Stabilization of a helical water chain in a metal-organic host of a trinuclear Schiff base complex

Three heterometallic trinuclear Schiff base complexes, [{GuL(1)(H2O)}(2)Ni(CN)(4)]center dot 4H(2)O (1), [{CuL2(H2O)}(2)Ni(CN)(4)] (2), and [{CuL3(H2O)}(2)Ni(CN)(4)] (3) (HL1 = 7-amino-4-methyl-5-azahept-3-en-2-one, HL2 = 7-methylamino-4-methyl-5-azahept-3-en-2-one, and HL3 = 7-dimethylamino-4-methyl-5-azahept-3-en-2-one), were synthesized. All three complexes were characterized by elemental analysis, IR and UV spectroscopies, and thermal analysis. Two of them (1 and 3) were also characterized by single crystal X-ray crystallography. Complex 1 forms a hydrogen-bonded one-dimensional metal-organic framework that stabilizes a helical water chain into its cavity, but when any of the amine hydrogen atoms of the Schiff base are replaced by methyl groups, as in L 2 and L 3, the water chain, vanishes, showing explicitly the importance of the host-guest H-bonding interactions for the stabilization of a water cluster.

Stabilization of two smallest possible diastereomeric beta-hairpins in a water soluble tetrapeptide containing non-coded alpha-amino isobutyric acid (Aib) and m-amino benzoic acid

Single crystal X-ray diffraction study reveals that the water soluble tetrapeptide H2N-Ile-Aib-Leu-m-ABA-CO2H, containing non-coded Aib (alpha-amino isobutyric acid) and m-ABA (meta-amino benzoic acid), crystallizes with two smallest possible diastereomeric beta-hairpin molecules in the asymmetric unit. Although in both of the molecules the chiralities at Ile(1) and Leu(3) are S, a conformational reversal in the back bone chain is observed to produce the beta-hairpins with beta-turn conformations of type II and II'. Interestingly Aib which is known to adopt helical conformation, adopts unusual semi-extended conformation with phi: -49.5(5)degrees, psi: 135.2(5)degrees in type II and phi: 50.6(6)degrees. psi: -137.0(4)degrees in type II' for occupying the i + 1 position of the beta-turns. The two hairpin molecules are further interlocked through intermolecular hydrogen bonds and electrostatic interactions between CO2- and -+NH3 groups to form dimeric supramolecular beta-hairpin aggregate in the crystal state. The CD measurement and 2D NMR study of the peptide in aqueous medium support the existence of beta-hairpin structure in water. (C) 2009 Elsevier B.V. All rights reserved.

Hydrogen-bond assisted stabilization of the less favored conformation of a tridentate Schiff base ligand in dinuclear nickel(II) complex: an experimental and theoretical study

The Schiff base ligand, HL (2-[1-(3-methylamino-propylimino)-ethyl]-phenol), the 1:1 condensation product of 2-hydroxy acetophenone and N-methyl-1,3-diaminopropane, has been synthesized and characterized by X-ray crystallography as the perchlorate salt [H2L]ClO4 (1). The structure consists of discrete [H2L](+) cations and perchlorate anions. Two dinuclear Ni-II complexes, [Ni2L2(NO2)(2)] (2), [Ni2L2(NO3)(2)] (3) have been synthesized using this ligand and characterized by single crystal X-ray analyses. Complexes 2 and 3 are centrosymmetric dimers in which the Ni-II ions are in distorted fac- and mer-octahedral environments, respectively, bridged by two mu(2)-phenolate ions of deprotonated ligand, L. The plane of the phenyl rings and the Ni2O2 basal plane are nearly coplanar in 2 but almost perpendicular in 3. We have studied and explained this different behavior using high level DFT calculations (RI-BP86/def2-TZVP level of theory). The conformation observed in 3, which is energetically less favorable, is stabilized via intermolecular non-covalent interactions. Under the excitation of ultraviolet light, characteristic fluorescence of compound 1 was observed; by comparison fluorescence intensity decreases in case of compound 3 and completely quenched in compound 2.

Stabilization of multi-stranded nucleic acid structures using 3'-S-phosphorothiolate linkages

3 '-S-Phosphorothiolate linkages incorporated into an oligodeoxynucleotide have been shown to stabilise duplex formation with a complementary RNA strand, but destabilise a duplex formed with a complementary DNA strand. The four-stranded i-motif structure is also stabilised this modification.

RuII(α-diimine) or RuIII(α-diimine·–)? Structural, spectroscopic, and theoretical evidence for the stabilization of a prominent metal-to-Ligand charge- transfer excited-state configuration in the ground state

The new compounds [Ru(R-DAB)(acac)2] (R-DAB = 1,4-diorganyl- 1,4-diazabuta-1,3-diene; R = tert-butyl, 4-methoxyphenyl, 2,6-dimethylphenyl; acac– = 2,4-pentanedionate) exhibit intrachelate ring bond lengths 1.297

Stabilization of the i-motif structure by the intra-strand cross-link formation

The i-motif structures are formed by oligonucleotides containing cytosine tracts under acidic conditions. The folding of the i-motif under physiological conditions is of great interest because of its biological role. In this study, we investigated the effect of the intra-strand cross-link on the stability of the i-motif structure. The 4-vinyl-substituted analog of thymidine (T-vinyl) was incorporated into the 5′-end of the human telomere complementary strand, which formed the intra-strand cross-link with the internal adenine. The intra-strand cross-linked i-motif displayed CD spectra similar to that of the natural i-motif at acidic pH, which was transformed into a random coil with the increasing pH. The pH midpoint for the transition from the i-motif to random coil increased from pH 6.1 for the natural one to pH 6.8 for the cross-linked one. The thermodynamic parameters were obtained by measuring the thermal melting behaviors by CD and UV, and it was determined that the intra-strand cross-linked i-motif is stabilized due to a favorable entropy effect. Thus, this study has clearly indicated the validity of the intra-strand cross-linking for stabilization of the i-motif structure.

Hydrogen-bonded interpolymer complexes. Formation, structure and applications

Noncovalent interactions play key roles in many natural processes leading to the self-assembly of molecules with the formation of supramolecular structures. One of the most important forces responsible for self-assembly is hydrogen bonding, which also plays an important role in the self-assembly of synthetic polymers in aqueous solutions. Proton-accepting polymers can associate with proton-donating polymers via hydrogen bonding in aqueous solutions and form polymer-polymer or interpolymer complexes. There has been an increased interest among researchers in hydrogen-bonded interpolymer complexes since the first pioneering papers were published in the early 1960s. Several hundred research papers have been published on various aspects of complex formation reactions in solutions and interfaces, properties of interpolymer complexes and their potential applications. This book focuses on the latest developments in the area of interpolymer complexation via hydrogen bonding. It represents a collection of original and review articles written by recognized experts from Germany, Greece, Kazakhstan, Poland, Romania, Russia, UK, Ukraine, and the USA. It highlights many important applications of interpolymer complexes, including the stabilization of colloidal systems, pharmaceuticals, and nanomaterials.

The analysis of ranked observations of soil structure using indicator geostatistics

Structure is an important physical feature of the soil that is associated with water movement, the soil atmosphere, microorganism activity and nutrient uptake. A soil without any obvious organisation of its components is known as apedal and this state can have marked effects on several soil processes. Accurate maps of topsoil and subsoil structure are desirable for a wide range of models that aim to predict erosion, solute transport, or flow of water through the soil. Also such maps would be useful to precision farmers when deciding how to apply nutrients and pesticides in a site-specific way, and to target subsoiling and soil structure stabilization procedures. Typically, soil structure is inferred from bulk density or penetrometer resistance measurements and more recently from soil resistivity and conductivity surveys. To measure the former is both time-consuming and costly, whereas observations made by the latter methods can be made automatically and swiftly using a vehicle-mounted penetrometer or resistivity and conductivity sensors. The results of each of these methods, however, are affected by other soil properties, in particular moisture content at the time of sampling, texture, and the presence of stones. Traditional methods of observing soil structure identify the type of ped and its degree of development. Methods of ranking such observations from good to poor for different soil textures have been developed. Indicator variograms can be computed for each category or rank of structure and these can be summed to give the sum of indicator variograms (SIV). Observations of the topsoil and subsoil structure were made at four field sites where the soil had developed on different parent materials. The observations were ranked by four methods and indicator and the sum of indicator variograms were computed and modelled for each method of ranking. The individual indicators were then kriged with the parameters of the appropriate indicator variogram model to map the probability of encountering soil with the structure represented by that indicator. The model parameters of the SIVs for each ranking system were used with the data to krige the soil structure classes, and the results are compared with those for the individual indicators. The relations between maps of soil structure and selected wavebands from aerial photographs are examined as basis for planning surveys of soil structure. (C) 2007 Elsevier B.V. All rights reserved.

Orographic precipitation in the tropics: large-eddy simulations and theory

Recent radar and rain-gauge observations from the island of Dominica, which lies in the eastern Caribbean sea at 15 N, show a strong orographic enhancement of trade-wind precipitation. The mechanisms behind this enhancement are investigated using idealized large-eddy simulations with a realistic representation of the shallow trade-wind cumuli over the open ocean upstream of the island. The dominant mechanism is found to be the rapid growth of convection by the bulk lifting of the inhomogenous impinging flow. When rapidly lifted by the terrain, existing clouds and other moist parcels gain buoyancy relative to rising dry air because of their different adiabatic lapse rates. The resulting energetic, closely-packed convection forms precipitation readily and brings frequent heavy showers to the high terrain. Despite this strong precipitation enhancement, only a small fraction (1%) of the impinging moisture flux is lost over the island. However, an extensive rain shadow forms to the lee of Dominica due to the convective stabilization, forced descent, and wave breaking. A linear model is developed to explain the convective enhancement over the steep terrain.

Ruthenium complexes of C,C '-bis(ethynyl)carboranes: an investigation of electronic interactions mediated by spherical pseudo-aromatic spacers

The complexes [Ru(1-C=C-1,10-C2B8H9)(dppe)Cp*] (3a), [Ru(1-C C-1,12-C2B10H11)(dppe)-Cp*] (3b), [{Ru(dppe)Cp*}(2){mu-1,10-(C C)(2)-1,10-C2B8H8}] (4a) and [{Ru(dppe)Cp*}(2){mu-1,12-(C C)2- 1,12-C2B10-H-10}] (4b), which form a representative series of mono- and bimetallic acetylide complexes featuring 10- and 12-vertex carboranes embedded within the dethynyl bridging ligand, have been prepared and structurally characterized. In addition, these compounds have been examined spectroscopically (UV-is-NIR, IR) in all accessible redox states. The significant separation of the two, one-electron anodic waves observed in the cyclic voltammograms of the bimetallic complexes 4a and 4b is largely independent of the nature of the electrolyte and is attributed to stabilization of the intermediate redox products [4a](+) and [4b](+) through interactions between the metal centers across a distance of ca. 12.5 angstrom. The mono-oxidized bimetallic complexes (4a](+) and [4b](+) exhibit spectroscopic properties consistent with a description of these species in terms of valence-localized (class II) mixed-valence compounds, including a unique low-energy electronic absorption band, attributed to an, IVCT-type transition that tails into the IR region. DFT calculations with model systems [4a-H](+) and [4b-H](+) featuring simplified ligand sets reproduce the observed spectroscopic data and localized electronic structures for the mixed-valence cations [4a](+) and [4b](+).

Modifying the adsorption characteristics of water on Ru{0001} with preadsorbed oxygen

The coadsorption of water and preadsorbed oxygen on Ru{0001) was studied by synchrotron-based high-resolution x-ray photoelectron spectroscopy. A dramatic change was observed in the interaction of water with oxygen between low and high oxygen precoverages. Low oxygen coverages below 0.18 ML induce partial dissociation, which leads to an adsorbed layer of H2O and OH. Around half the oxygen atoms take part in this reaction. All OH recombines upon heating to 200 K and desorbs together with H2O. Oxygen coverages between 0.20 and 0.50 ML inhibit dissociation, instead a highly stable intact water species is observed, which desorbs at 220 K. This species is significantly more stable than intact water on the clean surface. The stabilization is most likely due to the formation of hydrogen bonds with neighboring oxygen atoms. For intermediate oxygen coverages around 0.18 ML, the dissociation behavior depends on the preparation conditions, which points toward possible mechanisms and pathways for partial dissociation of water on Ru{0001}.