Christos Soukoulis

On quantitative determination of volatile organic compound concentrations using Proton Transfer Reaction Time-of-Flight Mass Spectrometry

Proton transfer reaction - mass spectrometry (PTR-MS) has become a reference technique in environmental science allowing for VOC monitoring with low detection limits. The recent introduction of time-of-flight mass analyzer (PTR-ToF-MS) opens new horizons in terms of mass resolution, acquisition time, and mass range. A standard procedure to perform quantitative VOC measurements with PTR-ToF-MS is to calibrate the instrument using a standard gas. However, given the number of compounds that can be simultaneously monitored by PTR-ToF-MS, such a procedure could become impractical, especially when standards are not readily available. In the present work we show that, under particular conditions, VOC concentration determinations based only on theoretical predictions yield good accuracy. We investigate a range of humidity and operating conditions and show that theoretical VOC concentration estimations are accurate when the effect of water cluster ions is negligible. We also show that PTR-ToF-MS can successfully be used to estimate reaction rate coefficients between H(3)O(+) and VOC at PTR-MS working conditions and find good agreement with the corresponding nonthermal theoretical predictions. We provide a tabulation of theoretical rate coefficients for a number of relevant volatile organic compounds at various energetic conditions and test the approach in a laboratory study investigating the oxidation of alpha-pinene.

Optimization of spray-drying process conditions for the production of maximally viable microencapsulated L. acidophilus NCIMB 701748

Inrecent years, the use of spray drying for the production of anhydrobiotics has gained the interest of functional food manufacturers, mainly due to cost efficiencies and enhanced product and process flexibility (e.g., enhanced shelf life). In the present work, spray-drying conditions (air inlet temperature and feed flow rate) were optimized for the microencapsulation of the thermo sensitive probiotic lactobacilli strains Lactobacillus acidophilus stabilized in a 60:20:20 (w/w) maltodextrin: whey protein concentrate: D-glucose carrier. A 23 full-factorial experimental design was constructed with air inlet temperature (120, 140, and 160°C) and feed flow rate (6, 7.5, and 9.0 mL/min) as the independent variables and total viable counts (TVC), water activity (a w ), and cyclone recovery (CR) defined as the dependent variables. The increase in air inlet temperature from 120 to 160°C induced a significant (p < 0.001) reduction in the TVC from 9.02 to 7.20 log cfu/g, which corresponds to a97.5% loss of the L. acidophilus viable counts. On the other hand, the increase in the feed flow rate from 6 to 7.5 mL/min significantly reduced (p < 0.001) the heat-induced viability loss. A further increase in the feeding rate did not further modify the achieved thermo protection, and a detrimental impact of cyclone recovery (reduction) and water activity (increase) of the powder was observed. Using pruned quadratic mathematical models, the optimum spray-drying conditions for the production of maximally viable microencapsulated L. acidophilus were 133.34°C and 7.14 mL/min. The physicochemical and structural characteristics of the powders produced were acceptable for application with regards to residual water content, particles mean size, and thermo physical properties to ensure appropriate storage stability under room temperature conditions, with a low inactivation rate of L. acidophilus. Microcapsules appeared partially collapsed by scanning electron microscope with a spherical shape with surface concavities.

Proton transfer reaction time‐of‐flight mass spectrometry monitoring of the evolution of volatile compounds during lactic acid fermentation of milk

We apply, for first time, the recently developed proton transfer reaction time-of-flight mass spectrometry (PTR-TOF-MS) apparatus as a rapid method for the monitoring of lactic acid fermentation (LAF) of milk. PTR-TOF-MS has been proposed as a very fast, highly sensitive and versatile technique but there have been no reports of its application to dynamic biochemical processes with relevance to the food industry. LAF is a biochemical-physicochemical dynamic process particularly relevant for the dairy industry as it is an important step in the production of many dairy products. Further, LAF is important in the utilization of the by-products of the cheese industry, such as whey wastewaters. We show that PTR-TOF-MS is a powerful method for the monitoring of major volatile organic chemicals (VOCs) formed or depleted during LAF, including acetaldehyde, diacetyl, acetoin and 2-propanone, and it also provides information about the evolution of minor VOCs such as acetic acid, 2,3-pentanedione, ethanol, and off-flavor related VOCs such as dimethyl sulfide and furfural. This can be very important considering that the conventional measurement of pH decrease during LAF is often ineffective due to the reduced response of pH electrodes resulting from the formation of protein sediments. Solid-phase microextraction gas chromatography/mass spectrometry (SPME-GC/MS) data on the inoculated milk base and final fermented product are also presented to supporting peak identification. We demonstrate that PTR-TOF-MS can be used as a rapid, efficient and non-invasive method for the monitoring of LAF from headspace, supplying important data about the quality of the final product and that it may be used to monitor the efficacy of manufacturing practices.

Monitoring of volatile compound emissions during dry anaerobic digestion of the Organic Fraction of Municipal Solid Waste by Proton Transfer Reaction Time-of-Flight Mass Spectrometry.

Volatile Organic Compounds (VOCs) formed during anaerobic digestion of aerobically pre-treated Organic Fraction of Municipal Solid Waste (OFMSW), have been monitored over a 30 day period by a direct injection mass spectrometric technique: Proton Transfer Reaction Time-of-Flight Mass Spectrometry (PTR-ToF-MS). Most of the tentatively identified compounds exhibited a double-peaked emission pattern which is probably the combined result from the volatilization or oxidation of the biomass-inherited organic compounds and the microbial degradation of organic substrates. Of the sulfur compounds, hydrogen sulfide had the highest accumulative production. Alkylthiols were the predominant sulfur organic compounds, reaching their maximum levels during the last stage of the process. H(2)S formation seems to be influenced by the metabolic reactions that the sulfur organic compounds undergo, such as a methanogenesis induced mechanism i.e. an amino acid degradation/sulfate reduction. Comparison of different batches indicates that PTR-ToF-MS is a suitable tool providing information for rapid in situ bioprocess monitoring.

Rapid characterization of dry cured ham produced following different PDOs by proton transfer reaction time of flight mass spectrometry (PTR-ToF-MS)

In the present study, the recently developed proton transfer reaction time of flight mass spectrometry (PTR-ToF-MS) technique was used for the rapid characterization of dry cured hams produced according to 4 of the most important Protected Designations of Origin (PDOs): an Iberian one (Dehesa de Extremadura) and three Italian ones (Prosciutto di San Daniele, Prosciutto di Parma and Prosciutto Toscano). In total, the headspace composition and respective concentration for nine Spanish and 37 Italian dry cured ham samples were analyzed by direct injection without any pre-treatment or pre-concentration. Firstly, we show that the rapid PTR-ToF-MS fingerprinting in conjunction with chemometrics (Principal Components Analysis) indicates a good separation of the dry cured ham samples according to their production process and that it is possible to set up, using data mining methods, classification models with a high success rate in cross validation. Secondly, we exploited the higher mass resolution of the new PTR-ToF-MS, as compared with standard quadrupole based versions, for the identification of the exact sum formula of the mass spectrometric peaks providing analytical information on the observed differences. The work indicates that PTR-ToF-MS can be used as a rapid method for the identification of differences among dry cured hams produced following the indications of different PDOs and that it provides information on some of the major volatile compounds and their link with the implemented manufacturing practices such as rearing system, salting and curing process, manufacturing practices that seem to strongly affect the final volatile organic profile and thus the perceived quality of dry cured ham.

Extending the dynamic range of proton transfer reaction time‐of‐flight mass spectrometers by a novel dead time correction

Proton transfer reaction time-of-flight mass spectrometry (PTR-TOF-MS) allows for very fast simultaneous monitoring of volatile organic compounds (VOCs) in complex environments. In several applications, food science and food technology in particular, peaks with very different intensities are present in a single spectrum. For VOCs, the concentrations range from the sub-ppt all the way up to the ppm level. Thus, a large dynamic range is necessary. In particular, high intensity peaks are a problem because for them the linear dependency of the detector signal on VOC concentration is distorted. In this paper we present, test with real data, and discuss a novel method which extends the linearity of PTR-TOF-MS for high intensity peaks far beyond the limit allowed by the usual analytical correction methods such as the so-called Poisson correction. Usually, raw data can be used directly without corrections with an intensity of up to about 0.1 ions/pulse, and the Poisson correction allows the use of peaks with intensities of a few ions/pulse. Our method further extends the linear range by at least one order of magnitude. Although this work originated from the necessity to extend the dynamic range of PTR-TOF-MS instruments in agro-industrial applications, it is by no means limited to this area, and can be implemented wherever dead time corrections are an issue.

PTR-ToF-MS and data mining methods: a new tool for fruit metabolomics

Proton Transfer Reaction-Mass Spectrometry (PTR-MS) in its recently developed implementation based on a time-of-flight mass spectrometer (PTR-ToF-MS) has been evaluated as a possible tool for rapid non-destructive investigation of the volatile compounds present in the metabolome of apple cultivars and clones. Clone characterization is a cutting-edge problem in technical management and royalty application, not only for apple, aiming at unveiling real properties which differentiate the mutated individuals. We show that PTR-ToF-MS coupled with multivariate and data mining methods may successfully be employed to obtain accurate varietal and clonal apple fingerprint. In particular, we studied the VOC emission profile of five different clones belonging to three well known apple cultivars, such as ‘Fuji’, ‘Golden Delicious’ and ‘Gala’. In all three cases it was possible to set classification models which can distinguish all cultivars and some of the clones considered in this study. Furthermore, in the case of ‘Gala’ we also identified estragole and hexyl 2-methyl butanoate contributing to such clone characterization. Beside its applied relevance, no data on the volatile profiling of apple clones are available so far, our study indicates the general viability of a metabolomic approach for volatile compounds in fruit based on rapid PTR-ToF-MS fingerprinting.

Stability of Lactobacillus rhamnosus GG in prebiotic edible films.

Highlights • The concept of prebiotic gelatine based edible films containing probiotics is presented.• Prebiotic edible films effectively protected L. rhamnosus GG.• Inulin and wheat fibre improved the storage stability of L. rhamnosus GG.• Glucose-oligosaccharides and polydextrose reduced lethality during air drying.• Prebiotics resulted in a more compact, less porous and reticular film structure.

Ice Cream as a Vehicle for Incorporating Health‐Promoting Ingredients: Conceptualization and Overview of Quality and Storage Stability

Ice cream is a product with peculiar textural and organoleptic features and is highly appreciated by a very broad spectrum of consumers. Ice creams structure and colloidal design, together with its low-temperature storage, renders it a very promising carrier for the stabilization and in vivo delivery of bioactive compounds and beneficial microorganisms. To date, many applications related to the design and development of functional ice cream have been documented, including products containing probiotics, prebiotics, synbiotics, dietary fibers, natural antioxidants such as polyphenols, essential and polyunsaturated fatty acids, and low glycemic index blends and blends fortified with mineral or trace elements. In this review, promising strategies for the incorporation of innovative functional additives to ice cream through the use of techniques such as microencapsulation, nanoemulsions, and oleogels are discussed, and current insights into the implications of matrix, processing, and digestion on bioactive compounds in frozen dairy desserts are comprehensively reviewed, thereby providing a holistic overview of the current and emerging trends in this functional food sector.

Effect of the pig rearing system on the final volatile profile of Iberian dry-cured ham as detected by PTR-ToF-MS

The volatile compound profile of dry-cured Iberian ham lean and subcutaneous fat from pigs fattened outdoors on acorn and pasture (Montanera) or on high-oleic concentrated feed (Campo) was investigated by proton transfer reaction time-of-flight mass spectrometry. In addition to the usual proton transfer ionization the novel switchable reagent ions system was implemented which allows the use of different precursor ions (H(3)O(+), NO(+) and O(2)(+)). The analysis of the lean and subcutaneous fat volatile compounds allowed a good sample discrimination according to the diet. Differences were evident for several classes of compounds: in particular, Montanera hams showed higher concentrations of aldehydes and ketones and lower concentrations of sulfur-containing compounds compared to Campo hams. The use of NO(+) as precursor ion confirmed the results obtained with H(3)O(+) in terms of classification capability and provides additional analytical insights.