Variable Amplitude Cross Polarization Research Articles

Comprehensive Solid-State Characterization of Rare Earth Fluoride Nanoparticles

The combination of multinuclear solid-state NMR spectroscopy and powder X-ray diffraction has been applied to characterize the octahedron-shaped crystalline nanoparticle products resulting from an inverse micelle synthesis. Rietveld refinements of the powder X-ray diffraction data from the nanoparticles revealed their general formula to be (H3O)Y3F10·xH2O. 1H magic-angle spinning (MAS) NMR experiments provided information on sample purity and served as an excellent probe of the zeolithic incorporation of atmospheric water. 19F MAS NMR experiments on a series of monodisperse nanoparticle samples of various sizes yielded spectra featuring three unique 19F resonances arising from three different fluorine sites within the (H3O)Y3F10·xH2O crystal structure. Partial removal of zeolithic water from the internal cavities and tunnels of the nanoparticles led to changes in the integrated peak intensities in the 19F MAS NMR spectra; the origin of this behavior is discussed in terms of 19F longitudinal relaxation. 19F–89Y variable-amplitude cross-polarization (VACP) NMR experiments on both stationary samples and samples under MAS conditions indicated that two distinct yttrium environments are present, and on the basis of the relative peak intensities, the population of one of the two sites is closely linked to the nanoparticle size. Both 19F MAS and 19F–89Y VACP/MAS experiments indicated small amounts of an impurity present in certain nanoparticles; these are postulated to be spherical amorphous YF3 nanoparticles. We discuss the importance of probing molecular-level structure in addition to microscopic structure and how the combination of these characterization methods is crucial for understanding nanoparticle design, synthesis, and application.

Mechanism of Nanoparticle Formation from Ternary Coground Phenytoin and Its Derivatives

The mechanism of drug nanoparticle formation of phenytoin (DPH) and its derivatives monomethylphenytoin (MDPH) and dimethylphenytoin (DMDPH) was investigated. The drug, polyvinylpyrrolidone K17 (PVP), and sodium dodecyl sulfate were coground to obtain the ground mixture (GM). The DPH GM was amorphous; however, MDPH and DMDPH GMs contained drug crystals. Spectral changes in infrared and (13)C solid-state nuclear magnetic resonance were observed in the DPH GM, partially observed in the MDPH GM, and hardly observed in the DMDPH GM. Mean particle sizes of the DPH, MDPH, and DMDPH GM nanosuspension were almost the same; however, stability after storage differed in the order of DPH > MDPH > DMDPH. The intermolecular interaction between the drug and PVP reflected not only the crystallinity of the drug in the GM but also the stability of the GM suspension. The size and stiffness of drug nanoparticles were evaluated using atomic force microscopy. Crystallization of the amorphous GM and agglomeration of the primary nanocrystals were observed in the DPH GM suspension. In contrast, primary nanocrystals were observed in the DMDPH GM suspension. The size of the drug nanocrystals formed from the different molecular states of the drug in the GM reflects the agglomerated states in water and stability.

Pyrolysis‐Gas Chromatography/Mass Spectrometry Characterization of Humic Acids in Coastal Spodosols from Southeastern Brazil

This study on humic acids (HAs) of podzol horizons from the southeastern region of Brazil investigated the accumulation and degradation of soil organic matter (SOM) in warm‐climate podzols. Humic acids from sandy coastal Spodosols (Histic Alaquod and Arenic Alorthod) from Cardoso Island in Sao Paulo State were characterized by pyrolysis in combination with gas chromatography and mass spectrometry (Py‐GC/MS). The soils developed on quartzitics, andy, nutrient‐poor parent materials under restinga forest in a coastal area. The Py‐GC/MS results show that the chemical composition of HAs in B horizons in one out of three profiles was influenced by both dissolved organic C (DOC) and C from in situ decaying roots. Carbon derived from DOC dominated in the deepest part of the B horizons. In the Arenic Alorthod (H9) profile, SOM from the B horizon seemed to be largely derived from roots. The DOC‐derived SOM was characterized by large contributions of phenol, methylphenols, and degraded polysaccharide products, while root contributions were mainly characterized by lignin products. Aliphatics were most abundant in A horizons (E and EB horizons were not analyzed). Both DOC‐derived and lignin‐derived SOM showed distinct degradation patterns. The Py‐GC/MS results corroborate those obtained by 13C variable amplitude cross polarization magic angle spinning nuclear magnetic resonance spectroscopy and Fourier‐transform infrared spectroscopy. Molecular chemistry showed that podzol B horizons are variable in composition, and local influences, such as drainage and vertical or lateral water transport, and SOM decomposition play an important role in podzolization processes in warm climates.

Effect of ramp size and sample spinning speed on CPMAS 13C NMR spectra of soil organic matter

Cross polarization (CP) magic angle spinning (MAS) 13C NMR spectroscopy is a solid state NMR technique widely applied to study the chemical composition of natural organic matter. In high magnetic fields (>7 T), fast sample spinning is required in order to reduce the influence of spinning sidebands underlying other chemical shift regions. As the spinning speed increases, the Hartmann–Hahn matching profiles break down into a series of narrow matching bands. In order to account for this instability variable amplitude cross polarization techniques (e.g. VACP, ramp-CP) have been developed. In the present study, we experimentally verified the stability of the Hartmann–Hahn condition under two MAS speeds for different samples with known structure and two different humic acids. For a complete restoration of flat matching profiles, large ramp sizes were needed. The matching profiles of the humic acids showed that both samples needed different ramp sizes to restore flat profiles. A set up based on the matching profiles of the commonly used glycine would have led to an insufficient ramp size for one of the humic acids. For the characterization of natural organic matter, we hence recommend to roughly set the matching conditions with a standard and subsequently optimize the matching conditions on a more complex, preferably representative, sample such as a humic acid. We would suggest to either run an array of different ramp sizes until maximum signal intensity is reached for all chemical shift regions or, in the case of unavailable measurement time, to use a ramp size twice the spinning speed.

Wildfires influence on soil organic matter in an Atlantic mountainous region (NW of Spain)

Abstract The principal aim of this research was to determine the influence of wildfires on soil organic matter (SOM) content and composition in soils located on the northern slope of the Cantabrian Cordillera, an Atlantic mountainous region in the North West of Spain, where wildfires are frequent. Samples from soils with similar aspect, slope, elevation and vegetation characteristics, but with different wildfires histories were collected. Total organic carbon and total nitrogen contents were determined as well as the C/N ratio. Furthermore, a qualitative characterization of the soil organic carbon (SOC) was carried out by 13C variable amplitude cross polarization magic angle spinning (VACP/MAS) Nuclear Magnetic Resonance (NMR) spectroscopy. Our results show that, on the one hand, all the sampled soils can be considered important pools of carbon in this Atlantic mountainous region, especially in the heath areas. On the other hand, the fire-affected soils present higher SOM contents than their unburnt counterparts. This could be attributed to an important reaccumulation of fresh vegetal material, which is probably a consequence of the decrease of SOM decomposition rates after fire. Moreover, charred organic compounds are not found in all the burnt soils, which could be due to the long time since the last fires events took place, to different fire severities, or to different post-fire erosion processes in the studied soils.

Studies of the Compositions of Humic Acids from Amazonian Dark Earth Soils

The compositions of humic acids (HAs) isolated from cultivated and forested "Terra Preta de Indio" or Amazonian Dark Earth soils (anthropogenic soils) were compared with those from adjacent non-anthropogenic soils (control soils) using elemental and thermogravimetric analyses, and a variety of solid-state nuclear magnetic resonance techniques. The thermogravimetric index, which indicates the molecular thermal resistance, was greater for the anthropogenic soils than for the control soils suggesting polycyclic aromatic components in the former. The cultivated anthropogenic soils were more enriched in C and depleted in H than the anthropogenic soils under forest, as the result of the selective degradation of aliphatic structures and the possible enrichment of H-deficient condensed aromatic structures. The combination of variable amplitude cross-polarization (VACP) and chemical shift anisotropy with total suppression of spinning sidebands experiments with composite pi pulses could be used to quantify the aromaticity of the HAs from the anthropogenic soils. From principal component analysis, using the VACP spectra, it was possible to separate the different constituents of the HAs, such as the carboxylated aromatic structures, from the anthropogenic soils and plant derived compounds. The data show that the HAs from anthropogenic soils have high contents of aryl and ionisable oxygenated functional groups, and the major functionalities from adjacent control soils are oxygenated functional groups from labile structures (carbohydrates, peptides, and with evidence for lignin structures). The anthropogenic soils HAs can be considered to be more recalcitrant, and with more stable reactive functional groups which may, in part, explain their more sustainable fertility due to the organic matter contribution to the soil cation exchange capacity.

Sensitivity considerations in polarization transfer and filtering using dipole–dipole couplings: Implications for biomineral systems

The robustness and sensitivities of different polarization-transfer methods that exploit heteronuclear dipole–dipole couplings are compared for a series of heterogeneous solid systems, including polycrystalline tetrakis(trimethylsilyl)silane (TKS), adamantane, a physical mixture of doubly 13C, 15N-enriched and singly 13C-enriched polycrystalline glycine, and a powder sample of siliceous marine diatoms, Thalossiosira pseudonana. The methods were analyzed according to their respective frequency-matching spectra or resultant signal intensities. For a series of 13C{ 1H} cross-polarization experiments, adiabatic passage Hartmann–Hahn cross-polarization (APHH-CP) was shown to have several advantages over other methods, including Hartmann–Hahn cross-polarization (HHCP), variable-amplitude cross-polarization (VACP), and ramped-amplitude cross-polarization (RACP). For X–Y systems, such as 13C{ 15N}, high and comparable sensitivities were obtained by using APHH-CP with Lee–Goldburg decoupling or by using the transferred-echo double resonance (TEDOR) experiment. The findings were applied to multinuclear 1H, 13C, 15N, and 29Si CP MAS characterization of a powder diatom sample, a challenging inorganic–organic hybrid solid that places high demands on NMR signal sensitivity.

Comparison of Molecular Mobility in the Glassy State Between Amorphous Indomethacin and Salicin Based on Spin-Lattice Relaxation Times

The purpose of the current study was to evaluate the molecular mobility of amorphous indomethacin and salicin in the relaxed glassy state based on spin-lattice relaxation times (T(1c)) and to clarify the effects of molecular mobility on their physical stability. Pulverized glassy amorphous indomethacin and salicin samples were completely relaxed, and the T(1c) values were investigated using solid-state (13)C-nuclear magnetic resonance (NMR) at temperatures below the glass transition temperature (T(g)). All NMR spectra were obtained using the T(1c) measurement method combined with variable-amplitude cross-polarization, the Torchia method, and total sideband suppression method. The T(1c) value of amorphous indomethacin indicated that 73% of carbons were in a state of monodispersive relaxation, suggesting that the amorphous state was relatively homogeneous and restricted, particularly in backbone carbons. On the other hand, 92% of carbons of amorphous salicin exhibited both fast and slow biphasic relaxation. Individual structures of the salicin molecules behaved heterogeneously, and thus the entire molecule showed relatively fast local as well as slow mobility. At temperatures below T(g), amorphous salicin had relatively greater molecular mobility than amorphous indomethacin. This difference in the molecular mobility of the two compounds is correlated with their crystallization behavior. Solid-state (13)C NMR provides valuable information on the physical stability of amorphous pharmaceuticals.

113Cd double-resonance NMR as a probe of clay mineral cation exchange sites

A lack of direct spectroscopic evidence linking cations to the clay mineral structure is a primary reason for many ambiguities regarding the location and structure of the binding sites. This study attempts to obtain such evidence through the observation of nuclear-spin interactions between adsorbed cations ( 113 Cd 2+ ) and nuclei present in the lattice structure of the clay ( 1 H and 27 Al) using solid-state NMR. 1 H- 113 Cd variable-amplitude cross-polarization (VACP) and 27 Al- 113 Cd spin-echo double-resonance (SEDOR) experiments were successfully performed on dried, Cd 2+ -exchanged beidellite, montmorillonite, and vermiculite samples, demonstrating for the first time a direct interaction between the adsorbed cations and the clay. VACP provides much greater cross-polarization (CP) efficiency which enhances signal intensity necessary for these experiments. Signal intensity varies between octahedral and tetrahedral binding sites because hydroxyls in the ditrigonal cavities of tetrahedral sites produce greater CP efficiency presumably due to shorter 1 H- 113 Cd distances in this environment. CP efficiency decreased in the order vermiculite>beidellite>montmorillonite. The observation of nuclear-spin coupling between cadmium and either 1 H or 27 Al in the minerals is consistent with the presence of the cations in the ditrigonal cavities of the tetrahedral sheet. Inter-sample comparison of the strengths of coupling interactions follow expected trends based on charge location in the crystal structure and Al speciation.

Simulation of CPMAS Signals at High Spinning Speeds

The spin dynamics of anS(12)INsystem during the CP mixing time of continuous wave and variable amplitude cross-polarization magic angle spinning (CWCPMAS and VACPMAS) experiments is discussed. The signal enhancement of a low abundantSspin, coupled to a set ofN= 6 coupled spins withI=12, is evaluated as a function of the length of the mixing time. For CWCPMAS this signal is first evaluated in the frequency domain and then transformed to the time domain. These calculations provide some additional insight into the CP spin dynamics and enable a practical approach toward the evaluation of CP signals of large spin systems. In addition the adiabatic character of the ramped VACPMAS experiments is discussed andS-spin signals of a spin system withN= 6 are simulated. Estimates of the upper bounds of the CP signals as a function of the number ofIspins in anS(12)INsystem are given and compared with the calculated values.

Enhancement of CP-MAS Signals by Variable-Amplitude Cross Polarization. Compensation for Inhomogeneous B1 Fields

Enhancement of CP-MAS Signals by Variable-Amplitude Cross Polarization. Compensation for Inhomogeneous B1 Fields