Microwave-assisted extraction of edible Cicerbita alpina shoots and its LC-MS phenolic profile.

BACKGROUND: Crude extracts obtained from the edible shoots of Cicerbita alpina using microwave-assisted extraction have been qualitatively profiled by liquid chromatography coupled with an ion trap mass spectrometry detector and an electrospray ionization interface (LC/ESI-MS(3) ) for their phenolic content. The main challenge of the present investigation was to create a working strategy designed to obtain a rich phenolic profile despite the limited amount of starting plant material and phytochemical data available. RESULTS: The best extraction conditions (temperature 90 °C; time 5 min; solvent methanol:water 50:50; sample weight 3 g) were achieved using a full factorial 2(4) experimental design. Fifteen compounds, including flavonoid conjugates and phenolic acid derivatives, were detected and tentatively identified. The total phenolic content varied from 93.58 mg g(-1) gallic acid equivalents (GAE), for the cultivated plant to 10.54 mg g(-1) GAE for the wild one, whereas the total flavonoid content varied from 145.00 mg g(-1) rutin for the cultivated plant to 25.22 mg g(-1) rutin for the wild one. CONCLUSION: A total of 11 compounds are herein reported, for the first time, as coming from this plant source.

Reliability of the ΔECN42 limit and global method for extra virgin olive oil purity assessment using different analytical approaches.

Two data elaboration approaches for evaluating olive oils authenticity were compared: (I) determination of the difference between the theoretical and actual amounts of triacylglycerols with partition number 42 (ΔECN42 ⩽ |0.2|); and (II) the global method, which considers also partition numbers 44 and 46 (returning a "correct"/"not correct" result). Analysis of 31 genuine extra virgin olive oil samples was performed using different analytical methods, namely liquid chromatography (LC) coupled with a refractive index detector (RID) and LC coupled with a mass spectrometry (MS), and the results compared. Several false positives were highlighted using the ΔECN42 limit with both instrumental approaches. The global method algorithm returned "correct" results for all the samples analysed (except two that gave no results) with LC-MS; on the other hand, 10 false positives were obtained elaborating data deriving from NARP-LC-RID analysis.

Simultaneous determination of volatile and semi-volatile aromatic hydrocarbons in virgin olive oil by headspace solid-phase microextraction coupled to gas chromatography/mass spectrometry.

A reliable, simple and relatively fast method for the simultaneous determination of volatile and semi-volatile aromatic hydrocarbons in virgin olive oil was developed, based on headspace solid-phase microextraction (HS-SPME). The investigation regarded eco-contaminants such as alkylated monoaromatic hydrocarbons from C1- to C4-benzenes and light polyaromatic hydrocarbons up to four aromatic rings. Sampling and chromatographic conditions were optimized by using standard solutions in deodorized olive oil and the analytical performances of the method were determined. The proposed method was then applied to real samples of virgin olive oil were the target hydrocarbons could be identified and quantified. Several of them had not been previously quantified in virgin olive oil. Moreover, by the analysis of olive oil samples an additional number of C4-benzenes could be tentatively identified.

Analysis of virgin olive oil volatile compounds by headspace solid-phase microextraction coupled to gas chromatography with mass spectrometric and flame ionization detection.

The efficiency of headspace solid-phase microextraction (SPME) was evaluated for the qualitative and semi-quantitative analysis of virgin olive oil volatile compounds. The behaviour of four fibre coatings was compared for sensitivity, repeatability and linearity of response. A divinylbenzene-Carboxen-polydimethylsiloxane fibre coating was found to be the most suitable for the analysis of virgin olive oil volatiles. Sampling and chromatographic conditions were examined and the SPME method, coupled to GC with MS and flame ionization detection, was applied to virgin olive oil samples. More than 100 compounds were isolated and characterised. The presence of some of these compounds in virgin olive oil has not previously been reported. The main volatile compounds present in the oil samples were determined quantitatively.

Presence of phytosterol oxides in crude vegetable oils and their fate during refining.

The content of phytosterol oxidation products was determined in samples of crude vegetable oils: peanut, sunflower, maize, palm nut, and lampante olive oils that were intended for refining and not for direct consumption. The 7 alpha- and 7 beta-hydroxy derivatives of beta-sitosterol, stigmasterol, and campesterol and the 7-keto-beta-sitosterol were the principal phytosterol oxides found in almost all of the oils analyzed. In some oils, the epoxy and dihydroxy derivatives of beta-sitosterol were also found at very low levels. The highest total concentrations of phytosterol oxides, ranging from 4.5 to 67.5 and from 4.1 to 60.1 ppm, were found in sunflower and maize oils, respectively. Lower concentrations were present in the peanut oils, 2.7-9.6 ppm, and in the palm nut oil, 5.5 ppm, whereas in the lampante olive oils, only three samples of the six analyzed contained a low concentration (1.5-2.5 ppm) of oxyphytosterols. No detectable levels of phytosterol oxides were found in the samples of palm and coconut oils. Bleaching experiments were carried out on a sample of sunflower oil at 80 degrees C for 1 h with 1 and 2% of both acidic and neutral earths. The bleaching caused a reduction of the hydroxyphytosterol with partial formation of steroidal hydrocarbons with three double bonds in the ring system at the 2-, 4-, and 6-positions (steratrienes). The same sunflower oil was deodorized at 180 degrees C under vacuum for 1 h, and no dehydration products were formed with a complete recovery of the hydroxyphytosterols. A bleaching test with acidic earths was carried out also with an extra virgin olive oil fortified with 7-keto-cholesterol, dihydroxycholesterol, and alpha-epoxy-cholesterol. There was no formation of steratrienes from these compounds, but dihydroxycholesterol underwent considerable decomposition and alpha-epoxycholesterol underwent ring opening with formation of the dihydroxy derivative, whereas 7-ketocholesterol was rather stable

Solid-phase microextraction in the analysis of virgin olive oil volatile fraction: modifications induced by oxidation and suitable markers of oxidative status.

Modifications of virgin olive oil subjected to accelerated storage were evaluated by HS-SPME analysis. To find a suitable marker of oxidative degradation, the volatile compounds showing variable concentration during the oxidative process have been identified and quantified by SPME coupled to GC-MS and GC-FID, respectively. The SPME analysis results were then compared with the parameters usually applied to assess the oxidative status of lipids, such as peroxide value, spectrophotometric absorbance, and loss of unsaturated fatty acids. Finally, the assessment of nonanal has been suggested as a marker of oxidative degradation. This rapid, inexpensive, and reliable method may allow screening of oils prior to testing by a panel of assessors.

Solid-phase microextraction in the analysis of virgin olive oil volatile fraction: characterization of virgin olive oils from two distinct geographical areas of northern Italy.

SPME was employed to characterize the volatile profile of virgin olive oils produced in two geographical areas of northern Italy: the region of the Gulf of Trieste and the area near Lake Garda. There are as yet no data on the headspace composition of virgin olive oils from these regions, characterized by particular conditions of growth for Olea europaea. Using the SPME technique coupled to GC-MS and GC-FID, the volatile components of 42 industrially produced virgin olive oil samples were identified and the principal compounds quantitatively analyzed. Significant differences in the proportion of volatile constituents from oils of different varieties and geographical origins were detected. The results suggest that besides the genetic factor, environmental conditions influence the volatile formation.

Influence of phenols mass fraction in olive (Olea europaea L.) paste on volatile compounds in Buza cultivar virgin olive oil.

The influence of the phenolic content in olive paste of cv. Buza increased by the addition of an aqueous solution of phenolic extract of freeze-dried olive pulp (cv. Istarska bjelica) on the final products of the lipoxygenase pathway in oil was studied. Increases by 12, 38, and 56% for ripe fruits (maturity index = 4.0) and by 38% for unripe fruits (maturity index = 1.2) were examined. Phenols in the olive paste were determined according to the HPLC method, whereas volatiles in oil were determined according to SPME-GC-MS. A significant negative effect on Z-3-hexenal and E-2-hexen-1-ol (Tukey's test, p < 0.05) was found for ripe fruits (average decreases of 55 and 60%, respectively), but not for the unripe sample. Positive effects in both ripening levels were found for Z-3-hexenyl acetate (average increase of 68% for ripe and a double increase for unripe fruits) and total C5 compounds (average increase of 32% for ripe and an increase of 30% for unripe fruits).