Measurement of squalene in olive oil by fractional crystallization or headspace solid phase microextraction coupled with gas chromatography

Squalene is the most abundant component in the unsaponifiable fraction of olive oil with strong antioxidant properties. Its concentration in olive oils varies between 0.2 and 16.2 g/kg depending on the cultivar(s) used. The propose of this work was to determine the effectiveness of two different extraction methods for squalene determination by gas chromatography (GC) coupled to a flame ionization detector (FID) or to mass spectrometry (MS). In a first approach, oil samples were dissolved in methanol/acetone mixture 7:3 (v/v) and triglycerides separated by fractional crystallization at −20°C. The organic layer was removed, reduced to dryness and the residue reconstituted in n-heptane (containing squalane as external standard) and analyzed by GC-FID. A headspace (HS) solid phase microextraction (SPME) GC-MS method has been also developed in order to have an environmentally friendly (i.e. solventless) extraction procedure. The linear range investigated with both methods was 1.0-10 g/kg. Within-day and between days precision values, expressed as RSD%, were 4 and 7% (GC-FID), and 3 and 6% (GC-MS), respectively. The limit of detection (LOD) at a signal-to-noise (S/N) ratio of 3 were 0.019 (GC-FID) and 0.003 (GC-MS) g/kg; the limit of quantification (LOQ) calculated at S/N = 10 were 0.063 (GC-FID) and 0.008 (GC-MS) g/kg, well below the typical squalene concentration levels found in olive oils. The obtained percentage recoveries were 70 ± 2 (GC-FID) and 98 ± 3 (GC-MS), and were not concentration dependent. The potential of the method has been demonstrated by the analysis of several different olive oil samples produced from different cultivars and different locations

Affective Contagion: How Attitudes Expressed by Others Influence Our Perception of Actions

Vitality forms represent a fundamental aspect of social interactions by characterizing how actions are performed and how words are pronounced on the basis of the attitude of the agent. Same action, such as a handshake, may have a different impact on the receiver when it is performed kindly or vigorously, and similarly, a gentle or rude tone of voice may have a different impact on the listener. In the present study, we carried out two experiments that aimed to investigate whether and how vocal requests conveying different vitality forms can influence the perception of goal-directed actions and to measure the duration of this effect over time. More specifically, participants were asked to listen to the voice of an actor pronouncing “give me” in a rude or gentle way. Then, they were asked to observe the initial part of a rude or a gentle passing action, continue it mentally, and estimate the time of its completion. Results showed that the perception of different vitality forms expressed by vocal requests influenced the estimation of action duration. Moreover, we found that this effect was limited to a certain time interval (800 ms), after which it started to decay

Ellipsometric Porosimetry for the Microstructure Characterization of Plasma-Deposited SiO2-Like Films

SiO2 layers have been deposited from Ar/O2/hexamethyldisiloxane mixtures in a remote expanding thermal plasma setup enabling a good control of both the ion flux (by changing the deposition chemistry and the arc plasma parameters) as well as the ion energy. This latter is achieved by an additional rf substrate biasing or a tailored ion biasing technique, i.e. a low frequency pulse-shaped bias. The role of the ion energy and ion-to-growth flux ratio on the film microstructure and densification at low substrate temperature (100ºC) has been investigated by means of ellipsometric porosimetry. This technique monitors the refractive index change due to the adsorption (and desorption) of ethanol vapors in the volume of macro-meso-micro pores in the SiO2 layer. From the analysis of the adsorption isotherm and the presence of hysteresis during the desorption step as a function of the equilibrium partial pressure, the open porosity in the layer can be determined. It is found that both biasing techniques lead to densification of the deposited layer, which experiences a transition from micro-/ mesoporosity to microporosity and eventually non-porosity, as function of the increasing ion energy. Although both biasing techniques lead to a comparable critical ion energy value per deposited SiO2 unit (about 100 eV), the ion-to-growth flux ratio and ion energy are not found to be interchangeable parameters. In fact, in the case of the rf bias, the meso- and large micropores are first affected leading to a quantitative decrease of porosity, i.e. from 11% to 3% at an ion energy less than 20 eV. A further increase in ion energy eventually reduces the presence of smaller micropores leading to non porous films at energy of 45 eV. When the pulse-shaped biasing technique is adopted, the micro- and mesopores are simultaneously affected over the whole range of available ion energy, leading to a non porous layer only at very high energy values, i.e. 240 eV. This difference is attributed to the increasing ion-to-growth flux ratio accompanying the rf biasing, as a consequence of the rf plasma generation in front of the substrate

Notifications Efficiency, Impact, and Interference in Second-Screen Scenarios

The growing use of second-screen devices stresses the importance of finding a balance between engagement, distraction, and disturbance of its users, while simultaneously watching television. In this framework, this article reports on a study designed to analyze the efficiency, impact, and interference of different notification strategies aiming to identify the best approach to be used when an alert is needed in second-screen scenarios. A prototype able to deliver synchronized information related with TV content, with intervals of 10, 30 and 60 s, followed by individual or combined notifications (e.g., audio, visual, and haptic—on the tablet and visual—on the TV) was developed. A laboratory adapted to replicate a living room was set up and a test that involved watching three segments of a 20-min clip while using the prototype was carried with 30 participants, under a cognitive walk-through protocol. Quantitative and qualitative results show that receiving notifications while watching TV is effective in alerting users about new information, despite its inherent cognitive disturbance for the TV viewing experience. It was also possible to highlight that in an HCI perspective, the most suitable strategy for integrating notifications (considering type and cadence) should be based on a combination of a visual notification (displayed only on the TV screen) along with a haptic notification (vibration on the tablet); spaced by an interval of at least 30 s

Supercritical CO2 Extraction of Phytocompounds from Olive Pomace Subjected to Different Drying Methods

Olive pomace is a semisolid by-product of olive oil production and represents a valuable source of functional phytocompounds. The valorization of agro-food chain by-products represents a key factor in reducing production costs, providing benefits related to their reuse. On this ground, we herein investigate extraction methods with supercritical carbon dioxide (SC-CO2) of functional phytocompounds from olive pomace samples subjected to two different drying methods, i.e., freeze drying and hot-air drying. Olive pomace was produced using the two most common industrial olive oil production processes, one based on the two-phase (2P) decanter and one based on the three-phase (3P) decanter. Our results show that freeze drying more efficiently preserves phytocompounds such as α-tocopherol, carotenoids, chlorophylls, and polyphenols, whereas hot-air drying does not compromise the β-sitosterol content and the extraction of squalene is not dependent on the drying method used. Moreover, higher amounts of α-tocopherol and polyphenols were extracted from 2P olive pomace, while β-sitosterol, chlorophylls, and carotenoids were more concentrated in 3P olive pomace. Finally, tocopherol and pigment/polyphenol fractions exerted antioxidant activity in vitro and in accelerated oxidative conditions. These results highlight the potential of olive pomace to be upcycled by extracting from it, with green methods, functional phytocompounds for reuse in food and pharmaceutical industries

Development, optimization, and comparison of different sample pre-treatments for simultaneous determination of vitamin e and vitamin K in vegetables

The absence of vitamin E from the diet can lead to cardiovascular disease, cancer, cataracts, and premature aging. Vitamin K deficiency can lead to bleeding disorders. These fat-soluble vitamins are important nutritional factors that can be determined in different methods in vegetables. In this work, the simultaneous determination of α-tocopherol, α-tocopheryl acetate, phylloquinone, and menaquinone-4 by gas chromatography-mass spectrometry (GC-MS) has been optimized using both direct injection and solid phase microextraction (SPME). Three different sample pre-treatment approaches based on: (A) solid-liquid-liquid-liquid extraction (SLE-LLE), (B) SLE, and (C) SPME were then applied to extract the target analytes from vegetables samples using menaquinone as internal standard. All the procedures allowed the determination of the target analytes in onion, carrot, celery, and curly kale samples. Similar results were obtained with the three different approaches, even if the one based on SPME offers the best performance, together with a reduced use of solvent, time consumption, and experimental complexity, which makes it the preferable option for industrial applications

Pheochromocytoma in Congenital Cyanotic Heart Disease

Studies on genome-wide transcription patterns have shown that many genetic alterations implicated in pheochromocytoma-paraganglioma (P-PGL) syndromes cluster in a common cellular pathway leading to aberrant activation of molecular response to hypoxia in normoxic conditions (the pseudohypoxia hypothesis). Several cases of P-PGL have been reported in patients with cyanotic congenital heart disease (CCHD). Patients affected with CCHD have an increased likelihood of P-PGL compared to those affected with noncyanotic congenital heart disease. One widely supported hypothesis is that chronic hypoxia represents the determining factor supporting this increased risk. We report the case of a 23-year-old woman affected with congenital tricuspid atresia surgically by the Fontan procedure. The patient was admitted to hospital with hypertensive crisis and dyspnea. Chest computed tomography revealed, incidentally, a 6-cm mass in the left adrenal lodge. Increased levels of noradrenaline (NA) and its metabolites were detected (plasma NA 5003.7 mu g/ml, n.v.< 480; urinary NA 1059.5 mu g/24 h, n.v.< 85.5; urinary metanephrine 489 mu g/24 h, n.v.< 320). The patient did not report any additional symptom related to catecholamine excess. The left adrenal tumor showed abnormal accumulation when 131I-metaiodobenzylguanidine scintigraphy was performed. A 18F-fluorodeoxyglucose positron emission tomography showed no significant metabolic activity in the left adrenal gland but intense uptake in the supra and subdiaphragmatic brown adipose tissue, probably due to noradrenergic-stimulated glucose uptake. The patient underwent left open adrenalectomy after preconditioning with alpha-and beta-blockers and histopathological examination confirmed the diagnosis of pheochromocytoma (Ki-67<5%). Screening for germline mutations did not show any genes mutation (investigated mutations: RET, TMEM127, MAX, SDHD, SDHC, SDHB, SDHAF2, SDHA, andVHL). Clinicians shouldconsider P-PGLwhenan-unexplained clinical deterioration occurs in CCHD patients, even in the absence of typical paroxysmal symptoms

Improving Convolutional Neural Network Design via Variable Neighborhood Search

An unsupervised method for convolutional neural network (CNN) architecture design is proposed. The method relies on a variable neighborhood search-based approach for finding CNN architectures and hyperparameter values that improve classification performance. For this purpose, t-Distributed Stochastic Neighbor Embedding (t-SNE) is applied to effectively represent the solution space in 2D. Then, k-Means clustering divides this representation space having in account the relative distance between neighbors. The algorithm is tested in the CIFAR-10 image dataset. The obtained solution improves the CNN validation loss by over 15% and the respective accuracy by 5%. Moreover, the network shows higher predictive power and robustness, validating our method for the optimization of CNN design. © Springer International Publishing AG 2017

The reductive activation of CO2 across a Ti═Ti double bond: synthetic, structural, and mechanistic studies

[Image: see text] The reactivity of the bis(pentalene)dititanium double-sandwich compound Ti(2)Pn(†)(2) (1) (Pn(†) = 1,4-{Si(i)Pr(3)}(2)C(8)H(4)) with CO(2) is investigated in detail using spectroscopic, X-ray crystallographic, and computational studies. When the CO(2) reaction is performed at −78 °C, the 1:1 adduct 4 is formed, and low-temperature spectroscopic measurements are consistent with a CO(2) molecule bound symmetrically to the two Ti centers in a μ:η(2),η(2) binding mode, a structure also indicated by theory. Upon warming to room temperature the coordinated CO(2) is quantitatively reduced over a period of minutes to give the bis(oxo)-bridged dimer 2 and the dicarbonyl complex 3. In situ NMR studies indicated that this decomposition proceeds in a stepwise process via monooxo (5) and monocarbonyl (7) double-sandwich complexes, which have been independently synthesized and structurally characterized. 5 is thermally unstable with respect to a μ-O dimer in which the Ti–Ti bond has been cleaved and one pentalene ligand binds in an η(8) fashion to each of the formally Ti(III) centers. The molecular structure of 7 shows a “side-on” bound carbonyl ligand. Bonding of the double-sandwich species Ti(2)Pn(2) (Pn = C(8)H(6)) to other fragments has been investigated by density functional theory calculations and fragment analysis, providing insight into the CO(2) reaction pathway consistent with the experimentally observed intermediates. A key step in the proposed mechanism is disproportionation of a mono(oxo) di-Ti(III) species to yield di-Ti(II) and di-Ti(IV) products. 1 forms a structurally characterized, thermally stable CS(2) adduct 8 that shows symmetrical binding to the Ti(2) unit and supports the formulation of 4. The reaction of 1 with COS forms a thermally unstable complex 9 that undergoes scission to give mono(μ-S) mono(CO) species 10. Ph(3)PS is an effective sulfur transfer agent for 1, enabling the synthesis of mono(μ-S) complex 11 with a double-sandwich structure and bis(μ-S) dimer 12 in which the Ti–Ti bond has been cleaved