The simulation of the thermal behavior of energetic materials based on DSC and HFC signals

Two small calibre and four medium calibre types of propellants were investigated non-isothermally (0.25–4K min⁻¹) by differential scanning calorimetry (DSC) in the range of RT-260°C and isothermally (60–100°C) by heat flow calorimetry (HFC). The data obtained from both techniques were used for the calculation and comparison of the kinetic parameters of the decomposition process. The application of HFC allowed to determine the kinetic parameters of the very early stage of the reaction (reaction progress α below 0.02) what, in turn, made possible the precise prediction of the reaction progress under temperature mode corresponding to real atmospheric changes according to STANAG 2895. In addition, the kinetic parameters obtained from DSC data enabled determination of self-accelerating decomposition temperature (SADT) and comparison of the predicted ignition temperature during slow cook-off with the experimental results. The study contains also the results of the calculation of the time to maximum rate (TMR_ad) of the propellants under adiabatic conditions.     

Locally compact covergece groups ad $$$$-trasitive actios

All \(\sigma \)-compact, locally compact groups acting sharply \(n\)-transitively and continuously on compact spaces \(M\) have been classified, except for \(n=2,3\) when \(M\) is infinite and disconnected. We show that no such actions exist for \(n=2\) and that these actions for \(n=3\) coincide with the action of a hyperbolic group on a space equivariantly homeomorphic to its hyperbolic boundary. We further characterize non-compact groups acting 3-properly and transitively on infinite compact sets as non-elementary boundary-transitive hyperbolic groups, which in turn were recently studied by Caprace, de Cornulier, Monod and Tessera. As an important tool, we generalize Bowditch’s topological characterization of discrete hyperbolic groups to locally compact hyperbolic groups. Finally, we show that if a locally compact group acts continuously, 4-properly and 4-cocompactly on a locally connected metrizable compactum M, then M has a global cut point, which is in sharp contrast to the \(3\)-proper, \(3\)-cocompact case due to the solution of Bowditch’s cut-point conjecture.     

A transferable ab initio based force field for aqueous ions

We present a new polarizable force field for aqueous ions (Li(+), Na(+), K(+), Rb(+), Cs(+), Mg(2 +), Ca(2 +), Sr(2 +), and Cl(-)) derived from condensed phase ab initio calculations. We use maximally localized Wannier functions together with a generalized force and dipole-matching procedure to determine the whole set of parameters. Experimental data are then used only for validation purposes and a good agreement is obtained for structural, dynamic, and thermodynamic properties. The same procedure applied to crystalline phases allows to parametrize the interaction between cations and the chloride anion. Finally, we illustrate the good transferability of the force field to other thermodynamic conditions by investigating concentrated solutions.     

Trimethylarsonium-Based Cationic Phospholipids for Gene Delivery

Abstract

Lipophosphoramide-based cationic lipids are a class of synthetic vectors used for gene delivery that can be produced in multigram scale. The use of trimethylarsonium moiety as a cationic polar head was beneficial to produce efficient gene delivery vectors for in vivo applications. Moreover, this type of cationic lipid can also exhibit some bactericidal effects.     

Spectra of elements in the range of strongly continuous unitary representations of Lie groups

The main result proved in this work is that, for a strongly continuous unitary representation of a Lie group, we have the following dichotomy: The representation is norm continuous or on an open neighborhood of the unit (which is the whole group for a weakly exponential Lie group), there is a residual set of elements whose range admits the entire torus as spectrum.     

Grain-boundary grooving and agglomeration of alloy thin films with a slow-diffusing species

We present a general phase-field model for grain-boundary grooving and agglomeration of polycrystalline alloy thin films. In particular, we study the effects of slow-diffusing species on the grooving rate. As the groove grows, the slow species becomes concentrated near the groove tip so that further grooving is limited by the rate at which it diffuses away from the tip. At early times the dominant diffusion path is along the boundary, while at late times it is parallel to the substrate. This change in path strongly affects the time dependence of grain-boundary grooving and increases the time to agglomeration. The present model provides a tool for agglomeration-resistant thin film alloy design.     

Gaining Insights on the Interactions of a Class of Decorated (2-([2,2′-Bipyridin]-6-yl)phenyl)platinum Compounds with c-Myc Oncogene Promoter G-Quadruplex and Other DNA Structures

Organometallic molecules offer some of the most promising scaffolds for interaction with G-quadruplex nucleic acids. We report the efficient synthesis of a family of organoplatinum(II) complexes, featuring a 2-([2,2′-bipyridin]-6-yl)phenyl tridentate (N^∧N^∧C) ligand, that incorporates peripheral side-chains aiming at enhancing and diversifying its interaction capabilities. These include a di-isopropyl carbamoyl amide, a morpholine ethylenamide, two enantiomeric proline imides and an oxazole. The binding affinities of the Pt-complexes were evaluated via UV-vis and fluorescence titrations, against 5 topologically-distinct DNA structures, including c-myc G-quadruplex, two telomeric (22AG) G-quadruplexes, a duplex (ds26) and a single-stranded (polyT) DNA. All compounds exhibited binding selectivity in favour of c-myc, with association constants (K_a) in the range of 2–5×10⁵ M⁻¹, lower affinity for both folds of 22AG and for ds26 and negligible affinity for polyT. Remarkable emission enhancements (up to 200-fold) upon addition of excess DNA were demonstrated by a subset of the compounds with c-myc, providing a basis for optical selectivity, since optical response to all other tested DNAs was low. A c-myc DNA-melting experiment showed significant stabilizing abilities for all compounds, with the most potent binder, the morpholine-Pt-complex, exhibiting a ΔT_m>30 °C, at 1 : 5 DNA-to-ligand molar ratio. The same study implied contributions of the diverse side-chains to helix stabilization. To gain direct evidence of the nature of the interactions, mixtures of c-myc with the four most promising compounds were studied via UV Resonance Raman (UVRR) spectroscopy, which revealed end-stacking binding mode, combined with interactions of side-chains with loop nucleobase residues. Docking simulations were conducted to provide insights into the binding modes for the same four Pt-compounds, suggesting that the binding preference for two alternative orientations of the c-myc G-quadruplex thymine ‘cap’ (‘open’ vs. ‘closed’), as well as the relative contributions to affinity from end-stacking and H-bonding, are highly dependent on the nature of the interacting Pt-complex side-chain.