On the 13C CP/MAS spectra of leucine.

The CP/MAS 13C NMR spectra of crystalline L-leucine and DL-leucine at 7 T are compared with previously reported spectra at lower field strengths. An increasing dominance of chemical shift effects over residual 14N-13C dipolar interactions is observed on the C alpha and C beta splittings with increasing field strength. A new structure is observed in the 25 ppm region of both samples. The spectra in this region were assigned by application of the depolarisation-repolarisation method. The assignment showed differences in the ordering of peaks between solid state and liquid state chemical shifts.     

13C CP MAS NMR and GIAO-CHF calculations of coumarins

13C cross-polarization magic-angle spinning NMR spectra were recorded for a series of solid coumarins. Ab initio calculations of shielding constants were performed with the use of GIAO-CHF method. The combined CPMAS NMR and theoretical approach was successful in characterizing solid-state conformations of coumarins; a relationship sigma (ppm) = -1.032 xdelta + 205.28 (R(2) = 0.9845) can be used to obtain structural information for coumarins, for which solid-state NMR or crystal structure data are not available.     

H/D isotope effect of 1H MAS NMR spectra and 79Br NQR frequencies of piperidinium p-bromobenzoate and pyrrolidinium p-bromobenzoate

H/D isotope effects onto ⁷⁹Br NQR frequencies of piperidinium p-bromobenzoate were studied by deuterium substitution of hydrogen atoms which form two kinds of N–H?O type hydrogen bonds, and the isotope shift of ca. 100 kHz were detected for a whole observed temperature range. In addition, ¹H MAS NMR spectra measurements of piperidinium and pyrrolidinium p-bromobenzoate were carried out and little isotope changes of NMR line shape were detected. In order to reveal effects of molecular arrangements into the obtained isotope shift of NQR frequencies, single-crystal X-ray measurement of piperidinium p-bromobenzoate-d2 and density-functional-theory calculation were carried out. Our estimation showed the dihedral-angle change between piperidine and benzene ring contributes to isotope shift rather than those of N–H lengths by deuterium substitution.     

Experimental method for low-temperature reaction studies in sealed samples by 13C CP/MAS NMR

A new, simple, and inexpensive technique is presented for monitoring high-resolution solid-state NMR of ¹³C at temperatures ranging between 85 and 450 K. In this procedure, the reaction conditions are controlled by preparing samples at 77 K in 5 mm NMR tubes, while attached to a vacuum system. The NMR tubes are prefitted with a rotor for spinning. After preparation, the samples are sealed, transferred to the double-resonance MAS NMR probe, and analyzed, all while the sample temperature is maintained as low as 85 K. The spinning rates vary from 3.0 kHz at 85 K to 5.2 kHz at 300 K using nitrogen drive gas. Probe design and performance, sample-preparation procedure, and details of the low-temperature experiment are described. In general, the technique may be applied in studies of low-temperature reaction mechanisms and kinetics. ¹³C CP/MAS spectra of ethylene adsorbed on silica-supported ruthenium catalyst are presented to illustrate its performance and possible application.     

Stability of {\text{SrCe}}_{{0.9}} {\text{Eu}}_{{0.1}} {\text{O}}_{{3 - \delta }} and {\text{SrZr}}_{{0.2}} {\text{Ce}}_{{0.7}} {\text{Eu}}_{{0.1}} {\text{O}}_{{3 - \delta }} under H2 atmospheres

Previous H₂ permeation tests showed a degradation of H₂ permeation flux with time. To understand the cause of degradation and develop a solution, the stability of $ {\text{SrCe}}_{{0.9}} {\text{Eu}}_{{0.1}} {\text{O}}_{{3 - \delta }} $ and $ {\text{SrZr}}_{{0.2}} {\text{Ce}}_{{0.7}} {\text{Eu}}_{{0.1}} {\text{O}}_{{3 - \delta }} $ samples were studied under dry and wet H₂ atmospheres. Total conductivity of $ {\text{SrCe}}_{{0.9}} {\text{Eu}}_{{0.1}} {\text{O}}_{{3 - \delta }} $ increased with time in dry H₂. The X-ray diffraction pattern of $ {\text{SrCe}}_{{0.9}} {\text{Eu}}_{{0.1}} {\text{O}}_{{3 - \delta }} $ after dry hydrogen atmosphere heat treatments show CeO₂ peaks indicating that $ {\text{SrCe}}_{{0.9}} {\text{Eu}}_{{0.1}} {\text{O}}_{{3 - \delta }} $ decomposes under dry H₂ atmospheres; scanning electron microscopy and energy dispersive X-ray spectroscopy analyses prove that decomposition proceeded along the grain boundaries. $ {\text{SrZr}}_{{0.2}} {\text{Ce}}_{{0.7}} {\text{Eu}}_{{0.1}} {\text{O}}_{{3 - \delta }} $ was investigated and demonstrated greater stability under dry hydrogen atmospheres. However, Zr substitution results in a tradeoff with electrical properties.     

Quantitative characterization of coal structure by high-resolution CP/MAS 13C solid-state NMR spectroscopy

A method for quantitatively characterizing the carbon skeletal structure of coal by variable contact time experiment using high-resolution CP/MAS ¹³C solid-state NMR spectroscopy is proposed in this paper. The initial polarization transfer intensity from protons directly bonded with carbons, instead of dipolar-dephasing techniques which had to run on a lower frequency NMR spectrometer (100.02 MHz for proton), was used to divide the bridgehead and protonated aromatic carbons, making all the NMR data in this paper obtained on a high frequency NMR spectrometer (500.12 MHz for proton). On this basis, the fractions of different carbons in coal were further divided by the initial polarization transfer intensity from spin diffusion of protons unbonded with carbons. The structure of Naomaohu coal, a subbituminous coal from China, was measured. The change of polarization transfer with contact time was analyzed quantitatively. The fractions of aromatic, aliphatic, carboxyl and carbonyl carbons, and corrective aromaticity are 0.61, 0.39, 0.1 and 0.51, respectively. The fractions of protonated and bridgehead aromatic carbons are 0.22 and 0.09, respectively. These results agreed with literatures, and bond concentration calculated by the carbon skeletal structure distribution of coal was reasonable.     

Crystal structure and 13C CP/MAS NMR of the p-xylene clathrate of Dianin's compound

Single-crystal X-ray diffraction and ¹³C solid state NMR spectroscopy were used to characterize the structure and dynamics of the p-xylene clathrate of Dianin's compound. In contrast to conclusions obtained from single-crystal ²H NMR and modelling, the diffraction results suggest there is a single (symmetry disordered) guest site without any significant distortion of the host framework. A single xylene guest statistically disordered over six overlapping equivalent positions can account for the ¹³C NMR spectrum at room temperature. The high crystal-lographic symmetry arises from space averaging. At high temperatures the ¹³C spectrum is consistent with the onset of dynamic processes that result in higher effective symmetry.     

~(13)C CP/MAS OF MOTIONS IN SOLID POLYMERS

High-resolution 13C spectra of solid polymers are often acquired with cross polarization with magic angle spinning (CP/MAS) to take advantage of the abunda ntly available protons in the polymer chains. The sequence for transferring mag netization from 1H to13C using Hartmann-Hahn spin locking in the rotating frame is now a standard in commercial solidstate NMR spectrometers.     

Observation of nitrogen-14, carbon-13 indirect spin-spin coupling in high-resolution 13C CP/MAS spectra of solids.

The 13C CP/MAS NMR spectrum of [(n-C3H7)4N][Cd(SCN)3], 1, indicates the presence of three non-equivalent thiocyanate ligands, in agreement with the results of a recent single-crystal X-ray diffraction study. Examination of the 13C MAS line shapes allows direct measurement of the indirect spin-spin coupling constants, 1J(14N, 13C) = 16 +/- 1 Hz and 2J(111/113Cd, 13C) = 75 +/- 5 Hz, for the unique N-bonded thiocyanate ligand. This is the first reported measurement of 1J(14N, 13C) and 2J(111/113Cd, 13C) in the solid state. Possible reasons for the failure to observe 1J(14N, 13C) values in previous high-resolution 13C CP/MAS NMR studies are summarized.     

Investigation of atmospheric {\text{O}}_{2}{\text{X}}{^{ 3}}{ \sum_{\text{g}}^{ - }} \,{\text{to}}\, {\text{b}}{^{ 1}}{ \sum_{\text{g}}^{ + }} using open-path tunable diode laser absorption spectroscopy

A tunable diode laser absorption spectroscopy (TDLAS) device fiber coupled to a pair of 12.5 in. telescopes was used to study atmospheric propagation for open path lengths of 100–1,000 meters. More than 50 rotational lines in the molecular oxygen A-band O₂ $ {\text{X}}{^{ 3}}{ \sum_{\text{g}}^{ - }} \,{\text{to}}\, {\text{b}}{^{ 1}}{ \sum_{\text{g}}^{ + }} $ transition near 760 nm were observed. Temperatures were determined from the Boltzmann rotational distribution to within 1.3 % (less than ±2 K). Oxygen concentration was obtained from the integrated spectral area of the absorption features to within 1.6 % (less than ±0.04 × 10¹⁸ molecules/cm³). Pressure was determined independently from the pressure-broadened Voigt lineshapes to within 10 %. A fourier transform interferometer (FTIR) was also used to observe the absorption spectra at 1 cm^?1 resolution. The TDLAS approach achieves a minimum observable absorbance of 0.2 %, whereas the FTIR instrument is almost 20 times less sensitive. Applications include atmospheric characterization for high energy laser propagation and validation of monocular passive raging.     

Structural and 14N EFG Information on Solid Imidazole by 13C CP/MAS NMR Data

Residual dipolar coupling between carbons and ¹⁴N nuclei in the ¹³C CPMAS NMR spectrum of solid imidazole is studied. Calculations of expected splittings with a previously reported equation leads to the complete assignment of the solid state carbon chemical shifts. Additionally, information is provided on the location of ¹⁴N electric field gradient axes at the N-H site.     

1H and 13C MAS NMR studies of light alkanes activation over MFI zeolite modified by Zn vapour

The early stages of methane, ethane and propane conversion were studied by in situ ¹H and ¹³C MAS NMR techniques over fully exchanged Zn²⁺/MFI catalyst obtained by the reaction with zinc vapour. The in situ techniques revealed strong interaction of alkanes with Zn²⁺ cations evidenced by significant shift of the corresponding NMR lines. Besides that, the formation of methyl zinc, ethyl zinc and n-propyl zinc species along with bridging and silanol surface OH-groups was detected already at the ambient temperature. These results pointed to dissociative adsorption of alkanes over (ZO)–Zn²⁺–(OZ) and (ZO)–Zn²⁺–(OSi) active sites of the catalyst. The dissociative adsorption was shown to be a dead-end surface reaction in the case of methane starting reactant, while in the case of ethane and propane, it appeared to be responsible for the initiation of the catalytic cycle leading to alkenes and dihydrogen formation and regeneration of zinc containing catalytic sites.     

Magnetic susceptibility effects on 13C MAS NMR spectra of carbon materials and graphite

13C high-resolution solid-state nuclear magnetic resonance (NMR) was employed to study carbon materials prepared through the thermal decomposition of four different organic precursors (rice hulls, endocarp of babassu coconut, peat, and PVC). For heat treatment temperatures (HTTs) above about 600 C, all materials presented 13C NMR spectra composed of a unique resonance line associated with carbon atoms in aromatic planes. With increasing HTT a continuous broadening of this resonance and a diamagnetic shift in its central frequency were verified for all samples. The evolution of the magnitude and anisotropy of the magnetic susceptibility of the heat-treated carbon samples with HTT explains well these findings. It is shown that these results are better understood when a comparison is made with the features of the 13C NMR spectrum of polycrystalline graphite, for which the magnetic susceptibility effect is also present and is much more pronounced.     

A 4-mm probe for (13)C CP/MAS NMR of solids at 21.15 T

The design of a broadband 4-mm magic-angle spinning (MAS) X-(1)H/(19)F double resonance probe for cross-polarization (CP)/MAS NMR studies at 21.15 T ((1)H at 900 MHz) is described. The high-frequency (1)H/(19)F channel employs a new and efficient transmission line tuning design. The first (13)C CP/MAS NMR spectra recorded at 21.15 T have been obtained with this probe and exhibit the best S/N per milligram sample of hexamethylbenzene achieved so far for a 4-mm rotor.     

Thermal maturity of type II kerogen from the New Albany Shale assessed by 13C CP/MAS NMR

Thermal maturity of oil and gas source rocks is typically quantified in terms of vitrinite reflectance, which is based on optical properties of terrestrial woody remains. This study evaluates 13C CP/MAS NMR parameters in kerogen (i.e., the insoluble fraction of organic matter in sediments and sedimentary rocks) as proxies for thermal maturity in marine-derived source rocks where terrestrially derived vitrinite is often absent or sparse. In a suite of samples from the New Albany Shale (Middle Devonian to the Early Mississippian, Illinois Basin) the abundance of aromatic carbon in kerogen determined by 13C CP/MAS NMR correlates linearly well with vitrinite reflectance.     

Lasing of optically pumped XeF and analysis of the spectrum of the laser transitionB^2 \sum _{{1 \mathord{\left/ {\vphantom {1 2}} \right. \kern-\nulldelimiterspace} 2}}^ + - X^2 \sum _{{1 \mathord{\left/ {\vphantom {1 2}} \right. \kern-\nulldelimiterspace} 2}}^ +

The operating principle of a photodissociation XeF laser (λ?350 nm) is discussed. A laser operating on the gas mixture XeF₂:N₂(SF₆):Ar pumped by radiation from an open high-current discharge is described. The maximum lasing duration is 5 μsec, the maximum output energy is 0.15 J. The vibrational structure of the XeF-molecule transition B²Σ_1/2 ⁺ ? X²Σ_1/2 ⁺, observed in absorption, luminescence, and stimulated emission, is investlgated. The vibrational quantum and the anharmonicity in the upper and lower states are measured: ω_e ^' = 308.7 cm^-1, ω_e ^'x_e ^' = 1.44 cm^-1, ω_e ^'' = 225.7 cm^-1, ω_e ^''x_e ^'' = 11.0 cm^-1. The difference between the equilibrium internuclear distances of the XeF molecule is determined for the excited (B) and ground (X) states, namely r_e ^' - r_e ^'' = 0.33 +- 0.01 Å.