No abstract

The proton and natural abundance carbon-13 NMR spectra of (±)-3-butyn-2-ol enriched in the S enantiomer (ee = 72%) and oriented in the chiral nematic liquid crystalline phase of [poly(γ-benzyl-l-glutamate)/deuterochloroform] have been obtained and analyzed. The residual 1H−H and 1H−13C dipolar couplings were corrected for the effects of molecular harmonic vibrational motions and used to determine the r α structure and the five independent order parameters, S αβ, for each enantiomer. It is shown that the data is consistent with the two enantiomers having an identical r α structure, but the order matrices differ in both the magnitudes of their elements and the orientation of their principal axes.

No abstract

No abstract

Distributions of nuclear magnetic resonance (NMR) relaxation times provide detailed information about the moisture absorbed in wood. In this work, T2*, T2, and T1 distributions were recorded from fresh sapwood and heartwood samples of pine (Pinus sylvestris) and spruce (Picea abies) at various temperatures. Below the melting point of bulk water, free water is frozen and its signal disappears from the distributions. Then, the low-temperature distributions of the unfrozen bound water contain more information about its components, because the large free water peaks hiding some smaller bound water peaks are absent and the exchange between free and bound water is prevented. Comparison of the total moisture signal integrals above and below the bulk melting point enables the determination of fiber saturation point (FSP), which, in this context, denotes the total water capacity of cell wall. T2*, T2, and T1 distributions offer different kinds of information about moisture components. All the peaks in the distributions were assigned, and it was demonstrated that the accessible hydroxyl site content and the amount of micropores can be estimated based on the peak integrals.

Experimentally and theoretically (ab initio) determined CC spin−spin coupling tensors and 1H and 13C nuclear shielding tensors are reported for ethane (13C2H6), ethene (13C2H4), and ethyne (13C2H2). The experimental anisotropies of the CC coupling tensors, ΔJ CC, for all these molecules, and also the combination J CC, xx − J CC, yy for ethene, were derived from sets of anisotropic couplings (D exp) analyzed from the 1H and 13C NMR spectra of molecules partially oriented in liquid−crystalline environments. Both harmonic vibrations and structural deformations arising from the correlation of vibrational and reorientational motions were taken into account in the D couplings. The ab initio calculations of all the J tensors were performed using MCSCF linear response theory. The best calculated and experimental ΔJ CC values (along with J CC, xx − J CC, yy for ethene) are found to be in good mutual agreement. Together with earlier work on the n J CC tensors in benzene, this study shows that the indirect contribution, 1/2 J CC aniso, to experimental couplings between differently hybridized carbons is small and can generally be omitted. This means that the use of experimental D CC couplings in the determination of molecular order tensors and/or conformation does not introduce serious errors. The experimental determination of the 1H and 13C shielding tensors was based on the liquid crystal director rotation by 90° in mixtures of thermotropic nematogens with opposite anisotropy of diamagnetic susceptibility. Ab initio SCF and MCSCF calculations utilizing gauge-including atomic orbitals produce results in good agreement with experiments.

This study reports experimentally and theoretically (ab initio) determined indirect CC spin−spin coupling tensors n J CC in benzene. The CC spin−spin coupling constants n J CC between the ortho, meta, and para (n = 1, 2, and 3) positioned carbons were experimentally determined in two ways:  firstly by utilizing the 2H/1H isotope effect on the carbon shieldings in neat monodeuteriobenzene and recording the 13C satellite spectrum in a 1H-decoupled 13C NMR spectrum, and secondly by recording the 13C NMR spectrum of fully 13C-enriched benzene (13C6H6) and carrying out its complete analysis. The anisotropies of the corresponding coupling tensors, Δ n J CC, were resolved experimentally by liquid crystal 1H and 13C NMR using dipolar couplings corrected for both harmonic vibrations and deformations. The results obtained in three thermotropic liquid crystal solvents are in good mutual agreement, indicating the reliability of the determinations. The anisotropy of the ortho, meta, and para CC indirect couplings are ca. +17, −4, and +9 Hz, respectively. Also, the signs of the coupling constants are unambiguously determined. The ab initio calculations were performed using multiconfiguration self-consistent field linear response theory with both single-reference and multireference wave functions. The results confirm the signs of the experimental anisotropies in all cases. The magnitude of the ortho coupling anisotropy is excellently reproduced, but the anisotropies are somewhat overestimated in the two other theoretical coupling tensors. The importance of the different physical contributions to the couplings and anisotropies is discussed.

No abstract