Effect of refining on the phenolic composition of crude olive oils

By definition, virgin olive oil is consumed unrefined, although a great proportion of the olive oil produced has to be refined to render it edible. Phenolic compounds are among the substances eliminated during the refining process; in the present work these were characterized by HPLC, and their evolution during the different refining steps was studied. The complete refining process removed most polyphenols from oils, but the behavior of individual compounds at each step also was observed. o-Diphenols (hydroxytyrosol, catechol, and hydroxytyrosol acetate) and flavonoids (luteolin and apigenin) were eliminated first during the alkaline treatment. Tyrosol and 4-ethylphenol remained in the oil until the deodorization step. A large amount of phenolic compounds was discovered in the refining by-products such as soapstocks and deodorization distillates. In the latter streams, the concentrations of tyrosol and 4-ethylphenol reached up to 149 and 3720 mg/kg by-product, respectively. This high level of 4-ethylphenol and its well-known strong off-odor can interfere during further processing of the deodorization distillates, and this must be taken into account when deciding what is to become of them. Similarly, the results of this work open the possibility of recovering phenolic compounds from the “second centrifugation olive oils” by adding a new washing step prior to the refining process. By including this new step, the most polar polyphenols, hydroxytyrosol and tyrosol, will diffuse from oil to water and a concentration of up to 1400 mg/L of hydroxytyrosol may be achieved.     

Pinoresinol and 1-acetoxypinoresinol, two new phenolic compounds identified in olive oil

Polyphenols of olive oil show autoprotective, sensory, and nutritional-therapeutic effects. Two new phenolic compounds have been isolated from virgin olive oils by preparative high-performance liquid chromatography and their structures established on the basis of their mass spectra and nuclear magnetic resonance spectral data. The compounds identified are the lignans pinoresinol and 1-acetoxypinoresinol. Both have been found in all the commercial virgin olive oils analyzed. Pinoresinol concentration was rather similar in all the oils. In contrast, 1-acetoxypinoresinol concentration was higher in oils of the Arbequina and Empeltre cultivars than in Picual or Picudo cultivars. Pinoresinol and 1-acetoxypinoresinol may represent the major phenolic compounds in some Arbequina and Empeltre oils. Lignans possess biological and pharmacological properties and, therefore, the two new compounds identified in olive oils may contribute to the reported beneficial effects which are attributed to polyphenols on human health of a diet rich in olive oil.     

The probability of death in road traffic accidents. How important is a quick medical response?

The number of deaths in road traffic accidents in Spain exceeds three thousand people each year. Public authorities have implemented some policies with the aim to reducing this number. Among them, the improvement of road quality standards and some legal changes encouraging careful driving behavior. However, less attention has been focused on one of the issues that may be critical to reducing the number of fatalities caused by traffic accidents: a quick emergency medical care. In this paper, we use a sample of more than 1400 accidents occurred on Spanish roads in May 2004. Our objective is to analyze to which extent a reduction of the time interval between the crash and the arrival of the emergency services to the crash scene is related to a lower probability of death. Our results suggest that a 10 min reduction of the medical response time can be statistically associated with an average decrease of the probability of death by one third, both on motorways and conventional roads.     

Triterpenic acids in table olives

An experimental investigation was carried out for the first time on the triterpenic acids in table olives. Maslinic acid was found in a higher concentration than oleanolic acid in the flesh of 17, unprocessed olive varieties, with the Picual and the Manzanilla varieties showing the highest and almost the lowest contents, respectively. The level of triterpenic acids in several types of commercial black and green olives ranged from 460 to 1470 mg/kg fruit, which represents a much higher value than reported for virgin olive oils. In fact, the NaOH treatment employed to debitter black and green olives reduced the concentrations of these substances in the flesh because of their solubilisation into alkaline solutions. Thus, natural black olives, which are not treated with NaOH, showed a higher concentration than 2000 mg/kg in the olive flesh. These results will contribute to the reevaluation of table olives from a nutritional and functional point of view because of the promising bioactivity properties attributed to olive triterpenic acids.     

Spectroelectrochemistry of Quantum Dots

Spectroelectrochemistry (SEC) is a set of techniques with many advantages in the study and characterization of materials. Although SEC has not yet been widely used to study quantum dots (QDs), the information extracted from SEC experiments about these nanostructures is very useful. Most of the works that use SEC to study QDs are high‐quality pieces of research. This review intends to show how to perform SEC in an easy way and what information can be obtained using these techniques. Most of the examples shown in this review are related to semiconductor and carbon QDs. After a brief introduction, some optoelectronic properties of QDs and the main SEC techniques are described. The capabilities of SEC for the study of QDs are illustrated with examples extracted from literature. Finally, the needs of SEC to become a user‐friendly technique and its evolution to become more powerful are commented in the last section of the review.     

Spatial scanning spectroelectrochemistry. Study of the electrodeposition of Pd nanoparticles at the liquid/liquid interface

Spatial scanning spectroelectrochemistry is a new analytical technique that provides spectral information at different distances from an electrified liquid/liquid interface where an electrochemical process takes place. As a proof of concept, we have studied two different electrochemical processes at the electrified liquid/liquid interface: (1) Ru(bpy)(3)(2+) transfer through the water/1,2-dichloroethane interface and (2) electrodeposition of Pd nanoparticles at the water/1,2-dichloroethane interface. The instrumental setup developed consists of a movable slit for the light beam to sample at well-defined positions on both sides of the interface, providing important information about the chemical process occurring. If the slit is scanned at different distances from the interface during an electrochemical experiment, a complete picture of the reactions and equilibria in the diffusion layer can be obtained. For example, in the case of the Ru(bpy)(3)(2+), the experiments show clearly how the complex is transferred from one phase to the other. In the case of electrosynthesis of Pd nanoparticles, it is demonstrated that nanoparticles are not only deposited at the interface but diffuse to the aqueous bulk solution. These in situ observations were confirmed by ex situ experiments using transmission electron microscopy.     

Enrichment of pomace olive oil in triterpenic acids during storage of “Alpeorujo” olive paste

Triterpenic acids are natural compounds present in plants and foods with beneficial properties for human health and thus they are desirable in the food, cosmetics and pharmaceutical industries. Pomace olive is considered a good source of these substances. In this study, oleanolic and maslinic acids were found to be the main triterpenic acids identified in pomace olive oil obtained from stored “Alpeorujo”. Determination of the two acids was achieved by a new procedure that consists of extracting the acids from the oil with a mixture of methanol/ethanol, and then separating and quantifying them by HPLC. Results showed that their concentration increased up to 16 g/kg of oil during storage of the pomace in large ponds for 7 months. The concentration of both triterpenic acids was similar in the pomace olive oil obtained by using the centrifugation system. By contrast, a much lower concentration of maslinic than oleanolic acid was detected in pomace olive oils obtained by solvent extraction from the previously centrifugated “Alpeorujo” paste. These triterpenic acids also contributed to the acidity of the crude oil. Likewise, the oil of the pomace paste was enriched in other substances such as 4‐ethylphenol and aliphatic alcohols during the storage of the paste in large ponds. Consequently, crude pomace olive oil can be considered a good source of triterpenic acids when obtained from a stored olive paste.     

Purification and characterization of natural Bet v 1 from birch pollen and related allergens from carrot and celery

Birch pollen allergy is predominantly caused by the major allergen Bet v 1 and can lead to crossreactions with homologous proteins in food. Two major cross-reactive food allergens are Dau c 1 from carrot and Api g 1 from celery, which have never been purified from their natural source. Here, we describe a non-denaturing purification method for obtaining natural Bet v 1, Dau c 1 and Api g 1, comprising of ammonium sulfate precipitation, hydrophobic interaction chromatography and size exclusion chromatography. This method resulted in 98-99% pure isoform mixtures for each allergen. Characterization of these isoform mixtures with Q-TOF MS/MS clearly showed earlier reported isoforms of Bet v 1, Dau c 1 and Api g 1, but also new isoforms. The presence of secondary structure in the three purified allergens was demonstrated via circular dichroism and showed high similarity. The immune reactivity of the natural allergens was compared with recombinant proteins by Western blot and ELISA and showed similar reactivity.     

Optimisation and validation of a specific analytical method for the determination of thiram residues in fruits and vegetables by LC–MS/MS

Thiram is a non-systemic dithiocarbamate fungicide, which is easily degraded during sample preparation since it is affected by pH, matrix components and temperature. In this work, specific methodology for thiram analysis in vegetable (eggplant and lettuce) and fruit (strawberry) samples has been developed based on liquid chromatography coupled to tandem mass spectrometry (LC–MS/MS). Minimising thiram degradation during standards storage and sample preparation was carefully studied. The effect of low temperature (about 5 °C), addition of a dehydrating agent (Na₂SO₄ anhydrous), pH regulator (NaHCO₃), and enzymatic activity reduction (EDTA) during extraction was evaluated. The optimised procedure was validated for eggplants, lettuces, and strawberries. Satisfactory recoveries, between 80% and 106%, and relative standard deviations below 10% were obtained at 0.1 and 0.01 mg/kg fortification levels (n = 5). Limits of detection below 0.0012 mg/kg were achieved. The validated method has been applied to eggplant and lettuce samples collected from different field trials as well as several strawberry and apple samples.     

Study of the anti-lactic acid bacteria compounds in table olives

The analysis and formation of anti-lactic acid bacteria compounds in olive brines was performed for the main worldwide olive varieties intended for table olives. The results demonstrated that the growth of lactic acid bacteria in the brines of olives non-treated with NaOH is, in some way, variety dependant. Likewise, the most active antimicrobial compound, the dialdehydic form of decarboxymethyl elenolic acid linked to hydroxytyrosol, was not detected in fresh fruits but it was formed during brining from the hydrolysis of oleuropein and this reaction was enzymatically catalysed. Thus, the inactivation of the enzyme by heating the olives produced (i) an accumulation of oleuropein in olives and brines, (ii) the inhibition of the formation of antimicrobials and (iii) the growth of Lactobacillus pentosus in olive brines. These results provide tools for a full understanding of the growth or inhibition of lactic acid bacteria during fermentation of table olives.