Direct injection mass spectrometry (DIMS) entails the direct introduction of a gaseous sample into a mass analyser without prior treatment or separation. DIMS techniques offer the opportunity to ...monitor processes in time, with limits of detection as low as 0.5 parts per trillion in volume (for a 1 s measurement time) while providing results with high informational content. This review provides insight into current and promising future developments of DIMS in the analysis of grape, wine and other alcoholic beverages. Thanks to its unique characteristics, DIMS allows the online monitoring of volatile organic compounds (VOCs) released by grapes during fermentative bioprocesses or by wine directly from the glass headspace or during drinking. A DIMS-based approach can also be adopted to perform quality control and high-throughput analysis, allowing us to characterise the volatile profile of large sample sets rapidly and in a comprehensive fashion. Furthermore, DIMS presents several characteristic elements of green analytical chemistry approaches, catalysing an interest linked to the development of sustainable paths in research and development activities in the field of viticulture and oenology.
Methanol, naturally present in small quantities in the distillation of alcoholic beverages, can lead to serious health problems. When it exceeds a certain concentration, it causes blindness, organ ...failure, and even death if not recognized in time. Analytical techniques such as chromatography are used to detect dangerous concentrations of methanol, which are very accurate but also expensive, cumbersome, and time-consuming. Therefore, a gas sensor that is inexpensive and portable and capable of distinguishing methanol from ethanol would be very useful. Here, we present a resistive gas sensor, based on tin oxide nanowires, that works in a thermal gradient. By combining responses at various temperatures and using machine learning algorithms (PCA, SVM, LDA), the device can distinguish methanol from ethanol in a wide range of concentrations (1–100 ppm) in both dry air and under different humidity conditions (25–75% RH). The proposed sensor, which is small and inexpensive, demonstrates the ability to distinguish methanol from ethanol at different concentrations and could be developed both to detect the adulteration of alcoholic beverages and to quickly recognize methanol poisoning.
Sweetness is one of the main drivers of consumer preference, and thus is given high priority in apple breeding programmes. Due to the complexity of sweetness evaluation, soluble solid content (SSC) ...is commonly used as an estimation of this trait. Nevertheless, it has been demonstrated that SSC and sweet taste are poorly correlated. Though individual sugar content may vary greatly between and within apple cultivars, no previous study has tried to investigate the relationship between the amount of individual sugars, or ratios of these, and apple sweetness. In this work, we quantified the major sugars (sucrose, glucose, fructose, xylose) and sorbitol and explored their influence on perceived sweetness in apple; we also related this to malic acid content, SSC and volatile compounds. Our data confirmed that the correlation between sweetness and SSC is weak. We found that sorbitol content correlates (similarly to SSC) with perceived sweetness better than any other single sugar or total sugar content. The single sugars show no differentiable importance in determining apple sweetness. Our predictive model based on partial least squares regression shows that after sorbitol and SSC, the most important contribution to apple sweetness is provided by several volatile compounds, mainly esters and farnesene.
Volatile compounds play a key role in the formation of the well-recognized and widely appreciated raspberry aroma. Studies on the isolation and identification of volatile compounds in raspberry fruit ...(Rubus idaeus L.) are reviewed with a focus on aroma-related compounds. A table is drawn up containing a comprehensive list of the volatile compounds identified so far in raspberry along with main references and quantitative data where available. Two additional tables report the glycosidic bond and enantiomeric distributions of the volatile compounds investigated up to now in raspberry fruit. Studies on the development and evolution of volatile compounds during fruit formation, ripening and senescence, and genetic and environmental influences are also reviewed. Recent investigations showing the potential role of raspberry volatile compounds in cultivar differentiation and fruit resistance to mold disease are reported as well. Finally a summary of research done so far and our vision for future research lines are reported.
The capacity to emit isoprene, among other stresses, protects plants from drought, but the molecular mechanisms underlying this trait are only partly understood. The Arecaceae (palms) constitute a ...very interesting model system to test the involvement of isoprene in enhancing drought tolerance, as their high isoprene emissions may have contributed to make them hyperdominant in neotropical dry forests, characterized by recurrent and extended periods of drought stress. In this study we isolated and functionally characterized a novel isoprene synthase, the gene responsible for isoprene biosynthesis, from Copernicia prunifera, a palm from seasonally dry tropical forests. When overexpressed in the non-emitter Arabidopsis thaliana, CprISPS conferred significant levels of isoprene emission, together with enhanced tolerance to water limitation throughout plant growth and development, from germination to maturity. CprISPS overexpressors displayed higher germination, cotyledon/leaf greening, water usage efficiency, and survival than WT Arabidopsis under various types of water limitation. This increased drought tolerance was accompanied by a marked transcriptional up-regulation of both ABA-dependent and ABA-independent key drought response genes. Taken together, these results demonstrate the capacity of CprISPS to enhance drought tolerance in Arabidopsis and suggest that isoprene emission could have evolved in Arecaceae as an adaptive mechanism against drought.
Methyl ethyl ketone (MEK) is an important compound in atmospheric chemistry.
While attention has been paid mostly to anthropogenic sources of MEK,
recently it has been shown that biogenic sources are ...globally as important as
anthropogenic ones. However, the origin of biogenic MEK has yet to be
completely elucidated. We present the full mechanism by which within-plant
transformation of methyl vinyl ketone (MVK) and, to a minor extent, of
2-butanol and 3-buten-2-ol, is a source of biogenic MEK. Such transformation
is observed in red oak for both exogenous MVK, taken up from the atmosphere,
and endogenous MVK generated within a plant when it experiences stress (e.g. heat stress).
Endogenous MVK emitted by plants is typically explained by within-plant
oxidation of isoprene caused by oxidative stress. In this study we show that
MVK and MEK emissions caused by heat stress are not related to isoprene in
isoprene-emitting plants, implying that the massive carbon investment that
plants commit to isoprene production is not explained by a direct antioxidant
role. The presented mechanism can be important for inclusion in plant
emission and in plant–atmosphere interaction models.
Volatile organic compounds (VOCs) and biogenic VOCs (BVOCs), in particular, are a major topic in food science and technology. They play an important role in the perception of odor and flavor and, ...thus, in food appreciation. Their fast, non-invasive detection helps to control product quality and to monitor fundamental and industrial processes. Furthermore, there is increasing concern about the impact of VOCs and BVOCs from food production on our environment and health.
In this contribution, we discuss food-related applications of proton transfer reaction mass spectrometry (PTR-MS), an emerging technique that allows direct, fast, sensitive monitoring of VOCs. After introducing the principles of PTR-MS, we review its applications in food science and technology, highlighting its capabilities from using complete mass spectra as characteristic fingerprints all the way to identifying and quantifying single compounds in a complex food matrix. We end with a description of fundamental studies from food sciences and outline new opportunities offered by recent technological advances.
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 H3O+ 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.
Mascarpone, a soft-spread cheese, is an unripened dairy product manufactured by the thermal-acidic coagulation of milk cream. Due to the mild flavor and creamy consistency, it is a base ingredient in ...industrial, culinary, and homemade preparations (e.g., it is a key constituent of a widely appreciated Italian dessert 'Tiramisù'). Probably due to this relevance as an ingredient rather than as directly consumed foodstuff, mascarpone has not been often the subject of detailed studies. To the best of our knowledge, no investigation has been carried out on the volatile compounds contributing to the mascarpone cheese aroma profile. In this study, we analyzed the Volatile Organic Compounds (VOCs) in the headspace of different commercial mascarpone cheeses by two different techniques: Headspace-Solid Phase Microextraction-Gas Chromatography-Mass Spectrometry (HS-SPME GC-MS) and Proton-Transfer Reaction-Mass Spectrometry coupled to a Time of Flight mass analyzer (PTR-ToF-MS). We coupled these two approaches due to the complementarity of the analytical potential-efficient separation and identification of the analytes on the one side (HS-SPME GC-MS), and effective, fast quantitative analysis without any sample preparation on the other (PTR-ToF-MS). A total of 27 VOCs belonging to different chemical classes (9 ketones, 5 alcohols, 4 organic acids, 3 hydrocarbons, 2 furans, 1 ester, 1 lactone, 1 aldehyde, and 1 oxime) have been identified by HS-SPME GC-MS, while PTR-ToF-MS allowed a rapid snapshot of volatile diversity confirming the aptitude to rapid noninvasive quality control and the potential in commercial sample differentiation. Ketones (2-heptanone and 2-pentanone, in particular) are the most abundant compounds in mascarpone headspace, followed by 2-propanone, 2-nonanone, 2-butanone, 1-pentanol, 2-ethyl-1-hexanol, furfural and 2-furanmethanol. The study also provides preliminary information on the differentiation of the aroma of different brands and product types.
Functional characterization of plant volatile organic compound (VOC) biosynthetic genes and elucidation of the biological function of their products often involve the screening of large numbers of ...plants from either independent transformation events or mapping populations. The low time resolution of standard gas chromatographic methods, however, represents a major bottleneck for in planta genetic characterization of VOC biosynthetic genes. Here we present a fast and highly-sensitive method for the high-throughput characterization of VOC emission levels/patterns by coupling a Proton Transfer Reaction Time-of-Flight Mass Spectrometer to an autosampler for automation of sample measurement. With this system more than 700 samples per day can be screened, detecting for each sample hundreds of spectrometric peaks in the
m/z
15–300 range. As a case study, we report the characterization of VOC emissions from 116 independent
Arabidopsis thaliana
lines transformed with a putative isoprene synthase gene, confirming its function also when fused to a C-terminal 3×FLAG tag. We demonstrate that the method is more reliable than conventional characterization of transgene expression for the identification of the most highly isoprene-emitting lines. The throughput of this VOC screening method exceeds that of existing alternatives, potentially allowing its application to reverse and forward genetic screenings of genes contributing to VOC emission, constituting a powerful tool for the functional characterization of VOC biosynthetic genes and elucidation of the biological functions of their products directly in planta.
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