Off-the-Shelf Gd(NO3)(3) as an Efficient High-Spin Metal Ion Polarizing Agent for Magic Angle Spinning Dynamic Nuclear Polarization

[Image: see text] Magic angle spinning nuclear magnetic resonance spectroscopy experiments are widely employed in the characterization of solid media. The approach is incredibly versatile but deleteriously suffers from low sensitivity, which may be alleviated by adopting dynamic nuclear polarization methods, resulting in large signal enhancements. Paramagnetic metal ions such as Gd(3+) have recently shown promising results as polarizing agents for (1)H, (13)C, and (15)N nuclear spins. We demonstrate that the widely available and inexpensive chemical agent Gd(NO(3))(3) achieves significant signal enhancements for the (13)C and (15)N nuclear sites of [2-(13)C,(15)N]glycine at 9.4 T and ∼105 K. Analysis of the signal enhancement profiles at two magnetic fields, in conjunction with electron paramagnetic resonance data, reveals the solid effect to be the dominant signal enhancement mechanism. The signal amplification obtained paves the way for efficient dynamic nuclear polarization without the need for challenging synthesis of Gd(3+) polarizing agents

Hydrogen and oxygen adsorption stoichiometries on silica supported ruthenium nanoparticles

Berthoud, Romain Delichere, Pierre Gajan, David Lukens, Wayne Pelzer, Katrin Basset, Jean-Marie Candy, Jean-Pierre Coperet, ChristopheTreatment under H-2 at 300 degrees C of Ru(COD)(COT) dispersed on silica yields 2 nm ruthenium nanoparticles, [Ru-p/SiO2], according to EXAFS, HRTEM and XPS, H-2 adsorption measurements on [Ru-p/SiO2] in the absence of O-2 show that Ru particles adsorb Lip to ca. 2H per surface ruthenium atoms (2H/Ru-s) oil various samples; this technique can therefore be used to measure the dispersion of Ru particles. In contrast, O-2 adsorption on [Ru-p/SiO2] leads to a partial oxidation of the bulk at 25 degrees C, to RuO2 at 200 degrees C and to sintering upon further reduction under H-2, Showing that O-2 adsorption cannot be used to measure the dispersion of Ru particles. (C) 2008 Published by Elsevier Inc

Molecular-level characterization of the structure and the surface chemistry of periodic mesoporous organosilicates using DNP-surface enhanced NMR spectroscopy

We present the molecular level characterization of a phenylpyridine-based periodicmesoporous organosilicate and its post-functionalized organometallic derivatives through the fast acquisition of high quality natural isotopic abundance 1D C-13, N-15, and Si-29 and 2D 1H-C-13 and 1H-Si-29 solid-state NMR spectra enhanced with dynamic nuclear polarization

Solid-State Dynamic Nuclear Polarization at 9.4 and 18.8 T from 100 K to Room Temperature

We thank Lenaic Leroux for technical help.International audienceEfficient dynamic nuclear polarization (DNP) in solids, which enables very high sensitivity NMR experiments, is currently limited to temperatures of around 100 K and below. Here we show how by choosing an adequate solvent, 1H cross effect DNP enhancements of over 80 can be obtained at 240 K. To achieve this we use the biradical TEKPol dissolved in a glassy phase of ortho-terphenyl (OTP). We study the solvent DNP enhancement of both TEKPol and BDPA in OTP in the range from 100 to 300 K at 9.4 and 18.8 T. Surprisingly, we find that the DNP enhancement decreases only relatively slowly for temperatures below the glass transition of OTP (Tg = 243 K), and 1H enhancements around 15–20 at ambient temperature can be observed. We use this to monitor molecular dynamic transitions in the pharmaceutically relevant solids Ambroxol and Ibuprofen

Influences of Dilute Organic Adsorbates on the Hydration of Low-Surface-Area Silicates

Competitive adsorption of dilute quantities of certain organic molecules and water at silicate surfaces strongly influence the rates of silicate dissolution, hydration, and crystallization. Here, we determine the molecular-level structures, compositions, and site-specific interactions of adsorbed organic molecules at low absolute bulk concentrations on heterogeneous silicate particle surfaces at early stages of hydration. Specifically, dilute quantities (similar to 0.1% by weight of solids) of the disaccharide sucrose or industrially important phosphonic acid species slow dramatically the hydration of low-surface-area (similar to 1 m(2)/g) silicate particles. Here, the physicochemically distinct adsorption interactions of these organic species are established by using dynamic nuclear polarization (DNP) surface-enhanced solid-state NMR techniques. These measurements provide significantly improved signal sensitivity for near-surface species that is crucial for the detection and analysis of dilute adsorbed organic molecules and silicate species on low-surface-area particles, which until now have been infeasible to characterize. DNP-enhanced 2D Si-29{H-1}, C-13{H-1}, and P-31{H-1} heteronuclear correlation and 1D Si-29{C-13} rotational-echo double-resonance NMR measurements establish hydrogen-bond-mediated adsorption of sucrose at distinct nonhydrated and hydrated silicate surface sites and electrostatic interactions with surface Ca2+ cations. By comparison, phosphonic acid molecules are found to adsorb electrostatically at or near cationic calcium surface sites to form Ca(2+)phosphonate complexes. Although dilute quantities of both types of organic molecules effectively inhibit hydration, they do so by adsorbing in distinct ways that depend on their specific architectures and physicochemical interactions. The results demonstrate the feasibility of using DNP-enhanced NMR techniques to measure and assess dilute adsorbed molecules and their molecular interactions on low-surface-area materials, notably for compositions that are industrially relevant