Guaianolides from Tanacetopsis karataviensis (Kovalevsk.) Kovalevsk.

In continuation of our phytochemical study on the aerial part of Tanacetopsis karataviensis (Kovalevsk.) Kovalevsk, three new guaiane-type sesquiterpene lactones were isolated namely karatanolide (1), 11,13ß-dihydrokaratanolide (2) and 11,13α-dihydrokaratanolide (3), in addition to the two known sesquiterpene lactones 1ß,10α-dihydroxyarglabin (4) and artefin (5). The structures of the isolated sesquiterpene lactones were elucidated by IR and NMR spectroscopy. Single crystal X-ray diffraction allowed to unambiguously confirm the structure of the isolated sesquiterpene lactones. Quantum chemical calculations of the guaianolides 1-3 suggested the existence of two conformations for the seven-membered cycle. All sesquiterpene lactones from Tanacetopsis karataviensis were isolated for the first time.

Sulfur substitution in a Ni(cyclam) derivative results in lower overpotential for CO2 reduction and enhanced proton reduction.

The replacement of the opposing nitrogen atoms in 1,4,8,11-tetraazacyclotetradecane (cyclam) with two sulfur atoms in 1,8-dithia-4,11-diazacyclotetradecane (dithiacyclam) enables the electrochemical reduction of protons and CO2via the corresponding nickel(ii) complex at more positive potentials. In addition, a 10-fold enhancement in the proton reduction rate of [Ni(dithiacyclam)]2+ relative to [Ni(cylcam)]2+ was observed. The study provides vital insight into Nature's choice of employing predominantly sulfur based ligand platforms in achieving biological proton and CO2 reductions.

Insight into trifluoromethylation - experimental electron density for Togni reagent I.

3,3-Dimethyl-1-(trifluoromethyl)-1,3-dihydro-1-λ3,2-benziodoxole represents a popular reagent for trifluoromethylation. The σ hole on the hypervalent iodine atom in this "Togni reagent" is crucial for adduct formation between the reagent and a nucleophilic substrate. The electronic situation may be probed by high resolution X-ray diffraction: the experimental charge density thus derived shows that the short intermolecular contact of 3.0 Å between the iodine and a neighbouring oxygen atom is associated with a local charge depletion on the heavy halogen in the direction of the nucleophile and visible polarization of the O valence shell towards the iodine atom. In agreement with the expectation for λ3-iodanes, the intermolecular O⋯I-Caryl halogen bond deviates significantly from linearity.

Is it all in the hinge? A kryptoracemate and three of its alternative racemic polymorphs of an aminonitrile.

Four polymorphs of 2-(perfluorophenyl)-2-(phenylamino)acetonitrile have been crystallized and structurally analyzed: in addition to three racemic crystals, a rare kryptoracemate has been obtained. The central single bonds allow for conformational flexibility: the kryptoracemate as well as two of the remaining polymorphs contain several independent molecules with different conformation. In contrast to these uncommon packing modes, the fourth phase is unexceptional and crystallizes with a single molecule in the asymmetric unit. Individual crystallization batches may contain several crystal forms concomitantly.

Exocytic clearing of degraded membrane material from pigment epithelial cells in frog retina.

Posterior eye cups of the frog Rana ridibunda were prefixed in the presence of tannic acid, osmicated and stained en bloc with uranyl acetate. Electron microscopy revealed the following features of membrane traffic in cells of the retinal pigment epithelium (RPE): (1) intracellular membranes with increased electron density undergo degradation within phagolysosomes and also outside lysosomes and are committed to be exocytized; (2) exocytized degraded membranes, organized as lamellar arrays, are evacuated through the basolateral extracellular space, through Bruch's membrane and into the choriocapillaris. Comparison of exocytic activity in animals kept either with a light cycle or in constant darkness suggests that exocytized lamellar arrays derive from membranes degraded through both lysosomal and non-lysosomal pathways. Autophagocytosis may contribute a substantial amount of material to exocytosis. On the other hand, exocytosis of heterophagosomes, if it takes place at all, involves only residual bodies at a final stage of degradation following slow proteolysis which is achieved within the RPE cells. Rapid transcytosis of heterophagosomes does not occur. Taken together, our observations suggest that, in the frog, exocytosis and subsequent evacuation of residual bodies is an efficient mechanism for clearing from worn-out organelles the metabolically highly active, non-dividing RPE cells.

In vivo effects of glycine on retinal ultrastructure and averaged electroretinogram.

Glycine, when injected intravitreally, has an inhibitory action on the electroretinogram (ERG) of the rabbit resulting in a transient loss of the oscillatory potentials of the b-wave. This inhibitory action is reversible within 24 h after glycine injection. In autoradiographs, after [3H] glycine administration, the radioactive label is mainly found over the inner nuclear layer (INL) and inner plexiform layer (IPL) without predilection of specific cell types and/or synapses. Electron microscopy reveals cytopathological changes in amacrine cells, in particular their cell membranes. These changes are conspicuous especially 1-2 h after the injection and the cells become normal again within 24 h. It is concluded that glycine has an inhibitory action upon the rabbit ERG in vivo. This action, on the basis of our morphological observations under our experimental conditions, may be due to an overall somatic membrane action rather than to an action as inhibitory neurotransmitter at the synaptic level. The reversible cellular lesions of amacrine cells after glycine administration with a concomitant, transient loss of oscillatory potentials (OP) supports the hypothesis that the cellular origin of OP is situated in amacrine cells.

Twinned dichlorobis(2,6-dichloropyrazine-N(4))zinc(II).

For crystals of the title compound, [ZnCl(2)(C(4)H(2)Cl(2)N(2))(2)], metric considerations suggest a monoclinic unit cell. However, the symmetry of the diffraction pattern shows the crystals to be triclinic, with very similar lattice constants a and b, and alpha and beta. All crystals examined were twinned. The discrepancy between the reliability indices for merging in the monoclinic lattice metric symmetry and the triclinic crystal symmetry constitutes an indicator for the volume ratio between the components. The asymmetric unit contains three independent molecules. At the molecular level, the compound shows a distorted tetrahedral coordination around one Zn atom.

Syntheses and structures of Mg(C5H5BMe)2, Mg(3,5-Me2C5H3BNMe2)2, the 2,2'-bipyridine adduct Mg(C5H5BMe)2(bipy), and the N-bonded aminoboratabenzene species Mg(3,5-Me2C5H3BNMe2)2(THF)2.

The donor-free magnesocene analogues bis(1-methylboratabenzene)magnesium (1) and bis[3,5-dimethyl-1- (dimethylamino)boratabenzene]magnesium (2) are synthesized in good yields by the reactions of dimethylmagnesium with (trimethylstannyl)dihydroborinine precursors 3 and 4. In the crystalline state, both 1 and 2 possess sandwich structures with eta 6-coordinated boratabenzene ligands and display crystallographic centrosymmetry. Compound 1 reacts with the nitrogen donor 2,2'-bipyridine to give the Lewis base adduct (1)(bipy) (identical to 5). In the crystal structure of 5, one boratabenzene ligand is eta 6-bonded to the central metal while the other ligand adopts an eta 1-bonding mode. Crystallization of compound 2 from THF produces the solvate (2)(THF)2 (identical to 6), which exhibits a distorted tetrahedral N2O2 coordination environment around the magnesium atom. The average Mg-N bond distance is 2.141(3) A, and the N-Mg-N angle is 148.0(1) degrees. The observation of an aminoboratabenzene that is solely sigma-bonded to a metal is without precedent.

Three conformational polymorphs of di-mu-chlorotetrakis(1-methylboratabenzene)diyttrium: synthesis, x-ray structures, quantum chemical calculations, and lattice energy minimizations.

The reaction of yttrium trichloride with lithium 1-methylboratabenzene (1/2) in toluene (110 degrees C, 3 days) afforded the donor-free dinuclear sandwich complex [(C(5)H(5)BMe)(2)Y(mu-Cl)](2) (1) in 85% yield as pale-yellow crystals. By means of single crystal and powder diffraction methods, three conformational polymorphs, alpha-1 [P2(1)/n (No. 14), monoclinic, a = 6.6124(8) A, b = 14.352(9) A, c = 14.120(1) A, beta = 95.57(1) degrees, V = 1333.7(9) A(3), Z = 2], beta-1 [P2(1)/a (No. 14), monoclinic, a = 8.542(2) A, b = 13.712(6) A, c = 11.76(1) A, beta = 102.60(4) degrees, V = 1344.5(13) A(3), Z = 2], and gamma-1 [Pbca (No. 61), orthorhombic, a = 20.091(5) A, b = 13.527(3) A, c = 9.976(2) A, V = 2711.2(11) A(3), Z = 4], were characterized in the solid state of 1. The molecules in the three phases vary remarkably in the rotational position of boratabenzene ligands with differences of 91.1, 133.1, and 24.9 degrees between each pair. DFT calculations at the B3LYP/LanL2DZ level reveal that the three molecular structures observed in the solid state correspond closely to three minima on the gas-phase potential energy surface. The beta conformation is 2.8 and 7.2 kJ/mol more stable than the alpha and gamma conformations, respectively. Lattice energy minimizations predict that the alpha-1 phase is about 5.5 and 18.7 kJ mol(-)(1) more stable than the beta-1 and gamma-1 modifications, in agreement with the packing coefficients and the molecular volumes of the three crystal structures. While the alpha-1 and beta-1 modifications have comparable total energies, the gamma-1 form is less stable. The total energy differences among the polymorphs are greater than generally expected.

[Biological effect of laser-photo-coagulation on the retina (author's transl)]. / Biologische Wirkung des Lasers auf die Netzhaut

The effects of laser-photo-coagulation on retina, pigment epithelium and choroid has been studied in animals (rabbit and mini-pig). During the first two hours after photocoagulation the permeability of the blood-retinal barrier and of the pigment epithelium is temporarily increased. Later on (2-4 days) pigment epithelial cells proliferate within the coagulated areas and "tighten" the epithelial leaks. Photoreceptor outer segments undergo during the same period reversible breakdown. Normal retinal blood vessels are hardly altered by photocoagulation whereas pathological or neoformed vessels may be obliterated. Functional deficiences are observed after extensive photocoagulations only and even then rarely implicated by the patients.