Four sulfur-containing compounds with anti-colon cancer effect from marine-derived fungus Aspergillus terreus.

Sulfur-containing natural products possess a variety of biological functions including antitumor, antibacterial, anti-inflammatory and antiviral activities. In this study, four previously undescribed sulfur-containing compounds asperteretals L and M, terreins A and B, together with 17 known compounds were obtained from a culture of marine fungus A. terreus supplemented with inorganic sulfur source Na2SO4. Their planar structures and absolute configurations were elucidated by NMR, HRESIMS, and ECD experiments. The in vitro cytotoxicities of compounds 1-21 against HCT-116 and Caco-2 were evaluated by SRB assay. Asperteretal M (2) exhibited activity against HCT-116 with the IC50 value at 30µM. The antiproliferative effect of asperteretal M was confirmed by colony formation assay and cell death staining. Furthermore, the preliminary study on the anti-colon cancer mechanism of asperteretal M was performed by RNA-seq analysis. Western blotting validated that asperteretal M significantly decreased the expression of cell-cycle regulatory proteins CDK1, CDK4, and PCNA in a concentration-dependent manner.

Supercritical Carbon Dioxide Extraction of Allium ursinum: Impact of Temperature and Pressure on the Extracts Chemical Profile.

The aim of this study was to extract Allium ursinum L. for the first time by supercritical carbon dioxide (SC-CO2 ) as green sustainable method. The impact of temperature in the range from 40 to 60 °C and pressure between 150 and 400 bar on the quality of the obtained extracts and efficiency of the extraction was investigated. The highest extraction yield (3.43 %) was achieved by applying the extraction conditions of 400 bar and 60 °C. The analysis of the extracts was performed by gas chromatography and mass spectrometry (GC/MS). The most dominant sulfur-containing constituent of the extracts was allyl methyl trisulfide with the highest abundance at 350 bar and 50 °C. In addition, the presence of other pharmacologically potent sulfur compounds was recorded including S-methyl methanethiosulfinate, diallyl trisulfide, S-methyl methylthiosulfonate, and dimethyl trisulfide. Multivariate data analysis tool was utilized to investigate distributions of the identified compounds among the extracts obtained under various extraction conditions and yields. It was determined that the SC-CO2 extraction can by efficiently used for A. ursinum.

Cyclic sulfur-containing compounds from Allium fistulosum 'Kujou'.

Sulfur-containing compounds, allicin and ajoene, etc., were isolated from Allium species. In a recent study, some sulfur-containing cyclic compounds were isolated from A. sativum, A. cepa, and A. fistulosum. Four new compounds with multiple rings with methyl disulfide or propyl disulfide at the side chain of the 7-position, kujounins A3 (1), B1 (2), B2 (3) and B3 (4), and two new thiolane type compounds with methoxy and methyl sulfoxide moiety at the 2- and 5-positions, and allium sulfoxides A2 (5) and A3 (6), were isolated from the acetone extract of the fresh white parts of Allium fistulosum 'Kujou' with three known compounds, kujounin A1 (7) and A2 (8), and allium sulfoxide A1 (9). The chemical structures of the new compounds were elucidated on the basis of physicochemical evidence. The kujounins had a rare molecular skeleton, which was tetrahydro-2H-difuro[3,2-b:2',3'-c]furan-5(5aH)-one.

Allithiolanes: Nine Groups of a Newly Discovered Family of Sulfur Compounds Responsible for the Bitter Off-Taste of Processed Onion.

The compounds responsible for the bitter off-taste of processed onion ( Allium cepa) were studied. Using a series of sensory-guided HPLC fractionations, the existence of nine groups of hitherto unknown sulfur compounds has been revealed. On the basis of spectroscopic data (MS, NMR, and IR), it was found that these compounds, trivially named allithiolanes A-I, are members of a large family of structurally closely related derivatives of 3,4-dimethylthiolane S-oxide, with the general formulas of C xH yO2S4, C xH yO3S5, and C xH yO4S6 ( x = 10-18, y = 18-30). The presence of multiple stereoisomers was observed for each group of allithiolanes. Allithiolanes possess an unpleasantly bitter taste with detection thresholds in the range of 15-30 ppm. Formation pathways of these newly discovered sulfur compounds were proposed.

Isolation and Identification of Three γ-Glutamyl Tripeptides and Their Putative Production Mechanism in Aged Garlic Extract.

We analyzed aged garlic extract (AGE) to understand its complex sulfur chemistry using post-column high-performance liquid chromatography with an iodoplatinate reagent and liquid chromatography high resolution mass spectrometry (LC-MS). We observed unidentified peaks of putative sulfur compounds. Three compounds were isolated and identified as γ-glutamyl-γ-glutamyl- S-methylcysteine, γ-glutamyl-γ-glutamyl- S-allylcysteine (GGSAC) and γ-glutamyl-γ-glutamyl- S-1-propenyl-cysteine (GGS1PC) by nuclear magnetic resonance and LC-MS analysis based on comparisons with chemically synthesized reference compounds. GGSAC and GGS1PC were novel compounds. Trace amounts of these compounds were detected in raw garlic, but the contents of these compounds increased during the aging process. Production of these compounds was inhibited using a γ-glutamyl transpeptidase (GGT) inhibitor in the model reaction mixtures. These findings suggest that γ-glutamyl tripeptides in AGE are produced by GGT during the aging process.

UPLC-QTOF-MS/MS-guided isolation and purification of sulfur-containing derivatives from sulfur-fumigated edible herbs, a case study on ginseng.

In this study, a novel ultra-performance liquid chromatography coupled with quadrupole/time-of-flight mass spectrometry (UPLC-QTOF-MS/MS)-guidance strategy was proposed for preparation of sulfur-containing derivatives in sulfur-fumigated edible herbs. Being versatile in both chromatographic separation and mass spectrometric detection, UPLC-QTOF-MS/MS was inducted into each experimental step for multifaceted purposes including finding, tracking, purity determination and structural elucidation of targeted compounds as well as UPLC-HPLC chromatographic conditions transplantation, whereby the isolation and purification procedures were greatly facilitated. Using this strategy, a new sulfur-containing ginsenoside Rg1 derivative (named compound I) was obtained from sulfur-fumigated ginseng. The chemical structure of compound I was elucidated to be (3ß, 6α, 12ß)-3, 12-dihydroxydammar-25-ene-6, 20-diylbis-ß-d-glucopyranoside, 24-sulfonic acid by QTOF-MS/MS, 1H-NMR and 13C-NMR analysis, and its generation mechanisms by sulfur-fumigation were accordingly discussed. The research deliverable suggests that the UPLC-QTOF-MS/MS-guidance strategy is promising for targeted preparation of sulfur-containing derivatives from sulfur-fumigated edible herbs.

Sulfur-containing compounds from the roots of Ferula latisecta and their cytotoxic activities.

Five new sulfur-containing compounds, with a new geometry (cis) of the propenyl moiety, and five known compounds were isolated from the roots of Ferula latisecta. The structures of these compounds, were elucidated on the basis of spectroscopic data including 1D and 2D NMR experiments and HRMS. All of the isolated compounds were tested against A2780, A549, HeLa, and HCT116 human cancer cell lines and some of them showed moderate cytotoxic activities.

Sulphur-containing compounds in the essential oil of Ferula alliacea roots and their mass spectral fragmentation patterns.

Context GC-MS analysis is the best way to characterize volatile sulphur-containing compounds. Ferula (Apiaceae) is a genus of perennial herbs. Due to the occurrence of essential oils or oleoresins in the Ferula species, these plants usually possess strong aromatic scent. Terpenoid compounds were the most abundant constituents of Ferula oils, however, in some of Ferula species, the essential oils were dominated by volatile sulphur-containing compounds. Objectives Ferula alliacea Boiss. is considered one of the sources of the oleo-gum-resin asafoetida. In this study, we analyzed the hydrodistilled essential oil from its dried roots and provide new data about retention indices and mass fragmentation patterns of some volatile sulphur-containing compounds that are useful for future studies on this class of compounds. Materials and methods The roots of F. alliacea were collected during the flowering stage of plant, from Bezgh, Kashmar to Neishabour road, Khorasan-Razavi province, Iran, in June 2012. The oil was obtained by hydrodistillation using a Clevenger apparatus and analyzed by GC-MS. Results This is the first report on phytochemical analysis of F. alliacea roots. Seventy-six components, representing 99.5% of the oil, were characterized. The major components were 10-epi-γ-eudesmol (22.3%), valerianol (12.5%), hinesol (8.3%), guaiol (7.3%) and Z-propenyl-sec-butyl trisulphide (6.5%). Predominant mass fragment ions of the identified sulphur-containing compounds are explained in this paper. Conclusion The volatile oil of F. alliacea mostly contains oxygenated sesquiterpenes, however, its odour was dominated by sulphur-containing compounds. The most abundant sulphur-containing compound includes Z-propenyl-sec-butyl trisulphide (6.5%).

Dirchromones: Cytotoxic Organic Sulfur Compounds Isolated from Dirca palustris.

Eight novel organic sulfur compounds featuring an unprecedented structure among natural organosulfur molecules are reported. The identified compounds, named dirchromones (1-8), were isolated from a dichloromethane extract of the roots, bark, and wood of Dirca palustris, an endemic shrub of eastern North America. Their identification was based on thorough NMR, IR, and HRMS spectroscopic data interpretation. These compounds showed cytotoxic and mild Gram-positive antibacterial activities in vitro, while being inactive against Gram-negative Escherichia coli and the yeast Candida albicans. This is the first report of sulfur-containing compounds from a species of the Thymelaeaceae.

Characterization of volatile components and odor-active compounds in the oil of edible mushroom Boletopsis leucomelas.

The volatile oil from Boletopsis leucomelas (Pers.) Fayod was extracted by hydrodistillation with diethylether, and the volatile components of the oil were analyzed by gas chromatography-mass spectrometry. The oil contained 86 components, representing 87.5% of the total oil. The main components of the oil were linoleic acid (15.0%), phenylacetaldehyde (11.2%), and palmitic acid (9.4%). Furthermore, sulfur-containing compounds including 3-thiophenecarboxaldehyde, 2-acetylthiazole, S-methyl methanethiosulfonate, and benzothiazole were detected using gas chromatography-pulsed flame photometric detection. The odor components were evaluated by the odor activity value, and aroma extract dilution analysis was performed through gas chromatography-olfactometry analysis. The oil had a mushroom-like, fatty, and burnt odor. The main components contributing to the mushroom-like and fatty odor were hexanal, nonanal, 1-octen-3-ol, and (2E)-nonenal, while the burnt odor was due to furfuryl alcohol, benzaldehyde, 5-methyl furfural, 2,3,5-trimethylpyrazine, 2-acethylthiazole, and indole.

Fusaodavinvin, a novel metabolite containing sulfur from the endophytic fungus Fusarium sp. (CTGU-ZL-34).

A novel metabolite containing sulfur, fusaodavinvin (1), was isolated from an endophytic fungus Fusarium sp.(CTGU-ZL-34), together with seven known compounds 2-8, and their structures were elucidated by NMR spectroscopy and MS. This is the first record of 3-(2R-hydroxyl-1-one-propane)-indole (compound 2) from nature. The isolated compounds were evaluated using the A549, Hep G2, Caski and MCF-7 cell lines by the MTT method, and compound 1 displayed significant inhibiting activity of four cancer cell lines with IC50 values of 11.5, 15.3, 15.2 and 60.5 microg/mL, respectively. However, compound 2 displayed no significant anticancer activity to the above four cancer cell lines.

Comparison between pre-fractionation and fractionation process of heavy gas oil for determination of sulfur compounds using comprehensive two-dimensional gas chromatography.

The separation of the organic sulfur compounds (OSC) of petroleum or its heavy fractions is a critical step and is essential for the correct characterization of these compounds, especially due to similar physical and chemical properties of polycyclic aromatic sulfur heterocycles (PASH) and polycyclic aromatic hydrocarbons (PAH). This similarity results in coelutions among PAH and PASH and for this reason former steps of fractionation are required before gas chromatographic analysis. The objective of this study was to evaluate the potential of GC×GC for the separation and identification of OSC in a heavy gas oil sample without fractionation, after pre-fractionation in an alumina column and also after fractionation process. This last one was performed with a modified stationary phase manufactured and characterized in the laboratory, called Pd(II)-MPSG, where palladium is chemically linked to silica through mercaptopropyl groups. The fractions obtained from both procedures were analyzed by GC×GC/TOFMS, which was effective to separate and identify various classes of OSC. A hundred and thirty-five compounds were tentatively identified in the sample that was only pre-fractionated. However, when the fractionation was also performed with the Pd(II)-MPSG phase, a larger number of sulfur compounds were found (317). Results have shown that the analysis of a pre-fractionated sample by GC×GC/TOFMS is suitable when the goal is a general characterization of classes of compounds in the sample, while a more detailed analysis of PASH can be performed, using also the fractionation Pd(II)-MPSG phase. GC×GC/TOFMS played a major role in the comparison of samples obtained from pre-fractionation and fractionation steps due to its high peak capacity, selectivity, organized distribution of chromatographic peaks and resolution.

Investigation of volatiles emitted from freshly cut onions (Allium cepa L.) by real time proton-transfer reaction-mass spectrometry (PTR-MS).

Volatile organic compounds (VOCs) in cut onions (Allium cepa L.) were continuously measured by PTR-MS during the first 120 min after cutting. The headspace composition changed rapidly due to the very reactive volatile sulfurous compounds emitted from onion tissue after cell disruption. Mass spectral signals corresponding to propanethial S-oxide (the lachrymatory factor) and breakdown products of this compound dominated 0-10 min after cutting. Subsequently, propanethiol and dipropyl disulfide predominantly appeared, together with traces of thiosulfinates. The concentrations of these compounds reached a maximum at 60 min after cutting. Propanethiol was present in highest concentrations and had an odor activity value 20 times higher than dipropyl disulfide. Thus, propanethiol is suggested to be the main source of the characteristic onion odor. Monitoring the rapid changes of VOCs in the headspace of cut onion necessitates a high time resolution, and PTR-MS is demonstrated to be a very suitable method for monitoring the headspace of freshly cut onions directly after cutting without extraction or pre-concentration.

High performance liquid chromatographic separations of gas oil samples and their hydrotreated products using commercial normal phases.

Three commercially available high performance liquid chromatography columns are used in normal phase or quasi-normal phase mode for the separation of gas oil samples. The columns are tested with 20 analytical standards to determine their suitability for separations of petroleum samples and their ability to separate the nitrogen group-types (pyrrole and pyridine) found in petroleum. The columns studied are polymeric hypercrosslinked polystyrene (HGN), a biphenyl phase, and a Chromegabond "DNAP" column from ES Industries. The HGN column separates gas oils based on both ring structure and heteroatom, while the biphenyl phase has low retention of most compounds studied in quasi-normal phase mode. The "DNAP" column is selective for nitrogen-containing compounds, separating them from PAHs as well as oxygen and sulphur compounds. Retention data of standards on all three columns is shown, along with chromatograms of gas oil samples on the HGN and "DNAP" columns.

Volatile flavours in raw egg yolk of hens fed on different diets.

BACKGROUND: Recent studies have suggested that the composition of lipophilic components of egg yolk is influenced by the feed. The aim of the present study was to isolate volatile flavours from egg yolk after different feeding trials using solvent extraction and thin layer high-vacuum distillation. The resulting aroma extract was analysed by various gas chromatographic techniques. Chickens were either fed with laying meal, laying meal plus cabbage and onion or laying meal plus rapeseed oil or held in free-range. RESULTS: The predominating odour impressions were described as onion-like. Comparing all analytical and sensory data of the flavour extracts, there were minimal differences among the respective samples. Free-range eggs contained fewer volatile compounds than the other samples, whereas rapeseed oil supplementation caused an enrichment of sulfur compounds. CONCLUSION: While data from gas chromatography/flame ionisation detection, gas chromatography/mass spectrometry and gas chromatography/olfactometry were less conclusive, the results from sulfur-specific analysis using gas chromatography/flame photometric detection showed a considerable effect. However, because of the low abundance of sulfur compounds in the yolk, these differences are not expected to be perceivable by the consumer.

[Modern technologies for extraction of balneological medicines from mineral waters].

A new technology for isolation of medicinal balneological preparations from mineral waters has been developed. It is based on the extraction of biologically active compounds (BAC) from mineral waters with ethanol following oxidative hydrolysis and water vapour distillation. This technology has no analogs both in this country and abroad. Unlike ordinary balneological medicines, those obtained by the new method do not contain inorganic matrix, show higher activity, and remain stable for a longer period. The primary composition of BACs isolated by the above technology was studied using solid-phase extraction and chromatomass-spectrometry. Analysis of Extramine, a medicinal preparation from Novonukutskaya hydrogen sulfide mineral water (Siberian Matsesta), allowed to identify active components responsible for its therapeutic effects and elucidate mechanisms of their action. The 15-year-long experience with practical application of BACs obtained with the help of the new technology has demonstrated that they possesses antiallergic, antiviral, and analeptic activities. These compounds increase general resistance of the organism to infection, promote removal of toxic substances, accelerate wound and injury healing, and prevent the development of herpes infection.

High antitrypanosomal activity of plant-derived sulphur-containing amides.

Chagas disease, caused by Trypanosoma cruzi, represents an important public health problem in endemic geographic regions in Middle and South America, affecting 15 million infected people. Treatment options are still limited due to the toxicity of available drugs, parasite resistance and poor drug activity during the chronic phase of the disease. In this study, we investigated the in vitro antitrypanosomal activity of 15 tropical plant-derived compounds with the aim of finding new drug candidates. Three novel sulphur-containing amides (methyldambullin, methylgerambullin and sakambullin) showed promising antitrypanosomal activities, with 50% effective concentrations (EC50 values) after 72 h exposure of 1.7, 1.23 and 5.18 µM, respectively, compared with EC50 values for amphotericin B and benznidazole of 0.71 µM and 30.89 µM, respectively.

Two novel sulfur compounds from the seeds of Raphanus sativus L.

The seeds of Raphanus sativus L., known as Lai-fu-zi in traditional Chinese Medicine, are always roasted before clinical use for avoiding nausea. During an investigation of the chemical difference between roasted and pre-roasted products, two novel sulfur-containing compounds, which mainly existed in the pre-roasted products, were isolated. Their structures and absolute configurations were established by spectroscopic and X-ray diffraction analysis.

Isolation and identification of a new cysteine sulfoxide and volatile sulfur compounds from Allium subgenus Melanocrommyum.

A new cysteine sulfoxide containing a pyridyl residue was identified in bulbs of Allium L. species belonging to the subgenus Melanocrommyum section Megaloprason. One of these species, Allium stipitatum, is widely used as a crop plant and in folk medicine in Central Asia. The new cysteine sulfoxide was identified as L-(+)-S-(2-pyridyl)-cysteine sulfoxide. Aside from this cysteine sulfoxide, several pyridyl compounds could be identified, which were formed out of cysteine sulfoxides by the action of alliinase. Found cysteine sulfoxides and their metabolites are chemically unstable; thus, the analysis is rather difficult. By combining high-performance liquid chromatography (HPLC), HPLC tandem mass spectrometry, NMR, IR, and photometric methods, full structure elucidation of the cysteine sulfoxide was possible. Alliinase reaction products were mainly determined by various MS techniques. The achieved results give new insights in the chemistry of Allium crop plants and are probably useful for chemotaxonomical classification of the subgenus Melanocrommyum.

Persicasulphide C, a new sulphur-containing derivative from Ferula persica.

A new sulphur-containing compound, persicasulphide C, was isolated from the roots of Ferula persica, and its structure was characterised by 1D- and 2D-NMR spectroscopy as well as HRMS. In addition, closer inspection of NMR spectra of the previously reported polysulphides (persicasulphides A and B) revealed that their structures are slightly different from those reported. In this article, the correct structures of persicasulphides A and B are also presented.