No abstract

Hexaazatriphenylene triimides (HAT) have been shown to be a novel class of disk-shaped p electron acceptors that pair with donors with complementary shape and electron demands, such as triphenylene (TP) derivatives. The donor-acceptor (DA) pair forms a strong charge-transfer complex in CH 2 Cl 2 with an association constant of 2.6 Â 10 4 M À1 , which is remarkable for a recognition system that is solely based on electrostatic interactions between two p systems. NMR studies, along with molecular modelling, have revealed a complementary charge distribution and an ''eclipsed'' conformation in the DA complex. The strong DA interaction results in extended alternating DA stacks in the thin film and mesophases.

Abnormal activation of the epidermal growth factor receptor (EGFR) due to a deletion of exons 2-7 of EGFR (EGFRvIII) is a common alteration in glioblastoma (GBM). While this alteration can drive gliomagenesis, tumors harboring EGFRvIII are heterogeneous. To investigate the role for EGFRvIII activation in tumor phenotype we used a neural progenitor cell-based murine model of GBM driven by EGFR signaling and generated tumor progenitor cells with high and low EGFRvIII activation, pEGFRHi and pEGFRLo. In vivo, ex vivo, and in vitro studies suggested a direct association between EGFRvIII activity and increased tumor cell proliferation, decreased tumor cell adhesion to the extracellular matrix, and altered progenitor cell phenotype. Time-lapse confocal imaging of tumor cells in brain slice cultures demonstrated blood vessel co-option by tumor cells and highlighted differences in invasive pattern. Inhibition of EGFR signaling in pEGFRHi promoted cell differentiation and increased cell-matrix adhesion. Conversely, increased EGFRvIII activation in pEGFRLo reduced cell-matrix adhesion. Our study using a murine model for GBM driven by a single genetic driver, suggests differences in EGFR activation contribute to tumor heterogeneity and aggressiveness.

We describe the synthesis and characterization of a series of desymmetrized donor-acceptor [2]catenanes where different donor and acceptor units are assembled within a confined catenated geometry. Remarkable translational selectivity is maintained in all cases, including two fully desymmetrized [2]catenanes where both donors and acceptors are different, as revealed by X-ray crystallography in the solid state, and by (1)H NMR spectroscopy and electrochemistry in solution. In all desymmetrized [2]catenanes the co-conformation is dominated by the strongest donor and acceptor pairs, whose charge-transfer interactions also determine the visible absorption properties. Voltammetric and spectroelectrochemical experiments show that the catenanes can be reversibly switched among as many as seven states, characterized by distinct electronic and optical properties, by electrochemical stimulation in a relatively narrow and easily accessible potential window. Moreover in some of these compounds the oxidation of the electron donor units or the reduction of the electron acceptor ones causes the circumrotation of one molecular ring with respect to the other. These features make these compounds appealing for the development of molecular electronic devices and mechanical machines.