Influence of connectivity and porosity on ligand-based luminescence in zinc metal-organic frameworks

Applications of metal-organic frameworks (MOFs) require close correlation between their structure and function. We describe the preparation and characterization of two zinc MOFs based on a flexible and emissive linker molecule, stilbene, which retains its luminescence within these solid materials. Reaction of trans-4,4'-stilbene dicarboxylic acid and zinc nitrate in N,N-dimethylformamide (DMF) yielded a dense 2-D network, 1, featuring zinc in both octahedral and tetrahedral coordination environments connected by trans-stilbene links. Similar reaction in N,N-diethylformamide (DEF) at higher temperatures resulted in a porous, 3-D framework structure, 2. This framework consists of two interpenetrating cubic lattices, each featuring basic zinc carboxylate vertices joined by trans-stilbene, analogous to the isoreticular MOF (IRMOF) series. We demonstrate that the optical properties of both 1 and 2 correlate with the local ligand environments observed in the crystal structures. Steady-state and time-resolved spectroscopic measurements reveal that the stilbene linkers in the dense structure 1 exhibit a small degree of interchromophore coupling. In contrast, the stilbenoid units in 2 display very little interaction in this low-density 3-D framework, with excitation and emission spectra characteristic of monomeric stilbenes, similar to the dicarboxylic acid in dilute solution. In both cases, the rigidity of the stilbene linker increases upon coordination to the inorganic units through inhibition of torsion about the central ethylene bond, resulting in luminescent crystals with increased emission lifetimes compared to solutions of trans-stilbene. The emission spectrum of 2 is found to depend on the nature of the incorporated solvent molecules, suggesting use of this or related materials in sensor applications.     

Structure Formation and Optical Activity of Cellulose Acetate Modified by the Vapors of Mesophasogenic Solvents

The effect of the vapors of mesophasogenic solvents, i.e., forming a lyotropic liquid-crystal phase with a polymer, on the structure formation and optical activity of acetate cellulose is studied. It is established that the action of vapors of such a type is accompanied by changes in the supramolecular structure of cellulose ester and spatial organization of macromolecules. Modification of a polymer by vapors of the mixtures of mesophasogenic solvents and water does not decrease (but in some cases enhances) the observed effects. As for individual solvents, the action of their mixtures with water obeys the dose–effect law, with a greater influence of small doses of absorbed vapors on the polymer structure and optical activity. The implementation of such conditions makes it possible to purposefully create different structures based on the same polymeric matrix and, thus, produce materials with improved properties and new functional potentialities.     

Varieties of Complete Pairs of Zero-Dimensional Subschemes of Lengths ≥2 and ≥4 in Algebraic Surfaces

We prove that the varieties of complete pairs of zero-dimensional subschemes of lengths d ₁ 2, d ₂ 4 on a smooth irreducible projective algebraic surface are singular.     

The electrical properties of schungite-containing compositions based on polypropylene and high-density polyethylene

Variations in the dc and ac conductivities of schungite-containing compositions based on polypropylene-high-density polyethylene (PP-PE) blends were studied depending on the composition of the polymeric blend, the volume concentration of the filler, and the order of the introduction of the composition components during the preparation of compositions. It was shown that the conductivities of the compositions could depend on the order of the introduction of the components. The structure of initial and schungite-containing PP-PE blends of different compositions was studied by atomic-force microscopy. It was shown that the structure of the compositions depended on the composition of the initial PP-PE blends and the order of the introduction of the components into schungite-filled PP-PE compositions.     

Photocatalytic properties and structure of chitosan-based porphyrin-containing systems

The photocatalytic activity of the disodium salt of substituted hematoporphyrin in a model reaction of tryptophan oxidation in the presence of chitosan with different molecular masses and a block copolymer of ethylene and propylene oxides (Pluronic F-127) is studied. It is shown that, in the presence of the Pluronic, the catalytic activity of the chitosan-porphyrin system increases. The structure of chitosan-Pluronic systems, depending on the molecular mass of chitosan and the presence of porphyrin, is examined by AFM. A pleasible mechanism of the influence of the Pluronic on the photocatalytic activity of chitosan-por-phyrin systems is proposed.