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The present work uses a scanning electrochemical microscopy technique to study systems containing the membrane-bound reaction center protein (RC) from the purple photosynthetic bacteria Rhodobacter spheroides to chromatophores (spherical reorganization of cell membrane following its mechanical rupture) and liposomes (reconstituted membrane systems at lower degree of complexity). Scanning electrochemical microscopy is a useful tool to investigate redox processes involving a RC, because the effective heterogeneous rate constants for the redox reaction with different mediators can be measured. The technique is also able to provide information on the role of the outer cell membrane permeation on the kinetics of the electron-transfer processes and to obtain more insight into the nature of the species involved.

Aflatoxin B1 (AfB1) is a carcinogenic mycotoxin that contaminates food and feed worldwide. We determined the AfB1-adsorption capability of non-viable Pleurotus eryngii mycelium, an edible fungus, as a potential means for removal of AfB1 from contaminated solutions. Lyophilized mycelium was produced and made enzymatically inert by sterilization at high temperatures. The material thus obtained was characterized by scanning electron microscopy with regard to the morpho-structural properties of the mycotoxin-adsorbing surfaces. The active surfaces appeared rough and sponge-like. The AfB1-mycelium system reached equilibrium at 37°C, 30 min, and pH 5–7, conditions that are compatible with the gastro-intestinal system of animals. The system remained stable for 48 h at room temperature, at pH 3, pH 7, and pH 7.4. A thermodynamic study of the process showed that this is a spontaneous and physical adsorption process, with a maximum of 85 ± 13% of removal efficiency of AfB1 by P. eryngii mycelium. These results suggest that biosorbent materials obtained from the mycelium of the mushroom P. eryngii could be used as a low-cost and effective feed additive for AfB1 detoxification. [ABSTRACT FROM AUTHOR]

BACKGROUND: Deoxynivalenol (DON) is the most common Fusarium mycotoxin occurring in wheat and wheat‐derived products, with several adverse and toxic effects in animals and humans. Although bran fractions produced by milling wheat have numerous health benefits, cereal bran is the part of the grain with the highest concentration of DON, thus representing a risk for consumers. Increased efforts have been made to develop analytical methods suitable for rapid DON screening. RESULTS: The applicability of Fourier transform near‐infrared (FTNIR), or mid‐infrared (FTMIR) spectroscopy, and their combination for rapid analysis of DON in wheat bran, was investigated for the classification of samples into compliant and non‐compliant groups regarding the EU legal limit of 750 µg kg−1. Partial least squares‐discriminant analysis (PLS‐DA) and principal component‐linear discriminant analysis (PC‐LDA) were employed as classification techniques using a cutoff value of 400 µg kg−1 DON to distinguish the two classes. Depending on the classification model, overall discrimination rates were from 87% to 91% for FTNIR and from 86% to 87% for the FTMIR spectral range. The FTNIR spectroscopy gave the highest overall classification rate of wheat bran samples, with no false compliant samples and 18% false noncompliant samples when the PC‐LDA classification model was applied. The combination of the two spectral ranges did not provide a substantial improvement in classification results in comparison with FTNIR. CONCLUSIONS: Fourier transform near‐infrared spectroscopy in combination with classification models was an efficient tool to screen many DON‐contaminated wheat bran samples and assess their compliance with EU regulations. © 2018 Society of Chemical Industry [ABSTRACT FROM AUTHOR]

Abstract: BACKGROUND: Deoxynivalenol (DON) is a mycotoxin, mainly produced by Fusarium sp., most frequently occurring in cereals and cereal‐based products. Wheat bran refers to the outer layers of the kernel, which has a high risk of damage due to chemical hazards, including mycotoxins. Rapid methods for DON detection in wheat bran are required. RESULTS: A rapid screening method using an electronic nose (e‐nose), based on metal oxide semiconductor sensors, has been developed to distinguish wheat bran samples with different levels of DON contamination. A total of 470 naturally contaminated wheat bran samples were analyzed by e‐nose analysis. Wheat bran samples were divided in two contamination classes: class A ([DON] ≤ 400 µg kg−1, 225 samples) and class B ([DON] > 400 µg kg−1, 245 samples). Discriminant function analysis (DFA) classified wheat bran samples with good mean recognizability in terms of both calibration (92%) and validation (89%). A pattern of 17 volatile compounds of wheat bran samples that were associated (positively or negatively) with DON content was also characterized by HS‐SPME/GC–MS. CONCLUSIONS: These results indicate that the e‐nose method could be a useful tool for high‐throughput screening of DON‐contaminated wheat bran samples for their classification as acceptable / rejectable at contamination levels close to the EU maximum limit for DON, reducing the number of samples to be analyzed with a confirmatory method. © 2018 Society of Chemical Industry [ABSTRACT FROM AUTHOR]

Abstract: A strong trend toward using highly selective mass spectrometry technologies for screening of multiple mycotoxins has been observed in recent years. In the present study, the process of validation of a multimycotoxin screening method based on liquid chromatography–high‐resolution mass spectrometry method is presented. The method was intended for the simultaneous screening of the major Fusarium toxins (deoxynivalenol, 3‐ and 15‐acetyl deoxynivalenol, T‐2 and HT‐2 toxins, zearalenone, enniatins A, A1, B, and B1, and beauvericin) in wheat. The sample preparation protocol was based on a double extraction (methanol followed by acetonitrile/water mixture) and purification through solid‐phase extraction C18 column. To provide insights for full exploitation of the potential of the double‐stage high‐resolution mass spectrometry detection, a full‐scan acquisition event followed by a sequence of 5 fragmentation events (variable data‐independent acquisition) was set for mycotoxin detection, the latter to be exploited for confirmatory purposes. Method analytical performances were evaluated through in‐house validation and small‐scale interlaboratory study, designed according to Commission Regulation 519/2014/EU, setting performance requirements for screening methods for mycotoxins. Screening target concentrations were close to European Union maximum permitted or indicative levels. The in‐house validation provided the precision of the response under repeatability conditions and the intermediate precision (both resulting lower than 30%), the cutoff value, and the rate of false suspect results for negative (free of the mycotoxin of interest) samples, which resulted lower than 0.1% in all cases. The collaborative study provided reproducibility and laboratory independent cutoff values. Analysis of reference materials proved method trueness and suitability for screening of the major Fusarium mycotoxins in wheat. Finally, the applicability of the full‐scan/variable data‐independent acquisition detection approach was successfully tested on a set of naturally contaminated wheat samples, where 2 characteristic product ions could be detected for all identified mycotoxins even at levels in the low μg/kg range. [ABSTRACT FROM AUTHOR]

Lentil samples coming from two different countries, i.e. Italy and Canada, were analysed using untargeted 1 H NMR fingerprinting in combination with chemometrics in order to build models able to classify them according to their geographical origin. For such aim, Soft Independent Modelling of Class Analogy (SIMCA), k-Nearest Neighbor (k-NN), Principal Component Analysis followed by Linear Discriminant Analysis (PCA-LDA) and Partial Least Squares-Discriminant Analysis (PLS-DA) were applied to the NMR data and the results were compared. The best combination of average recognition (100%) and cross-validation prediction abilities (96.7%) was obtained for the PCA-LDA. All the statistical models were validated both by using a test set and by carrying out a Monte Carlo Cross Validation: the obtained performances were found to be satisfying for all the models, with prediction abilities higher than 95% demonstrating the suitability of the developed methods. Finally, the metabolites that mostly contributed to the lentil discrimination were indicated. [ABSTRACT FROM AUTHOR]

BACKGROUND Although table grape is one of the most cultivated and consumed fruits worldwide, no study has been reported on its geographical origin or agronomic practice based on stable isotope ratios. This study aimed to evaluate the usefulness of isotopic ratios (i.e. 2H/ 1H, 13C/ 12C, 15N/ 14N and 18O/ 16O) as possible markers to discriminate the agronomic practice (conventional versus organic farming) and provenance of table grape. RESULTS In order to quantitatively evaluate which of the isotopic variables were more discriminating, a t test was carried out, in light of which only δ 13C and δ 18O provided statistically significant differences ( P ≤ 0.05) for the discrimination of geographical origin and farming method. Principal component analysis ( PCA) showed no good separation of samples differing in geographical area and agronomic practice; thus, for classification purposes, supervised approaches were carried out. In particular, general discriminant analysis ( GDA) was used, resulting in prediction abilities of 75.0 and 92.2% for the discrimination of farming method and origin respectively. CONCLUSION The present findings suggest that stable isotopes (i.e. δ 18O, δ 2H and δ 13C) combined with chemometrics can be successfully applied to discriminate the provenance of table grape. However, the use of bulk nitrogen isotopes was not effective for farming method discrimination. © 2016 Society of Chemical Industry [ABSTRACT FROM AUTHOR]

The aim of this study was to investigate the impact of botanical origin and harvesting period on carbon stable isotope ratio (13C/12C), colour intensity ( CI), radical scavenging activity (% RSA), P and Sn content of Greek unifloral honeys. Thus, twenty-four honey samples were collected during harvesting periods 2011-2012 and 2012-2013, from four different regions in Greece. 13C/12C ratios and minerals were determined using isotope ratio mass spectrometry ( IRMS) and inductively coupled plasma optical-emission spectroscopy ( ICP- OES), respectively. CI and % RSA were measured using spectrophotometric assays. Results showed that only 13C/12C values and % RSA were affected by both botanical origin and harvesting period ( P < 0.05). Applying then chemometric analyses to the collected data set, honeys were correctly classified according to honey type (correct classification rate 87.5% and 79.2% using the original and cross-validation method, respectively). The use of different origin parameters has the potential to aid in honey authentication. [ABSTRACT FROM AUTHOR]

Objective: The aim of this study was to determine whether the volatile organic compounds (VOCs) pattern in colorectal cancer (CRC) patients is modified by curative surgery for a potential application in the oncologic follow-up. Background: CRC has been proved to induce metabolic derangements detectable by high through-output techniques in exhaled breath showing a specific pattern of VOCs. Methods: Forty-eight CRC patients and 55 healthy controls (HC) entered the study. Thirty-two patients (M/F: 1.4; mean age 63 years) attended the oncologic follow-up (mean 24 months) and were found disease-free. Breath samples were collected under similar environmental conditions into a Tedlar bags and processed offline by thermal-desorption gas chromatography-mass spectrometry (TD-GC-MS). VOCs were selected by U test to build a Probabilistic Neural Network (PNN) model to set-up a training phase, which was cross-validated using the leave-one out method. Results: A total of 11 VOCs were finally selected for their excellent discriminant performance in identifying disease-free patients in follow-up from CRC patients before surgery, (sensitivity 100%, specificity 97.92%, accuracy 98.75%, and AUC: 1). The same VOCs pattern discriminated follow-up patients from HC, with a sensitivity of 100%, specificity of 90.91%, accuracy of 94.25%, and AUC 0.959. Conclusions: Exhaled VOCs pattern from CRC patients is modified by cancer removal confirming the tight relationship between tumor metabolism and exhaled VOCs. PNN analysis provides a high discriminatory tool to identify patients disease-free after curative surgery suggesting potential implications in CRC screening and secondary prevention. [ABSTRACT FROM AUTHOR]

The photoreactivity of 4-thiothymidine (S4TdR) under visible light in the presence of Rose Bengal (RB), acting as a photosensitizer, was investigated in aqueous solutions at pH 7 and 12, using UV-vis, FTIR-ATR and 1H-NMR spectroscopic techniques, time resolved absorption spectroscopy and electrospray ionization mass spectrometry (ESI-MS). Evidence for the generation of thymidine (TdR) as the main product, after one hour of irradiation, was obtained from UV-Vis data, that suggested 4-thiothymidine photodegradation to be faster at basic pH, and confirmed by FTIR-ATR and 1H-NMR data. Clues for the presence of a further product, likely corresponding to a dimeric form of S4TdR, were obtained from the latter techniques. Besides indicating the presence of thymidine, the ESI-MS and MS/MS spectra of the reaction mixtures enabled the identification of the additional product as a S–S bridged covalent dimer of 4-thiothymidine. The concentration of the dimeric species could be estimated with the aid of 1H-NMR data and was found to be lower than that of thymidine in pH 7 reaction mixtures and almost negligible in the pH 12 ones. From a mechanistic point of view, time-resolved absorption spectroscopy measurements provided direct evidence that the formation of the two products cannot be ascribed to a photoinduced electron transfer involving S4TdR and the excited triplet state of RB. Rather, their generation can be interpreted as the result of a bimolecular reaction occurring between singlet state oxygen (1O2), photogenerated by RB, and S4TdR, as demonstrated by the direct detection of 1O2 through IR luminescence spectroscopy. More specifically, a sequential reaction pathway, consisting in the generation of an electrophilic hydroxylated form of S4TdR and its subsequent, rapid reaction with S4TdR, was hypothesized to explain the presence of the S–S bridged covalent dimer of 4-thiothymidine in the reaction mixtures. The described processes make S4TdR an interesting candidate in the role of molecular probe for the detection of 1O2 under different pH conditions. [ABSTRACT FROM AUTHOR]

Extra virgin olive oil (EVOO) is well known for containing relevant amounts of healthy phenolic compounds. The European Food Safety Authority (EFSA) allowed a health claim for labelling olive oils containing a minimum amount of hydroxytyrosol (OHTyr) and its derivatives, including tyrosol (Tyr). Therefore, harmonized and standardized analytical protocols are required in support of an effective application of the health claim. Acid hydrolysis performed after extraction and before chromatographic analysis has been shown to be a feasible approach. Nevertheless, other fast, green, and easy methods could be useful for on-site screening and monitoring applications. In the present research, a natural deep eutectic solvent (NADES) composed of lactic acid and glucose was used to perform a liquid/liquid extraction on EVOO samples, followed by UV-spectrophotometric analysis. The spectral features of the extracts were related with the content of total OHTyr and Tyr, determined by the acid hydrolysis method. The second derivative of spectra allowed focusing on three single wavelengths (i.e., 299 nm, 290 nm, and 282 nm) significantly related with total OHTyr, total Tyr, and their sum, respectively. In particular, the sum of OHTyr and Tyr could be determined with a root mean square error of prediction of 29.5 mg kg−1, while the limits of quantitation and detection were respectively 11.8 and 4.9 mg kg−1. The proposed method, therefore, represents an easy screening tool, with the use of a green, food-derived solvent, and could be considered as an attempt to pave the way for food grade analytical chemistry. [ABSTRACT FROM AUTHOR]

Mentha piperita essential oil (EO) has high economic importance because of its wide usage area and health-beneficial properties. Besides health-beneficial properties, Mentha piperita EO has great importance in the flavor and food industries because of its unique sensory and quality properties. High-valued essential oils are prone to being adulterated with economic motivations. This kind of adulteration deteriorates the quality of authentic essential oil, injures the consumers, and causes negative effects on the whole supply chain from producer to the consumer. The current research used fast, economic, robust, reliable, and effective ATR-FTIR spectroscopy coupled chemometrics of hierarchical cluster analysis(HCA), principal component analysis (PCA), partial least squares regression (PLSR) and principal component regression (PCR) for monitoring of Mentha spicata EO and L-menthol adulteration in Mentha piperita EOs. Adulterant contents (Mentha spicata and L-menthol) were successfully calculated using PLSR and PCR models. Standard error of the cross-validation SECV values changed between 0.06 and 2.14. Additionally, bias and press values showed alteration between 0.06 and1.43 and 0.03 and 41.15, respectively. Authentic Mentha piperita was successfully distinguished from adulterated samples, Mentha spicata and L-menthol, by HCA and PCA analysis. The results showed that attenuated total reflectance-Fourier transform infrared (ATR-FTIR) spectroscopy, coupled with chemometrics could be effectively used for monitoring various adulterants in essential oils. [ABSTRACT FROM AUTHOR]

• Table grape quality was evaluated by three analytical methods and chemometrics. • 1H NMR, LC-HRMS, and HS-SPME/MS-eNose were used in an untargeted approach. • Two types of discriminations were tested by PCA-LDA and PLS-DA. • MS-eNose gave models showing the best performances for both discriminations. • Good models were also obtained with NMR and HRMS in the marketability discrimination. Three non-targeted methods, i.e. 1H NMR, LC-HRMS, and HS-SPME/MS-eNose, combined with chemometrics, were used to classify two table grape cultivars (Italia and Victoria) based on five quality levels (5, 4, 3, 2, 1). Grapes at marketable quality levels (5, 4, 3) were also discriminated from non-marketable quality levels (2 and 1). PCA-LDA and PLS-DA were applied, and results showed that, the MS-eNose provided the best results. Specifically, with the Italia table grapes , mean prediction abilities ranging from 87% to 88% and from 98% to 99% were obtained for discrimination amongst the five quality levels and of marketability/non-marketability, respectively. For the cultivar Victoria, mean predictive abilities higher than 99% were achieved for both classifications. Good models were also obtained for both cultivars using NMR and HRMS data, but only for classification by marketability. Satisfying models were further validated by MCCV. Finally, the compounds that contributed the most to the discriminations were identified. [ABSTRACT FROM AUTHOR]

The present study aimed to develop and optimize liposome formulation for the colonic delivery of biologically active compounds. A strategy to facilitate such targeting is to formulate liposomes with a polymer coating sensitive to the pH shifts in the gastrointestinal tract. To this end, liposomes encapsulating curcumin—chosen as the biologically active compound model—and coated with the pH-responsive polymer Eudragit S100 were prepared and characterized. Curcumin was encapsulated into small unilamellar vesicles (SUVs) by the micelle-to-vesicle transition method (MVT) in a simple and organic solvent-free way. Curcumin-loaded liposomes were coated with Eudragit S100 by a fast and easily scalable pH-driven method. The prepared liposomes were evaluated for size, surface morphology, entrapment efficiency, stability, in vitro drug release, and curcumin antioxidant activity. In particular, curcumin-loaded liposomes displayed size lower than 100 nm, encapsulation efficiency of 98%, high stability at both 4 °C and 25 °C, high in vitro antioxidant activity, and a cumulative release that was completed within 200 min. A good Eudragit S100 coating which did not alter the properties of the curcumin-loaded liposomes was obtained. The present work therefore provides a fast and solvent-free method to prepare pH-responsive polymer-coated liposomes for the colonic delivery of biologically active compounds. [ABSTRACT FROM AUTHOR]

Abstract: In order to investigate the effects of cryomaceration and reductive vinification on chemical and physical indices and on antioxidant compounds of Sauvignon blanc wines, four wine-making procedures were applied: traditional white vinification, skin cryomaceration, vinification in a reductive environment, and a combination of the last two procedures. Significant differences were highlighted by both conventional analyses and NMR spectroscopy. The strongest changes were for organic acid concentrations (tartaric, in particular) and phenolic content. Cryomaceration caused a strong precipitation of tartaric acid, which may be desired if grapes have high acidity values. Cryomaceration protected those flavans reactive with vanillin from the action of oxidative enzymes. Vinification in a reductive environment, alone or combined with a cryomaceration step, gave wines with the highest solids content and caused a greater extraction of phenolic compounds from skins compared to traditional winemaking or cryomaceration alone, due to SO2 solubilisation. Grape oenological expression can be strongly affected by the application of the investigated wine-making procedures. [Copyright &y& Elsevier]

Highlights • The use of FT-NIR or FT-MIR spectroscopy was evaluated for OTA analysis in wheat. • PLS-DA and PC-LDA chemometric models were compared for samples classification. • FT-MIR classification models showed the best predictive performances. Abstract The use of infrared spectroscopy for the screening of 229 unprocessed durum wheat samples naturally contaminated with OTA has been investigated. Samples were analysed by both Fourier Transform near- and mid-infrared spectroscopy (FT-NIR, FT-MIR). Partial-Least Squares-Discriminant Analysis (PLS-DA) and Principal Component-Linear Discriminant Analysis (PC-LDA) classification models were used to differentiate highly contaminated durum wheat samples from low contaminated ones and the performances of the resulting models were compared. The overall discrimination rates were higher than 94% for both FT-NIR and FT-MIR range by using a cut-off limit set at 2 µg/kg OTA, independently from the classification model used thus confirming the reliability of the two statistical approaches used. False compliant rates of 6% were obtained for both spectral ranges and both classification models. These findings indicate that FT-NIR, as well as FT-MIR analysis, might be a promising, inexpensive and easy-to-use screening tool to rapidly discriminate unprocessed wheat samples for OTA content. [ABSTRACT FROM AUTHOR]

Highlights • Discrimination of geographical origin of oranges was performed by MS-based e-nose. • Three supervised statistical models were tested. • Classification by SELECT/LDA provided best prediction abilities in validation. • Twenty-eight VOCs had a different content in oranges from different geographical origins. Abstract An untargeted method using headspace solid-phase microextraction coupled to electronic nose based on mass spectrometry (HS-SPME/MS-eNose) in combination with chemometrics was developed for the discrimination of oranges of three geographical origins (Italy, South Africa and Spain). Three multivariate statistical models, i.e. PCA/LDA, SELECT/LDA and PLS-DA, were built and relevant performances were compared. Among the tested models, SELECT/LDA provided the highest prediction abilities in cross-validation and external validation with mean values of 97.8% and 95.7%, respectively. Moreover, HS-SPME/GC-MS analysis was used to identify potential markers to distinguish the geographical origin of oranges. Although 28 out of 65 identified VOCs showed a different content in samples belonging to different classes, a pattern of analytes able to discriminate simultaneously samples of three origins was not found. These results indicate that the proposed MS-eNose method in combination with multivariate statistical analysis provided an effective and rapid tool for authentication of the orange's geographical origin. [ABSTRACT FROM AUTHOR]

Aflatoxin B 1 (AfB 1 ) is a carcinogenic mycotoxin that contaminates food and feed worldwide. We determined the AfB 1 -adsorption capability of non-viable Pleurotus eryngii mycelium, an edible fungus, as a potential means for removal of AfB 1 from contaminated solutions. Lyophilized mycelium was produced and made enzymatically inert by sterilization at high temperatures. The material thus obtained was characterized by scanning electron microscopy with regard to the morpho-structural properties of the mycotoxin-adsorbing surfaces. The active surfaces appeared rough and sponge-like. The AfB 1 -mycelium system reached equilibrium at 37°C, 30 min, and pH 5-7, conditions that are compatible with the gastro-intestinal system of animals. The system remained stable for 48 h at room temperature, at pH 3, pH 7, and pH 7.4. A thermodynamic study of the process showed that this is a spontaneous and physical adsorption process, with a maximum of 85 ± 13% of removal efficiency of AfB 1 by P. eryngii mycelium. These results suggest that biosorbent materials obtained from the mycelium of the mushroom P. eryngii could be used as a low-cost and effective feed additive for AfB 1 detoxification.

An interlaboratory comparison (ILC) was organized with the aim to set up quality control indicators suitable for multicomponent quantitative analysis by nuclear magnetic resonance (NMR) spectroscopy. A total of 36 NMR data sets (corresponding to 1260 NMR spectra) were produced by 30 participants using 34 NMR spectrometers. The calibration line method was chosen for the quantification of a five-component model mixture. Results show that quantitative NMR is a robust quantification tool and that 26 out of 36 data sets resulted in statistically equivalent calibration lines for all considered NMR signals. The performance of each laboratory was assessed by means of a new performance index (named Qp-score) which is related to the difference between the experimental and the consensus values of the slope of the calibration lines. Laboratories endowed with a Qp-score falling within the suitable acceptability range are qualified to produce NMR spectra that can be considered statistically equivalent in terms of relative intensities of the signals. In addition, the specific response of nuclei to the experimental excitation/relaxation conditions was addressed by means of the parameter named NR. NR is related to the difference between the theoretical and the consensus slopes of the calibration lines and is specific for each signal produced by a well-defined set of acquisition parameters.

Exhaled breath contains thousands of volatile organic compounds (VOCs) in gaseous form, which may be used as markers of airway inflammation and lung disease. Electronic noses enable quick and real-time pattern analysis of VOC spectra. It has been shown that the exhaled breath of patients with obstructive sleep apnoea (OSA) differs from that of non-obese controls. We aimed to assess the influence of obesity in the composition of exhaled VOCs by comparing obese subjects with and without OSA. Moreover, we aimed to identify the discriminant VOCs in the two groups.19 obese patients with established OSA (OO; age 51.2 ± 6.8; body mass index (BMI) 34.3 ± 3.5), 14 obese controls without OSA (ONO; age 46.5 ± 7.6; BMI 33.5 ± 4.1) and 20 non-obese healthy controls (HC; age 41.1 ± 12.6; BMI 24.9 ± 3.8) participated in a cross-sectional study. Exhaled breath was collected by a previously described method and sampled by using an electronic nose (Cyranose 320) and by gas chromatography-mass spectrometry (GC-MS) analysis. Breathprints were analyzed by canonical discriminant analysis on principal component reduction. Cross-validation accuracy (CVA) was calculated. Breathprints from the HC group were separated from those of OO (CVA = 97.4%) and ONO (CVA = 94.1%). Breathprints from OO were moderately separated from those of ONO (CVA = 67.6%).The presence of OSA alters the exhaled VOC pattern in obese subjects. The incomplete separation of breathprints between OO and ONO may be due to the same underlying inflammation caused by obesity.

The discovery of a storeroom full of barley and other cereals (L.9512) in the proto-historic site of Ebla has provided a unique opportunity to study the centralized storage system of the early city-state from a different perspective. Epigraphic evidence available within the site reveals a complex system of taxation which included gathering grain tributes from satellite sites and redistributing semi-finished products such as flour. In this paper, we intend to explore the possibilities of a combined approach to studying the storage system, based on estimated barley grain volumes and δ(13)C-δ(15)N analyses. This approach is used to distinguish between grain from different harvesting sites and to identify any grain cultivated using special agricultural practices (e.g. manuring or irrigation). The basic assumption for this kind of analysis is that the growth-site conditions, natural or anthropogenic, of harvested cereals are reflected in their grain size and δ(13)C-δ(15)N values. Since the remains found in the storeroom were charred, the first task was to evaluate the effect of carbonization on the δ(13)C-δ(15)N and the size of the grains. Thus, the effect of charring was tested on modern samples of Syrian barley landraces. Once it had been ascertained that fresh grains reduced to charred remains retain their original biometric and isotopic traits, the ancient material was examined. Thirteen groups were identified, each characterized by a specific average volume and specific carbon and nitrogen values. The analysis revealed that what had first appeared to be a homogeneous concentration of grain was in fact an assemblage of barley harvested from different sites., (Copyright © 2012 John Wiley & Sons, Ltd.)

Background: The LAST operation, in spite of few drawbacks, represents a good option for single Left Anterior Descending (LAD) revascularization. This procedure does not allow multivessel revascularization, where hybrid procedure have been previous described. We report preliminary experience with the LAST operation performed in high risk patients., Material and Methods: From October 2004 to February 2005, 11 male high risk patients (mean age 74 +/- 8 years) underwent the LAST operation. Mean predicted death with EUROSCORE and Parsonnet score were 29% and 31% respectively. All patients had a proximal LAD lesion either not suitable for PTCA and multivessel coronary artery disease. The mean preoperative Ejection Fraction was 42 +/- 5% (27-55%). Four patients (36.4%) had previous surgical myocardial revascularization. An incision of about 6 cm was made in the appropriate intercostal space and the LIMA (Left Internal Mammary Artery) was harvested using a special costal retractor. After heparin administration the LIMA is distally divided to check the adequacy of the blood flow. Following the insertion of a temporary intracoronary shunt, the LIMA was LAD anastomosis was carried out with a continuous 8-0 polypropylene suture., Results: No hospital or late mortality was observed. Uneventful conversion to midline sternotomy was necessary in one patient with low value of mammary flow. All patients were discharged within the first postoperative week., Conclusions: The use of the LAST operation enhances the role of minimally invasive surgery also in high risk patients who need coronary revascularization.

Two methods for the determination of dichlorvos in durum wheat by electrochemical assay and gas chromatography, respectively, have been developed. Dichlorvos, an organophosphorus anticholinesterase pesticide, was extracted from wheat with hexane, and the filtered extract was directly analyzed by gas chromatography with nitrogen-phosphorus flame detection (NPD). Recoveries of dichlorvos from milled wheat spiked at 0.25-1.5 microg/g ranged from 96.5 to 100.9%, and the limit of detection was 0.02 microg/g. The electrochemical assay was based on the detection of choline, the acetylcholinesterase product, via a choline oxidase biosensor. An aliquot of the filtered hexane extract was partitioned with phosphate buffer solution, and the organic layer was evaporated prior to electrochemical analysis. A limit of detection of 0.05 microg/g of dichlorvos was obtained with mean recoveries of 97-103% at spiking levels of 0.25-1.5 microg/g. A good correlation (r = 0.9919) was found between the results obtained with the electrochemical and those obtained with the gas chromatographic methods. The electrochemical method was peer-validated in two laboratories that analyzed 10 blind samples (5 duplicates), including a blank and 4 spiked samples with dichlorvos at levels of 0.25, 0.60, 1.00, and 1.50 microg/g. Within-laboratory repeatability (RSDr) and between-laboratory reproducibility (RSDR) ranged from 5.5 to 7.8% and from 9.9 to 17.6%, respectively.