Thermodynamic and kinetic studies on the binding of nitric oxide to a new enzyme mimic of cytochrome p450

A new model for the P450 enzyme carrying a SO(3)(-) ligand coordinated to iron(III) (complex 2) reversibly binds NO to yield the nitrosyl adduct. The rate constant for NO binding to 2 in toluene is of the same order of magnitude as that found for the nitrosylation of the native, substrate-bound form of P450(cam) (E.S-P450(cam)). Large and negative activation entropy and activation volume values for the binding of NO to complex 2 support a mechanism that is dominated by bond formation with concomitant iron spin change from S = (5)/(2) to S = 0, as proposed for the reaction between NO and E.S-P450(cam). In contrast, the dissociation of NO from 2(NO) was found to be several orders of magnitude faster than the corresponding reaction for the E.S-P450(cam)/NO system. In a coordinating solvent such as methanol, the alcohol coordinates to iron(III) of 2 at the distal position, generating a six-coordinate, high-spin species 5. The reaction of NO with 5 in methanol was found to be much slower in comparison to the nitrosylation reaction of 2 in toluene. This behavior can be explained in terms of a mechanism in which methanol must be displaced during Fe-NO bond formation. The thermodynamic and kinetic data for NO binding to the new model complexes of P450 (2 and 5) are discussed in reference to earlier results obtained for closely related nitrosylation reactions of cytochrome P450(cam) (in the presence and in the absence of the substrate) and a thiolate-ligated iron(III) model complex.     

Synthesis of 17-epi-calcitriol from a common androstane derivative, involving the ring B photochemical opening and the intermediate triene ozonolysis

An efficient synthesis of 17-epi-calcitriol 2, an epimer of natural hormone, via 17-epi-cholesterol 5a is described. Synthesis of 5a includes palladium-catalyzed cyclopropanation of the common androstane derivative 7 with an alkyl diazoacetate, reductive fission of the less shielded side of cyclopropane carboxylic acid esters 6, oxidation of the products into acid 11a, and alkylation of ester 11b. Photolysis of 7,8-dedydro-17-epi-25-hydroxycholesterol 19b and consecutive thermal rearrangement gave a mixture of several products that was subjected to ozonolysis to provide, after chromatography, hydroxy ketone 3a. The silyl derivative 3b was coupled with the respective ring A building block.     

Concerning closed invariant subspaces for endomorphisms of the space (s)

We show that every (continuous) endomorphism of the complex space (s) has a proper closed invariant subspace which is either of dimension one or of codimension one. We give also a related result for the real space (s). This revised version was published online in June 2006 with corrections to the Cover Date.     

Linear baryons and SU(3) breaking

The recently proposed mechanism of dynamical SU(3) symmetry breaking in linear baryons is applied to the α-γ sector after taking into account two types of α and γ trajectories. The observed splitting pattern of leading strange baryon trajectories is qualitatively explained. The implications of the scheme for ground state baryons are discussed.     

Quantum scattering in the strip: From ballistic to localized regimes

Quantum scattering is studied in a system consisting of randomly distributed point scatterers in the strip. The model is continuous yet exactly solvable. Varying the number of scatterers (the sample length) we investigate a transition between the ballistic and the localized regimes. By considering the cylinder geometry and introducing the magnetic flux we are able to study time reversal symmetry breaking in the system. Both macroscopic (conductance) and microscopic (eigenphases distribution, statistics of S-matrix elements) characteristics of the system are examined. Received: 28 January 1998 / Revised: 16 June 1998 / Accepted: 6 July 1998     

On improving the accuracy of Horner’s and Goertzel’s algorithms

It is known that Goertzels algorithm is much less numerically accurate than the Fast Fourier Transform (FFT) (cf. [2]). In order to improve accuracy we propose modifications of both Goertzels and Horners algorithms based on the divide-and-conquer techniques. The proof of the numerical stability of these two modified algorithms is given. The numerical tests in Matlab demonstrate the computational advantages of the proposed modifications. The appendix contains the proof of numerical stability of Goertzels algorithm of polynomial evaluation. AMS subject classification 65F35, 65G50     

Total absorption spectroscopy of the β-delayed proton emitter 117Ba

The very neutron-deficient ¹¹⁷Ba nuclei were produced in ⁵⁸Ni-induced reactions on a ⁶³Cu target and selected for spectroscopic studies by using BaF⁺ molecules formed in the ion source of the GSI on-line mass separator. The -decay of ¹¹⁷Ba was investigated by means of the total absorption -ray spectrometer and a telescope for -delayed particle detection. In the analysis combining the -delayed -ray and proton data the energy window available for -delayed proton emission, the branching ratios for proton transitions to the ¹¹⁶Xe levels and the -feeding of the -ray and proton-emitting ¹¹⁷Cs states were determined. The -strength function for ¹¹⁷Ba derived from the measured -feeding distribution revealed the existence of a broad resonance structure at ¹¹⁷Cs excitation energy of about 4-5 MeV. The results of the -delayed proton studies and -strength measurements are confronted with theoretical predictions.     

Study of time changes of anion exchanger electrode characteristics

The elution of the anion exchanger from the membranes of ion-selective electrodes and its influence on the electrode characteristics are studied. The decrease of the exchanger concentration in the PVC membrane depends on the exchanger lipophilicity and the concentration of the counter ion in the external solution. On this basis it is possible to estimate the electrode life time and limit of detection.Dedicated to Professor W. Simon on the occasion of his 60th birthday     

The Equivalence of Ergodicity and Weak Mixing for Infinitely Divisible Processes

The equivalence of ergodicity and weak mixing for general infinitely divisible processes is proven. Using this result and [9], simple conditions for ergodicity of infinitely divisible processes are derived. The notion of codifference for infinitely divisible processes is investigated, it plays the crucial role in the proofs but it may be also of independent interest.