Transesterification of an RNA model in buffer solutions in H2O and D2O

Transesterification of a phosphodiester bond of RNA models has been studied in various buffer solutions, under neutral and slightly alkaline conditions in H₂O and D₂O. The results show that imidazole is the only buffer system where a clear buffer catalysis on the cleavage of a phosphodiester bond is observed. The rate enhancement in sulphonic acid buffers is smaller, and a sulphonate base, particularly, is inactive as a catalyst. The rate‐enhancing effect of imidazole is, however, catalytic, and the catalytic inactivity of sulphonate buffers can be attributed to their structure and/or charge. The catalysis by imidazole is a complex system which, in addition to first‐order reactions, involves a process that shows a second‐order dependence in imidazole concentration. The latter reaction becomes significant in acidic imidazole buffers (pH < pK_a), as the buffer concentration increases. The kinetic solvent deuterium isotope effect k_H/k_D, referring to first‐order catalysis by imidazole base, is 2.3 ± 0.3. That referring to second‐order catalysis is most probably much larger, but an accurate value could not be obtained. Copyright © 2007 John Wiley & Sons, Ltd.     

Orthogonal Cationic and Radical RAFT Polymerizations to Prepare Bottlebrush Polymers

An orthogonal combination of cationic and radical RAFT polymerizations is used to synthesize bottlebrush polymers using two distinct RAFT agents. Selective consumption of the first RAFT agent is used to control the cationic RAFT polymerization of a vinyl ether monomer bearing a secondary dormant RAFT agent, which subsequently allows side‐chain polymers to be grafted from the pendant RAFT agent by a radical‐mediated RAFT polymerization of a different monomer, thus completing the synthesis of bottlebrush polymers. The high efficiency and selectivity of the cationic and radical RAFT polymerizations allow both polymerizations to be conducted in one‐pot tandem without intermediate purification.     

Fluorine NMR studies of solid SiF4

Fluorine NMR second moments and spin-lattice relaxation times were measured for solid SiF₄. The results indicate a hindered molecular motion and piezoelectricity in solid SiF₄.     

Hydrolytic reactions of diadenosine 5',5'-triphosphate

The hydrolysis of diadenosine 5',5'-triphosphate to AMP and ADP has been studied over a wide pH-range. Under acidic conditions the reaction shows a first-order dependence on the hydronium ion concentration. Below pH 3 the rate-increase begins to level off. From pH 6 to 9 the hydrolysis is slow and pH-independent. Base-catalysed hydrolysis is observed in NaOH-solutions. Under alkaline conditions an intramolecular nucleophilic attack on the phosphate producing 3',5'-cAMP is also observed, but it is slower than the intermolecular reaction. Depurination of the adenosine moieties competes with the hydrolysis both under acidic and alkaline conditions, but the mechanisms are different. The temperature-dependence of the hydrolysis of Ap(3)A and the depurination of adenosine moieties were studied under acidic conditions, and the activation parameters of the reactions were calculated. The results of the work reflect the fact that the negatively charged polyphosphate group is very resistant towards nucleophilic attack. An efficient catalysis is only observed under acidic conditions, where the phosphate group becomes protonated. General acids or bases did not catalyse the hydrolysis. Furthermore, hydroxide ion catalysed cleavage is only observed at high base concentrations and other negatively charged nucleophiles did not attack the phosphate groups of diadenosine polyphosphates.     

Microscopic structure of fundamental excitations in N = Z nuclei

An extended mean-field model is presented that describes states of different isospin in odd-odd and even-even nuclei. Excitation energies of the T = 1 states in even-even as well as T = 0 and T = 1 states in odd-odd N = Z nuclei are calculated. It is shown that the structure of these states can be determined in a consistent manner when both isoscalar and isovector pairing collectivity as well as isospin projection (treated here within the isocranking approximation) are taken into account. In particular, in odd-odd N = Z nuclei, the interplay between quasiparticle excitations (relevant for the case of T = 0 states) and isorotations (relevant for the case of T = 1 states) explains the near degeneracy of these states.     

Rotations in isospace: a doorway to the understanding of neutron-proton superfluidity in N = Z nuclei

The T = 2 excitations in even-even N = Z nuclei are calculated within the isospin cranked mean-field approach. The response of pairing correlations to rotation in isospace is investigated. Whereas the isovector pairing rather modestly modifies the single-particle moment of inertia in isospace, the isoscalar pairing strongly reduces its value. This reduction of the isomoments of inertia with respect to its rigid body value is a strong indicator of collective isoscalar pairing correlations. These results are further generalized yielding beautiful analogies between the role of isovector pairing for the case of spatial rotations and the role of isoscalar pairing for the case of isorotations.     

Local structure and magnetism of Fe, Co and Ni doped Cr3Si

The lattice site occupation of 3d-type impurities in Cr₃Si doped with Fe, Co and Ni were studied using the Extended X-ray Absorption Fine Structure (EXAFS) technique, X-rays and magnetic susceptibility measurements. The EXAFS measurements were performed particularly carefully on the K-edge of chromium and cobalt. EXAFS data strengthened by simulations of the spectra show unambiguously that the impurities are occupying mostly Cr-sites. The magnetic state of the alloys has been studied theoretically using the Wien2k code. It is observed that if calculations are not carried out on an appropriately fine mesh of points in k-space, one can get the result indicating ferromagnetism although the overall magnetic moment per formula unit is weak.     

Angular Distribution of Hyperfine Magnetic Field in Fe3O4 and Fe66Ni34 from Mössbauer Polarimetry

Nuclear resonance studies of the two different types impurity doped potassium hexachloro-stannates, the isomorphic system such as (K–Rb)₂SnCl₆ and K₂(Sn–Re)Cl₆ and the nonisomorphic system K₂SnCl₆:Al³⁺ in the high temperature cubic phase revealed contrasting features with one the other characterized by static in the former and dynamic feature in the latter case respectively. The resonance spectra of the nonisomorphic system indicate additionally a sign of the local structural transition above the conventional structural phase transition temperature. This seems to be triggered by the ligand-deficient octahedral defects and can be explained in terms of the enhanced activity of the octahedral defects for the hindered rotation.     

Study of Amorphous Ferrimagnet Fe0.66Er0.19B0.15 by Means of Monochromatic Circularly Polarised Source

Properties of amorphous alloy Fe_0.66Er_0.19B_0.15 are reported. A reorientation of the Fe and Er magnetic moments during sample cooling through the compensation point in a large magnetic field is found by means of monochromatic circularly polarised radiation. This revised version was published online in August 2006 with corrections to the Cover Date.