A multianalyte chemosensor on a single molecule: promising structure for an integrated logic gate

A novel fluorescent probe that possess both BODIPY and Rhodamine moieties has been designed for the selective detection of Hg(2+) and Ba(2+) ions on the controlling by a logic gate. The characteristic fluorescence of the Ba(2+)-selective OFF-ON and the Hg(2+)-selective fluorescence bathochromic shift can be observed, and the concept has been used to construct a combinational logic circuit at the molecular level. These results will be useful for further molecular design to mimic the function of the complex logic gates on controlling.     

Cytotoxicity of labdane-type diterpenoids from Hedychium forrestii

Two new labdane-type diterpenoids, hedyforrestin D (1) and 15-ethoxy-hedyforrestin D (2), and three known compounds, yunnancoronarin A (4), B (3) and C (5) were isolated from the rhizomes of Hedychium forrestii. The structure of the new diterpenoids was established as 6beta,15xi-dihydroxylabda-8(17),11,13-trien-15,16-olide (1), and 6beta-hydroxy-15xi-ethoxylabda-8(17),11,13-trien-15,16-olide (2) on the basis of spectroscopic analyses. In addition, the isolated compounds were evaluated for their cytotoxicity against the lung adenocarcinoma cells A549 and leukemia cells K562 through 3-[4,5-dimethylthiazol-2-yl]-2,5-diphenyltetrazolium bromide (MTT) assays. Of these, compounds 3 and 4 exhibited the most activity with IC(50) values of 0.92 and 2.20 microM, respectively, whereas 5 was inactive against A549 cells and 1 was inactive against both cell lines up to a concentration of 300.81 microM. This shows that both the hydroxy substitution and orientation of unsaturated lactone group in the five-membered ring of C-13 to C-16 seem to play an important role in the anti-tumor activities of human lung adenocarcinoma and leukemia.     

Preparation and structural characterization of the Ih and the D5h isomers of the endohedral fullerenes Tm3N@C80: icosahedral C80 cage encapsulation of a trimetallic nitride magnetic cluster with three uncoupled Tm3+ ions

We report an efficient method for the preparation and purification of the Ih and the D5h isomers of Tm3N@C80. Following preparation in a Kratschmer-Huffman electric-arc generator, the Tm3N@C80 isomers were obtained by a chemical separation process followed by a one-stage isomer selective chromatographic high-performance liquid chromatography (HPLC) separation (pyrenyl, 5PYE column). The HPLC chromatographic retention behavior on a pentabromobenzyl (5PBB) column suggests a charge transfer of approximately 6 electrons; [M3N] 6+@C80(6-) and the chromatographic retention mechanisms of the Ih and the D5h isomers of Tm3N@C80 on both 5PBB and 5PYE columns are discussed. Single-crystal X-ray diffraction data demonstrate that the Tm3N cluster has a planar structure but represents a tight fit for trapping the Tm3N cluster inside the I h - and the D 5h -C 80 cages. Specifically, the Tm atoms punch out the cage carbon atoms adjacent to them. The "punched out" effect can be demonstrated by cage radii and pyramidal angles at cage carbon atoms near the Tm atoms. The magnetic susceptibility (chiT) for Tm3N@ Ih -C80 was found to exhibit Curie-Weiss behavior with C = 23.4 emu.K/mol, which is consistent with the calculated value for three uncoupled Tm3+ ions by considering the spin and orbital contributions with no quenching of the orbital angular momentum ( L = 5, S = 1, and J = 6; Ccalcd = 23.3 emu.K/mol). The electrochemical measurements demonstrate that both the Ih and the D5h isomers of Tm3N@C80 have a large electrochemical gap.     

Ferroelectric heterobimetallic clusters with ferromagnetic interactions

Two homochiral trinuclear clusters, {(MeTp)2Fe2(CN)6Ni[(1R,2R)-chxn]2} (1) and {(MeTp)2Fe2(CN)6Ni[(1S,2S)-chxn]2} (2) [chxn = 1,2-diaminocyclohexane; MeTp = methyltris(pyrazolyl)borate], have been synthesized and structurally characterized. Ferroelectric and magnetic measurements reveal that they are rare examples of metal-organic compounds bearing ferroelectricity and intramolecular ferromagnetic interactions.     

Correlation between rheological behavior and structure of multi-component polymer systems

Rheological measurement has been an effective method to characterize the structure and properties for multiphase/multi-component polymers, owing to its sensitivity to the structure change of hetero- geneous systems. In this article, recent progress in the studies on the morphology/structure and rheological properties of heterogeneous systems is summarized, mainly reporting the findings of the authors and their collaborators, involving the correlation between the morphology and viscoelastic relaxation of LCST-type polymer blends, the microstructure and linear/nonlinear viscoelastic behavior of block copolymers, time scaling of shear-induced crystallization and rheological response of poly- olefins, and the relationship between the structure/properties and rheological behavior of filled polymer blends. It is suggested that a thorough understanding of the characteristic rheological response to the morphology/structure evolution of multiphase/multi-component polymers facilitates researchers’ op- timizing the morphology/structure and ultimate mechanical properties of polymer materials.     

Photoreduction of mercury(II) in the presence of algae, Anabaena cylindrical

The photochemical and biological reduction of Hg(II) in the presence of algae, anabaena cylindrical, was investigated under the irradiation of metal halide lamps placed in cooling trap for maintaining constant temperature by water circulation (lambda >or=365 nm, 250 W). The photoreduction rate of Hg(II) increased with increasing algae concentration. The addition of Fe(III) and humic substances into the suspensions of algae also enhanced the photoreduction of Hg(II). Alteration of pH value affected the photoreduction of Hg(II) in aqueous solution with or without the addition of algae. The concentration of dissolved gaseous mercury (DGM), the reduced product of Hg(II), increased with increasing exposure time and then gradually approached to a steady state. The influence of initial Hg(II) concentration on the photoreduction of Hg(II) with algae was studied by irradiating the suspensions of anabaena cylindrical at pH 7.0 with initial concentrations (C(0)) of Hg(II) at 50, 100, 120, 150 and 180 microg L(-1), respectively, the light-induced reduction of Hg(II) followed the apparent pseudo first-order kinetics. The initial photoreduction rate could be expressed by the equation: r(A)=0.0871+0.00129 C(0), with a correlation coefficient R=0.9994. The overall mercury mass balance study on the photo-reductive process revealed that more than 39.86% of Hg(II) from the algal suspension was reduced to volatile metallic mercury.     

Selectivity in nickel-catalyzed rearrangements of cyclopropylen-ynes

The Ni/NHC-catalyzed rearrangement of cyclopropylen-ynes is described. Two different heterocycles, cyclopentane- or cycloheptene-based, were obtained. However, by employing ItBu as the NHC ligand, cyclopentane products were obtained selectively under mild conditions.     

A nickel-catalyzed route to pyridines

A mild and general route for preparing pyridines from nitriles and diynes is described. Ni/imidazolyidene complexes were used to mediate cyclization alkynes and both aryl and alkyl nitriles at ambient temperature. In addition, the efficacy of this protocol allows for the preparation of a fused seven-membered pyridone and for intermolecular cyclizations. When an asymmetrical diyne was employed, cyclization afforded a single pyridine regioisomer.     

Poly(ethylene glycol) (PEG) enhances dynamic surface activity of a bovine lipid extract surfactant (BLES)

Shortage or malfunction of pulmonary surfactant in alveolar space leads to a critical condition termed respiratory distress syndrome (RDS). Surfactant replacement therapy, the major method to treat RDS, is an expensive treatment. In this paper, the effect of poly(ethylene glycol) (PEG) to improve dynamic surface activity of a bovine lipid extract surfactant (BLES) was studied by axisymmetric drop shape analysis (ADSA) and a captive bubble method. The activity of BLES+PEG mixtures was compared to that of a natural surfactant containing surfactant proteins A and D. When PEG was added into BLES mixtures, the surface tension hysteresis of BLES films was minimized when the films were compressed by more than 50%. PEG also helps to quickly restore surfactant films after film collapse. Thus, as far as surface tension effects go, the findings suggest that PEG might be used as a substitute for surfactant-associated protein SP-A in therapeutic surfactant products, and might also be used to reduce the amount of BLES required in clinical applications.     

两个酉算子的线性组合与框架分解

In this paper, we prove that the norm closure of all linear combinations of two unitary operators is equal to the norm closure of all invertible operators in B(H). We apply the results to frame representations and give some simple and alternative proofs of the propositions in “P. G. Casazza, Every frame is a sum of three (but not two) orthonormal bases-and other frame representations, J. Fourier Anal. Appl., 4(6)(1998), 727-732.”