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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 Na 2 SO 4 . 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 IC 50 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., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

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-β-CD (Succ-β-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., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2021 The Authors. Published by Elsevier B.V. All rights reserved.)

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 (R 2 ) 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 -1 , while PASH levels were -1 . Dibenzothiophene was the compound presented in the highest concentration in all samples, with values up to 249 ng g -1 . The results indicated contributions of pyrogenic sources from all compounds. The developed method can potentially be applied to extract trace levels of compounds in different solid matrices to minimize extraction time and solvent consumption., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2021. Published by Elsevier B.V.)

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., (Copyright © 2020 Elsevier Ltd. All rights reserved.)

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%.

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.

The aim of this study was to extract Allium ursinum L. for the first time by supercritical carbon dioxide (SC-CO 2 ) 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-CO 2 extraction can by efficiently used for A. ursinum., (© 2021 Wiley-VHCA AG, Zurich, Switzerland.)

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 (V mic  = 0.185 m 3 /g) and adsorption capacity (q e  = 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 m 2 /g, the total pore volume of 0.187 cm 3 /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., Competing Interests: Declaration of competing interest The authors declare no competing financial interest., (Copyright © 2020 Elsevier Inc. All rights reserved.)

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., Competing Interests: Declaration of Competing Interest We declare that we have no conflicts of interest to this work. Meanwhile, we also declare that we do not have any commercial or associative interest that represents a conflict of interest in connection with the work submitted., (Copyright © 2020. Published by Elsevier B.V.)

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).

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 (MFe 3 (SO 4 ) 2 (OH) 6 , M = K + , NH 4 + ) and gypsum (CaSO 4 ·2H 2 O), which further declined the pyritic sulfur bio-oxidation efficiency and total sulfur removal efficiency., (Copyright © 2019 Elsevier B.V. All rights reserved.)

Background: Gracilaria has been shown to be an important source of marine bioactive natural biomaterials and compounds. Although there are no enough patents used Gracilaria worldwide, the current study tries to put the Gracilaria on the spot for further important patents in the future., Objective: The current study investigates the pharmaceuticals and biochemical activity of Gracilaria because no previous studies have been carried out to examine the biochemical and pharmaceutical activates of Gracilaria from the Suez Canal of Egypt as an excellent source for bioactive compounds., Methods: Different advanced experimental models and analytical techniques, such as cytotoxicity, total antioxidant capacity, anticancer, and anti-inflammatory profiling were applied. The phytochemical analysis of different constituents was also carried out., Results: The mineral analysis revealed the presence of copper (188.3 ppm) and iron (10.07 ppm) in addition to a remarkable wealth of selenium and sulfur contents giving up to 36% of its dry mass. The elemental analysis showed high contents of sulfur and nitrogen compounds. The GCMS profiling showed varieties of different bioactive compounds, such as fatty acids, different types of carotenoids in addition to pigments, alkaloids, steroids. Many other compounds, such as carbohydrates and amino acids having antioxidant, anti-inflammatory, and antiviral activities, etc. were identified. The cytotoxicity activity of Gracilaria marine extract was very effective against cancerous cell lines and showed high ability as a potent antitumor due to their bioactive constituents. Specialized screening assays using two anticancer experimental models, i.e., PTK and SKH1 revealed 77.88% and 84.50% inhibition anticancer activity; respectively. The anti-inflammatory activities investigated using four different experimental models, i.e., COX1, COX2, IL6, and TNF resulted in 68%, 81.76%, 56.02% and 78.43% inhibition; respectively. Moreover, Gracilaria extracts showed potent anti-Alzheimer with all concentrations., Conclusion: Gracilaria proved to be a multi-product source of marine natural products for different biotechnological applications. Our recommendation is to investigate the Gracilaria bioactive secondary metabolites in order to create and innovate in more patents from current important seaweeds (Gracilaria)., (Copyright© Bentham Science Publishers; For any queries, please email at epub@benthamscience.net.)

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.

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.

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 A 3 (1), B 1 (2), B 2 (3) and B 3 (4), and two new thiolane type compounds with methoxy and methyl sulfoxide moiety at the 2- and 5-positions, and allium sulfoxides A 2 (5) and A 3 (6), were isolated from the acetone extract of the fresh white parts of Allium fistulosum 'Kujou' with three known compounds, kujounin A 1 (7) and A 2 (8), and allium sulfoxide A 1 (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.

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 (H 2 S) 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 H 2 S synthesis.

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.

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 x H y O 2 S 4 , C x H y O 3 S 5 , and C x H y O 4 S 6 ( 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.

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 Rg 1 derivative (named compound I) was obtained from sulfur-fumigated ginseng. The chemical structure of compound I was elucidated to be (3β, 6α, 12β)-3, 12-dihydroxydammar-25-ene-6, 20-diylbis-β-d-glucopyranoside, 24-sulfonic acid by QTOF-MS/MS, 1 H-NMR and 13 C-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., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

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., (Copyright © 2018. Published by Elsevier B.V.)

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.

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., (Copyright © 2017. Published by Elsevier B.V.)

This study investigated the aroma contribution of volatile sulfur compounds (VSCs) in Moutai liquors. The VSCs were analyzed using headspace solid-phase microextraction-gas chromatography-pulsed flame photometric detection (HS-SPME-GC-PFPD). The influences of SPME fibers, ethanol content in the sample, pre-incubation time, and extraction temperature and time on the extraction of VSCs were optimized. The VSCs were optimally extracted using a divinylbenzene/carboxen/polydimethylsiloxane fiber, by incubating 10 mL diluted Chinese liquor (5% vol.) with 3 g NaCl at 30 °C for 15 min, followed by a subsequent extraction for 40 min at 30 °C. The optimized method was further validated. A total of 13 VSCs were identified and quantified in Moutai liquors. The aroma contribution of these VSCs were evaluated by their odor activity values (OAVs), with the result that 7 of 13 VSCs had OAVs > 1. In particular, 2-furfurylthiol, methanethiol, dimethyl trisulfide, ethanethiol, and methional had relatively high OAVs and could be the key aroma contributors to Moutai liquors., Practical Application: In this study, a method for analyzing volatile sulfur compounds in Chinese liquors has been developed. This method will allow an in-depth study the aroma contribution of volatile sulfur compounds in Chinese liquors. Seven volatile sulfur compounds were identified as potential key aroma contributors for Moutai liquors, which can help to the quality control of Moutai liquors., (© 2017 Institute of Food Technologists®.)

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%).

Rationale: Many species of Alternaria damage important agricultural crops, including small grains and tomatoes. These fungi can produce a variety of secondary metabolites, some of which are toxic to humans and animals. Interest in screening for conjugated or 'modified' mycotoxins has increased because of their tendency to evade traditional analytical screening methods. Two sulfoconjugated Alternaria toxins have been reported and the potential exists for many more., Methods: One hundred and forty-eight Canadian strains of Alternaria spp., about half of them isolated from grain, were grown on Potato Dextrose Agar in Petri dishes for 7 days. Plugs of each strain were removed, extracted and screened by a rapid liquid chromatography (LC)/data-dependent tandem mass spectrometry (MS(2)) method in negative electrospray ionization mode. Data generated on an Orbitrap Q-Exactive mass spectrometer was processed by post-acquisition neutral loss filtering (NLF). Seven isolates that produced sulfoconjugates of known Alternaria toxins were selected for growth on three additional types of fermentation media., Results: Collision-induced dissociation of sulfoconjugated ions displayed a distinctive neutral loss of SO3 (79.957 Da) that was detected in the MS(2) datasets using post-acquisition NLF. A total of 108 of the 148 isolates screened produced sulfoconjugated metabolites on agar plates. Analysis of the seven isolates grown in liquid culture, on rice and Cheerios, led to the discovery of six new, two previously reported and 30 unidentified sulfoconjugated compounds., Conclusions: NLF of HRMS(2) data from an Orbitrap Q-Exactive is a powerful tool for the rapid discovery of sulfoconjugated fungal metabolites. This technique could also be applied to the detection of other important conjugated mycotoxins such as glucosides. The majority of the Canadian isolates of Alternaria spp. studied produced sulfoconjugated metabolites, some of which had no known 'free' Alternaria precursor metabolite, indicating that they are possibly new metabolites. The advantage of sulfoconjugation to Alternaria spp. is unknown, and warrants further study into the mechanisms behind the sulfur assimilatory pathways., (Copyright © 2015 John Wiley & Sons, Ltd.)

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.

A marine-derived Streptomyces strain, SSC21, was isolated from the sediment of Suncheon Bay, Republic of Korea. Chemical analysis of the bacterial strain resulted in the isolation of four new metabolites, suncheonosides A-D (1-4, respectively), each bearing a sulfur atom. The planar structures of the suncheonosides were identified as hexasubstituted benzothioate glycosides by combined spectroscopic analyses. Analysis of the configuration of the sugar moieties based on ROESY nuclear magnetic resonance correlations, one-bond (1)H-(13)C coupling constant analysis, and chemical derivatizations indicated that the suncheonosides incorporate only l-rhamnose. Suncheonosides A, B, and D promoted adiponectin production in a concentration-dependent manner during adipogenesis in human mesenchymal stem cells, suggesting antidiabetic potential.

Antifungal bioactivity-guided fractionation of the organic extract of the sponge Polymastia boletiformis, collected from the west coast of Ireland, led to the isolation of two new sulfated steroid-amino acid conjugates (1 and 2). Extensive 1D and 2D NMR analyses in combination with quantum mechanical calculations of the electronic circular dichroism (ECD) spectra, optical rotation, and 13C chemical shifts were used to establish the chemical structures of 1 and 2. Both compounds exhibited moderate antifungal activity against Cladosporium cucumerinum, while compound 2 was also active against Candida albicans. Marine natural products containing steroidal and amino acid constituents are extremely rare in nature.

Volatiles from initially frozen, dense phase carbon dioxide (DPCD)- and thermally treated guava purees were isolated by solid phase microextraction (SPME), chromatographically separated and identified using a combination of gas chromatography-mass spectrometry (GC-MS), GC-olfactometry (GC-O), and GC-pulsed flame photometric detector (GC-PFPD, sulfur mode). Fifty-eight volatiles were identified using GC-MS consisting of: 6 aldehydes, 2 acids, 15 alcohols, 6 ketones, 21 esters, and 8 terpenes. Eleven volatiles were newly identified in guava puree. Hexanal was the most abundant volatile in all 3 types of guava puree. Ten sulfur compounds were identified using GC-PFPD of which 3 possessed aroma activity and 3 were not previously reported in guava puree. Both treatments profoundly reduced total sulfur peak areas and produced different peak patterns compared to control. Thermal treatment reduced total sulfur peak area 47.9% compared to a loss of 34.7% with DPCD treatment. Twenty-six volatiles possessed aroma activity. (Z)-3-Hexenyl hexanoate was the major contributor to the aroma of the freshly thawed and DPCD-treated guava puree. DPCD treatment reduced total MS ion chromatogram (MS TIC) peak area 35% but produced a GC-O aroma profile very similar to control. Whereas thermal treatment reduced total TIC peak area only 8.7% compared to control but produced a 35% loss in total GC-O peak intensities., (© 2015 Institute of Food Technologists®)

Ultraperformance convergence chromatography/tandem triple quadrupole mass spectrometry (UPC(2)-MS/MS) is a novel tool in separation science that combines the advantages of supercritical fluid chromatography with ultraperformance liquid chromatography/MS/MS technology. The use of nontoxic CO2 fluid and a postcolumn additive to complement MS/MS allows better control of analyte retention for chiral separation and high-sensitivity determination with different chiral stationary phases. This paper reports the stereoselective separation and determination of the chiral neonicotinoid sulfoxaflor in vegetables and soil by UPC(2)-MS/MS. Baseline resolution (Rs ≥ 1.56) of and high selectivity (LOQ ≤ 1.83 μg/kg) for the four stereoisomers were achieved by postcolumn addition of 1 % formic acid-methanol to a Chiralpak IA-3 using CO₂/isopropanol/acetonitrile as the mobile phase at 40 °C, 2,500 psi, and for 6.5 min in electrospray ionization positive mode. Rearranged Van't Hoff equations afforded the thermodynamic parameters ΔH (ο) and ΔS (ο), which were analyzed to promote understanding of the enthalpy-driven separation of sulfoxaflor stereoisomers. The interday mean recovery, intraday repeatability, and interday reproducibility varied from 72.9 to 103.7%, from 1.8 to 9.2%, and from 3.1 to 9.4%, respectively. The proposed method was used to study the pharmacokinetic dissipation of sulfoxaflor stereoisomers in soil under greenhouse conditions. The estimated half-life ranged from 5.59 to 6.03 d, and statistically nonsignificant enantioselective degradation was observed. This study not only demonstrates that the UPC(2)-MS/MS system is an efficient and sensitive method for sulfoxaflor stereoseparation, but also provides the first experimental evidence of the pharmacokinetic dissipation of sulfoxaflor stereoisomers in the environment.

In the search for novel natural compounds endowed with potential antihypertensive activity, a new sulfur-containing indole alkaloid, N-demethylglypetelotine (2), and its known analogue glypetelotine (1), were isolated from the leaves of Glycosmis petelotii. Their structures were established on the basis of spectroscopic evidence. The two alkaloids were assessed for vasorelaxing activity on rat aorta rings and for L-type Ba(2+) current [I(Ba(L))] blocking activity on single myocytes isolated from rat tail artery. Both glypetelotine and N-demethylglypetelotine inhibited phenylephrine-induced contraction with IC50 values of 20 and 50 μM, respectively. The presence of endothelium did not modify their spasmolytic effect. Neither glypetelotine nor N-demethylglypetelotine affected Ca(2+) release from the sarcoplasmic reticulum induced by phenylephrine. The spasmolytic effect of glypetelotine increased with membrane depolarization. In the presence of 60 mM K(+), both compounds inhibited, in a concentration-dependent manner, the contraction induced by cumulative addition of Ca(2+), this inhibition being inversely related to Ca(2+) concentration. Glypetelotine and, less efficiently N-demethylglypetelotine, inhibited I(Ba(L)), the former compound also affecting I(Ba(L)) kinetics. In conclusion, glypetelotine is a novel vasorelaxing agent which antagonizes L-type Ca(2+) channels.

Capillary electrokinetic fractionation (CEkF) is investigated as a new, simple, and robust approach for semipreparative and analytical sample analysis based on pKa -dependant pH-driven electrophoretic mobility. CEkF was optimized with contactless conductivity detection and conducted with 10 kV reverse voltage for 10 min, then coupled on/at-line to ESI/MS. We propose a semi-empirical model with 14 representative compounds based on the correlation between sample/medium pH regulating the partial charge, the electrokinetic loading of the capillary and intensity (I) of analytes. According to the model, an empirical function (I = f (pH)) could be derived to calculate the acid dissociation constant (pKa ) of various model compounds based on their pH-dependant MS intensity profiles with the RSD < 4.05. Using the ultrahigh-resolution of ion cyclotron resonance Fourier transform MS, the pKa model was further illustrated in real samples into the structure prediction of important compounds in wine over two vintages. The established CEkF was successfully used to selectively fractionate sulfur compounds from the complex wine samples at pH 1.66. The proposed CEkF approach should allow in the future the simultaneous pKa evaluation of multiple constituents without complicated separation out of a complex mixture in metabolomics or environmental chemistry., (© 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The 1,3-dithiane is a protected formaldehyde anion equivalent that could serve as a useful labeled synthon. We report a facile synthesis of 1,3-[2-(13)C]- and 1,3-[2-(13)C, 2-(2)H2]dithiane in two steps from [(13)C]- or [(13) C, (2)H3 ]methyl phenyl sulfoxide. We have previously reported the high yield synthesis of [(13)C]methyl phenyl sulfide from [(13)C]MEOH and the oxidation of [(13)C]methyl phenyl sulfide to [(13)C]methyl phenyl sulfoxide. Here, we describe the facile exchange of deuterium from (2) H2 O into [(13)C]methyl phenyl sulfoxide to yield [(13)C, (2)H3]methyl phenyl sulfoxide. Thus, from [(13)C]MEOH and (2)H2O, all possible C2 stable isotopomers of 1,3-dithiane are available. Our synthetic route is also amenable to preparation of radiolabeled 1,3-dithianes., (Copyright © 2014 John Wiley & Sons, Ltd.)

Metal-impregnated carbons (Cu--AC; Ag--AC and Pd--AC) were studied as adsorbents for the desulphurization of liquid fuels. A real gasoline was examined for sulphur compounds. Textural characteristics of adsorbents were determined by nitrogen adsorption/desorption isotherms at 77 K. The adsorption isotherms were obtained by frontal analysis in a single fixed bed at 30 degrees C and 45 degrees C. Breakthrough curves were simulated according to a mathematical model that assumed axially dispersed flow and mass transfer described by a linear driving force approximation and nonlinear adsorption equilibrium reached instantaneously on the external surface of the adsorbents particles. The model was solved numerically by orthogonal collocation in finite elements, using the commercial solver gPROMS. The proposed model matched experimental data reasonably well. Resistance to mass transfer was significant and thought to be due to intraparticle diffusion kinetics. The results confirmed the efficiency of the use of activated carbon (AC) in the adsorption of sulphur compounds, especially when its surface is modified with metals. Comparing adsorption capacities of sulphur compounds from real gasoline, AC-Pd material appeared more selective than other materials, even presenting a behaviour of rapid saturation explained by the presence of other components competing for adsorption sites, reducing their effectiveness in removing sulphur compounds. Both pristine AC and Pd--AC showed good regenerability. The regenerated Pd--AC sorbent can recover about 85% of the desulphurization capacity.

Three new thiodiketopiperazines, named phomazines A-C (1-3), along with 10 known analogues (4-13), were isolated from the fermentation broth of an endophytic fungus, Phoma sp. OUCMDZ-1847, associated with the mangrove plant Kandelia candel. The structures including the absolute configurations of the new compounds were unambiguously elucidated by spectroscopic, X-ray crystallographic, and Mosher's methods along with quantum ECD and (13)C NMR calculations. Compounds 2, 4, 5, 11, and 12 showed cytotoxicities against the HL-60, HCT-116, K562, MGC-803, and A549 cell lines with IC50 values in the range 0.05 to 8.5 μM.

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.

In this paper, the effect of urea-hydrogen peroxide (UHP) solution on desulphurization and demineralization of coal with high sulphur and high ash by using HNO3 and microwave pretreatment was investigated. The oxidation process is strongly dependent on irradiation power and time for microwave pretreatment, UHP concentration, leaching time and temperature of the UHP solution. X-ray diffraction and Fourier transform infrared technique have been performed for the raw and treated coals. Compared with the UHP alone, successive treatments with HNO3 and microwave pretreatment resulted in the significant removal of total sulphur and mineral matter from the coal. The proposed experimental method has the meaning of practical guide to the desulphurization and deashing of coal by microwave.

This study introduces a silica-based monolith in a capillary format (0.1 mm × 100 mm) as a support for immobilization of liposomes and its characterization in immobilized liposome chromatography. Silica-based monolithic capillary columns prepared by acidic hydrolysis of tetramethoxysilane in the presence of polyethylene glycol and urea were modified by (3-aminopropyl)trimethoxysilane, whereby amino groups were introduced to the monolithic surface. These groups undergo reaction with glutaraldehyde to form an iminoaldehyde, allowing covalent binding of pre-formed liposomes containing primary amino groups. Two types of phospholipid vesicles were used for column modification; these were 2-oleoyl-1-palmitoyl-sn-glycero-3-phosphatidyl choline with and without 1,2-diacyl-sn-glycero-3-phospho-L-serine. The prepared columns were evaluated under isocratic separation conditions employing 20mM phosphate buffer at pH 7.4 as a mobile phase and a set of unrelated drugs as model analytes. The liposome layer on the synthesized columns significantly changed the column selectivity compared to the aminopropylsilylated monolithic stationary phase. Monolithic columns modified by liposomes were stable under the separation conditions, which proved the applicability of the suggested preparation procedure for the synthesis of capillary columns dedicated to study analyte-liposome interactions. The column efficiency originating from the silica monolith was preserved and reached, e.g., more than 120,000 theoretical plates/m for caffeine as a solute., (Copyright © 2013 Elsevier B.V. All rights reserved.)

The kinetic and metabolic behavior of an aerobic granular sludge to nitrify, denitrify and nitrify-denitrify was evaluated in batch cultures. In nitrification control, ammonium, 4-methylphenol and sulfide were consumed efficiently (∼100%) and recovered as NO3(-), CO2, S(0) and SO4(2-), respectively. In denitrification control, S(0) and nitrate were efficiently consumed and recovered as SO4(2-) and N2, respectively. Sequential nitrification-denitrification process was evaluated by applying oxic/anoxic conditions. Ammonium, 4-methylphenol and sulfide were oxidized to nitrate, CO2 and mainly S(0), respectively, under aerobic conditions. After that, anoxic conditions were established where S(0) reduced all nitrate to N2, with molecular nitrogen yield (YN2) of 1.03 ± 0.06 mg/mg NH4(+)-N consumed. This is the first study to show the capability of an aerobic granular sludge in simultaneous removal of ammonium, 4-methylphenol and sulfide by sequential nitrification-denitrification process in the same bioreactor., (Copyright © 2013 Elsevier Ltd. All rights reserved.)

Liquid-liquid extraction is an alternative method that can be used for desulfurization and denitrification of gasoline and diesel fuels. Recent approaches employ different ionic liquids as selective solvents, due to their general immiscibility with gasoline and diesel, negligible vapor pressure, and high selectivity to sulfur- and nitrogen-containing compounds. For that reason, five imidazolium-based ionic liquids and one pyridinium-based ionic liquid were selected for extraction of thiophene, dibenzothiophene, and pyridine from two model solutions. The influences of hydrodynamic conditions, mass ratio, and number of stages were investigated. Increasing the mass ratio of ionic liquid/model fuel and multistage extraction promotes the desulfurization and denitrification abilities of the examined ionic liquids. All selected ionic liquids can be reused and regenerated by means of vacuum evaporation.

Mixed-mode chromatographic materials are more and more often used for the purification of biomolecules, such as peptides and proteins. In many instances they in fact exhibit better selectivity values and therefore improve the purification efficiency compared to classical materials. In this work, a model to describe biomolecules retention in cation-exchange/reversed-phase (CIEX-RP) mixed-mode columns under diluted conditions has been developed. The model accounts for the effect of the salt and organic modifier concentration on the biomolecule Henry coefficient through three parameters: α, β and γ. The α parameter is related to the adsorption strength and ligand density, β represents the number of organic modifier molecules necessary to displace one adsorbed biomolecule and γ represents the number of salt molecules necessary to desorb one biomolecule. The latter parameter is strictly related to the number of charges on the biomolecule surface interacting with the ion-exchange ligands and it is shown experimentally that its value is close to the biomolecule net charge. The model reliability has been validated by a large set of experimental data including retention times of two different peptides (goserelin and insulin) on five columns: a reversed-phase C8 column and four CIEX-RP columns with different percentages of sulfonic groups and various concentration values of the salt and organic modifier. It has been found that the percentage of sulfonic groups on the surface strongly affects the peptides adsorption strength, and in particular, in the cases investigated, a CIEX ligand density around 0.04μmol/m(2) leads to optimal retention values., (Copyright © 2013. Published by Elsevier B.V.)

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., (Copyright © 2012 Elsevier B.V. All rights reserved.)

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.

Ampelopsis brevipedunculata var. heterophylla is extensively cultivated in Asia, and the dried leaves and branches have a characteristic odor and have been used as a tea. To investigate the odorants contributing to the characteristic odor of A. brevipedunculata var. heterophylla, the aroma extraction dilution analysis method was performed through gas chromatography olfactometry. In addition, volatile sulfur compounds were evaluated using pulsed flame photometric detector. As a result, 86 compounds were identified in the oils of leaves and 78 in branches, accounting for 80.0% and 68.3%, respectively, of the compounds identified. The main compounds in the essential oil of leaves were palmitic acid (12.5%), phenylacetaldehyde (4.1%) and hexahydrofarnesyl acetone (3.9%). On the other hand, the essential oil of branches contained palmitic acid (12.7%), terpinen-4-ol (4.4%) and α-cadinol (3.7%). The total number of odor-active compounds identified in the leaf and branch oils was 39. The most odorous compounds of leaves and branches of A. brevipedunculata var. heterophylla were (E, Z)-2,6-nonadienal (melon, green odor), (E)-2-nonenal (grassy odor), phenylacetaldehyde (honey-like) and (E)-linalool oxide (woody odor).

A method is described for characterization of sulfur compounds in unaged and aged whisky. The method is based on full evaporation dynamic headspace (FEDHS) of 100 μL of whisky samples followed by selectable one-dimensional ((1)D) or two-dimensional ((2)D) retention-time-locked (RTL) gas chromatography (GC)-mass spectrometry (MS) with simultaneous element-specific detection using a sulfur chemiluminescence detector (SCD) and a nitrogen chemiluminescence detector (NCD). Sequential heart-cuts of the 16 sulfur fractions were used to identify each individual sulfur compound in the unaged whisky. Twenty sulfur compounds were positively identified by a MS library search, linear retention indices (LRI), and formula identification using MS calibration software. Additionally eight formulas were also identified for unknown sulfur compounds. Simultaneous heart-cuts of the 16 sulfur fractions were used to produce the (2)D RTL GC-SCD chromatograms for principal component analysis. PCA of the (2)D RTL GC-SCD data clearly demonstrated the difference between unaged and aged whisky, as well as two different whisky samples. Fourteen sulfur compounds could be characterized as key sulfur compounds responsible for the changes in the aging step and/or the difference between two kinds of whisky samples. The determined values of the key sulfur compounds were in the range of 0.3-210 ng mL(-1) (RSD: 0.37-12%, n=3)., (Copyright © 2012 Elsevier B.V. All rights reserved.)

The short peptide Boc-Phe-Aib-Phe-OH was synthesized and immobilized onto porous silica using grafting methodology. The resulting peptide-bonded silica was characterized using DRIFT-mode FT-IR, elemental analysis, thermogravimetric analysis, solid state C(13) NMR spectroscopy and the successful immobilization of the peptide on the silica support was confirmed. This grafted phase was packed into a stainless steel column and used for mixed-mode chromatography such as reversed-phase high-performance liquid chromatography and hydrophilic interaction liquid chromatography for the efficient separation of hydrophobic compounds, small polar molecules, and drug molecules. Compared with ODS and phenyl columns, this new stationary phase shows considerably higher molecular-planarity selectivity towards polyaromatic hydrocarbons and also available for separation of nucleo-analytes and sulfa-drug molecules in a hydrophilic interaction liquid chromatography mode. The multiple interactions induced by polar carbonyl group and hydrophobic phenyl group allow this peptide-modified silica to serve as a multi-mode stationary phase in high performance liquid chromatography., (Copyright © 2012 Elsevier B.V. All rights reserved.)

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.

Mixtures of volatile reduced sulphur compounds (VRSCs) like hydrogen sulphide (H(2)S), methylmercaptan (MM), dimethyl sulphide (DMS) and dimethyl disulphide (DMDS) are found in gaseous emissions of several industrial activities creating nuisance in the surroundings. Hydrogen sulphide (H(2)S) decreases the removal efficiency of volatile reduced sulphur compounds (VRSCs) in biofilters but the kinetics of this effect is still unknown. Kinetic expressions that represent the rate of bio-oxidation of H(2)S, MM, DMS and DMDS are proposed. In order to observe and quantify this effect, equimolar mixtures of MM, DMS and DMDS were fed into a biotrickling filter inoculated with Thiobacillus thioparus at different H(2)S loads. Experimental results shown a good agreement with the simulations generated by the model considering the kinetic equations proposed. The estimated kinetic constants show that H(2)S and MM have a significant inhibitory effect on the bio-oxidation of DMS and DMDS, having the H(2)S the higher effect., (Copyright © 2012 Elsevier Ltd. All rights reserved.)

An orthogonally protected disaccharide (GlcN(α1→4)Glc) with a β-linked 2'-aminoethyl linker was used to generate a series of sulfated derivatives (sulfoforms), with a 6-O-sulfate on the glucose residue and one or more sulfate esters on the terminal glucosamine. Deprotection and sulfonation steps were performed in solution and in variable order, with isolated yields of 36-54% (85-90% per operation) after HPLC purification. The modular deprotection-sulfonation sequences can be performed with efficient recovery of the polysulfate products, and avoids complications associated with heterogeneous reactivity in solid-phase synthesis., (Copyright © 2012 Elsevier Ltd. All rights reserved.)

The application of an HPLC bioactivity profiling/microtiter plate technique in conjunction with microprobe NMR instrumentation and access to the AntiMarin database has led to the isolation of a new 1. In this example, 1 was isolated from a cytotoxic fraction of an extract obtained from marine-derived Streptomyces sp. cultured on Starch Casein Agar (SCA) medium. The 1D and 2D (1)H NMR and ESIMS data obtained from 20 μg of compound 1 fully defined the structure. The known 2 was also isolated and readily dereplicated using this approach.