The mechanism of MIO-based aminomutases in beta-amino acid biosynthesis

Beta-amino acids are widely used building blocks in both natural and synthetic compounds. Aromatic beta-amino acids can be biosynthesized directly from proteinogenic alpha-amino acids by the action of MIO (4-methylideneimidazole-5-one)-based aminomutase enzymes. The uncommon cofactor MIO plays a role in both ammonia lyases and 2,3-aminomutases; however, the precise mechanism of the cofactor has not been resolved. Here we provide evidence that the electrophilic cofactor uses covalent catalysis through the substrate amine to direct the elimination and subsequent readdition of ammonia. A mechanism-based inhibitor was synthesized and the X-ray cocomplex structure was determined to 2.0 A resolution. The inhibitor halts the chemistry of the reverse reaction, providing a stable complex that establishes the mode of substrate binding and the importance of tyrosine 63 in the chemistry. The proposed mechanism is consistent with the biochemistry of aminomutases and ammonia lyases and provides strong support for an amine-adduct mechanism of catalysis for this enzyme class.     

A counterexample for lightning flash modules over E(e1, e2)

We give a counterexample to Theorem 5 in Section 18.2 of Margolis’ book, “Spectra and the Steenrod Algebra” and make remarks about the proofs of some later theorems in the book that depend on it. The counterexample is a module which does not split as a sum of lightning flash modules and free modules.     

Zur Moleculargewichtsbestimmung

Ohne Zusammenfassung     

Oxygen diffusion pathways in a cofactor-independent dioxygenase

Molecular oxygen plays an important role in a wide variety of enzymatic reactions. Through recent research efforts combining computational and experimental methods a new view of O₂ diffusion is emerging, where specific channels guide O₂ to the active site. The focus of this work is DpgC, a cofactor-independent oxygenase. Molecular dynamics simulations, together with mutagenesis experiments and xenon-binding data, reveal that O₂ reaches the active site of this enzyme using three main pathways and four different access points. These pathways connect a series of dynamic hydrophobic pockets, concentrating O₂ at a specific face of the enzyme substrate. Extensive molecular dynamics simulations provide information about which pathways are more frequently used. This data is consistent with the results of kinetic measurements on mutants and is difficult to obtain using computational cavity-location methods. Taken together, our results reveal that although DpgC is rare in its ability of activating O₂ in the absence of cofactors or metals, the way O₂ reaches the active site is similar to that reported for other O₂-using proteins: multiple access channels are available, and the architecture of the pathway network can provide regio- and stereoselectivity. Our results point to the existence of common themes in O₂ access that are conserved among very different types of proteins.     

Graphite layer open tubular (GLOT) columns in gas chromatography and environmental analysis

Summary The preparation of graphite layer open tubular (GLOT) columns is described together with their application to the analysis of priority pollutants and polar compounds such as alcohols, free carboxylic acids, aliphatic amines and phenols at the sub-nanogram level.A specific application of GLOT columns is for the direct analysis of aqueous solutions avoiding solvent extraction procedures. Several chromatograms of critical separations are reported together with calibration curves. A study of the reproducibility of column preparation is reported in terms of the standard deviation of the capacity ratio and of the minimum HETP obtained.     

Measurement of Lambda and Lambda(macro) particles in Au+Au collisions at the square root of S(NN) = 130 GeV

We present results on the measurement of Lambda and Lambda(macro) production in Au+Au collisions at square root of (S (NN) = 130 GeV with the PHENIX detector at the Relativistic Heavy Ion Collider. The transverse momentum spectra were measured for minimum bias and for the 5% most central events. The Lambda;/Lambda ratios are constant as a function of p(T) and the number of participants. The measured net Lambda density is significantly larger than predicted by models based on hadronic strings (e.g., HIJING) but in approximate agreement with models which include the gluon-junction mechanism.     

Flow measurements via two-particle azimuthal correlations in Au + Au collisions at sqrt [s(NN)]=130 GeV

Two-particle azimuthal correlation functions are presented for charged hadrons produced in Au+Au collisions at the Relativistic Heavy Ion Collider (sqrt [s(NN)]=130 GeV). The measurements permit determination of elliptic flow without event-by-event estimation of the reaction plane. The extracted elliptic flow values (v2) show significant sensitivity to both the collision centrality and the transverse momenta of emitted hadrons, suggesting rapid thermalization and relatively strong velocity fields. When scaled by the eccentricity of the collision zone epsilon, the scaled elliptic flow shows little or no dependence on centrality for charged hadrons with relatively low p(T). A breakdown of this epsilon scaling is observed for charged hadrons with pT >1.0 GeV/c.     

Double helicity asymmetry in inclusive midrapidity pi0 production for polarized p+p collisions at square root s = 200 GeV

We present a measurement of the double longitudinal spin asymmetry in inclusive pi(0) production in polarized proton-proton collisions at sqrt[s]=200 GeV. The data were taken at the Relativistic Heavy Ion Collider with average beam polarizations of 0.27. The measurements are the first in a program to study the longitudinal spin structure of the proton, using strongly interacting probes, at collider energies. The asymmetry is presented for transverse momenta 1-5 GeV/c at midrapidity, where next-to-leading-order perturbative quantum chromodynamic (NLO pQCD) calculations well describe the unpolarized cross section. The observed asymmetry is small and is compared to a NLO pQCD calculation with a range of polarized gluon distributions.