Q-band EPR and ENDOR of low temperature X-irradiated beta-D-fructose single crystals

Beta-D-fructose single crystals were in situ X-irradiated at 80 K and measured using electron paramagnetic resonance (EPR), electron nuclear double resonance (ENDOR) and ENDOR-induced EPR (EIE) techniques at Q-band (34 GHz) microwave frequencies. The measurements revealed the presence of at least four carbon-centered radicals stable at 80 K. By means of ENDOR angular variations in the three principal crystallographic planes, six proton hyperfine coupling tensors could be determined and were assigned to four different radicals by the aid of EIE. Two of the radicals exhibit only beta-proton hyperfine couplings and reveal almost identical EIE spectra. For the other two radicals, the major hyperfine splitting originates from a single alpha-proton hyperfine coupling and their EIE spectra were also quite similar. The similarity of the EIE spectra and hyperfine tensors led to the assumption that there are only two essentially different radical structures. The radical exhibiting only beta-proton hyperfine couplings was assigned to a C3 centered radical arising from H3 abstraction and the other radical suggested to be an open-ring species with a disrupted C2-C3 bond and a double C2-O2 bond. A possible formation mechanism for the latter open-ring radical is presented. By means of cluster density functional theory (DFT) calculations, the structures of the two radicals were determined and a fairly good agreement between the calculated and experimental hyperfine tensors was found.     

Density functional investigation of high-spin XY (X = Cr, Mo, W and Y = C, N, O) molecules

The performance of a density functional theory approach in calculating the equilibrium bond length, dipole moment, and harmonic vibrational frequency in a series of group 6 (Cr, Mo, W) transition metal-containing diatomic molecules is evaluated. Using flexible basis sets comprised of Slater type functions, a wide range of exchange-correlation functionals is investigated. Comparing with known experimental values and published results from high-level theoretical calculations, the most suitable functional form is selected. The importance of relativistic effects is checked, and predictions are made for several unknown dipole moments. The best agreement with experimental parameters is obtained when using a general gradient approximation, while special and hybrid functional forms give less accurate results.     

A Multi-Frequency EPR and ENDOR Study of Rh and Ir Complexes in Alkali and Silver Halides

Aliovalent Rh and Ir cations have been frequently used to influence the photographic properties of silver halide emulsions. The doping introduces several types of related defects with distinct trapping and recombination properties. EPR and ENDOR are, in principle, ideally suited for the determination of the microscopic structure of the individual centres but it will be demonstrated that well-chosen, sometimes sophisticated multi-frequency experiments are necessary in order to (partially) reach this goal. Model studies on single crystals of AgCl and NaCl also appeared indispensable for the unravelling of the spectra.

In the review of Rh-centres in NaCl and AgCl special attention is paid to methods that allow to detect cation vacancies near Rh^2? complexes. An alternative explanation for the high temperature behaviour of the [RhCl₆]^4? complexes in AgCl is presented.     

Friedel-Crafts alkylation of benzo[b]furan with activated cyclopropanes catalyzed by a calcium(II) complex

The synthesis of γ-benzo[b]furanyl malonates was achieved through the addition of benzo[b]furan to activated cyclopropanes. These Friedel-Crafts reactions were catalyzed by calcium bis(trifluoromethanesulfonimide), Ca(NTf₂)₂ with tetrabutylammonium hexafluorophosphine as a co-catalyst. The additions proceeded with complete regioselectivity and in good to excellent yield. Optimization of the reaction conditions and investigation into the scope of the methodology with regards to substitution on the cyclopropane are reported.     

Crystal and molecular structure of a steroidal spirocyclic lactone, C29H34O4

The X-ray crystal structure of the title compound, as crystallized from methanol–methylene chloride was determined. The asymmetric unit contains two steroid molecules, which differ primarily in the orientation of the aromatic rings of the benzyl ethers. The title compound crystallizes in the noncentrosymmetric space group P2(1), with a = 7.558(2), b = 16.673(3), c = 18.735(4) Å, = 97.610(10)°, and D _calc = 1.268 g cm^–1 for Z = 4.     

Electron paramagnetic resonance study of a Eu2+ related defect in CsBr:Eu needle image plates for computed radiography

The electron paramagnetic resonance (EPR) spectrum of needle image plates of CsBr doped with Eu(2+), which are proposed as new X-ray storage phosphors for computed radiography, is studied at room temperature and Q-band microwave frequencies (34 GHz). X-ray diffraction analysis demonstrates that the CsBr:Eu(2+) needles have an 001 out of plane (perpendicular to the plate) orientation, and contrary to expectation that the in plane orientation is not random. The room temperature EPR spectrum is attributed to a single centre which is related to Eu(2+) with axial 001 symmetry. Using the spin Hamiltonian parameters extracted from the spectrum recorded with the magnetic field parallel to the needles' axes, we convincingly simulate both the spectrum of a powdered image plate and the single crystal like angular dependence of intact pieces of image plate. The knowledge of the symmetry of this centre, which appears to be related with the radiation sensitivity of the plate, presents a first step in finding its model and role in the X-ray storage process.     

Vibrational spectroscopy of nitroalkane chains using electron autodetachment and ar predissociation

If the binding energy of an excess electron is lower than some of the vibrational levels of its host anion, vibrational excitation can lead to autodetachment. We use excitation of CH stretching modes in nitroalkane anions (2700-3000 cm(-1)), where the excess electron is localized predominantly on the NO2 group. We present data on nitroalkane anions of various chain lengths, showing that this technique is a valid approach to the vibrational spectroscopy of such systems extending to nitroalkane anions at least the size of nitropentane. We compare spectra taken by using vibrational autodetachment with spectra obtained by monitoring Ar evaporation from Ar solvated nitroalkane anions. The spectra of nitromethane and nitroethane are assigned on the basis of ab initio calculations with a detailed analysis of Fermi resonances of CH stretching fundamentals with overtones and combination bands of HCH bending modes.     

On the origins of sudden adhesion loss at a critical relative humidity: examination of bulk and interfacial contributions

The origins for abrupt adhesion loss at a critical relative humidity (RH) for polymeric adhesives bonded to inorganic surfaces have been explored using a model poly(methyl methacrylate) (PMMA) film on glass. The interfacial and bulk water concentrations within the polymer film as a function of D 2O partial pressure were quantified using neutron reflectivity. Adhesion strength of these PMMA/SiO 2 interfaces under the same conditions was quantified using a shaft loaded blister test. A drop in adhesion strength was observed at a critical RH, and at this same RH, a discontinuity in the bulk moisture concentration occurred. The moisture concentration near the interface was higher than that in the bulk PMMA, and at the critical RH, the breadth of the interfacial water concentration distribution as a function of distance from the SiO 2/PMMA interface increased dramatically. We propose a mechanism for loss of adhesion at a critical RH based upon the interplay between bulk swelling induced stress and weakening of the interfacial bond by moisture accumulation at the PMMA/SiO 2 interface.     

Multifrequency electron paramagnetic resonance study on deproteinized human bone

Irradiated samples of deproteinized powdered human bone (femur) have been examined by electron paramagnetic resonance (EPR) spectroscopy in X, Q and W bands. In the bone powder sample only one type of CO2- radical ion is stabilized in the hydroxyapatite structure in contrast to powdered human tooth enamel, a material also containing hydroxyapatite, widely used for EPR dosimetry and in which a few radicals are stable at room temperature. It is suggested that the use of deproteinized bone for EPR dosimetry could improve the accuracy of dose determination.     

Genetic microheterogeneity of human transthyretin detected by IEF

Mutations of the human transthyretin (TTR) gene have attracted medical interest as a cause of amyloidosis. Recently, we have described in detail an electrophoretic procedure with PAGE followed by IEF in urea gradients for the study of the microheterogeneity of TTR monomers (Altland, K., Winter, P., Sauerborn, M. K., Electrophoresis 1999, 20, 1349-1364). In this paper, we present a study on 49 different mutations of TTR including 33 that result in electrically neutral amino acid substitutions. The aims of the investigation were to test the sensitivity of the procedure to detect TTR variants in patients with TTR amyloidosis and their relatives and to identify some common characteristics that could explain the amyloidogenicity of these variants. We found that all tested amyloidogenic mutations could be detected by our method with the exception of those for which the corresponding variant was absent in plasma samples. Most of the electrically neutral amyloidogenic TTR variants had in common a reduced conformational stability of monomers by the activity of protons and urea. For three variants, e.g. TTR-F64L, TTR-I107V and TTR-V122I, the monomers had a conformational stability close to that of normal monomers but we found experimental and structural arguments for a weakening of the monomer-monomer contact. All types of amyloidogenic mutations affected the stability of TTR tetramers.