Seco-Abietanoids from Cryptomeria japonica and Their Inhibitory Activity Toward Xanthine Oxidase

Chemistry of Natural Compounds - A new seco-abietanoid, 12-methoxy-7-oxo-6,7-secoabieta-8,11,13-trien-6-oic acid (1), and a known seco-abietanoid,12-hydroxy-6,7-secoabieta-8,11,13-triene-6,7-dial...     

Inclusion of thymol into cucurbiturils: density functional theory approach with dispersion correction and natural bond orbital analysis

Journal of Inclusion Phenomena and Macrocyclic Chemistry - Stability of inclusion complexes of thymol (a natural flavour) with cucurbit[n]urils was interpreted by using density functional theory...     

Synthesis of activated carbon foams with high specific surface area using polyurethane elastomer templates for effective removal of methylene blue

Carbon foams have gained significant attention due to their tuneable properties that enable a wide range of applications including catalysis, energy storage and wastewater treatment. Novel synthesis pathways enable novel applications via yielding complex, hierarchical material structure. In this work, activated carbon foams (ACFs) were produced from waste polyurethane elastomer templates using different synthesis pathways, including a novel one-step method. Uniquely, the produced foams exhibited complex structure and contained carbon microspheres. The ACFs were synthesized by impregnating the elastomers in an acidified sucrose solution followed by direct activation using CO₂ at 1000 ℃. Different pyrolysis and activation conditions were investigated. The ACFs were characterized by a high specific surface area (S_BET) of 2172 m²/g and an enhanced pore volume of 1.08 cm³/g. Computer tomography and morphological studies revealed an inhomogeneous porous structure and the presence of numerous carbon spheres of varying sizes embedded in the porous network of the three-dimensional carbon foam. X-ray diffraction (XRD) and Raman spectroscopy indicated that the obtained carbon foam was amorphous and of turbostratic structure. Moreover, the activation process enhanced the surface of the carbon foam, making it more hydrophilic via altering pore size distribution and introducing oxygen functional groups. In equilibrium, the adsorption of methylene blue on ACF followed the Langmuir isotherm model with a maximum adsorption capacity of 592 mg/g. Based on these results, the produced ACFs have potential applications as adsorbents, catalyst support and electrode material in energy storage systems.     

Experimental evidence of chiral crown ether complexation with aromatic amino acids

The complexation of L ‐ and D ‐enantiomers of phenylglycine, phenylalanine, and tryptophan with D ‐mannonaphto‐crown‐6‐ether in methanol solution was studied by NMR and isothermal titration calorimetry (ITC) at 298.15 K. The total heat effects attributed to the binding phenomena were measured in the range of 1.8 to 7.7 mJ, and the complexation was found stereo‐specific. The binding topologies were estimated basing on ¹H 2D‐ROESY experiments. The analysis of Job plots obtained from ¹H NMR‐monitored titrations proved the coexistence of 1:1 and 1:2 (crown ether:amino acids) complexes, which thermodynamic parameters, K_s, ΔG, ΔH°, and TΔS were determined with the aid of ITC. The 1:1 complexes were found enthalpically stabilized, generally by electrostatic interactions between the charged NH group of amino acid and crown ether macrocyclic moiety, while the binding of the second amino acid molecule was driven entropically due to solvatophobic effect. Strong enthalpy–entropy compensation points towards the uniform binding mode of all complexes studied. The mode of complex formation was found solvent dependent. For phenylalanine guest studied in various solvent systems, in contrast to the aqueous media, the noticeable chiral recognition is observed in methanol solution, and the complex stoichiometry (1:2 ether:Phe) differs from the 2:1 one, determined previously for the same host‐guest system in water (J. Thermal. Anal. Cal. 2006; 83: 575–578). Copyright © 2007 John Wiley & Sons, Ltd.     

Abnormal adsorption behavior of dimethyl disulfide on gold surfaces

Adsorption of dimethyl disulfide (DMDS) on gold colloidal nanoparticle surfaces has been examined to check its binding mechanism. Differently from previous results, DMDS molecules adsorbed on the gold surface at high concentration showed the S–S stretching band at 500 cm⁻¹ in surface-enhanced Raman scattering (SERS) spectra, which indicates the presence of intact adsorption of DMDS molecules. However, it was found that the S–S bond of disulfides was easily cleaved on the gold surface at low concentration. These behaviors were not observed for diethyl disulfide (DEDS) or diphenyl disulfide (DPDS). Our results indicate that DMDS molecules with the shortest alkyl chains on the gold surface can be inserted into self-assembled monolayers (SAMs) without the S–S bond cleavage during self-assembly due to insufficient lateral van der Waals interaction and the low adsorption activity of disulfides, whereas DEDS with longer alkyl chains or DPDS with the weak disulfide bond dissociation energy would not. These unusual DMDS adsorption behaviors were examined by scanning tunneling microscopy (STM) and X-ray photoelectron spectroscopy (XPS). We also compared the bonding dissociation energy of the S–S bonds of various disulfides by means of a density functional theory (DFT) calculation.     

2- and 2,7-Substituted para-N-Methylpyridinium Pyrenes: Syntheses,Molecular and Electronic Structures,Photophysical, Electrochemical,and Spectroelectrochemical Properties and Binding to Double-Stranded (ds) DNA

Two N-methylpyridinium compounds and analogous N-protonated salts of 2- and 2,7-substituted 4-pyridyl-pyrene compounds were synthesised and their crystal structures, photophysical properties both in solution and in the solid state, electrochemical and spectroelectrochemical properties were studied. Upon methylation or protonation, the emission maxima are significantly bathochromically shifted compared to the neutral compounds, although the absorption maxima remain almost unchanged. As a result, the cationic compounds show very large apparent Stokes shifts of up to 7200 cm⁻¹. The N-methylpyridinium compounds have a single reduction at ca. −1.5 V vs. Fc/Fc⁺ in MeCN. While the reduction process was reversible for the 2,7-disubstituted compound, it was irreversible for the mono-substituted one. Experimental findings are complemented by DFT and TD-DFT calculations. Furthermore, the N-methylpyridinium compounds show strong interactions with calf thymus (ct)-DNA, presumably by intercalation, which paves the way for further applications of these multi-functional compounds as potential DNA-bioactive agents.     

超微Ni(OH)2纳米粒子的合成及其对Li+的超高吸附性能

在葡萄糖水溶液中合成得到平均粒径为5 nm的α-Ni(OH)2超微纳米粒子。研究结果发现,在水溶液中葡萄糖浓度能够控制α-Ni(OH)2纳米粒子粒径的大小,我们对其中的原理进行了剖析。当没有葡萄糖存在时,合成得到的Ni(OH)2晶型为β型,且颗粒粒径尺寸分布为微米级别。另外,研究发现α-Ni(OH)2超微纳米粒子室温下对中性水溶液中Li^+具有较强的吸附性能,且这种吸附性能随粒径的减小而剧烈增大;粒径为5 nm的α-Ni(OH)2粒子对Li^+的最大吸附量为214 mg·g^-1(远大于文献报道的有关吸附剂对Li^+的吸附容量),而粒径为1μm的β-Ni(OH)2在相同条件下对Li^+的最大吸附量低于30 mg·g^-1。计算分析表明,Li^+在α-Ni(OH)2纳米粒子表面吸附满足Freundlich方程,符合层层吸附模型。     

Nafion-graphene composite film modified glassy carbon electrode for voltammetric determination of p-aminophenol

A Nafion-graphene (Nafion-GR) nanocomposite film modified glassy carbon electrode was fabricated by a simple drop-casting method, and used in the electrochemical detection of p-aminophenol (4-AP). Owing to the large surface area, good conductivity of GR and good affinity of Nafion, the sensor exhibited excellent electrocatalytic activity for the oxidation of 4-AP. The electrochemical behaviors of 4-AP on Nafion/GR film modified glassy carbon electrodes were investigated by cyclic voltammetry and differential pulse voltammetry. A calibration curve is constructed in the same matrix, urine, as the unknown samples to be analyzed. The Nafion-GR film modified electrode was linearly dependent on the 4-AP concentration and the linear analytical curve was obtained in the ranges of 0.5–200 μM with differential pulse voltammetry (DPV) and the detection limit was 0.051 μM. The Nafion-graphene nanocomposite modified electrode exhibited good reusability than pure graphene modified GCE. This procedure can be used for the determination of p-aminophenol in the presence of its degradation products and paracetamol. Finally, the proposed method was successfully used to determine p-aminophenol in local tap water samples in urine samples and pharmaceutical preparations.