Chemistry Central Journal最新文献

Background: We are interested in comparing the levels of harmful or potentially harmful constituents in Swedish and American smokeless tobacco products (STPs). We report here the concentrations of the IARC Group 2 A (probable human) carcinogen ethyl carbamate (EC) in seventy commercial STPs from the US and Sweden, representing 80-90% of the market share of the major STP categories in these countries. We also examine the effects of various additives, processing and storage conditions on EC concentrations in experimental snus samples.

Results: EC was determined from aqueous extracts of the STPs using ultra performance liquid chromatography tandem mass spectrometry (UPLC/MS/MS). EC was undetectable (< 20 ng/g wet weight basis WWB) in 60% of the commercial STPs, including all the chewing tobacco (CT), dry snuff (DS), hard pellet (HP), soft pellet (SP), and plug products. Measurable levels of EC were found in 11/16 (69%) of the moist snuff (MS) samples (average 154 ng/g in those samples containing EC) and 19/32 (59%) of the Swedish snus samples (average 35 ng/g). For the experimental snus samples, EC was only observed in ethanol treated samples. EC concentrations increased significantly with ethanol concentrations (0-4%) and with storage time (up to 24 weeks) and temperature (8 °C vs 20 °C). EC concentrations were lower at lower pHs but were unaffected by adding nitrogenous precursors identified from food studies (citrulline and urea), increasing water content or by pasteurisation. Added EC was stable in the STP matrix, but evaporative losses were significant when samples were stored for several weeks in open containers at 8 °C.

Conclusions: EC was found in measurable amounts only in some moist STPs i.e. pasteurised Swedish snus and unpasteurised US MS; it is not a ubiquitous contaminant of STPs. The presence of ethanol contributed significantly to the presence of EC in experimental snus samples, more significantly at higher pH levels. Sample age also was a key determinant of EC content. In contrast, pasteurisation and fermentation do not appear to directly influence EC levels. Using published consumption rates and mouth level exposures, on average STP consumers are exposed to lower EC levels from STP use than from food consumption.

Neem (Azadirachta indica) extract is well-known as a natural pesticide for the control of agricultural pests. Azadirachtin A and its structural analogues are considered as active compounds. However, the amounts of azadirachtins varies in neem extracts, providing a variety of insecticidal activities. In this study, a novel method of automated online solid-phase extraction coupled with liquid chromatography/quadrupole-time-of-flight mass spectrometry (SPE-LC-Q-TOF-MS) was developed and validated for simultaneous quantification of five azadirachtins (azadirachtins A, B, D, H and I) in seed and leaf extracts of A. indica. Different experimental parameters (such as SPE cartridge, injection volume and washing step) were optimized. The optimized SPE-LC-Q-TOF-MS method showed good recovery (82.0-102.8%), linearity (r² ≥ 0.9991) and precision (0.83-4.83%). The limit of detections (LODs) for the five analytes ranged from 0.34 to 0.76 ng mL^-1. The validated method was successfully applied for determination of the analytes in the neem leaves and seeds from different locations and a neem formulation. The online SPE-LC-Q-TOF-MS method was found to be a simple, precise and accurate and can be used as a powerful tool for quality control of neem extracts or its formulations.

A variety of imine derivatives have been synthesized via Suzuki cross coupling of N-(4-bromophenyl)-1-(3-bromothiophen-2-yl)methanimine with various arylboronic acids in moderate to good yields (58-72%). A wide range of electron donating and withdrawing functional groups were well tolerated in reaction conditions. To explore the structural properties, Density functional theory (DFT) investigations on all synthesized molecules (3a-3i) were performed. Conceptual DFT reactivity descriptors and molecular electrostatic potential analyses were performed by using B3LYP/6-31G(d,p) method to explore the reactivity and reacting sites of all derivatives (3a-3i).

Background: Tetramic acid, thiophene and hydrazone derivatives were found to exhibit favorable antifungal activity. Aiming to discover novel template molecules with potent antifungal activity, a series of novel 3-(thiophen-2-yl)-1,5-dihydro-2H-pyrrol-2-one derivatives containing a hydrazone group were designed, synthesized, and evaluated for their antifungal activity.

Results: The structures of 3-(thiophen-2-yl)-1,5-dihydro-2H-pyrrol-2-one derivatives bearing a hydrazone group were confirmed by FT-IR, ¹H NMR, ¹³C NMR, ¹H-¹H NOESY, EI-MS and elemental analysis. Antifungal assays indicated that some title compounds exhibited antifungal activity against Fusarium graminearum (Fg), Rhizoctorzia solani (Rs), Botrytis cinerea (Bc) and Colletotrichum capsici (Cc) in vitro. Strikingly, the EC₅₀ value of 5e against Rs was 1.26 µg/mL, which is better than that of drazoxolon (1.77 µg/mL). Meanwhile, title compounds 5b, 5d, 5e-5g, 5n-5q and 5t exhibited remarkable anti-Cc activity, with corresponding EC₅₀ values of 7.65, 9.97, 6.04, 6.66, 7.84, 7.59, 9.47, 5.52, 6.41 and 7.53 µg/mL, respectively, which are better than that of drazoxolon (19.46 µg/mL).

Conclusions: A series of 3-(thiophen-2-yl)-1,5-dihydro-2H-pyrrol-2-one derivatives bearing a hydrazone group were designed, synthesized and evaluated for their antifungal activity against Fg, Rs, Bc and Cc. Bioassays indicated that some target compounds exhibited obvious antifungal activity against the above tested fungi. These results provide a significant basis for the further structural optimization of tetramic acid derivatives as potential fungicides.

A flavonoids-rich extract of Scutellaria baicalensis shoots and its eight high content flavonoids were investigated for their inhibitory effects against α-glucosidase and α-amylase. Results show that abilities of the extract in inhibiting the two enzymes were obviously higher than those of acarbose. Moreover, inhibitory abilities of all the eight individual flavonoids against the two enzymes show exactly a same order (i.e., apigenin > baicalein > scutellarin > chrysin > apigenin-7-O-glucuronide > baicalin > chrysin-7-O-glucuronide > isocarthamidin-7-O-glucuronide), and their structure-activity relationship could be well-interpretated by the refined assign-score method. Furthermore, based on the inhibitory abilities and their contents in the extract, it was found that the eight flavonoids made predominant contributions, among which baicalein and scutellarin played roles as preliminary contributors, to overall inhibitory effects of the extract against the two enzymes. Beyond these, contributions of the eight flavonoids to the overall enzyme inhibitory activity were compared with those to the overall antioxidant activity characterized in our recent study, and it could be inferred that within the basic flavonoid structure the hydroxyl on C-4' of ring B was more effective than that on C-6 of ring A in enzyme inhibitory activities while they behaved inversely in antioxidant activities; scutellarin and apigenin contributed more to the overall enzyme inhibitory activity, and baicalin and scutellarin, to the overall antioxidant activity of the extract; and flavonoids of the extract, apart from directly inhibiting enzymes, might also be conducive to curing type 2 diabetes via scavenging various free radicals caused by increased oxidative stresses.

The removal of malachite green (MG) from aqueous solution using teak leaf litter powder (TLLP) was investigated. The process was influenced by initial concentration, pH and temperature of dye solution as well as TLLP dosage. Optimum removal of MG per gram of TLLP occurred at 2 g/L and at pH 6-8. Dubinin-Radushkevich and Freundlich isotherm models fit the batch adsorption data better than Langmuir isotherm. The monolayer capacity of TLLP was 333.33 mg/g at 293-313 K. The mean free energy of 7.07 kJ/mol implied physical adsorption. The pseudo-second order model fit the kinetic data better than the pseudo-first order model. Both intraparticle diffusion and film diffusion mechanisms jointly influenced the adsorption process but the latter was the rate-controlling step. Thermodynamic data indicated that the process was endothermic, spontaneous and feasible. Therefore, TLLP could be an important low-cost adsorbent for removal of MG from aqueous solution.

Polymeric membranes are usually prepared from solvents like n-methylpyrrolidone (NMP) because of the strong dissolving power and high boiling point. Yet, the solvent is costly, toxic and has environmental issues. In this work, nontoxic solvents such as methyl L-lactate, ethyl lactate, propylene carbonate, tributyl o-acetylcitrate, tributyl citrate, triethyl phosphate, and γ-butyrolactone (GBL) were introduced during membrane preparation. It was found that all the solvents were unable to dissolve polyetherimide except GBL. The membranes made by GBL and NMP were evaluated for gas separation, and they have almost similar hydrogen-to-methane selectivity, but, hydrogen permeance was better in NMP membranes.

Background: Although polypropylene (PP) has been widely used, its brittleness restricts even further applications.

Methods: In this study, we have used a melt blending process to synthesize styrene acrylonitrile (SAN)/PP blends containing 0, 5, 10, 15 and 20 wt% SAN. The effects of adding various amount of SAN on the blends characteristics, mechanical properties, thermal behavior and morphology were investigated.

Results: The results demonstrated that SAN had no obviously effect on crystal form but reduced the crystallinity of PP and increased the viscosity. The heat deflection temperature and Vicat softening temperature were enhanced for all SAN/PP blends, in particular for blends with low SAN content (5 and 10 wt%). The morphology of SAN/PP blends with 10 wt% SAN revealed the presence of nanoparticles dispersed on the surface, while SAN/PP blends with 20 wt% SAN exhibited the presence of spherical droplets and dark holes. All SAN/PP blends showed higher impact strength compared to pure PP, especially for SAN/PP blend containing 10 wt% SAN for which the impact strength was 2.3 times higher than that of pure PP.

Conclusions: The reason for significant increase in impact properties seemed to have a strong correlation with nanoparticles morphology and the decrease of PP crystallinity.

Phenolic wastewater was treated using anaerobic submerged membrane bioreactor (ASMBR). Effect of different solids retention times on MBR performance was studied. Various ratios of carbon to nitrogen were used in the synthetic wastewaters. During the operation, phenol concentration of feed was changed from 100 to 1000 mg L^-1. Phenol concentration was increased stepwise over the first 30 days and kept constant at 1000 mg L^-1, thereafter. For the first 100 days, a chemical oxygen demand (COD) to N ratio of 100:5.0 was used and this resulted in phenol and COD removal more than 99 and 95%, respectively. However, the ammonium removal decreased from 95 to 40% by increasing the phenol concentration of feed, from 100 to 1000 mg L^-1. For the last 25 days, a COD to N ratio of 100:2.1 was used due to the ammonium accumulation in the ASMBR. This led to the complete ammonium removal and no ammonium was detected in the ASMBR permeate. These results suggest that in the ASMBR at high phenol loading of 1000 mg L^-1, COD to N ratio of the phenolic wastewater must be 100:2.1 for ammonium removal, while at low phenol loading, COD to N ratio of 100:5.0 can be used.

A stable and porous amino-functionalized zirconium-based metal organic framework (Zr-MOF-NH₂) containing missing linker defects was prepared and fully characterized by FTIR, scanning electron microscopy, powder X-ray diffraction, and BET surface area measurement. The Zr-MOF-NH₂ was then applied as an adsorbent in pipette-tip solid phase extraction (PT-SPE) of carbamazepine. Important parameters affecting extraction efficiency such as pH, sample volume, type and volume of eluent, amount of adsorbent, and number of aspirating/dispensing cycles for sample solution and eluent solvent were investigated and optimized. The best extraction efficiency was obtained when pH of 100 µL of sample solution was adjusted to 7.5 and 5 mg of the sorbent was used. Eluent solvent was 10 µL methanol. Linear dynamic range was found to be between 0.1 and 50 µg L^-1 and limit of detection for 10 measurement of blank solution was 0.05 µg L^-1. This extraction method was coupled to HPLC and was successfully employed for the determination of carbamazepine in urine and water samples. The strategy combined the advantages of fast and easy operation of PT-SPE with robustness and large adsorption capacity of Zr-MOF-NH₂.