Hierarchical Superstructures with Control of Helicity from the Self‐Assembly of Chiral Bent‐Core Molecules

Herein, two asymmetric chiral bent‐core molecules, 3‐[(4‐{[4‐(heptyloxy)benzoyl]oxy}benzoyl)oxy]‐phenyl‐4‐[(4‐{[(1R)‐1‐methylheptyl]oxy}benzoyl)oxy] benzoate (BC7R) and 3‐[(4‐{[4‐(heptyloxy)benzoyl]oxy}benzoyl)oxy]‐phenyl‐4‐[(4‐{[(1S)‐1‐methylheptyl]oxy}benzoyl)oxy] benzoate (BC7S), were synthesized to demonstrate control of the helicity of their self‐assembled hierarchical superstructures. Mirror‐imaged CD spectra showed a split‐type Cotton effect after the formation of self‐assembled aggregates of BC7R and BC7S, thereby suggesting the formation of intermolecular exciton couplets with opposite optical activities. Both twisted and helical ribbons with preferential helicity that corresponded to the twisting character of the intermolecular exciton couplet were found in the aggregates. The formation of helical ribbons was attributed to the merging of twisted ribbons through an increase in width to improve morphological stability. As a result, control of the helicity of hierarchical superstructures from the self‐assembly of bent‐core molecules could be achieved by taking advantage of the transfer of chiral information from the molecular level onto the hierarchical scale.     

The synthesis of Lewis acid ZrO2 nanoparticles and their applications in phospholipid adsorption from Jatropha oil used for biofuel

ZrO(2) nanoparticles were successfully fabricated via a facile hydrothermal process. The diameter and surface area of the as-prepared ZrO(2) nanoparticles were approximately 5-10 nm and 102 m(2)/g, respectively. For the first time, Zr atoms with partial positive charges in a Lewis acid ZrO(2) nanoparticle adsorbent were used for the adsorption of negatively charged phospholipids from Jatropha oil. The capacity for phospholipid adsorption using the ZrO(2) nanoparticles was better than that of commercial ZrO(2) powder due to the larger surface area of the ZrO(2) nanoparticles. Phospholipid removal makes Jatropha oil a potential oil for biofuel applications.     

Synthesis of high-quality carbon nanodots from hydrophilic compounds: role of functional groups

A simple one-pot hydrothermal approach has been demonstrated for the preparation of highly water soluble and photoluminescent carbon nanodots (C-dots) from low-cost organic compounds. We found that the compounds incorporating amino and carboxylic acid groups are suitable for the preparation of highly photoluminescent and water-soluble C-dots.     

Induction of apoptosis in human breast adenocarcinoma cells MCF-7 by monapurpyridine A, a new azaphilone derivative from Monascus purpureus NTU 568

A new azaphilonidal derivative, monapurpyridine A (MPA), has recently been isolated from the fermented products of Monascus purpureus NTU 568. The structure of MPA was elucidated by nuclear magnetic resonance (1H-NMR, 13C-NMR, COSY, HMQC, and HMBC) and other spectroscopic analyses. Biological evaluation revealed that MPA could induce cell death in human breast adenocarcinoma cells MCF-7, and it has no significant toxicity to normal mammary epithelial cells M10. The MTT assay and flow cytometric analysis were employed to investigate cell viability and cell cycle influenced by MPA. Moreover, we used Western blot and caspase activity assay to demonstrate the activation of caspase-3, -8 and -9 resulted from MPA. All evidence supported that MPA was suitable for developing into a chemotherapeutic or chemopreventive agent against breast cancer.     

Induction of Apoptosis by Ethanolic Extract of <em>Corchorus olitorius </em>Leaf in Human Hepatocellular Carcinoma (HepG2) Cells via a Mitochondria-Dependent Pathway

Corchorus olitorius L., is a culinary and medicinal herb, widely used as a vegetable in several countries in Asia. Many studies have shown that C. olitorius contains several antioxidants and exhibits anti-inflammatory and anti-proliferative activities in various in vitro and in vivo settings. Recently, C. olitorius has been approved for its antitumor activity; however, the underlying molecular mechanisms remain unclear. The goal of this study was to investigate the effects of ethanol extract of C. olitorius (ECO) on the growth of human hepatocellular carcinoma (HepG2) cells and gain some insights into the underlying mechanisms of its action. We found that HepG2 cells, treated with ECO for 24 h at a concentration higher than 12.5 μg/mL, displayed a strong reduction in cell viability, whereas normal FL83B hepatocytes were not affected. DNA fragmentation and nuclear condensation were evidenced by the increased subG1 population of ECO-treated HepG2 cells. ECO triggered the activation of procaspases-3 and -9 and caused the cleavage of downstream substrate, poly ADP-ribose polymerase (PARP), followed by down-regulation of the inhibitor of caspase-activated DNase (ICAD) signaling. Moreover, the increased release of cytochrome c from mitochondria with decreased membrane potential demonstrated the apoptosis induced through the caspases cascade. Our findings indicated that ECO might be effective against hepatocellular carcinoma through induction of apoptosis via mitochondria-dependent pathway.     

Intriguing electrochemical behavior of free base porphyrins: effect of porphyrin-meso-phenyl interaction controlled by position of substituents on meso-phenyls

Electrochemical properties of substituted free base meso-tetraphenylporphyrins (H(2)T(o,o'-X)PP, H(2)T(o-X)PP, and H(2)T(p-X)PP, where X = OCH(3), CH(3), H, F, or Cl on the phenyl rings) are examined by cyclic voltammetry. When a substituent is located only at the para position of the meso-phenyl group, the difference between the first and second oxidation potentials (ΔE(ox), i.e., E(2)(ox) - E(1)(ox)), is generally significantly smaller than those of the H(2)TPPs with bulky o,o'-substituents on the phenyl group. This trend is elucidated with density functional theory calculations and attributed mainly to the sterically controlled π-conjugation of the meso-phenyl groups to the central porphyrin ring, rather than the often discussed deformation of porphyrin.     

Atomic layer deposition synthesis of platinum-tungsten carbide core-shell catalysts for the hydrogen evolution reaction

Pt was deposited onto tungsten carbide powders using atomic layer deposition to produce core-shell catalysts for the hydrogen evolution reaction (HER). The Pt loading on these catalysts was reduced nearly ten-fold compared to a bulk Pt catalyst while equivalent HER activities were observed.     

Diindenothieno[2,3-b]thiophene arene for efficient organic photovoltaics with an extra high open-circuit voltage of 1.14 ev

We report a novel diindenothieno[2,3-b]thiophene ladder-type hexacyclic arene for constructing a donor-acceptor copolymer PDITTDTBT. A device based on PDITTDTBT:PC(71)BM exhibited a high V(oc) of 0.92 V with an impressive PCE of 5.8%, while a PDITTDTBT:DMPCBA-based device showed an extra high V(oc) of 1.14 V.     

The importance of p-n junction interfaces for efficient small molecule-based organic solar cells

The efficiency of small-molecule solar cells critically depends on the match of the junction of the donor and acceptor semiconductors used in these devices to create charged carriers and on the mobility of individual components to transport holes and electrons. In the present study, a 2% efficient bilayer organic solar cell consisting of a p-type semiconductor, pentacene, and an n-type semiconductor, N,N'-diheptyl-3,4,9,10-perylenetetracarboxylic diimide (PTCDI-C(7)), is fabricated. The morphology of PTCDI-C(7) interestingly follows pentacene due to the matched surface energy of these two active layers and the easily deposited PTCDI-C(7) monomers on an inclined plane of the pentacene grains. This condition results in the low trap states in the PTCDI-C(7) film and at the pentacene/PTCDI-C(7) interface for the enhancement of exciton dissociation and carrier transport compared with the photoactive layer comprised of pentacene and N,N-ditridecyl-3,4,9,10-perylenetetracarboxylic diimide (PTCDI-C(13)). The detailed exciton and carrier transport mechanisms are investigated using time-resolved photoluminescence and X-ray diffraction spectroscopy.     

Multi‐Dimensional Cobalt(II) and Nickel(II) Coordination Polymers

A series of metal coordination polymers, [Co₂(NB)₄(bpp)₂(H₂O)]·H₂O ( 1 ), [Co₂(e,e‐trans‐chdc)(e,a‐cis‐chdc)(bpp)₂] ( 2 ), [Ni(e,e‐trans‐chdc)(bpp)(H₂O)₂] ( 3 ), [Ni₂(PDA)₂(bpp)₂(H₂O)₃]·H₂O ( 4 ), and [Ni‐(mBDC)(bpp)] ( 5 ) (NB = 3‐nitrobenzoate anion; bpp = 4,4′‐trimethylene dipyridine; chdc = cyclohexane‐1,4‐dicarboxylate anion; PDA = 1,4‐phenylenediacetate anion; mBDC = 1,3‐benzene dicarboxylate anion), were synthesized from metal ions and organic mixed‐ligands by hydrothermal reactions. The single crystal structure analysis revealed that 1, 3, and 4 were 2D sheets with bilayer (1 and 4) and 2‐fold interpenetrated layers (3), 2 is a 3D binodal (4,5)‐connected framework, and 5 is a 1D chains. The non‐covalent interactions of H‐bonds and π–π stacking caused this conformation of highly cross‐linked networks. Compounds 1‐5 were further characterized by thermal gravimetric analysis, powder X‐ray diffraction, UV‐vis, infrared, and PL spectroscopy.