Synthesis,structure and magnetism of a one-dimensional silicotungstate array: K3H4Cu0.5{Cu[Cu7.5Si2W16O60(H2O)4(OH)4]2} · 9H2O

A structurally distinct, multi-copper(II)-substituted silicotungstate K₃H₄Cu_0.5{Cu[Cu_7.5Si₂W₁₆O₆₀(H₂O)₄(OH)₄]₂} · 9H₂O (1) has been synthesized and characterized by FT-IR spectroscopy, elemental analysis, variable-temperature magnetic measurements, electron spin resonance, and X-ray diffraction. Green crystalline plates of 1 were obtained by the reaction of K₈[γ-SiW₁₀O₃₆] · 12H₂O with 8 equiv. of Cu(II) in a 50% ethylene glycol solution. A cationic copper center connects the terminal oxygen atoms of neighboring polyanions, resulting in a one-dimensional structure. Magnetic susceptibility measurements indicate weak ferromagnetic superexchange between the Jahn–Teller-distorted S = 1/2 Cu(II) centers.     

Formation of cubane-like photodimers from 2-naphthalenecarbonitrile

Irradiation of 2-naphthalenecarbonitrile (2-NpCN) in solution with a light lambda > 280 nm results in the formation of three rigid cubane-like photodimers, anti-head-to-head 1, anti-head-to-tail 2, and syn-head-to-tail 3, which are not in line with the previously recognized regioselectivity. These cubane-like photodimers have been well characterized by spectroscopic investigation and/or X-ray crystal structural analysis in this work. Moreover, the separation of the optically pure enantiomers of 1, 2, and 3 has been achieved by HPLC resolution.     

Anticancer activity and quantitative analysis of flavone of Cirsium japonicum DC

Cirsium japonicum DC, a traditional Chinese medicine, has been widely used as an antihemorrhagic and diuretic agent. The objective of this study was to perform quantitative analysis of flavone by reversed-phase HPLC and examine the anticancer activity of C. japonicum DC in the S180 and H22 mice. Cirsium japonicum DC was separated and purified with several chromatography techniques and two flavone compounds, pectolinarin and 5,7-dihydroxy-6,4'-dimethoxyflavone, were isolated. The content of these two compounds in the methanol, ethanol, and aqueous extractions respectively was determined by HPLC as follows: pectolinarin 1.87%, 1.65%, 1.27%; 5,7-dihydroxy-6,4'-dimethoxyflavone: 0.515%, 0.42%, 0.221%. Furthermore, the effect of the two flavones on the anticancer activity in S180 and H22 mice was studied. Our research shows that these two flavones greatly inhibit cancer cell growth. The rate of inhibiting S180 mice was 55.77% at 50 mg kg( - 1), and the rate of life lengthening was 99.13% at 50 mg kg( - 1) in H22 mice.     

The pH-dependent role of superoxide in riboflavin-catalyzed photooxidation of 8-oxo-7,8-dihydroguanosine

[reaction: see text]. The riboflavin-catalyzed photooxidation of 2',3',5'-tri-O-acetyl-8-oxo-7,8-dihydroguanosine generates a radical intermediate that is competitively trapped by H(2)O, O2(-)(*), or O(2). The products of H(2)O trapping have been previously described as the spiroiminodihydantoin (pH >or= 7) and iminoallantoin/guanidinohydantoin (pH < 7) nucleosides. Trapping by O2(-)(*) leads to the oxaluric acid (pH or= 8.6) pathways (R' ', R' ' = H or 2,3,5-tri-O-Ac-ribofuranosyl). The pH-dependent role of superoxide was probed using Mn-SOD and compared to guanosine and 8-methoxyguanosine photooxidation.     

Preparation, characterization and application of a new stir bar sorptive extraction based on poly(vinylphthalimide-co-N,N'-methylenebisacrylamide) monolith

In this study, a new stir bar sorptive extraction (SBSE) coating based on poly(vinylphthalimide-co-N,N'-methylenebisacrylamide) monolith (SBSE-VPMB) was prepared. The influences of the contents of monomer in polymerization mixture and the percentage of porogen solvent on the extraction performance were investigated thoroughly. Several characteristic techniques, such as elemental analysis, scanning electron microscopy, mercury intrusion porosimetry and infrared spectroscopy, were used to characterize the monolithic material. The analysis of oxfendazole (OFZ) and mebendazole (MBZ) in milk and honey samples by the combination of SBSE with HPLC with diode array detection was selected as paradigms for the practical evaluation of the new coating. Under the optimized extraction conditions, the limits of detection (S/N=3) for OFZ and MBZ were 0.23-0.60 μg/L in milk and 0.24-1.08 μg/L in honey, respectively. The method also showed good linearity, repeatability, high feasibility and acceptable recoveries for real samples. At the same time, the extraction performance and the distribution coefficients (K(VPMB/W)) of OFZ and MBZ on SBSE-VPMB were compared with other SBSEs based on porous monoliths and commercial SBSE.     

Influence of electric field intensity, ionic strength, and migration distance on the mobility and diffusion in DNA surface electrophoresis

In order to increase the separation rate of surface electrophoresis while preserving the resolution for large DNA chains, e.g., genomic DNA, the mobility and diffusion of Lambda DNA chains adsorbed on flat silicon substrate under an applied electric field, as a function of migration distance, ionic strength, and field intensity, were studied using laser fluorescence microscope. The mobility was found to follow a power law with the field intensity beyond a certain threshold. The detected DNA peak width was shown to be constant with migration distance, slightly smaller with stronger field intensity, but significantly decreased with higher ionic strength. The molecular dynamics simulation demonstrated that the peak width was strongly related with the conformation of DNA chains adsorbed onto surface. The results also implied that there was no diffusion of DNA during migration on surface. Therefore, the Nernst-Einstein relation is not valid in the surface electrophoresis and the separation rate could be improved without losing resolution by decreasing separation distance, increasing buffer concentration, and field intensity. The results indicate the fast separation of genomic DNA chains by surface electrophoresis is possible.     

Effects of conjugation length, electron donor and acceptor strengths on two-photon absorption cross sections of asymmetric zinc-porphyrin derivatives

Exceptionally large two-photon absorption cross sections at the infrared region have been revealed by time-dependent density functional theory calculations for asymmetric charge-transfer conjugated zinc-porphyrin derivatives. The largest two-photon cross section is found to be more than one order of magnitude larger than for the conventional two-photon active organic molecules. The calculations show that the formation of strong charge-transfer states depends on the length of the conjugation bridge between the zinc-porphyrin core and the electron donor/acceptor. The two-photon absorption cross section can be greatly enhanced by increasing the strengths of the electron donor/acceptor.     

One-step conversion of cellobiose to C6-alcohols using a ruthenium nanocluster catalyst

The one-step conversion of cellulose to C6-alcohols via green and energy efficient approaches has, as far as we are aware, not been reported. Such a process presents a considerable challenge, the two key problems being (1) finding a suitable solvent that dissolves the cellulose, and (2) the development of advanced catalytic chemistry for selective cleavage of the C-O-C bonds (glycosidic bonds) connecting glucose residues. The dissolution of cellulose has been recently realized by using ionic liquids as green solvents; there is still no efficient method, such as selective hydrogenation, for the precise C-O-C cleavage under mild conditions, however. Cellobiose is a glucose dimer connected by a glycosidic bond and represents the simplest model molecule for cellulose. We disclose in this communication that the one-step conversion of cellobiose to C6-alcohols can be realized by selectively breaking the C-O-C bonds via selective hydrogenation using a water-soluble ruthenium nanocluster catalyst under 40 bar H2 pressure.