Determination of the rate of intramolecular exchange between two complex spin systems from the NMR spectra

Reversible 1,2-shifts of the ethyl group in the 9-ethyl-9, 10-dimethylphenanthrenonium ion lead to a reversible change of the ring hydrogen states (A′B′C′D′ ? A″B″C″D″). Line shape analysis for the determination of the exchange rate was performed for this case of intramolecular exchange between the two multi-spin systems. The calculations are based on density matrix formalism.     

Modulation of NMR spin echoes in coupled systems

A new theoretical approach to NMR spin echoes is described. The xy magnetizations which correspond to the lines in the spectrum are dealt with directly, by the use of the angular momentum properties of Liouville space. This simplifies the calculations for the AB spin systems and opens the way to larger systems.     

19F DOSY NMR analysis for spin systems with nJFF couplings

NMR is a powerful method for identification and quantification of drug components and contaminations. These problems present themselves as mixtures, and here, one of the most powerful tools is DOSY. DOSY works best when there is no spectral overlap between components, so drugs containing fluorine substituents are well‐suited for DOSY analysis as ¹⁹F spectra are typically very sparse. Here, we demonstrate the use of a modified ¹⁹F DOSY experiment (on the basis of the Oneshot sequences) for various fluorinated benzenes. For compounds with significant ⁿJ_FF coupling constants, as is common, the undesirable J‐modulation can be efficiently suppressed using the Oneshot45 pulse sequence. This investigation highlights ¹⁹F DOSY as a valuable and robust method for analysis of molecular systems containing fluorine atoms even where there are large fluorine–fluorine couplings. Copyright © 2014 John Wiley & Sons, Ltd.     

Low-temperature 15N NMR spectra of reduced 1,3-heterocyclic systems

The ¹⁵N NMR spectra of the O-inside cis-fused conformer of perhydropyrido[1,2-c][1,3]thiazine shows a shielding of the nitrogen of 23.0 ppm relative to the trans-fused conformer. In contrast, ¹⁵N shifts for the cis-and trans-fused conformers of perhydro-oxazolo[3,4-a]pyridine and perhydrothiazolo[3,4-a]pyridine show corresponding shieldings of only 0.6 and 2.5 ppm, respectively.     

Selective 1D HCH experiment: a fast NMR tool that connect protons belonging to different spin systems

A selective 1D version of the HCH experiment (selHCH) is proposed for the efficient and fast correlation between protons belonging to different spin systems. The experiment consists of two consecutive, doubly selective heteronuclear J(CH) transfer steps that can individually be optimized. As any conventional proton-selective 1D experiment, the successful application of a frequency-selective 180° pulse on a well-isolated proton is the only practical requirement. The resulting clean selHCH spectrum probes to be an excellent complement to the conventional selTOCSY experiment to trace out proton-proton J connectivities through transparent non-protonated carbons or heteroatom centers. Several selHCH examples on small molecules are provided showing the improvements with respect to the selTOCSY experiment.     

Assignments of the 1H and 13C NMR spectra of pseudo-symmetric heterocyles using the HMQC-TOCSY experiment to differentiate overlapping spin systems

The ¹H nmr spectra of phenanthro[9′,10′:4,5]thieno[2,3-c]quinoline, benzo[f]phenanthro-[9′,10′:4,5]thieno[2,3-c]quinoline and benzo[h]phenanthro[9′,10′:4,5]thieno[2,3-c]quinoline are highly congested. For each compound, all protons abide in an aromatic environment complicated by pseudo-symmetric regions which result in multiple overlap of the different spin systems these molecules contain. We illustrate here the utility of the HMQC-TOCSY experiment to identify spin systems when the proton spectrum is highly congested. To complete the assignment of the ¹H and ¹³C nmr spectra of each compound the HMBC experiment is used to assign the quaternary carbons.     

Simultaneous detection and deconvolution of congested NMR spectra containing three isotopically labeled species

We present a procedure for isolating subspectra corresponding to individual protein or peptide components in a ternary mixture or complex. Each of the three-component species is labeled differently: species A uniformly with 15N, species B uniformly with 15N and 13C, and species C uniformly with 15N but selectively with 13C' or 13Calpha. By using the dual carbon label selective HSQC (DCLS-HSQC) pulse sequence and exploiting differences in 1J 15N-13C coupling patterns to filter selected 15N resonances from detection during a constant time period, a subspectrum from each species can be generated from three spectra acquired from a single sample. Many important biological pathways involve dynamic interactions among members of multicomponent protein assemblies, and this approach offers a powerful way to monitor such processes.     

Coalescence of magnetically non-equivalent proton signals in NMR spectra and spin decoupling by torsional transitions

The complex effect of torsional librations on high resolution NMR spectra, which can coalesce non-equivalent proton signals with relatively high Δν_AB and also decouple spin systems by averaging the chemical shift in excited torsional states, is determined and analyzed.     

NMR spectra of pyrimidines

The chemical shifts of the protons in the even positions of the pyrimidine ring in 2- and 4-substituted pyrimidines in dimethyl sulfoxide solutions were determined. The correlation equations that link the relative chemical shifts (with allowance for corrections for the magnetic anisotropy of the substituents and the ring) with the F and R substituent constants were calculated. The ratios obtained were analyzed by comparison with the corresponding correlation equations for monosubstituted benzenes. The reasons for the significant increase in the transmission of the conjugation effects of the substituents to the even positions of the pyrimidine ring as compared with the meta positions of the benzene ring and the appreciable weakening of the conductivity of their inductive effects when the heteroring nitrogen atom is situated between a resonating proton and the substituent are discussed.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 673–677, May, 1978.     

NMR spectra of arylaziridines

The ¹³C and ¹H NMR spectra of 1-arylaziridines, 2-phenyl-1-arylaziridines, and 2-aryl-1-phenylaziridines were studied. The additive contributions of aziridinyl, 1-phenyl-2-aziridinyl, and 2-phenyl-1-aziridinyl substituents to the shielding of the aromatic protons were calculated. It is shown that with respect to its donor capacity the aziridine ring occupies an intermediate position between amines and amides. The temperature dependences of the PMR spectra of 1-aryl-substituted aziridines were investigated, and the barriers to inversion of the latter were calculated. The dependence of G on the ^– constants was correlated.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 338–341, March, 1978.     

NMR spectra of halopermethylpolysilanes

Proton NMR spectra were determined for the series X(SiMe₂)_nX (n = 3, 4, 6 and X  F, Cl, I) and Me(SiMe₂)₆X. Fluorine-19 NMR spectrafor the fluorosilanes of these series were also determined. The chemical shift of the methyl protons of the SiMe₂X group appears at higher field as the chain length increases. This chemical shift also is at higher field for monohalopolysilanes than for the corresponding dihalopolysilanes. These observations are consistent with increased donation from halogens to vacant polysilane orbitals with increased chain length and with transmission of the effect of a second halogen through the silicon chain.