4,185 research outputs found

    The Role of Chain Length in Cucurbit[8]uril Complexation of Methyl Alkyl Viologens

    Get PDF
    Viologens are among the most studied guests for cucurbit[8]uril (CB[8]) and their complexation is usually driven by bipyridyl core inclusion inside the cavity to maximize both hydrophobic and cation-dipole interactions. The presence of alkyl substituents on the guest alters this complexation mode, switching to aliphatic chain inclusion in U-folded conformation. Herein, we report a thorough study of the influence of the alkyl chain length on the binding mode of methyl alkyl viologens. The chain length of the studied guests was increased by two methylene groups starting from methyl dodecyl viologen (MVC12) to the octadecyl analogue (MVC18). Complexation in water, investigated by NMR spectroscopy and ITC, revealed a clear switch from 1 : 1 to 2 : 1 host/guest stoichiometry moving from 12 to 16 carbon atoms, as a consequence of the chain folding of the major portion of the longer alkyl chain in one CB[8] cavity and the inclusion of the full viologen unit by another host molecule. The CB[8]2.MVC18 complex crystal structure evidences the unprecedented 2 : 1 stoichiometry and quantified in 12 the number of carbon atoms necessary to fill the CB[8] cavity in U-shaped conformation

    Methyl Hexadecyl Viologen Inclusion in Cucurbit[8]uril: Coexistence of Three Host-Guest Complexes with Different Stoichiometry in a Highly Hydrated Crystal

    Get PDF
    The host-guest inclusion complexes of cucurbiturils with alkyl viologen have interesting architectures, chemical properties, and potential applications in sensors and nanotechnology. A highly hydrated triclinic crystal of cucurbit[8]uril (CB[8]) complexed by methyl hexadecyl viologen (MVC16) is characterized by the unprecedented coexistence in the crystal of three host-guest complexes with 3:2, 2:2, and 1:1 stoichiometries. In all these complexes, the hook-shaped alkyl chain of the MVC16 is hosted in the CB[8] macrocycles, while the methyl viologen moieties have various environments. In the Z-shaped 3:2 complex, a central CB[8] unit hosts two viologen heads in the cavity, while the 2:2 complex is held together by \u3c0-stacking interactions between two viologen units. In the square 2D tiling crystal packing of CB[8] macrocycles, the same site which favors the dimerization observed in the 2:2 complex is also statistically occupied by a single methyl viologen moiety of the 1:1 complex. The rational interpretation of the crystal structure represented an intriguing challenge, due to the complicated statistical disorder in the alkyl chains hosted in CB[8] units and in the methyl viologen moieties of 2:2 and 1:1 complexes. In contrast with the solution behavior dominated by the 2:1 complex, the coexistence of three host-guest complexes with 3:2, 2:2, and 1:1 ratios highlights the fundamental importance of packing effects in the crystallized supramolecular complexes. Therefore, the crystallization process has permitted us to capture different host-guest systems in a single crystal, revealing a supramolecular landscape in a single photo

    Solar variability indications from Nimbus 7 satellite data

    Get PDF
    The cavity pyrheliometer sensor of the Nimbus 7 Earth Radiation Experiment indicated low-level variability of the total solar irradiance. The variability appears to be inversely correlated with common solar activity indicators in an event sense. the limitations of the measuring system and available data sets are described

    High speed video capture for mobile phone cameras

    Get PDF
    We consider an electromechanical model for the operation of a voice coil motor in a mobile phone camera, with the aim of optimizing how a lens can be moved to a desired focusing motion. Although a methodology is developed for optimizing lens shift, there is some concern about the experimentally-determined model parameters that are at our disposal. Central to the model is the value of the estimated magnetic force constant, Kf: its value determines how far it is actually possible to move lens, but it appears that, from the value given, it would not be possible to shift the lens through the displacements desired. Furthermore, earlier experiments have also estimated the value of the back EMF constant, Kg , to be roughly five times greater than Kf, even though we present two theoretical arguments that show that Kf = Kg: a conclusion supported by readily-available manufacturers’ data

    Phosphorylation: The Molecular Switch of Double-Strand Break Repair

    Get PDF
    Repair of double-stranded breaks (DSBs) is vital to maintaining genomic stability. In mammalian cells, DSBs are resolved in one of the following complex repair pathways: nonhomologous end-joining (NHEJ), homologous recombination (HR), or the inclusive DNA damage response (DDR). These repair pathways rely on factors that utilize reversible phosphorylation of proteins as molecular switches to regulate DNA repair. Many of these molecular switches overlap and play key roles in multiple pathways. For example, the NHEJ pathway and the DDR both utilize DNA-PK phosphorylation, whereas the HR pathway mediates repair with phosphorylation of RPA2, BRCA1, and BRCA2. Also, the DDR pathway utilizes the kinases ATM and ATR, as well as the phosphorylation of H2AX and MDC1. Together, these molecular switches regulate repair of DSBs by aiding in DSB recognition, pathway initiation, recruitment of repair factors, and the maintenance of repair mechanisms
    corecore