Three-dimensional structure of ribonuclease T-1 complexed with an isosteric phosphonate substrate analogue of GpU: Alternate substrate binding modes and catalysis

The X-ray crystal structure of a complex between ribonuclease T-1 and guanylyl(3'-6')-6'-deoxyhomouridine (GpcU) has been determined at 2.0 Angstrom resolution. This Ligand is an isosteric analogue of the minimal RNA substrate, guanylyl(3'-5')uridine (GpU), where a methylene is substituted for the uridine 5'-oxygen atom. Two protein molecules are part of the asymmetric unit and both have a GpcU bound at the active site in the same manner. The protein-protein interface reveals an extended aromatic stack involving both guanines and three enzyme phenolic groups. A third GpcU has its guanine moiety stacked on His92 at the active site on enzyme molecule A and interacts with GpcU on molecule B in a neighboring unit via hydrogen bonding between uridine ribose 2'- and 3'-OH groups. None of the uridine moieties of the three GpcU molecules in the asymmetric unit interacts directly with the protein. GpcU-active-site interactions involve extensive hydrogen bonding of the guanine moiety at the primary recognition site and of the guanosine 2'-hydroxyl group with His40 and Glu58. on the other hand, the phosphonate group is weakly bound only by a single hydrogen bond with Tyr38, unlike ligand phosphate groups of other substrate analogues and 3'-GMP, which hydrogen-bonded with three additional active-site residues. Hydrogen bonding of the guanylyl 2'-OH group and the phosphonate moiety is essentially the same as that recently observed for a novel structure of a RNase T-1-3'-GMP complex obtained immediately after in situ hydrolysis of exo-(S-p)-guanosine 2',3'-cyclophosphorothioate [Zegers et al. (1998) Nature Struct. Biol. 5, 280-283]. It is likely that GpcU at the active site represents a nonproductive binding mode for GpU [:Steyaert, J., and Engleborghs (1995) fur. J. Biochem. 233, 140-144]. The results suggest that the active site of ribonuclease T-1 is adapted for optimal tight binding of both the guanylyl 2'-OH and phosphate groups (of GpU) only in the transition state for catalytic transesterification, which is stabilized by adjacent binding of the leaving nucleoside (U) group.

Asymmetric post-natal development of superior cervical ganglion of paca (Agouti paca)

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

The Growing Impact of Niobium in Organic Synthesis and Catalysis

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Enzymatic toxins from snake venom: structural characterization and mechanism of catalysis

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Search for charge-asymmetric production of W ' bosons in t(t)over-bar + jet events from pp collisions at root s=7 TeV

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Asymmetric exclusion model with impurities

An integrable asymmetric exclusion process with impurities is formulated. The model displays the full spectrum of the stochastic asymmetric XXZ chain plus new levels. We derive the Bethe equations and calculate the spectral gap for the totally asymmetric diffusion at half filling. While the standard asymmetric exclusion process without impurities belongs to the KPZ universality class with an exponent 3/2, our model has a scaling exponent 5/3.

Asymmetric microbial reduction of ketones: absolute configuration of trans-4-ethyl-1-(1S-hydroxyethyl)cyclohexanol

A set of five fungal species, Botrytis cinerea, Trichoderma viride and Eutypa lata, and the endophytic fungi Colletotrichum crassipes and Xylaria sp., was used in screening for microbial biocatalysts to detect monooxygenase and alcohol dehydrogenase activities (for the stereoselective reduction of carbonyl compounds). 4-Ethylcyclohexanone and acetophenone were biotransformed by the fungal set. The main reaction pathways involved reduction and hydroxylations at several positions including tertiary carbons. B. cinerea was very effective in the bioreduction of both substrates leading to the chiral alcohol (S)-1-phenylethanol in up to 90% enantiomeric excess, and the cis-trans ratio for 4-ethylcyclohexanol was 0:100. trans-4-Ethyl-1-(1S-hydroxyethyl)cyclohexanol, obtained from biotransformation by means of an acyloin-type reaction, is reported here for the first time. The absolute configurations of the compounds trans-4-ethyl-1-(1S-hydroxyethyl)cyclohexanol and 4-(1S- and 4-(1R-hydroxyethyl)cyclohexanone were determined by NMR analysis of the corresponding Mosher's esters. (C) 2009 Elsevier Ltd. All rights reserved.

Variable influence of ferric and cupric ions on Saccharomyces cerevisiae strains used in asymmetric organic synthesis.

Fe (III) and Cu (II) each at 50 mu M in four commercial strains of Saccharomyces cerevisiae induced an increase of NAD(P)(+) reduction in one strain (Turkish), but two others (Chilean and Brazilian), the presence of Fe(III) and/or Cu(II) diminished NAD(P)(+) reduction presumably due to free radicals formation inside these living cells. Suprisingly, in the American strain, Fe(III) induced a decrease and Cu (II) an increase of NAD(P)(+) reduction.

Catalysis and temperature dependence on the formation of ZnO nanoparticles and of zinc acetate derivatives prepared by the sol-gel route

The chemical and structural nature of powders prepared from the zinc acetate-derived precursor using the sol-gel route is discussed. The influence of the synthesis temperature and of the hydrolytic catalyst on the structural features of the powder is focused on the basis of X-ray powder diffraction (XRPD) and extended X-ray absorption fine structure (EXAFS) measurements and complemented with density and thermoanalysis (TG-DTA) results. EXAFS and XRPD results show that no-washed nanoparticulate powders are composed of a mixture of ZnO (wurtzite), zinc acetate, and zinc hydroxyacetate. The latter has a layered structure typical of hydroxy double salts (HDS). The main component of no-washed powders is always unreacted zinc acetate solid but the relative amount of the zinc-based compounds depends on the nature of the hydrolytic catalyst, hydrolysis ratio, and of synthesis temperature. According to the proportion of the three zinc-based compounds, three families of powders could be distinguished. The amount of ZnO nanoparticles (1.6 +/- 0.6 nm) decreases as the synthesis temperature increases, as the hydrolysis ratio decreases, or by changing from basic to acid catalysis. This finding suggests that the formation of zinc compounds is controlled by the equilibrium between hydrolysis-condensation and complexation-reprecipitation reactions.

Solvent free esterification reactions using Lewis acids in solid phase catalysis

A clean, efficient and fast method for esterification reactions for sterically (biodiesels) or otherwise inactive (aromatic) precursors was developed, using catalysts supported in a solid phase under solvent free conditions, and whose reactions can be promoted by MW irradiation. (c) 2006 Elsevier B.V. All rights reserved.

The high-eccentricity asymmetric expansion of the disturbing function for non-planar resonant problems

In this paper we present an extension to the nonplanar case of the asymmetric expansion of the averaged resonant disturbing function of Ferraz-Mello & Sato (1989, A&A 225, 541-547). Comparions with the exact averaged disturbing function are also presented. The expansion gives a good approximation of the exact function in a wide region around the center of expansion.

Resonance and chaos .2. Exterior resonances and asymmetric libration

The motion of a test particle in the vicinity of exterior resonances is examined in the context of the planar, circular, restricted three-body problem. The existence of asymmetric periodic orbits associated with the 1 : n resonances (where n = 2, 3, 4, 5) is confirmed; there is also evidence of asymmetric resonances associated with larger values of n. A detailed examination of the evolution of the family of orbits associated with the 1:2 resonance shows the sequence that leads to asymmetric libration. on the basis of numerical studies of the phase space it is concluded that the existence of asymmetric libration means that the region exterior to the perturbing mass is more chaotic than the interior region. The apparent absence of 'particles' in 1 : n resonances in the solar system may reflect this inherent bias.

Thermal effects on the catalysis by a magnetic field

We show that the formation of condensates in the presence of a constant magnetic field in 2+1 dimensions is extremely unstable. It disappears as soon as a heat bath is introduced with or without a chemical potential. The value of the condensate as well as other observables are shown to become nonanalytic at finite temperature.

Resonance and chaos: II. Exterior resonances and asymmetric libration

The motion of a test particle in the vicinity of exterior resonances is examined in the context of the planar, circular, restricted three-body problem. The existence of asymmetric periodic orbits associated with the 1 : n resonances (where n = 2, 3, 4, 5) is confirmed; there is also evidence of asymmetric resonances associated with larger values of n. A detailed examination of the evolution of the family of orbits associated with the 1:2 resonance shows the sequence that leads to asymmetric libration. On the basis of numerical studies of the phase space it is concluded that the existence of asymmetric libration means that the region exterior to the perturbing mass is more chaotic than the interior region. The apparent absence of 'particles' in 1 : n resonances in the solar system may reflect this inherent bias.