Novel binding of beryllium to dicarboxyimidazole-based model compounds and polymers

The ligand 4,5-dicarboxyimidazole (H(2)DCI) and its methyl derivative 1-methyl-4,5-dicarboxyimidazole (H(2)MDCI) have been shown to bind to Be(II) forming a zwitterionic species that has been structurally characterized. A new dicarboxyimidazole-based polymer has been prepared and its Be-binding properties have been studied using NMR ((1)H and (9)Be) and fluorescence spectroscopy; it represents a rare example of beryllium binding to a polymer. Models of the mononuclear and polymeric Be(II)-binding sites have been studied using density functional theory (DFT), and the (9)Be NMR chemical shifts of these model materials have been calculated for the purpose of direct comparison to experimentally observed values. Differences in the binding modes of the mononuclear and polymeric species are discussed.     

On some contact problems for composite half-spaces PMM vol. 31, no. 6, 1967, pp. 1001–1008

Solutions are presented herein of some contact problems connected with the torsion of a composite half-space. In the general case the problem of the torsion of a composite elastic half-space is examined by means of the rotation of a stiff finite cylinder welded into a vertical recess of this half-space. Moreover, the following particular problems on the torsion of such a half-space are considered.

1. 1) A composite half-space with a vertical elastic infinite core, twisted by means of the rotation of a stiff stamp affixed to the upper endplate of the elastic core.

2. 2) A half-space with a vertical cylindrical infinite hole, twisted by means of the rotation of a stiff finite cylinder welded into the upper part of this hole.

In the general case the solution of the problem reduces to the solution of an integral equation of the second kind on a half-line. The question of the solvability of this fundamental integral equation is investigated, and it is shown that its solution may be constructed by successive approximations.

Let us note that the problem of the torsion of a homogeneous half space and of an elastic layer by means of rotation of a stiff stamp has been considered by Rostovtsev [1], Reissner and Sagoci [2], Ufliand [3], Florence [4], Grilitskii [5] and others.

The problem of the torsion of a circular cylindrical rod and the half-space welded to it which are subject to a torque applied to the free endface of the rod has been considered by Grilitskii and Kizyma[6].

The torsion of an elastic half-space with a vertical cylindrical inclusion of some other material by the rotation of a stiff stamp on the surface of this half-space has been considered in [7], wherein it has been assumed that the stamp is symmetrically disposed relative to the axis of the inclusion and lies simultaneously on both materials.     

Crystal Structures of Hydrochlorides of 2,3-Pentamethylene-3, 4-dihydroquinazolin-4-one

The crystal structures of hydrate (1) and anhydrate (2) forms of 2,3-pentamethylene-3,4-dihydroquinazolin-4-one hydrochloride have been determined by X-ray structure analysis. Crystal data of 1 are 2(C₁₃H₁₄N₂O)*3(HCl)*4.5 (H₂O), triclinic P?1, Z=2, a=8.004(5), b=13.129(7), c=15.725(7) Å, α=106.45(4), β=92.61(4), γ=97.98(5), R=0.0652 and 2 are C₁₃H₁₄N₂O*HCl, monoclinic C2/c, Z=8, a=21.360(4), b=5.954(1), c=21.263(4), β=117.89(3), R=0.0556. The crystal of the hydrate form 1is unstable. This form collapses easily with evaporation of H₂O and part of HCl molecules from crystals. By recrystallizing destroyed form has been obtained stable crystal form 2.     

The design and synthesis of porphyrin/oligiothiophene hybrid monomers

In an effort to build effective photovoltaic cells based on porphyrin-functionalised polythiophenes we have focused on synthetic routes to three monomer types. By controlling the geometric structure of the monomer, oxidation of these materials should produce polymers with different architectural structures, and as a result, different opto-electronic properties. Employing Wittig protocols allowed access to monomers in which the porphyrin moiety is connected to the beta-position of the thiophene via an alkene linkage. In addition, monomers were constructed using porphyrin condensation methods to afford alpha-thiophene meso-substituted porphryins. Another set of monomers was also prepared via porphyrin condensation routes, but instead utilising beta-formylthiophenes. By utilising different formyloligothiophenes we were able to generate a series of monomers that can be used to control the loading of the porphyrin in the polythiophene matrix.     

Thermal stereomutations and stereochemically elucidated [1,3]-carbon sigmatropic shifts of 1-(E)-propenyl-2-methylcyclobutanes giving 3,4-dimethylcyclohexenes

The thermal stereomutations and [1,3] carbon sigmatropic shifts shown by (+)-(1S,2S)-trans-1-(E)-propenyl-2-methylcyclobutane and by (-)-(1S,2R)-cis-1-(E)-propenyl-2-methylcyclobutane in the gas phase at 275 degrees C leading to 3,4-dimethylcyclohexenes have been followed. The reaction-time-dependent data for concentrations and enantiomeric excess values for substrates and [1,3] shift products have been deconvoluted to afford rate constants for the discrete isomerization processes. Both trans and cis substrates react through four stereochemically distinct [1,3] carbon shift paths. For one enantiomer of the trans reactant the relative rate constants are k(si) = 58%, k(ar) = 5%, k(sr) = 33%, and k(ai) = 4%. For a single enantiomer of the cis reactant, k'(si) = 18%, k'(ar) = 11%, k'(sr) = 51%, and k'(ai) = 20%. A trans starting material reacts through orbital symmetry allowed suprafacial,inversion and antarafacial,retention paths to give trans-3,4-dimethylcyclohexenes 63% of the time. A cis isomer reacts to give the more stable trans-3,4-dimethylcyclohexenes through orbital symmetry-forbidden suprafacial,retention and antarafacial,inversionpaths 71% of the time. The [1,3] carbon sigmatropic shifts are not controlled by orbital symmetry constraints. They seem more plausible rationalized as proceeding through diradical intermediates having some conformational flexibility after formation and before encountering an exit channel. The distribution of stereochemical outcomes may well be conditioned by dynamic effects. The thermal stereomutations of the 1-(E)-propenyl-2-methylcyclobutanes take place primarily through one-center epimerizations. For the trans substrate, the relative importance of the three distinction rate constants are k(2) = 48%, k(1) = 34%, and k(12) = 18%. For the cis isomer, k'(2) = 44%, k'(1) = 32%, and k'(12) = 24%. These patterns are reminiscent of ones determined for stereomutations in 1,2-disubstitued cyclopropanes.