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.

Stereoselective separation of sulfoxaflor by electrokinetic chromatography and applications to stability and ecotoxicological studies.

An Electrokinetic Chromatography method was developed for the stereoselective analysis of sulfoxaflor, a novel sulfoximine agrochemical with two chiral centers. A screening with fourteen negatively charged CDs was performed and Succinyl-ß-CD (Succ-ß-CD) was selected. A 15 mM concentration of this CD in a 100 mM borate buffer (pH 9.0), using an applied voltage of 20 kV and a temperature of 15 °C made possible the baseline separation of the four stereoisomers of sulfoxaflor in 13.8 min. The evaluation of the linearity, accuracy, precision, LODs and LOQs of the method developed showed its performance to be applied to the analysis of commercial agrochemical formulations, the evaluation of the stability of sulfoxaflor stereoisomers under biotic and abiotic conditions, and to predict, for the first time, sulfoxaflor toxicity (using real concentrations instead of nominal concentrations), on two non-target aquatic organisms, the freshwater plant, Spirodela polyrhiza, and the marine bacterium, Vibrio fischeri.

Microscale extraction combined with gas chromatography/mass spectrometry for the simultaneous determination of polycyclic aromatic hydrocarbons and polycyclic aromatic sulfur heterocycles in marine sediments.

This paper describes a novel method based on an ultrasound-assisted extraction microscale device (UAE-MSD) for the rapid and simultaneous determination of polycyclic aromatic hydrocarbons (PAH) and polycyclic aromatic sulfur heterocycles (PASH) in marine sediments. Solvent extraction conditions were optimized by applying a simplex-centroid mixture design. Optimum conditions were used to validate and determine the concentrations of 17 PAH and 7 PASH. The best conditions were obtained by extracting sediments with 500 µL of DCM:MeOH (65:35, v:v) over 23 min of sonication. Analytes were determined by gas chromatography/mass spectrometry in selective ion monitoring (GC-MS/SIM). Matrix effects were evaluated, and matrix-matched calibration was used for quantitation. Analytical method validation was carried out using the certified reference material NIST SRM 1941b, as well as sediment spiked with PASH at three concentration levels. Recoveries ranged between 70.0 ± 3.5% and 119 ± 9.1% for PAH and 80.6 ± 10.4% and 120 ± 10% for PASH. Linearity (R2) was ≥0.99 for all compounds. Method detection limits ranged from 8.8 to 30.2 ng g-1, while limits of quantification ranged from 29.4 to 1011 ng g-1. UAE-MSD was applied to marine sediments exposed to different anthropogenic impacts collected in Todos os Santos Bay, Brazil. PAH concentrations ranged from

Effect of Oversulfation on the Composition, Structure, and In Vitro Anti-Lung Cancer Activity of Fucoidans Extracted from Sargassum aquifolium.

Intensive efforts have been undertaken in the fields of prevention, diagnosis, and therapy of lung cancer. Fucoidans exhibit a wide range of biological activities, which are dependent on the degree of sulfation, sulfation pattern, glycosidic branches, and molecular weight of fucoidan. The determination of oversulfation of fucoidan and its effect on anti-lung cancer activity and related signaling cascades is challenging. In this investigation, we used a previously developed fucoidan (SCA), which served as a native fucoidan, to generate two oversulfated fucoidan derivatives (SCA-S1 and SCA-S2). SCA, SCA-S1, and SCA-S2 showed differences in compositions and had the characteristic structural features of fucoidan by Fourier transform infrared (FTIR) and nuclear magnetic resonance (NMR) analyses. The anticancer properties of SCA, SCA-S1, and SCA-S2 against human lung carcinoma A-549 cells were analyzed in terms of cytotoxicity, cell cycle, Bcl-2 expression, mitochondrial membrane potential (MMP), expression of caspase-3, cytochrome c release, Annexin V/propidium iodide (PI) staining, DNA fragmentation, and the underlying signaling cascades. Our findings indicate that the oversulfation of fucoidan promotes apoptosis of lung cancer cells and the mechanism may involve the Akt/mTOR/S6 pathway. Further in vivo research is needed to establish the precise mechanism whereby oversulfated fucoidan mitigates the progression of lung cancer.

Sulfated and Sulfur-Containing Steroids and Their Pharmacological Profile.

The review focuses on sulfated steroids that have been isolated from seaweeds, marine sponges, soft corals, ascidians, starfish, and other marine invertebrates. Sulfur-containing steroids and triterpenoids are sourced from sedentary marine coelenterates, plants, marine sediments, crude oil, and other geological deposits. The review presents the pharmacological profile of sulfated steroids, sulfur-containing steroids, and triterpenoids, which is based on data obtained using the PASS program. In addition, several semi-synthetic and synthetic epithio steroids, which represent a rare group of bioactive lipids that have not yet been found in nature, but possess a high level of antitumor activity, were included in this review for the comparative pharmacological characterization of this class of compounds. About 140 steroids and triterpenoids are presented in this review, which demonstrate a wide range of biological activities. Therefore, out of 71 sulfated steroids, thirteen show strong antitumor activity with a confidence level of more than 90%, out of 50 sulfur-containing steroids, only four show strong antitumor activity with a confidence level of more than 93%, and out of eighteen epithio steroids, thirteen steroids show strong antitumor activity with a confidence level of 91% to 97.4%.

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.

Isolation and identification of putative precursors of the volatile sulfur compounds and their inhibition methods in heat-sterilized melon juices.

Volatile sulfur compounds, such as dimethyl sulfide, dimethyl disulfide and dimethyl trisulfide, cause the off-flavor in heat-sterilized juices and limit the commercial production of juices. In this study, we investigated the precursors for these volatile sulfur compounds and analyzed the potential inhibition methods. Upon separation of melon juice components using resin column, the dimethyl sulfide precursor was present in the acidic fraction whereas the dimethyl trisulfide precursor was present in neutral and acidic fractions. Exogenous addition experiments indicated S-methyl methionine was the precursor of dimethyl sulfide, and methionine was the precursor of dimethyl disulfide and dimethyl trisulfide. The release of volatile sulfur compounds was reduced by decreasing the pH to 2.0, or by adding epicatechin. We concluded S-methyl methionine and methionine were degraded into volatile sulfur compounds through nucleophilic substitution and Strecker degradation. This study can help establishing protocols for controlling the release of volatile sulfur compounds in heat-sterilized juices.

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.

Electrospinning fabrication for cloth-like carbon nanofiber films with hierarchical porous structure and their application in deep desulfurization.

A strategy for clean fuel by selective adsorption processing was deemed to be convenient and environmental-friendly in past decades. However, the development of adsorption desulfurization was tremendously subject to the fabrication of high-performance adsorbents with large capacity and high stability. Herein, we designed a novel route to fabricate the cloth-like carbon nanofiber film with a hierarchical porous structure by electrospinning. The structure and properties of the cloth-like carbon nanofiber films were determined by a series of characterizations. Subsequently, the desulfurization performance of the cloth-like carbon nanofiber films was examined by the simulated thiophene (TH) oil. Furthermore, the effect of adsorption conditions on the adsorption capacity was intensively investigated, such as carbonization temperature, initial concentration and desulfurization temperature. The results found that at optimal calcination temperature of 700 °C, the cloth-like carbon nanofiber films possessed the highest micropore volume (Vmic = 0.185 m3/g) and adsorption capacity (qe = 96.6 mg/g) at 800 mg/L initial concentration under the adsorption temperature of 25 °C. The results corroborated that the physical properties of the cloth-like carbon nanofiber films with the surface area of 417.8 m2/g, the total pore volume of 0.187 cm3/g and average pore diameter of 1.36 nm had an important influence on the high adsorption capacity. On this basis, the adsorption experimental data were best fitted to pseudo-second-order kinetic and Langmuir isotherm models. Furthermore, the other highlight of the cloth-like carbon nanofiber films was convenient for the separation from oil, thus achieving the desirable reused performance.

Development of the Method for Determination of Volatile Sulfur Compounds (VSCs) in Fruit Brandy with the Use of HS-SPME/GC-MS.

Volatile sulfur compounds (VSCs) play an important role in the aroma profile of fermented beverages. However, because of their low concentration in samples, their analysis is difficult. The headspace solid-phase microextraction (HS-SPME) technique coupled with gas chromatography and mass spectrometry (GC-MS) is one of the methods successfully used to identify VSCs in wine and beer samples. However, this method encounters more obstacles when spirit beverages are analyzed, as the ethanol content of the matrix decreases the method sensitivity. In this work, different conditions applied during HS-SPME/GC-MS analysis, namely: ethanol concentration, salt addition, time and temperature of extraction, as well as fiber coating, were evaluated in regard to 19 sulfur compounds. The best results were obtained when 50/30 µm Divinylbenzene/Carboxen/Polydimethylsiloxane (DVB/CAR/PDMS) was used to preconcentrate the analytes from the sample at 35 °C for 30 min. The dilution of samples to 2.5% v/v ethanol and the addition of 20% w/v NaCl along with 1% EDTA significantly improves the sensitivity of extraction. The optimized method was applied to three fruit brandy samples (plum, pear, and apple) and quantification of VSCs was performed. A total of 10 compounds were identified in brandy samples and their concentration varied greatly depending on the raw material used from production. The highest concentration of identified VSCs was found in apple brandy (82 µg/L).

Effect of microbial nutrients supply on coal bio-desulfurization.

Research on coal desulfurization is very important for economic, social, and environmentally sustainable development. In this study, three batches of shake flask experiments were conducted for coal bio-desulfurization using Acidithiobacillus ferrooxidans to explore the relationship between microbial nutrients (iron-free M9 K medium) supply and coal bio-desulfurization efficiency. The results showed that the removal rates of pyritic sulfur and total sulfur from coal effectively increased following reintroduction of coal into the filtrate from previous batch. The removal rates of pyritic sulfur and total sulfur were 55.6% and 10.0%, 77.1% and 16.1%, and 86.5% and 28.2%, respectively, in the three batch experiments without iron-free M9 K medium addition. In contrast, the removal rates of pyritic sulfur and total sulfur reached 87.5% and 28.2%, 89.1% and 31.6%, and 92.0% and 29.1%, respectively, in the three batch experiments with 6.7% iron-free M9 K medium addition. However, addition of excessive iron-free M9 K medium was detrimental to coal bio-desulfurization because of the synthesis of jarosite (MFe3(SO4)2(OH)6, M = K+, NH4+) and gypsum (CaSO4·2H2O), which further declined the pyritic sulfur bio-oxidation efficiency and total sulfur removal efficiency.

VOC Profiles of Saliva in Assessment of Halitosis and Submandibular Abscesses Using HS-SPME-GC/MS Technique.

Halitosis and submandibular abscesses are examples of mouth-related diseases with the possible bacterial origin. Salivary volatile organic compounds (VOCs) are potential biomarkers of them, once they can be addressed as metabolites of bacterial activity. Healthy patients (n = 15), subjects with submandibular abscesses located in fascial deep space (n = 10), and subjects with halitosis (n = 5) were enrolled in the study. Saliva samples were subjected to headspace solid-phase microextraction (HS-SPME) and gas chromatography coupled to mass spectrometry (GC/MS) analysis. A total number of 164 VOCs was detected by the developed methodology, 23 specific for halitosis and 41 for abscess. Halitosis' profiles were characterized by a larger number of sulfur compounds, while for abscess they had a higher variety of alcohols, aldehydes, and hydrocarbons-biomarkers of inflammatory processes. Principal components analysis allowed visualization of clusters formed according to the evaluated conditions. Kruskal-Wallis test indicated that 39 VOCs presented differentiated responses between the studied groups, with statistical relevance (p < 0.05). Random forest was applied, and a prediction model based on eight VOCs (2-butanone, methyl thioacetate, 2-methylbutanoic acid, S-methyl pentanethioate, dimethyl tetrasulfide, indolizine, pentadecane, and octadecanal) provided 100% of sensitivity, 82% of specificity, and 91% of balanced accuracy, indicating the specific presence of submandibular abscess.

Enhancement of using combined packing materials on the removal of mixed sulfur compounds in a biotrickling filter and analysis of microbial communities.

BACKGROUND: Packing materials is a critical design consideration when employing biological reactor to treat malodorous gases. The acidification of packing bed usually results in a significant drop in the removal efficiency. In the present study, a biotrickling filter (BTF2) packed with plastic balls in the upper layer and with lava rocks in the bottom layer, was proposed to mitigate the acidification. RESULTS: Results showed that using combined packing materials efficiently enhanced the removal performance of BTF2 when compared with BTF1, which was packed with sole lava rocks. Removal efficiencies of more than 92.5% on four sulfur compounds were achieved in BTF2. Average pH value in its bottom packing bed was about 4.86, significantly higher than that in BTF1 (2.85). Sulfate and elemental sulfur were observed to accumulate more in BTF1 than in BTF2. Analysis of principal coordinate analysis proved that structure of microbial communities in BTF2 changed less after the shutdown but more when the initial pH value was set at 5.5. Network analysis of significant co-occurrence patterns based on the correlations between microbial taxa revealed that BTF2 harbored more diverse microorganisms involving in the bio-oxidation of sulfur compounds and had more complex interactions between microbial species. CONCLUSIONS: Results confirmed that using combined packing materials effectively improved conditions for the growth of microorganisms. The robustness of reactor against acidification, adverse temperature and gas supply shutdown was greatly enhanced. These provided a theoretical basis for using mixed packing materials to improve removal performance.

Characterization of sulfur-compound metabolism underlying wax-ester fermentation in Euglena gracilis.

Euglena gracilis is a microalga, which has been used as a model organism for decades. Recent technological advances have enabled mass cultivation of this species for industrial applications such as feedstock in nutritional foods and cosmetics. E. gracilis degrades its storage polysaccharide (paramylon) under hypoxic conditions for energy acquisition by an oxygen-independent process and accumulates high amount of wax-ester as a by-product. Using this sequence of reactions referred to as wax-ester fermentation, E. gracilis is studied for its application in biofuel production. Although the wax-ester production pathway is well characterized, little is known regarding the biochemical reactions underlying the main metabolic route, especially, the existence of an unknown sulfur-compound metabolism implied by the nasty odor generation accompanying the wax-ester fermentation. In this study, we show sulfur-metabolomics of E. gracilis in aerobic and hypoxic conditions, to reveal the biochemical reactions that occur during wax-ester synthesis. Our results helped us in identifying hydrogen sulfide (H2S) as the nasty odor-producing component in wax-ester fermentation. In addition, the results indicate that glutathione and protein degrades during hypoxia, whereas cysteine, methionine, and their metabolites increase in the cells. This indicates that this shift of abundance in sulfur compounds is the cause of H2S synthesis.

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.

Identification of Odor-Active Compounds Released from a Damaged Plant of the Asian Skunk Cabbage Symplocarpus renifolius.

Symplocarpus renifolius (Asian skunk cabbage) is a perennial herb of the Araceae family. As its common name implies, this plant produces a strong garliclike irritant odor with a rotten note when the plant parts are crushed. To elucidate the odor characteristics, the volatile compounds released from crushed plant parts (rhizome, petioles, and leaf blades) of S. renifolius were identified by a dynamic headspace method. Fifteen sulfur compounds were identified as odor-active compounds by gas chromatography-mass spectrometry-olfactometry (GC-MS-O). The sulfur compounds may be responsible for the strong odor emitted by crushed skunk cabbage. Many of the compounds lack a carbon-carbon bond, and all of the carbon atoms are connected to sulfur. This is regarded as the characteristic structure of the sulfur compounds released from the damaged plant parts of the skunk cabbage. Nine of the sulfur compounds were detected in all three of the plant parts analyzed in this study: hydrogen sulfide, methanethiol, 1-hexanethiol, methyl dithioformate, 2,4-dithiapentane, dimethyl trisulfide, methional, 2,3,5-trithiahexane, and tris(methylthio)methane. Methyl dithioformate and methylthiomethyl dithioformate were identified for the first time as natural products.

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.

Volatile sulfur compounds in tropical fruits.

Global production and demand for tropical fruits continues to grow each year as consumers are enticed by the exotic flavors and potential health benefits that these fruits possess. Volatile sulfur compounds (VSCs) are often responsible for the juicy, fresh aroma of tropical fruits. This poses a challenge for analytical chemists to identify these compounds as most often VSCs are found at low concentrations in most tropical fruits. The aim of this review is to discuss the extraction methods, enrichment techniques, and instrumentation utilized to identify and quantify VSCs in natural products. This will be followed by a discussion of the VSCs reported in tropical and subtropical fruits, with particular attention to the odor and taste attributes of each compound. Finally, the biogenesis and enzymatic formation of specific VSCs in tropical fruits will be highlighted along with the contribution each possesses to the aroma of their respective fruit.

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.