Enantioselective addition of diethylzinc to aldehydes catalyzed by optically active C2-symmetrical bis-beta-amino alcohols

The syntheses of new optically active C(2)-symmetrical bis-beta-amino alcohols 1-6 from (S)-2-(1-hydroxy-1,1-diphenylmethyl)-pyrrolidine are described. Especially attention is focused on bridges, which link the two beta-amino alcohol units. These new chiral ligands have been successfully applied in the catalytic enantioselective addition of diethylzinc to aldehydes to give sec-alcohols in good yields with up to 95% enantiomeric excess.     

Identification of a hydroxy substituted calamenene--a sesquiterpene associated with wound reactions in non-infected xylem of Tilia spp

Xylem of lime trees (Tilia spp.) with wound reactions was structurally investigated by scanning (SEM) and transmission electron microscopy (TEM) as well as chemically analyzed by direct thermal desorption-gas chromatography-mass spectrometry (DTD-GC-MS). Wound reactions in the outer xylem lead to distinct discolorations around the wound. Within a 4-week response no fungal infection occurred in discoloured xylem. At the fine structural level, wound reactions become primarily visible as the secretion of dark-staining substances from parenchyma cells into lumens of vessels and fibres. With increasing reaction time vessels aggregate large amounts of secretion products, whereas in fibres wall-associated linings are formed and the inner secondary wall appears incrusted. After 2-3 months a narrow, greenish-brown boundary developed at the transition between the discoloured outer and the unchanged inner xylem. This green-brown boundary layer remained non-infected also in older wounds. DTD-GC-MS analyses revealed that the sesquiterpene Hydroxycalamenene represents a key substance of wound reactions in non-infected lime trees. Other substances such as fatty acids or their esters and coniferyl aldehydes or their derivatives were also found. TEM investigations of the samples after DTD-GC-MS showed less pronounced cell wall-attached linings in fibres as well as reduced incrustation of inner secondary walls. The massive deposits in the vessel lumens remained unchanged. The role of these wound reaction products and their ways of synthesis are discussed.     

Comparative enantiocontrol with allyl phenyldiazoacetates in asymmetric catalytic intramolecular cyclopropanation

Dirhodium(II) azetidinone-carboxylates are effective asymmetric catalysts for diazo decomposition of allyl diazoacetates and their subsequent intramolecular cyclopropanations. The effect of alkene substituents on enantiocontrol has been examined and modest selectivities have been achieved. Steric influences from substituents on the diazo carbon are seen to diminish enantioselectivities.     

The tissue plasminogen activator (tPA)/plasmin extracellular proteolytic system regulates seizure-induced hippocampal mossy fiber outgrowth through a proteoglycan substrate

Short seizure episodes are associated with remodeling of neuronal connections. One region where such reorganization occurs is the hippocampus, and in particular, the mossy fiber pathway. Using genetic and pharmacological approaches, we show here a critical role in vivo for tissue plasminogen activator (tPA), an extracellular protease that converts plasminogen to plasmin, to induce mossy fiber sprouting. We identify DSD-1-PG/phosphacan, an extracellular matrix component associated with neurite reorganization, as a physiological target of plasmin. Mice lacking tPA displayed decreased mossy fiber outgrowth and an aberrant band at the border of the supragranular region of the dentate gyrus that coincides with the deposition of unprocessed DSD-1-PG/phosphacan and excessive Timm-positive, mossy fiber termini. Plasminogen-deficient mice also exhibit the laminar band and DSD- 1-PG/phosphacan deposition, but mossy fiber outgrowth through the supragranular region is normal. These results demonstrate that tPA functions acutely, both through and independently of plasmin, to mediate mossy fiber reorganization.     

Attenuation of seizure in P77PMC rats with an HSV-vector expressing IL-1ra in brain

Ｅｐｉｌｅｐｓｙｉｓｏｎｅｏｆｔｈｅｃｏｍｍｏｎｄｉｓｅａｓｅｓｄｕｒｉｎｇｃｈｉｌｄｈｏｏｄｉｎｃｌｉｎｉｃａｌｐｒａｃｔｉｃｅ.Ｂｅｃａｕｓｅｏｆｃｏｍｐｌｅｘｅｔｉｏｌｏｇｙ,ｍｏｌｅｃｕｌａｒｍｅｃｈａｎｉｓｍｓｏｆｅｐｉｌｅｐｔｏｇｅｎｅｓｉｓａｒｅｎｏｔｆｕｌｌｙｃｌｅａｒ.Ａｓｗｅｋｎｏｗｅｐｉｌｅｐｓｙｉｓｃａｕｓｅｄｂｙｉｍｂａｌａｎｃｅｂｅｔｗｅｅｎｅｘｃｉｔａｔｉｏｎａｎｄｓｕｐｐｒｅｓｓｉｏｎｏｆｔｈｅｂｒａｉｎ.Ｉｔｈａｓｂｅｅｎｓｈｏｗｎｉｎｈｕｍａｎａｎｄａｎｉｍａｌｍ…     

Regional excitatory and inhibitory amino acid levels in epileptic El mouse brain

Inbred mutant El mice are highly susceptible to convulsive seizures upon tossing stimulation. The levels of excitatory (e.g. glutamate and aspartate) and inhibitory amino acids [e.g. -aminobutyrate (GABA)] were examined in discrete regions of stimulated El mice [El(+)] non-stimulated El mice [El(-)] and ddY mice, which do not have convulsive disposition. In comparison with ddY, a general increased levels of aspartate, glutamate, glutamine, and taurine were detected in brain regions of El(-). The levels of GABA and glycine were almost the same in ddY and El(-). Compared to El(+), the levels of aspartate, glutamate, glutamine, and GABA in El(-) were either the same or higher. In the case of taurine and glycine, the levels in El(-) were either the same or lower than El(+). Alanine is special in that El(-) have a higher level than El(+) in hippocampus but lower in cerebellum. Furthermore, while marked changes were registered in several brain regions, none of the amino acids investigated showed any significant differences in the hypothalamus of three different groups of mice.     

Insertion reactions of organic anhydrides and the Cu(I) alkoxide [CuOBu]

The synthesis and structural characterization of the copper salts [Cu₈(benzoate)₈(THF)₆] (1), [Cu₂{(CO₂)₂C₆H₂(Boc)₂}dppm₂]₂ (2) and [Cu₂{(CO₂)₂C₁₀H₄(Boc)₂}dppm₂]₂ (3) [Boc = tert-butoxycarbonyl, dppm = 1,2-bis(diphenylphosphino)methane] prove that cyclic organic anhydrides and dianhydrides readily insert into the Cu-O bond of [CuO^tBu] forming carboxylate ligands with ester functionalities in the ligand periphery. [Mn₃(o-Boc-benzoate)₆(DME)₂] (4) (DME = 1,2-dimethoxyethane) was synthesized by the metathesis reaction of [Cu(I)(o-Boc-benzoate)] with MnCl₂.     

Darkness improves growth and delays necrosis in a nonchlorophyllous habituated sugarbeet callus: Biochemical changes

The transfer of light-cultured green normal (N) and white habituated (HNO) sugarbeet callus to darkness reduced the growth of N callus and improved growth and delayed necrosis in the HNO callus. The decrease of dry matter of N callus under darkness was accompanied by a reduced content of carotenoids and by decreased CO₂ fixation, which was compensated by an increased dependency on externally supplied sucrose. The levels of some organic nitrogen compounds such as glutamate, proline, and free polyamines were not affected by transfer to darkness of N or HNO callus. Darkness decreased ethylene emissions in both callus types. In the HNO callus, the sucrose growth dependency and the CO₂ fixation were unaffected by darkness. Chlorophylls were absent both in light and darkness, whereas some carotenoids were accumulated in the HNO callus only in dark conditions. In another connection, a significant increase of peroxidase activity, which did not occur in the N callus, was induced by darkness in the HNO callus. A decreased content of thio-barbituric acid (TBA)-reactive substances was measured in the HNO callus transferred to darkness, whereas an increase was noticed in the N callus placed in the same conditions. These metabolic changes and the reduction of cellular damage in darkness revealed light-induced stress reactions leading to necrosis and to reduced growth of HNO callus. It appeared that darkness allowed the HNO callus to avoid the photooxidation stress. Therefore, the favorable effect of darkness on HNO growth might be explained by the suppression of photooxidative damage due to the absence of carotenoids. The higher peroxidase activity in the HNO callus maintained in darkness raised the problem of heme synthesis in this heterotrophic callus.     

Structural heterogeneity in waxy-rice starch

Alpha-amylase of B. amyloliquefaciens was used for the structural characterization of the amylopectin from waxy-rice starch. Fractions of -dextrins with a degree of polymerization (d.p.) <5000 were isolated from amylopectin hydrolysates after 1 and 3 h. φ,β-Limit dextrins were prepared by successive phosphorolysis and beta-amylolysis of the fractions and these were analysed by a second alpha-amylolysis. Based on the hydrolysis pattern, the limit dextrins were divided into two major groups, A and B, which possessed units of clusters of d.p. 100–200 and 90–130, respectively. An extensive alpha-amylolysis resulted in characteristic distributions of dextrins with d.p. <80 which represented branched building blocks. Type A dextrins possessed more larger building blocks with d.p. 40, but less intermediate and small blocks, than type B. The φ,β-limit dextrin of the original amylopectin had a distinct distribution enriched in small building blocks. A model is proposed in which the two types of dextrins originate from regular and less regular structural domains of the amylopectin fraction within the starch granules.