Photoredox chemistry of AOT: electron transfer and hydrogen abstraction in microemulsions involving the surfactant

Time-resolved magnetic resonance experiments (TREPR and CIDNP) are used to investigate previously unobserved redox chemistry of the surfactant dioctyl sulfosuccinate ester (AOT) using the photoexcited triplet state of anthraquinone 2,6-disulfonate (3AQDS*). Several different free radicals resulting from two independent oxidation pathways (electron transfer and hydrogen abstraction) are observed. These include the radical ions of AQDS and sulfite from electron-transfer processes, carbon-centered radicals from H-atom abstraction reactions, and an additional carbon-centered radical formed by electron transfer from the AOT sulfonate head group followed by the loss of SO3. The radicals exhibit intense chemically induced dynamic electron spin polarization (CIDEP) in their TREPR spectra. The intensity ratios of the observed TREPR signals for each radical depend on the water pool size and temperature, which in turn affect the predominant CIDEP mechanism. All signal carriers are accounted for by simulation, and CIDNP results provide strong supporting evidence for the assignments.     

Harsanyi power solutions for graph-restricted games

We consider cooperative transferable utility games, or simply TU-games, with limited communication structure in which players can cooperate if and only if they are connected in the communication graph. Solutions for such graph games can be obtained by applying standard solutions to a modified or restricted game that takes account of the cooperation restrictions. We discuss Harsanyi solutions which distribute dividends such that the dividend shares of players in a coalition are based on power measures for nodes in corresponding communication graphs. We provide axiomatic characterizations of the Harsanyi power solutions on the class of cycle-free graph games and on the class of all graph games. Special attention is given to the Harsanyi degree solution which equals the Shapley value on the class of complete graph games and equals the position value on the class of cycle-free graph games. The Myerson value is the Harsanyi power solution that is based on the equal power measure. Finally, various applications are discussed.     

Ditopic complexes of silene H2SiCH2 with bidentate ligands Me2NCH2SiHnF3-n. Structures, formation energies, AIM and ELF analyses.

Ditopic complex formation of silene H₂SiCH₂ with bidentate ligands Me₂NCH₂SiH_nF_3-n (n = 0-3) was studied at the MP4(SDQ(T)6-311G(d,p))//MP2/6-31G(d,p) levels of theory. The AIM and ELF analyses have shown that π-bonding in the silenic Si¹C moiety in the relatively weak (H₂Si¹CH₂)·(Me₂NCH₂Si²H_nF_3-n) (n = 2, 3) ditopic complexes is partially preserved.     

Porosity and surface properites of SBA-15 with grafted PNIPAAM: a water sorption calorimetry study

Mesoporous silica SBA-15 was modified in a three-step process to obtain a material with poly-N-isopropylacrylamide (PNIPAAM) grafted onto the inner pore surface. Water sorption calorimetry was implemented to characterize the materials obtained after each step regarding the porosity and surface properties. The modification process was carried out by (i) increasing the number of surface silanol groups, (ii) grafting 1-(trichlorosilyl)-2-(m-/p-(chloromethylphenyl) ethane, acting as an anchor for (iii) the polymerization of N-isopropylacrylamide. Water sorption isotherms and the enthalpy of hydration are presented. Pore size distributions were calculated on the basis of the water sorption isotherms by applying the BJH model. Complementary measurements with nitrogen sorption and small-angle X-ray diffraction are presented. The increase in the number of surface silanol groups occurs mainly in the intrawall pores, the anchor is mainly located in the intrawall pores, and the intrawall pore volume is absent after the surface grafting of PNIPAAM. Hence, PNIPAAM seals off the intrawall pores. Water sorption isotherms directly detect the presence of intrawall porosity. Pore size distributions can be calculated from the isotherms. Furthermore, the technique provides information regarding the hydration capability (i.e., wettability of different chemical surfaces) and thermodynamic information.     

Negative group velocity and three-wave mixing in dielectric crystals

We investigate extraordinary features of optical parametric amplification of Stokes electromagnetic waves that originate from the three-wave mixing of a backward phonon wave with negative group velocity and two ordinary electromagnetic waves. Such properties were earlier shown to exist only in plasmonic negative-index metamaterials that are very challenging to fabricate. Nonlinear optical photonic devices with properties similar to those predicted for negative-index metamaterials are proposed.     

Phosphorylated Calixarenes as Receptors of L-Amino Acids and Dipeptides: Calorimetric Determination of Gibbs Energy,Enthalpy and Entropy of Complexation

The metal cation binding ability of cone-p-tert-butylhexahomotrioxacalix[3]arene tris(acetic acid) was investigated by ¹H NMR and complementary semi-empirical calculations. NMR showed significant shifts with Na⁺, K⁺, Ag⁺ and, to a lesser extent, Pb²⁺. The macrocyclic protons undergoing the greatest shifts imply that these cations bind inside the cavity composed of the phenoxy and carbonyl oxygen atoms. Metal complexes were modelled using a semi-empirical approach and, in general, their geometry optimised structures were in agreement with NMR data. U-tube transport experiments demonstrated that the macrocycle actively transported Cr³⁺, Fe³⁺, Co²⁺ and Cu²⁺ through the organic phase.     

On Phosphorylation of Dihydric Phenols with Amines of Phosphoric and Phenylphosphonic Acids

Abstract

With the aim to create macrocyclic phosphorus-containing heterocycles (new phosphorus crown-ethers) and corresponding polyesters the interaction between dihydric phenols and complete anides of phosphoric and phenylphosphonic acids was studied. It was shown that, according to reaction conditions and reagents ratio, the resulting products can have a linear structure, with oligo- (A) or polymexic (B) molecules, and a macrocyclic structure (C) alike : phospho(III)arylene crown-ethers obtained for example by the consecutive assembling of planned macrocyclic systems or by the direct interaction.     

Complete systems of partial derivatives of entire functions and frequently hypercyclic operators

We find some sufficient conditions for a system of partial derivatives of an entire function to be complete in the space H(C^d)$H({\mathbb{C}}^d)$ of all entire functions of d   variables. As an application of this result we describe new classes of frequently hypercyclic operators on H(C^d)$H({\mathbb{C}}^d)$.     

Scheduling problems in transportation networks of line topology

In this paper we consider online scheduling problems for linear topology under various objective functions: minimizing the maximum completion time, minimizing the largest delay, and minimizing the sum of completion times. We give optimal solutions for uni-directional version of the problem for each of the objectives and show that for the two-directional versions of each problem, no online algorithm can deterministically achieve the optimal solution for any of the considered objective functions. We also propose 2-approximation on-line algorithms for the MinMakespan and the MinSum minimization objectives. We also prove that no online algorithm can deterministically achieve the optimal solution for any of the considered objective functions for the weighted case of uni-directional scenarios.     

Thienopyrazine or dithiadiazatrindene containing low band gap conjugated polymers for polymer solar cells

Four new low-band-gap alternating copolymers （P-1, P-2, P-3 and P-4） based on electron-rich benzodithiophene and newly developed electron-deficient units, thienopyrazine or dithiadiazatrindene derivatives, were synthesized by Stille polycondensation. All polymers exhibit good solubility in common organic solvents and a broad absorption band in the visible to near-infrared regions. The film optical band gaps of the polymers are in the range of 1.28-2.07 eV and the highest occupied molecular orbital （HOMO） energy levels are in the range of-4.99 eV to -5.28 eV. Bulk heterojunction polymer solar cells （PSCs） of the polymers were fabricated with phenyl-C61-butyric acid methyl ester （PC61BM） as acceptor material, and a power conversion efficiency of 0.80% was realized with P-1 as donor material.