Expanding the Topological Landscape by a G-Column Flip of a Parallel G-Quadruplex

Canonical G-quadruplexes can adopt a variety of different topologies depending on the arrangement of propeller, lateral, or diagonal loops connecting the four G-columns. A novel intramolecular G-quadruplex structure is derived through inversion of the last G-tract of a three-layered parallel fold, associated with the transition of a single propeller into a lateral loop. The resulting (3+1) hybrid fold features three syn⋅anti⋅anti⋅anti G-tetrads with a 3’-terminal all-syn G-column. Although the ability of forming a duplex stem-loop between G-tracts seems beneficial for a propeller-to-lateral loop rearrangement, unmodified G-rich sequences resist folding into the new (3+1) topology. However, refolding can be driven by the incorporation of syn-favoring guanosine analogues into positions of the fourth G-stretch. The presented hybrid-type G-quadruplex structure as determined by NMR spectroscopy may provide for an additional scaffold in quadruplex-based technologies.     

Tetrakis(pentafluoroethyl)gallate, [Ga(C2F5)4]−, Ionic Liquids

We synthesized new imidazolium-based tunable aryl alkyl ionic liquids (TAAILs) with the weakly coordinating tetrakis(pentafluoroethyl)gallate anion, [Ga(C₂F₅)₄]⁻. Phenyl and phenyl derivatives (2-Me, 4-OMe, 2,4-F) were combined with varying alkyl chain lengths at the imidazolium core leading to TAAILs, which were investigated with regard to their viscosity, conductivity, and electrochemical window and compared to EMIM and BMIM standard cations. Remarkable low viscosities of 29 cP at 25 °C for [BMIM][Ga(C₂F₅)₄] were achieved. However, the EMIM and BMIM gallates show electrochemical instability, releasing pentafluoroethane at a voltage of 1.5 V. The 2-Me-substituted gallate-TAAILs slowly decompose over several weeks, whereas all other gallate-TAAILs showed no decomposition at all. With electrochemical windows of up to 5.15 V and low viscosities in a range of 66–162 cP, the gallate-TAAILs are promising candidates as electrolytes in electrochemical applications.     

Quadruplex–Duplex Junction: A High-Affinity Binding Site for Indoloquinoline Ligands

A parallel quadruplex derived from the Myc promoter sequence was extended by a stem-loop duplex at either its 5′- or 3′-terminus to mimic a quadruplex–duplex (Q–D) junction as a potential genomic target. High-resolution structures of the hybrids demonstrate continuous stacking of the duplex on the quadruplex core without significant perturbations. An indoloquinoline ligand carrying an aminoalkyl side chain was shown to bind the Q–D hybrids with a very high affinity in the order K_a≈10⁷ m ⁻¹ irrespective of the duplex location at the quadruplex 3′- or 5′-end. NMR chemical shift perturbations identified the tetrad face of the Q–D junction as specific binding site for the ligand. However, calorimetric analyses revealed significant differences in the thermodynamic profiles upon binding to hybrids with either a duplex extension at the quadruplex 3′- or 5′-terminus. A large enthalpic gain and considerable hydrophobic effects are accompanied by the binding of one ligand to the 3′-Q–D junction, whereas non-hydrophobic entropic contributions favor binding with formation of a 2:1 ligand-quadruplex complex in case of the 5′-Q–D hybrid.     

Non-linear deformation properties of materials with stochastically distributed anisotropic inclusions

In the present contribution, the problem of non-linear deformation of materials with stochastically distributed anisotropic inclusions is considered on the basis of the methods of mechanics of stochastically non-homogeneous media. The homogenization model of materials of stochastic structure with physically non-linear components is developed for the case of a matrix which is strengthened by unidirectional ellipsoidal inclusions. It is assumed that the matrix is isotropic, deforms non-linearly; inclusions are linear-elastic and have transversally-isotropic symmetry of physical and mechanical properties. Stochastic differential equations of physically non-linear elasticity theory form the underlying equations. Transformation of these equations into integral equations by using the Green's function and application of the method of conditional moments allow us to reduce the problem to a system of non-linear algebraic equations. This system of non-linear algebraic equations is solved by the Newton-Raphson method. On the analytical as well as the numerical basis, the algorithm for determination of the non-linear effective characteristics of such a material is introduced. The non-linear behavior of such a material is caused by the non-linear matrix deformations. On the basis of the numerical solution, the dependences of homogenized Poisson's coefficients on macro-strains and the non-linear stress-strain diagrams for a material with randomly distributed unidirectional ellipsoidal pores are predicted and discussed for different volume fractions of pores. (© 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)     

Modeling of polycrystals with gradient crystal plasticity: A comparison of strategies

This paper treats the computational modeling of size dependence in microstructure models of metals. Different gradient crystal plasticity strategies are analyzed and compared. For the numerical implementation, a dual-mixed finite element formulation which is suitable for parallelization is suggested. The paper ends with a representative numerical example for polycrystals.     

Spray coating of cellulose aerogel particles in a miniaturized spouted bed

Cellulose - Aim of this work is to apply protective and homogeneous shellac coating layers on the surface of hydrophilic open-pore cellulose aerogel particles with low...