Active site structure and mechanism of human glyoxalase I-an ab initio theoretical study.

The structure of the active site of human glyoxalase I and the reaction mechanism of the enzyme-catalyzed conversion of the thiohemiacetal, formed from methylglyoxal and glutathione, to S-D-lactoylglutathione has been investigated by ab initio quantum chemical calculations. To realistically represent the environment of the reaction center, the effective fragment potential methodology has been employed, which allows systems of several hundred atoms to be described quantum mechanically. The methodology and the active site model have been validated by optimizing the structure of a known enzyme-inhibitor complex, which yielded structures in good agreement with the experiment. The same crystal structure has been used to obtain the quantum motif for the investigation of the glyoxalase I reaction. The results of our study confirm that the metal center of the active site zinc complex plays a direct catalytic role by binding the substrate and stabilizing the proposed enediolate reaction intermediate. In addition, our calculations yielded detailed information about the interactions of the substrate, the reaction intermediates, and the product with the active site of the enzyme and about the mechanism of the glyoxalase I reaction. The proton transfers of the reaction proceed via the two highly flexible residues Glu172 and Glu99. Information about the structural and energetic effect of the protein on the first-shell complex has been attained by comparison of the structures optimized in the local protein environment and in a vacuum. The environment of the zinc complex disturbs the Cs symmetry found for the complex in a vacuum, which suggests an explanation for the stereochemical behavior of glyoxalase I.     

Nachweis und Bestimmung des Eisens, sowie seine Trennung von anderen Elementen

Ohne Zusammenfassung     

Measurement of Residence Time Distribution with Radiotracers Using Periodic Pseudo-Random Binary Signal Sequences

A review about the properties of several types of tracerinput signals is given and in particular the stochastic signals are discussed. An estimation of the necessary measuring time shows, that true stochastic signals are unimportant for tracer experiments. The use of periodic pseudo-random binary signals (PRBS) permits a strong reduction of the measuring time. Therefore their practical application for tracer experiments is possible. The PRBS-method has special advantages in comparison with impulse methods, if fluctuations and disturbances exist within the investigated systems. Correlations for the estimation of parameters, needed for the realization of PRBS-measurements, are given and several measuring arrangements are discussed.

The application of the PRBS-method for measurements of residence time distributions (RDC) of a mixer-settler extractor is described.     

Certification aspects of the fast gradient method for solving the dual of parametric convex programs

This paper examines the computational complexity certification of the fast gradient method for the solution of the dual of a parametric convex program. To this end, a lower iteration bound is derived such that for all parameters from a compact set a solution with a specified level of suboptimality will be obtained. For its practical importance, the derivation of the smallest lower iteration bound is considered. In order to determine it, we investigate both the computation of the worst case minimal Euclidean distance between an initial iterate and a Lagrange multiplier and the issue of finding the largest step size for the fast gradient method. In addition, we argue that optimal preconditioning of the dual problem cannot be proven to decrease the smallest lower iteration bound. The findings of this paper are of importance in embedded optimization, for instance, in model predictive control.     

Bioinspired Metal-Free Formal Decarbonylation of α-Branched Aliphatic Aldehydes at Ambient Temperature

A sequence of a Baeyer–Villiger oxidation and a Lewis acid-promoted reduction of the resulting formate with Et₃SiH enabled the metal-free formal decarbonylation of tertiary and secondary aliphatic aldehydes. The new methodology mimics the biosynthetic decarbonylation pathway through oxidative C−C bond cleavage rather than the C(O)−H bond activation known from conventional Tsuji–Wilkinson-type reactions. The substrate scope is complementary to existing transition-metal-catalyzed protocols.     

Synthese,Strukturen, NMR‐ und EPR‐Untersuchungen der binuklearen Bis(N,N,N‴,N‴‐tetraisobutyl‐N′,N″‐isophthaloylbis(selenoureato))‐Komplexe des NiII und CuII

Synthesis, Structures, NMR and EPR Investigations of Binuclear Bis(N,N,N‴,N‴‐tetraisobutyl‐N′,N″‐isophthaloylbis(selenoureato)) Complexes of Ni^II and Cu^II The synthesis of binuclear Cu^II and Ni^II complexes of the quadridentate ligand N,N,N‴,N‴‐tetraisobutyl‐N′,N″‐isophthaloylbis(selenourea) and their crystal structures are reported. The complexes crystallize monoclinic, P2₁/c (Z = 2). In the EPR spectra of the binuclear Cu^II complex exchange‐coupled Cu^II‐Cu^II pairs were observed. In addition the signals of a mononuclear Cu^II species are observed what will be explained with the assumption of an equilibrium between the binuclear Cu^II‐complex (Cu^II‐Cu^II pairs) and oligomeric complexes with “isolated” Cu^II ions. Detailed ¹³C and ⁷⁷Se NMR investigations on the ligand and the Ni^II complex allow an exact assignment of all signals of the heteroatoms.