Mitigation of Off-Flavor in Huanglongbing-Affected Orange Juice Using Natural Citrus Non-Volatile Compounds.

Huanglongbing (HLB) disease has reduced orange yield and flavor quality in Florida. Orange juice (OJ) and peel molasses (PM) compounds are "from the named fruit" (FTNF) and were tested for their effects on HLB-affected OJ taste. These and other "target" compounds, reportedly found in citrus, were spiked into off-flavored, HLB-affected reference juices. The spiked juice was evaluated by a sensory panel in comparison with unspiked juice for "sweetness", "sourness", "bitterness", "astringency", and "aftertaste". Of the target compounds, feruloyl putrescine, taxifolin, and neodiosmin most effectively reduced "bitterness", feruloyl putrescine reduced "astringency" and "aftertaste", while feruloyl putrescine and neodiosmin enhanced perceived "sweetness", perhaps due to reduced bitterness. OJ and PM fractions containing reported bitter limonoids, hydroxycinnamates, hesperidin, and/or polymethoxylated flavones enhanced "sourness', "bitterness", "astringency", and "aftertaste", and/or suppressed perceived "sweetness" (perhaps due to enhanced bitterness). Other fractions, containing feruloyl putrescine and/or vicenin-2 enhanced "sweetness" and reduced "bitterness", "sourness", "astringency", and/or "aftertaste". These potentially FTNF compounds may be useful for management of HLB-affected OJ juice flavor.

Investigation on Key Molecules of Huanglongbing (HLB)-Induced Orange Juice Off-flavor.

Orange fruits from huanglongbing (HLB)-infected trees do not fully mature and show a severe off-flavor described as bitter-harsh, metallic, and less juicy and fruity. The investigation of juice from HLB-infected (HLBOJ) and healthy control oranges (COJ) by gas chromatography-mass spectrometry showed higher concentrations of fruity esters, such as ethyl butyrate and ethyl 2-methylbutyrate, and soapy-waxy alkanals, such as octanal and decanal, in the COJ, whereas the HLBOJ showed higher concentrations of green aldehydes such as hexanal and degradation compounds of limonene and linalool such as α-terpineol. Application of aroma extract dilution analysis on terpeneless peel oil led to the identification of long-chained aldehydes such as ( E, E)-2,4-decadienal, ( Z)-8-tetradecenal, trans-4,5-epoxy-( E)-2-decenal, ( Z)-4-decenal, and octanal with the highest flavor dilution factors among 25 odor-active volatiles in the peel oil of healthy oranges. Taste-guided fractionation and identification of the HLBOJ secondary metabolites followed by sensory validation revealed that flavanoids such as hesperidin may modulate the flavor to evoke the unacceptable harsh/metallic taste impression. Quantitation of the bitter components showed good correlation between the limonoid and flavanoid concentrations with the off-flavor and quality of the oranges obtained throughout the season.

Comprehensive two-dimensional gas chromatography and food sensory properties: potential and challenges.

Modern omics disciplines dealing with food flavor focus the analytical efforts on the elucidation of sensory-active compounds, including all possible stimuli of multimodal perception (aroma, taste, texture, etc.) by means of a comprehensive, integrated treatment of sample constituents, such as physicochemical properties, concentration in the matrix, and sensory properties (odor/taste quality, perception threshold). Such analyses require detailed profiling of known bioactive components as well as advanced fingerprinting techniques to catalog sample constituents comprehensively, quantitatively, and comparably across samples. Multidimensional analytical platforms support comprehensive investigations required for flavor analysis by combining information on analytes' identities, physicochemical behaviors (volatility, polarity, partition coefficient, and solubility), concentration, and odor quality. Unlike other omics, flavor metabolomics and sensomics include the final output of the biological phenomenon (i.e., sensory perceptions) as an additional analytical dimension, which is specifically and exclusively triggered by the chemicals analyzed. However, advanced omics platforms, which are multidimensional by definition, pose challenging issues not only in terms of coupling with detection systems and sample preparation, but also in terms of data elaboration and processing. The large number of variables collected during each analytical run provides a high level of information, but requires appropriate strategies to exploit fully this potential. This review focuses on advances in comprehensive two-dimensional gas chromatography and analytical platforms combining two-dimensional gas chromatography with olfactometry, chemometrics, and quantitative assays for food sensory analysis to assess the quality of a given product. We review instrumental advances and couplings, automation in sample preparation, data elaboration, and a selection of applications.

Evaluation of process parameters governing the aroma generation in three hazelnut cultivars (Corylus avellana L.) by correlating quantitative key odorant profiling with sensory evaluation.

The majority of the world hazelnut crop is roasted, thus developing a unique aroma that depends on the cultivar used and on the roasting conditions applied. Although several studies have investigated the volatile fraction of different cultivars and have correlated the data with overall sensory profiles, studies establishing a correlation between key odorants among the bulk of odorless volatiles and the respective aroma profiles are not yet available. On the basis of recently published stable isotope dilution assays (SIDAs) using comprehensive two-dimensional gas chromatography-time-of-flight mass spectrometry (GC×GC-TOF-MS), differences in concentrations of key odorants in different hazelnut cultivars roasted under defined conditions were monitored and compared with sensory data obtained by projective mapping, aroma profile analysis, and triangle tests. The results showed that the aroma-active compounds 2-acetyl-1-pyrroline, 2-propionyl-1-pyrroline, 5-methyl-(E)-2-hepten-4-one, 2,3-diethyl-5-methylpyrazine, 3,5-dimethyl-2-ethylpyrazine, and 2-furfurylthiol are appropriate marker odorants to differentiate the various nut aromas. In particular, the appreciated roasty, nutty aroma of optimally roasted hazelnuts was developed if both 5-methyl-(E)-2-hepten-4-one and 3-methyl-4-heptanone were >450 µg/kg, whereas the sum of the two 2-acyl-1-pyrrolines and two pyrazines should not exceed 400 µg/kg to avoid an over-roasted smell. Such a desired aroma can be obtained for each cultivar, but obviously specific roasting times, temperatures, and roasting techniques had to be applied.

Sensomics analysis of key hazelnut odorants (Corylus avellana L. 'Tonda Gentile') using comprehensive two-dimensional gas chromatography in combination with time-of-flight mass spectrometry (GC×GC-TOF-MS).

Comprehensive two-dimensional gas chromatography-mass spectrometry (GC×GC-MS) has been used a few times to identify and quantitate single aroma-active compounds, but the capability of this technique to monitor a complete set of key odorants evoking the aroma of a given food in one run has not been exploited so far. A fast, multiodorant analysis using GC×GC-TOF-MS in combination with stable isotope dilution assays (SIDA) was developed to quantitate the entire set of aroma compounds, the sensometabolome, of raw and roasted hazelnuts ( Corylus avellana L. 'Tonda Gentile') previously established by GC-olfactometry. The capability of the method to evaluate the aroma contribution of each sensometabolite was evaluated by introducing a new term, the limit of odor activity value (LOAV), indicating whether a given aroma compound can be determined down to an odor activity value (OAV) of 1 (odor activity value = ratio of concentration to odor threshold). The advantage of the new method was proven by comparing the performance parameters with a traditional one-dimensional approach using GC-ion trap mass-spectrometry (GC-IT-MS). The results showed that the detector linearity and sensitivity of GC×GC-TOF-MS was on average higher by a factor of 10 compared to GC-IT-MS, thus enabling the quantitation of the aroma relevant amounts of 22 key odorants of hazelnuts in one run of the 30 aroma-active compounds. Seven novel isotopically labeled internal standards were synthesized to meet the analytical requirements defined by electron impact ionization in TOF-MS, that is, to keep the label. On the basis of the quantitative results obtained, it was possible to closely mimic the aroma of raw and roasted 'Tonda Gentile' hazelnuts by preparing an aroma recombinate containing the key odorants at their natural concentrations occurring in the nuts.

Performance evaluation of non-targeted peak-based cross-sample analysis for comprehensive two-dimensional gas chromatography-mass spectrometry data and application to processed hazelnut profiling.

The continuous interest in non-targeted profiling induced the development of tools for automated cross-sample analysis. Such tools were found to be selective or not comprehensive thus delivering a biased view on the qualitative/quantitative peak distribution across 2D sample chromatograms. Therefore, the performance of non-targeted approaches needs to be critically evaluated. This study focused on the development of a validation procedure for non-targeted, peak-based, GC×GC-MS data profiling. The procedure introduced performance parameters such as specificity, precision, accuracy, and uncertainty for a profiling method known as Comprehensive Template Matching. The performance was assessed by applying a three-week validation protocol based on CITAC/EURACHEM guidelines. Optimized ¹D and ²D retention times search windows, MS match factor threshold, detection threshold, and template threshold were evolved from two training sets by a semi-automated learning process. The effectiveness of proposed settings to consistently match 2D peak patterns was established by evaluating the rate of mismatched peaks and was expressed in terms of results accuracy. The study utilized 23 different 2D peak patterns providing the chemical fingerprints of raw and roasted hazelnuts (Corylus avellana L.) from different geographical origins, of diverse varieties and different roasting degrees. The validation results show that non-targeted peak-based profiling can be reliable with error rates lower than 10% independent of the degree of analytical variance. The optimized Comprehensive Template Matching procedure was employed to study hazelnut roasting profiles and in particular to find marker compounds strongly dependent on the thermal treatment, and to establish the correlation of potential marker compounds to geographical origin and variety/cultivar and finally to reveal the characteristic release of aroma active compounds.