Analysis of ESE signal decay modulation for H atoms trapped in 8 M H2SO4 at 77 K

A method is proposed to analyze modulation effects induced in an electron spin echo by weak hyperfine interactions with protons. This method allows one to distinguish the contribution from the protons of the first sphere surrounding a H atom trapped in 8 M H₂SO₄ and that from the matrix protons.     

Rademacher multiplicator spaces equal to

Let be a rearrangement invariant function space on [0,1]. We consider the Rademacher multiplicator space of measurable functions such that for every a.e. converging series , where are the Rademacher functions. We characterize the situation when . We also discuss the behaviour of partial sums and tails of Rademacher series in function spaces.

     

Structural studies of the molybdenum center of the pathogenic R160Q mutant of human sulfite oxidase by pulsed EPR spectroscopy and 17O and 33S labeling

Electron paramagnetic resonance (EPR) investigation of the Mo(V) center of the pathogenic R160Q mutant of human sulfite oxidase (hSO) confirms the presence of three distinct species whose relative abundances depend upon pH. Species 1 is exclusively present at pH < or = 6, and remains in significant amounts even at pH 8. Variable-frequency electron spin echo envelope modulation (ESEEM) studies of this species prepared with (33)S-labeled sulfite clearly show the presence of coordinated sulfate, as has previously been found for the "blocked" form of Arabidopsis thaliana at low pH (Astashkin, A. V.; Johnson-Winters, K.; Klein, E. L.; Byrne, R. S.; Hille, R.; Raitsimring, A. M.; Enemark, J. H. J. Am. Chem. Soc. 2007, 129, 14800). The ESEEM spectra of Species 1 prepared in (17)O-enriched water show both strongly and weakly magnetically coupled (17)O atoms that can be assigned to an equatorial sulfate ligand and the axial oxo ligand, respectively. The nuclear quadrupole interaction (nqi) of the axial oxo ligand is substantially stronger than those found for other oxo-Mo(V) centers studied previously. Additionally, pulsed electron-nuclear double resonance (ENDOR) measurements reveal a nearby weakly coupled exchangeable proton. The structure for Species 1 proposed from the pulsed EPR results using isotopic labeling is a six-coordinate Mo(V) center with an equatorial sulfate ligand that is hydrogen bonded to an exchangeable proton. Six-coordination is supported by the (17)O nqi parameters for the axial oxo group of the model compound, (dttd)Mo(17)O((17)Otms), where H2dttd = 2,3:8,9-dibenzo-1,4,7,10-tetrathiadecane; tms = trimethylsilyl. Reduction of R160Q to Mo(V) with Ti(III) gives primarily Species 2, another low pH form, whereas reduction with sulfite at higher pH values gives a mixture of Species 1 and 2, as well as the "primary" high pH form of wild-type SO. The occurrence of significant amounts of the "sulfate-blocked" form of R160Q (Species 1) at physiological pH suggests that this species may be a contributing factor to the lethality of this mutation.     

1H pulsed ENDOR and ESEEM evidence that the bis-imidazole complexes of iron(III) tetraphenylchlorin and tetraphenylporphyrin have the same order of g values, and the same electronic ground state.

The electronic structures of the bis-imidazole complexes of iron(III) tetraphenylporphyrin ([(TPP)Fe(ImH)(2)](+)) and iron(III) tetraphenylchlorin ([(TPC)Fe(ImH)(2)](+)) in frozen glassy solutions have been studied by the pulsed electron nuclear double resonance (ENDOR) technique of Mims and by electron spin-echo envelope modulation (ESEEM) spectroscopy. ESEEM spectra have been used to determine the orientation of the imidazole ligand planes with respect to the g tensor axes. In the ENDOR spectra, the manifestations of the implicit TRIPLE effect described and explained earlier by Doan et al. (J. Am. Chem. Soc. 1996, 118, 7014) were seen. In this work, the explicit expressions describing this effect were derived for the first time and used to successfully simulate the proton ENDOR spectra at the low- (LF) and high-field (HF) edges of the EPR spectrum. Using pulsed ENDOR, we have been able to determine the spin density distributions in the pi-systems of both tetrapyrroles and show that [(TPC)Fe(ImH)(2)](+) has the electronic orbital ground state (d(xy)())(2)(d(xz)(),d(yz)())(3), the same as that known for [(TPP)Fe(ImH)(2)](+), and the largest principal g value corresponds to the g tensor axis 3, which is normal to the heme plane. For the TPP complex, the g tensor axis 1, corresponding to the smallest principal g value, was found to be at an angle phi(1) of 30-35 degrees from the N-Fe-N axis, with the ligand planes rotated by the angle of 20-25 degrees in the opposite direction. For the TPC complex, phi(1) was found to be about 25 degrees from the direction N(I)-Fe-N(III), where N(I) corresponds to the nitrogen of the saturated pyrrole ring. The ligand planes in this complex were found to be oriented at an angle of about 10 degrees in the opposite direction.     

On a Property of Rearrangement Invariant Spaces whose Second Köthe Dual is Nonseparable

Mathematical Notes - We study the family of rearrangement invariant spaces E containing subspaces on which the E-norm is equivalent to the L1-norm and a certain geometric characteristic related to...