DNA Conserved in Diverse Animals Since the Precambrian Controls Genes for Embryonic Development.

DNA that controls gene expression (e.g. enhancers, promoters) has seemed almost never to be conserved between distantly related animals, like vertebrates and arthropods. This is mysterious, because development of such animals is partly organized by homologous genes with similar complex expression patterns, termed "deep homology." Here, we report 25 regulatory DNA segments conserved across bilaterian animals, of which 7 are also conserved in cnidaria (coral and sea anemone). They control developmental genes (e.g. Nr2f, Ptch, Rfx1/3, Sall, Smad6, Sp5, Tbx2/3), including six homeobox genes: Gsx, Hmx, Meis, Msx, Six1/2, and Zfhx3/4. The segments contain perfectly or near-perfectly conserved CCAAT boxes, E-boxes, and other sequences recognized by regulatory proteins. More such DNA conservation will surely be found soon, as more genomes are published and sequence comparison is optimized. This reveals a control system for animal development conserved since the Precambrian.

An immune-suppressing protein in human endogenous retroviruses.

Motivation: Retroviruses are important contributors to disease and evolution in vertebrates. Sometimes, retrovirus DNA is heritably inserted in a vertebrate genome: an endogenous retrovirus (ERV). Vertebrate genomes have many such virus-derived fragments, usually with mutations disabling their original functions. Results: Some primate ERVs appear to encode an overlooked protein. This protein is homologous to protein MC132 from Molluscum contagiosum virus, which is a human poxvirus, not a retrovirus. MC132 suppresses the immune system by targeting NF- κ B, and it had no known homologs until now. The ERV homologs of MC132 in the human genome are mostly disrupted by mutations, but there is an intact copy on chromosome 4. We found homologs of MC132 in ERVs of apes, monkeys and bushbaby, but not tarsiers, lemurs or non-primates. This suggests that some primate retroviruses had, or have, an extra immune-suppressing protein, which underwent horizontal genetic transfer between unrelated viruses. Contact: mcfrith@edu.k.u-tokyo.ac.jp.

Synthesis and structures of ruthenium-NHC complexes and their catalysis in hydrogen transfer reaction.

Ruthenium complexes [Ru(L1)2(CH3CN)2](PF6)2 (1), [RuL1(CH3CN)4](PF6)2 (2) and [RuL2(CH3CN)3](PF6)2 (3) (L1= 3-methyl-1-(pyrimidine-2-yl)imidazolylidene, L2 = 1,3-bis(pyridin-2-ylmethyl)benzimidazolylidene) were obtained through a transmetallation reaction of the corresponding nickel-NHC complexes with [Ru(p-cymene)2Cl2]2 in refluxing acetonitrile solution. The crystal structures of three complexes determined by X-ray analyses show that the central Ru(II) atoms are coordinated by pyrimidine- or pyridine-functionalized N-heterocyclic carbene and acetonitrile ligands displaying the typical octahedral geometry. The reaction of [RuL1(CH3CN)4](PF6)2 with triphenylphosphine and 1,10-phenanthroline resulted in the substitution of one and two coordinated acetonitrile ligands and afforded [RuL1(PPh3)(CH3CN)3](PF6)2 (4) and [RuL1(phen)(CH3CN)2](PF6)2 (5), respectively. The molecular structures of the complexes 4 and 5 were also studied by X-ray diffraction analysis. These ruthenium complexes have proven to be efficient catalysts for transfer hydrogenation of various ketones.

2-{4-[Bis(4-bromo-phen-yl)amino]-benzyl-idene}malono-nitrile.

In the crystal structure of the title compound, C22H13Br2N3, the two bromo-phenyl rings are rotated out of the plane of the central benzyl-idene ring by 68.7 (1) and 69.3 (1)°. Both cyano substituents are located nearly in the plane of the benzylidene ring, with the mean plane of the methylmalononitrile group being inclined to this ring by 5.8 (1)°. In the crystal, the mol-ecules are linked by weak C-H⋯N hydrogen bonds into layers parallel to the bc plane.

Bis(1H-imidazole-κN)bis-(2-methyl-benzoato-κO)bis-(2-methyl-benzoic acid-κO)copper(II).

The structure of the title compound, [Cu(C(8)H(7)O(2))(2)(C(3)H(4)N(2))(2)(C(8)H(8)O(2))(2)], consists of centrosymmetric monomeric units, in which the Cu(II) atom has a tetra-gonally distorted octa-hedral coordination involving two imidazole N atoms and two carboxyl-ate O atoms in the square plane [Cu-N = 1.964 (3) and Cu-O = 1.960 (2) Å] and 2-methyl-benzoic acid O atoms in axial sites [Cu-O = 2.753 (3) Å]. Within the complex, the carb-oxy-lic acid forms intra-molecular O-H⋯O hydrogen bonds, while the mol-ecules are assembled through N-H⋯O(carbox-yl) hydrogen bonds into chains extending along the a-axis direction. These chains are further linked by weak π-π inter-actions [centroid-centroid separation = 3.930 (2) Å].

Aqua-(2,9-dimethyl-1,10-phenanthroline-κN,N')diformato-κO,O';κO-nickel(II) monohydrate.

The asymmetric unit of the title compound, [Ni(HCO(2))(2)(C(14)H(12)N(2))(H(2)O)]·H(2)O, contains a mononuclear complex mol-ecule hydrogen bonded to a lattice water mol-ecule. The Ni(II) atom exhibits a distorted octa-hedral coordination geometry formed by the N atoms from a 2,9-dimethyl-1,10-phenanthroline ligand, two O atoms of a chelating formate anion, one aqua O atom and one O atom of a coordinating formate anion. The mol-ecules are assembled into chains extending along [100] through by O-H⋯O hydrogen bonds. The supra-molecular chains are further linked into layers parallel to (011) by weak π-π packing inter-actions [centroid-centroid separation = 3.768 (2) Å]. The resulting layers are stacked to meet the requirement of close-packing patterns.

Bis(2-methyl-benzoato-κO,O')(1,10'-phenanthroline-κN,N')copper(II).

In the title compound, [Cu(C(8)H(7)O(2))(2)(C(12)H(8)N(2))], the Cu(II) atom assumes a distorted octa-hedral coordination geometry, chelated by two N atoms from the 1,10'-phenanthroline ligand and four O atoms from two 2-methyl-benzoate anions. A significant Jahn-Teller distortion is observed with two axial Cu-O distances significantly longer than those in the equatorial CuO(2)N(2) plane. In the crystal, π-π stacking inter-actions, with centroid-centroid distances of 3.547 (3) or 3.728 (3) Šbetween the phenanthroline rings, form layers parallel to (011).

Tetra-µ-2-methyl-benzoato-κO:O'-bis-[(ethanol-κO)copper(II)].

In the title dinuclear complex, [Cu(2)(C(8)H(7)O(2))(4)(C(2)H(5)OH)(2)], four 2-methyl-benzoato anions form a cage around two Cu(II) ions in a syn-anti configuration. Two ethanol mol-ecules coordinate the Cu atoms in apical positions, giving an overall square-pyramidal coordination geometry. The Cu⋯Cu separation is 2.600 (1) Å. In the crystal, mol-ecules are assembled into chains extending in [001] through O-H⋯O hydrogen bonds.

rac-syn-Diethyl 2-hy-droxy-4-oxo-1-phenyl-cyclo-hexane-1,2-dicarboxyl-ate.

The title compound, C(18)H(22)O(6), was obtained by the domino oxa-Michael-aldol (DOMA) reaction and has the cyclo-hexa-none ring in a chair conformation with intra-annular torsion angles in the range 49.9 (2)-58.9 (2)°. The two eth-oxy-carbonyl substituents on the cyclo-hexa-none ring adopt a syn configurations. In the crystal, the mol-ecules self-assemble through duplex inter-molecular hy-droxy-carbonyl O-H⋯O hydrogen bonds, giving centrosymmetric cyclic dimers [graph set R(2) (2)(12)] which inter-associate through weak C-H⋯O hydrogen-bonding inter-actions.

Aqua-(2,9-dimethyl-1,10-phenanthroline-κN,N')(formato-κO,O')(formato-κO)cobalt(II) monohydrate.

The asymmetric unit of the title compound, [Co(HCO(2))(2)(C(14)H(12)N(2))(H(2)O)]·H(2)O, contains a mononuclear complex mol-ecule hydrogen bonded to a lattice water mol-ecule. The Co(II) cation is in a distorted octa-hedral coordination environment defined by the two N atoms of the 2,9-dimethyl-1,10-phenanthroline ligand and four O atoms. Two of these are from a chelating formate anion, one from a monodentate formate and the last from an aqua ligand. In the crystal, mol-ecules are connected by O-H⋯O hydrogen bonds, forming double chains along [100] with the 2,9-dimethyl-1,10-phenanthroline ligands pointing outwards from each chain. These chains are further linked into layers parallel to (011) by inter-chain π-π stacking inter-actions with centroid-centroid distances of 3.61 (1) Å.

Electron correlation in the GK state of the hydrogen molecule.

The second excited (1)Sigma(g)(+) state of the hydrogen molecule, the so-called GK state, has a potential energy curve with double minima. At the united atom limit it converges to the 1s3d configuration of He. At large internuclear distances R, it dissociates to two separated atoms, one in the ground state and another in the 2p excited state. Radial pair density calculations and natural orbital analyses reveal unusual effect of electron correlation around the K minimum of the potential energy curve. As R>2.0 a.u., a natural orbital of sigma(u) symmetry joins the two natural orbitals of sigma(g) symmetry at smaller R. The average interelectronic distance decreases as the internuclear distance increases from R=2.0 to 3.0 a.u. Around R=3.0 a.u. the singly peaked pair density curve splits into two peaks. The inner peak can be attributed to the formation of the ionic electron configuration (1s)(2), where both 1s electrons are on the same nucleus. As the two 1s electrons run into different nuclei, one of the two 1s electrons is promoted to the 2p state, which results in the outer peak in the pair density curve. The Rydberg 1s2p configuration persists as the nuclei stretch, and becomes dominant at large R where four natural orbitals, two of sigma(g) and two of sigma(u) symmetry, become responsible.

Synthesis and bioactivity of aripiprazole derivatives.

Ten aripirazole (CAS 129722-12-9) derivatives were prepared and examined for dopamine receptor antagonist activity. The structures of these newly synthesized compounds were confirmed by their elemental analyses and by IR, 1H-NMR and mass spectra. It was demonstrated that all the new compounds have dopamine receptor antagonist activity to a certain extent. Three compounds showed more potent activity than aripiprazole.