Large-scale ab initio simulations of MAS DNP enhancements using a Monte Carlo optimization strategy

Magic-angle-spinning (MAS) dynamic nuclear polarization (DNP) has recently emerged as a powerful technology enabling otherwise unrealistic solid-state NMR experiments. The simulation of DNP processes which might, for example, aid in refining the experimental conditions or the design of better performing polarizing agents, is, however, plagued with significant challenges, often limiting the system size to only 3 spins. Here, we present the first approach to fully ab initio large-scale simulations of MAS DNP enhancements. The Landau-Zener equation is used to treat all interactions concerning electron spins, and the low-order correlations in the Liouville space method is used to accurately treat the spin diffusion, as well as its MAS speed dependence. As the propagator cannot be stored, a Monte Carlo optimization method is used to determine the steady-state enhancement factors. This new software is employed to investigate the MAS speed dependence of the enhancement factors in large spin systems where spin diffusion is of importance, as well as to investigate the impacts of solvent and polarizing agent deuteration on the performance of MAS DNP

Reducing t1 noise through rapid scanning

The so-called t1 noise, which arises due to random instabilities in the spectrometer hardware, remains the primary source of noise that limits the sensitivity of most 2D NMR experiments, particularly in the expanding group of solid-state NMR methods that utilize dipolar-recoupling. In this communication we revisit the relationship between the signal intensity and the t1 noise produced. It is shown that since the latter scales linearly with the signal strength, the use of a conventional relaxation delay of 1.3T1 may prove far from optimal. In cases where the fluctuations occur on a shorter timescale than the recycle delay, a considerably faster repetition rate should be used to maximize the time sensitivity in a 2D experiment than what is used to maximize the sensitivity in 1D. This is demonstrated with the acquisition of 1H{13C} Dipolar-mediated Heteronuclear Multiple-Quantum Correlation (D-HMQC) type spectra in which the sensitivity could be nearly doubled by choosing a very short relaxation delay corresponding to 0.2T1

High-Field MAS Dynamic Nuclear Polarization Using Radicals Created by γ-Irradiation

High-field magic angle spinning dynamic nuclear polarization (MAS DNP) is often used to enhance the sensitivity of solid-state nuclear magnetic resonance (ssNMR) experiments by transferring spin polarization from electron spins to nuclear spins. Here, we demonstrate that γ-irradiation induces the formation of stable radicals in inorganic solids, such as fused quartz and borosilicate glasses as well as organic solids such as glucose, cellulose, and a urea/polyethylene polymer. The radicals were then used to polarize 29Si or 1H spins in the core of some of these materials. Significant MAS DNP enhancements (ε) greater than 400 and 30 were obtained for fused quartz and glucose, respectively. For other samples negligible ε were obtained likely due to low concentrations of radicals or the presence of abundant quadrupolar spins. These results demonstrate that ionizing radiation is a promising alternative method for generating stable radicals suitable for high-field MAS DNP experiments

t1-Noise Eliminated Dipolar Heteronuclear Multiple-Quantum Coherence Solid-State NMR Spectroscopy

Heteronuclear correlation (HETCOR) spectroscopy is one of the key tools in the arsenal of the solid-state NMR spectroscopist to probe spatial proximity between two different nuclei and enhance spectral resolution. Dipolar heteronuclear multiple-quantum coherence (D-HMQC) is a powerful technique that can be potentially utilized to obtain 1H detected 2D HETCOR solid-state NMR spectra of any NMR active nucleus. A long-standing problem in 1H detected D-HMQC solid-state NMR experiments is the presence of t1-noise which reduces sensitivity and impedes spectral interpretation. In this contribution, we describe novel pulse sequences, termed t1-noise eliminated (TONE) D-HMQC, that suppress t1-noise and can provide higher sensitivity and resolution than conventional D-HMQC. Monte-Carlo and numerical simulations confirm that t1-noise in conventional D-HMQC primarily occurs because random MAS frequency fluctuations cause variations in the NMR signal amplitude from scan to scan, leading to imperfect cancellation of uncorrelated signals by phase cycling. The TONE D-HMQC sequence uses 1H p-pulses to refocus the evolution of 1H CSA across each recoupling block, improving the stability of the pulse sequence to random MAS frequency fluctuations. The 1H refocusing pulses also restore the orthogonality of in-phase and anti-phase magnetization for all crystallite orientations, enabling the use of 90° flip-back or LG spin-lock trim pulses to reduce the intensity of uncorrelated signals. We demonstrate the application of these methods to acquire detected 2D 1H-35Cl and 1H-13C HETCOR spectra of histidine•HCl•H2O with reduced t1-noise. To show generality, we also apply these methods to obtain 2D 1H-17O spectra of 20%-17O fmoc-alanine and for the first time at natural abundance, 2D 1H-25Mg HETCOR spectra of magnesium hydroxide. The TONE D-HMQC sequences are also used to probe 1H-25Mg and 1H-27Al proximities in Mg-Al layered double hydroxides and confirm the even mixing of Mg and Al in these materials

Direct 17O Dynamic Nuclear Polarization of Single-Site Heterogeneous Catalysts

We utilize direct 17O DNP for the characterization of non-protonated oxygens in heterogeneous catalysts. The optimal sample preparation and population transfer approach for 17O direct DNP experiments performed on silica surfaces are determined and applied to the characterization of Zr- and Y-based mesoporous silica-supported single-site catalysts

High-Field Magic Angle Spinning Dynamic Nuclear Polarization Using Radicals Created by γ-Irradiation

High-field magic angle spinning dynamic nuclear polarization (MAS DNP) is often used to enhance the sensitivity of solid-state nuclear magnetic resonance experiments by transferring spin polarization from electron spins to nuclear spins. Here, we demonstrate that γ-irradiation induces the formation of stable radicals in inorganic solids, such as fused quartz and borosilicate glasses, as well as organic solids, such as glucose, cellulose, and a urea/polyethylene polymer. The radicals were then used to polarize 29Si or 1H spins in the core of some of these materials. Significant MAS DNP enhancements (ε) of more than 400 and 30 were obtained for fused quartz and glucose, respectively. For other samples, negligible values of ε were obtained, likely due to low concentrations of radicals or the presence of abundant quadrupolar spins. These results demonstrate that ionizing radiation is a promising alternative method for generating stable radicals that are suitable for high-field MAS DNP experiments

Enhanced 1H-X D-HMQC performance through improved 1H homonuclear decoupling

The sensitivity of solid-state NMR experiments that utilize 1H zero-quantum heteronuclear dipolar recoupling, such as D-HMQC, is compromised by poor homonuclear decoupling. This leads to a rapid decay of recoupled magnetization and an inefficient recoupling of long-range dipolar interactions, especially for nuclides with low gyromagnetic ratios. We investigated the use, in symmetry-based 1H heteronuclear recoupling sequences, of a basic R element that was principally designed for efficient homonuclear decoupling. By shortening the time required to suppress the effects of homonuclear dipolar interactions to the duration of a single inversion pulse, spin diffusion was effectively quenched and long-lived recoupled coherence lifetimes could be obtained. We show, both theoretically and experimentally, that these modified sequences can yield considerable sensitivity improvements over the current state-of-the-art methods and applied them to the indirect detection of 89Y in a metal-organic framework

Improved strategies for DNP-enhanced 2D 1H-X heteronuclear correlation spectroscopy of surfaces

We demonstrate that dynamic nuclear polarization (DNP)-enhanced 1H-X heteronuclear correlation (HETCOR) measurements of hydrogen-rich surface species are better accomplished by using proton-free solvents. This approach notably prevents HETCOR spectra from being obfuscated by the solvent-derived signals otherwise present in DNP measurements. Additionally, in the hydrogen-rich materials studied here, which included functionalized mesoporous silica nanoparticles and metal organic frameworks, the use of proton-free solvents afforded higher sensitivity gains than the commonly used solvents containing protons. We also explored the possibility of using a solvent-free sample formulation and the feasibility of indirect detection in DNP-enhanced HETCOR experiments

Identifying low-coverage surface species on supported noble metal nanoparticle catalysts by DNP-NMR

DNP-NMR spectroscopy has been applied to enhance the signal for organic molecules adsorbed on γ-Al2O3-supported Pd nanoparticle catalysts. By offering \u3e2500-fold time savings, the technique enabled the observation of 13C–13C cross-peaks for low coverage species, which were assigned to products from oxidative degradation of methionine adsorbed on the nanoparticle surface