Diego Carnevale

Dynamic nuclear polarization of quadrupolar nuclei using cross polarization from protons: surface-enhanced aluminium-27 NMR

The surface of γ-alumina nanoparticles can be characterized by dynamic nuclear polarization (DNP) surface-enhanced NMR of (27)Al. DNP is combined with cross-polarization and MQ-MAS to determine local symmetries of (27)Al sites at the surface.

Insights into the Catalytic Activity of Nitridated Fibrous Silica (KCC-1) Nanocatalysts from 15 N and 29 Si NMR Spectroscopy Enhanced by Dynamic Nuclear Polarization**

Fibrous nanosilica (KCC-1) oxynitrides are promising solid-base catalysts. Paradoxically, when their nitrogen content increases, their catalytic activity decreases. This counterintuitive observation is explained here for the first time using (15) N-solid-state NMR spectroscopy enhanced by dynamic nuclear polarization.

Analysis of sensitivity enhancement by dynamic nuclear polarization in solid-state NMR: a case study of functionalized mesoporous materials

We systematically studied the enhancement factor (per scan) and the sensitivity enhancement (per unit time) in (13)C and (29)Si cross-polarization magic angle spinning (CP-MAS) NMR boosted by dynamic nuclear polarization (DNP) of functionalized mesoporous silica nanoparticles (MSNs). Specifically, we separated contributions due to: (i) microwave irradiation, (ii) quenching by paramagnetic effects, (iii) the presence of frozen solvent, (iv) the temperature, as well as changes in (v) relaxation and (vi) cross-polarization behaviour. No line-broadening effects were observed for MSNs when lowering the temperature from 300 to 100 K. Notwithstanding a significant signal reduction due to quenching by TOTAPOL radicals, DNP-CP-MAS at 100 K provided global sensitivity enhancements of 23 and 45 for (13)C and (29)Si, respectively, relative to standard CP-MAS measurements at room temperature. The effects of DNP were also ascertained by comparing with state-of-the-art two-dimensional heteronuclear (1)H{(13)C} and (29)Si{(1)H} correlation spectra, using, respectively, indirect detection or Carr-Purcell-Meiboom-Gill (CPMG) refocusing to boost signal acquisition. This study highlights opportunities for further improvements through the development of high-field DNP, better polarizing agents, and improved capabilities for low-temperature MAS.

Polychromatic Decoupling of a Manifold of Homonuclear Scalar Interactions in Solution‐State NMR

Window-acquired tetrachromatic irradiation allows one to decouple simultaneously four amide protons in cyclosporine A (wavy arrows; see figure) leading to simplified multiplets of the alpha protons. By inserting a manifold of polychromatic pulses in each dwell time, several subsystems can be decoupled simultaneously.

Broadband excitation in solid-state NMR using interleaved DANTE pulse trains with N pulses per rotor period

We analyze the direct excitation of wide one-dimensional spectra of nuclei with spin I=1/2 or 1 in rotating solids submitted to pulse trains in the manner of Delays Alternating with Nutations for Tailored Excitation (DANTE), either with one short rotor-synchronized pulse of duration τp in each of K rotor periods (D1(K)) or with N interleaved equally spaced pulses τp in each rotor period, globally also extending over K rotor periods (D(N)(K)). The excitation profile of D(N)(K) scheme is a comb of rf-spikelets with Nν(R)=N/T(R) spacing from the carrier frequency, and a width of each spikelet inversely proportional to the length, KT(R), of D(N)(K) scheme. Since the individual pulse lengths, τp, are typically of a few hundreds of ns, D(N)(K) scheme can readily excite spinning sidebands families covering several MHz, provided the rf carrier frequency is close enough to the resonance frequency of one the spinning sidebands. If the difference of isotropic chemical shifts between distinct chemical sites is less than about 1.35/(KT(R)), D(N)(K) scheme can excite the spinning sidebands families of several sites. For nuclei with I=1/2, if the homogeneous and inhomogeneous decays of coherences during the DANTE sequence are neglected, the K pulses of a D1(K) train have a linearly cumulative effect, so that the total nutation angle is θ(tot)=K2πν1τp, where ν1 is the rf-field amplitude. This allows obtaining nearly ideal 90° pulses for excitation or 180° rotations for inversion and refocusing across wide MAS spectra comprising many spinning sidebands. If one uses interleaved DANTE trains D(N)(K) with N>1, only spinning sidebands separated by intervals of Nν(R) with respect to the carrier frequency are observed as if the effective spinning speed was Nν(R). The other sidebands have vanishing intensities because of the cancellation of the N contributions with opposite signs. However, the intensities of the remaining sidebands obey the same rules as in spectra obtained with νR. With increasing N, the intensities of the non-vanishing sidebands increase, but the total intensity integrated over all sidebands decreases. Furthermore, the NK pulses in a D(N)(K) train do not have a simple cumulative effect and the optimal cumulated flip angle for optimal excitation, θ(tot)(opt)=NK2πν1τp, exceeds 90°. Such D(N)(K) pulse trains allow achieving efficient broadband excitation, but they are not recommended for broadband inversion or refocusing as they cannot provide proper 180° rotations. Since D(N)(K) pulse trains with N>1 are shorter than basic D1(K) sequences, they are useful for broadband excitation in samples with rapid homogeneous or inhomogeneous decay. For nuclei with I=1 (e.g., for (14)N), the response to basic D1(K) pulse train is moreover affected by inhomogeneous decay due to 2nd-order quadrupole interactions, since these are not of rank 2 and therefore cannot be eliminated by spinning about the magic angle. For large quadrupole interactions, the signal decay produced by second-order quadrupole interaction can be minimized by (i) reducing the length of D(N)(K) pulse trains using N>1, (ii) fast spinning, (iii) large rf-field, and (iv) using high magnetic fields to reduce the 2nd-order quadrupole interaction.

NMR spectroscopy and DFT calculations of a self-assembled arene ruthenium rectangle obtained from a combination of coordination and hydrogen bonds

The hydrogen-bonded arene ruthenium metalla-rectangle, [(p-cymene)2Ru2(OO∩OO)(UPy)2]2(4+), obtained from 1-(4-oxo-6-undecyl-1,4-dihydropyrimidin-2-yl)-3-(pyridin-4-ylmethyl)urea (UPy) and the dinuclear arene ruthenium clip (p-cymene)2Ru2(OO∩OO)Cl2 (OO∩OO = 2,5-dioxido-1,4-benzoquinonato), is investigated by means of solution-phase NMR spectroscopy. Rotating frame nuclear Overhauser effect measurements are used to probe the H-bond network that drives the UPy self-assembly as well as the full rectangular supramolecular system. An effective distance that takes into account both intra- and intermolecular polarization-transfer pathways is utilised for data analysis. The experimental findings are corroborated by DFT calculations of NMR parameters and internuclear distances, thus confirming the formation of a very stable tetranuclear metalla-assembly.

Dynamic nuclear polarization enhancement of protons and vanadium-51 in the presence of pH-Dependent vanadyl radicals

We report applications of dynamic nuclear polarization to enhance proton and vanadium‐51 polarization of vanadyl sulfate samples doped with TOTAPOL under magic angle spinning conditions. The electron paramagnetic resonance response stemming from the paramagnetic 51V species was monitored as a function of pH, which can be adjusted to improve the enhancement of the proton polarization. By means of cross‐polarization from the proton bath, 51V spins could be hyperpolarized. Enhancement factors, build‐up times, and longitudinal relaxation times T1(1H) and T1(51V) were investigated as a function of pH. Copyright

Solid-state carbon-13 NMR and computational characterization of the N719 ruthenium sensitizer adsorbed on TiO2 nanoparticles

The ruthenium-containing sensitizing dye N719 grafted on TiO2 nanoparticles was investigated by solid-state NMR. The carbon resonances are assigned by means of (13)C cross-polarized dipolar dephasing experiments. DFT calculations of the carbon magnetic shielding tensors accurately describe the changes in chemical shifts observed upon grafting onto a titania surface via one or two carboxylic functions in the plane defined by the two isothiocyanate groups.

Homonuclear decoupling for spectral simplification of carbon-13 enriched molecules in solution-state NMR enhanced by dissolution DNP.

Complex overlapping multiplets due to scalar couplings (n)J((13)C, (13)C) in fully (13)C-enriched molecules can be simplified by polychromatic irradiation of selected spins. The signal intensities of the remaining non-irradiated signals are proportional to the concentrations, as shown in this work for the anomeric (13)C signals of the α- and β-conformers of glucose. Homonuclear decoupling can therefore be useful for quantitative NMR studies. The resulting decoupled lineshapes show residual fine structures that have been investigated by means of numerical simulations. Simulations also show that homonuclear decoupling schemes remain effective despite inhomogeneous static fields that tend to hamper in cellulo and in vivo studies. Homonuclear decoupling schemes can be combined with dissolution DNP to obtain signal enhancements of more than four orders of magnitude. Polychromatic irradiation of selected spins does not cause significant losses of hyperpolarization of the remaining non-irradiated spins.

Dipolar couplings in solid polypeptides probed by 14N NMR spectroscopy

The acquisition of 14N NMR spectra in solid samples is challenging due to quadrupolar couplings with magnitudes up to several MHz. This nucleus is nonetheless important as it is involved in the formation of essential secondary structures in biological systems. Here we report the structural study of the atomic environment of amide functions in polypeptides using magic-angle spinning NMR spectroscopy of the ubiquitous 14N isotope. The cyclic undecapeptide cyclosporin, in which only four hydrogen atoms are directly bound to nitrogen atoms, is chosen for illustration. Structural details of different environments can be revealed without resorting to isotopic enrichment. The network of inter- and intra-residue dipolar couplings between amide 14N nuclei and nearby protons can be probed and mapped out up to a tunable cutoff distance. Density functional theory calculations of NMR quadrupolar interaction tensors agree well with the experimental evidence and allow the unambiguous assignment of all four non-methylated NH nitrogen sites and neighboring proton nuclei.Solid-state NMR of nitrogen nuclei offers a powerful way to solve protein structures but often requires isotopic labeling. Here through-space interactions between nitrogen-14 and protons allows structural assignment of cyclosporin without the need for isotopic enrichment with nitrogen-15.