Utilization of Environmentally Benign Dicyandiamide as a Precursor for the Synthesis of Ordered Mesoporous Carbon Nitride and its Application in Base‐Catalyzed Reactions

Assisted by a new dissolution procedure, dicyandiamide (DCDA), an environmentally benign and cheap precursor, has been employed for the synthesis of mesoporous carbon nitride (CN) materials through a nanocasting approach. The synthesized mesoporous materials possessed high specific surface areas (269–715 m² g^?1) with narrow pore‐size distributions (about 5 nm) and faithfully replicated the mesostructures of the SBA‐15 and FDU‐12 templates. Several characterization techniques, including XRD, SAXS, TEM, Raman and FTIR spectroscopy, XPS, and CO₂‐TPD, were used to analyze the physicochemical properties of these materials and the results showed that the mesoporous CND materials had graphitic‐like structures and consisted of CN heterocycles, as well as amino groups. In a series of Knoevenagel condensation reactions, as exemplified by the reaction of various aldehydes and nitriles, these mesoporous CND materials demonstrated high and stable catalytic activities, owing to an abundance of basic sites.     

Phosphine‐Catalyzed [3+2] Cycloaddition Reactions of Azomethine Imines with Electron‐Deficient Alkenes: A Facile Access to Dinitrogen‐Fused Heterocycles

An efficient method for the phosphine‐catalyzed [3+2] cycloaddition reaction of azomethine imines with diphenylsulfonyl alkenes to give dinitrogen‐fused bi‐ or tricyclic heterocyclic compounds in high yields has been described. Moreover, two phenylsulfonyl groups installed on the heterocyclic products could be conveniently removed or transformed to other functional groups, making the reaction more useful.     

Efficient approach to allylated quinolines via palladium-catalyzed cyclization–allylation of 1-azido-2-(2-propynyl) benzenes with allyl methyl carbonate

The palladium-catalyzed cyclization–allylation reaction of ortho-azido propynylbenzenes 1 and allyl methyl carbonate 2d gives the corresponding allylated quinolines in moderate to good yields. The reaction of 1-azido-2-(2-propynyl)benzene 1a proceeds smoothly with 10 mol % Pd(PPh₃)₄ and 5 equiv K₃PO₄ or NaOAc in DMF at 100 °C to afford 3,4-diallylquinoline 3a in 69% yield in the case of R² = H and 3-allylquinoline 4 in 67% yield in the case of R² ≠ H.     

Study of Cl−(H2O)n (n = 1–4) using basin‐hopping method coupled with density functional theory

Cl^?(H₂O)_n (n = 1–4) clusters were investigated using a basin‐hopping (BH) algorithm coupled with density functional theory (DFT). Structures, energetics, thermodynamics, vertical detachment energies, and vibrational frequencies were obtained from high‐level ab initio calculations. Through comparisons with previous theoretical and experimental data, it was demonstrated that the combination of the BH method and DFT could accurately predict the global and local minima of Cl^?(H₂O)_n (n = 1–4). Additionally, to optimize larger Cl^?(H₂O)_n (n > 4) clusters, several popular density functionals as well as DF‐LMP2 (Schütz et al., J. Chem. Phys. 2004, 121, 737) (second‐order Møller‐Plesset perturbation theory using local and density fitting approximations) were tested with appropriate basis sets through comparisons with MP2 optimized results. DF‐LMP2 will be used in future studies because its overall performance in describing the relative binding energies and the geometrical parameters of Cl^?(H₂O)_n (n = 1–4) was outstanding in this study. © 2013 Wiley Periodicals, Inc.     

Genetic profile characterization and population study of 21 autosomal STR in Chinese Kazak ethnic minority group

Short tandem repeat loci have been recognized as useful tools in the routine forensic application and in recent decades, more and more new short tandem repeat (STR) loci have been constantly discovered, studied, and applied in forensic caseworks. In this study, we investigated the genetic polymorphisms of 21 STR loci in the Kazak ethnic minority as well as the genetic relationships between the Kazak ethnic minority and other populations. Allelic frequencies of 21 STR loci were obtained from 114 unrelated healthy Kazak individuals in the Ili Kazak Autonomous Prefecture, Xinjiang Uigur Autonomous Region of China. We observed a total of 159 alleles in the group with the allelic diversity values ranging from 0.0044 to 0.5088. The highest polymorphism was found at D19S433 locus and the lowest was found at D1S1627. Statistical analysis of the generated data indicated no deviation from Hardy–Weinberg equilibriums at all 21 STR loci. In order to estimate the population differentiation, allelic frequencies of all STR loci of the Kazak were compared with those of other neighboring populations using analysis of molecular variance method. Statistically significant differences were found between the studied population and other populations at 2–7 STR loci. A neighbor‐joining tree was constructed based on allelic frequencies of the 21 STR loci and phylogenetic analysis indicates that the Kazak has a close genetic relationship with the Uigur ethnic group. The present results may provide useful information for forensic sciences and population genetics studies, and can also increase our understanding of the genetic background of this group. The present findings showed that all the 21 STR loci are highly genetically polymorphic in the Kazak group, which provided valuable population genetic data for the genetic information study, forensic human individual identification, and paternity tests.     

Raman mapping and in situ SERS spectroelectrochemical studies of 6-mercaptopurine SAMs on the gold electrode

The self-assembled monolayers (SAMs) of 6-mercaptopurine (6MP) were formed at the roughened polycrystalline gold surfaces in acid and alkaline media. The time-dependent Raman mapping spectral analysis in conjunction with the quantum calculations for the vibrational modes using ab initio BLYP/6-31G method suggested that both of the resulted 6MP SAMs adopted the same adsorption mode through the S atom of pyrimidine moiety and the N7 atom of the imidazole moiety anchoring the gold surface in a vertical way. The in situ surface-enhanced Raman scattering spectroelectrochemical experiment was conducted to examine the stability of the SAMs at various bias potentials. It was found that the detaching process of the 6MP SAMs from the surface involved one electron reduction as the voltage was applied at ca. 0.7 V vs a standard calomel electrode.     

Hierarchical self-assembly of bolaamphiphiles with a hybrid spacer and L-glutamic acid headgroup: pH- and surface-triggered hydrogels, vesicles, nanofibers, and nanotubes

Bolaamphiphiles with L-glutamic acid headgroups and hybrid linkers, each composed of two rigid benzene rings and different polymethylene units, were designed, and morphological controls of the hierarchical self-assemblies were realized via changing solution pH and application to solid surfaces. At a low pH of 3, bolaamphiphiles formed hydrogels with water and molecules with short and long spacers formed nanofibers and helical nanoribbon-nanotubes, respectively. In a pH 12 aqueous solution, vesicles were observed from cryo-TEM measurements for amphiphiles with short spacers that could transfer to huge vesicles when cast onto a mica surface. Amphiphiles with longer spacers self-assembled into nanoparticles in a pH 12 aqueous solution while micellar fibers were formed on a mica surface. Those assemblies were characterized with UV-vis, CD, and FT-IR spectroscopy and AFM and TEM observations. With molecular structure modification and the fine tuning of conditions, morphology transitions between various nanostructures were obtained from the self-assembled bolaamphiphiles. The environmental pH can induce different interaction modes between the headgroups, and at high pH, there are strong interactions between molecular assemblies and the mica surface. It is suggested that the active headgroups, rigid necks, and flexible linkers with different lengths render molecules with diverse aggregation morphologies.     

Synthesis,crystal structures and anticancer activities of two decavanadate compounds

Two ammonium decavanadate(V) compounds, (H₂tmen)₃V₁₀O₂₈·6H₂O (1) and (H₂en)₃V₁₀O₂₈·2H₂O (2), where H₂tmen and H₂en represent the doubly protonated N,N,N′,N′-tetramethylethylenediammonium ion and doubly protonated ethylenediammonium ion, respectively, have been synthesized and structurally characterized by elemental analyses, spectroscopic (i.r., e.s.r.) studies, and single-crystal X-ray diffraction. Both crystal structures reveal the presence of the [V₁₀O₂₈]⁶⁻ cluster anions, doubly protonated diammonium cations, and lattice water molecules. Hydrogen bonds assemble these two compounds to form three-dimensional networks. The in vitro anticancer activity against A549 and P388 tumor cells lines has also been determined by the MTT-based assay, and the results suggest that both compounds can inhibit proliferation of these two kinds of tumor cells.     

Synthesis of a fluorescein–porphyrin hybrid and its supramolecular self-assembly with amino-porphyrinatocopper(II) by hydrogen bonding

A fluorescein–porphyrin hybrid (Fl-PTPP) has been synthesized and characterized by UV/Vis, IR, ¹H NMR, ES-MS and elemental analysis. The supramolecular self-assembly of Fl-PTPP with the copper(II) complex of 5-(p-amino-phenyl)-10,15,20-triphenylporphyrin, (CuAPTPP), by hydoxyl-amino type hydrogen bonding was studied using vapor pressure osmometry (VPO) measurements, ES-MS, UV/Vis, ¹H NMR and fluorescence spectroscopic titration. The data indicate formation of a (Fl-PTPP)–CuAPTPP supramolecular complex. Fluorescence strengthening character was observed in a spectroscopic titration experiment for the Fl-PTPP/CuAPTPP system. The association constant of the supramolecular complex was calculated from the fluorescence titration data, and found to be less than that of a carboxyl–carboxyl type hydrogen-bonding system.