Nanostructured Ion-Selective MCM-48 Membranes

Templated MCM-48 silica was prepared using CTAB as surfactant. The MCM-48 powders and thin films were characterized by different techniques. MCM-48 layers were deposited on macroporous α-alumina supports and silicon nitride microsieves. The water permeability of MCM-48 was compared with the permeability of conventional mesoporous γ-alumina membranes. The applicability of MCM-48 as ion-selective electric field-driven switchable interconnect for microfluidic devices was demonstrated.     

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Analysis of spin states, spin barriers, and trans-effects involved in the coordination and stabilization of dinitrogen by biomimetic iron complexes

Coordination of dinitrogen to Sellmann-type iron (II) complexes in a sulfur-dominated coordination sphere, which emulates the environment of iron centers in the FeMo-cofactor of nitrogenase, is analyzed with respect to spin states, spin barriers, and the effect of trans-ligands. Such detailed investigations became only recently feasible when the reliability of density functional methods, which are the only quantum chemical methods capable of describing large transition metal complexes, could significantly be improved for the calculation of energies for states of different spin. It is found that the actual binding energy of dinitrogen is of sufficient magnitude for a reasonably strong fixation of N₂ by Sellmann-type coordination compounds. However, potential fixation is determined by additional factors which reduce the binding energy. One factor is the change in spin state of the N₂-free metal fragment, which lowers the total energy and quenches the thermodynamic stabilization effect of the binding energy. In addition, the metal fragment rearranges and gains even more stabilization energy for the un-coordinated state. Apart from these thermodynamical effects, the existence of spin barriers, which must be overcome upon binding of dinitrogen, leads to kinetical effects, which cannot be neglected.     

Ab initio calculation of the NH(3sigma-)-NH(3sigma-) interaction potentials in the quintet, triplet, and singlet states

We present the ab initio potential-energy surfaces of the NH-NH complex that correlate with two NH molecules in their 3sigma- electronic ground state. Three distinct potential-energy surfaces, split by exchange interactions, correspond to the coupling of the S(A) = 1 and S(B) = 1 electronic spins of the monomers to dimer states with S = 0, 1, and 2. Exploratory calculations on the quintet (S = 2), triplet (S = 1), and singlet (S = 0) states and their exchange splittings were performed with the valence bond self-consistent-field method that explicitly accounts for the nonorthogonality of the orbitals on different monomers. The potential surface of the quintet state, which can be described by a single Slater determinant reference function, was calculated at the coupled cluster level with single and double excitations and noniterative treatment of the triples. The triplet and singlet states require multiconfiguration reference wave functions and the exchange splittings between the three potential surfaces were calculated with the complete active space self-consistent-field method supplemented with perturbative configuration interaction calculations of second and third orders. Full potential-energy surfaces were computed as a function of the four intermolecular Jacobi coordinates, with an aug-cc-pVTZ basis on the N and H atoms and bond functions at the midpoint of the intermolecular vector R. An analytical representation of these potentials was given by expanding their dependence on the molecular orientations in coupled spherical harmonics, and representing the dependence of the expansion coefficients on the intermolecular distance R by the reproducing kernel Hilbert space method. The quintet surface has a van der Waals minimum of depth D(e) = 675 cm(-1) at R(e) = 6.6a0 for a linear geometry with the two NH electric dipoles aligned. The singlet and triplet surfaces show similar, slightly deeper, van der Waals wells, but when R is decreased the weakly bound NH dimer with S = 0 and S = 1 converts into the chemically bound N2H2 diimide (also called diazene) molecule with only a small energy barrier to overcome.     

Highly efficient recycling of a "sandwich" type polyoxometalate oxidation catalyst using solvent resistant nanofiltration

A "sandwich" type polyoxometalate catalyst ([MeN(n-C8H17)3]12[WZn3(ZnW9O34)2]) was very efficiently recycled by nanofiltration with almost quantitative retention, using an alpha-alumina supported mesoporous gamma-alumina membrane.     

Conformational control in the cyclization of hydrogen-bonded supramolecular polymers

Bifunctional 2-ureido-4[1H]-pyrimidinone (UPy) derivatives can form small cyclic oligomers as well as long supramolecular polymers in chloroform solutions using the quadruple hydrogen-bonding motif. Ring-chain equilibria of a set of supramolecular monomers containing methyl-substituted alkyl linkers between the hydrogen-bonding UPy moieties were investigated by (1)H NMR spectroscopy and viscometry. The data were characterized in terms of critical concentration (CC, denoting the onset of polymerization) and equilibrium cyclic dimer concentration (EDC, representing preorganization of the monomer toward selective formation of cyclic dimer). Methyl substituents in the monomer were found to promote conformations favorable for cyclic dimerization, leading to an increase in both the EDC and the CC with respect to unsubstituted monomer. Furthermore, we observed an odd-even effect in the CC and EDC with increasing length of the linker between the hydrogen-bonding units. The combined results allow tuning of the critical concentration over a broad range and offer detailed information on the correlation between monomer structure, conformation, and polymerizability which may provide new insights for the study and design of other ring-chain equilibria or helix-random coil transitions.     

Thermodynamic Quantities and Defect Structure of La0.6Sr0.4Co1−yFeyO3−δ(y=0–0.6) from High-Temperature Coulometric Titration Experiments

The partial energies and entropies of O₂in perovskite-type oxides La_0.6Sr_0.4Co_1−yFe_yO_3−δ(y=0, 0.1, 0.25, 0.4, 0.6) were determined as a function of nonstoichiometryδby coulometric titration of oxygen in the temperature range 650–950°C. An absolute reference value ofδwas obtained by thermogravimetry in air. The nonstoichiometry at a given oxygen pressure and temperature decreases with iron contenty. At low nonstoichiometries the oxygen chemical potential decreases withδ. The observed behavior can be interpreted by assuming random distribution of oxygen vacancies, an electronic structure with both localized donor states on Fe, and a partially filled itinerant electron band, of which the density of states at the Fermi level scales with the Co content. The energy of the Fe states is close to the energy at the Fermi level in the conduction band. The observed trends of the thermodynamic quantities can be interpreted in terms of the itinerant electron model only when the iron content is small. At high values ofδthe chemical potential of O₂becomes constant, indicating partial decomposition of the perovskite phase. The maximum value ofδat which the compositions are single-phase increases with temperature.     

Comparison of the structural and chemical composition of giant T-even phage heads.

A study has been made of the structure of the capsids of T4D giant phage produced from mutants in gene 23 and temperature-sensitive mutants in gene 24, and T4D and T2L giant phage formed by the addition of L-canavanine followed by an Larginine chase in the growth medium. All the giant phage capsids have been shown to be built according to the same geometrical architecture. This consists of a near-hexagonal surface net, lattice constant 129.5 A, folded into a left-handed T = 13 prolate icosahedron elongated along one of its fivefold symmetry axes. Their only apparent difference from wild-type T-even phage capsids is their abnormally elongated tubular part. A comparison of the capsomere morphologies and protein compositions of the giant phage capsids showed that all T4D giants are identical but differ from T2L: The T4D capsomere has a complex (6 + 6 + 1)-type morphology, whereas the T2L has a simple 6-type. T2L phage, however, lack two capsid proteins, "soc" and "hoc", present in T4D. The difference in capsomere morphology can therefore be related to the difference in the protein compositions of these two phage. Possible differences between the initiation and means of length regulation of giant phage heads and the aberrant polyheads are discussed.