Measurement Of Coupling Constants Research Articles

Multidimensional Spectroscopy of Nuclear Spin Clusters in Diamond.

Optically active spin defects in solids offer promising platforms to investigate nuclear spin clusters with high sensitivity and atomic-site resolution. To leverage near-surface defects for molecular structure analysis in chemical and biological contexts using nuclear magnetic resonance (NMR), further advances in spectroscopic characterization of nuclear environments are essential. Here, we report Fourier spectroscopy techniques to improve localization and mapping of the test bed ^{13}C nuclear spin environment of individual, shallow nitrogen-vacancy centers at room temperature. We use multidimensional spectroscopy, well-known from classical NMR, in combination with weak measurements of single-nuclear-spin precession. We demonstrate two examples of multidimensional NMR: (i)improved nuclear spin localization by separate encoding of the two hyperfine components along spectral dimensions and (ii)spectral editing of nuclear-spin pairs, including measurement of internuclear coupling constants. Our work adds important tools for the spectroscopic analysis of molecular structures by single-spin probes.

Rapid Measurement of Heteronuclear Coupling Constants in Complex NMR Spectra.

The NMR analysis of fluorine-containing molecules, increasingly widespread due to their importance in pharmaceuticals and biochemistry, poses significant challenges. Severe peak overlap in the proton spectrum often hinders the extraction of critical structural information in the form of heteronuclear scalar coupling constants, which are crucial for determining pharmaceutical properties and biological activity. Here, a new method, IPAP-FESTA, is reported that drastically simplifies measurements of the signs and magnitudes of proton-fluorine couplings. Its usefulness is demonstrated for the structural study of the steroidal drug fluticasone propionate extracted from a commercial formulation and for assessing solvent effects on the conformational equilibrium in a physically inseparable fluorohydrin mixture.

First measurement of the strange axial coupling constant using neutral-current quasielastic interactions of atmospheric neutrinos at KamLAND

First measurement of the strange axial coupling constant using neutral-current quasielastic interactions of atmospheric neutrinos at KamLAND

Conformational flexibility of the disaccharide β-L-Fucp-(1→4)-α-D-Glcp-OMe as deduced from NMR spectroscopy experiments and computer simulations.

Carbohydrates in biological systems are referred to as glycans and modification of their structures is a hallmark indicator of disease. Analysis of the three-dimensional structure forms the basis for further insight into how they function and comparison of crystal structure with solution-state conformation(s) is particularly relevant, which has been performed for the disaccharide β-L-Fucp-(1→4)-α-D-Glcp-OMe. In water solution the conformational space at the glycosidic linkage between the two sugar residues is identified from molecular dynamics (MD) simulations as having a low-energy exo-syn conformation, deviating somewhat from the solid-state conformation, and two anti-conformational states, i.e., anti-ϕ and anti-ψ, indicating flexibility at the glycosidic linkage. NMR data were obtained from 1D 1H,1H-NOESY and STEP-NOESY experiments, measurement of transglycosidic 3JCH coupling constants and NMR spin-simulation. The free energy profile of the ω torsion angle computed from MD simulation was in excellent agreement with the rotamer distribution from NMR experiment being for gt:gg:tg 38 : 53 : 9, respectively, with a proposed inter-residue O5'⋯HO6 hydrogen bond being predominant in the gg rotamer. Quantum mechanics methodology was used to calculate transglycosidic NMR 3JCH coupling constants, averaged over a conformational ensemble of structures representing various rotamers of exocyclic groups, in good to excellent agreement with Karplus-type relationships previously developed. Furthermore, 1H and 13C NMR chemical shifts were calculated using the same methodology and were found to be in excellent agreement with experimental data.

Single π0 production in μe scattering at MUonE

The recently proposed MUonE experiment at CERN aims at providing a novel determination of the leading order hadronic contribution to the muon anomalous magnetic moment through the study of elastic muon-electron scattering at relatively small momentum transfer. The anticipated accuracy of the order of 10ppm demands for high-precision prediction in radiative corrections to the μe scattering as well as for robust quantitative estimates of all possible background processes. In this letter, the contribution due to the emission of a neutral pion through the process μe→μeπ0 is studied and its numerical impact is discussed in different phase space configurations by means of the upgraded Monte Carlo event generator MESMER. In fact, single π0 production could be a source of reducible background for the measurement of the QED running coupling constant at MUonE and it could be also an important background for possible New Physics searches at MUonE involving 2→3 processes, in phase space regions complementary to the ones characteristic of the elastic μe scattering.

Isolation and detailed 1H and 13C NMR structural assignment for three trachylobanes from Psiadia punctulata (Asteraceae) grown in Africa

• New NMR data for three trachylobanes, are presented for the first time in Literature. • The presented data completely clarified the 1H and 13C NMR data assignments for these trachylobanes. • A new methodology, recently published, was applied to clarify all multiplicities, measuring all J values for all substances. • A stereochemistry clarification including W-coupling measuring is provided for each studied compound. The first isolation of a trachylobane from an African specimen of Psiadia punctulata (Asteraceae) is presented in this paper. A complete 1 H and 13 C NMR spectral analysis of this compound and two other trachylobane diterpenes, previously isolated from the same plant, are also provided. The use of NMR techniques such as g COSY, g HSQC, g HMBC and 2D- J -resolved, in combination with a software-assisted methodology, led to a complete and unequivocal assignment of 1 H and 13 C signals. This was achieved together with the measurement of all homonuclear hydrogen coupling constants. The presented detail level of the assignment data has never been published before for trachylobanes. Furthermore, with all determined NMR experimental data from the spectra and to obtain a reliability assessment, signals were simulated in the FOMSC3 and NMR_MultSim software.

Double echo symmetry-based REDOR and RESPDOR pulse sequences for proton detected measurements of heteronuclear dipolar coupling constants

1H{X} symmetry-based rotational echo double resonance pulse sequences (S-REDOR) and symmetry-based rotational echo saturation pulse double resonance (S-RESPDOR) solid-state NMR experiments have found widespread application for 1H detected measurements of difference NMR spectra, dipolar coupling constants, and internuclear distances under conditions of fast magic angle spinning (MAS). In these experiments the supercycled R412 (SR412) symmetry-based recoupling pulse sequence is typically applied to the 1H spins to reintroduce heteronuclear dipolar couplings. However, the timing of SR412 and other symmetry-based pulse sequences must be precisely synchronized with the rotation of the sample, otherwise, the evolution of 1H CSA and other interactions will not be properly refocused. For this reason, significant distortions are often observed in experimental dipolar dephasing difference curves obtained with S-REDOR or S-RESPDOR pulse sequences. Here we introduce a family of double echo (DE) S-REDOR/S-RESPDOR pulse sequences that function in an analogous manner to the recently introduced t1-noise eliminated (TONE) family of dipolar heteronuclear multiple quantum coherence (D-HMQC) pulse sequences. Through numerical simulations and experiments the DE S-REDOR/S-RESPDOR sequences are shown to provide dephasing difference curves similar to those obtained with S-REDOR/S-RESPDOR. However, the DE sequences are more robust to the deviations of the MAS frequency from the ideal value that occurs during typical solid-state NMR experiments. The DE sequences are shown to provide more reliable 1H detected dipolar dephasing difference curves for nuclei such as 15N (with isotopic labelling), 183W and 35Cl. The double echo sequences are therefore recommended to be used in place of conventional S-REDOR/S-RESPDOR sequences for measurement of weak dipolar coupling constants and long-range distances.

Through-Space Scalar 19F-19F Couplings between Fluorinated Noncanonical Amino Acids for the Detection of Specific Contacts in Proteins.

Fluorine atoms are known to display scalar 19F-19F couplings in nuclear magnetic resonance (NMR) spectra when they are sufficiently close in space for nonbonding orbitals to overlap. We show that fluorinated noncanonical amino acids positioned in the hydrophobic core or on the surface of a protein can be linked by scalar through-space 19F-19F (TSJFF) couplings even if the 19F spins are in the time average separated by more than the van der Waals distance. Using two different aromatic amino acids featuring CF3 groups, O-trifluoromethyl-tyrosine and 4-trifluoromethyl-phenylalanine, we show that 19F-19F TOCSY experiments are sufficiently sensitive to detect TSJFF couplings between 2.5 and 5 Hz in the 19 kDa protein PpiB measured on a two-channel 400 MHz NMR spectrometer with a regular room temperature probe. A quantitative J evolution experiment enables the measurement of TSJFF coupling constants that are up to five times smaller than the 19F NMR line width. In addition, a new aminoacyl-tRNA synthetase was identified for genetic encoding of N6-(trifluoroacetyl)-l-lysine (TFA-Lys) and 19F-19F TOCSY peaks were observed between two TFA-Lys residues incorporated into the proteins AncCDT-1 and mRFP despite high solvent exposure and flexibility of the TFA-Lys side chains. With the ready availability of systems for site-specific incorporation of fluorinated amino acids into proteins by genetic encoding, 19F-19F interactions offer a straightforward way to probe the spatial proximity of selected sites without any assignments of 1H NMR resonances.

Simultaneous determination of multiple coupling networks by high-resolution 2D J-edited NMR spectroscopy

J coupling constitutes an important NMR parameter for molecular-level composition analysis and conformation elucidation. Dozens of J-based approaches have been exploited for J coupling measurement and coupling network determination, however, they are generally imposed to insufficient spectral resolution to resolve crowded NMR resonances and low measurement efficiency that a single experiment records one J coupling network. Herein, we propose a general NMR method to collect high-resolution 2D J-edited NMR spectra, which are characterized with advantages of pure absorptive lineshapes, decoupled chemical shift dimension, as well as eliminated axial peaks, thus facilitating J coupling partner assignments and J coupling constant measurements. More meaningfully, this protocol allows simultaneous determination of multiple coupling networks for highly efficient multiplet analyses via addressing multiple protons within one single experiment. Additionally, another variant is proposed for high-resolution applications under adverse magnetic field conditions. Therefore, this study provides a useful NMR protocol for configurational and structural studies with extensive applications in chemistry, biology, and material science.

Unambiguous and accurate measurement of scalar coupling constants through a selective refocusing NMR experiment

Scalar coupling plays an important role in the analysis of molecular structure and dynamics. A great number of nuclear magnetic resonance (NMR) selective refocusing experiments, such as 2D G-SERF and PSYCHEDELIC, were developed to extract scalar coupling constants involving a selected proton from overlapped spectra. However, intense axial peaks occur in this type of experiments, leading to possible ambiguity in the assignment of spectral peaks and subsequent accurate measurement of 1H–1H scalar coupling constants. Here, a method based on selective coherence transfer and PSYCHEDELIC module is designed to acquire absorption-mode selective refocusing spectrum while suppressing intense axial peaks. Therefore, unambiguous and accurate measurement of scalar coupling constants involving the selectively excited proton can be achieved. The performances of the proposed method are demonstrated on several samples.

A simple data post-processing method for axial peaks free 2D PSYCHEDELIC NMR spectra

Homonuclear scalar coupling plays an important role in the elucidation of molecular structure and dynamics. However, complex multiplets due to 1H–1H scalar coupling splittings complicate the assignment of peaks in overcrowded spectral regions. Although many methods focusing on disentangling couplings have been proposed in recent years, some defects like intense axial peaks and dispersive components still exist. Herein, a simple data post-processing method based on the interleaved acquisition mode PSYCHEDELIC (Pure Shift Yielded by CHirp Excitation to DELiver Individual Couplings) is designed to acquire absorption-mode 2D J spectrum while eradicating axial peaks. This approach provides a high resolution and pure absorptive spectrum, permitting unambiguous and accurate measurement of scalar coupling constants involving a given proton.

Electronic structure of the ytterbium monohydroxide molecule to search for axionlike particles

Recently the YbOH molecule has been suggested as a candidate to search for the electron electric dipole moment (eEDM) which violates spatial parity (P) and time-reversal (T) symmetries [I. Kozyryev and N. R. Hutzler, Phys. Rev. Lett. 119, 133002 (2017)]. In the present paper we show that the same system can be used to measure coupling constants of the interaction of electrons and nucleus with axionlike particles. The electron-nucleus interaction produced by the axion exchange induces T,P-violating a EDM of the whole molecular system. We express the corresponding T,P-violating energy shift produced by this effect in terms of the axion mass and product of the axion-nucleus and axion-electron coupling constants.

Fully Exploiting the Power of 2D NMR J-Resolved Spectroscopy.

Nuclear magnetic resonance (NMR) spectroscopy is a powerful analytical tool that enables one to study molecular properties and interactions. Homonuclear couplings provide valuable structural information but are often difficult to disentangle in crowded 1H NMR spectra where complex multiplets and signal overlap commonly exist. Multidimensional NMR experiments push the power of NMR to a new level by providing better signal dispersion. Among them, 2D J-resolved spectroscopy is widely used for multiplet analysis and the measurement of scalar coupling constants. Here, we present a new 2D J-resolved method, CASCADE, through which easier multiplet analysis and unambiguous measurement of specific coupling constants can be achieved at the same time, fully exploiting the power of 2D J-resolved spectroscopy. It is expected that this method may replace a conventional 2D J experiment in many cases, facilitating structural and configurational studies as well as chemical and biological analyses.

The electronic and steric effects of neutral and ionic phosphines on Ir(I)-complex catalyzed hydroaminomethylation of olefins

The electronic and steric effects of a series of neutral and ionic (mono-/di-)phosphines on the performance of Ir(I)-complex catalysts for the hydroaminomethylation of olefins were systematically investigated by means of 1J31P-77Se coupling constant measurement, single-crystal X-ray diffraction, and high pressure in situ FTIR spectroscopy. It was found that the neutral mono-phosphines of L1 with the moderate π-accepting nature (1J31P-77Se of 753 Hz) and relatively less steric hindrance was able to spur the activities of the corresponding Ir-catalysts. In addition, the catalytic performances over the Ir(I)- and Rh(I)-precursors was compared under the same reaction conditions. The advantages of Ir(I)-catalyst over Rh(I)-catalyst for this tandem reaction were also discussed in detail.

Polaron and Exciton Delocalization in Oligomers of High-Performance Polymer PTB7.

A key characteristic of organic photovoltaic cells is the efficient charge separation in the active layer. Sufficient delocalization of the positive polaron in organic photovoltaics is considered essential for the effective separation of the opposite charges and the suppression of recombination. We use light-induced EPR and ENDOR spectroscopy combined with DFT calculations to determine the electronic structure of the positive polaron in PTB7-type oligomers. Utilizing the superior spectral resolution of high-frequency (130 GHz) D-band EPR, the principal components of the g tensors were determined. Pulsed ENDOR spectroscopy at X-band allowed the measurement of 1H hyperfine coupling constants. A comparison of g tensors and 1H hyperfine coupling constants of the PTB7-type oligomers with the high-performance PTB7 polymer revealed a delocalization of the positive polaron in the polymer over about four monomeric units, corresponding to about 45 Å in length. Our current study thus not only determines the polaron delocalization length in PTB7 but also validates the approach combining EPR/ENDOR spectroscopy with DFT-calculated magnetic resonance parameters. This is of importance in those cases where oligomers of defined length are not easily obtained. In addition, the delocalization of the neutral triplet exciton was also determined in the oligomers and compared with polymer PTB7. The analysis revealed that the neutral triplet exciton is substantially more delocalized than the positive polaron, exceeding 10 monomeric units.

The Lewis acidity of borylcarboranes

The dimesitylborylcarborane [1-BMes2-2-Me-closo-1,2-C2B10H10] (1) has been prepared. The Lewis acidity of 1 has been assessed by the Gutmann-Beckett method and found to be effectively identical to that of the previously reported 2-H and 2-Ph analogues. Similarly, the new catecholylborylcarboranes [1-Bcat-closo-1,2-C2B10H11] (2) and [1-Bcat-2-Me-closo-1,2-C2B10H10] (3), although more strongly Lewis acidic than the dimesitylborylcarboranes, were found to have Acceptor Numbers very close to that of the known 2-Ph analogue. [μ-2,2ʹ-BPh-(1-1ʹ-closo-1ʹ,2ʹ-C2B10H10)-closo-1,2-C2B10H10] (4), a compound with a boryl fragment attached to two carboranyl units [in the form of bis(ortho-carborane)] has been prepared and found to be highly Lewis acidic, reflecting the strongly electron-withdrawing property of C-bound carboranyl groups. The first example of a compound in which both Lewis acidic and Lewis basic substituents are appended to a single carborane cage, [1-Bcat-7-PPh2-closo-1,7-C2B10H10] (5), is reported. In 5 the Acceptor Number of the Bcat substituent is very close to those of 2 and 3 and the basicity of the PPh2 substituent, assessed by measurement of the 1JPSe NMR coupling constant of the related selenide [1-Bcat-7-P(Se)Ph2-closo-1,7-C2B10H10] (5Se), is very close to that of [1-PPh2-closo-1,7-C2B10H11], suggesting that the properties of both substituents in 5 are effectively unaffected by the presence of the other.

Solution NMR Structural Studies of Glycans

AbstractIn this account, we present a summary of our progress in the study of glycan solution conformations by NMR spectroscopy. We begin by comparing the structural biology of glycans to that of proteins. We continue by defining the challenges in solution structural studies of glycans as we see them and show what we have done to help address those challenges. This includes Residual Dipolar Coupling studies and their hurdles, accurate coupling constant measurement in the presence of strong 1H‐1H coupling, direct detection of hydrogen bonds where the NHs, OHs or CHs are the hydrogen bond donors, and on‐cell NMR structural studies. We also suggest some future approaches to glycan structure determination.

On the Basicity of Carboranylphosphines.

Three new carboranylphosphines, [1-(1'-closo-1',7'-C2B10H11)-7-PPh2-closo-1,7-C2B10H10], [1-(1'-7'-PPh2-closo-1',7'-C2B10H10)-7-PPh2-closo-1,7-C2B10H10], and [1-{PPh-(1'-closo-1',2'-C2B10H11)}-closo-1,2-C2B10H11], have been prepared, and from a combination of these and literature compounds, eight new carboranylphosphine selenides were subsequently synthesized. The relative basicities of the carboranylphosphines were established by (i) measurement of the 1JPSe NMR coupling constant of the selenide and (ii) calculation of the proton affinity of the phosphine, in an attempt to establish which of several factors are the most important in controlling the basicity. It is found that the basicity of the carboranylphosphines is significantly influenced by the nature of other substituents on the P atom, the nature of the carborane cage vertex (C or B) to which the P atom is attached, and the charge on the carboranylphosphine. In contrast, the basicity of the carboranylphosphines appears to be relatively insensitive to the nature of other substituents on the carborane cage, the isomeric form of the carborane, and whether the cage is closo or nido (insofar as that does not alter the charge on the cluster). Such information is likely to be of significant importance in optimizing future applications of carboranylphosphines, e.g., as components of frustrated Lewis pairs.

Pushing resolution limits for extracting 1H-1H scalar coupling constants by a resolution-enhanced selective refocusing method.

Nuclear magnetic resonance (NMR) spectroscopy enables one to study molecular structure and dynamics in a noninvasive manner and has long served as a versatile and indispensable analytical tool in physics, chemistry, and biology. Scalar coupling, an essential feature in NMR spectroscopy, provides rich information regarding molecular structure and conformation. The measurement of scalar coupling constants, therefore, constitutes an important issue in NMR spectroscopy. Homonuclear 2D J-resolved spectroscopy is a powerful tool for multiplet analysis and coupling measurement. Recently, a number of phase-sensitive J-resolved methods and selective measuring methods have been developed to facilitate the extraction of coupling constants. However, resolution remains a crucial challenge when extracting small coupling constants or under inhomogeneous fields. In this paper, we present a resolution-enhanced selective refocusing (RESERF) method for the extraction of coupling constants. The effect of magnetic field inhomogeneity can be eliminated, resulting in very narrow linewidths. Therefore, samples with small coupling constants or under inhomogeneous fields can be well analyzed. The RESERF method may be of great value for structural and conformational studies in chemistry and biology.

Probing CP-violating Higgs sectors via the precision measurement of coupling constants

We study how effects of the CP violation can be observed indirectly by precision measurements of Higgs boson couplings at a future Higgs factory such as the international linear collider. We consider two Higgs doublet models with the softly broken discrete symmetry. We find that by measuring the Higgs boson couplings very precisely we are able to distinguish the two Higgs doublet model with CP violation from the CP conserving one.