Large‐Area Aminated‐Graphdiyne Thin Films for Direct Methanol Fuel Cells

A two‐dimensional (2D) carbon nanofilm with uniform artificial nanopores is an ideal material to ultimately suppress the fuel permeation in the proton exchange membrane fuel cells. Graphdiyne has great mechanical strength, high dimensional stability, and controllable nanopores, and has good prospects to play this crucial role. It is found that graphdiyne nanofilm with amino groups and natural nanopores can be easily prepared with high integrity. The aminated graphdiyne has good compatibility with the Nafion matrix owing to the acid–base interaction between them. The excellent comprehensive properties of graphdiyne in selectivity, dimensional stability, and integrity effectively improve the power performance and stability of fuel cells at wide temperature. Our results can be developed into a universal method that can easily realize the selective separation of ions and small molecules, and open a new way for the emerging applications in green energy.     

Determination of total mercury and methylmercury in human hair by graphite-furnace atomic absorption spectrophotometry using 2,3-dimercaptopropane-1-sulfonate as a complexing agent.

For the determination of total mercury in hair, an amount (25.0 mg) of hair sample was digested with conc. HNO3 (400 microl) at 90 degrees C for 10 min in a 7-ml teflon microreaction vessel. After digestion, the pH of the acidic hair mixture was adjusted to 5.0-6.0 by NaOH and was then passed through a clean-up Sep-Pak C18 cartridge. To the eluate, 2,3-dimercaptopropane-1-sulfonate (DMPS) and sodium acetate buffer (pH = 6.0) were added to form a mercury-DMPS complex. This complex was preconcentrated on two Sep-Pak C18 cartridges in series, and each cartridge was eluted with methanol and adjusted to 2.00 ml. A portion (50 microl) was introduced into a graphite cuvette and then atomized according to a temperature program. The method detection limit (MDL, 3sigma) was 0.064 (microg g(-1)); the calibration graph was linear up to 7.52 microg g(-1). Good accuracies were obtained when testing two human hair certified reference materials (GBW 09101 and BCR-397). Six real samples were analyzed, and the recoveries were 95.8 - 98.2% with a relative standard deviation (RSD, n = 3) < 2.1%. For the determination of methylmercury (CH3Hg+), 25.0 mg of hair sample was extracted with 2.0 mol dm(-3) HCl (1.0 ml) by ultrasonicating for 1 h. The supernatant solution was used for CH3Hg+ analysis and the hair residue was used for the analysis of inorganic mercury (Hg2+). The MDL of CH3Hg+ was 0.068 microg g(-1); the calibration graph was linear up to 6.00 microg g(-1). Six real samples were analyzed, and the recoveries were 96.0-99.2% with RSD (n = 3) < 2.3%. The sum of the concentrations of CH3Hg+ and Hg2+ was very close to that of the total mercury measured with a relative error within 3.6%. The proposed method can be accurately applied to the measurement of CH3Hg+, Hg2+, and total mercury in hair samples.     

Asymmetric Three‐Component Heck Arylation/Amination of Nonconjugated Cyclodienes

Substituted cyclohexylamines are becoming increasingly important in drug discovery. Asymmetric Heck insertion/amination of nonconjugated cyclodienes proceeds to give 5‐aryl cyclohexenylamines with good enantioselectivity and exclusive trans configurations. Primary and secondary anilines, indoline, and benzylamines are suitable amines. The weakly donating diphosphite Kelliphite forms a deep unsymmetrical pocket, which is essential for stereoselective anti attack of amines.     

Synthesis of 2,2’-Biflavanones from Flavone via Electroreduction and Photolysis

Biflavonoids, widely distributed in natural plants, had strong biological activities including spasmolysis, peripheral vasodilatation, antibradykinin activity and antispasmogenic action against prostaglandin PGE1, inhibition of cyclic GMP and cyclic AMP phosphodiesterase and inhibition of hepatoma cells. Recently, some biflavonoids were demonstrated to enhance suppersion of lymphocyte proliferation, inhibition of phospholipaseCr1, anti-inflammatory activity, anti-HIV activity, anticompleme…     

Quantitative analysis of multiple urinary biomarkers of carcinoid tumors through gold-nanoparticle-assisted laser desorption/ionization time-of-flight mass spectrometry

A simple technique for quantitative analysis of four urinary biomarkers, tryptophan (TRP), 5-hydroxytryptophan (5-HTP), 5-hydroxytryptamine (5-HT) and 5-hydroxyindole acetic acid (5-HIAA) of carcinoid tumors is developed using gold nanoparticles as the assisted matrix in surface-assisted laser desorption/ionization time-of-flight mass spectrometry (SALDI–TOF MS). The optimal SALDI conditions for the efficient ionization of those biomarkers are systematically explored by the adjustments of the concentrations of gold nanoparticles and internal standards. The mass spectra with strong signals and minimal background noise are obtained using 1-naphthaleneacetamide (NAD) as the internal standard. The calibration curves of the biomarker concentrations are determined using SALDI–TOF MS and the high linearity is obtained in all samples. For future clinical testing, multiplexed detection of those biomarkers in the urine samples of healthy males is performed. The successful quantitative detections of TRP, 5-HTP, 5-HT and 5-HIAA indicate that our technique provided great potentials to be developed a simple and rapid platform for the tumor biomarker detections.     

Quantitative analysis of multiple urinary biomarkers of carcinoid tumors through gold-nanoparticle-assisted laser desorption/ionization time-of-flight mass spectrometry

A highly selective and sensitive coumarin-based chemodosimeter 1 for Cu(2+) in water is reported in this work. 1 was designed and facilely synthesized by a one-step reaction with coumarin as a fluorophore and 2-picolinic acid as the binding moiety, which showed very week fluorescence in buffer solution, and its fluorescence was considerably enhanced by the addition of Cu(2+) at room temperature in 5 min. Mechanism study suggested that Cu(2+) promoted the hydrolysis of 1 via the catalytic sensing cycle, generating a highly fluorescent product 7-hydroxycoumarin with fluorescence signal greatly amplified. The probe exhibited remarkably selective fluorescence enhancement to Cu(2+) over other metal ions at 454 nm, with a detection limit of 35 nM Cu(2+). Under optimal condition, 1 was successfully used for the determination of Cu(2+) in fetal equine serum and two water samples.     

An algorithm for the calculation of the electrostatic repulsion between surface coated with a charge membrane

We propose a numerical procedure for the calculation of the electrostatic repulsion force between two identical, parallel surfaces immersed in anab electrolyte solution. These surfaces are coated with an ion-penetrable membrane carrying fixed charges. The amount of fixed charges is governed by the dissociation of the functional groups in the membrane phase. The effect of pH on the degree of dissociation of these functional groups is taken into account. The difficulty of extensive use of Jacobi elliptic function in the numerical treatment of Poisson-Boltzmann equation can be circumvented by resorting to the present algorithm.     

Cytotoxic phenylpropanoids and a new triterpene, turformosinic acid, from Turpinia formosana Nakai

One new phenylpropanoid, turformosin A (1), and one new triterpene, turformosinic acid (2), together with 16 known compounds, were isolated from the stems of Turpinia formosana Nakai. All structures were elucidated on the basis of spectroscopic analysis, including 1D- and 2D-NMR techniques and MS analysis. Selected isolated compounds were evaluated for in vitro cytotoxicity against four human cancer cell lines and antioxidant scavenging effects on DPPH. (-)-(7'S,8'S)-threo-carolignan X (3) exhibited cytotoxicity against Hep2, WiDr, Daoy, and MCF-7 cell lines with ED(50) values of 3.60, 4.45, 6.07, and 13.7 μg/mL, respectively. Turformosin A (1), (-)-(7'S,8'S)- threo-carolignan X (3), methoxyhydroquinone-4-β-D-glucopyranoside (5), and methoxy-hydroquinone-1-β-D-glucopyranoside (6), exhibited similar anti-oxidative activity. Hep2 cells treated with 10 μg/mL of 3 showed elevation of sub-G1 population (from 20% at 8 h to 60% at 48 h), and activation of caspase-9/caspase-3/PARP cascade. Compound 3 induced intrinsic apoptotic pathway in Hep2 cells with dose and time dependence (10 μg/mL for 8 h).     

Synthesis and characterization of segmented liquid crystal poly(azoxy polyester-co-polyoxypropylene)

In this study a series of a segmented copolyester, poly(4,4′-dioxy-2,2′-dimethyl-azoxybenzene dodecanedioyl) (PMABD)-co-polyoxypropylene 400 (POP), was prepared. The chain length of PMABD studied (n) was varied from 7.8-18.2, and that of POP was unchanged. The intrinsic viscosity of the segmented copolyesters was 1.04-1.30, and the number average molecular weight obtained was 2.53 × 10⁴?3.49 × 10⁴ g/mol. The mesophase texture and thermal properties of the segmented copolyesters were measured as functions of n. It was found that the insert of flexible POP between those liquid crystalline domains of PMABD did affect thermotropic properties of PMABD. As the n value was 9.0 and 7.8 (or 7.4 and 8.6% by weight POP) the texture appeared as cholesteric-like oily streaks. The effect could not be attained by simply copolymerizing a mesogenic moiety with a pair of spacers of different lengths. The fluidity and domain structure of the flexible dodecanedioyl-POP-dodcanedioyl segments are taken into account for the obtained results. © 1995 John Wiley & Sons, Inc.     

An electron-rich molybdenum-molybdenum quintuple bond spanned by one lithium atom

Take five: A unique quintuply bonded dimolybdenum complex [Mo(2)(μ-Li){μ-HC(N-2,6-Et(2)C(6)H(3))(2)}(3)] (see picture) was synthesized and characterized. The Mo-Mo interaction includes an unexpected bridging Li(+) ion. Calculations indicate the bridging Li(+) ion does not perturb the Mo-Mo bond length (2.0612(4)??), but results in a relatively small effective Mo-Mo bond order of 3.67.