The post-SCF quantum chemistry characteristics of the guanine-guanine stacking B-DNA

The stacking interactions of two guanine molecules were analyzed detail at the DF-MP2/aug-cc-pVDZ level of theory for conformations appearing B-DNA. The dependence of intermolecular interaction energies on the pairs of step parameters (shift, slide, rise, tilt, roll and twist) was determined. The values of these parameters were chosen to cover the whole range of variability appearing crystallographic data. The scanning procedure was performed by subsequent changes of two variables with fixed values of the remaining base-pair and base-step BDNA parameters. Additionally, the hybrid variational-perturbational scheme was applied for the decomposition of the interaction energy into physically meaningful contributions at the MP2 level of theory. The significant impact of the mutual orientations of guanine bases was observed not only on the total intermolecular energy but also on its components. The second-order dispersion interaction is the most significant contribution to stabilization energy and is about eight times larger compared to the first-order electrostatic term with relaxation effects, which is also of stabilizing character. The dispersion interactions may vary up to 9.6 kcal mol(-1) between different guanine-guanine conformations. The parameters defining the mutual orientation of stacked guanine molecules have a different impact on the stabilization of the investigated complex. The following base-step parameters have only a minor impact on the stabilization energies: shift-slide, shift-roll, shift-twist, slide-twist and roll-twist. On the other hand, parameters such as rise and tilt significantly influence intermolecular interactions, i.e. strong attraction occurs only for a limited range of their values.     

Removal of cadmium(II) and lead(II) ions from model aqueous solutions using sol–gel-derived inorganic oxide adsorbent

A study was conducted concerning the preparation and application of a novel synthetic oxide adsorbent of MgO-SiO₂ type. The material was prepared via a sol–gel route, utilizing magnesium ethoxide and tetraethoxysilane as precursors of magnesium oxide and silica respectively, and ammonia as a catalyst. The powder was comprehensively analyzed with regard to chemical composition (EDS method), crystalline structure, morphology, characteristic functional groups, electrokinetic stability and porous structure parameters (BET and BJH models). The synthesized oxide adsorbent is amorphous, with irregularly shaped particles, a relatively large surface area of 612 m²/g, and negative surface charge over almost the whole pH range. Comprehensive adsorption studies were performed to investigate the adsorption of Cd(II) and Pb(II) ions on the MgO–SiO₂ oxide adsorbent, including evaluation of adsorption kinetics and isotherms, the effect of pH, contact time and mass of adsorbent. It was shown that irrespective of the conditions of the adsorption process, the synthesized MgO–SiO₂ adsorbent exhibits slightly better affinity to lead(II) than to cadmium(II) ions (sorption capacity of 102.02 mg(Pb²⁺)/g and 94.05 mg(Cd²⁺)/g). The optimal time for removal of the analyzed metal ions was 60 min, although adsorption reached equilibrium within 10 min for Pb(II) and within 15 min for Cd(II) ions, which was found to fit well with a type 1 pseudo-second-order kinetic model. Additionally, adsorption efficiency was affected by the pH of the reaction system—better results were obtained for pH ≥7 irrespective of the type of metal ion.     

A new mesogenic mixture with antiferroelectric phase only at a broad temperature range

New compounds (S)-4?-(1-methylheptyloxycarbonyl)biphenyl-4-yl 4-[3-(2,2,3,3,4,4,5,5,5-nonafluoropentyloxy)prop-1-oxy]benzoates were synthesised and characterised. Their mesomorphic properties were tested by means of polarising optical microscopy and differential scanning calorimetry. The multicomponent antiferroelectric high tilt mixture with long pitch has been also formulated and characterised. The helical pitch of prepared mixture was estimated with selective reflection method.     

Complementation and decompositions in some weakly Lindelöf Banach spaces

Let Γ denote an uncountable set. We consider the questions if a Banach space X of the form C(K) of a given class (1) has a complemented copy of c₀(Γ) or (2) for every c₀(Γ)⊆X has a complemented c₀(E) for an uncountable E⊆Γ or (3) has a decomposition X=A⊕B where both A and B are nonseparable. The results concern a superclass of the class of nonmetrizable Eberlein compacts, namely Ks such that C(K) is Lindelöf in the weak topology and we restrict our attention to Ks scattered of countable height. We show that the answers to all these questions for these C(K)s depend on additional combinatorial axioms which are independent of ZFC ± CH. If we assume the P-ideal dichotomy, for every c₀(Γ)⊆C(K) there is a complemented c₀(E) for an uncountable E⊆Γ, which yields the positive answer to the remaining questions. If we assume ♣, then we construct a nonseparable weakly Lindelöf C(K) for K of height ω+1 where every operator is of the form cI+S for c∈R and S with separable range and conclude from this that there are no decompositions as above which yields the negative answer to all the above questions. Since, in the case of a scattered compact K, the weak topology on C(K) and the pointwise convergence topology coincide on bounded sets, and so the Lindelöf properties of these two topologies are equivalent, many results concern also the space Cp(K).     

Solving a kind of boundary-value problem for ordinary differential equations using Fermi—The next generation CUDA computing architecture

The aim of this paper is to show that a special kind of boundary value problem for solving second-order ordinary differential equations can be efficiently solved on modern heterogeneous computer architectures based on CPU and GPU Fermi processors. Such a problem reduces to the problem of solving a large tridiagonal system of linear equations with an almost Toeplitz structure. The considered algorithm is based on the recently developed divide and conquer method for solving linear recurrence systems with constant coefficients.     

Thermal properties and flammability of nanocomposites based on diene rubbers and naturally occurring and activated halloysite nanotubes

This article presents a procedure of the activation of halloysite and a method of the synthesis of nucleus-sheath type filler. The effects of the nanoadditives obtained on the thermal properties, flammabilities and fire hazards of peroxide and sulfur vulcanizates of NBR and SBR rubbers, are discussed. Based on the test results obtained by derivatography, oxygen index, FAA micro-calorimeter and cone calorimeter, the thermal stability, flammability, and fire hazard of the nanocomposites investigated were determined. The results obtained were interpreted from the point of view of the chemical structure of the diene elastomers investigated, their spatial network structure, and the method of halloysite modification.     

2,4-D based herbicidal ionic liquids

Herbicidal ionic liquids (HILs) with a 2,4-D anion were synthesized and characterized. These salts have chemical and thermal stability. HILs exhibited higher biological activity than currently used salts of 2,4-D. HILs are nonvolatile and showed substantially lower water solubility than starting herbicides.     

Crystal and electronic structure, lattice dynamics and thermal properties of Ag(I)(SO3)R (R = F, CF3) Lewis acids in the solid state

Trifluoromethansulfonate of silver(I), AgSO(3)CF(3) (abbreviated AgOTf), extensively used in organic chemistry, and its fluorosulfate homologue, AgSO(3)F, have been structurally characterized for the first time. The crystal structures of both homologues differ substantially from each other. AgOTf crystallizes in a hexagonal system (R3 space group, No.148) with a = b = 5.312(3) ? and c = 32.66(2) ?, while AgSO(3)F crystallizes in a monoclinic system in the centrosymmetric P2(1)/m space group (No.11) with a = 5.4128(10) ?, b = 8.1739(14) ?, c = 7.5436(17) ?, and β = 94.599(18)°, adopting a unique structure type (100 K data). There are two types of fluorosulfate anions in the structure; in one type the F atom is engaged in chemical bonding to Ag(I) and in the other type the F atom is terminal; accordingly, two resonances are seen in the (19)F NMR spectrum of AgSO(3)F. Theoretical analysis of the electronic band structure and electronic density of states, as well as assignment of the mid- and far-infrared absorption and Raman scattering spectra for both compounds, have been performed based on the periodic DFT calculations. AgSO(3)F exhibits an unusually low melting temperature of 156 °C and anomalously low value of melting heat (ca. 1 kJ mol(-1)), which we associate with (i) disorder of its anionic sublattice and (ii) the presence of 2D sheets in the crystal structure, which are weakly bonded with each other via long Ag-O(F) contacts. AgSO(3)F decomposes thermally above 250 °C, yielding mostly Ag(2)SO(4) and liberating SO(2)F(2). AgOTf is much more thermally stable than AgSO(3)F; it undergoes two consecutive crystallographic phase transitions at 284 °C and 326 °C followed by melting at 383 °C; its thermal decomposition commences above 400 °C leading at 500 °C to crystalline Ag(2)SO(4) and an unidentified phase as major products of decomposition in the solid state.