Synthesis of 2,3-unsaturated C-glycosides by HClO4-SiO2 catalyzed Ferrier rearrangement of glycals

Alkyl 2,3-unsaturated C-glycopyranosides have been prepared by Ferrier rearrangement of acyl or alkyl protected glycals catalyzed by HClO(4)-SiO(2).     

Selective deprotection of terminal isopropylidene acetals and trityl ethers using HClO4 supported on silica gel

Terminal isopropylidene acetals are selectively cleaved to the corresponding 1,2-diols in good to excellent yields in 6-24 h at room temperature by using the 'HClO4.SiO2' reagent system. Likewise, trityl ethers are readily cleaved to the corresponding alcohols in good to excellent yields within 2-3 h at room temperature. Work-up involves merely filtration of the reagent followed by purification of the crude product.     

Acylation of carbohydrates over Al2O3: preparation of partially and fully acylated carbohydrate derivatives and acetylated glycosyl chlorides

Selective and per-O-acylation of carbohydrate derivatives using acyl chlorides and Al2O3, a solid support reagent, is reported. This protocol does not require the addition of any base or activator. This methodology has been further extended to the selective acylation of carbohydrate diols and the one-pot preparation of acetylated glycosyl chlorides direct from free reducing sugars. The yields obtained in most of the cases are excellent.     

Fast oxidation of thioglycosides to glycosyl sulfones using KMnO4/CuSO4*5H2O under neutral reaction conditions

A rapid oxidation of thioglycosides to glycosyl sulfones has been achieved using a combination of KMnO4 and CuSO4*5H2O in acetonitrile and water. This reaction protocol has many advantages compared to other methods available for this transformation, including compatibility with acid and base labile functional groups used for the protection of carbohydrates, high yields, fast reaction times, and moderate reaction temperatures. The yields obtained were excellent in all cases.     

The identification of substituted benzothiophene derivatives as PGE(2) subtype 4 receptor antagonists: From acid to non-acid

We disclose herein our preliminary SAR study on the identification of substituted benzothiophene derivatives as PGE₂ subtype 4 receptor antagonists. A potent EP₄ antagonist 6a (K_i = 1.4 nM with 10% HSA) was identified. Furthermore, we found that an acidic group was not essential for the EP₄ antagonizing activity in the series and neutral replacements were identified. This opens a new direction for future EP₄ antagonist design.     

Convergent synthesis of a trisaccharide as its 2-(trimethylsilyl)ethyl glycoside related to the flavonoid triglycoside from Gymnema sylvestre

The glycone part of the flavonoid triglycoside, kaempferol 3-O-beta-D-glucopyranosyl-(1-->4)-alpha-L-rhamnopyranosyl-(1-->6)-beta-D-galactopyranoside, has been synthesized in good yield and stereoselectivity using N-iodosuccinimide and HClO4-silica promoted glycosylations of thioglycoside donors.     

Na_2SeO_4对蛹虫草子实体生长的影响

蛹虫草是一种药食两用真菌,具有与冬虫夏草相似的功能,且富硒能力较强。本研究通过大量的人工栽培试验,旨在探究不同浓度Na_2SeO_4对新疆本地蛹虫草子实体生长的影响。试验表明,质量浓度为20 mg/L的Na_2SeO_4对蛹虫草的生长不产生显著影响,但蛹虫草各项生物学指标均随着培养基中外源Na_2SeO_4浓度的增加而呈下降趋势,说明随着外源Na_2SeO_4浓度的增加会对蛹虫草的生长产生抑制效应,当外源Na_2SeO_4质量浓度达到200 mg/L时,生产的蛹虫草已不具备商品价值。由此可见,20 mg/L的质量浓度是以Na_2SeO_4为硒源进行蛹虫草富硒研究的安全浓度。该研究为富硒产品开发寻找新的硒源开辟了新思路,为新疆地区进一步大规模栽培富硒蛹虫草提供一定的参考,但是对以Na_2SeO_4为硒源的最佳富硒浓度还有待于进一步研究。     

Hydrophilicity effect on CO2/CH4 separation using carbon nanotube membranes: insights from molecular simulation

Abstract

Molecular simulation methods were applied to study the effect of hydrophilicity on CO₂/CH₄ separation using carbon nanotube (CNT) membranes. CNTs with a diameter of ~1 nm were functionalised by varying amounts of carbonyl groups, in order to achieve various hydrophilicity. The presence of –CO groups inside the CNT allow a significant gain in the diffusion selectivity of CO₂, while in contrast the adsorption selectivity is hardly changed. The corresponding permeation selectivity increases as the hydrophilicity of the CNT-based membrane increases. However, the permeability of CO₂ decreases due to a combination of the intermolecular interactions between the gas and functional groups and the steric effects of the added functional groups. Considering both the permeation selectivity and permeability, it was found that the maximum separation performance is achieved in a certain hydrophilic CNT membrane. Moreover, the separation performance of hydrophilic CNTs for CO₂/CH₄ mixtures breaks the Robeson upper bound.     

Leukotriene D4-induced adhesion of Caco-2 cells is mediated by prostaglandin E2 and upregulation of alpha2beta1-integrin

Cell-cell and extracellular matrix adhesions play important roles in the progression of cancer. We investigated the involvement of the inflammatory mediator leukotriene D4 (LTD4) in the regulation of cell-matrix adhesion of colon cancer (Caco-2) cells. We observed that LTD4 acted via its CysLT1 receptor in these cells to induce increased adhesion to collagen I. LTD4 also enhanced the activation and expression of alpha2beta1-integrins on the cell surface, which we found to be responsible for mediating the increased adhesion to collagen I. LTD4 simultaneously augmented expression of the prostaglandin-generating enzyme cyclooxygenase-2 (COX-2) and increased prostaglandin E2 (PGE2) production in Caco-2 cells. The adhesive capacity of the Caco-2 cells was reduced by specific inhibition of COX-2 and was subsequently restored by PGE2, but not by LTD4. A selective PGE2 receptor antagonist abolished the increased adhesion and the augmented alpha2beta1-integrin expression induced by both PGE2 and LTD4. Summarizing, the inflammatory mediator LTD4 regulates the adhesive properties and migration of the Caco-2 cell line by upregulating COX-2 and stimulating PGE2-induced expression of alpha2beta1-integrins. This suggests that inflammatory mediators such as LTD4 can be involved in the dissemination and survival of colon cancer cells.     

Leukotriene D4 activates distinct G-proteins in intestinal epithelial cells to regulate stress fibre formation and to generate intracellular Ca2+ mobilisation and ERK1/2 activation

We have shown that the pro-inflammatory mediator LTD4, via its G-protein-coupled receptor CysLT1, signals through both pertussis-toxin-sensitive and -insensitive G-proteins to induce various cellular responses. To further characterise the initial step of the different signalling pathways emanating from the CysLT1 receptor, we transfected intestinal epithelial cells, Int 407, with different mini vectors that each express a specific inhibitory peptide directed against a unique alpha subunit of a specific heterotrimeric G-protein. Our results revealed that LTD4-induced stress fibre formation is inhibited approximately 80% by a vector expressing an inhibitory peptide against the pertussis-toxin-insensitive Galpha12-protein in intestinal epithelial Int 407 cells. Control experiments revealed that the LPA-induced stress fibre formation, mediated via the Galpha12-protein in other cell types, was blocked by the same peptide in intestinal Int 407 cells. Furthermore, the CysLT1-receptor-mediated calcium signal and activation of the proliferative ERK1/2 kinase are blocked in cells transfected with a vector expressing an inhibitory peptide against the Galphai3-protein, whereas in cells transfected with an empty ECFP-vector or vectors expressing inhibitory peptides against the Galphai1-2-, Galpha12-, GalphaR-proteins these signals are not significantly affected. Consequently, the CysLT1 receptor has the capacity to activate at least two distinctly different heterotrimeric G-proteins that transduce activation of unique downstream cellular events.     

Improving of Catalase Stability Properties by Encapsulation in Alginate/Fe3O4 Magnetic Composite Beads for Enzymatic Removal of H2O2

The aim of this study was enhancing of stability properties of catalase enzyme by encapsulation in alginate/nanomagnetic beads. Amounts of carrier (10–100 mg) and enzyme concentrations (0.25–1.5 mg/mL) were analyzed to optimize immobilization conditions. Also, the optimum temperature (25–50°C), optimum pH (3.0–8.0), kinetic parameters, thermal stability (20–70°C), pH stability (4.0–9.0) operational stability (0–390 min), and reusability were investigated for characterization of the immobilized catalase system. The optimum pH levels of both free and immobilized catalase were 7.0. At the thermal stability studies, the magnetic catalase beads protected 90% activity, while free catalase maintained only 10% activity at 70°C. The thermal profile of magnetic catalase beads was spread over a large area. Similarly, this system indicated the improving of the pH stability. The reusability, which is especially important for industrial applications, was also determined. Thus, the activity analysis was done 50 times in succession. Catalase encapsulated magnetic alginate beads protected 83% activity after 50 cycles.     

Molecular insight into the micro-behaviors of CH4 and CO2 in montmorillonite slit-nanopores

Abstract

The Grand Canonical Monte Carlo (GCMC) and molecular dynamics (MD) simulation methods were used to investigate the adsorption and diffusion properties of CH₄ and CO₂ in montmorillonite slit-nanopores. It is found that, both CH₄ and CO₂ could adsorb closely onto the pore surface, while different adsorption states occur for CH₄ and CO₂, respectively, in montmorillonite slit-nanopores. Competitive adsorption of CO₂ over CH₄ exists in montmorillonite slit-nanopores, especially at the lower pressures, which is attributed to the different interaction intensity between the CH₄–CO₂ molecules and the pore surface. The diffusion coefficients of CH₄ and CO₂ both decrease with the enhanced pressures, while the CO₂ has a relative weak diffusion coefficient comparing with CH₄. A well displacement of the residual CH₄ by CO₂ in montmorillonite slit-nanopores was investigated, which is found that the displacement efficiency increases with the enhanced bulk pressures. It was determined that, the CO₂ can be captured and reserved in the montmorillonite slit-nanopores during the displacement, and the sequestration amount of CO₂ gets enhanced with the bulk pressure increasing. This study provides micro-behaviours of CH₄ and CO₂ in montmorillonite slit-nanopores, for the purpose to give out useful guidance for enhancing shale gas extraction by injecting CO₂.     

One-pot synthesis of per-O-acetylated thioglycosides from unprotected reducing sugars

A sequential per-O-acetylation and thioglycosidation of unprotected reducing sugars using a stoichiometric quantity of acetic anhydride and alkyl- or arylthiols is reported. These reactions, which are catalyzed by BF3.OEt2, together constitute an efficient one-pot method for the synthesis of acetylated thioglycosides.     

On the role of bicarbonate in peroxidations catalyzed by Cu,Zn superoxide dismutase

The interaction of Cu,ZnSOD with H2O2 generates an oxidant at the active site that can then cause either the inactivation of this enzyme or the oxidation of a variety of exogenous substrates. We show that the rate of inactivation, imposed by 10-mM H2O2 at 25 degrees C and pH 7.2, is not influenced by 10-mM HCO3-; whereas the oxidation of 2,2'-azino-bis-[3-ethylbenzothiazoline sulfonate] (ABTS=) is virtually completely dependent upon HCO3-. The reduction of the active site Cu(II) by H2O2, which precedes inactivation of the enzyme, occurred at the same rate in phosphate buffer with or without bicarbonate added. These results indicate that HCO3- does not play a role in facilitating the interaction of H2O2 with the active site copper, but they can be accommodated by the proposal that HCO3- is oxidized to HCO3*, which then diffuses from that site and causes the oxidation of substrates, such as ABTS=, that are too large to traverse the solvent access channel to the Cu(II).     

Role of Janus kinase-2 in IgE receptor-mediated leukotriene C4 production by mast cells

We have previously shown that Janus kinase 3, a member of the family of non-receptor protein tyrosine kinases, plays a critical role in the regulation of FcεRI-mediated mast cell responses. In the current study, we investigated the role of another JAK family member, JAK2, in these responses. Our results show that the treatment of IgE-sensitized mouse mast cells with an inhibitor of JAK2 (AG490) blocked the release of leukotriene C₄ in a dose-dependent fashion after antigen challenge. However, prostaglandin PG D₂ production and degranulation were not affected under identical experimental conditions. Transfection of RBL-2H3 mast cells with JAK-2 specific small interfering RNA resulted in a 50% reduction of LTC₄ release in response to FcεRI crosslinking, but did not inhibit mast cell degranulation or calcium ionophore-induced LTC₄ release, indicating involvement of JAK2 in IgE receptor-mediated leukotriene release. Taken together, these data suggest that JAK2 is a critical regulator of IgE/antigen-induced production of LTC₄ in mast cells.     

Production of leukotriene B4 and prostaglandin E2 by turbot (Scophthalmus maximus) leukocytes

Production of two eicosanoids derived from lipoxygenase and cyclooxygenase activities: leukotriene B₄ (LTB₄) and prostaglandin E₂ (PGE₂), respectively, have been simultaneously determined in turbot (Scophthalmus maximus) blood leucocyte and kidney macrophage supernatants by a reverse phase high performance liquid chromatography (HPLC) system coupled with a Diode–Array detector. Levels of LTB₄ after calcium ionophore challenge were 4.08 ng ml⁻¹ in blood leukocyte supernatants and 0.25 ng ml⁻¹ in kidney macrophage supernatants. The levels found for PGE₂ were 428.23 and 606.67 ng ml⁻¹ in blood leukocytes and kidney macrophage supernatants, respectively. When blood leukocytes were treated with the respective inhibitors for the enzymes implicated on the synthesis of both compounds an inhibition of 90.35% was observed for PGE₂ and 76.44% for LTB₄. The detection limit of the method was 0.15 ng ml⁻¹ for LTB₄ and 50 ng ml⁻¹ for PGE₂.     

Optimization of H2SO4-catalyzed hydrothermal pretreatment of rapeseed straw for bioconversion to ethanol: Focusing on pretreatment at high solids content

A central composite design of response surface method was used to optimize H₂SO₄-catalyzed hydrothermal pretreatment of rapeseed straw, in respect to acid concentration (0.5–2%), treatment time (5–20 min) and solid content (10–20%) at 180 °C. Enzymatic hydrolysis and fermentation were also measured to evaluate the optimal pretreatment conditions for maximizing ethanol production. The results showed that acid concentration and treatment time were more significant than solid content for optimization of xylose release and cellulose recovery. Pretreatment with 1% sulfuric acid and 20% solid content for 10 min at 180 °C was found to be the most optimal condition for pretreatment of rapeseed straw for ethanol production. After pretreatment at the optimal condition and enzymatic hydrolysis, 75.12% total xylan and 63.17% total glucan were converted to xylose and glucose, respectively. Finally, 66.79% of theoretical ethanol yielded after fermentation.     

Influence of cis-[Re2GABA2Cl4]Cl2 on the antioxidant defense system parameters of normal human blood

The effect of the rhenium complex cis-[Re₂GABA₂Cl₄]Cl₂ on the antioxidant parameters of normal human blood in vitro have been studied. The results suggest that the complex influences various enzymes in the cascade of reactions utilizing active oxygen metabolites. However, the manifestation of this activity varies over the studied concentration range of the complex in the preincubation medium (10^–12-10^–4 M), so the effects appear to be concentration-dependent. The largest differences in antioxidant parameters in comparison with control were observed for the concentrations 10^–8, 10^–5, and 10^–4 M. Thus, correlations between the peroxidation level, superoxide dismutase (SOD) activity, antioxidant factor (F), and indexes of resistance of erythrocytes for hemolysis (TR) were found.     

免耕施肥对稻田甲烷与氧化亚氮排放及其温室效应的影响

2008年采用静态箱-气相色谱法对鄂东南免耕不施肥(NT₀)、翻耕不施肥(CT₀)、免耕施肥(NTC)和翻耕施肥(CTC) 4种处理下稻田CH₄和N₂O的排放进行测定.结果表明：各处理CH₄排放均呈先升高后降低的季节性规律,而N₂O排放的季节性规律不明显;施肥显著提高了稻田CH₄和N₂O的排放.与翻耕不施肥相比,免耕不施肥显著提高了CH₄的排放量,并显著降低了N₂O的排放量;与翻耕施肥相比,免耕施肥仅略降低了CH₄的排放量和略提高了N₂O的排放量.对稻田CH₄和N₂O两种气体的综合温室效应分析表明,与翻耕不施肥相比,免耕不施肥的综合温室效应提高了25.9%,与翻耕施肥相比,免耕施肥的综合温室效应降低了10.1%.因此,合理的肥料运筹和稻田免耕技术可降低两种气体的综合温室效应.