Parahydrogen-Induced Polarization in Hydrogenation Reactions Mediated by a Metal-Free Catalyst

We report nuclear spin hyperpolarization of various alkenes achieved in alkyne hydrogenations with parahydrogen over a metal-free hydroborane catalyst (HCAT). Being an intramolecular frustrated Lewis pair aminoborane, HCAT utilizes a non-pairwise mechanism of H-2 transfer to alkynes that normally prevents parahydrogen-induced polarization (PHIP) from being observed. Nevertheless, the specific spin dynamics in catalytic intermediates leads to the hyperpolarization of predominantly one hydrogen in alkene. PHIP enabled the detection of important HCAT-alkyne-H-2 intermediates through substantial H-1, B-11 and N-15 signal enhancement and allowed advanced characterization of the catalytic process.Peer reviewe

Ultrafast multidimensional Laplace NMR for a rapid and sensitive chemical analysis

Traditional nuclear magnetic resonance (NMR) spectroscopy relies on the versatile chemical information conveyed by spectra. To complement conventional NMR, Laplace NMR explores diffusion and relaxation phenomena to reveal details on molecular motions. Under a broad concept of ultrafast multidimensional Laplace NMR, here we introduce an ultrafast diffusion-relaxation correlation experiment enhancing the resolution and information content of corresponding 1D experiments as well as reducing the experiment time by one to two orders of magnitude or more as compared with its conventional 2D counterpart. We demonstrate that the method allows one to distinguish identical molecules in different physical environments and provides chemical resolution missing in NMR spectra. Although the sensitivity of the new method is reduced due to spatial encoding, the single-scan approach enables one to use hyperpolarized substances to boost the sensitivity by several orders of magnitude, significantly enhancing the overall sensitivity of multidimensional Laplace NMR

Diffusion measurements of hydrocarbons in H-MCM-41 extrudates with pulsed-field gradient nuclear magnetic resonance spectroscopy

Mesoporous materials are promising catalysts for production of biofuels. Herein, H-MCM-41 catalysts with different concentrations of the silica Bindzil binder (10-50 wt%) were prepared and characterized using pulsed-field gradient (PFG) NMR in the powder form and as extrudates. Effective diffusion coefficients (D-e) are measured in all cases. Diffusivities of n-hexadecane were found smaller for extrudates as compared to the powder catalysts. The estimates of diffusive tortuosity were also determined. PFG NMR data showed one major component that reveals diffusion in interconnected meso- and micropores and one other minor component (1-2%) that may correspond to more isolated pores or may represent complex effects of restricted diffusion. Therefore, several approaches including initial slope analysis of spin-echo attenuation curves, two-component fitting and Laplace inversion were used to discuss different aspects of diffusional transport in the studied H-MCM-41 materials. Correlations between D-e and the amount of Bindzil, the specific surface area, the micropore volume, the particle size, the total acid sites and the Lewis acid sites are discussed

Spontaneous N-15 Nuclear Spin Hyperpolarization in Metal-Free Activation of Parahydrogen by Molecular Tweezers

The ability of frustrated Lewis pairs (FLPs) to activate H-2 is of significant interest for metal-free catalysis. The activation of H-2 is also the key element of parahydrogen-induced polarization (PHIP), one of the nuclear spin hyper polarization techniques. It is demonstrated that o-phenylene-based ansa-aminoboranes (AABs) can produce H-1 nuclear spin hyperpolarization through a reversible interaction with parahydrogen at ambient temperatures. Heteronuclei are useful in NMR and MRI as well because they have a broad chemical shift range and long relaxation times and may act as background-free labels. We report spontaneous formation of N-15 hyperpolarization of the N-H site for a family of AABs. The process is efficient at the high magnetic field of an NMR magnet (7 T), and it provides up to 350-fold N-15 signal enhancements. Different hyperpolarization effects are observed with various AAB structures and in a broad temperature range. Spontaneous hyperpolarization, albeit an order of magnitude weaker than that for N-15, was also observed for B-11 nuclei.Peer reviewe

Hyperpolarized Laplace NMR

Abstract Laplace nuclear magnetic resonance (NMR), dealing with NMR relaxation and diffusion experiments, reveals details of molecular motion and provides chemical resolution complementary to NMR spectra. Laplace NMR has witnessed a great progress in past decades due to the development of methodology and signal processing, and it has lots of extremely interesting applications in various fields, including chemistry, biochemistry, geology, archaeology, and medicine. The aim of this minireview is to give a pedagogically oriented overview of Laplace NMR. It does not provide a full literature review of the field, but, instead, it elucidate the benefits and features of Laplace NMR methods through few selected examples. The minireview describes also recent progress in multidimensional Laplace NMR and Laplace inversion methods. Furthermore, the potential of modern hyperpolarization methods as well as ultrafast approach to increase the sensitivity and time‐efficiency of the Laplace NMR experiments is highlighted

Xenon porometry:a novel method for characterization of porous materials by means of ¹²⁹Xe NMR spectroscopy of xenon dissolved in a medium

Abstract The present thesis describes the development of a novel method, referred to as xenon porometry, for the determination of the structural properties of porous materials by means of xenon NMR spectroscopy. The method exploits the high sensitivity of the chemical shift of the ¹²⁹Xe isotope to its local environment. The purpose of the medium added to the sample is to slow down the diffusion of xenon so that the NMR signal of a xenon atom is characteristic of the properties of one pore, and the signals of all the atoms in the sample represent the distribution of the properties. Two types of porous materials (controlled pore glasses and silica gels) with well-known properties and three different media (acetonitrile, cyclohexane, and naphthalene) were used in the studies. The behavior of the medium and dissolved xenon at different temperatures around the melting point of the medium was explained. By varying the pore size of the material, three different correlations that make it possible to measure the pore sizes of unknown materials were experimentally determined. The chemical shift of xenon inside pockets built up in the pores during solidification of the medium turned out to be especially sensitive to pore size, and this correlation makes it possible to determine the pore size distribution. The curious behavior of the chemical shift as a function of pore size was explained by using a model based on the fast exchange between xenon adsorbed on the walls of the pockets and free xenon in the middle of the pockets. It was also proved that the porosity of the materials can be determined by comparing the intensities of two signals originating from xenon dissolved in a liquid medium. A comparison of the xenon porometry method with other methods used for pore size characterization leads to the following conclusions: The range of applications of the method is relatively wide, the measurements are fast and easy to do, the analysis of the spectra is simple on the basis of the information presented in this thesis, and the properties of the materials can be extracted from the spectral data with basic mathematical conversions. Because there are several different types of correlations available in the same spectra that represent the properties of the porous material, the complementary information of all the correlations make it possible to obtain a picture of the structures of very complex systems

Ultrafast methods for relaxation and diffusion

Abstract Relaxation and diffusion NMR measurements offer an approach to studying rotational and translational motion of molecules non-invasively, and they also provide chemical resolution complementary to NMR spectra. Multidimensional experiments enable the correlation of relaxation and diffusion parameters as well as the observation of molecular exchange phenomena through relaxation or diffusion contrast. This review describes how to accelerate multidimensional relaxation and diffusion measurements significantly through spatial encoding. This so-called ultrafast Laplace NMR approach shortens the experiment time to a fraction and makes even single-scan experiments possible. Single-scan experiments, in turn, significantly facilitate the use of nuclear spin hyperpolarization methods to boost sensitivity. The ultrafast Laplace NMR method is also applicable with low-field, mobile NMR instruments, and it can be exploited in many disciplines. For example, it has been used in studies of the dynamics of fluids in porous materials, identification of intra- and extracellular metabolites in cancer cells, and elucidation of aggregation phenomena in atmospheric surfactant solutions

Ultrafast NMR diffusion measurements exploiting chirp spin echoes

Abstract Standard diffusion NMR measurements require the repetition of the experiment multiple times with varying gradient strength or diffusion delay. This makes the experiment time-consuming and restricts the use of hyperpolarized substances to boost sensitivity. We propose a novel single-scan diffusion experiment, which is based on spatial encoding of two-dimensional data, employing the spin-echoes created by two successive adiabatic frequency-swept chirp π pulses. The experiment is called ultrafast pulsed-field-gradient spin-echo (UF-PGSE). We present a rigorous derivation of the echo amplitude in the UF-PGSE experiment, justifying the theoretical basis of the method. The theory reveals also that the standard analysis of experimental data leads to a diffusion coefficient value overestimated by a few per cent. Although the overestimation is of the order of experimental error and thus insignificant in many practical applications, we propose that it can be compensated by a bipolar gradient version of the experiment, UF-BP-PGSE, or by corresponding stimulated-echo experiment, UF-BP-pulsed-field-gradient stimulated-echo. The latter also removes the effect of uniform background gradients. The experiments offer significant prospects for monitoring fast processes in real time as well as for increasing the sensitivity of experiments by several orders of magnitude by nuclear spin hyperpolarization. Furthermore, they can be applied as basic blocks in various ultrafast multidimensional Laplace NMR experiments

Characterization of pore structures of hydrated cements and natural shales by ¹²⁹Xe NMR spectroscopy

Abstract ¹²⁹Xe NMR of adsorbed xenon gas is a sensitive tool for the characterization of porous materials. Here we exploit, for the first time, ¹²⁹Xe NMR to investigate the nanoscale porous structures in hydrated white cements and natural shale. Signals of xenon in mesopores and larger voids are well resolved in the spectra of the cement samples, and the exchange rate between these sites was determined to be 100−300 s⁻¹ at room temperature. The spectra imply that the mesopore size is the smallest and the exchange rate is the highest in the sample with the lowest initial water/cement ratio. The heat of adsorption of xenon in the cements is similar to that in silica gels, about 12 kJ/mol. The shale spectra include a very broad signal, covering a range of about 600 ppm, implying that the adsorbed xenon interacts with the paramagnetic impurities present in the samples