A Copper‐Catalyzed Decarboxylative Amination/Hydroamination Sequence: Switchable Synthesis of Functionalized Indoles

A copper‐catalyzed decarboxylative amination/hydroamination sequence of propargylic carbamates with various nucleophiles is described for the first time. It features an earth‐abundant metal catalyst, mild reaction conditions, and high efficiency. Further treatments of the resultant key intermediates using an acid or a base in one pot enable the controllable and divergent synthesis of two types of functionalized indoles. Moreover, experiments to demonstrate the synthetic potential of this methodology are performed.     

The Nanoparticle Size Effect in Graphene Cutting: A “Pac‐Man” Mechanism

Metal‐nanoparticle‐catalyzed cutting is a promising way to produce graphene nanostructures with smooth and well‐aligned edges. Using a multiscale simulation approach, we unambiguously identified a “Pac‐Man” cutting mechanism, characterized by the metal nanoparticle “biting off” edge carbon atoms through a synergetic effect of multiple metal atoms. By comparing the reaction rates at different types of edge sites, we found that etching of an entire edge carbon row could be triggered by a single zigzag‐site etching event, which explains the puzzling linear dependence of the overall carbon‐atom etching rate on the nanoparticle surface area observed experimentally. With incorporation of the nanoparticle size effect, the mechanisms revealed herein open a new avenue to improve controllability in graphene cutting.     

The population‐level impact of HBV and its vaccination on HIV transmission dynamics

Hepatitis B virus (HBV) and its vaccination strategy may affect human immunodeficiency virus (HIV) transmission dynamics because both viruses have synergistic effects. To quantitatively assess the potential impact of HBV and its vaccination strategy on HIV transmission dynamics at the population level, in this paper, we formulate a deterministic compartmental model that describes the joint dynamics of HBV and HIV. We first derive the explicit expressions for the basic reproduction numbers of HIV and HBV and analyze the dynamics of HIV and HBV subsystems, respectively. Then a systematic qualitative analysis of the full system is also provided, which includes the local and global behavior. By using a set of reasonable parameter values, the full system is numerically investigated to assess the potential impact of HBV and its vaccination strategy on HIV transmission. The direct and indirect population level impact of HBV on HIV is demonstrated by calculating the fraction of HIV infections attributable to HBV and the difference between HIV prevalence in the presence and absence of HBV, respectively. The findings imply that the increase of HBV vaccination rate may unusually accelerate HIV epidemics indirectly, although the direct effect of HBV on HIV transmission decreases as HBV vaccination rate increases. Finally, the potential impact of HIV on HBV transmission dynamics is investigated by way of parenthesis. Copyright © 2016 John Wiley & Sons, Ltd.     

Determination of arsenic species in Solanum Lyratum Thunb using capillary electrophoresis with inductively coupled plasma mass spectrometry

A simple and highly efficient interface to couple capillary electrophoresis with inductively coupled plasma mass spectrometry by a microflow polyfluoroalkoxy nebulizer and a quadruple ion deflector was developed in this study. By using this interface, six arsenic species, including arsenite, arsenate, monomethylarsonic acid, dimethylarsinic acid, arsenobetaine, and arsenocholine, were baseline‐separated and determined in a single run within 11 min under the optimized separation conditions. The instrumental detection limit was in the range of 0.02–0.06 ng/mL for the six arsenic compounds. Repeatability expressed as the relative standard deviation (n = 5) of both migration time and peak area were better than 2.5 and 4.3% for six arsenic compounds. The proposed method, combined with a closed‐vessel microwave‐assisted extraction procedure, was successfully applied for the determination of arsenic species in the Solanum Lyratum Thunb samples from Anhui province in China with the relative standard deviations (n = 5) ≤4%, method detection limits of 0.2–0.6 ng As/g and a recovery of 98–104%. The experimental results showed that arsenobetaine was the main speciation of arsenic in the Solanum Lyratum Thunb samples from different provinces in China, with a concentration of 0.42–1.30 μg/g.     

Multiresidue determination of 114 multiclass pesticides in flue‐cured tobacco by solid‐phase extraction coupled with gas chromatography and tandem mass spectrometry

A sensitive and robust multiresidue method for the simultaneous analysis of 114 pesticides in tobacco was developed based on solid‐phase extraction coupled with gas chromatography and tandem mass spectrometry. In this strategy, tobacco samples were extracted with acetonitrile and cleaned up with a multilayer solid‐phase extraction cartridge Cleanert TPT using acetonitrile/toluene (3:1) as the elution solvent. Two internal standards of different polarity were used to meet simultaneous pesticides quantification demands in the tobacco matrix. Satisfactory linearity in the range of 10–500 ng/mL was obtained for all 114 pesticides with linear regression coefficients higher than 0.994. The limit of detection and limit of quantification values were 0.02–5.27 and 0.06–17.6 ng/g, respectively. For most of the pesticides, acceptable recoveries in the range of 70–120% and repeatabilities (relative standard deviation) of <11% were achieved at spiking levels of 20, 100, and 400 ng/g. Compared with the reported multiresidue analytical method, the proposed method provided a cleaner test solution with smaller amounts of pigments, fatty acids as well as other undesirable interferences. The development and validation of the high sensitivity, high selectivity, easy automation, and high‐throughput analytical method meant that it could be successfully used for the determination of pesticides in tobacco samples.     

A new stabilized finite element method for advection‐diffusion‐reaction equations

In this article, a new stabilized finite element method is proposed and analyzed for advection‐diffusion‐reaction equations. The key feature is that both the mesh‐dependent Péclet number and the mesh‐dependent Damköhler number are reasonably incorporated into the newly designed stabilization parameter. The error estimates are established, where, up to the regularity‐norm of the exact solution, the explicit‐dependence of the diffusivity, advection, reaction, and mesh size (or the dependence of the mesh‐dependent Péclet number and the mesh‐dependent Damköhler number) is revealed. Such dependence in the error bounds provides a mathematical justification on the effectiveness of the proposed method for any values of diffusivity, advection, dissipative reaction, and mesh size. Numerical results are presented to illustrate the performance of the method. © 2015 Wiley Periodicals, Inc. Numer Methods Partial Differential Eq 32: 616–645, 2016     

<Emphasis Type="Italic">Cis</Emphasis>/<Emphasis Type="Italic">trans</Emphasis> Fluorescent Recognition by Naphthalimide Dyes ⊂ CB [7] Assembly

A novel method to recognize cis/trans isomers was studied here. The naphthalimide dye as guest could bind with host cucurbit [7]uril (CB [7]) and 1:1 naphthalimide dye ? CB [7] assembly was formed. Moreover, this assembly was used as a fluorescent probe to recognized Fumaric acid (FA) and maleic acid (MA) via fluorescence titration. Two carboxyls in MA are in the same side, they could form stable interaction with the assembly and the fluorescence intensity decreased obviously when naphthalimide dye ? CB [7] was titrated by MA (nearly quenched in 1.5 equiv). But two carboxyls in FA are in opposite sides, the interaction between FA and the assembly was weak and not stable, and the fluorescence intensity changed inconspicuously when the assembly was titrated by FA.     

Synthesis of selenium/EDTA-derived porous carbon composite as a Li–Se battery cathode

The carbon substrate with unique 3D macroporous structure has been prepared through the immediate carbonization of ethylenediaminetetraacetic acid (EDTA) and KOH mixture. The porous carbon composed of micro- and small mesoporous (2–5 nm) structure has a BET specific surface area of 1824.8 m² g^?1. The amorphous and nanosized Se is uniformly encapsulated into the porous structure of porous carbon using melting diffusion route, and the weight content of Se in target Se/C composite can be as high as ~50 %. As an Li–Se battery cathode, the Se/C composite delivers a reversible (2nd) discharge capacity of 597.4 mAh g^?1 at 0.24C and retains a discharge capacity of 538.4 mAh g^?1 at 0.24C after 100 cycles. Furthermore, the composite also has a stable capacity of 291.0 mAh g^?1 at a high current of 4.8C. The high specific area and good porous size of EDTA-derived carbon substrate may a be responsibility for the excellent electrochemical performances of Se/C composite.     

Phosphorus(V) porphyrins with axial carbazole-based dendritic substituents

[structure: see text] Three phosphorus(V) porphyrins with axial carbazole-based dendritic substituents (D-A-D) have been designed and synthesized, which are nonfluorescent due to their effective electron transfer from the carbazole dendron to the excited porphyrin within the dendritic matrix. The incident photon to current conversion efficiencies (IPCE) spectra demonstrate that the molecular structure of the dendrimers can significantly affect the photovoltaic response to the visible light.     

Enantiomeric resolution of new triazole compounds by high-performance liquid chromatography

Cellulose tris(3,5-dimethylphenylcarbamate) (CDMPC) was synthesized and coated on aminopropylsilica to prepare a chiral stationary phase (CSP). HPLC methods were developed for the direct enantioseparation of 12 chiral triazole compounds on the CSP. The separations were made using normal phase methodology with a mobile phase consisting of n-hexane-alcohol (ethanol, 1-propanol, 1-butanol, 2-propanol, and t-butanol) in various portions. The column temperatures were studied for the optimization of the resolutions. The effects of structural features of the solutes on the discrimination between the enantiomers were examined. Baseline separation was easily obtained in many cases.