Dipolar Shift Research Articles

Three-dimensional magnetothermal evolution of off-centred dipole magnetic field configurations in neutron stars

ABSTRACT Off-centred dipole configurations have been suggested to explain different phenomena in neutron stars, such as natal kicks, irregularities in polarization of radio pulsars and properties of X-ray emission from millisecond pulsars. Here, for the first time, we model magnetothermal evolution of neutron stars with crust-confined magnetic fields and off-centred dipole moments. We find that the dipole shift decays with time if the initial configuration has no toroidal magnetic field. The decay time-scale is inversely proportional to magnetic field. The octupole moment decreases much faster than the quadrupole. Alternatively, if the initial condition includes strong dipolar toroidal magnetic field, the external poloidal magnetic field evolves from centred dipole to off-centred dipole. The surface thermal maps are very different for configurations with weak B = 1013 G and strong B = 1014 G magnetic fields. In the former case, the magnetic equator is cold while in the latter case, it is hot. We model light curves and spectra of our magnetothermal configurations. We found that in the case of cold equator, the pulsed fraction is small (below a few per cent in most cases) and spectra are well described with a single blackbody. Under the same conditions, models with stronger magnetic fields produce light curves with pulsed fraction of tens of per cent. Their spectra are significantly better described with two blackbodies. Overall, the magnetic field strength has a more significant effect on bulk thermal emission of neutron stars than does the field geometry.

Vapor-liquid equilibria of binary mixtures containing Stockmayer-type model fluids from Monte-Carlo simulations

In this contribution, the vapor-liquid equilibria (VLE) of binary mixtures containing Lennard-Jones (LJ), Stockmayer (LJ + point dipole, ST), and shifted Stockmayer (sST) fluids are investigated with molecular simulations. The LJ and ST fluids are commonly used nonpolar and polar model fluids, respectively. The sST fluid differs from the ST fluid in that the dipole is shifted away from the dispersive center, which results in the sST fluid exhibiting H-bonding-like behavior. By varying the dispersion energy of the LJ fluid and the dipole moments of the ST and sST fluids, and the dipole shift of the sST fluids, different mixtures are generated, which are investigated at several temperatures and concentrations. Differences in the phase behavior between mixtures containing ST and sST fluids are quantified and linked to differences in fluid structure. The reported data include the VLE envelopes, coexisting densities, activity coefficients, and enthalpies for liquid and vapor phases, as well as structural information on the fluids’ intermolecular orientations.

Hydrodynamics of dipole-conserving fluids.

Dipole-conserving fluids serve as examples of kinematically constrained systems that can be understood on the basis of symmetry. They are known to display various exotic features including glassylike dynamics, subdiffusive transport, and immobile excitations' dubbed fractons. Unfortunately, such systems have so far escaped a complete macroscopic formulation as viscous fluids. In this work, we construct a consistent hydrodynamic description for fluids invariant under translation, rotation, and dipole shift symmetry. We use symmetry principles to formulate a thermodynamic theory for dipole-conserving systems at equilibrium and apply irreversible thermodynamics in order to elucidate dissipative effects. Remarkably, we find that the inclusion of the energy conservation not only renders the longitudinal modes diffusive rather than subdiffusive but also diffusion is present even at the lowest order in the derivative expansion. This work paves the way towards an effective description of many-body systems with constrained dynamics such as ensembles of topological defects, fracton phases of matter, and certain models of glasses.

Determination of the relative orientation between 15N-1H dipolar coupling and 1H chemical shift anisotropy tensors under fast MAS solid-state NMR

In this work, we have proposed a proton-detected three-dimensional (3D) 15N-1H dipolar coupling (DIP)/1H chemical shift anisotropy (CSA)/1H chemical shift (CS) correlation experiment to measure the relative orientation between the 15N-1H dipolar coupling and the 1H CSA tensors under fast magic angle spinning (MAS) solid-state NMR. In the 3D correlation experiment, the 15N-1H dipolar coupling and 1H CSA tensors are recoupled using our recently developed windowless C-symmetry-based C331-ROCSA (recoupling of chemical shift anisotropy) DIPSHIFT and C331-ROCSA pulse-based methods, respectively. The 2D 15N-1H DIP/1H CSA powder lineshapes extracted using the proposed 3D correlation method are shown to be sensitive to the sign and asymmetry of the 1H CSA tensor, a feature that allows the determination of the relative orientation between the two correlating tensors with improved accuracy. The experimental method developed in this study is demonstrated on a powdered U-15N L-Histidine.HCl·H2O sample.

Exploring the use of cobalt(II) dipolar shifts in refining the structure of a zinc finger peptide

The uses of dipolar shifts due to cobalt(II) substituted for zinc(II) in a consensus zinc finger peptide for refining the NMR-determined structure were examined. Substantial differences between the calculated and observed chemical shift differences between the cobalt(II) and zinc(II) complexes were observed when these dipolar shifts were not used as constraints in the structure refinement. However, inclusion of these constraints resulted in excellent agreement with minor adjustments in the structure and a slight improvement in the precision of the structure determination. Other calculations revealed that the dipolar shifts were not adequate to determine the overall folded structure by themselves, but were useful in increasing the accuracy and precision of a structure determined based only on nuclear Overhauser effects constraints involving only backbone atoms.

Dipolar and Contact Paramagnetic NMR Chemical Shifts in AnIV Complexes with Dipicolinic Acid Derivatives.

Actinide +IV complexes (AnIV = ThIV, UIV, NpIV, and PuIV) with two dipicolinic acid derivatives (DPA and Et-DPA) have been studied by 1H and 13C NMR spectroscopies and first-principles calculations. The Fermi contact and dipolar contributions to the actinide-induced shifts (AIS) are evaluated from a temperature dependence analysis, combined with ab initio results. It allows an experimental estimation of the axial anisotropy of the magnetic susceptibility Δχax and of the hyperfine coupling constants of the NMR-active nuclei. Due to the compactness of the coordination sphere, the magnetic anisotropy of the paramagnetic center is small, and this makes the contact contribution to be the dominant one, even on the remote atoms. The sign of the hyperfine coupling constants and related spin densities is alternating on the nuclei of the ligand cycle, denoting a preponderant spin polarization mechanism. This is well reproduced by unrestricted density functional theory (DFT) calculations. Those values are furthermore slightly decreasing in the actinide series, which indicates a small decrease of the covalency from UIV to PuIV.

Solid-State NMR Dipolar and Chemical Shift Anisotropy Recoupling Techniques for Structural and Dynamical Studies in Biological Systems.

With the development of NMR methodology and technology during the past decades, solid-state NMR (ssNMR) has become a particularly important tool for investigating structure and dynamics at atomic scale in biological systems, where the recoupling techniques play pivotal roles in modern high-resolution MAS NMR. In this review, following a brief introduction on the basic theory of recoupling in ssNMR, we highlight the recent advances in dipolar and chemical shift anisotropy recoupling methods, as well as their applications in structural determination and dynamical characterization at multiple time scales (i.e., fast-, intermediate-, and slow-motion). The performances of these prevalent recoupling techniques are compared and discussed in multiple aspects, together with the representative applications in biomolecules. Given the recent emerging advances in NMR technology, new challenges for recoupling methodology development and potential opportunities for biological systems are also discussed.

Dihedral Angle Measurements for Structure Determination by Biomolecular Solid-State NMR Spectroscopy.

In structural studies of immobilized, aggregated and self-assembled biomolecules, solid-state NMR (ssNMR) spectroscopy can provide valuable high-resolution structural information. Among the structural restraints provided by magic angle spinning (MAS) ssNMR the canonical focus is on inter-atomic distance measurements. In the current review, we examine the utility of ssNMR measurements of angular constraints, as a complement to distance-based structure determination. The focus is on direct measurements of angular restraints via the judicious recoupling of multiple anisotropic ssNMR parameters, such as dipolar couplings and chemical shift anisotropies. Recent applications are highlighted, with a focus on studies of nanocrystalline polypeptides, aggregated peptides and proteins, receptor-substrate interactions, and small molecule interactions with amyloid protein fibrils. The review also examines considerations of when and where ssNMR torsion angle experiments are (most) effective, and discusses challenges and opportunities for future applications.

Dipole-Dipole Frequency Shifts in Multilevel Atoms.

Dipole-dipole interactions lead to frequency shifts that are expected to limit the performance of next-generation atomic clocks. In this work, we compute dipolar frequency shifts accounting for the intrinsic atomic multilevel structure in standard Ramsey spectroscopy. When interrogating the transitions featuring the smallest Clebsch-Gordan coefficients, we find that a simplified two-level treatment becomes inappropriate, even in the presence of large Zeeman shifts. For these cases, we show a net suppression of dipolar frequency shifts and the emergence of dominant nonclassical effects for experimentally relevant parameters. Our findings are pertinent to current generations of optical lattice and optical tweezer clocks, opening a way to further increase their current accuracy, and thus their potential to probe fundamental and many-body physics.

Dynamics in Flexible Pillar[n]arenes Probed by Solid-State NMR.

Pillar[n]arenes are supramolecular assemblies that can perform a range of technologically important molecular separations which are enabled by their molecular flexibility. Here, we probe dynamical behavior by performing a range of variable-temperature solid-state NMR experiments on microcrystalline perethylated pillar[n]arene (n = 5, 6) and the corresponding three pillar[6]arene xylene adducts in the 100–350 K range. This was achieved either by measuring site-selective motional averaged 13C 1H heteronuclear dipolar couplings and subsequently accessing order parameters or by determining 1H and 13C spin–lattice relaxation times and extracting correlation times based on dipolar and/or chemical shift anisotropy relaxation mechanisms. We demonstrate fast motional regimes at room temperature and highlight a significant difference in dynamics between the core of the pillar[n]arenes, the protruding flexible ethoxy groups, and the adsorbed xylene guest. Additionally, unexpected and sizable 13C 1H heteronuclear dipolar couplings for a quaternary carbon were observed for p-xylene adsorbed in pillar[6]arene only, indicating a strong host–guest interaction and establishing the p-xylene location inside the host, confirming structural refinements.

Evaluation of chitosan crystallinity: A high-resolution solid-state NMR spectroscopy approach

We propose a novel approach relied on high-resolution solid-state 13C NMR spectroscopy to quantify the crystallinity index of chitosans (Ch) prepared with variable average degrees of acetylation (DA¯) from 5% to 60 % and average weight molecular weight (M¯w) ranged in 0.15 × 106 g mol−1–1.2 × 106 g mol−1. The Dipolar Chemical Shift Correlation (DIPSHIFT) curve of the C(6)OH segment revealed increased mobility dynamic, which induced different distribution from trans-to-gauche conformations in relation to C(4). Indeed, 1H-13C Heteronuclear Correlation (2D HETCOR) showed that distinguished C4 chemical shifts correlates with the same aliphatic protons. The short-range ordering can be assigned to C4/C6 signals on 13C CPMAS and, for our case, the deconvolution procedure between disordered and ordered phases revealed increasing crystallinity with DA¯, as confirmed by SVD multivariate analysis. This work extended the knowledge regarding the use of 13C CPMAS technique to predict the crystallinity of chitosans without the use of amorphous standards.

Detecting axisymmetric magnetic fields using gravity modes in intermediate-mass stars

Context.Angular momentum (AM) transport models of stellar interiors require improvements to explain the strong extraction of AM from stellar cores that is observed with asteroseismology. One of the frequently invoked mediators of AM transport are internal magnetic fields, even though their properties, observational signatures, and influence on stellar evolution are largely unknown.Aims.We study how a fossil, axisymmetric internal magnetic field affects period spacing patterns of dipolar gravity mode oscillations in main sequence stars with masses of 1.3, 2.0, and 3.0 M⊙. We assess the influence of fundamental stellar parameters on the magnitude of pulsation mode frequency shifts.Methods.We computed dipolar gravity mode frequency shifts due to a fossil, axisymmetric poloidal–toroidal internal magnetic field for a grid of stellar evolution models, varying stellar fundamental parameters. Rigid rotation was taken into account using the traditional approximation of rotation, and the influence of the magnetic field was computed using a perturbative approach.Results.We find magnetic signatures for dipolar gravity mode oscillations in terminal-age main sequence stars that are measurable for a near-core field strength larger than 105G. The predicted signatures differ appreciably from those due to rotation.Conclusions.Our formalism demonstrates the potential for the future detection and characterization of strong fossil, axisymmetric internal magnetic fields in gravity-mode pulsators near the end of core-hydrogen burning fromKeplerphotometry, if such fields exist.

UV Pretreatment Impairs the Enzymatic Degradation of Polyethylene Terephthalate.

The biocatalytic degradation of polyethylene terephthalate (PET) emerged recently as a promising alternative plastic recycling method. However, limited activity of previously known enzymes against post-consumer PET materials still prevents the application on an industrial scale. In this study, the influence of ultraviolet (UV) irradiation as a potential pretreatment method for the enzymatic degradation of PET was investigated. Attenuated total reflection Fourier transform infrared (ATR-FTIR) and 1H solution nuclear magnetic resonance (NMR) analysis indicated a shortening of the polymer chains of UV-treated PET due to intra-chain scissions. The degradation of UV-treated PET films by a polyester hydrolase resulted in significantly lower weight losses compared to the untreated sample. We also examined site-specific and segmental chain dynamics over a time scale of sub-microseconds to seconds using centerband-only detection of exchange, rotating-frame spin-lattice relaxation (T1ρ), and dipolar chemical shift correlation experiments which revealed an overall increase in the chain rigidity of the UV-treated sample. The observed dynamic changes are most likely associated with the increased crystallinity of the surface, where a decreased accessibility for the enzyme-catalyzed hydrolysis was found. Moreover, our NMR study provided further knowledge on how polymer chain conformation and dynamics of PET can mechanistically influence the enzymatic degradation.

Electrical injection and transport in Teflon-diluted hole transport materials

Abstract Diluting small molecule organic semiconductor hole transport materials with Teflon AF (TAF) dramatically increases their thermal/morphological stability while counterintuitively also increasing the current density in hole-only diodes. Here, we explore the origin of this current enhancement in co-evaporated blends of TAF and N,N′-Di(1-naphthyl)-N,N′-diphenyl-(1,1′-biphenyl)-4,4′-diamine (NPD) and find that it results from improved hole injection and not from a mobility enhancement due to semiconductor dilution effects. Whereas electroabsorption measurements indicate that an interface dipole shift of up to 0.5 eV (depending on TAF concentration) aides hole injection at the indium-tin-oxide anode, time-of-flight and temperature-dependent current-voltage measurements show that the mobility of 25 vol% TAF:NPD blends decreases by roughly an order of magnitude relative to neat NPD despite having slightly lower energetic disorder. For comparison, diluting with 25 vol% high density polyethylene achieves a similar reduction in energetic disorder but only decreases the mobility by a factor of two. These results highlight the tradeoff between reducing energetic disorder and frustrating percolation in diluted organic semiconductors, and represent a step toward thermally-evaporated polymer-small molecule composites that maintain high mobility while offering improved morphological stability and lower refractive index for organic light emitting diodes.

Elucidating natural product structures using a robust measurement of carbon residual chemical shift anisotropy combined with DFT.

Determination of configurations and conformations is an important step in the structural characterization of small molecules. Apart from utilizing isotropic J-couplings and nuclear overhauser effect (NOEs) measured in isotropic solution, anisotropic Nuclear Magnetic resonance (NMR) data such as residual dipolar couplings and residual chemical shift anisotropies (RCSAs) were also used to elucidate complex small molecule structures. Measuring RCSA has always been historically difficult due to the isotropic shift effect accompanied by molecular alignment and therefore only occasionally applied in a few examples. Here, we present a robust measurement of carbon RCSAs using a smaller gel-stretching device to determine the structures of a few small molecules. A systematic study on how different density functional theory computed anisotropies of the chemical shift anisotropy tensors impact RCSA data interpretation has also been discussed. We also discuss the effect of utilizing various carbons as reference nuclei for RCSA data extraction as well as the orientation behavior of estrone in orthogonal alignment media.

NMR “Crystallography” of Membrane Proteins Aligned in Native-Like Bilayers

Oriented-sample (OS) solid-state NMR can be used to determine structures of membrane proteins without crystallization and use of cryogenic temperatures. Here, the orientationally dependent dipolar couplings and chemical shifts provide direct input for structure calculations. However, so far only the 1H-15N dipolar couplings and 15N chemical shifts have been routinely assessed in 15N labeled protein samples. While highly efficient for determining the tilt angles of short α-helical peptides, these two measurements alone are likely insufficient for determining protein structures of arbitrary topology. Therefore, determination of tertiary structures of membrane proteins by OS NMR requires measurements of additional angular restraints. Here we have developed a new experimental triple-resonance NMR technique, which was applied to uniformly doubly (15N, 13C) labeled Pf1 coat protein reconstituted in magnetically aligned DMPC/DHPC bicelles. The previously inaccessible 1Hα-13Cα dipolar couplings, which represent powerful chiral angular restraints, have been measured for the resolved NMR resonances of the transmembrane domain of Pf1. Inclusion of the third restraint makes it possible to determine the torsion angles Φ and Ψ between the adjacent peptide planes without assuming α-helical structure a priori. Using our recently developed structure calculation algorithm [1], simultaneous fitting of three restraints per peptide plane has resulted in families of structures which have subsequently been filtered using various Rosetta scoring functions including the energetics within the membrane environment, hydrogen bonding, and potential steric clashes. Such structural validation protocol has led to a consensus α-helical transmembrane structure for Pf1 coat protein, albeit obtained in a de novo fashion, thus greatly enhancing utility of OS NMR as a “crystallography” in near-native membrane environments. [1]. Lapin, J. and Nevzorov A.A., Validation of protein backbone structures calculated from NMR angular restraints using Rosetta, J. Biomol. NMR, 2019; 73(5):229-244.

NMR “Crystallography” for Uniformly (13C, 15N)‐Labeled Oriented Membrane Proteins

AbstractIn oriented‐sample (OS) solid‐state NMR of membrane proteins, the angular‐dependent dipolar couplings and chemical shifts provide a direct input for structure calculations. However, so far only 1H–15N dipolar couplings and 15N chemical shifts have been routinely assessed in oriented 15N‐labeled samples. The main obstacle for extending this technique to membrane proteins of arbitrary topology has remained in the lack of additional experimental restraints. We have developed a new experimental triple‐resonance NMR technique, which was applied to uniformly doubly (15N, 13C)‐labeled Pf1 coat protein in magnetically aligned DMPC/DHPC bicelles. The previously inaccessible 1Hα–13Cα dipolar couplings have been measured, which make it possible to determine the torsion angles between the peptide planes without assuming α‐helical structure a priori. The fitting of three angular restraints per peptide plane and filtering by Rosetta scoring functions has yielded a consensus α‐helical transmembrane structure for Pf1 protein.

Self-assembly of magnetic colloids with radially shifted dipoles.

Anisotropic potentials in Janus colloids provide additional freedom to control particle aggregation into structures of different sizes and morphologies. In this work, we perform Brownian dynamics simulations of a dilute suspension of magnetic spherical Janus colloids with their magnetic dipole moments shifted radially towards the surface of the particle in order to gain valuable microstructural insight. Properties such as the mean cluster size, orientational ordering, and nucleation and growth are examined dynamically. Differences in the structure of clusters and in the aggregation process are observed depending on the dipolar shift (s)-the ratio between the displacement of the dipole and the particle radius-and the dipolar coupling constant (λ)-the ratio between the magnetic dipole-dipole and Brownian forces. Using these two dimensionless quantities, a structural "phase" diagram is constructed. Each phase corresponds to unique nucleation and growth behavior and orientational ordering of dipoles inside clusters. At small λ, the particles aggregate and disaggregate resulting in short-lived clusters at small s, while at high s the particles aggregate in permanent triplets (long-lived clusters). At high λ, the critical nuclei formed during the nucleation process are triplets and quadruplets with unique orientational ordering. These small clusters then serve as building blocks to form larger structures, such as single-chain, loop-like, island-like, worm-like, and antiparallel-double-chain clusters. This study shows that dipolar shifts in colloids can serve as a control parameter in applications where unique size, morphology, and aggregation kinetics of clusters are required.

Ferroelectric nonlinear anomalous Hall effect in few-layer WTe2

Under broken time reversal symmetry such as in the presence of external magnetic field or internal magnetization, a transverse voltage can be established in materials perpendicular to both longitudinal current and applied magnetic field, known as classical Hall effect. However, this symmetry constraint can be relaxed in the nonlinear regime, thereby enabling nonlinear anomalous Hall current in time-reversal invariant materials – an underexplored realm with exciting new opportunities beyond classical linear Hall effect. Here, using group theory and first-principles theory, we demonstrate a remarkable ferroelectric nonlinear anomalous Hall effect in time-reversal invariant few-layer WTe2 where nonlinear anomalous Hall current switches in odd-layer WTe2 except 1T′ monolayer while remaining invariant in even-layer WTe2 upon ferroelectric transition. This even-odd oscillation of ferroelectric nonlinear anomalous Hall effect was found to originate from the absence and presence of Berry curvature dipole reversal and shift dipole reversal due to distinct ferroelectric transformation in even and odd-layer WTe2. Our work not only treats Berry curvature dipole and shift dipole on an equal footing to account for intraband and interband contributions to nonlinear anomalous Hall effect, but also establishes Berry curvature dipole and shift dipole as new order parameters for noncentrosymmetric materials. The present findings suggest that ferroelectric metals and Weyl semimetals may offer unprecedented opportunities for the development of nonlinear quantum electronics.

Phosphorene and Black Phosphorus: The 31P NMR View.

This work aims at characterizing for the first time the 31P spin interactions determining the nuclear magnetic resonance (NMR) properties of solid black phosphorus (bP) and of its few-layer exfoliated form (fl-bP). Indeed, the knowledge of these properties is still very poor, despite the great interest received by this layered phosphorus allotrope and its exfoliated 2D form, phosphorene. By combining density functional theory (DFT) calculations and solid-state NMR experiments on suspensions of fl-bP nanoflakes and on solid bP, it has been possible to characterize the 31P homonuclear dipolar and chemical shift interactions, identifying the network of 31P nuclei more strongly dipolarly coupled and highlighting two kinds of magnetically nonequivalent 31P nuclei. These results add an important missing piece of information to the fundamental chemico-physical knowledge of bP and support future extensive applications of NMR spectroscopy to the characterization of phosphorene-based materials.