Sensory properties of rehydrated Toona sinensis shoots after dehydrated by different drying methods and association with gamma-glutamyl transferase reaction.

Sulfur-containing compounds are responsible for the aroma of Toona sinensis shoot (TS). In this study, vacuum-freeze-drying (VFD), microwave-drying (MD), and hot-air-drying at 100 and 40 °C (HAD100 and HAD40, respectively), were applied to dehydrate perishable TS for preservation. VFD-TS retained most aroma of fresh/raw TS after rehydration. The content of sulfur-containing compounds reached to 118.00 µg/g with leading by methyl thiirane, (E,E)/(E,Z)/(Z,Z)-bis-(1-propenyl) disulfides, and (Z)/(E)-2-mercapto-3,4-dimethyl-2,3-dihydrothiophenes accounting for 86.33 %. They were undetected in the rehydrated MD-TS and HAD100-TS, as the indigenous enzymes in TS were deactivated under their dehydration conditions. Interestingly, the sulfur-containing compounds was restored by 77.47 % after the TS was treated by gamma-glutamyl transferase (GGT). Thus, the release of sulfur-containing compounds from TS could depend on GGT reaction. It was different from alliaceous vegetables relying on alliinase reaction. The results revealed the aroma formation in TS and provided an approach to enhance the aroma of TS dried by different methods.

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

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

Release characteristics and risk assessment of volatile sulfur compounds in a municipal wastewater treatment plant with odor collection device.

Due to the malodorous effects and health risks of volatile sulfur compounds (VSCs) emitted from wastewater treatment plants (WWTPs), odor collection devices have been extensively utilized; however, their effectiveness has rarely been tested. In the present investigation, the characteristics of VSCs released in a WWTP equipped with gas collection hoods are methodically examined by gas chromatography. The obtained results indicate that the concentration of VSCs in the ambient air can be substantially reduced, and the primary treatment unit still achieves the highest concentration of VSCs. Compared to WWTPs without odor collection devices, the concentration of H2S in this WWTP is not dominant, but its sensory effects and health risks are still not negligible. Additionally, research on the emission of VSCs from sludge reveals that the total VSCs emitted from dewatering sludge reaches the highest level. Volatile organic sulfur compounds play a dominant role in the component and sensory effects of VSCs released by sludge. This study provides both data and theoretical support for analyzing the effectiveness of odor collection devices in WWTPs, as well as reducing the source of VSCs. The findings can be effectively employed to optimize these devices and improve their performance.

Development of an analytic method for organosulfur compounds in Welsh onion and its use for nutritional quality analysis of five typical varieties in China.

A reliable, simple, and sensitive method capable of quantifying six organosulfur compounds (OSCs) was established. The samples were extracted by water containing 3 % formic acid with a simple vortex, ultrasound, and centrifugation step, and the solutions were analyzed by ultra-high-performance liquid chromatography separation system coupled with a triple-quadrupole mass spectrometry (UHPLC - MS/MS). Then the method was applied for the analysis of six OSCs in five varieties of two types Welsh onions in China, and the moisture content, reducing sugar, total polyphenols, and 21 free amino acids were also analyzed to study the characters of these Welsh onions intensively. Multivariate statistical analysis was used to investigate the differences in OSCs and free amino acids profiles among the samples. This study showed that enzymatic inhibition method combined with UHPLC - MS/MS is an effective technique to analyze OSCs in Welsh onion, and could be valuable for the routine quantitation of OSCs in other foods.

Optimization of complex coacervation parameters for the production of encapsulated black garlic using response surface methodology.

The purpose of this study was to optimize black garlic encapsulation parameters (core/coating ratio, extract concentration, and coacervate/maltodextrin [MD] ratio) using central composite design of the response surface methodology based on encapsulation efficiency (EE) (%). The optimum parameters were determined as 4.0 for the coating material/core ratio, 50% for the extract concentration, and 6.0 for the MD/coacervate ratio depending on the EE (%). The antioxidant activity values were determined as 101 and 134 µmol Trolox/100 g dry weight (DW) for the 2,2-diphenyl-1-picrylhydrazyl and 2,2'-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid) methods, respectively, whereas the total phenolic content was 49 mg gallic acid equivalent/100 g DW for the encapsulated black garlic samples. S-Allyl-l-cysteine (SAC), γ-l-glutamyl-SAC (GSAC), γ-l-glutamyl-(S)-trans-1-propenyl-l-cysteine, and allicin were the organosulfur (OS) compounds determined in the samples. The SAC concentration of the encapsulated black garlic samples was determined as 22.36 mg/g, whereas the GSAC content was found at a lower concentration (0.33 mg/g) compared to SAC. The allicin content was quantified to be 0.31 mg/g. The encapsulated samples were also characterized by scanning electron microscopy (SEM) and Fourier transform infrared (FT-IR) spectroscopy. The FT-IR analysis revealed specific functional groups, including hydroxyl, carbonyl, and glycosidic linkage. The interaction between lentil protein isolate and pectin was strong enough to encourage capsule formation as visualized in the SEM images. This study shows the potential of black garlic coacervates as a functional ingredient for the food industry due to their stability, solubility, and preservation of OS and antioxidant compounds.

Investigation of volatile sulfur compound level and halitosis in patients with gingivitis and periodontitis.

This study aimed to measure the levels of volatile sulfur compounds and investigate the occurrence of halitosis in patients with gingivitis and periodontitis. Additionally, the incidence rates of gingivitis and periodontitis in patients with halitosis were investigated. Through various statistical analyses, we attempted to determine the relationship between periodontal disease and halitosis. One-hundred-and-four participants (52 females and 52 males, mean age: 46.49 ± 16.03 years) were enrolled in this cross-sectional study, comprising 33 healthy controls, 43 patients with gingivitis, and 28 patients with periodontitis. Gas chromatography was used to measure hydrogen sulfide (H2S) and methyl mercaptan (CH3SH), which are representative VSCs. The VSC cut-off values for diagnosing halitosis were 65.79 ppb for women and 79.94 ppb for men. Total VSC level was significantly higher in the gingivitis than the healthy control group (186.72 ± 374.83 ppb vs. 19.80 ± 40.19 ppb, p = 0.035). There was no significant difference between the gingivitis and periodontitis (153.79 ± 278.51 ppb) groups. H2S level was significantly higher in the gingivitis (100.51 ± 183.69 ppb) and periodontitis (91.57 ± 132.06 ppb) groups than in healthy controls (14.97 ± 31.22 ppb), and CH3SH level was significantly higher in gingivitis group (29.31 ± 59.16 ppb) than in the healthy control (5.73 ± 14.10 ppb) (all p < 0.05). Halitosis was found in 3% of healthy controls and 39.5% and 42.9% of patients with gingivitis and periodontitis patients, respectively, making it significantly higher in the gingivitis and periodontitis groups than the healthy controls (p = 0.005). Conversely, among participants with halitosis, 53.1% had gingivitis, 37.5% had periodontitis, and 90.6 incidence had periodontal disease. Multivariate logistic regression analysis to predict the presence of halitosis, found periodontal disease was a significant predictor of halitosis (OR = 3.607, 95% CI 1.023-12.718, p = 0.046). Considering area under curve value for halitosis, the cut-off value of healthy control (H2S:61.5 ppb, CH3SH:3.5 ppb), gingivitis (H2S:50.0 ppb, CH3SH:6 ppb), and periodontitis (H2S:62.0 ppb, CH3SH:3.5 ppb) were (all p < 0.05). Our results emphasize the close and strong relationship between periodontal disease and halitosis through human clinical evidence based on the high co-occurrence rate of mutual diseases. Additionally, the presence of periodontal disease increased the probability of halitosis by 3.607 times. These results suggest that H2S can be used as a biomarker of halitosis in patients with periodontal disease.

Multi-dimension analysis of volatile sulfur compound emissions from an urban wastewater treatment plant.

Long-term monitoring of volatile sulfur compounds (VSCs) released at the water-air interface from different treatment units of an anaerobic/oxic (A/O) wastewater treatment plant (WWTP) was carried out to assess the temporal and spatial emission characteristics of VSCs, to explore relationships between wastewater quality and VSC release. The VSC from non-aerated and aerated units were collected using dynamic and static chambers, respectively, and determined using gas chromatography. The VSC emission fluxes diminished in the order of primary sedimentation tank (PST) > anaerobic areas (ANA) > oxic section 1 (OX1). VSCs were not detected in the oxic section 2 (OX2), the oxic areas section 3 (OX3), and the final setting basin (FSB). Release capacities of VSCs descended in the order of summer > fall > spring > winter, with July, August, and September being the months with the highest VSC release capacities. VSC emission fluxes correlated well with wastewater temperatures, sulfate concentrations, and COD. VSC emission flux empirical equations based on wastewater temperature, sulfate concentrations, and COD were established. Based on the established VSC emission empirical equation, a control strategy to reduce the operating costs of deodorization facilities was proposed. This strategy is economically efficient and reduces the consumption of electrical energy.

Selenium-binding protein 1 (SELENBP1) is a copper-dependent thiol oxidase.

Selenium-binding protein 1 (SELENBP1) was reported to act as a methanethiol oxidase (MTO) in humans, catalyzing the conversion of methanethiol to hydrogen peroxide, hydrogen sulfide and formaldehyde. Here, we identify copper ions as essential to this novel MTO activity. Site-directed mutagenesis of putative copper-binding sites in human SELENBP1 produced as recombinant protein in E. coli resulted in loss of its enzymatic function. On the other hand, the eponymous binding of selenium (as selenite) was no requirement for MTO activity and only moderately increased SELENBP1-catalyzed oxidation of methanethiol. Furthermore, SEMO-1, the SELENBP1 ortholog recently identified in the nematode C. elegans, also requires copper ions, and MTO activity was enhanced or abrogated, respectively, if worms were grown in the presence of cupric chloride or of a Cu chelator. In addition to methanethiol, we identified novel substrates of SELENBP1 from the group of volatile sulfur compounds, ranging from ethanethiol to 1-pentanethiol as well as 2-propene-1-thiol. Gut microbiome-derived methanethiol as well as food-derived volatile sulfur compounds (VSCs) account for malodors that may contribute to extraoral halitosis in humans, if not metabolized properly. As SELENBP1 is particularly abundant in tissues exposed to VSCs, such as colon, liver, and lung, it appears to contribute to copper-dependent VSC degradation.

Enhanced degradation of herbicides in groundwater using sulfur-containing reductants and spinel zinc ferrite activated persulfate.

A challenge to successfully implementing an injection-based remedial treatment in aquifers is to ensure that the oxidative reaction is efficient and lasts long enough to contact the contaminated plume. Our objective was to determine the efficacy of zinc ferrite nanocomposites (ZnFe2O4) and sulfur-containing reductants (SCR) (i.e., dithionite; DTN and bisulfite; BS) to co-activate persulfate (S2O82-; PS) and treat herbicide-contaminated water. We also evaluated the ecotoxicity of the treated water. While both SCRs delivered excellent PS activation in a 1:0.4 ratio (PS:SCR), the reaction was relatively short-lived. By including ZnFe2O4 in the PS/BS or PS/DTN activations, herbicide degradation rates dramatically increased by factors of 2.5 to 11.3. This was due to the SO4- and OH reactive radical species that formed. Radical scavenging experiments and ZnFe2O4 XPS spectra results revealed that SO4- was the dominant reactive species that originated from S(IV)/PS activation in solution and from the Fe(II)/PS activation that occurred on the ZnFe2O4 surface. Based on liquid chromatography mass spectrometry (LC-MS), atrazine and alachlor degradation pathways are proposed that involve both dehydration and hydroxylation. In 1-D column experiments, five different treatment scenarios were run using 14C-labeled and unlabeled atrazine, and 3H2O to quantify changes in breakthrough curves. Our results confirmed that ZnFe2O4 successfully prolonged the PS oxidative treatment despite the SCR being completely dissociated. Toxicity testing showed treated 14C-atrazine was more biodegradable than the parent compound in soil microcosms. Post-treatment water (25 %, v/v) also had less impact on both Zea Mays L. and Vigna radiata L. seedling growth, but more impact on root anatomies, while ≤4 % of the treated water started to exert cytotoxicity (<80 % viability) on ELT3 cell lines. Overall, the findings confirm that ZnFe2O4/SCR/PS reaction is efficient and relatively longer lasting in treating herbicide-contaminated groundwater.

Hydrogen sulfide production during early yeast fermentation correlates with volatile sulfur compound biogenesis but not thiol release.

Yeasts undergo intensive metabolic changes during the early stages of fermentation. Previous reports suggest the early production of hydrogen sulfide (H2S) is associated with the release of a range of volatile sulfur compounds (VSCs), as well as the production of varietal thiol compounds 3-sulfanylhexan-1-ol (3SH) and 3-sulfanylhexyl acetate (3SHA) from six-carbon precursors, including (E)-hex-2-enal. In this study, we investigated the early H2S potential, VSCs/thiol output, and precursor metabolism of 11 commonly used laboratory and commercial Saccharomyces cerevisiae strains in chemically defined synthetic grape medium (SGM) within 12 h after inoculation. Considerable variability in early H2S potential was observed among the strains surveyed. Chemical profiling suggested that early H2S production correlates with the production of dimethyl disulfide, 2-mercaptoethanol, and diethyl sulfide, but not with 3SH or 3SHA. All strains were capable of metabolizing (E)-hex-2-enal, while the F15 strain showed significantly higher residue at 12 h. Early production of 3SH, but not 3SHA, can be detected in the presence of exogenous (E)-hex-2-enal and H2S. Therefore, the natural variability of early yeast H2S production contributes to the early output of selected VSCs, but the threshold of which is likely not high enough to contribute substantially to free varietal thiols in SGM.

Spatiotemporal accumulation differences of volatile compounds and bacteria metabolizing pickle like odor compounds during stacking fermentation of Maotai-flavor baijiu.

Pickle like odor (PLO) is undesirable in Maotai-flavor baijiu; however, its formation mechanism is unclear. Furthermore, there is a lack of understanding of the spatiotemporal accumulation of volatile compounds (including PLO compounds, PLOC) and of the microorganisms responsible for the production of PLOC during stacking fermentation. In this study, we analyzed the spatiotemporal distribution differences of 132 volatile compounds in piled fermented grains. PLOC (n = 5) were higher in pile surface than in pile center, reaching their highest levels at 6th and 5th rounds, respectively. The microorganisms in pile center were more conducive to the formation of alcohols, while those in the pile surface more promoted the synthesis of esters. Rhodococcus and Zygosaccharomyces promoted the formation of PLOC. Acetobacter was negatively correlated with the content of sulfur compounds by promoting their conversion into non-volatile sulfur compounds, thereby reducing the content of PLOC. This study provides information on the spatiotemporal differences of volatile compounds (especially PLOC) in piled fermented grains and identified the microorganisms that produce PLOC.

Sulfur-fluoride exchange (SuFEx)-enabled lead discovery of AChE inhibitors by fragment linking strategies.

SuFEx click chemistry has been a method for the rapid synthesis of functional molecules with desirable properties. Here, we demonstrated a workflow that allows for in situ synthesis of sulfonamide inhibitors based on SuFEx reaction for high-throughput testing of their cholinesterase activity. According to fragment-based drug discovery (FBDD), sulfonyl fluorides [R-SO2F] with moderate activity were identified as fragment hits, rapidly diversified into 102 analogs in SuFEx reactions, and the sulfonamides were directly screened to yield drug-like inhibitors with 70-fold higher potency (IC50 = 94 nM). Moreover, the improved molecule J8-A34 can ameliorate cognitive function in Aß1-42-induced mouse model. Since this SuFEx linkage reaction succeeds on picomole scale for direct screening, this methodology can accelerate the development of robust biological probes and drug candidates.

Organosulfur Compounds of Allium Subgenus Nectaroscordum Species.

Organosulfur compounds formed upon comminuting the bulbs of two Allium subgenus Nectaroscordum species (Allium siculum and Allium tripedale) were analyzed by HPLC-PDA-MS/MS. The major organosulfur components were isolated and structurally characterized (MS, NMR), including several previously unknown compounds. It was found that the organosulfur chemistry occurring when these plants are cut is very similar to that observed in onion (Allium cepa). In all cases, however, the organosulfur compounds found in Nectaroscordum species were higher homologues of those observed in onion, being formed by various combinations of C1 and C4 building blocks derived from methiin and homoisoalliin/butiin, respectively. Thiosulfinates, bis-sulfine, cepaenes, and several cepaene-like compounds were identified among the major organosulfur components present in the homogenized bulbs. Several groups of 3,4-diethylthiolane-based compounds, structurally homologous with onionin A, cepathiolane A, allithiolanes A-H, and cepadithiolactone A, found in onion, were also detected.

Recent Advances in Organocatalyzed Asymmetric Sulfa-Michael Addition Triggered Cascade Reactions.

The sulfa-Michael addition reaction is a crucial subset of the Michael addition reaction, and aroused the interest of numerous synthetic biologists and chemists. In particular, sulfa-Michael addition triggered cascade reaction has developed quickly in recent years because it offers an efficient method to construct C-S bonds and other bonds in one approach, which is widely applicable for building chiral pharmaceuticals, their intermediates, and natural compounds. This review emphasizes the recent advancements in sulfa-Michael addition-triggered cascade reactions for the stereoselective synthesis of sulfur-containing compounds, including sulfa-Michael/aldol, sulfa-Michael/Henry, sulfa-Michael/Michael, sulfa-Michael/Mannich and some sulfa-Michael triggered multi-step processes. Moreover, some reaction mechanisms and derivatization experiments are introduced appropriately.

Tunning active oxygen species for boosting Hg0 removal and SO2-resistance of Mn-Fe oxides supported on (NH4)2S2O8 doping activated coke.

Active oxygen species (AOS) play an essential role in modulating the activity of activated coke (AC) based samples. In this paper, AC was endowed with abundant AOS by modifying with (NH4)2S2O8 and MnOx-FeOx for Hg0 removal. (NH4)2S2O8 treatment induced abundant micropores and oxygen-containing functional groups, and thus provided more anchoring sites for the dispersion of MnOx-FeOx. The synergy of MnOx-FeOx and interaction between MnOx-FeOx and NAC support contributed to a larger surface area, highly-dispersed active components, stronger reducibility, and more metal ions with high valence of MnFe/NAC. The optimal MnFe/NAC exhibited superior Hg0 removal efficiency above 90% at 120∼180 â„ƒ, as well as excellent performance for simultaneous removal of Hg0 and NO, and 600 ppm SO2 and 8 vol.% H2O addition led to a slight deterioration. XPS and Hg-TPD revealed that mercury adsorbed on MnFe/NAC included phy-Hg, C=O-Hg, COO-Hg, and OL-HgO. Besides, the priority of AOS for Hg0 chemisorption was C=O > COO- > OL, and Hg2+ was also detected in the outlet. Moreover, the SO2-poisoning effect was ascribed to the sulfation of MnOx and the occupation of COO- and C=O, and FeOx incorporation enhanced the SO2-resistance through weakening SO2 adsorption on C=O and COO-. The motivation of O2 mainly contributed to the regeneration of AOS, especially OL. The excellent regeneration performance and stability further affirmed the application potential of MnFe/NAC for Hg0 capture from coal-fired flue gas.

Role of Sulfur Compounds in Vegetable and Mushroom Aroma.

At the base of the food pyramid is vegetables, which should be consumed most often of all food products, especially in raw and unprocessed form. Vegetables and mushrooms are rich sources of bioactive compounds that can fulfill various functions in plants, starting from protection against herbivores and being natural insecticides to pro-health functions in human nutrition. Many of these compounds contain sulfur in their structure. From the point of view of food producers, it is extremely important to know that some of them have flavor properties. Volatile sulfur compounds are often potent odorants, and in many vegetables, belonging mainly to Brassicaeae and Allium (Amaryllidaceae), sulfur compounds determine their specific flavor. Interestingly, some of the pathways that form volatile sulfur compounds in vegetables are also found in selected edible mushrooms. The most important odor-active organosulfur compounds can be divided into isothiocyanates, nitriles, epithionitriles, thiols, sulfides, and polysulfides, as well as others, such as sulfur containing carbonyl compounds and esters, R-L-cysteine sulfoxides, and finally heterocyclic sulfur compounds found in shiitake mushrooms or truffles. This review paper summarizes their precursors and biosynthesis, as well as their sensory properties and changes in selected technological processes.

Effects of sulfated polysaccharides from Laminaria japonica on regularating the gut microbiotan and alleviating intestinal inflammation in obese mice.

Due to their known health-enhancing properties, Laminaria japonica polysaccharides (LJP) may alleviate obesity via unknown mechanisms. This study aimed to investigate beneficial LJP effects and mechanism(s) of action using an animal obesity model (ICR mice fed a high-fat diet). First, LJP were confirmed to consist of sulfated polysaccharides via infrared spectroscopy. Next, LJP administration to mice was found to induce weight loss, reduce liver fat accumulation, and support healthy obesity-related blood serum indicator levels. Notably, LJP treatment significantly reduced TC and LDL levels and significantly increased HDL, LPL, UCP-2, and PPAR-α levels. Furthermore, examinations of tissues of LJP-treated mice revealed significantly reduced intestinal tissue inflammation as compared to corresponding results obtained for untreated obese controls. Additionally, LJP treatment relieved colonic shortening and reduced colonic levels of inflammatory factors TNF-α and IL-6. Further exploration of LJP treatment effects on mouse gut microbiota conducted via fecal 16S rRNA gene sequence-based gut microbiome profiling analysis revealed that LJP treatment increased the Bacteroidetes/Firmicutes ratio and increased gut abundances of probiotics Bacteroides acidifaciens, s_Lactobacillus intestinalis, and s_Lactobacillus murinus. In conclusion, these results collectively suggest that LJP use as a food supplement may alleviate obesity and related gut microbiota dysbiosis and intestinal inflammatory disorders.

A simple method for routine measurement of organosulfur compounds in complex liquid and gaseous matrices.

The measurement of VOSCs in complex matrices is challenging due to their volatile and reactive nature. A straightforward method using headspace chromatography was developed for routine analyses of organosulfur compounds in a high saline liquid matrix with a pH of 8.4. Direct sample acidification with a 1M acetate buffer (pH 3.6) showed an increased response for methanethiol, ethanethiol, propanethiol, dimethyl sulfide, dimethyl disulfide and diethyl disulfide. A good quadratic fit (R2 <0.995) was obtained for each compound over a calibration range of 5 µM-S until 125 µM-S (µmol sulfur/L). Gas standards were measured using the same chromatographic conditions over a calibration range of 0.08 µM-S until 1.85 µM-S (R2 <0.999). Gas standards could also be used to calibrate the liquid phase with a response ratio of 105.2% for ET, 107% for DMS, 105.7% for PT, 108.9% for DMDS and 106% for DEDS. This alternative calibration strategy reduced the preparation time and does not rely on liquid standards, which were unstable over time. This method was used to determine Henry constants for the organosulfur compounds both in demineralized water and the high saline liquid matrix and to analyze samples from a bio electrochemical experiment that treated methanethiol. This new method allows for routine analysis of samples originating from natural gas desulfurization plants and can potentially also be used to analyze organosulfur compounds in other complex waste streams.

Ultrafast oxidative desulfurization of diesel fuel catalyzed by a polyoxometalate-based catalyst immobilized on functionalized Y-SBA-15.

Y-SBA-15 was synthesized by doping yttrium (Y) into SBA-15 using a solvent-free solid-state grinding method, and 1-butyl-3-methylimidazolium phosphomolybdic salt ([Bmim]3PMo12O40, abbreviated as [Bmim]PMoO) was also synthesized. [Bmim]PMoO/Y-SBA-15 was prepared and used for oxidative desulfurization (ODS). The physicochemical characteristics of the catalyst have been characterized by FT-IR, XRD, N2 adsorption-desorption, FESEM, TEM, XPS, contact angle testing, EPR, etc. A lipophilic surface is beneficial for making the catalyst well disperse in an oil phase, and a hydrophilic core can help to store aqueous oxidants. Therefore, the amphiphilic catalyst 25[Bmim]PMoO/10Y-SBA-15 exhibited high catalytic activity in dibenzothiophene (DBT) ODS, and sulfur compounds can be removed completely within 40 min under the following conditions: VOil = 10 mL, mcatalyst = 0.1 g, m[Bmim]PMoO : m[Bmim]PMoO/10Y-SBA-15 = 25%, and O/S = 4 (molar ratio). In addition, the concentration of aromatics exerted little effect on the DBT ODS. Sulfur compounds in real diesel might be reduced to 8 µg g-1. The hydroxyl radical ˙OH and superoxide radical ˙O2- play crucial roles in the ODS reaction, and the ODS reaction mechanism was also proposed.

Side-Chain Anchoring Strategies for the Synthesis of Peptide Thioesters and Selenoesters.

Peptides bearing C-terminal thioester and selenoester functionalities are essential precursors for the chemical synthesis of larger proteins using ligation chemistry, including native chemical ligation (NCL) and diselenide-selenoester ligation (DSL). The use of a side-chain anchoring thioesterification or selenoesterification approach offers a robust method to access peptide thioesters or peptide selenoesters in excellent yields and in high purity. Importantly, this methodology overcomes solubility issues and epimerization of the C-terminal amino acid residue that can occur using solution-phase approaches. Detailed methods for the solid-phase synthesis of peptide thioesters and selenoesters using a side-chain anchoring approach are outlined in this article.