Nanozyme sensor array based on Fe, Se co-doped carbon material for the discrimination of Sulfur-containing compounds.

Developing methods for the accurate identification and analysis of sulfur-containing compounds (SCCs) is of great significance because of their essential roles in living organisms and the diagnosis of diseases. Herein, Se-doping improved oxidase-like activity of iron-based carbon material (Fe-Se/NC) was prepared and applied to construct a four-channel colorimetric sensor array for the detection and identification of SCCs (including biothiols and sulfur-containing metal salts). Fe-Se/NC can realize the chromogenic oxidation of 3,3',5,5'-tetramethylbenzidine (TMB) by activating O2 without relying on H2O2, which can be inhibited by different SCCs to diverse degrees to produce different colorimetric response changes as "fingerprints" on the sensor array. Principal component analysis (PCA) and hierarchical cluster analysis (HCA) revealed that nine kinds of SCCs could be well discriminated. The sensor array was also applied for the detection of SCCs with a linear range of 1-50 µM and a limit of detection of 0.07-0.2 µM. Moreover, colorimetric sensor array inspired by the different levels of SCCs in real samples were used to discriminate cancer cells and food samples, demonstrating its potential application in the field of disease diagnosis and food monitoring. ENVIRONMENTAL IMPLICATIONS: In this work, a four-channel colorimetric sensor array for accurate SCCs identification and detection was successfully constructed. The colorimetric sensor array inspired by the different levels of SCCs in real samples were also used to discriminate cancer cells and food samples. Therefore, this Fe-Se/NC based sensor array is expected to be applied in the field of environmental monitoring and environment related disease diagnosis.

Comprehensive metabolite and biological profile of "Sulmona Red Garlic" ecotype's aerial bulbils.

"Sulmona Red Garlic" is a well-known Italian traditional product. Bulbs, used for culinary purposes, have been largely investigated for their medicinal properties whereas aerial bulbils are usually removed as waste material. Here, for the first time, chemical composition and biological properties of the hydroalcoholic extract from aerial bulbils were investigated. Complementary information on metabolite composition were obtained using both NMR based untargeted and HPLC-DAD targeted methodologies. The NMR analysis revealed the presence of sugars, organic acids, amino acids, organosulphur compounds (methiin, alliin, allicin and cycloalliin), and other secondary metabolites. In particular, methiin and alliin were identified for the first time in the NMR spectra of aerial bulbil garlic extracts. Polyphenol content was determined by HPLC-DAD analysis: catechin, chlorogenic acid, and gallic acid turned out to be the most abundant phenolics. Hydroalcoholic extract blocked cell proliferation of colon cancer cell line HCT116 with an IC50 of 352.07 µg/mL, while it was non-toxic to myoblast cell line C2C12. In addition, it caused seedling germination reduction of two edible and herbaceous dicotyledon species, namely Cichorium intybus and C. endivia. Moreover, the same extract reduced the gene expression of TNF-α (tumor necrosis factor), HIF1-α (hypoxia-inducible factor), VEGFA (vascular endothelial growth factor), and transient receptor potential (TRP) M8 (TRPM8) indicating the ability to contrast cancer development through the angiogenic pathway. Final, in silico experiments were also carried out supporting the biological effects of organosulphur compounds, particularly alliin, which may directly interact with TRPM8. The results here reported suggest the potential use of garlic aerial bulbils often considered a waste product as a source in phytotherapeutic remedies.

Novel Cytotoxic Sesquiterpene Coumarin Ethers and Sulfur-Containing Compounds from the Roots of Ferula turcica.

Six new sesquiterpene coumarin ethers, namely turcicanol A (1), turcicanol A acetate (2), turcicanol B (3), turcica ketone (4), 11'-dehydrokaratavicinol (5), and galbanaldehyde (6), and one new sulfur-containing compound, namely turcicasulphide (7), along with thirty-two known secondary metabolites were isolated from the root of the endemic species Ferula turcica Akalin, Miski, & Tuncay through a bioassay-guided isolation approach. The structures of the new compounds were elucidated by spectroscopic analysis and comparison with the literature. Cell growth inhibition of colon cancer cell lines (COLO205 and HCT116) and kidney cancer cell lines (UO31 and A498) was used to guide isolation. Seventeen of the compounds showed significant activity against the cell lines.

Portable chemical detection platform for on-site monitoring of odorant levels in natural gas.

The adequate odorization of natural gas is critical to identify gas leaks and to reduce accidents. To ensure odorization, natural gas utility companies collect samples to be processed at core facilities or a trained human technician smells a diluted natural gas sample. In this work, we report a detection platform that addresses the lack of mobile solutions capable of providing quantitative analysis of mercaptans, a class of compounds used to odorize natural gas. Detailed description of the platform hardware and software components is provided. Designed to be portable, the platform hardware facilitates extraction of mercaptans from natural gas, separation of individual mercaptan species, and quantification of odorant concentration, with results reported at point-of-sampling. The software was developed to accommodate skilled users as well as minimally trained operators. Detection and quantification of six commonly used mercaptan compounds (ethyl mercaptan, dimethyl sulfide, n-propylmercaptan, isopropyl mercaptan, tert­butyl mercaptan, and tetrahydrothiophene) at typical odorizing concentrations of 0.1-5 ppm was performed using the device. We demonstrate the potential of this technology to ensure natural gas odorizing concentrations throughout distribution systems.

Aroma Characterization of Roasted Meat and Meat Substitutes Using Gas Chromatography-Mass Spectrometry with Simultaneous Selective Detection and a Dedicated Software Tool, AromaMS.

The development of healthier and more sustainable food products, such as plant-based meat substitutes (PBMSs), have received significant interest in recent years. A thorough understanding of the aroma composition can support efforts to improve the sensory properties of PBMS products and promote their consumer acceptability. Here, we developed an integrated hardware and software approach for aroma analysis of roasted food based on simultaneous analysis with three complementary detectors. Following the standard procedure of aroma headspace sampling and separation using solid-phase microextraction-gas chromatography, the column flow was split into three channels for the following detectors for the selective detection of nitrogen and sulfur (N/S)-containing compounds: an electron ionization-mass spectrometry for identification through a library search, a nitrogen-phosphorous detector, and a flame-photometric detector (FPD)/pulsed-FPD. Integration of results from the different types of detectors was achieved using a software tool, called AromaMS, developed in-house for data processing. As stipulated by the user, AromaMS performed either non-targeted screening for all volatile organic compounds (VOCs) or selective screening for N/S-containing VOCs that play a major role in the aroma experience. User-defined parameters for library matching and the retention index were applied to further eliminate false identifications. This new approach was successfully applied for comparative analysis of roasted meat and PBMS samples.

Biochemical Composition, Antioxidant Activity and Antiproliferative Effects of Different Processed Garlic Products.

Garlic (Allium sativum L.) is a type of agricultural product that is widely used as a food spice, herb and traditional medicine. White garlic (WG) can be processed into several kinds of products, such as green garlic (GG), Laba garlic (LAG) and black garlic (BG), which have multiple health effects. In this study, GC-MS (gas chromatography-mass spectrometry), DPPH (1,1'-diphenyl-2-propionyl hydrazide) radical scavenging, hydroxyl radical scavenging and MTT (3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyl tetrazolium bromide) in vitro assays were used to compare the composition, antioxidant and antiproliferation effects of different processed garlic extracts. The relationship between the constituents and the bioactivities was analyzed using the principal components analysis (PCA) and heatmap analysis. BG showed the highest antioxidant activity (IC50 = 0.63 ± 0.02 mg/mL) in DPPH radical assays and the highest antioxidant activity (IC50 = 0.80 ± 0.01 mg/mL) by hydroxyl radical assay. Moreover, GC-MS results showed that 12 organosulfur compounds were detected in the extracts of four garlic products, and allyl methyl trisulfide showed a positive relation with the anticancer activity on SMMC-7721 cells (hepatocellular carcinoma cells). The results suggested that the processing of garlic had a significant influence on the constituents and antioxidant effects and that GG, LAG and BG might be better candidates for the related functional food products compared to WG.

Effect of face masks on salivary parameters and halitosis: Randomized controlled crossover trial.

BACKGROUND: Face masking is associated with self-perceived dry mouth and halitosis. Aim of the study was to measure the effect of different face masks on salivary parameters and halitosis. METHODS: The randomized controlled crossover clinical trial with four periods included 40 oral healthy participants using different face masks (cloth mask, surgical mask, filtering facepiece 2 [FFP2] mask) or no mask (control) for 4 h in random order. Unstimulated salivary flow rate (primary outcome) and stimulated salivary flow rate, salivary pH and buffer capacity of stimulated and unstimulated saliva (secondary outcomes, blinded), and volatile sulfur compounds (secondary outcome) were measured before and after the 4-h periods. Statistical analysis was performed by repeated measures ANOVA (p < 0.05). RESULTS: Of 40 randomized participants, 39 completed the study. Unstimulated salivary flow rate prior to face masking amounted to 0.6 ± 0.3 ml/min. Face masking had no significant effect on unstimulated salivary flow (p = 0.550). Face masking had also no significant effect on the other salivary parameters (p ≥ 0.518). The concentration of volatile sulfur compounds (VSC) prior to face masking amounted to 157.3 ± 59.7 ppb. After face masking, the concentration of VSC increased slightly, but not significantly (p = 0.055): 168.1 ± 76.3 ppb (control), 199.3 ± 132.7 ppb (cloth masks), 188.5 ± 101.1 ppb (surgical masks), and 189.7 ± 90.1 ppb (FFP2 masks). CONCLUSION: Four hours of face masking did not change the salivary flow rate, pH, and buffer capacity, and had no significant effect on VSC's levels. Wearing face masks does not seem to result in measurable side-effects on salivary parameters such as a reduced salivary flow rate or VSC's levels. CLINICAL TRIAL REGISTRATION: The protocol was prospectively registered at ClinicalTrials.gov (NCT04914208) on June 4, 2021.

Concerning perceived and clinically-measured levels of halitosis.

The different types of self-reported halitosis complaints include those where one feels that one's breath smells bad, where one feels that one has bad breath because of the attitudes of others, and where others have pointed out the presence of bad breath. The results of previous studies comparing the objective and subjectives measures of halitosis are inconsistent, and few studies have used gas chromatography (GC) to measure halitosis in a large sample. This study aimed to examine the objectively measured halitosis levels based on the reasons individuals are concerned about halitosis. We included 2063 patients who visited the halitosis clinic at a university dental hospital. Halitosis was assessed using GC, self-administered questionnaires, and oral examinations. Levels of volatile sulphur compounds (VSCs; H2S, CH3SH, and (CH3)2S) were set as objective measures of halitosis. Patients were grouped based on their answers to 'What made you concerned about bad breath?' into groups: 'self-perceived,' 'attitudes of others,' 'told by others,' and other reasons. Univariate and multivariable linear regression analyses were performed to examine factors associated with VSCs and objective halitosis levels. Age, sex, oral health status, smoking, drinking, and breakfast habits were used as confounders. Patients who answered 'told by others' (n= 691, 33.5%) showed the highest VSCs. Individuals whose halitosis was pointed out by others had higher objectively measured halitosis levels, while those concerned about the attitudes of others or perceived their own halitosis had lower objectively measured halitosis levels. These results suggest that the objective level of halitosis can differ on the basis of the reason underlying an individual's concern about their bad breath. Categorizing halitosis complaints and comparing them with objective halitosis levels may help reduce the anxiety of those who are concerned about halitosis and confirm the need for intervention for those with objective halitosis.

Seeing the smell of garlic: Detection of gas phase volatiles from crushed garlic (Allium sativum), onion (Allium cepa), ramsons (Allium ursinum) and human garlic breath using SESI-Orbitrap MS.

Allicin is the main flavour component of crushed raw garlic. This plant defence molecule has strong antibiotic properties. While measurements in the liquid phase using LC-MS are established, accessing reactive organosulfur compounds in the gas phase is still a challenge due to heat-degradation in the gas chromatograph. Using a gentle secondary electrospray ionisation coupled Orbitrap mass spectrometry procedure (SESI-Orbitrap MS), we measured gas phase concentrations of allicin evaporating from a pure solution. Despite the mild conditions, two quantitatively major allicin-derived breakdown products were found. The SESI-Orbitrap MS technique was used to follow the known chemistry of alliin, isoallin and methiin conversion in garlic, onion and ramsons. Allicin and its metabolites were also measured over two hours in human breath after garlic consumption. These results demonstrate the utility of SESI-Orbitrap MS for analysis of sulfur-containing volatiles from plants in the genus Allium and potentially for capturing volatilomes of foodstuffs in general.

Detection of volatile sulfur compounds (VSCs) in exhaled breath as a potential diagnostic method for oral squamous cell carcinoma.

BACKGROUND: Oral squamous cell carcinoma causes a significant proportion of global cancer morbidity and mortality. The aim of this study is to investigate whether the exhaled breath test can be a new, non-invasive, and effective method for diagnosing oral squamous cell carcinoma. METHODS: A comparative analysis of exhaled breath between patients with oral squamous cell carcinoma (OSCC) and healthy controls (HC) was performed with the Twin Breasor II™, a simple gas chromatography system. RESULTS: Both hydrogen sulfide (H2S) and methyl mercaptan (Ch3SH) were significantly higher in the OSCC group than in the HC group. The total sulfur concentration was also higher in the OSCC group, but there was no significant difference in the ratio of Ch3SH to H2S between the two groups. Using logistic regression, we constructed a new variable with an area under the curve (AUC) of 0.740, 68.0% sensitivity, and 72.0% specificity. CONCLUSIONS: Exhaled gas analysis via simple gas chromatography can potentially serve as an accessory non-invasive method for OSCC diagnosis.

Comprehensive Two-Dimensional Gas Chromatography as a Powerful Strategy for the Exploration of Broas Volatile Composition.

Broa is a Portuguese maize bread with characteristic sensory attributes that can only be achieved using traditional maize varieties. This study intends to disclose the volatile compounds that are mainly associated with the baking process of broas, which can be important contributors to their aroma. Twelve broas were prepared from twelve maize flours (eleven traditional maize varieties and one commercial hybrid). Their volatile compounds were analyzed by GC×GC-ToFMS (two-dimensional gas chromatography coupled with time-of-flight mass spectrometry) for an untargeted screening of the chemical compounds mainly formed during baking. It was possible to identify 128 volatiles that belonged to the main chemical families formed during this stage. Among these, only 16 had been previously detected in broas. The most abundant were furans, furanones, and pyranones, but the most relevant for the aroma of broas were ascribed to sulfur-containing compounds, in particular dimethyl trisulfide and methanethiol. Pyrazines might contribute negatively to the aroma of broas since they were present in higher amounts in the commercial broa. This work constitutes the most detailed study of the characterization of broas volatile compounds, particularly those formed during the Maillard reaction. These findings may contribute to the characterization of other maize-based foodstuffs, ultimately improving the production of foods with better sensory features.

Profiling volatile compounds from culture supernatants of periodontal bacteria using gas chromatography/mass spectrometry/olfactometry analysis with a monolithic silica gel adsorption device.

Halitosis is formed mainly by the volatile compounds produced by periodontal bacteria. Three volatile sulfur compounds (VSCs), hydrogen sulfide, methanethiol, and dimethyl sulfide, have attracted attention as major components of halitosis. However, these compounds cannot account for all odors. In this study, we profiled volatile compounds from the culture supernatants of periodontal bacteria using gas chromatography/mass spectrometry/olfactometry analysis with a monolithic silica gel adsorption device to investigate the potential odorous compounds. Periodontal bacteria have been found to produce volatile compounds belonging to various classes, such as alcohols, ketones, fatty acids, and aromatic compounds, in addition to VSCs. In addition, VSCs different from hydrogen sulfide and methanethiol, which are considered important causative compounds, may also influence to halitosis.

Case-control study related to the use of L-cysteine in the differential diagnosis of oral halitosis.

Oral halitosis is characterized by a foul, unpleasant breath that emanates from the oral cavity due to local or systemic conditions. Approximately 90% of offensive odors are caused by volatile sulfur compounds (VSCs). L-cysteine, used as a test solution to control bad breath, induces the formation of VSCs and serves as a preliminary rinse. The study aim was to investigate the effectiveness of L-cysteine solution in differentiating the origin of oral halitosis using a gas chromatography apparatus. Methods: In total, 37 patients with an average age of 49.56 years were evaluated and divided into two groups: halimetry before the use of L-cysteine (n= 37) and halimetry after the use of L-cysteine (n= 37). Patients over 18 years of age, without severe systemic health impairment or infectious/contagious diseases, and who did not use medicines that influenced their breath were included. Halimetry was performed using the OralCroma™ device. In the halimetry before the use of L-cysteine group, 5.40%, 5.40%, and 64.86% of the patients had high levels of sulfide, methyl mercaptan, and dimethyl sulfide, respectively. After the use of L-cysteine, 48.64%, 8.10%, and 37.84% of the patients had high levels of sulfide, methyl mercaptan, and dimethyl sulfide. In this study, L-cysteine proved to be important for the assessment of oral halitosis and effective in differentiating the origin of oral halitosis; therefore, this compound could be used for the differential diagnosis of oral halitosis origin using the OralChroma™ device.

Identification of volatile sulfur-containing compounds and the precursor of dimethyl sulfide in cold-pressed rapeseed oil by GC-SCD and UPLC-MS/MS.

Volatile sulfur-containing compounds (VSCs) provide an important contribution to foods due to their special odors. In this study, VSCs in 21 cold-pressed rapeseed oils (CROs) from 9 regions in China were extracted and separated by headspace solid-phase microextraction combined with gas chromatography coupled with sulfur chemiluminescence detection. 19 VSCs were identified by authentic standards, and the total concentration of VSCs in all CROs ranged from 49.0 to 18129 µg/kg. Dimethyl sulfide (DMS), with its high odor activity value (7-14574), was the most significant aroma contributor to the CROs. Furthermore, S-methylmethionine (SMM) in rapeseed was first affirmed by ultra-performance liquid chromatography-tandem mass spectrometry and isotope quantitation. The positive correlation coefficient between DMS and SMM was 0.793 (p < 0.05), which confirmed SMM as a crucial precursor of DMS in CROs. This study provided a theoretical basis for selecting rapeseed materials by the distribution of essential VSCs and the source of DMS.

Intake Estimation of Phytochemicals in a French Well-Balanced Diet.

Phytochemicals contribute to the health benefits of plant-rich diets, notably through their antioxidant and anti-inflammatory effects. However, recommended daily amounts of the main dietary phytochemicals remain undetermined. We aimed to estimate the amounts of phytochemicals in a well-balanced diet. A modelled diet was created, containing dietary reference intakes for adults in France. Two one-week menus (summer and winter) were devised to reflect typical intakes of plant-based foods. Existing databases were used to estimate daily phytochemical content for seven phytochemical families: phenolic acids, flavonoids (except anthocyanins), anthocyanins, tannins, organosulfur compounds, carotenoids, and caffeine. The summer and winter menus provided 1607 and 1441 mg/day, respectively, of total polyphenols (phenolic acids, flavonoids, anthocyanins, and tannins), the difference being driven by reduced anthocyanin intake in winter. Phenolic acids, flavonoids (including anthocyanins), and tannins accounted for approximately 50%, 25%, and 25% of total polyphenols, respectively. Dietary carotenoid and organosulfur compound content was estimated to be approximately 17 and 70 mg/day, respectively, in both seasons. Finally, both menus provided approximately 110 mg/day of caffeine, exclusively from tea and coffee. Our work supports ongoing efforts to define phytochemical insufficiency states that may occur in individuals with unbalanced diets and related disease risk factors.

Deodorization films based on polyphenol compound-rich natural deodorants and polycaprolactone for removing volatile sulfur compounds from kimchi.

As natural polyphenols have been known to have the deodorizing activity, the deodorizing properties and mechanisms of action of polyphenols, the main constituents of green tea extract (GTE), black tea extract (BTE), and grape seed extract (GSE), against volatile sulfur compounds (VSCs) in kimchi were investigated. Six VSCs were targeted and detected to be in high abundance in kimchi. The deodorizing activity (%) toward VSCs was found to be in the following order: GSE (58.4 to 91.8) >GTE (37.6 to 73.8) >BTE (28.4 to 60.3). This was attributed to the high phenolic (892.6 ± 10.5 mg GAE/g) and flavonoid (666.5 ± 23.9 mg CE/g) contents in GSE, that is, polymeric proanthocyanidins (85.97%). Particularly, the hydroxyl groups in the polyphenols showed deodorizing activity against VSCs via a sulfur-capture reaction. For packaging applications, deodorization films based on GSE and polycaprolactone were developed, and the GSE/polycaprolactone 20% films exhibited strong deodorizing effects (54.9 to 99.8%) against kimchi VSCs.

Comparative phytochemical profile of the elephant garlic (Allium ampeloprasum var. holmense) and the common garlic (Allium sativum) from the Val di Chiana area (Tuscany, Italy) before and after in vitro gastrointestinal digestion.

This study is aimed to comparatively investigate the phytochemical profiles, focusing on the nutritional and phytochemical properties of common garlic (Allium sativum L.; CG) and elephant garlic (EG) (Allium ampeloprasum var. holmense) collected from the Val di Chiana area (Tuscany, Italy). The results showed a lower amount of fibers, demonstrating a higher digestibility of the bulb, and sulfur-containing compounds in EG rather than in CG. Untargeted metabolomic profiling followed by supervised and unsupervised statistics allowed understanding the differences in phytochemical composition among the two bulbs, both as raw bulbs, processed following the in vitro gastrointestinal digestion process. Typical sulfur-containing compounds, such as alliin and N-gamma-glutamyl-S-allyl cysteine, could notably be detected in lower amounts in EG. EG maintains a distinct phytochemical signature during in vitro gastrointestinal digestion. Our findings support the distinct sensorial attributes of the bulbs.

Generation of key aroma compounds in Beijing roasted duck induced via Maillard reaction and lipid pyrolysis reaction.

This study explores the evolution of key aroma compounds and the chemical changes of their precursors, including reducing sugars, free amino acids, free fatty acids, thiamine and proximate compositions in Beijing roasted duck during roasting for 0-80 min. The results showed that the amounts and contents of 9 key aroma compounds in roasted ducks first quickly increased (p < 0.05) and subsequently remained constant (p > 0.05) after 50 min, except for a slight decrease between 70 and 80 min. Cysteine, cystine and methionine were the main free amino acids and could react with glucose and ribose to generate 2-furfurylthiol, dimethyl trisulfide and methional. Linoleic acid, α-linolenic acid and arachidonic acid had important effects on the increase of hexanal, octanal and nonanal together with the emergence and formation of heptanal, (E, E)-2,4-decadienal and 1-octene-3-ol. However, thiamine might not be the main precursor of the key aroma compounds in Beijing roasted duck.

Trapping and preconcentration of volatile organic sulfur compounds in water samples by portable and battery-powered trapping device prior to gas chromatography-sulfur chemiluminescence determination.

A simple, portable and battery-powered trapping device (iTrap) consisting of a purification tube, a trapping unit and a miniature air pump was developed for the pre-concentration of volatile organic sulfur compounds (VOSCs). The tested VOSCs, including methanthiol (MT), ethanethiol (ET), dimethyl sulfide (DMS), diethyl sulfide (DES) and dimethyl disulfide (DMDS), were firstly purged from water samples and then in situ pre-concentrated with the iTrap prior to their analysis by thermal desorption gas chromatography coupling with a sulfur chemiluminescence detector (TD-GC-SCD). Twenty-six adsorbents were studied to find the most suitable adsorbent for the efficient pre-concentration of VOSCs. Under optimal conditions, limits of detection of 6, 8, 6, 2 and 3 ng L-1 were obtained for MT, ET, DMS, DES and DMDS, respectively. The precisions were better than 5.3% (relative standard deviations, RSDs). The iTrap was successfully applied for the analysis of VOSCs in Certified Reference Materials, several surface water, underground water and wastewater samples collected from Pengzhou city, Sichuan, China. Moreover, the VOSCs trapped in the iTrap were much more stable than those directly stored in water samples and the recoveries for all samples could be maintained at acceptable levels (>73%), even their preservation time as long as 8 h.

Evaluation of endobronchial volatile sulfur compounds for rapid diagnosis of lung abscesses caused by obligate anaerobes using Oral Chroma™: A pilot study.

Endobronchial volatile sulfur compounds in patients with lung abscess or lung cancer were measured using the Oral Chroma™ gas chromatograph. High levels of hydrogen sulfide and methyl mercaptan were observed in some patients with lung abscess but not in patients with lung cancer. Measuring endobronchial volatile sulfur compounds could be useful for the rapid diagnosis of lung abscess caused by obligate anaerobes.