Defects and transport in SrFe1−xCoxO3−δ

The non-stoichiometry and chemical diffusion coefficient of SrFe_1−xCo_xO_3-δ have been measured by steady state and transient thermogravimetry in the temperature range 750–1200 °C at different oxygen partial pressures. At high oxygen partial pressures, the chemical diffusion coefficient was in the range 1·10⁻⁴ – 7·10⁻⁴ cm²/s. This, combined with high concentration of disordered vacancies make these materials perhaps the fastest solid oxygen ion diffusers known at high temperatures and high oxygen partial pressures. However, due to the high concentration of defects in SrFe_1−xCo_xO_3-δ the compound transforms from a cubic (disordered) perovskite to a brownmillerite type of structure under reduced oxygen partial pressures below approx. 900 °C. Due to this phase transition, the mobility of oxygen vacancies in SrFe_1−xCo_xO_3-δ decreases up to about an order of magnitude at 850 °C. We also observe an ordering effect at 1000 °C, although smaller in size, and this is suggested to be due to short range ordering of four-coordinated polyhedra of Fe. For possible use as oxygen separation membranes, phase stability against sulphur and carbon containing atmospheres is also discussed with respect to the formation of carbonates and sulphates. Paper presented at the 6th Euroconference on Solid State Ionics, Cetraro, Calabria, Italy, Sept. 12–19, 1999.     

Base-Pairing Properties of Double-Headed Nucleotides

Nucleotides that contain two nucleobases (double-headed nucleotides) have the potential to condense the information of two separate nucleotides into one. This presupposes that both bases must successfully pair with a cognate strand. Here, double-headed nucleotides that feature cytosine, guanine, thymine, adenine, hypoxanthine, and diaminopurine linked to the C2′-position of an arabinose scaffold were developed and examined in full detail. These monomeric units were efficiently prepared by convergent synthesis and incorporated into DNA oligonucleotides by means of the automated phosphoramidite method. Their pairing efficiency was assessed by UV-based melting-temperature analysis in several contexts and extensive molecular dynamics studies. Altogether, the results show that these double-headed nucleotides have a well-defined structure and invariably behave as functional dinucleotide mimics in DNA duplexes.     

One-bond 1J(15N,H) coupling constants at sp2-hybridized nitrogen of Schiff bases,enaminones and similar compounds: A theoretical study

¹J(¹⁵N,H) coupling constants for enaminones and NH-forms of intramolecularly hydrogen-bonded Schiff bases as model compounds for sp²-hybridized nitrogen atoms are evaluated using density functional theory (DFT) to find the optimal functionals and basis sets. Ammonia is used as a test molecule and its one-bond coupling constant is compared with experiment. A methylamine Schiff base of a truncated molecule of gossypol is used for checking the performance of selected B3LYP, O3LYP, PBE, BHandH, and APFD density functionals and standard, modified, and dedicated basis sets for coupling constants. Both in vacuum and in chloroform, modeled by the simple continuum model of solvent, the modified basis sets predict significantly better the ¹J(¹⁵N,H) value in ammonia and in the methylamine Schiff base of a truncated molecule of gossypol than the standard basis sets. This procure is then used on a broad set of intramolecularly hydrogen-bonded molecules, and a good correlation between calculated and experimental one-bond NH coupling constants is obtained. The ¹J(¹⁵N,H) couplings are slightly overestimated. The calculated data show for hydrogen-bonded NH interatomic distances that the calculated values depend on the NH bond lengths. The shorter the bond lengths, the larger the ¹J(¹⁵N,H). A useful correlation between ¹J(¹⁵N,H) and NH bond length is derived that enables realistic predictions of one-bond NH coupling constants. The calculations reproduce experimentally observed trends for the studied molecules.     

Phase transition in hexacelsian at about 580 K

Temperature-induced structure and microstructure changes in hexacelsians (BaAl₂Si₂O₈) that have been synthesised from the Ba-exchanged LTA and FAU zeolites (hexacelsian_LTA and hexacelsian_FAU) show that the phase transition near 580?K exists only in hexacelsian_LTA. The X-ray powder diffraction method has been used to follow the evolution of the structure during the phase transition, as described here. The excess thermodynamic quantities Gibbs free energy (G), entropy (S) and enthalpy (H) are obtained through the Landau theory of phase transition. The constants of proportionality between the G and ordering parameter (Q) are: h?=??170345?J?mol^?1, a?=??66.6?J?mol^?1?K^?1 and b?=??410534?J?mol^?1. The abrupt change in the trigonal distortion of the single six-member tetrahedral [SiO₄]^4? and [AlO₄]^5? ring near 580?K is responsible for the phase transition. The phase transition is non-convergent, ferroelastic, pure and proper.     

Determination of Formation Regions of Titanium Phosphates; Determination of the Crystal Structure ofβ-Titanium Phosphate, Ti(PO4)(H2PO4), from Neutron Powder Data

The formation region of the various types of layered titanium hydrogen phosphate hydrates was investigated. The materials were prepared by hydrothermal methods, treating amorphous titanium phosphate with phosphoric acid (8 to 16M) in the temperature range 175 to 250°C. The materials obtained were:α-Ti(HPO₄)₂·H₂O,γ-Ti(PO₄)(H₂PO₄)·2H₂O, and its anhydrous formβ-Ti(PO₄)(H₂PO₄). The structure ofβ-Ti(PO₄)(H₂PO₄) has been determined by Rietveld powder refinement of high resolution neutron diffraction data. The structure is refined in the monoclinic space groupP2₁/n(No. 14). The unit cell parameters are:a=18.9503(4) Å,b=6.3127(1) Å,c=5.1391(1) Å,β=105.366(2)°;Z=4. The final agreement factors were:R_p=2.9% andR_wp=3.8%. The structure ofβ-Ti(PO₄)(H₂PO₄) is built from TiO₆octahedra linked together by tertiary phosphate (PO₄) and dihydrogen phosphate ((OH)₂PO₂) tetrahedra. The layers are held together by hydrogen bonds.     

Stabilisation of a nucleic acid three-way junction by an oligonucleotide containing a single 2'-C to 3'-O-phosphate butylene linkage prepared by a tandem RCM-hydrogenation method

A cyclic dinucleotide with a butylene linker between the upper 2'-C position and the 3'-O-phosphate linkage was synthesised from simple nucleoside building blocks via a tandem ring-closing metathesis and hydrogenation procedure. The major of two phosphorus epimers was incorporated into an oligodeoxynucleotide, as well as into an LNA-DNA mixmer oligonucleotide. These were evaluated as parts in three different secondary structures, a duplex, a bulged duplex and a three-way junction, with both DNA and RNA complements. In the DNA:RNA hybrid molecule, the oligodeoxynucleotide containing this single 2'-C to 3'-O-phosphate butylene linkage was found to stabilise a three-way junction.     

CH,CD, CC and HH coupling constants in isotopically enriched cyclobutene

¹H, ²H and ¹³C NMR studies of cyclobutene and a series of isotopically enriched species have led to a determination of the ¹H? ¹H, ¹³C? ¹H, ¹³C? ²H and ¹³C? ¹³C coupling constants in these compounds. In agreement with general observations, ¹J(CH) is found to depend on the hybridization of the carbon atoms. Likewise, ²J(HH), ²J(CC), ³J(HH) and ³J(CH), but not ²J(CH), depend on the angles between the bonds connecting the coupled nuclei. When comparing cyclobutene with thiete 1,1-dioxide (thiete sulphone) an increase of almost 20 Hz is observed for ¹J(C-2, H-2) in the latter compound. All but one of the observed deuterium isotope effects on chemical shifts are negative. In the case of isotope effects upon the one-bond coupling constants, the obtained values support the results of the theoretical calculations of Sergeev and Solkan.     

Computational Prediction of 1H and 13C NMR Chemical Shifts for Protonated Alkylpyrroles: Electron Correlation and Not Solvation is the Salvation

Prediction of chemical shifts in organic cations is known to be a challenge. In this article we meet this challenge for α-protonated alkylpyrroles, a class of compounds not yet studied in this context, and present a combined experimental and theoretical study of the ¹³C and ¹H chemical shifts in three selected pyrroles. We have investigated the importance of the solvation model, basis set, and quantum chemical method with the goal of developing a simple computational protocol, which allows prediction of ¹³C and ¹H chemical shifts with sufficient accuracy for identifying such compounds in mixtures. We find that density functional theory with the B3LYP functional is not sufficient for reproducing all ¹³C chemical shifts, whereas already the simplest correlated wave function model, Møller–Plesset perturbation theory (MP2), leads to almost perfect agreement with the experimental data. Treatment of solvent effects generally improves the agreement with experiment to some extent and can in most cases be accomplished by a simple polarizable continuum model. The only exception is the NH proton, which requires inclusion of explicit solvent molecules in the calculation.