Protic ionic liquids with fluorous anions: physicochemical properties and self-assembly nanostructure

A series of 11 new protic ionic liquids with fluorous anions (FPILs) have been identified and their self-assembled nanostructure, thermal phase transitions and physicochemical properties were investigated. To the best of our knowledge this is the first time that fluorocarbon domains have been reported in PILs. The FPILs were prepared from a range of hydrocarbon alkyl and heterocyclic amine cations in combination with the perfluorinated anions heptafluorobutyrate and pentadecafluorooctanoate. The nanostructure of the FPILs was established by using small- and wide-angle X-ray scattering (SAXS and WAXS). In the liquid state many of the FPILs showed an intermediate range order, or self-assembled nanostructure, resulting from segregation of the polar and nonpolar hydrocarbon and fluorocarbon domains of the ionic liquid. In addition, the physicochemical properties of the FPILs were determined including the melting point (T(m)), glass transition (T(g)), devitrification temperature (T(c)), thermal stability and the density ρ, viscosity η, air/liquid surface tension γ(LV), refractive index n(D), and ionic conductivity κ. The FPILs were mostly solids at room temperature, however two examples 2-pyrrolidinonium heptafluorobutyrate (PyrroBF) and pyrrolidinium heptafluorobutyrate (PyrrBF) were liquids at room temperature and all of the FPILs melted below 80 °C. Four of the FPILs exhibited a glass transition. The two liquids at room temperature, PyrroBF and PyrrBF, had a similar density, surface tension and refractive index but their viscosity and ionic conductivity were very different due to dissimilar self-assembled nanostructure.     

The string landscape: On formulas for counting vacua

We derive formulas for counting certain classes of vacua in the string/M theory landscape. We do so in the context of the moduli space of M-theory compactifications on singular manifolds with _G2$G_2$ holonomy. Particularly, we count the numbers of gauge theories with different gauge groups but equal numbers of U(1)$U(1)$ factors which are dual to each other. The vacua correspond to various symmetry breaking patterns of grand unified theories. Counting these dual vacua is equivalent to counting the number of conjugacy classes of elements of finite order inside Lie groups. We also point out certain cases where the conventional expectation is that symmetry breaking patterns by Wilson lines and Higgs fields are the same, but we show they are in fact different.     

The Effect of Cluster Size on the Intra-Cluster Ionic Polymerization Process

Polyaromatic hydrocarbons (PAHs) are widespread in the interstellar medium (ISM). The abundance and relevance of PAHs call for a clear understanding of their formation mechanisms, which, to date, have not been completely deciphered. Of particular interest is the formation of benzene, the basic building block of PAHs. It has been shown that the ionization of neutral clusters can lead to an intra-cluster ionic polymerization process that results in molecular growth. Ab-initio molecular dynamics (AIMD) studies in clusters consisting of 3–6 units of acetylene modeling ionization events under ISM conditions have shown maximum aggregation of three acetylene molecules forming bonded C₆H₆⁺ species; the larger the number of acetylene molecules, the higher the production of C₆H₆⁺. These results lead to the question of whether clusters larger than those studied thus far promote aggregation beyond three acetylene units and whether larger clusters can result in higher C₆H₆⁺ production. In this study, we report results from AIMD simulations modeling the ionization of 10 and 20 acetylene clusters. The simulations show aggregation of up to four acetylene units producing bonded C₈H₈⁺. Interestingly, C₈H₈⁺ bicyclic species were identified, setting a precedent for their astrochemical identification. Comparable reactivity rates were shown with 10 and 20 acetylene clusters.     

Ultrafast nonadiabatic photodissociation dynamics of F2 in solid Ar

We explore the ultrafast spin-flip dynamics in a diatomic molecule imbedded in a rare gas matrix using the combination of a quantum mechanical and a semiclassical surface hopping method. Specifically, we investigate (1) the extent to which the phenomenon of electronically-localized eigenstates in strongly-coupled manifolds survives in the presence of rapid decay and a multitude of electronically coupled states; (2) the ability of the surface hopping method to predict the short time dynamics; and (3) the time range over which frozen lattice models are valid. Our results point to the active role played by a large number of coupled electronic states in the F₂/Ar dynamics while substantiating our confidence in the validity of the popular surface hopping approach for the system considered.     

Disrupting the MAD2L2-Rev1 Complex Enhances Cell Death upon DNA Damage

DNA-damaging chemotherapy agents such as cisplatin have been the first line of treatment for cancer for decades. While chemotherapy can be very effective, its long-term success is often reduced by intrinsic and acquired drug resistance, accompanied by chemotherapy-resistant secondary malignancies. Although the mechanisms causing drug resistance are quite distinct, they are directly connected to mutagenic translesion synthesis (TLS). The TLS pathway promotes DNA damage tolerance by supporting both replication opposite to a lesion and inaccurate single-strand gap filling. Interestingly, inhibiting TLS reduces both cisplatin resistance and secondary tumor formation. Therefore, TLS targeting is a promising strategy for improving chemotherapy. MAD2L2 (i.e., Rev7) is a central protein in TLS. It is an essential component of the TLS polymerase zeta (ζ), and it forms a regulatory complex with Rev1 polymerase. Here we present the discovery of two small molecules, c#2 and c#3, that directly bind both in vitro and in vivo to MAD2L2 and influence its activity. Both molecules sensitize lung cancer cell lines to cisplatin, disrupt the formation of the MAD2L2-Rev1 complex and increase DNA damage, hence underlining their potential as lead compounds for developing novel TLS inhibitors for improving chemotherapy treatments.     

Left-right noncommutative Poisson algebras

The notions of left-right noncommutative Poisson algebra (NP^lr-algebra) and left-right algebra with bracket AWB^lr are introduced. These algebras are special cases of NLP-algebras and algebras with bracket AWB, respectively, studied earlier. An NP^lr-algebra is a noncommutative analogue of the classical Poisson algebra. Properties of these new algebras are studied. In the categories AWB^lr and NP^lr-algebras the notions of actions, representations, centers, actors and crossed modules are described as special cases of the corresponding wellknown notions in categories of groups with operations. The cohomologies of NP^lr-algebras and AWB^lr (resp. of NP^r-algebras and AWB^r) are defined and the relations between them and the Hochschild, Quillen and Leibniz cohomologies are detected. The cases P is a free AWB^r, the Hochschild or/and Leibniz cohomological dimension of P is ≤ n are considered separately, exhibiting interesting possibilities of representations of the new cohomologies by the well-known ones and relations between the corresponding cohomological dimensions.     

Ball-and-socket stacking of supercharged geodesic polyarenes: bonding by interstitial lithium ions

Unprecedented supramolecular stacks of highly reduced geodesic pi-systems were prepared by the reduction of the derivatized fullerenes Me(5)C(60)H and Ph(5)C(60)H and corannulene with lithium metal (R(5)C(60)(5)(-)/Cor(4)(-)/9Li(+)). The host--guest assemblies form because of the enhanced electrostatic interactions between the lithium cations and the anionic moieties, in addition to the structural compatibility between the curved hydrocarbons. The high stability of these new supramolecular assemblies (heterodimers) enables the introduction of another organization motif to the system. This is achieved by using tethered corannulenes as host molecules, which leads to the formation of tethered bis-heterodimers ((Me(5)C(60)(5)(-)/Cor(4)(-))(2)(CH(2))(8)/18Li(+)).     

Fidelity discrimination in DNA polymerase beta: differing closing profiles for a mismatched (G:A) versus matched (G:C) base pair

Understanding fidelity-the faithful replication or repair of DNA by polymerases-requires tracking of the structural and energetic changes involved, including the elusive transient intermediates, for nucleotide incorporation at the template/primer DNA junction. We report, using path sampling simulations and a reaction network model, strikingly different transition states in DNA polymerase beta's conformational closing for correct dCTP versus incorrect dATP incoming nucleotide opposite a template G. The cascade of transition states leads to differing active-site assembly processes toward the "two-metal-ion catalysis" geometry. We demonstrate that these context-specific pathways imply different selection processes: while active-site assembly occurs more rapidly with the correct nucleotide and leads to primer extension, the enzyme remains open longer, has a more transient closed state, and forms product more slowly when an incorrect nucleotide is present. Our results also suggest that the rate-limiting step in pol beta's conformational closing is not identical to that for overall nucleotide insertion and that the rate-limiting step in the overall nucleotide incorporation process for matched as well as mismatched systems occurs after the closing conformational change.     

Current-induced rotation of helical molecular wires

We show that electric current running through a nanojunction with a biased helical molecule can induce unidirectional rotation of the molecular component. In an electric field, conduction electrons injected into the molecule are accelerated along the helical path going through its body, thereby gaining directed angular momentum. Conservation laws require that an angular momentum of the same size but opposite sense is imparted to the rigid-body rotation of the helix. We describe the angular momentum exchange processes that underlie the operation of the nanorotor, discuss factors limiting its efficiency, and propose potential applications.