13C cross‐polarization magic angle spinning NMR of ferrocene derivatives

The 13C chemical shifts of the CP/MAS NMR for ferrocene derivatives have been measured. Copyright © 2002 John Wiley & Sons, Ltd.     

Heating caused by radiofrequency irradiation and sample rotation in 13C magic angle spinning NMR studies of lipid membranes

Application of rapid sample rotation and radiofrequency irradiation in magic angle spinning (MAS) NMR of lipid bilayers can significantly increase the sample temperature. In this work, we studied the extent of heating during the acquisition of 1H-decoupled 13C MAS spectra of hydrated dimyristoylphosphatidylcholine (DMPC) in the L(alpha) phase. First, we describe a simple procedure for determining the increase in temperature by observing the shift of the 1H water signal. The method is then used to identify and assess the various factors that contribute to the sample heating. The important factors discussed in this paper include: (i) the spinning speed, (ii) the variable-temperature gas pressure, (iii) the rotor geometry, (iv) the power, duration and frequency of the radiofrequency irradiation and (v) the hydration level. A comparison of different heteronuclear decoupling schemes in terms of their ability to produce highly resolved 13C spectra of DMPC is also reported.     

13C CP MAS NMR and DFT Studies of 6-Chromanyl Ethereal Derivatives

Vitamin E consists of a group of compounds including α- β- γ- and δ-tocopherols and α- β- γ- and δ-tocotrienols, containing the chroman-6-ol system. The recognition of the structural and dynamic properties of this system, present in all vitamers, seems to be important for the full explanation of the mechanism of the biological activity of vitamin E. This paper presents results of the structural analysis of the chosen 6-chromanyl ethereal derivatives using experimental (¹³ C NMR-in solution and solid state, as well as variable temperature experiments; single crystal X-ray diffraction) and theoretical (DFT) methods. For one of the studied compounds, 2,2,5,7,8-pentamethyl-6-((tetrahydro-2H-pyran-2-yl)oxy) chroman, the splitting of some signals was observed in the ¹³C dynamic NMR spectra. This observation was explained by the application of a conformational analysis and subsequent DFT optimization, followed by the calculation of NMR properties.     

13C/15N distance determination by CPMAS NMR in uniformly 13C labeled molecules

The REDOR and CPMAS techniques are applied for measuring 13C-15N dipolar coupling constants in glycine. It is shown that the selective CP or SPECIFIC CP technique removes the coherent evolution of the spin system under homonuclear 13C-13C J couplings. While the large coupling constant (approximately 900 Hz) is readily determined because of the presence of large oscillations in the CPMAS dynamics, their absence precludes the measurement of the small coupling constant (approximately 200 Hz). The experimental results and numerical simulations demonstrate that the determination of 13C-15N coupling constants of medium size (<1 kHz) by the CPMAS technique is mainly limited by the strength of the 1H decoupling field and the size of the 13C and 15N chemical shift anisotropies.     

Evidence of a phase transition of RbHCO3 from high-resolution solid-state 13C and 87Rb NMR by comparison with KHCO3

A variable-temperature high-resolution 13C and 87Rb solid-state NMR study of powder rubidium hydrogencarbonate, RbHCO3, is presented for the first time. At ambient temperature, RbHCO3 is formed by centrosymmetric dimers linked by hydrogen bonds, but almost no information is available on this compound concerning proton disorder and the low-temperature phase. However, potassium hydrogencarbonate, KHCO3, which has an isomorphic structure for the high temperature phase, was well studied: it undergoes a non-ferroic, non-ferroelectric phase transition at Tc = 318 K between two monoclinic structures. The protons are disordered in an asymmetric double-well potential in the low-temperature phase, and the double-well potential becomes symmetric in the high-temperature phase. By comparison with recent solid-state NMR experimental results on KHCO3, we show that RbHCO3 undergoes a phase transition at Tc approximately 245 K, and give evidence that the proton dynamic disorder in both compounds is very similar.     

Conformation analysis and molecular mobility of ethylene and tetrafluoroethylene copolymer using solid-state 19F MAS and 1H --> 19F CP/MAS NMR spectroscopy

The changes in the conformation and molecular mobility accompanied by a phase transition in the crystalline domain were analyzed for ethylene (E) and tetrafluoroethylene (TFE) copolymer, ETFE, using variable-temperature (VT) solid-state 19F magic angle spinning (MAS) and 1H --> 19F cross-polarization (CP)/MAS NMR spectroscopy. The shifts of the signals for fluorines in TFE units to higher frequency and the continuing decrease and increase in the T1rho(F) values suggest that conformational exchange motions exist in the crystalline domain between 42 and 145 degrees C. Quantum chemical calculations of magnetic shielding constants showed that the high-frequency shift of TFE units should be induced by trans to gauche conformational changes at the CH2-CF2 linkage in the E-TFE unit. Although the 19F signals of the crystalline domain are substantially overlapped with those of the amorphous domain at ambient probe temperature (68 degrees C), they were successfully distinguished by using the dipolar filter and spin-lock pulse sequences at 145 degrees C. The dipolar coupling constants for the crystalline domain, which can be estimated by fitting the dipolar oscillation behaviors in the 1H --> 19F CP curve, showed a significant decrease with increasing temperature from 42 to 145 degrees C. This is due to the averaging of 1H-19F dipolar interactions originating from the molecular motion in the crystalline domain. The increase in molecular mobility in the crystalline domain was clearly shown by VT T1rho(F) and 1H --> 19F CP measurements in the phase transition temperature range.     

High-resolution solid-state MAS 73Ge NMR spectra of some organogermanes

High-resolution solid-state magic angle spinning (73)Ge NMR spectra of some organogermanium compounds were measured. Most tetrasubstituted germanes with identical substituents exhibited signals except for one case. Tetrasubstituted germanes with two kinds of different but somewhat similar substituents exhibited broad peaks. Trisubstituted germanes failed to show signals, indicating the importance of symmetry around germanium.     

Phosphorylated amino acids: model compounds for solid-state 31P NMR spectroscopic studies of proteins

Solid-state 31P NMR spectroscopy was applied to measure the isotropic chemical shifts, chemical shift anisotropies and asymmetry parameters of three phosphorylated amino acids, O-phospho-L-serine, O-phospho-L-threonine and O-phospho-L-tyrosine. The cross-polarization buildup rates and longitudinal relaxation times of 31P and 1H were-determined and compared with the values measured for a triphosphate (GppCH2p) bound to a crystalline protein (Ras). It is shown that the phosphorylated amino acids are well-suited model compounds, e.g. for the optimization of experiments on crystalline proteins. Two-dimensional exchange experiments on O-phospho-L-tyrosine indicate the existence of an exchange between the two different conformations of the molecule.     

Solid‐state CP/MAS 13C NMR studies on conformational polymorphism in sertraline hydrochloride,an antidepressant drug

The C(2) isotropic chemical shift values in solid‐state CP/MAS ¹³C NMR spectra of conformational polymorphs Form I (δ 28.5) and III (δ 22.9) of (1S,4S)‐sertraline HCl ( 1 ) were correlated with a γ‐gauche effect resulting from the respective 162.6° antiperiplanar and 68.8° (+)‐synclinal C(2)? C(1)? N? CH₃ torsion angles as measured by X‐ray crystallography. The similarity of the solution‐state C(2) chemical shifts in CD₂Cl₂ (δ 22.8) and DMSO‐d₆ (δ 23.4) with that for Form III (and other polymorphs having C(2)? C(1)? N? CH₃ (+)‐synclinal angles) strongly suggests that a conformational bias about the C(1)? N bond exists for 1 in both solvents. This conclusion is supported by density functional theory B3LYP/6‐31G(d)‐calculated relative energies of C(1)? N rotameric models: (kcal) 0.00 [73.8 °C(2)? C(1)? N? CH₃ torsion angle], 0.88 (168.7°), and 2.40 (?63.4°). A Boltzmann distribution of these conformations at 25 °C is estimated to be respectively (%) 80.3, 18.3, and 1.4. Copyright © 2002 John Wiley & Sons, Ltd.     

Solid‐state 1H → 19F/19F → 1H CP/MAS NMR study of poly(vinylidene fluoride)

Solid‐state ¹H → ¹⁹F and ¹⁹F → ¹H cross‐polarization magic angle spinning (CP/MAS) NMR spectra have been investigated for a semicrystalline fluoropolymer, namely poly(vinylidene fluoride) (PVDF). The ¹H → ¹⁹F CP/MAS spectra can be fitted by five Lorentzian functions, and the amorphous peaks were selectively observed by the DIVAM CP pulse sequences. Solid‐state spin‐lock experiments showed significant differences in T_1ρ^F and T_1ρ^H between the crystalline and amorphous domains, and the effective time constants, T_HF* and T_1ρ*, which were estimated from the ¹H → ¹⁹F CP curves, also clarify the difference in the strengths of dipolar interactions. Heteronuclear dipolar oscillation behaviour is observed in both standard CP and ¹H → ¹⁹F inversion recovery CP (IRCP) experiments. The inverse ¹⁹F → ¹H CP‐MAS and ¹H → ¹⁹F CP‐drain MAS experiments gave complementary information to the standard ¹H → ¹⁹F CP/MAS spectra in a manner reported in our previous papers for other fluoropolymers. The value of N_F/N_H (where N is a spin density) estimated from the CP‐drain curve is within experimental error equal to unity, which is consistent with the chemical structure. Copyright © 2001 John Wiley & Sons, Ltd.     

Solid-phase synthesis and 1H and 13C high-resolution magic angle spinning NMR of 13C-labeled resin-bound saccharides

We show how high-resolution magic angle-spinning NMR spectroscopy can be used to characterize 13C-labeled saccharides that have been prepared using solid-phase synthesis techniques while they are still bound to a solid-support resin. With the use of 13C-labeled glucose as the starting material, we have successfully synthesized mono-, di- and trisaccharides with uniform 13C labeling of the saccharide rings. Using these materials, we have been able to assign the 13C and 1H spectra and to characterize various impurities on the resin beads.     

Variable temperature CP/MAS13C NMR study of cyclodextrin complexes of benzaldehyde

Fully hydrated as well as dried benzaldehyde complexes of - and -cyclodextrins were studied by using CP/MAS¹³C NMR techniques. Variable temperature studies have shown that below 200 K the guest is rigidly held in the complex, whereas at 328 K, only the aromatic ring performs rapid two-fold flips about the C₁–C₄ axis. In the -Cd complex the benzaldehyde performs more general reorientation. Removal of water causes marked changes in both guest and host spectra, generally consistent with a loss of short-range order and increase in guest motional rate.NRCC No. 27826.     

Assignment of 13C resonances of a nematic liquid crystal using off-magic angle spinning

A novel method for assigning the resonances in the 13C NMR spectrum of a static liquid crystalline sample in its nematic phase is proposed. The method is based on the fact that the carbon chemical shifts in the isotropic phase and in the oriented phase under static and off-magic angle spinning (OMAS) conditions are uniquely related by the tensorial property of the CSA tensor, requiring just one OMAS spectrum and the assignment in the isotropic phase. A computational procedure is proposed to take into account deviations arising out of non-ideal experimental conditions and the assignments are made by identifying the minimum in the differences in the frequencies between calculated and experimental line positions. Practical implementation of the method has also been demonstrated in the case of the liquid crystal N-(4-ethoxybenzylidene)-4-n-butylaniline.     

Structural studies on aryl‐substituted enaminoketones and their thio analogues. Part I. Analysis of high‐resolution 1H, 13C NMR and 13C CP MAS spectra combined with GIAO‐DFT calculations

A series of aryl‐substituted enaminoketones and their thio analogues in CDCl₃ solution and in the solid state were studied by the use of high‐resolution ¹H and ¹³C as well as ¹³C cross polarization magic angle spinning (CP MAS) NMR spectra in combination with gauge including atomic orbitals‐density functional theory (GIAO‐DFT) calculations performed at the B3PW91/6–311 + + G(d,p) level of theory using the B3PW91/6‐311 + + G(d,p)‐optimized geometries. The analysis of the ¹³C NMR spectra in solution was done by using the Incredible Natural Abundance DoublE QUAntum Transfer Experiment (INADEQUATE) technique, whereas trends observed in the ¹³C shielding constants, calculated for the compounds studied, were a great help in assigning most of the signals in the ¹³C CP MAS NMR spectra. It was established on the basis of the experimental and theoretical NMR data that both groups of compounds exist in the form of Z‐s‐Z‐s‐E isomers in CDCl₃ solution as well as in the solid state, with the NH hydrogen atom involved in intramolecular hydrogen bonding. This conclusion is in agreement with the fact that some of the compounds studied reveal liquid‐crystalline properties. Three‐bond H, H and C, H coupling constants measured in solution played a crucial role in the structure elucidation. Copyright © 2009 John Wiley & Sons, Ltd.     

Dynamic and magnetic susceptibility effects on the MAS NMR linewidth of a tetrapeptide bound to different resins

Under magic angle spinning, the NMR spectrum of the tetrapeptide Ala‐Ile‐Gly‐Met bound to a Wang resin, and swollen in DMF, exhibits proton and carbon linewidths that are sharp enough to allow the complete characterization of the peptide using classical liquid‐state NMR methods. The proton linewidths of the bound peptide remain, however, about three times larger than those of the free peptide in solution. The residual NMR linewidth originates essentially from incompletely averaged magnetic susceptibility effects due to the Wang resin. Replacing the aromatic Wang resin with a PEGA or POEPOP resin removes this effect. To investigate the contribution to line broadening of the peptide dynamics, relaxation studies were performed on the peptide bound to Wang and POEPOP resins. Copyright © 2001 John Wiley & Sons, Ltd.     

Characterization of cyclotriveratrylene inclusion compounds by means of solid state13C NMR

Solid inclusion compounds of cyclotriveratrylene (CTV) with benzene, toluene, acetone, tetrahydrofuran, acetic acid and chloroform, as well as two hydrated forms, were prepared and characterized by solid state¹³C NMR. The inclusion process for CTV appears to be quite selective, and in some instance depends critically on the presence or absence of water. A number of different structural types are indicated by the solid state¹³C NMR splitting paterns. For the guests listed above,¹H NMR in solution indicated a guest to host ratio close to 0.5, except for chloroform, for which the ratio is closer to 2.     

CP/MAS ~(13)C NMR技术对木浆纤维微观结构的研究

利用交叉极化结合魔角旋转技术~(13)C核磁共振法(CP/MAS ~(13)C NMR)对桉木浆纤维的微观结构进行研究,为进一步研究木质纤维素材料开发过程中反应障碍特征奠定基础.通过对NMR光谱C1区(δ 102～108)进行洛仑兹拟合,得到桉木浆纤维中纤维素Iα的相对含量为26.92%,纤维素Iβ的相对含量为52.04%,主要以纤维素Iβ晶体形式为主.通过计算纤维素C4结晶区(δ 86～92)和非结晶区(δ 80～86)的相对含量得到桉木浆的纤维素结晶度为47%.通过洛仑兹和高斯函数的混合模型对NMR光谱C4区(δ 80～92)进行拟合得到基原纤尺寸和微原纤横向尺寸分别为4.0与17.9 nm,并通过计算不同形态的结晶纤维素的相对含量得到纤维素结晶度为51%,证实了在微原纤内部次晶纤维素的存在.     

Solid‐state NMR studies of 1,3‐imidazolidine‐2‐selenone and some related compounds

Solid‐state cross‐polarization magic angle spinning ¹³C, ⁷⁷Se and ¹⁵N NMR spectra were recorded for 1,3‐imidazolidine‐2‐selenone, its N‐substituted derivatives and some related compounds. The spinning sideband manifold intensities were used to obtain principal values of ¹³C and ⁷⁷Se chemical shift tensors. Large selenium chemical shift anisotropies were observed for these selenones. Copyright © 2003 John Wiley & Sons, Ltd.