Promotion effect of adsorbed water/OH on the catalytic performance of Ag/activated carbon catalysts for CO preferential oxidation in excess H2

Activated carbon (AC) supported silver catalysts were prepared by incipient wetness impregnation method and their catalytic performance for CO preferential oxidation (PROX) in excess H₂ was evaluated. Ag/AC catalysts, after reduction in H₂ at low temperatures (≤200 °C) following heat treatment in He at 200 °C (He200H200), exhibited the best catalytic properties. Temperature-programmed desorption (TPD), X-ray diffraction (XRD) and temperature-programmed reduction (TPR) results indicated that silver oxides were produced during heat treatment in He at 200 °C which were reduced to metal silver nanoparticles in H₂ at low temperatures (≤200 °C), simultaneously generating the adsorbed water/OH. CO conversion was enhanced 40% after water treatment following heat treatment in He at 600 °C. These results imply that the metal silver nanoparticles are the active species and the adsorbed water/OH has noticeable promotion effects on CO oxidation. However, the promotion effect is still limited compared to gold catalysts under the similar conditions, which may be the reason of low selectivity to CO oxidation in PROX over silver catalysts. The reported Ag/AC-S-He catalyst after He200H₂00 treatment displayed similar PROX of CO reaction properties to Ag/SiO₂. This means that Ag/AC catalyst is also an efficient low-temperature CO oxidation catalyst.     

Synthesis,isolation and characterization of methyl levulinate from cellulose catalyzed by extremely low concentration acid

A direct synthesis of methyl levulinate from cellulose alcoholysis in methanol medium under mild condition (180–210 °C) catalyzed by extremely low concentration sulfuric acid (≤0.01 mol/L) and the product isolation were developed in this study. Effects of different process variables towards the catalytic performance were performed as a function of reaction time. The results indicated that sulfuric acid concentration, temperature and initial cellulose concentration had significant effects on the synthesis of methyl levulinate. An optimized yield of around 50% was achieved at 210 °C for 120 min with sulfuric acid concentration of 0.01 mol/L and initial cellulose concentration below 100 g/L. The resulting product mixture was isolated by a distillation technique that combines an atmospheric distillation with a vacuum distillation where n-dodecane was added to help distill the heavy fraction. The light fraction including mainly methanol could be reused as the reaction medium without any substantial change in the yield of methyl levulinate. The chemical composition and structural of lower heavy fraction were characterized by GC/MS, FTIR, ¹H-NMR and ¹³C-NMR techniques. Methyl levulinate was found to be a major ingredient of lower heavy fraction with the content over 96%. This pathway is efficient, environmentally benign and economical for the production of pure levulinate esters from cellulose.     

Development of hyperbranched polymers with non-covalent interactions for extraction and determination of aflatoxins in cereal samples

A novel approach for assembling homogeneous hyperbranched polymers based on non-covalent interactions with aflatoxins was developed; the polymers were used to evaluate the extraction of aflatoxins B1, B2, G1 and G2 (AFB1, AFB2, AFG1 and AFG2) in simulant solutions. The results showed that the extraction efficiencies of three kinds of synthesized polymers for the investigated analytes were not statistically different; as a consequence, one of the representative polymers (polymer I) was used as the solid-phase extraction (SPE) sorbent to evaluate the influences of various parameters, such as desorption conditions, pH, ionic strength, concentration of methanol in sample solutions, and the mass of the sorbent on the extraction efficiency. In addition, the extraction efficiencies for these aflatoxins were compared between the investigated polymer and the traditional sorbent C18. The results showed that the investigated polymer had superior extraction efficiencies. Subsequently, the proposed polymer for the SPE packing material was employed to enrich and analyze four aflatoxins in the cereal powder samples. The limits of detection (LODs) at a signal-to-noise (S/N) ratio of 3 were in the range of 0.012–0.120 ng g⁻¹ for four aflatoxins, and the limits of quantification (LOQs) calculated at S/N = 10 were from 0.04 to 0.40 ng g⁻¹ for four aflatoxins. The recoveries of four aflatoxins from cereal powder samples were in the range of 82.7–103% with relative standard deviations (RSDs) lower than 10%. The results demonstrate the suitability of the SPE approach for the analysis of trace aflatoxins in cereal powder samples.     

Optimization of chemical and instrumental parameters in hydride generation laser-induced breakdown spectrometry for the determination of arsenic,antimony, lead and germanium in aqueous samples

A laser induced breakdown spectrometry hyphenated with on-line continuous flow hydride generation sample introduction system, HG-LIBS, has been used for the determination of arsenic, antimony, lead and germanium in aqueous environments. Optimum chemical and instrumental parameters governing chemical hydride generation, laser plasma formation and detection were investigated for each element under argon and nitrogen atmosphere. Arsenic, antimony and germanium have presented strong enhancement in signal strength under argon atmosphere while lead has shown no sensitivity to ambient gas type. Detection limits of 1.1 mg L⁻¹, 1.0 mg L⁻¹, 1.3 mg L⁻¹ and 0.2 mg L⁻¹ were obtained for As, Sb, Pb and Ge, respectively. Up to 77 times enhancement in detection limit of Pb were obtained, compared to the result obtained from the direct analysis of liquids by LIBS. Applicability of the technique to real water samples was tested through spiking experiments and recoveries higher than 80% were obtained. Results demonstrate that, HG-LIBS approach is suitable for quantitative analysis of toxic elements and sufficiently fast for real time continuous monitoring in aqueous environments.     

Theoretical Study on Hydrogen Bonding of Mono‐ and Dihydrated Complexes of 7‐(3′‐Pyridyl)indole in Excited States

The intermolecular hydrogen bonds of mono‐ and dihydrated complexes of 7‐(3′‐Pyridyl)indole (7‐3′PI) have been investigated using the time‐dependent density functional theory (TD‐DFT) method. The electrostatic potential analysis of monomer 7‐3′PI and 7‐(3′‐Pyridyl)indole‐water (7‐3′PI‐W) indicates that an intermolecular hydrogen bond between two waters can be formed for 7‐(3′‐Pyridyl)indole‐2water (7‐3′PI‐2W) complex. The calculated bond lengths of the intermolecular hydrogen bonds of 7‐3′PI‐W and 7‐3′PI‐2W in the S₁ state (the first excited singlet state) are all shortened compared to the ground state. By the analysis of bond length, charge population and infrared spectra, it is demonstrated that the intermolecular hydrogen bonds of 7‐3′PI‐W and 7‐3′PI‐2W are all strengthened upon electronic excitation to the S1 state. Moreover, the fluorescence of 7‐3′PI‐W and 7‐3′PI‐2W are all red‐shifted to larger wavelength compared to monomer 7‐3′PI. The red‐shift of fluorescence peak of 7‐3′PI‐W and 7‐3′PI‐2W should be attributed to the change of hydrogen bond interaction before and after photoexcitation. Therefore, it can be concluded that the intermolecular hydrogen bonding strengthening in the excited S₁ state induces the fluorescence weakening of 7‐3′PI.     

Graphene as Solid-Phase Extraction Adsorbent for CZE Determination of Sulfonamide Residues in Meat Samples

A solid-phase extraction (SPE) using graphene as adsorbent coupled with capillary zone electrophoresis method was developed for the determination of four sulfonamide residues (sulfadimidine, sulfadimethoxine, sulfathiazole and sulfadiazine) in meat sample. Several condition parameters, such as elution solvents and volumes, sample pH and sample volume were optimized to obtain high SPE recoveries and extraction efficiency. Intra-day precisions of sulfonamides were in the range of 2.5–2.6 % and the inter-day precisions of sulfonamides were in the range of 2.6–3.4 %. Recoveries were 60.9–66.6 % for sulfadiazine and 86.1–111.4 % for other three sulfonamides in spiked meat sample. The developed method was successfully applied for the determination of sulfonamides in meat samples.     

Five New Cycloartane‐Type Triterpenoid Saponins from Nervilia fordii

Five new cycloartane glycosides, nervisides D–H ( 1 – 5 ), were isolated from the AcOEt‐ and H₂O‐soluble portions of the 90% EtOH extract of the aerial part of the plant Nervilia fordii. The structures of the isolated glycosides were elucidated by extensive spectroscopic analysis including HR‐ESI‐MS and NMR data. The isolated nervisides D–H were evaluated for the cytotoxic activity in vitro against human‐tumor cell lines (CNE, Hep‐2 and HepG2) with the MTT method.     

Two New Abietane Diterpenoids from the Roots of Tripterygium wilfordii Hook. f.

Two new abietane‐type diterpenoids, named triptobenzene R ( 1 ) and triptobenzene S ( 2 ), together with three known abietane‐type diterpenoids, triptophenolide ( 3 ), triptonodiol ( 4 ), and triptonoterpene methyl ether ( 5 ), were isolated from the roots of Tripterygium wilfordii Hook . f. Their structures and relative configurations were established by detailed spectral studies, including 1D‐ and 2D‐NMR (HSQC, HMBC, and NOESY), and HR‐ESI‐TOF‐MS, and by comparison with published data. Their absolute configurations were assigned by the CD technique, applied for the first time to abietane diterpenes from Tripterygium wilfordii. Compound 2 is the first abietane‐type norditerpenoid isolated from the genus Tripterygium.     

The Efficient Syntheses of Three Novel Bridging Phenanthroline Ligands and Their Binuclear Ruthenium(II) Complexes

Three bridging ligands (L) and their binuclear phenanthroline ruthenium(II) complexes {[Ru(1, 10-phenanthroline)₂]₂(L)}(PF₆)₄ were synthesized and characterized by IR, ¹H NMR, and elemental analysis, where L are 1,8-adipoylamido-bis(1,10-phenanthroline-5-yl) (L₁), 1,11-azelaoylamidobis(1,10-phenanthroline-5-yl) (L₂), and p-phthaloylamido-bis(1,10-phenanthroline-5-yl) (L₃).