New syntheses and chemistry of hexafluorotropone

Two new routes to hexafluorotropone have been developed, one from hexachlorotropone and a superior synthesis from hexafluorobenzene. Hexafluorotropone was found to be a very weak base, with a conjugate acid pK(a) of -6.2 +/- 0.5. The tropone adds in [6 + 4] fashion to cyclopentadiene and photocyclizes to hexafluorobicyclo[3.2.0]hepta-3,6-dien-2-one. Lithium hydroxide in benzene transforms the tropone into pentafluorotropolone, which functions as a bidentate ligand.     

Convenient procedure of Horner-Wadsworth-Emmons olefination for the synthesis of simple and functionalized α,β-unsaturated nitriles

A mild and practical procedure of Horner-Wadsworth-Emmons olefination promoted by lithium hydroxide and α-cyano phosphonates has been set up for the synthesis of α,β-unsaturated nitriles. The reaction conditions are tolerated by functionalized ketones and the exclusive formation of E-γ-hydroxy α,β-unsaturated nitriles has been observed.     

Optical properties of nanocrystalline Y2O3:Eu depending on its odd structure

The structure of nanocrystalline Y2O3:Eu prepared by a combustion reaction was analyzed by XRD and high-resolution electron microscopy. Compared with a large-scale particles, 5-nm Y2O3:Eu particles presented as distorted crystallite and rough surfaces. Luminescent and absorption properties of nano-Y2O3:Eu showed remarkably particle size effects. At Y2O3:Eu particle sizes smaller than 10 nm some new results were observed: (a) a red shift of the charge-transfer-state absorption; (b) new emission bands of Eu3+ in the 5D0 --> 7F2 region; (c) luminescent decay of energy level 5D0 of Eu3+ turning to a two-step exponential; and (d) a pronounced increase in quenching concentration and much lower phonon density compared with those of the bulk material. All these phenomena can be attributed to the effect of the softened lattice and surface state of the nanomaterial. The latter was confirmed by stronger excitation by the host absorption after the surface modification.     

Alkaloids from Juglans Mandshurica maxim induce distinctive cell death in hepatocellular carcinoma cells

The aim of this work was to further investigate the anticancer potential of Juglans mandshurica Maxim, including the separation of active constituents and their anti-proliferative effects with underlying mechanism of action. Five alkaloids (1–5) were isolated from the bark of J. mandshurica. Among them, 1 showed the highest cytotoxic activities against Hep3B and HepG2 cells with an IC50 values of 61.80 and 56.24 μM, respectively. Therefore, the cellular mechanism involved 1 was subsequently studied. Our results showed that 1 markedly caused apoptosis and autophagy, but without cell cycle arrest in HepG2 cells. Interestingly, only autophagic cell death was induced in 1-treated Hep3B cells. It is concluded that the isolated alkaloids exerted a certain anti-hepatoma potential, and our results may provide a basis for the further investigation of the alkaloids extracted from J. mandshurica.     

AIEgens/Nucleic Acid Nanostructures for Bioanalytical Applications

DNA occupies significant roles in life processes, which include encoding the sequences of proteins and accurately transferring genetic information from generation to generation. Recent discoveries have demonstrated that a variety of biological functions are correlated with DNA′s conformational transitions. The non‐B form has attained great attention among the diverse forms of DNA over the past several years. The main reason for this is that a large number of studies have shown that the non‐B form of DNA is associated with gross deletions, inversions, duplications, translocations as well as simple repeating sequences, which therefore causes human diseases. Consequently, the conformational transition of DNA between the B‐form and the non‐B form is important for biology. Conventional fluorescence probes based on the conformational transitions of DNA usually need a fluorophore and a quencher group, which suffers from the complex design of the structure and tedious synthetic procedures. Moreover, conventional fluorescence probes are subject to the aggregation‐caused quenching (ACQ) effect, which limits their application toward imaging and analyte detection. Fluorogens exhibiting aggregation‐induced emission (AIE) have attracted tremendous attention over the past decade. By taking advantage of this unique behavior, plenty of fluorescent switch‐on probes without the incorporation of fluorescent quenchers/fluorophore pairs have been widely developed as biosensors for imaging a variety of analytes. Herein, the recent progress in bioanalytical applications on the basis of aggregation‐induced emission luminogens (AIEgens)/nucleic acid nanostructures are presented and discussed.     

Polybismuthide Anions as Ligands: The Homoleptic Complex [(Bi7)Cd(Bi7)]4− and the Ternary Cluster [(Bi6)Zn3(TlBi5)]4−

We present the results from a reactivity study of the binary anion (TlBi₃)^2? towards Group 12 metal compounds MPh₂ (M=Zn, Cd, Hg) to gain access to coordination compounds of polycyclic polypnictide molecules such as Bi₇^3? or Bi₁₁^3?. The coordination chemistry of these polybismuthide cages has been unprecedented to date, while it has been known for a long time for the lighter Group 15 anions Pn₇^3? (Pn=P, As, Sb). The use of (TlBi₃)^2?, previously shown to release Tl under certain conditions in situ, resulted in the formation of the first heterometallic polyanion in which a nortricyclane‐type polybismuthide coordinates a transition‐metal atom, [(Bi₇)Cd(Bi₇)]^4?. Reactions with the lighter Group 12 metal precursor yielded the uncommon ternary cluster [(Bi₆)Zn₃(TlBi₅)]^4?, most likely representing a reaction intermediate, and at the same time hinting at the formation of the nortricyclane‐shaped cage. Quantum‐chemical studies provide deeper insight into the stability trends of the [(E₇)M(E₇)]^4? anion family and reveal a complex bonding situation in [(Bi₆)Zn₃(TlBi₅)]^4?, which features both localized and multi‐center bonding.     

Synthesis,characterization and biological activity of bis(3‐Aryl‐1‐hexahydropyrimidinyl)methanes. Novel heterocyclic polyamine derivatives

A method is described for the synthesis of bis(3‐aryl‐1‐hexahydropyrimidinyl)methanes 1, by condensation of N‐aryl‐1,3‐propanediarnines 2 with formaldehyde. The reaction mechanism involves N‐arylhexahydropyrimidines 3 as intermediates. Such compounds can also be prepared efficiently by a methylene exchange reaction between bis‐hexahydropyrimidines 1 and the corresponding diamines 2. The antimicrobial activity of compounds 1 was evaluated by the disk diffusion method and some of them showed moderate to good growth inhibition activity.     

Hydrate isomerism in [Cu(en)2(H2O)1.935]2[Fe(CN)6]·4H2O

The title compound, bis[di­aqua­bis­(ethyl­enedi­amine‐κ²N,N′)copper(II)­] hexa­cyano­iron(II) tetrahydrate, [Cu(C₂H₈N₂)₂(H₂O)_1.935]₂[Fe(CN)₆]·4H₂O, was crystallized from an aqueous reaction mixture initially containing CuSO₄, K₃[Fe(CN)₆] and ethyl­enedi­amine (en) in a 3:2:6 molar ratio. Its structure is ionic and is built up of two crystallographically different cations, viz. [Cu(en)₂(H₂O)₂]²⁺ and [Cu(en)₂(H₂O)_1.87]²⁺, there being a deficiency of aqua ligands in the latter, [Fe(CN)₆]⁴⁻ anions and disordered solvent water mol­ecules. All the metal atoms lie on centres of inversion. The Cu atom is octahedrally coordinated by two chelate‐bonded en mol­ecules [mean Cu—N = 2.016 (2) Å] in the equatorial plane, and by axial aqua ligands, showing very long distances due to the Jahn–Teller effect [mean Cu—O = 2.611 (2) Å]. In one of the cations, significant underoccupation of the O‐atom site is observed, correlated with the appearance of a non‐coordinated water mol­ecule. This is interpreted as the partial contribution of a hydrate isomer. The [Fe(CN)₆]⁴⁻ anions form quite regular octahedra, with a mean Fe—C distance of 1.913 (2) Å. The dominant intermolecular interactions are cation–anion O—H⋯N hydrogen bonds and these inter­actions form layers parallel to (001).