THEORETICAL STUDIES OF BILIPROTEIN CHROMOPHORES AND RELATED BILE PIGMENTS BY MOLECULAR ORBITAL AND RAMACHANDRAN TYPE CALCULATIONS

Ramachandran calculations have been used to gain insight into steric hindrance in bile pigments related to biliprotein chromophores. The high optical activity of denatured phycocyanin, as compared to phycoerythrin, has been related to the asymmetric substitution at ring A, which shifts the equilibrium towards the P-helical form of the chromophore. Geometric effects on the electronic structures and transitions have then been studied by molecular orbital calculations for several conjugation systems including the chromophores of phycocyanin. phytochrome P,, cations, cation radicals and tautomeric forms. For these different chromophores some general trends can be deduced. For instance, for a given change in the gross shape (e.g. either unfolding of the molecule from a cyclic-helical to a fully extended geometry, or upon out-of-plane twists of the pyrrole ring A) of the molecules under study, the predicted absorption spectra all change in a simikar way. Nonetheless, there are characteristic distinctions between the different n-systems, both in the transition energies and the charge distribution, which can be related to their known differences in spectroscopic properties and their reactivity

Th substituted SmFeAsO: structural details and superconductivity with Tc above 50 K

Superconducting poly- and single-crystalline samples of Sm1-xThxFeAsO with partial substitution of Sm3+ by Th4+ were synthesized and grown under high pressure and their structural, magnetic and transport properties are studied. The superconducting Tc reaches values higher than 50 K. Bulk superconducting samples (x = 0.08, 0.15, 0.3) do not show any signs of a phase transition from tetragonal to orthorhombic crystal structure at low temperatures. With Th substitution the unit cell parameters a and c shrink and the fractional atomic coordinate of the As site zAs remains almost unchanged, while that of Sm/Th zSm/Th increases. Upon warming from 5 K to 295 K the expansion of the FeAs layer thickness is dominant, while the changes in the other structural building blocks are smaller by a factor of 1/5, and they compensate each other, since the As-Sm/Th distance appears to contract by about the same amount as the O-Sm/Th expands. The poly- and single-crystalline samples are characterized by a full diamagnetic response in low magnetic field, by a high intergrain critical-current density for polycrystalline samples, and by a critical current density of the order of 8 x 105 A/cm2 for single crystals at 2 K in fields up to 7 T. The magnetic penetration depth anisotropy {\gamma}{\lambda} increases with decreasing temperature, a similar behavior to that of SmFeAsO1-xFy single crystals. The upper critical field estimated from resistance measurements is anisotropic with slopes of 5.4 T/K (H//ab plane) and 2.7 T/K (H//c axis), at temperatures sufficiently far below Tc. The upper critical field anisotropy {\gamma}H is in the range of 2, consistent with the tendency of a decreasing {\gamma}H with decreasing temperature, already reported for SmFeAsO1-xFy single crystals.Comment: 30 pages, 2 tables, 15 figure

Diaqua­bis­(dimethyl sulfoxide-κO)bis(saccharinato-κN)cobalt(II)

The title complex, [Co(C7H4NO3S)2(C2H6OS)2(H2O)2], contains a Co2+ cation in an octa­hedral coordination environment. The metal atom is surrounded by two different neutral ligands, namely dimethyl­sulfoxide (DMSO) and water, each coordinating through the O atom. The anionic saccharinate (sac; 1,1,3-trioxo-2,3-dihydro-1λ6,2-benzothia­zol-2-ide) ligand coordinates through the N atom. Each of the three similar ligand pairs is in a trans configuration with respect to each other. The Co atom lies on a crystallographic center of symmetry and the octa­hedral geometry is not significantly distorted. A short O—H⋯O hydrogen bond is present between a water H atom and the ketone O atom; two longer hydrogen bonds (intra- and inter­molecular) are also present between a water H and a sulfonic O atom, forming a supramolecular assembly through head-to-tail aggregation between adjacent complexes

Interplay of composition, structure, magnetism, and superconductivity in SmFeAs1-xPxO1-y

Polycrystalline samples and single crystals of SmFeAs1-xPxO1-y were synthesized and grown employing different synthesis methods and annealing conditions. Depending on the phosphorus and oxygen content, the samples are either magnetic or superconducting. In the fully oxygenated compounds the main impact of phosphorus substitution is to suppress the N\'eel temperature TN of the spin density wave (SDW) state, and to strongly reduce the local magnetic field in the SDW state, as deduced from muon spin rotation measurements. On the other hand the superconducting state is observed in the oxygen deficient samples only after heat treatment under high pressure. Oxygen deficiency as a result of synthesis at high pressure brings the Sm-O layer closer to the superconducting As/P-Fe-As/P block and provides additional electron transfer. Interestingly, the structural modifications in response to this variation of the electron count are significantly different when phosphorus is partly substituting arsenic. Point contact spectra are well described with two superconducting gaps. Magnetic and resistance measurements on single crystals indicate an in-plane magnetic penetration depth of 200 nm and an anisotropy of the upper critical field slope of 4-5. PACS number(s): 74.70.Xa, 74.62.Bf, 74.25.-q, 81.20.-nComment: 36 pages, 13 figures, 2 table

Diaqua­bis­(dimethyl sulfoxide-κO)­disaccharinatocadmium

The title compound, [Cd(C7H4NO3S)2(C2H6OS)2(H2O)2], contains a Cd2+ cation in an octahedral coordination environment. The metal atom is surrounded by the two different neutral ligands dimethyl sulfoxide (DMSO) and water, each coordin­ating through the O atom. The anionic saccharinate (sac; 1,1,3-trioxo-2,3-dihydro-1λ6,2-benzothia­zol-2-ide) ligand coordin­ates through the N atom. Each of the three similar ligand pairs is in a trans configuration with respect to each other. The Cd atom lies on a crystallographic center of symmetry. The DMSO ligand coordinates through the lone pair of electrons on the O atom, as can be seen from the Cd—O—S bond angle of 123.96 (9)°

Giant crystal-electric-field effect and complex magnetic behavior in single-crystalline CeRh3Si2

Single-crystalline CeRh3Si2 was investigated by means of x-ray diffraction, magnetic susceptibility, magnetization, electrical resistivity, and specific heat measurements carried out in wide temperature and magnetic field ranges. Moreover, the electronic structure of the compound was studied at room temperature by cerium core-level x-ray photoemission spectroscopy (XPS). The physical properties were analyzed in terms of crystalline electric field and compared with results of ab-initio band structure calculations performed within the density functional theory approach. The compound was found to crystallize in the orthorhombic unit cell of the ErRh3Si2 type (space group Imma -- No.74, Pearson symbol: oI24) with the lattice parameters: a = 7.1330(14) A, b = 9.7340(19) A, and c = 5.6040(11) A. Analysis of the magnetic and XPS data revealed the presence of well localized magnetic moments of trivalent cerium ions. All physical properties were found to be highly anisotropic over the whole temperature range studied, and influenced by exceptionally strong crystalline electric field with the overall splitting of the 4f1 ground multiplet exceeding 5700 K. Antiferromagnetic order of the cerium magnetic moments at TN = 4.70(1)K and their subsequent spin rearrangement at Tt = 4.48(1) K manifest themselves as distinct anomalies in the temperature characteristics of all investigated physical properties and exhibit complex evolution in an external magnetic field. A tentative magnetic B-T phase diagram, constructed for B parallel to the b-axis being the easy magnetization direction, shows very complex magnetic behavior of CeRh3Si2, similar to that recently reported for an isostructural compound CeIr3Si2. The electronic band structure calculations corroborated the antiferromagnetic ordering of the cerium magnetic moments and well reproduced the experimental XPS valence band spectrum.Comment: 32 pages, 12 figures, to appear in Physical Review

Non-Fermi liquid behavior in a fluctuating valence system, the filled skutterudite compound CeRu_{4}As_{12}

Electrical resistivity $\rho$, specific heat C, and magnetic susceptibility $\chi$ measurements made on the filled skutterudite CeRu_4As_{12} reveal non-Fermi liquid (NFL) T - dependences at low T, i.e., $\rho$(T) $\sim$ T^{1.4} and weak power law or logarithmic divergences in C(T)/T and $\chi$(T). Measurements also show that the T - dependence of the thermoelectric power S(T) deviates from that seen in other Ce systems. The NFL behavior appears to be associated with fluctuations of the Ce valence between 3^+ and 4^+ rather than a typical Kondo lattice scenario that would be appropriate for an integral Ce valence of 3^+.Comment: 18 pages, 5 figure

2′-Hy­droxy­methyl-1′-(4-methyl­phen­yl)-2′-nitro-1′,2′,5′,6′,7′,7a′-hexa­hydro­spiro­[indoline-3,3′-pyrrolizin]-2-one

In the title compound, C22H23N3O4, the tolyl ring is almost perpendicular [83.86 (7)°] to the best plane through the eight atoms of the pyrrolizidine ring system. The mol­ecular conformation is stabilized by an intra­molecular O—H⋯O hydrogen bond. The crystal packing features inversion dimers with R 2 2(8) motifs linked by pairs of N—H⋯O hydrogen bonds

Ethyl 6-(6-meth­oxy-2-naphth­yl)-2-oxo-4-(2-thien­yl)cyclo­hex-3-ene-1-carboxyl­ate

The title compound, C24H22O4S, was prepared by reaction between (2E)-3-(6-meth­oxy-2-naphth­yl)-1-(2-thien­yl)prop-2-en-1-one and ethyl acetoacetate. In the crystal, the cyclo­hexenone ring shows a distorted half-chair conformation. The length of the double bond in the cyclohexenone ring [1.343 (4) Å] is normal