Identification of ethyl vanillin in strawberry (Fragaria × ananassa) using a targeted metabolomics strategy: From artificial to natural.

Improving flavor can be an important goal of strawberry through breeding that is enhanced through the accurate identification and quantification of flavor compounds. Herein, a targeted metabolomics strategy was developed using liquid-liquid extraction, an in-house standard database, and GC-MS/MS analysis. The database consisted of key food odorants (KFOs), artificial flavor compounds (AFCs) and volatiles. A total of 131 flavor compounds were accurately identified in Medallion® 'FL 16.30-128' strawberry. Importantly, ethyl vanillin was identified for the first time in natural food. Multiple techniques, including GC-MS, GC-MS/MS and UPLC-MS/MS were applied to ensure the identification. The ethyl vanillin in the Medallion® samples were determined in a range of concentrations from 0.070 ± 0.0006 µg/kg to 0.1372 ± 0.0014 µg/kg by using stable isotope dilution analysis. The identification of ethyl vanillin in strawberry implys the future commercial use a natural flavor compound and the potential to identify genes and proteins associated with its biosynthesis.

Interactions between kafirin and pickle-like odorants in soy sauce flavor Baijiu: Aroma profile change and binding mechanism.

The pickle-like odor, which was caused by the excess volatile sulfur compounds (VSCs), is an undesirable odor in soy sauce flavor Baijiu (SSB). The aim of this study was to explore the suppressing effect of kafirin, the internal prolamin of the raw material of Baijiu, on the pickle-like odor of SSB. The instrumental analysis (comprehensive two-dimensional gas chromatography, ultraviolet and visible spectrophotometry), human perceptions (aroma profile, odor thresholds) and in silico analysis methods (molecular docking) were combined to detect the changes of the pickle-like odor. After the addition of kafirin, the aroma profile of the pickle-like SSB changed and approached to that of the normal SSB. The volatility and the odor thresholds of VSCs decreased 22.05%-64.28% and increased 87.29%-232.57%, respectively. In conclusion, kafirin exhibited a significant suppressing effect on the pickle-like off-odor of SSB, and this effect could be used to reduce the off-odor of SSB and SSB-derived alcoholic beverages.

Reconstitution of the Flavor Signature of Laobaigan-Type Baijiu Based on the Natural Concentrations of Its Odor-Active Compounds and Nonvolatile Organic Acids.

Nonvolatile organic acids (NVOAs) associated with the Laobaigan flavor type of Baijiu were analyzed by a derivatization method, and 37 NVOAs were quantified. In addition, 33 odorants were judged to have high flavor dilution factors by application of aroma extract dilution analysis and quantification by gas chromatography coupled with mass spectrometry (GC-MS) and GC combined with quadrupole time-of-flight MS. The quantitative data obtained for the odorants and NVOAs were used to recombine the overall flavor of Baijiu. The odor of the reconstitution of the odor-active volatiles and the NVOAs was more similar to that of the original Baijiu sample than the sample that only contained odor-active volatiles, and the alcoholic and sweety flavor odor characters were reduced, while others, that is, fruity, acidic, floral, jujube and grain, were amplified. It was shown for the first time that NVOAs have effects on the volatiles in Baijiu and might obviously influence the intensity of certain aroma qualities.

A flavoromics strategy for the differentiation of different types of Baijiu according to the non-volatile organic acids.

Non-volatile organic acids (NVOAs) in 12 main flavor types of Baijiu were analyzed by a derivatization method combined with GC-MS and 38 NVOAs were quantified. Meanwhile, a flavoromics strategy based on the contents of NVOAs in the 12 flavor types of Baijiu was successfully used to the differentiation of Baijiu. PLS-DA models (explained variation, predictive capability) were used to consider different categories: fermentation process (0.931, 0.870), starter (0.921, 0.834), fermentation container (0.899, 0.810) and raw material (0.951, 0.909). Based on the selected categories, suitable separations were achieved, and the classification ability of these models were nearly 100%. As a result, the model demonstrated its ability to perfectly distinguish different types of Baijiu. Seventeen potential markers were identified by variable importance in projection method and were further processed using heatmap and hierarchical cluster analysis, indicating that the NVOAs had great discrimination power to differentiate Baijiu.

Interaction mechanism of kafirin with ferulic acid and tetramethyl pyrazine: Multiple spectroscopic and molecular modeling studies.

Ferulic acid (FA) and tetramethyl pyrazine (TMP) are intrinsic bioactive compounds in baijiu, and kafirin is the major protein of sorghum, which is the raw material of baijiu. In this study, the interactions of kafirin-FA and kafirin-TMP were investigated by multiple spectroscopic and molecular modeling techniques. Fluorescence spectra showed that intrinsic fluorescence of kafirin drastically quenched because of the formations of kafirin-FA and kafirin-TMP complexes. The CD studies indicated that the combination with FA or TMP decreased the α-helix content of kafirin slightly. The shifts and intensity changes of UV-Vis, FTIR and fluorescence spectra confirmed the formations of complexes. Moreover, the molecular docking and molecular dynamics studies showed that hydrophobic interactions and hydrogen bonds played major roles in the formations of kafirin-FA and kafirin-TMP complexes, and the formations of complexes made kafirin structures more compact. This work is of great importance for further quality improvement in baijiu and alcoholic beverages.

Analysis, occurrence, and potential sensory significance of tropical fruit aroma thiols, 3-mercaptohexanol and 4-methyl-4-mercapto-2-pentanone, in Chinese Baijiu.

Fruity notes are important to the flavor of Baijiu (Chinese Liquor) and are considered to originate from ester compounds; however, little is known about the other chemicals that contribute to the fruity aroma. In this study, the sensory impacts of two tropical fruit aroma thiols, 3-mercaptohexanol (3MH) and 4-methyl-4-mercapto-2-pentanone (4MP), in Chinese Light-, Strong- and Soy sauce flavor type Baijiu were systemically subjected to a sensory evaluation, qualitative and quantitative analysis, and multivariate statistical analyses. The flavor dilution factors of 3MH and 4MP were 9-729. The contents of 3MH and 4MP were the highest (p < 0.001) in Strong- and Soy sauce aroma-type Baijiu, respectively. According to their odor activity values (OAVs), 3MH (OAV: 1-22) and 4MP (OAV: 1-9) are important to the aroma of Baijiu. Notably, 4MP was identified for the first time in Baijiu, and the multivariate statistical analysis demonstrated that 3MH and 4MP could be used to differentiate Baijiu.

Insights into the Role of 2-Methyl-3-furanthiol and 2-Furfurylthiol as Markers for the Differentiation of Chinese Light, Strong, and Soy Sauce Aroma Types of Baijiu.

The sensory impacts of two thiols, 2-methyl-3-furanthiol (MFT) and 2-furfurylthiol (FFT), in Chinese soy sauce aroma-type Baijiu (SSB), strong aroma-type Baijiu (STB), and light aroma-type Baijiu (LTB) (liquor) were evaluated and combined with partial least squares discriminant analysis (PLS-DA) to differentiate Chinese Baijiu. The flavor dilution factors of these two thiols ranged from 81 to 6561, and quantitative results showed that MFT and FFT were significantly more abundant (p < 0.001) in SSB than in STB and LTB. The determined odor activity values (OAVs) suggest that MFT (OAV: 34-121) and FFT (OAV: 11-103) contribute significantly to the overall aroma profiles of LTB and STB. Interestingly, the OAVs of these two thiols were high (256-263) and did not significantly differ (p > 0.05) in SSB. Notably, hierarchical cluster analysis and PLS-DA results revealed that these compounds can be used to differentiate Chinese LTB, STB, and SSB. According to their prominent organoleptic and distinguishing roles, these two thiols can be regarded as flavor markers for SSB.

Untargeted and targeted metabolomics strategy for the classification of strong aroma-type baijiu (liquor) according to geographical origin using comprehensive two-dimensional gas chromatography-time-of-flight mass spectrometry.

A metabolomics strategy was developed to differentiate strong aroma-type baijiu (SAB) (distilled liquor) from the Sichuan basin (SCB) and Yangtze-Huaihe River Basin (YHRB) through liquid-liquid extraction coupled with GC×GC-TOFMS. PCA effectively separated the samples from these two regions. The PLS-DA training model was excellent, with explained variation and predictive capability values of 0.988 and 0.982, respectively. As a result, the model demonstrated its ability to perfectly differentiate all the unknown SAB samples. Twenty-nine potential markers were located by variable importance in projection values, and twenty-four of them were identified and quantitated. Discrimination ability is closely correlated to the characteristic flavor compounds, such as acid, esters, furans, alcohols, sulfides and pyrazine. Most of the marker compounds were less abundant in the SCB samples than in the YHRB samples. The quantitated markers were further processed using hierarchical cluster analysis for targeted analysis, indicating that the markers had great discrimination power to differentiate the SAB samples.

Evolution of the key odorants and aroma profiles in traditional Laowuzeng baijiu during its one-year ageing.

Changes of key odorants and aroma profiles of Chinese Laowuzeng baijiu during its one-year ageing were determined by HS-SPME-AEDA and direct injection-AEDA (DI-AEDA). Ethyl hexanoate, (E,E)-2,4-decadienal, and 2-phenylethyl acetate showed the highest FD value (486) in all ageing stages. With regards to aroma profiles, fruity, floral, acidic, sweet/honey and cheesy aromas were enhanced during storage, while pickled vegetable, grain and alcoholic notes weakened during the ageing. Quantitation and OAVs showed that most of the aroma compounds (OAVs > 1), including ethyl esters, aldehydes, and acids, increased their contents within the same period, whereas nonanal, 2-phenylethyl acetate, ethyl benzoate, 4-ethylguaiacol, propanol and 3-methyl-1-butanol decreased in content after the storage of 365 days. Simulated aged samples, in which fresh samples were spiked with 18 compounds, were examined by triangle tests, which indicated that the "fruity" compounds were crucial for maintaining the special aroma profile of an aged sample.

Characterization of key aroma-active sulfur-containing compounds in Chinese Laobaigan Baijiu by gas chromatography-olfactometry and comprehensive two-dimensional gas chromatography coupled with sulfur chemiluminescence detection.

Volatile sulfur-containing compounds (VSCs) often exist at extremely low concentrations, making them difficult to be determined. The VSCs in Laobaigan (LBG) Baijiu were analyzed by headspace solid-phase microextraction (HS-SPME) coupled with GC × GC-SCD, by which 12 VSCs were identified. Among the 65 odor-active compounds that were determined by GC-O with the aid of aroma extract dilution analysis (AEDA), benzenemethanethiol and 2-methyl-3-furanthiol were found to possess the highest FD values of 6561. The limits of detection (LODs) of the identified VSCs determined by GC × GC-SCD were found to be extremely low at 0.05-1.53 ng/L, with their analytical recoveries from 85% to 116%. The VSCs in the LBG samples were determined in a range of concentrations from 0.77 ±â€¯0.02 µg/L to 60.04 ±â€¯2.32 µg/L. Benzenemethanethiol, dimethyl trisulfide, 2-methyl-3-furanthiol and 2-furfurylthiol exhibited odor activity values (OAVs) > 100 and significantly contributed to the overall aroma of LBG Baijiu.

DeID - a data sharing tool for neuroimaging studies.

Funding institutions and researchers increasingly expect that data will be shared to increase scientific integrity and provide other scientists with the opportunity to use the data with novel methods that may advance understanding in a particular field of study. In practice, sharing human subject data can be complicated because data must be de-identified prior to sharing. Moreover, integrating varied data types collected in a study can be challenging and time consuming. For example, sharing data from structural imaging studies of a complex disorder requires the integration of imaging, demographic and/or behavioral data in a way that no subject identifiers are included in the de-identified dataset and with new subject labels or identification values that cannot be tracked back to the original ones. We have developed a Java program that users can use to remove identifying information in neuroimaging datasets, while still maintaining the association among different data types from the same subject for further studies. This software provides a series of user interaction wizards to allow users to select data variables to be de-identified, implements functions for auditing and validation of de-identified data, and enables the user to share the de-identified data in a single compressed package through various communication protocols, such as FTPS and SFTP. DeID runs with Windows, Linux, and Mac operating systems and its open architecture allows it to be easily adapted to support a broader array of data types, with the goal of facilitating data sharing. DeID can be obtained at http://www.nitrc.org/projects/deid.

Measure the Semantic Similarity of GO Terms Using Aggregate Information Content.

The rapid development of gene ontology (GO) and huge amount of biomedical data annotated by GO terms necessitate computation of semantic similarity of GO terms and, in turn, measurement of functional similarity of genes based on their annotations. In this paper we propose a novel and efficient method to measure the semantic similarity of GO terms. The proposed method addresses the limitations in existing GO term similarity measurement techniques; it computes the semantic content of a GO term by considering the information content of all of its ancestor terms in the graph. The aggregate information content (AIC) of all ancestor terms of a GO term implicitly reflects the GO term's location in the GO graph and also represents how human beings use this GO term and all its ancestor terms to annotate genes. We show that semantic similarity of GO terms obtained by our method closely matches the human perception. Extensive experimental studies show that this novel method also outperforms all existing methods in terms of the correlation with gene expression data. We have developed web services for measuring semantic similarity of GO terms and functional similarity of genes using the proposed AIC method and other popular methods. These web services are available at http://bioinformatics.clemson.edu/G-SESAME.