Spin state selective coherence transfer: a method for discrimination and complete analyses of the overlapped and unresolved 1H NMR spectra of enantiomers

In general, the proton NMR spectra of chiral molecules aligned in the chiral liquid crystalline media are broad and featureless. The analyses of such intricate NMR spectra and their routine use for spectral discrimination of R and S optical enantiomers are hindered. A method is developed in the present study which involves spin state selective two dimensional correlation of higher quantum coherence to its single quantum coherence of a chemically isolated group of coupled protons. This enables the spin state selective detection of proton single quantum transitions based on the spin states of the passive nuclei. The technique provides the relative signs and magnitudes of the couplings by overcoming the problems of enantiomer discrimination, spectral complexity and poor resolution, permitting the complete analyses of the otherwise broad and featureless spectra. A non-selective 180 degrees pulse in the middle of MQ dimension retains all the remote passive couplings. This accompanied by spin selective MQ-SQ conversion leads to spin state selective coherence transfer. The removal of field inhomogeneity contributes to dramatically enhanced resolution. The difference in the cumulative additive values of chemical shift anisotropies and the passive couplings, between the enantiomers, achieved by detecting Nth quantum coherence of N magnetically equivalent spins provides enhanced separation of enantiomer peaks. The developed methodology has been demonstrated on four different chiral molecules with varied number of interacting spins, each having a chiral centre.     

Discerning the degenerate transitions of scalar coupled H NMR spectra: Correlation and resolved techniques at higher quantum

The blend of spin topological filtering and the spin state selective detection of single quantum transitions by the two dimensional multiple quantum-single quantum correlation and higher quantum resolved techniques have been employed for simplifying the complexity of scalar coupled ¹H NMR spectra. The conventional two dimensional COSY and TOCSY experiments, though identify the coupled spin networks, fail to differentiate them due to severe overlap of transitions. Non-selective excitation of homonuclear higher quantum of protons results in filtering of spin systems irrespective of their spin topologies. The spin state selection by passive ¹⁹F spins provides fewer transitions in each cross section of the single quantum dimension simplifying the analyses of the complex spectra. The degenerate single quantum transitions are further discerned by spin selective double and/or triple quantum resolved experiments that mimic simultaneous heteronuclear and selective homonuclear decoupling in the higher quantum dimension. The techniques aided the determination of precise values of spectral parameters and relative signs of the couplings.     

Chemical shift anisotropy edited complete unraveling of overlapped 1H NMR spectra of enantiomers: application to small chiral molecules

The differential values of NMR spectral parameters like chemical shift anisotropies, dipolar couplings and quadrupolar couplings of enantiomers in chiral liquid crystalline media are employed not only for their visualization but also for their quantification. Large differences in chemical shift anisotropies and the quadrupolar couplings between the enantiomers enable the use of 13C and extensive 2H NMR detection for such a purpose. In spite of high magnetic moment, high sensitivity and abundant presence of protons in all the chiral molecules, 1H detection is not routinely employed due to severe overlap of unresolved transitions arising from short and long distance couplings. Furthermore, the doubling of the spectra from two enantiomers and their indistinguishable overlap due to negligible difference in chemical shift anisotropies hampers their discrimination. The present study demonstrates the use of proton chemical shift anisotropy as an exclusive parameter for such a discrimination. The method employs the non-selective excitation of homonuclear Nth quantum coherence of N coupled protons. The simultaneous flipping of all the coupled spins results in a single transition in the multiple quantum dimension at the cumulative sum of their anisotropic chemical shifts for each enantiomer, with the measurable difference between them, resulting in their complete unraveling.     

Spin-selective multiple quantum excitation: relative signs of the couplings and ambiguous situations

Homonuclear higher quantum NMR spectra of heteronuclear spin systems result in fewer transitions aiding the analyses. In such experiments the spin states of the heteronuclei do not get disturbed in both single and multiple quantum dimensions resulting in the separation of active homonuclear and passive heteronuclear couplings in two dimensions. The cross sections of the single-quantum dimension get displaced according to the strengths of the passive couplings. The directions of the displacement of these cross sections provide relative signs among the passive couplings. The present study demonstrates the situations when the displacement vectors, though provide the relative signs, could be ambiguous. The dynamics of the spin systems in homo- and heteronuclear multiple quantum studies have been discussed using polarization operator approach. The experimental results on ¹³C- and ¹⁵N-labeled isotopomers of acetonitrile, in both isotropic and thermotropic liquid crystalline phases, are reported.     

Spin-state-selective excitation in selective 1D inverse NMR experiments

A general and very simple strategy for achieving clean spin-state-selective excitation with full sensitivity in carbon-selective gradient-enhanced 1D HMQC and HSQC pulse schemes is presented. The incorporation of an additional hard 90 degrees (13)C pulse applied along a specific orthogonal axis just prior to acquisition into the conventional sequences allows us to select a simultaneous coherence transfer pathway which usually is not detected. The superimposition of this resulting antiphase magnetization to the conventional in-phase magnetization gives the exclusive excitation of the directly attached proton showing only the alpha or beta spin state of the passive (13)C nucleus. The propagation of this particular spin state to other protons can be accomplished by adding any homonuclear mixing process just after this supplementary pulse. Such an approach affords a suite of powerful selective 1D (13)C-edited NMR experiments which are helpful for resonance assignment purposes in overcrowded proton spin systems and also for the accurate determination of the magnitude and sign of long-range proton-carbon coupling constants in CH spin sytems for samples at natural abundance. Such measurements are performed by measuring the relative displacement of relayed signals in the corresponding alpha and beta 1D subspectra.     

A 1D sensitivity-enhanced 1H spin diffusion experiment for determining membrane protein topology

A sensitivity-enhanced 1D (1)H spin diffusion experiment, CHH, for determining membrane protein topology is introduced. By transferring the magnetization of the labeled protein (13)C to lipid and water protons for detection, the CHH experiment reduces the time of the original 2D (13)C-detected experiment by two orders of magnitude. The sensitivity enhancement results from (1)H detection and the elimination of the (13)C dimension. Consideration of the spin statistics of the membrane sample indicates that the CHH sensitivity depends on the (13)C labeling level and the number of protein protons relative to the mobile protons. 5-35% of the theoretical sensitivity was achieved on two extensively (13)C labeled proteins. The experimental uncertainties arise from incomplete suppression of the equilibrium (1)H magnetization and the magnetization of lipid protons directly bonded to natural-abundance carbons. The technique, demonstrated on colicin Ia channel domain, confirms the presence of a transmembrane domain and the predominance of surface-bound helices.     

Selective detection of single-enantiomer spectrum of chiral molecules aligned in the polypeptide liquid crystalline solvent: Transition selective one-dimensional 1H–1H COSY

One-dimensional (1D) proton NMR spectra of enantiomers are generally undecipherable in chiral orienting poly-γ-benzyl-l-glutamate (PBLG)/CDCl₃ solvent. This arises due to large number of couplings, in addition to superposition of spectra from both the enantiomers, severely hindering the ¹H detection. On the other hand in the present study the benefit is derived from the presence of several couplings among the entire network of interacting protons. Transition selective 1D ¹H–¹H correlation experiment (1D-COSY) which utilizes the coupling assisted transfer of magnetization not only for unraveling the overlap but also for the selective detection of enantiopure spectrum is reported. The experiment is simple, easy to implement and provides accurate eanantiomeric excess in addition to the determination of the proton–proton couplings of an enantiomer within a short experimental time (few minutes).     

ENDOR evidence for the quantum exchange of the methylene protons

ENDOR spectroscopy was used for studying methylene proton couplings in the 6-yl (or H-addition) radical in a single crystal of 1-methyluracil at 4.2K. The two methylene protons were magnetically equivalent in all crystal (radical) orientations in the magnetic field, indicating proton quantum exchange. The two protons compose magnetically single entity with spin I=1. The observed small ENDOR line splittings of about 0.60MHz agree well with the theoretical expectations for such a system.     

Quantum Fisher information and coherence in one-dimensional XY spin models with Dzyaloshinsky-Moriya interactions

We investigate quantum phase transitions in XY spin models using Dzyaloshinsky-Moriya(DM) interactions. We identify the quantum critical points via quantum Fisher information and quantum coherence, finding that higher DM couplings suppress quantum phase transitions. However, quantum coherence(characterized by the l_1-norm and relative entropy) decreases as the DM coupling increases. Herein, we present both analytical and numerical results.     

Indirect detection of nitrogen-14 in solids via protons by nuclear magnetic resonance spectroscopy

This Communication describes the indirect detection of 14N nuclei (spin I=1) in solids by nuclear magnetic resonance (NMR) spectroscopy. The two-dimensional correlation method used here is closely related to the heteronuclear multiple quantum correlation (HMQC) experiment introduced in 1979 to study molecules in liquids, which has recently been used to study solids spinning at the magic angle. The difference is that the coherence transfer from neighboring 1H nuclei to 14N is achieved via a combination of J couplings and residual dipolar splittings (RDS). Projections of the two-dimensional correlation spectra onto the 14N dimension yield powder patterns which reflect the 14N quadrupolar interaction. In contrast to the indirect detection of 14N via 13C nuclei that was recently demonstrated [Gan, J. Am. Chem. Soc. 128 (2006) 6040; Cavadini et. al., J. Am. Chem. Soc., 128 (2006) 7706], this approach may benefit from enhanced sensitivity, and does not require isotopic enrichment in 13C, although the 1H line-widths may have to be reduced upon selective deuteration.     

Spin readout and initialization in a semiconductor quantum dot

Electron spin qubits in semiconductors are attractive from the viewpoint of long coherence times. However, single spin measurement is challenging. Several promising schemes incorporate ancillary tunnel couplings that may provide unwanted channels for decoherence. Here, we propose a novel spin-charge transduction scheme, converting spin information to orbital information within a single quantum dot by microwave excitation. The same quantum dot can be used for rapid initialization, gating, and readout. We present detailed modeling of such a device in silicon to confirm its feasibility.     

Band selective small flip angle COSY: a simple experiment for the analyses of 1H NMR spectra of small chiral molecules

The NMR spectroscopic discrimination of enantiomers in the chiral liquid crystalline solvent is more often carried out using ²H detection in its natural abundance. The employment of ¹H detection for such a purpose is severely hampered due to significant loss of resolution in addition to indistinguishable overlap of the spectra from the two enantiomers. This study demonstrates that the band selected small flip angle homonuclear correlation experiment is a simple and robust technique that provides unambiguous discrimination, very high spectral resolution, reduced multiplicity of transitions, relative signs of the couplings and enormous saving of instrument time.     

Anisotropic Orientation of Lactate in Skeletal Muscle Observed by Dipolar Coupling in H NMR Spectroscopy

Double quantum (DQ), J-resolved (1)H NMR spectra from rat and bovine skeletal muscle showed a splitting frequency ( approximately 24 Hz) for the lactate methyl protons that varied with the orientation of the muscle fibers relative to the magnetic field. In contrast, spectra of lactate in solution consist of a J-coupled methyl doublet and a J-coupled methine quartet (J(HH) = 7 Hz) with no sensitivity to sample orientation. Spectra acquired in magnetic fields of 4.7, 7, and 11 T showed that the splitting was not due to inhomogeneities in magnetic susceptibility within the muscle, because the magnitude of the splitting did not scale with the strength of B(0) fields. Triple quantum coherence (TQC) spectra revealed two distinct transition frequencies on the methyl resonance. These frequencies resulted from intra-methyl and methine-methyl couplings in this four spin system (A(3)X). Decoupling experiments on the triple quantum coherence showed that the observed frequency splitting was due mainly to the dipolar interactions between the methine and methyl protons of the lactate molecule. Thus, all the proton resonances of the lactate molecules in muscle behave anisotropically in the magnetic field. Adequate design and interpretation of spectroscopic experiments to measure lactate in muscle, and possibly in any cell and organ which contain asymmetric structures, require that both the dipolar coupling described here and the well-known scalar coupling be taken into account.     

J-ONLY-TOCSY: efficient suppression of RDC-induced transfer in homonuclear TOCSY experiments using JESTER-1-derived multiple pulse sequences

The main purpose of homonuclear Hartmann-Hahn or TOCSY experiments is the assignment of spin systems based on efficient coherence transfer via scalar couplings. In partially aligned samples, however, magnetization is also transferred via residual dipolar couplings (RDCs) and therefore through space correlations can be observed in COSY and TOCSY experiments that make the unambiguous assignment of covalently bound spins impossible. In this article, we show that the JESTER-1 multiple pulse sequence, originally designed for broadband heteronuclear isotropic Hartmann-Hahn transfer, efficiently suppresses the homonuclear dipolar coupling Hamiltonian. This suppression can be enhanced even further by variation of the supercycling scheme. The application of the resulting element in homonuclear TOCSY periods results in coherence transfer via J-couplings only. As a consequence, the assignment of scalar coupled spin systems is also possible in partially aligned samples. The bandwidth of coherence transfer for the JESTER-1-derived sequences is comparable to existing TOCSY multiple pulse sequences. Results are demonstrated in theory and experiment.     

Anomalous decoherence effect in a quantum bath

Decoherence of quantum objects in noisy environments is important in quantum sciences and technologies. It is generally believed that different processes coupled to the same noise source have similar decoherence behaviors and stronger noises cause faster decoherence. Here we show that in a quantum bath, the case can be the opposite. We predict that the multitransition of a nitrogen-vacancy center spin-1 in diamond can have longer coherence time than the single transitions, even though the former suffers twice stronger noises from the nuclear spin bath than the latter. This anomalous decoherence effect is due to manipulation of the bath evolution via flips of the center spin.     

Resolution enhancement in spectra of natural products dissolved in weakly orienting media with the help of 1H homonuclear dipolar decoupling during acquisition: application to 1H-13C dipolar couplings measurements

In weakly orienting media such as poly-gamma-benzyl-L-glutamate (PBLG) a polymer that forms a chiral liquid crystal in organic solvents, the spectral resolution for embedded molecules is usually poor because of numerous (1)H, (1)H dipolar couplings that generally broaden proton spectra. Therefore (1)H, (13)C dipolar couplings are difficult or impossible to measure. Here, we incorporate Flip-Flop decoupling during detection into an HSQC experiment. Flip-Flop removes the (1)H, (1)H dipolar couplings and scales the chemical shifts of the protons as well as the (1)H, (13)C dipolar couplings during detection. A resolution gain by a factor 1.5-4.2 and improved signal intensity by an average factor of 1.6-1.7 have been obtained. This technique is demonstrated on (+)-menthol dissolved in a PBLG/CDCl(3) phase.     

Heteronuclear Double-Quantum MAS NMR Spectroscopy in Dipolar Solids

A new pulse sequence for high-resolution solid-state heteronuclear double-quantum MAS NMR spectroscopy of dipolar-coupled spin-12 nuclei is introduced. It is based on the five-pulse sequence known from solution-state NMR, which is here applied synchronously to both spin species. The heteronuclear double-quantum (HeDQ) spinning-sideband patterns produced by this experiment are shown to be sensitive to the heteronuclear distance, as well as the relative orientations of the chemical-shift and dipolar tensors. In particular, it is shown that the HeDQ patterns exhibit an enhanced sensitivity to the chemical shielding tensors as compared with the single-quantum spinning-sideband patterns. The detection of HeDQ patterns via the I and S spins is discussed. The isolated (13)C-(1)H spin pair in deuterated ammonium formate with (13)C in natural abundance was chosen as a model system, and the perturbing influence of dipolar couplings to surrounding protons on the (13)C-(1)H DQ coherence is discussed. The pulse sequence can also be used as a heteronuclear double-quantum filter, hence providing information about heteronuclear couplings, and thus allowing the differentiation of quaternary and CH(n) bonded carbons. The elucidation of (13)C-(1)H dipolar proximities is presented for a sample of bisphenol A polycarbonate with (13)C in natural abundance, recorded with a broadband version of the synchronized five-pulse sequence.     

Methylene spectral editing in solid-state 13C NMR by three-spin coherence selection

A robust new solid-state nuclear magnetic resonance (NMR) method for selecting CH2 signals in magic-angle spinning (MAS) 13C NMR spectra is presented. Heteronuclear dipolar evolution for a duration of 0.043 ms, under MREV-8 homonuclear proton decoupling, converts 13C magnetization of CH2 groups into two- and three-spin coherences. The CH2 selection in the SIJ (C H H) spin system is based on the three-spin coherence S(x)I(z)J(z), which is distinguished from 13C magnetization (S(x)) by a 1H 0 degrees/90 degrees pulse consisting of two 45 degrees pulses. The two-spin coherences of the type S(y)I(z) are removed by a 13C 90 degrees x-pulse. The three-spin coherence is reconverted into magnetization during the remainder of the rotation period, still under MREV-8 decoupling. The required elimination of 13C chemical-shift precession is achieved by a prefocusing 180 degrees pulse bracketed by two rotation periods. The selection of the desired three-spin coherence has an efficiency of 13% theoretically and of 8% experimentally relative to the standard CP/MAS spectrum. However, long-range couplings also produce some three-spin coherences of methine (CH) carbons. Therefore, the length of the 13C pulse flipping the two-spin coherences is increased by 12% to slightly invert the CH signals arising from two-spin coherences and thus cancel the signal from long-range three-spin coherences. The signal intensity in this cleaner spectrum is 6% relative to the regular CP/TOSS spectrum. The only residual signal is from methyl groups, which are suppressed at least sixfold relative to the CH2 peaks. The experiment is demonstrated on cholesteryl acetate and applied to two humic acids.     

Selective dephasing of OH and NH proton magnetization based on (1)H chemical-shift anisotropy recoupling

A method for selectively suppressing the signals of OH and NH protons in (1)H combined rotation and multiple-pulse spectroscopy (CRAMPS) and in (1)H-(13)C heteronuclear correlation (HETCOR) solid-state NMR spectra is presented. It permits distinction of overlapping CH and OH/NH proton signals, based on the selective dephasing of the magnetization of OH and NH protons by their relatively large (1)H chemical-shift anisotropies. For NH protons, the (14)N-(1)H dipolar coupling also contributes significantly to this dephasing. The dephasing is achieved by a new combination of heteronuclear recoupling of these anisotropies with (1)H homonuclear dipolar decoupling. Since the 180 degrees pulses traditionally used for heteronuclear dipolar and chemical-shift anisotropy recoupling would result in undesirable homonuclear dephasing of proton magnetization, instead the necessary inversion of the chemical-shift Hamiltonian every half rotation period is achieved by inverting the phases of all the pulses in the HW8 multiple-pulse sequence. In the HETCOR experiments, carefully timed (13)C 180 degrees pulses remove the strong dipolar coupling to the nearby (13)C spin. The suppression of NH and OH peaks is demonstrated on crystalline model compounds. The technique in combination with HETCOR NMR is applied to identify the CONH and NH-CH groups in chitin and to distinguish NH and aromatic proton peaks in a peat humin.