using the optimal conditions obtained with the Doehlert experimental design. The amount of kahweol and cafestol obtained from the same green coffee oil is equal to 43.5 and 30.072 g kg(-1)oil, respectively. Results are slightly higher compared to the ones obtained with the batch procedure. This can be explained by a better mixing of the coffee oil with the reagents and a faster transesterification reaction.

USO DA EQUAÇÃO DE ESTADO DE PENG-ROBINSON COM REGRA DE MISTURA DEPENDENTE DA COMPOSIÇÃO NA PREDIÇÃO DO EQUILÍBRIO DE FASES DO SISTEMA TERNÁRIO CO2-LIMONENO-CITRAL

Phase equilibrium data at high pressures for CO2-Limonene and CO2-Citral binary systems and for CO2-Limonene-Citral ternary systems were collected from literature and employed in a thermodynamic modelling that uses the PENG-ROBINSON equation of state with: (1) classical mixture rule; (2) STRYJEK & VERA composition dependant mixture rule. The binary interaction parameters for the CO2-Limonene and CO2-Citral systems were obtained by fitting the models to the experimental data using two computational programmes that involved the minimisation of an objective function by the simplex method as suggested by NELDER & MEAD, written as a function of the deviation between experimental and calculated data. The phase equilibrium for the ternary systems was calculated using the previously fitted binary interaction parameters fitting, disregarding those parameters relative to Limonene and Citral. The results showed that, under supercritical conditions, the two models employed in the present work were capable of qualitatively predicting the phase equilibrium for the ternary systems.

Pressurized liquid extraction of flavanols and alkaloids from cocoa bean shell using ethanol as solvent

Cocoa shell (CS) is a co-product of the cocoa industry used mainly as fuel for boilers but with secondary applications as fertilizer and in animal feed. Although it is known that this material is rich in flavanols and alkaloids, to date, a study has not been conducted that has quantitatively identified these compounds in CS. Thus, the aim of this work was to characterize CS in terms of its composition, regarding catechin, epicatechin, procyanidin B2, caffeine and theobromine, and to evaluate the extraction kinetics of the total flavanols using pressurized liquid extraction (PLE) with absolute ethanol. For the determination of the extraction kinetic data, the DMAC method was used, while each compound was quantified using a UPLC-MS/MS analysis. The major compounds found were theobromine and epicatechin (mean values of 9.89 and 3.5 mg/g CS, respectively). PLE proved to be quite effective; the flavanols extraction yield was enhanced by increasing the temperature and extraction time however, high extraction times and temperatures degraded the procyanidins B2. Pelegs model applied to extraction data description provided a reasonable agreement with the experimental results, which allows their application in modeling and optimization of solid-liquid extraction of the total flavanols from cocoa bean shell.