Effect of Salt Addition and Fermentation Time on Phenolics,Microbial Dynamics,Volatile Organic Compounds,and Sensory Properties of the PDO Table Olives of Gaeta (Italy)

‘Oliva di Gaeta’ is almost certainly the most important and well-known PDO denomination for table olives in Italy. Their production is based on a specific two-stage trade preparation called the ‘Itrana’ method. In this work, we investigated how variations in the duration of the initial water fermentation (i.e., 15 and 30 days) and the salt concentration (i.e., 6% and 8% NaCl) influence the chemical features, microbial dynamics, polyphenols, volatile organic compounds, and sensory features of ‘Oliva di Gaeta’. The time of the addition of salt did not affect the final concentration in the brine, but a longer initial water fermentation (before salt addition) led to lower pH values. The bacterial count constantly increased until the salt addition (i.e., either 15 or 30 days), while the yeast population peaked on day 30. Generally, the two different salt concentrations did not affect the count of microorganisms at the end of fermentation, with the only exception being a higher lactic acid bacteria count for the treatment with 6% salt added at 30 days. At commercial maturity, the crucial bitter tastant oleuropein was not completely removed from the drupes, and differences in salt concentration and the length of the first-stage water fermentation did not influence its content at the end of olive curing. Richer volatile profiles of olives were detected with higher-salt treatments, while the combination of low salt and early saline treatment provided a more distinct profile. Longer initial water fermentation caused a small increase in some phenolic compounds (e.g., iso-verbascoside, verbascoside, and hydroxytyrosol-glucoside). A panel test indicated that salt application at 30 days resulted in a more “Sour” and “Bitter” taste, irrespective of the salt concentration. The low salt concentration coupled with the late saline treatment resulted in more “Fruity” notes, probably due to the higher production of esters by lactobacilli. The slightly bitter perception of the olives was consistent with the partial removal of oleuropein. Our work revealed the characteristics of the ‘Itrana’ method and that the variation in salt concentration and its time of application changes parameters ranging from the microbial dynamics to the sensory profile. Specifically, our data indicate that 6% NaCl coupled with a longer initial water fermentation is the most different condition: it is less effective in blocking microbial growth but, at the same time, is more potent in altering the nutritional (e.g., polyphenols) and sensorial qualities (e.g., bitterness and fruitiness) of ‘Oliva di Gaeta’.     

Identification of chemicals and their metabolites from PHY906, a Chinese medicine formulation,in the plasma of a patient treated with irinotecan and PHY906 using liquid chromatography/tandem mass spectrometry (LC/MS/MS)

Traditional Chinese Medicine (TCM) is increasingly being used in combination with Western medicine. In general, TCM is comprised of multiple components in sharp contrast to Western medicine, where a single active chemical is used. Presently, there are no well-established standards for most of the chemical compounds of TCM and their respective metabolites. Moreover, there are no formal analytical methods for the identification of these chemicals, especially in trace amounts. The ability to measure the pharmacokinetic behaviors of chemicals and their metabolites from these herbal formulations are critical in understanding of the action of TCM. This paper describes the use of LC/MS/MS along with enzyme treatments and n-octanol/water partition coefficient, to investigate the chemical components of PHY906 and their metabolites in the plasma of a patient with metastatic colorectal cancer (mCRC) treated with irinotecan and PHY906. The chemicals from an aqueous extract of PHY906 and the plasma from a patient was prepared and separated on an Agilent ZORBAX-SB C₁₈ column, and eluted with acetonitrile/0.05% (v/v) formic acid. From the PHY906 aqueous extract, a total of 57 compounds and 27 metabolites were identified and tentatively assigned structures based on their identified mass spectrometry, enzyme digestion and n-octanol/water partition coefficient. In contrast, analysis of patient plasma identified only 33 chemicals and new metabolites. These findings demonstrated that LC/MS/MS was and effective and reliable method for studying the parent chemicals of the Chinese herbal medicine PHY906 and their metabolites in a patient with metastatic colorectal cancer.     

Mechanism of the interaction of color reagent 1, 3-N, N'-bis-4-(4'-nitro benzenediazo) phenyl squaraine with oxoacid anions

By AM1 method, the interactions between 1, 3-N, N′-Bis-4-(4′-nitro benzenediazo) phenyl squaraine (BNBPS) and several oxoacid anions have been studied on the basis of the proposed model. The mechanism of the color reactions is suggested and the answers to the question of whether or not BNBPS colorates with HCO_3~-, CO_3~(2-), NO_2~(-), NO_3~-, etc. are given. It is theoretically predicted that BNBPS might be used as the color reagent for SO_4~(2-).     

A Green Extraction Method to Achieve the Highest Yield of Limonin and Hesperidin from Lime Peel Powder (Citrus aurantifolia)

Green extraction is aimed at reducing energy consumption by using renewable plant sources and environmentally friendly bio-solvents. Lime (Citrus aurantifolia) is a rich source of flavonoids (e.g., hesperidin) and limonoids (e.g., limonin). Manufacturing of lime products (e.g., lime juice) yields a considerable amount of lime peel as food waste that should be comprehensively exploited. The aim of this study was to develop a green and simple extraction method to acquire the highest yield of both limonin and hesperidin from the lime peel. The study method included ethanolic-aqueous extraction and variable factors, i.e., ethanol concentrations, pH values of solvent, and extraction temperature. The response surface methodology was used to optimize extraction conditions. The concentrations of limonin and hesperidin were determined by using UHPLC-MS/MS. Results showed that the yields of limonin and hesperidin significantly depended on ethanol concentrations and extraction temperature, while pH value had the least effect. The optimal extraction condition with the highest amounts of limonin and hesperidin was 80% ethanol at pH 7, 50 °C, which yields 2.072 and 3.353 mg/g of limonin and hesperidin, respectively. This study illustrates a green extraction process using food waste, e.g., lime peel, as an energy-saving source and ethanol as a bio-solvent to achieve the highest amount of double bioactive compounds.     

Selective Acid Hydrolysis Condition for the Composition and Linkage with a Fructofuranosyl Backbone of a Polysaccharide from Angelica sinensis （Oliv） Diels

Angelica sinensis is a well-known Chinese traditional herbal medicine. Its roots have been widely used over two thousand years for tonifying blood, promoting blood circulation, regulating menorrhea and subduing inflammation1. The polysaccharide of the ASD…     

Archaeometrical study of paleometallurgical materials from the archaeological site “Cerro de las Balsas — Chinchorro” (La Albufereta, Alacant, Spain)

An Iberian archaeological site located in the east of Spain is one of the most important cupellation centers found in the 4th century b.c. Different metallurgical materials were found in the archaeological site as minerals, cast slags, forged slags, metallic lead, cupella fragments and bronzes. Also was found reverbs remains used for cupper-based materials and cupellation procedure, and hearth forge remains for obtained iron material. The recuperated samples were studied by comparing samples of the same type of material by macroanalysis and microanalysis. The microanalysis and quantitation of the different archaeological materials was carried out by SEM/EDX. The information provides about the knowledge of a metallurgic process such as that of silver production by lead cupellation. The microanalysis results reflect the variety of elements that constitute the slags and other materials, and that come from the forge of the worked metallic materials. Also, the process cupellation was confirmed by the identification of lead and silver. The presence of forge slag corroborates the use of the great amount of recovered heart forges in the excavation like metallurgical structures for the iron work.     

Simultaneous determination of three dipeptides (JBP485, Gly–Sar and JBP923) in the cell lysates by liquid chromatography‐tandem mass spectrometry: application to identify the function of the PEPT1 transfected cell

A simple and rapid liquid chromatography–tandem mass spectrometry (LC‐MS/MS) method for the simultaneous determination of JBP485, Gly–Sar and JBP923 in the cell lysates using methanol as a deproteinization solvent was developed and validated. Detection was performed by turbo ionspray ionization in multiple reaction monitoring mode using the transitions of m/z 147.1 → m/z 90.1 for Gly–Sar, m/z 201.1 → m/z 86.1 for JBP485, m/z 219.1 → m/z 86.1 for JBP923 and m/z 152.0 → m/z 110.0 for paracetamol (internal standard). The analytes were separated on a Hypersil ODS C₁₈ HPLC column using isocratic elution mode with a mobile phase containing 0.1% formic acid in water–methanol (97:3, v/v) at a flow rate of 0.2 mL/min. The calibration curves were demonstrated to be linear over the concentration range of 5.00?5000 nm with coefficient of 0.9968 for Gly–Sar, 0.9975 for JBP485 and 0.9952 for JBP923. The intra‐ and inter‐day precisions were <10.2% for each quality contro; level, and the accuracy was within ±5.6% for each analyte. The matrix effect, the extraction recovery and stabilities of LC‐MS/MS analysis were also investigated. This validated method was successfully applied to the simultaneous determination of JBP485, Gly–Sar and JBP923 in the cell lysates for identification of stably transfected HeLa cells with human PEPT1. Copyright © 2014 John Wiley & Sons, Ltd.     

Quantitative analysis by liquid chromatography-tandem mass spectrometry of glycidamide using the cob(I)alamin trapping method: validation and application to in vitro metabolism of acrylamide

Glycidamide (GA) is the epoxy metabolite of acrylamide (AA). A sensitive analytical method for quantitative measurement of GA from in vitro metabolism studies is useful in several contexts, e.g. in studies of enzyme kinetics in different species and factors influencing the metabolism of AA to GA. It is however difficult to analyse compounds like GA, mainly due to their inherent reactivity. In the present study cob(I)alamin {Cbl(I)}, a reduced form of vitamin B(12), was used for trapping of GA. Cbl(I) can react with electrophilic species, such as an epoxide, 10(5) times faster than standard nucleophiles. The trapping of GA by Cbl(I) results in the formation of an alkylcobalamin (GA-Cbl) that was used for quantitative analysis of the epoxide. The alkylcobalamin was analysed by LC-MS/MS using an electrospray ionization source in the positive ion mode. The Cbl(I) method was validated for measurement of GA in liver S9 fractions from human and rat. GA levels down to 0.01 μM were measured in the S9 fractions, providing a sensitivity that was ca. 100 times higher than that earlier estimated by the Cbl(I) method for measurement of other (e.g. butadiene) epoxides. Compared to current analytical methods for measurement of GA, the Cbl(I) method was 10-100 times more sensitive. The method was applied to quantify GA formed from the metabolism of AA in liver S9 from human and rat.     

Determination of the furaltadone metabolite 5-methylmorpholino-3-amino-2-oxazolidinone (AMOZ) using liquid chromatography coupled to electrospray tandem mass spectrometry during the nitrofuran crisis in Portugal

The use of nitrofuran veterinary drugs as antibacterial compounds in food-producing animals has been banned in the EU since 1995. As nitrofurans are extensive and rapidly metabolized, control of their illegal use in animal production must be done in edible tissues by LC-MS/MS analysis in order to determine persistent tissue-bound metabolites. The introduction during 2002 of the multi-residue detection of nitrofuran tissue-bound metabolites by LC-MS/MS for nitrofuran control in Portuguese Residues Monitoring Plan, revealed the presence of 5-morpholinomethyl-3-amino-2-oxozolidinone (AMOZ), the bound residue of furaltadone, in a large number of samples, namely in meat poultry samples. From the 226 analysed samples in the last 4 months of 2002, 78 were non-compliant due to the presence of AMOZ (61 broilers, 11 turkeys, 5 quails and 1 pig). In this context, the aim of this paper is to describe the analytical data obtained on meat samples collected from various animal species under official Portuguese control for nitrofuran drug residues during the so-called “Portuguese nitrofuran crisis”. Presented at the AOAC Europe Workshop, November 2006, Limassol, Cyprus.     

Fatty Acid Ethyl Esters (FAEE): A New,Green and Renewable Solvent for the Extraction of Carotenoids from Tomato Waste Products

Currently there is a drive towards the minimisation and reclamation of valuable materials from the waste products of the food and beverage industry. This can be achieved through the extraction of residual nutraceuticals from such materials. Tomato pomace contains carotenoids and other chemicals which can be extracted directly into edible oils to improve the health-giving properties of such oils. We report here a novel green solvent, fatty acid ethyl esters (FAEE), which is significantly more effective than sunflower oil and hexane for the extraction of lycopene and beta-carotene from tomato skin waste. FAEE are a non-toxic renewable resource that is environmentally friendly and to our knowledge has never been used as a vegetal extraction fluid. The efficiency of FAEE extraction was significantly improved relative to both sunflower oil and hexane under ultrasound-assisted extraction (UAE) conditions. In addition, FAEE have the additional and significant advantage that once enriched with the extracted nutraceuticals can be used directly as a food additive.     

A liquid chromatography-tandem mass spectrometry assay for the determination of nemonoxacin (TG-873870), a novel nonfluorinated quinolone, in human plasma and urine and its application to a single-dose pharmacokinetic study in healthy Chinese volunteers

Nemonoxacin (TG‐873870) is a novel C‐8‐methoxy nonfluorinated quinolone with higher activity than ciprofloxacin, levofloxacin and moxifloxacin against Gram‐positive pathogens including methicillin‐susceptible or methicillin‐resistant Staphylococcus aureus and Streptococcus pneumoniae with various resistant phenotypes. A rapid, sensitive and selective liquid chromatography–tandem mass spectrometric (LC‐MS/MS) method was developed and validated to determine the concentration of nemonoxacin in human plasma and urine. Protein precipitation and liquid–liquid extraction were employed for plasma and urine sample preparations, respectively, and extract was then injected into the system. Separation was performed on a C₁₈ reversed‐phase column using acetonitrile–0.1% formic acid as a mobile phase. Both analyte and internal standard (gatifloxacin) were determined using electrospray ionization and the MS data acquisition via the selected reaction monitoring in positive‐ion mode. The lower limit of quantification was 5 ng/mL and the calibration curves were linear in the concentration range of 5–1000 ng/mL. The accuracy, precision, selectivity, linearity, recovery, matrix effect and stability were validated for TG‐873870 in human plasma and urine. The method was successfully applied to a pharmacokinetic study enrolling 12 healthy Chinese volunteers administered nemonoxacin malate capsules. Copyright © 2012 John Wiley & Sons, Ltd.     

General applications of fused silica capillary column (FSCC) chromatography to the analysis of non-priority pollutant organics in environmental samples

Further applications of fused silica capillary columns (FSCC) to the analysis of environmental samples are presented. The chromatographic behavior (RT, RRT) of organic compounds of environmental significance not listed as Consent Decree Priority Pollutants is investigated on an SE-54 FSCC. Retention indices (RRT) and mass spectral response factors (RF) are presented for a total of 28 compounds including a number of chloro- and nitro-substituted anilines, alkylpyridines, and alkylquinoline derivatives. The direct application of the FSCC/MS interface to the analysis of these compounds in actual environmental samples is presented, including vent emissions from a fungicide manufacturing process, and contaminated soil and water samples from two metropolitan Boston construction sites.     

Analytical pyrolysis with in situ thermally assisted derivatisation, Py(HMDS)-GC/MS, for the chemical characterization of archaeological birch bark tar

An analytical method based on pyrolysis in the presence of hexamethyldisilazane followed by gas chromatographic/mass spectrometric analysis, Py(HMDS)-GC/MS, was used for the first time to study birch bark tar, an adhesive that has been used since the Palaeolithic period. Py(HMDS)-GC/MS enabled us to obtain information simultaneously both on polymerised and solvent soluble fractions of birch bark tar. A very particular chromatographic pattern was obtained, which was mainly characterised by the presence of homologous series of linear saturated and unsaturated monocaboxylic fatty acids, and homologous series of straight-chain alkenes and alkanes. The pattern can be linked to suberin and suberan, which are known to be present in birch barks. In addition, lupane-type triterpenoids were also revealed. Py(HMDS)-GC/MS was initially applied to a reference material, and was then used to study the archaeological adhesives from a wooden spindle recovered in a Gallo-Roman burial (3rd century AD) and from the golden sheath of a Thracian dagger (8th-7th centuries BC) recovered in Belogradets (Bulgaria).     

Coupling HPLC to on-line, post-column (bio)chemical assays for high-resolution screening of bioactive compounds from complex mixtures

It is challenging to screen and identify bioactive compounds from complex mixtures. We review a recently developed technique that couples high-performance liquid chromatography (HPLC) to on-line, post-column (bio)chemical assays and parallel chemical analysis to screen and identify bioactive compounds from complex mixtures without the need for cumbersome purification and subsequent screening. In this system, HPLC separates complex mixtures and a post-column (bio)chemical assay determines the activity of the individual compounds present in the mixtures. Parallel chemical-detection methods (e.g., diode-array detection, mass spectrometry and nuclear magnetic resonance) identify and quantify the active compounds simultaneously. We focus on relatively widely used on-line, post-column assays for antioxidant screening and less widely used hyphenated systems involving assays based on enzymes and receptors. These strategies have proved to be very useful for rapid profiling and identification of individual active components in mixtures to provide a powerful method for natural product-based drug discovery.     

The application of high performance liquid chromatography, coupled to nuclear magnetic resonance spectroscopy and mass spectrometry (HPLC-NMR-MS), to the characterisation of ibuprofen metabolites from human urine

Summary The use of HPLC-NMR-MS for the detection and identification of the metabolites of ibuprofen present in a solid phase extract of human urine is described. Gradient reversed-phase HPLC was used to separate the components present in the extract, which were then characterised by a combination of stopped-flow¹H NMR and on line electrospray-MS. This approach led to the rapid identification of the known phase 1 human metabolites of ibuprofen, including hydroxy- and carboxy- metabolites, together with their respective glucuronide conjugates. In addition a probable artefact resulting from the dehydration of one of the side chainhydroxylated glucuronides was also identified.     

Study of 19th century inks from archives in the Palazzo Ducale (Venice, Italy) using various analytical techniques

Inks and paper are the main materials and components of library and archive collections. Since the Third century B.C. there has been a continual succession of ink recipes from all over the world, with varying levels of documentation of the recipes used; however, it was only in the 19th century that Europe became the main producer and industrial leader in the discovery of new products. The aim of this study is to find out more about this last historical period, when new inks were created that had never been known or used in the past. In this study we chose four inks: they belong to documents preserved in the archive of the Superintendence Beni architettonici per il paesaggio e per il patrimonio storico artistico ed etnoantropologico (BAPPDAD) of Venice Lagoon, held in the Palazzo Ducale (Ducal Palace) of Venice.Fourier Transform Infrared Spectroscopy (ATR), Scanning Electron Microscopy (SEM-EDS) and pyrolysis coupled to a gas chromatograph with mass spectrometric detector (Py–GC–MS) allowed us to obtain a qualitative characterization of organic and inorganic elements in three different ink typologies.     

Evaluation of Transient Absorption Spectra of N, N, N, N- Tetra - ( p -methylphenyl ) - 4, 4- diamino - 1, 1- diphenyl Ether ( TPDAE ) for Electron Transfer from TPDAE to Fullerenes ( C_(60) / C_(70) ) by Laser Flash Photolysis

Fullerenes C60 and C70 have high electron affinity ( 2.6 - 2.8 ev ) and readily form anions on electronchemical reduction1, which were famous as electron acceptor in photo-excitation because of symmetrical shape, large size, and properties of its p - electron system2. After observation of molecular ferromagnetism3 in the tetrakis (dimethylamino ) ethylene salt of C60 as well as the occurrence of ultra-fast photoinduced electron transfer within the dimethyl aniline - C60 complex4, prompted us…     

Evaluation of Transient Absorption Spectra of N, N, N′, N′- Tetra - ( p -methylphenyl ) - 4, 4′- diamino - 1, 1′- diphenyl Ether ( TPDAE ) for Electron Transfer from TPDAE to Fullerenes ( C60 / C70 ) by Laser Flash Photolysis

Photoinduced electron transfer processes between fullerenes (C60 / C70) and N, N, N′, N′- tetra - ( p-methylphenyl ) - 4, 4′- diamino - 1, 1′- diphenyl ether ( TPDAE ) have been studied by nanosecond laser flash photolysis. Quantum yields and rate constants of electron transfer from TPDAE to excited triplet state of fullerenes (C60 / C70 ) in benzonitrile have been evaluated by observing the transient absorption bands in the near-IR region where the excited triplet state, radical anion of fullerenes ( C60 / C70 ) and radical cations of TPDAE appear.     

Effect of gamma irradiation with or without hot water dip and transportation from Thailand to Canada on nutritional qualities, ripening index and sensorial characteristics of Thai mangoes (Nahng Glahng Wahn variety)

Two lots of mangoes of the Nahng Glahng Wahn variety from Thailand were irradiated at the Thai Irradiation Center (TIC) at 0.49 to 0.77 kGy. Following this, one batch was retained in Thailand while the other was shipped to the Canadian Irradiation Center (CIC) for investigation of the same variables during storage. This way, it was hoped to compare the effects of gamma radiation with hot water dip (HWI) or without (I) before and after transportation on the ripening, vitamin C and vitamin A content and sensory qualities of mangoes. The results indicate that the I and HWI treatments delayed the ripening of the mangoes. The irradiated groups appeared to have a slightly higher content of ascorbic acid on the first day after irradiation than their corresponding controls. The sensory evaluation indicates that the panelists mostly favoured the I and HWI irradiated groups for the overall appearance and texture of whole mangoes and pulp and in taste and palatability of the pulp alone. Transportation stress did not appear to have much of an effect on the ascorbic acid and dehydroascorbic acid levels and the sensorial tests. The mangoes stored and studied in Canada appeared to have a lower vitamin A content.