Angle Spinning Spectra Research Articles

Boosting Electrocatalytic CO 2 Reduction with Conjugated Bimetallic Co/Zn Polyphthalocyanine Frameworks

Boosting Electrocatalytic CO ₂ Reduction with Conjugated Bimetallic Co/Zn Polyphthalocyanine Frameworks

Signal Deconvolution and Generative Topographic Mapping Regression for Solid-State NMR of Multi-Component Materials.

Solid-state nuclear magnetic resonance (ssNMR) spectroscopy provides information on native structures and the dynamics for predicting and designing the physical properties of multi-component solid materials. However, such an analysis is difficult because of the broad and overlapping spectra of these materials. Therefore, signal deconvolution and prediction are great challenges for their ssNMR analysis. We examined signal deconvolution methods using a short-time Fourier transform (STFT) and a non-negative tensor/matrix factorization (NTF, NMF), and methods for predicting NMR signals and physical properties using generative topographic mapping regression (GTMR). We demonstrated the applications for macromolecular samples involved in cellulose degradation, plastics, and microalgae such as Euglena gracilis. During cellulose degradation, 13C cross-polarization (CP)–magic angle spinning spectra were separated into signals of cellulose, proteins, and lipids by STFT and NTF. GTMR accurately predicted cellulose degradation for catabolic products such as acetate and CO2. Using these methods, the 1H anisotropic spectrum of poly-ε-caprolactone was separated into the signals of crystalline and amorphous solids. Forward prediction and inverse prediction of GTMR were used to compute STFT-processed NMR signals from the physical properties of polylactic acid. These signal deconvolution and prediction methods for ssNMR spectra of macromolecules can resolve the problem of overlapping spectra and support macromolecular characterization and material design.

Solid state NMR investigation of the roman Acqualadroni rostrum: tenth year assessment of the consolidation treatment of the wooden part

This work follows a previous one dealing with the state of conservation study of the wooden part of the roman Acqualadroni rostrum soon after its finding in the seabed of Acqualadroni (Messina, Italy). The archaeological survey and recovery were particularly relevant since this artefact is one of the two rostrums, nowadays known, found together with its wooden part. Following the recovery, it was consolidated by immersion in a melamine-formaldehyde resin (Kauramin) aqueous solution for eight months at the “Centro di Restauro del Legno Bagnato” (Pisa, Italy). The present investigation is aimed to determine at microscopic scale the wood state of conservation and to highlight interactions of the consolidant with wood components, by using solid-state NMR spectroscopy ten years after the consolidation treatment. Sampling by coring was exceptionally authorized, and the wood core was divided into seven aliquots as a function of depth. 13C cross-polarization magic angle spinning (13C{1H} CP-MAS NMR) spectra and variable contact time (VCT) experiments have been carried out to determine the cellulose crystallinity index, the lignin condensation degree and the holocellulose-lignin ratio. The interactions between the resin and the wood components were highlighted by T1ρH relaxation times determination and two-dimensional 13C–1H correlation (FSLG CP HETCOR) NMR experiments. Findings revealed specific interactions between the aromatic part of the resin and the lignin, as well as a network of hydrogen bonds involving all components of the system.

1H NMR linewidths of small organic guest molecules physisorbed on different mesoporous silicas

The excessive linewidths of 1H NMR spectra of solids is a longstanding difficulty. Organic molecules (crystalline at room temperatures) of different chemical characters (camphor, menthol, HMB, HMTA, biphenyl, terphenyl, anthracene, perylene, etc.) have been confined or physisorbed in regular (MCM-41, SBA-15) and irregular (aerogel) silica mesopores. Unexpectedly, steadily decreasing proton NMR linewidths have been observed upon increasing pore sizes. Comparison of the static 1H NMR spectra of the confined and “free” bulk molecules showed an impressive resolution improvement (a factor of 5–10). Static 1H NMR and 2H magic angle spinning (MAS) spectra pointed out the increased molecular mobility as origin. In a qualitative approach the possible reasons of mobility have been thoroughly discussed. The increased mobility seems to be easiest achievable in aerogel and so, in the future, this extreme light mesoporous silica nanomaterial (MSN) may be considered as “active” filling material in solid state NMR spectroscopy. Since sensitivity is not an issue in 1H MAS measurements the proposal - simultaneous dilution of the dense 1H–1H spin network and increasing the molecular mobility of the molecules of interest by confinement or physisorption in/on silica mesopores - may find applications, especially in laboratories where high magnetic fields and state of art ultra-fast MAS rotation are not available.

Surface structural analysis of selectively 13C-labeled cellulose II by solid-state NMR spectroscopy

The local structure on the surface of plate-like cellulose II oligomer crystals (CIIOCs) was investigated by NMR spectroscopy. CIIOCs with reducing ends that were selectively labeled with 13C were enzymatically synthesized using cellodextrin phosphorylase. The solid-state 13C cross polarization/magic angle spinning spectra of the 13C-labeled CIIOCs clearly exhibited two resonance peaks (labeled as C1Rα and C1Rβ) derived from the C1 atoms of the reducing ends. The 2D 13C double quantum/13C single quantum homonuclear correlation spectrum indicated that two magnetically nonequivalent glucopyranose rings (Rα and Rβ units) coexisted at the reducing end units. The 1H/13C heteronuclear correlation spectrum suggested that there was a large difference between the local environments around the anomeric carbons of Rα and Rβ units. The abundance ratio of C1Rβ to C1Rα in the solid state was 4:1, whereas that of C1α and C1β in solution was 1:1. When the oligomer chains are packed in the cellulose II crystal, the reducing end units located on the surface of the plate-like crystal may tend to have β-anomeric structure, which would be more sterically stable than the α-anomeric structure.

19F Dynamic Nuclear Polarization at Fast Magic Angle Spinning for NMR of HIV-1 Capsid Protein Assemblies.

We report remarkably high, up to 100-fold, signal enhancements in 19F dynamic nuclear polarization (DNP) magic angle spinning (MAS) spectra at 14.1 T on HIV-1 capsid protein (CA) assemblies. These enhancements correspond to absolute sensitivity ratios of 12-29 and are of similar magnitude to those seen for 1H signals in the same samples. At MAS frequencies above 20 kHz, it was possible to record 2D 19F-13C HETCOR spectra, which contain long-range intra- and intermolecular correlations. Such correlations provide unique distance restraints, inaccessible in conventional experiments without DNP, for protein structure determination. Furthermore, systematic quantification of the DNP enhancements as a function of biradical concentration, MAS frequency, temperature, and microwave power is reported. Our work establishes the power of DNP-enhanced 19F MAS NMR spectroscopy for structural characterization of HIV-1 CA assemblies, and this approach is anticipated to be applicable to a wide range of large biomolecular systems.

Levels of choline-containing compounds in normal liver and liver metastases of colorectal cancer as recorded by 1 H MRS.

A relatively high signal for choline-containing compounds (total choline, tCho) is commonly found in 1 H MR spectra of malignant tumors, but it is unclear if this also occurs in tumors in the liver. We evaluated the potential of the tCho signal in single voxel 1 H MR spectra of the human liver to assess metastases of colorectal cancers. MR spectra of an 8cm3 PRESS-localized voxel were obtained at 3T from the livers of 12 healthy volunteers and from metastatic lesions in 20 patients in two different sessions. To correct for motion artifacts, sequentially recorded spectra were individually phased and frequency aligned before averaging. Spectra were analyzed using LCModel and tissue levels estimated by water referencing. Repeatability was assessed with Bland-Altman analyses. To estimate tumor necrosis, diffusion-weighted imaging of the liver was performed. High resolution magic angle spinning (HRMAS) spectra of tumor and normal liver samples were obtained at 11.7T. With increasing tumor volumes, tCho levels decreased, indicating a partial volume effect. Mean tCho content in tumors larger than the PRESS voxel (>8cm3 ) was significantly lower (p<0.01) than for normal liver: 1.6 (range 0.0-3.4) versus 6.9 (range 4.9-11.1) mmol/kg wet weight, while it was comparable for tumors smaller than 8cm3 : 7.0 (range 3.8-9.3) mmol/kg. The higher 90th percentile apparent diffusion coefficient value in the larger lesions indicates more necrosis. Measurement repeatability was average in normal livers and poor in tumors. HRMAS did not show substantial differences in choline-containing compounds between normal liver and metastasis. An increased tCho content was not observed in 1 H MR spectra of liver metastasis of colorectal cancer, compared with normal liver. This may be due to the background of a high tCho signal in spectra of normal liver or to an intrinsic lower tCho content in these tumors, but is most likely the result of necrosis in metastatic tumor tissue.

A 13C solid-state NMR investigation of four cocrystals of caffeine and theophylline.

We report an analysis of the 13C solid-state NMR chemical shift data in a series of four cocrystals involving two active pharmaceutical ingredient (API) mimics (caffeine and theophylline) and two diacid coformers (malonic acid and glutaric acid). Within this controlled set, we make comparisons of the isotropic chemical shifts and the principal values of the chemical shift tensor. The dispersion at 14.1 T (600 MHz 1H) shows crystallographic splittings in some of the resonances in the magic angle spinning spectra. By comparing the isotropic chemical shifts of individual C atoms across the four cocrystals, we are able to identify pronounced effects on the local electronic structure at some sites. We perform a similar analysis of the principal values of the chemical shift tensors for the anisotropic C atoms (most of the ring C atoms for the API mimics and the carbonyl C atoms of the diacid coformers) and link them to differences in the known crystal structures. We discuss the future prospects for extending this type of study to incorporate the full chemical shift tensor, including its orientation in the crystal frame of reference.

Directly vs Indirectly Enhanced 13C in Dynamic Nuclear Polarization Magic Angle Spinning NMR Experiments of Nonionic Surfactant Systems

A study of dynamic nuclear polarization (DNP) in polyethylene glycol and related nonionic surfactants is presented. In these experiments, we found the surprising result that DNP enhanced 13C magic angle spinning (MAS) spectra display two sets of resonances, one with broad and one with sharp spectral features that are 180° opposite in phase. These two sets indicate the presence of a direct polarization transfer channel as expected for 13C MAS experiments, and a second unexpected indirect polarization transfer channel. Plots of DNP enhancements as a function of applied magnetic field for the two resonances show a superposition of two DNP enhancement profiles for AMUpol in the nonionic surfactant C10E6. The indirect polarization channel can be suppressed by application of a string of 1H 180° pulses during 13C DNP buildup. The presence of direct and indirect polarization channels is observed in a total of four different nonionic surfactants and with three different radicals, showing that these concurring pola...

Metathesis Polymerization Reactions Induced by the Bimetallic Complex (Ph4P)2[W2(μ-Br)3Br6

The reactivity of the bimetallic complex (Ph4P)2[W2(μ-Br)3Br6] ({W 2.5 W}7+, a′2e3) towards ring opening metathesis polymerization (ROMP) of norbornene (NBE) and some of its derivatives, as well as the mechanistically related metathesis polymerization of phenylacetylene (PA), is presented. Our results show that addition of a silver salt (AgBF4) is necessary for the activation of the ditungsten complex. Polymerization of PA proceeds smoothly in tetrahydrofuran (THF) producing polyphenylacetylene (PPA) in high yields. On the other hand, the ROMP of NBE and its derivatives is more efficient in CH2Cl2, providing high yields of polymers. 13C Cross Polarization Magic Angle Spinning (CPMAS) spectra of insoluble polynorbornadiene (PNBD) and polydicyclopentadiene (PDCPD) revealed the operation of two mechanisms (metathetic and radical) for cross-linking, with the metathesis pathway prevailing.

Application of (13)C ramp CPMAS NMR with phase-adjusted spinning sidebands (PASS) for the quantitative estimation of carbon functional groups in natural organic matter.

The composition of carbon (C) functional groups in natural organic matter (NOM), such as dissolved organic matter, soil organic matter, and humic substances, is frequently estimated using solid-state (13)C NMR techniques. A problem associated with quantitative analysis using general cross polarization/magic angle spinning (CPMAS) spectra is the appearance of spinning side bands (SSBs) split from the original center peaks of sp (2) hybridized C species (i.e., aromatic and carbonyl C). Ramp CP/phase-adjusted side band suppressing (PASS) is a pulse sequence that integrates SSBs separately and quantitatively recovers them into their inherent center peaks. In the present study, the applicability of ramp CP/PASS to NOM analysis was compared with direct polarization (DPMAS), another quantitative method but one that requires a long operation time, and/or a ramp CP/total suppression side band (ramp CP/TOSS) technique, a popular but non-quantitative method for deleting SSBs. The test materials were six soil humic acid samples with various known degrees of aromaticity and two fulvic acids. There were no significant differences in the relative abundance of alkyl C, O-alkyl C, and aromatic C between the ramp CP/PASS and DPMAS methods, while the signal intensities corresponding to aromatic C in the ramp CP/TOSS spectra were consistently less than the values obtained in the ramp CP/PASS spectra. These results indicate that ramp CP/PASS can be used to accurately estimate the C composition of NOM samples.

More insight into characterization of the waterlogged wooden part of Acqualadroni Roman Rostrum by solid-state NMR

Solid-state NMR spectroscopy was applied to characterize the wooden part of a roman Rostrum recovered in the Tyrrhenian Sea in the Acqualadroni area (Messina, Italy). The Acqualadroni Rostrum has been, in the recent past, investigated to establish its provenance and conservation. In this paper, solid-state NMR was used to obtain information on the conservation state of the wood as a preliminary step for the conservation process.A wooden sample of this artifact, collected by coring, was divided in four parts in order to correlate the conservation state to the depth. Results were compared with those obtained for a modern wood of the same species.A structural study was performed by acquiring 13C cross-polarization magic angle spinning spectra to evaluate the cellulose crystallinity degree and the lignin condensation degree. In addition, the holocellulose–lignin ratio and the cellulose–lignin residual interactions were determined through variable contact time experiments and relaxation times determination respectively.Being the solid-state NMR a non-destructive technique, all measurements were performed with no modification of the samples such as solvent extraction or other chemical treatment, making the samples available for further analytical investigation.

Solid- and Solution-State Nuclear Magnetic Resonance Analyses of Ecuadorian Asphaltenes: Quantitative Solid-State Aromaticity Determination Supporting the “Island” Structural Model. Aliphatic Structural Information from Solution-State 1H–13C Heteronuclear Single-Quantum Coherence Experiments

Solid- and solution-state nuclear magnetic resonance (NMR) studies of six Ecuadorian asphaltenes have provided insight into using NMR to characterize asphaltenes. For these asphaltenes, free radicals prevent obtaining quantitatively meaningful 1H–13C cross-polarization magic angle spinning (CPMAS) spectra but facilitate obtaining meaningful carbon aromaticity values in direct polarization with 13C pulse excitation. The benefit of studying any asphaltene by obtaining a series of CPMAS spectra with multiple contact times, rather than just a single contact time, is demonstrated. Analyzing the CPMAS and direct 13C pulse spectra indicates that, on average, condensed aromatic ring systems become larger as the aromaticity increases, which seems more consistent with “island” than “archipelago” aromatic structures, just as recently proposed for asphaltenes. Solution-state two-dimensional (2D) 1H–13C heteronuclear single-quantum coherence (HSQC) spectra of the asphaltenes provide a wealth of structural information ...

First solid-state NMR spectroscopy evaluation of complexes of benznidazole with cyclodextrin derivatives

Complexation of benznidazole (BZL), a drug of choice for the treatment of Chagas’neglected disease, with cyclodextrin (CD) derivatives was analyzed by solid-state NMR. 13C cross polarization/magic angle spinning spectra were recorded from BZL and from BZL:β-CD, BZL:methyl β-CD and BZL:hydroxypropyl β-CD complexes, which were obtained by the solvent evaporation technique. No significant evidence was obtained on BZL inclusion complexes involving either β-CD or hydroxypropyl β-CD. Conversely, BZL:methyl β-CD displayed BZL resonances characteristic of an amorphous drug and data analysis confirmed the presence of stable BZL:methyl β-CD inclusion complexes, with benzene encapsulated into the host cavity. Further evidences on complex structure and dynamics were obtained from proton and carbon spin–lattice relaxation times in the rotating frame. These data are consistent with a common guest–host spin reservoir. The BZL interaction with methyl β-CD provided a route to stabilize amorphous BZL. Physical mixtures with identical BZL and CD compositions were also studied for comparison.

Observing Apparent Nonuniform Sensitivity Enhancements in Dynamic Nuclear Polarization Solid-State NMR Spectra of Polymers.

High-field dynamic nuclear polarization (DNP) may enhance the sensitivity of solid-state NMR experiments on a wide range of systems, including synthetic polymers, owing to the transfer of electron spin polarization from radicals to nuclei upon microwave irradiation (usually at cryogenic temperatures). Provided that the radicals are homogeneously dispersed in the sample, a uniform DNP enhancement is expected for all the signals in the 13C cross-polarization magic angle spinning (CPMAS) spectrum. Here, we show that, in the case of methyl group containing polymers, a change in the cross-polarization (CP) dynamics induced by the moderate increase in sample temperature due to microwave irradiation may lead to the observation of apparent nonuniform enhancements in the DNP-enhanced 13C CPMAS spectra. This peculiar behavior should be accounted for when measuring 13C CP DNP enhancements on polymer materials, especially for heterogeneous polymer samples (for which truly nonuniform DNP enhancements could potentially be detected), or when quantitative results are sought.

Dynamic Nuclear Polarization NMR of Low-γ Nuclei: Structural Insights into Hydrated Yttrium-Doped BaZrO3.

We demonstrate that solid-state NMR spectra of challenging nuclei with a low gyromagnetic ratio such as yttrium-89 can be acquired quickly with indirect dynamic nuclear polarization (DNP) methods. Proton to (89)Y cross polarization (CP) magic angle spinning (MAS) spectra of Y(3+) in a frozen aqueous solution were acquired in minutes using the AMUPol biradical as a polarizing agent. Subsequently, the detection of the (89)Y and (1)H NMR signals from technologically important hydrated yttrium-doped zirconate ceramics, in combination with DFT calculations, allows the local yttrium and proton environments present in these protonic conductors to be detected and assigned to different hydrogen-bonded environments.

NMR in Li2 M 3Al(MoO4)4 triple molybdates (M = Rb, Cs)

Nuclear magnetic resonance (magic angle spinning) spectra of 7Li, 27Al, 87Rb, and 133Cs nuclei are measured in Li2M3Al(MoO4)4 triple molybdates (M = Rb, Cs) for the first time. Analysis of the nuclear magnetic resonance spectra reveal considerable asymmetry in the distribution of the electric charge throughout the crystal lattices of the compounds.

Selectively dispersed isotope labeling for protein structure determination by magic angle spinning NMR

The power of nuclear magnetic resonance spectroscopy derives from its site-specific access to chemical, structural and dynamic information. However, the corresponding multiplicity of interactions can be difficult to tease apart. Complimentary approaches involve spectral editing on the one hand and selective isotope substitution on the other. Here we present a new "redox" approach to the latter: acetate is chosen as the sole carbon source for the extreme oxidation numbers of its two carbons. Consistent with conventional anabolic pathways for the amino acids, [1-(13)C] acetate does not label α carbons, labels other aliphatic carbons and the aromatic carbons very selectively, and labels the carboxyl carbons heavily. The benefits of this labeling scheme are exemplified by magic angle spinning spectra of microcrystalline immunoglobulin binding protein G (GB1): the elimination of most J-couplings and one- and two-bond dipolar couplings provides narrow signals and long-range, intra- and inter-residue, recoupling essential for distance constraints. Inverse redox labeling, from [2-(13)C] acetate, is also expected to be useful: although it retains one-bond couplings in the sidechains, the removal of CA-CO coupling in the backbone should improve the resolution of NCACX spectra.

EASY-GOING deconvolution: Automated MQMAS NMR spectrum analysis based on a model with analytical crystallite excitation efficiencies

The EASY-GOING deconvolution (EGdeconv) program is extended to enable fast and automated fitting of multiple quantum magic angle spinning (MQMAS) spectra guided by evolutionary algorithms. We implemented an analytical crystallite excitation model for spectrum simulation. Currently these efficiencies are limited to two-pulse and z-filtered 3QMAS spectra of spin 3/2 and 5/2 nuclei, whereas for higher spin-quantum numbers ideal excitation is assumed. The analytical expressions are explained in full to avoid ambiguity and facilitate others to use them. The EGdeconv program can fit interaction parameter distributions. It currently includes a Gaussian distribution for the chemical shift and an (extended) Czjzek distribution for the quadrupolar interaction. We provide three case studies to illustrate EGdeconv’s capabilities for fitting MQMAS spectra. The EGdeconv program is available as is on our website http://egdeconv.science.ru.nl for 64-bit Linux operating systems.

Intramolecular Hydrogen Bonds in Cardiolipin

Cardiolipin was first isolated in 1941, and has since been implicated in several critical physiological roles. The distribution of cardiolipin species in tissues across prokaryotes and eukaryotes, and its concentration in membranes across which proton gradients drive energy production, is well characterized. The various functions attributed to cardiolipin include the structural stabilization of oxidative phosphorylation complexes in the inner mitochondrial membrane, where it constitutes about 25% of lipid. Its acid-base titration profile suggests a variable head group pKa in the physiological range, which leads to the hypothesis that cardiolipin also serves as a proton reservoir for energy-related protein complexes in the mitochondrial inter membrane space, thylakoid lumen, and at the outer leaflet of bacterial membranes. The importance of cardiolipin in these ascribed roles is further underscored by its involvement in diseases such as Barth's syndrome, where mitochondrial dysfunction is a major factor. In contrast to this physiological importance, Cardiolipin remains one of the least well characterised lipids from a biophysical perspective. In particular, there is still no consensus on whether it is a hydrogen bond between a protonated phosphate and the free 2-hydroxyl of the bridging glycerol of cardiolipin that explains its anomalous pKa. Furthermore, static 31P solid-state NMR characterisations of the head group have been difficult to interpret. We use our new Boltzmann-statistics maximum entropy analysis to globally analyse slow magic angle spinning spectra, and explain the uncharacteristic 31P static NMR spectra. Together with differential scanning calorimetry analysis, intriguing evidence emerges for the hydrogen bond hypothesis. We further pursue the hypothesis with additional solid-state NMR 31P{1H} heteronuclear correlations (HETCOR) and rotational-echo double-resonance (REDOR) experiments.