Highly Efficient Trityl-Nitroxide Biradicals for Biomolecular High-Field Dynamic Nuclear Polarization

Dynamic nuclear polarization (DNP) is a powerful method to enhance the sensitivity of solid-state magnetic nuclear resonance (ssNMR) spectroscopy. However, its biomolecular applications at high magnetic fields (preferably>14 T) have so far been limited by the intrinsically low efficiency of polarizing agents and sample preparation aspects. Herein, we report a new class of trityl-nitroxide biradicals, dubbed SNAPols that combine high DNP efficiency with greatly enhanced hydrophilicity. SNAPol-1, the best compound in the series, shows DNP enhancement factors at 18.8 T of more than 100 in small molecules and globular proteins and also exhibits strong DNP enhancements in membrane proteins and cellular preparations. By integrating optimal sensitivity and high resolution, we expect widespread applications of this new polarizing agent in high-field DNP/ssNMR spectroscopy, especially for complex biomolecules.     

Finite quotients of the multiplicative group of a finite dimensional division algebra are solvable

We prove that finite quotients of the multiplicative group of a finite dimensional division algebra are solvable. Let be a finite dimensional division algebra having center , and let be a normal subgroup of finite index. Suppose is not solvable. Then we may assume that is a minimal nonsolvable group (MNS group for short), i.e. a nonsolvable group all of whose proper quotients are solvable. Our proof now has two main ingredients. One ingredient is to show that the commuting graph of a finite MNS group satisfies a certain property which we denote Property . This property includes the requirement that the diameter of the commuting graph should be , but is, in fact, stronger. Another ingredient is to show that if the commuting graph of has Property , then is open with respect to a nontrivial height one valuation of (assuming without loss of generality, as we may, that is finitely generated). After establishing the openness of (when is an MNS group) we apply the Nonexistence Theorem whose proof uses induction on the transcendence degree of over its prime subfield to eliminate as a possible quotient of , thereby obtaining a contradiction and proving our main result.

     

Tube-wave propagation in a fluid-filled borehole generated by a single point force applied to the surrounding formation

Propagation of tube waves in an infinite fluid-filled borehole, generated by a single-force point source placed in the elastic surrounding formation, is analyzed in the long-wave approximation. Integral representations of the precise solution are obtained both for fast and slow formations. An asymptotic analysis of tube-wave propagation in the fluid-filled borehole is performed on the basis of these two integral representations. The complete asymptotic wave field in the borehole fluid for a fast formation consists of P and SV phases and the lowest eigenmode of the Stoneley wave (tube wave). For a slow formation the conical Stoneley wave (Mach wave) is generated. It appears only behind the critical angle defined by the ratio of the S wave velocity in the formation to the low-frequency Stoneley wave velocity and decays weakly with an offset. Asymptotic wave forms are in good agreement with wave forms obtained by straightforward calculations.     

Coordination chemistry of tripyridinedimethane

The ligand tripyridinedimethane (tpdm), consisting of three pyridine residues linked at their ortho carbons by two CH(2) groups, is shown to be a sterically flexible ligand capable of binding in a meridional arrangement in trigonal bipyramidal (tpdm) Cu(II)Cl(2) but binding in a facial arrangement in tetrahedral (tpdm) Cu(I)Cl. Nucleophilic substitution of chloride by (t)BuO(-) and PhC[triple bond]C(-) is possible, and deprotonation of the acidic benzylic protons does not take place because the resulting carbanion cannot achieve coplanarity with the aryl rings. RhCl(3) forms, with tpdm in boiling methanol, a 1:1 kinetic mixture of fac- and mer-isomers RhCl(3)(tpdm). The former isomerizes slowly at RT (room temperature) in DMSO solution into the latter with Rh-N bond dissociation as the rate-determining step.     

Precipitation of inorganic salts inside hollow micrometer-sized polyelectrolyte shells

Hollow polymer shells formed by layer-by-layer adsorption of oppositely charged polyelectrolytes onto micrometer-sized colloidal particles with subsequent decomposition of the colloidal core were employed as a model system for the study of inorganic crystallization reactions in restricted volumes. The size-selective permeability of shells is used for spatially controlling the precipitation of inorganic salts CaCO3 and BaCO3 into the shell interior. Outside the shells the precipitation was suppressed by the polymers, which are unable to penetrate the shell wall. The precipitates were studied by scanning electron microscopy and atomic force microscopy. The fundamental and applied aspects of research on spatially confined synthesis of inorganic particles are under discussion.     

Theory of ferromagnetism in Ca(1-x)La(x)B(6)

Novel ferromagnetism in Ca(1-x)La(x)B(6) is studied in terms of the Ginzburg-Landau theory for excitonic-order parameters, taking into account symmetry of the wave functions. We found that the minima of the free energy break both inversion and time-reversal symmetries, while the product of these two remains preserved. This explains various novelties of the ferromagnetism and predicts a number of magnetic properties, including the magnetoelectric effect, which can be tested experimentally.