Hydrated electron: Nonempirical cluster approach

Interface water anions composed of several chainlike or cyclic fragments were simulated with a 6‐31++G** basis set at the unrestricted Hartree–Fock level with the second‐order Moeller–Plesset perturbation theory corrections taken into account. The estimated vertical electron detachment energies (VDEs) of (H₂O) anions were approximated by a VDE‐n^?1/3 dependence close to the experimental one. A hypothesis about the predominant formation of interface structures under conditions of molecular flows is put forward. The atomic population analysis, character of the highest occupied molecular orbital, and changes in the geometry of interface anions with an increase in their molecular size reveal the compact localization of the excess electron density in water clusters and allow evaluating the effective excess‐electron radius of condensed water as 2.5 Å, in good agreement with a similar empirical estimate. The scope of the data obtained shows the relatively low probability of the formation of octahedral hydration shells compared to the tetrahedral coordination of solvating water molecules. © 2002 Wiley Periodicals, Inc. Int J Quantum Chem, 2002     

Molecular Recognition and Catalysis: from Macrocyclic Receptors to Molecularly Imprinted Metal Complexes

Summary: The results of studying a number of reactions catalyzed by several types of soluble macromolecular catalytic systems capable of selectively binding organic substrates, namely, modified cyclodextrins, calixarenes and dendrimers are presented. The use of modified cyclodextrins as components of a catalytic system in the phenol and benzene hydroxylation by hydrogen peroxide allows one both to increase the catalytic activity and to change significantly the chemical selectivity. Phosphorilated calixarene – Rh catalytic systems was found to be catalytically active in hydroformylation of linear alkenes C₇–C₁₂. The results of experiments on the oxidation of C₇–C₁₆ alkenes show that, when the ligand is the dendrimer molecule, the fraction of forming methyl ketones substantially increases for the substrates C₇–C₉. For the higher alkenes, this effect is not observed.     

Unusual spiral structures formed by glycated β-casein in the presence of thioflavin T: amyloid transformation?

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Monomer sequencing and microstructural analysis on polymers of dimethyl norbornene dicarboxylate and 7‐oxanorbornene dicarboxylic derivatives employing ruthenium catalysts by ring‐opening metathesis polymerization

The physiochemical properties, comonomer sequencing, and regiospecificity of the linkages between monomeric units within homo/copolymers based on 5,6‐di‐substituted norbornene and 7‐oxanorbornene type monomers by ring‐opening metathesis polymerization are reported and correlated to their primary and secondary structural elements. In general, first‐generation Grubbs‐ I1 ruthenium catalyst generates polymers with high trans content that exhibits an extended secondary structure with exo,exo substituents, whereas second‐generation Grubbs‐ I2 catalyst produces polymers with high cis content that forms tight turns, resulting in a compact structure. Furthermore, I2 ‐produced polymers exhibit a high level of alternating cis–trans double bonds along their polymeric backbone. In stark contrast, both first‐ and second‐generation Grubbs catalysts display complete reversal in cis/trans selectivity when an oxygen atom is in position‐7 of the norbornene‐ring along with mono‐endo‐substitution in position‐5 or 6, and hence highlighting the importance of stereoelectronic complexation by the catalyst with the next incoming monomer for cis/trans selectivity. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 2477–2501     

Short range order in anomalous liquid metals

Liquid metals with anomalous physical properties such as increasing sound velocity with temperature or density anomalies, exhibit a complex structure in their one dimensional experimental diffraction patterns. Typically, their radial distribution functions are characterized by an asymmetric first peak and a subsidiary peak or shoulder on the right hand side of the first main peak. It has been hypothesized that the complex structure is associated with short range ordering the liquid. Specifically in the liquid pnictides, it has been proposed that such order may be associated with the underlying solid A7 structure. We present an analysis of the short range order in liquids using a modified quasi-crystalline model of liquid structure. This model is shown to fit the experimental radial distribution function very well and to reproduce the experimentally observed structure factor. Using this model we find that the short range order in the liquid pnictides is dominated by an A7-like structure with two types of bonds, in close agreement with the underlying solid phase. The existence of two bond lengths is necessary within this model to explain the asymmetry in the first peak as well as the change in coordination number along the pnictide series. The quasi-crystalline model is discussed and shown to correlate with the Lindemann melting criterion.