Local diffusion in paramagnetic solutions by NMR relaxometry at one frequency

The relative diffusion coefficient D of a paramagnetic species and a diamagnetic probe molecule bearing nuclear spins is obtained from their measured relaxation times T1 and T2 (or T1rho). This is achieved by introducing the longitudinal relaxivity, r1, a linear expression of 1/T1, and the mixed relaxivity, rmix, a linear expression of 1/T1 and 1/T2 (or 1/T1rho). Under weak assumptions, D is proportional to (rmix - r1) to the power -2/3 and to rmix to the power -1, with easy-to-determine proportionality factors. The method is noninvasive and easy to use on standard NMR spectrometers and imagers. It is validated through the study of various solutions of a Gd(III)-based contrast agent for magnetic resonance imaging.     

Higher-order conformal decomposition finite element method

Numerical simulations of structures using higher-order finite elements is still a challenging task, in particular for domains with curved boundaries. A new higher-order accurate approach is proposed, combining the advantages of the classical p-FEM with embedded domain methods. Boundaries and/or interfaces are described implicitly using the level set method. In the elements cut by the zero level set, an automatic decomposition into interface aligned, i. e. conforming sub-elements is realized. Transfinite mappings are utilized to construct higher-order sub-elements by mappings of reference elements to the two sides of the boundary or interface. It is shown that although the resulting sub-elements are not always well-shaped, optimal convergence rates are possible. (© 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)     

Stereoselective synthesis of side chain-functionalized tetrahydropyrans from 5-hexenols

Molecular oxygen stereoselectively converts 5-hexenols into 2,6-trans-, 2,5-trans-, and 2,4-cis-derivatives of 2-methyltetrahydropyran via oxidative cyclization/radical functionalization cascades, when activated by fluoro-substituted cobalt(II) bis-(β-diketonate) complexes in solutions of cyclohexa-1,4-diene (CHD). Aerobic 5-hexenol oxidations in solutions of bromotrichloromethane and CHD furnish products of 6-exo-bromocyclization, as exemplified by synthesis of diastereomerically pure 2,4,6-substituted tetrahydropyrans. The cobalt method extends to intermolecular alkene/alkanol cross-coupling and to multi-component reactions between dimethyl fumarate, CHD, a 5-hexenol, and dioxygen, providing α-tetrahydropyranyl-2-methyl succinates in synthetically useful yields.     

High relaxivity and stability of a hydroxyquinolinate-based tripodal monoaquagadolinium complex for use as a bimodal MRI/optical imaging agent

An octadentate ligand based on triazacyclononane and 8-hydroxyquinolinate/phenolate binding units leads to very soluble, highly stable lanthanide complexes. The monoaquagadolinium complex shows a high relaxivity as a result of the unusually long rotational correlation time, fast water exchange rate, and slow electronic relaxation. The ligand also acts as sensitizer of the near-IR luminescence emission of the Yb and Nd ions. It appears as an excellent candidate for use as a bimodal imaging agent.     

Evaluating results from the Relativistic Heavy Ion Collider with perturbative QCD and hydrodynamics

We review the basic concepts of perturbative quantum chromodynamics (QCD) and relativistic hydrodynamics, and their applications to hadron production in high energy nuclear collisions. We discuss results from the Relativistic Heavy Ion Collider (RHIC) in light of these theoretical approaches. Perturbative QCD and hydrodynamics together explain a large amount of experimental data gathered during the first decade of RHIC running, although some questions remain open. We focus primarily on practical aspects of the calculations, covering basic topics like perturbation theory, initial state nuclear effects, jet quenching models, ideal hydrodynamics, dissipative corrections, freeze-out and initial conditions. We conclude by comparing key results from RHIC to calculations.     

A Gadolinium‐Binding Cyclodecapeptide with a Large High‐Field Relaxivity Involving Second‐Sphere Water

A new cyclodecapeptide incorporating two prolylglycine sequences as β‐turn inducers and bearing four side chains with acidic carboxyl groups for cation complexation has been prepared. Structural analysis in water by ¹H NMR spectroscopy and CD shows that this template adopts a conformation suitable for the complexation of lanthanide ions Ln³⁺, with its carboxyl groups oriented on the same face of the peptide scaffold. Luminescence titrations show that mononuclear Ln–PA complexes are formed with apparent stability constants of log β₁₁₀≈6.5 (pH 7). The high‐field water relaxivity values arising from the Gd–PA complex at 200–500 MHz have been interpreted with molecular parameters determined independently. The experimentally determined water relaxivities are undoubtedly 30 % higher than the expected values for this complex with two inner‐sphere (IS) water molecules and a medium‐range rotational correlation time (τ_R=386 ps (±10 %)). This led us to propose the existence of a large second‐sphere (2S) contribution to the relaxivity caused by the interaction of water molecules with the hydrophilic peptide ligand by hydrogen‐bonding.     

Azimuthal asymmetry of direct photons in high energy nuclear collisions

We show that a sizable azimuthal asymmetry, characterized by a coefficient nu2, is to be expected for large pT direct photons produced in noncentral high energy nuclear collisions. This signal is generated by photons radiated by jets interacting with the surrounding hot plasma. The anisotropy is out of phase by an angle pi/2 with respect to that associated with the elliptic anisotropy of hadrons, leading to negative values of nu2. Such an asymmetry, if observed, could be a signature for the presence of a quark gluon plasma and would establish the importance of jet-plasma interactions as a source of electromagnetic radiation.     

Zur Kontrolle von Solid-phase Peptidsynthesen durch Eluat-Chloridbestimmung

The origin of chloride ion in chloroform and methylene chloride solutions of tertiary amines is studied. The applicability of such solutions in the analytical control of solid phase peptide synthesis must be seriously questioned. An alternative procedure, amenable to automation, is suggested.