Functionalized nanodiamonds part I. An experimental assessment of diamantane and computational predictions for higher diamondoids

The structures, strain energies, and enthalpies of formation of diamantane 1, triamantane 2, isomeric tetramantanes 3-5, T(d)-pentamantane 6, and D(3d)-hexamantane 7, and the structures of their respective radicals, cations, as well as radical cations, were computed at the B3LYP/6-31G* level of theory. For the most symmetrical hydrocarbons, the relative strain (per carbon atom) decreases from the lower to the higher diamondoids. The relative stabilities of isomeric diamondoidyl radicals vary only within small limits, while the stabilities of the diamondoidyl cations increase with cage size and depend strongly on the geometric position of the charge. Positive charge located close to the geometrical center of the molecule is stabilized by 2-5 kcal mol(-1). In contrast, diamondoid radical cations preferentially form highly delocalized structures with elongated peripheral C-H bonds. The effective spin/charge delocalization lowers the ionization potentials of diamondoids significantly (down to 176.9 kcal mol(-1) for 7). The reactivity of 1 was extensively studied experimentally. Whereas reactions with carbon-centered radicals (Hal)(3)C(*) (Hal=halogen) lead to mixtures of all possible tertiary and secondary halodiamantanes, uncharged electrophiles (dimethyldioxirane, m-chloroperbenzoic acid, and CrO(2)Cl(2)) give much higher tertiary versus secondary selectivities. Medial bridgehead substitution dominates in the reactions with strong electrophiles (Br(2), 100 % HNO(3)), whereas with strong single-electron transfer (SET) acceptors (photoexcited 1,2,4,5-tetracyanobenzene) apical C(4)-H bridgehead substitution is preferred. For diamondoids that form well-defined radical cations (such as 1 and 4-7), exceptionally high selectivities are expected upon oxidation with outer-sphere SET reagents.     

Sulfonated and sulfoacylated poly(styrene-divinylbenzene) copolymers as packing materials for cation chromatography

Three different types of cation exchangers were produced from four basic poly(styrene-divinylbenzene) substrates with different properties. Porous PS-DVB resin beads were functionalized by sulfonation and sulfoacylation under various conditions to produce sulfonated resins with exchange capacities of 0.03-1.80 mM g(-1). The matrix with 50% of cross-linking is most suitable for updating by the proposed technique. Sulfuric and chlorosulfonic acids were used as the reagents for sulfonation. The sulfonating conditions, capacities, and the technique of the synthesis are given. The effects of parameters of the sulfonation reaction and the composition of the reactionary mixture on ion-exchange capacity of the sorbents were investigated. Selectivity and efficiency of the separation of some inorganic cations and derivatives of amines and hydrazines on the resins obtained are compared by ion chromatography with conductometric detection. As a result, the sulfoacylated resin was proved more efficient for the separation of these analytes. The resolution of the analytes strongly depends on the degree of functionalization. The best performance about 19,000 plates m(-1) was obtained using the sulfopropionylated beads with an ion-exchange capacity of 0.3 mM g(-1). The prepared sulfoacylated cation exchanger was compared with the commercially available Dionex CS-12 packing material. It was found that the separation of alkaline ions and 1,1-dimethylhydrazine (UDMH) were much better that those for the commercial material.     

Single-molecule magnets constructed from cyanometalates: {[Tp*Fe(III)(CN)3M(II)(DMF)4]2[OTf]2} x 2DMF (M(II) = Co, Ni)

Treatment of several divalent transition-metal trifluoromethanesulfonates [M(II)(OTf)2; M(II) = Mn, Co, Ni] with [NEt4][Tp*Fe(III)(CN)3] [Tp* = hydridotris(3,5-dimethylpyrazol-1-yl)borate] in DMF affords three isostructural rectangular clusters of {[Tp*Fe(III)(CN)3M(II)(DMF)4]2[OTf]2} x 2DMF (M(II) = Mn, 3; Co, 4; Ni, 5) stoichiometry. Magnetic studies of 3-5 indicate that the Tp*Fe(CN)3(-) centers are highly anisotropic and exhibit antiferromagnetic (3 and 4) and ferromagnetic (5) exchange to afford S = 4, 2, and 3 spin ground states, respectively. ac susceptibility measurements suggest that 4 and 5 exhibit incipient single-molecule magnetic behavior below 2 K.     

Long-range correlations in the structure of fractal films

Hierarchically granulated films formed on a material subjected to the action of a high-temperature plasma have been microscopically studied. The statistical self-similarity of the structure of the surface from nanoscale to macroscale, as well as long-range correlations in the relief that are due to the statistically inhomogeneous structure of granularity, has been revealed.     

Towards stabilization of the potential response of Mn(III) tetraphenylporphyrin-based solid-state electrodes with selectivity for salicylate ions

Journal of Solid State Electrochemistry - We report a new type of solid-state electrode (type I) of a simple design with polyvinyl chloride membranes based on Mn(III) tetraphenylporphyrin and with...     

Thermalization of the flow of sputtered target atoms during ion-plasma deposition of films

The boundary of the zone in which sputtered atoms are thermalized in the substrate–target drift space during the ion-plasma magnetron deposition of films is determined theoretically and experimentally. A comparison of the thicknesses of films deposited on the front and back sides of substrates situated at different distances from the target makes it possible to divide the flow of atoms sputtered toward substrates into direct and diffusion flows and to determine the dimensions of the spatial zone in which sputtered atoms are thermalized. The experimental data are in quantitative agreement with the results of a statistical simulation of the thermalization process of atomic particles during the ion-plasma deposition. This simulation enables optimization of the technology of defect-free growth of films with uniform thickness on substrates with complex 3D configuration.     

Synthesis of chlorophyll a glycoconjugates using olefin cross-metathesis

Chlorophyll a glycoconjugates were obtained by cross-metathesis between olefin moieties of chlorophyll derivatives and allylβ-galactopyranoside tetraacetate.     

Phase Transition,Ordering and Lateral Diffusion in Phospholipid Bilayers in the Presence of Poly(Ethylene Oxide)

The thermal behaviour, molecular orientation and lateral diffusion in the bilayered systems of dimyristoylphosphatidylcholine (DMPC) in the presence of poly(ethylene oxide) (PEO) were studied by NMR and DSC techniques, and it was found that PEO decreases the melting temperature (of vesicles and flat multibilayers) and affects the degree of orientation of DMPC molecules relative to the bilayer normal, but it does not influence the lateral diffusion of DMPC molecules.