Residual Dipolar Interactions Research Articles

Chain Dynamics of Partially Disentangled UHMWPE around Melting Point Characterized by 1H Low-Field Solid-State NMR.

Melts of ultrahigh molecular weight polyethylene (UHMWPE) entangled significantly, suffering processing difficulty. In this work, we prepared partially disentangled UHMWPE by freeze-extracting, exploring the corresponding enchantment of chain mobility. Fully refocused 1H free induction decay (FID) was used to capture the difference in chain segmental mobility during the melting of UHMWPE with different degrees of entanglement by low-field solid-state NMR. The longer the polyethylene (PE) chain is in a less-entangled state, the harder the process of merging into mobile parts after detaching from crystalline lamella during melting. 1H double quantum (DQ) NMR was further used to obtain information caused by residual dipolar interaction. Before melting, the DQ peak appeared earlier in intramolecular-nucleated PE than in intermolecular-nucleated PE because of the strong constraints of crystals in the former one. During melting, less-entangled UHMWPE could keep disentangled while less-entangled high density polyethylene (HDPE) could not. Unfortunately, no noticeable difference was found in DQ experiments between PE melts with different degrees of entanglement after melting. It was ascribed to the small contribution of entanglements compared with total residual dipolar interaction in melts. Overall, less-entangled UHMWPE could reserve its disentangled state around the melting point long enough to achieve a better way of processing.

1H spin-lattice NMR relaxation in the presence of residual dipolar interactions – Dipolar relaxation enhancement

A model of spin-lattice relaxation for spin-1/2 nuclei in the presence of a residual dipole-dipole coupling has been presented. For slow dynamics the model predicts a bi-exponential relaxation at low frequencies, when the residual dipole-dipole interaction dominates the Zeeman coupling. Moreover, according to the model a frequency-specific relaxation enhancement, referred to as Dipolar Relaxation Enhancement (DRE) in analogy to the Quadrupole Relaxation Enhancement (QRE) is expected. The frequency position of the relaxation maximum is determined by the amplitude of the residual dipole-dipole interaction. Experimental examples of relaxation properties that might be attributed to the DRE are presented. The DRE effect has the potential to be exploited, in analogy to QRE, as a unique source of information about molecular dynamics and structure.

“Pseudo solid” nuclear spin echo study of poly(ethylene oxide) grafted on silica. Comparison with magic‐angle spinning technique results

AbstractThe polymer/solid interface of Poly (ethylene oxide) (PEO) grafted on silica is studied by 1H NMR. For grafted polymers, the dipolar interaction is an important factor in the spin–spin relaxation process. For this purpose, the part of the dipolar interaction that is not averaged to zero by the motion is used. The “pseudo solid” spin echo can indeed give an estimation of the nonzero average dipolar interactions. The appropriate pulse sequence permits a standard measurement of the average dipolar spin coupling involved in the transverse magnetization relaxation. The influence of some major parameters such as molecular weights of the chains, grafting ratios, and temperatures on the relaxation and ultimately on the concentration is followed by “pseudo solid” spin echo. The magic‐angle spinning technique is also used. The sample rotation confirms by the narrowing of the central line and the appearance of side bands, the existence of a residual dipolar interaction which reveals the concentration of high monomer units at the surface. The study of the side bands permits to calculate the second moment as a function of temperature. A fair agreement is obtained by these two independent techniques: pseudo solid echo and magic‐angle spinning.

Investigation of chloromethane complexes of cryptophane-A analogue with butoxy groups using ¹³C NMR in the solid state and solution along with single crystal X-ray diffraction.

Host‐guest complexes between cryptophane‐A analogue with butoxy groups (cryptophane‐But) and chloromethanes (chloroform, dichloromethane) were investigated in the solid state by means of magic‐angle spinning 13C NMR spectroscopy. The separated local fields method with 13C‐1H dipolar recoupling was used to determine the residual dipolar coupling for the guest molecules encaged in the host cavity. In the case of chloroform guest, the residual dipolar interaction was estimated to be about 19 kHz, consistent with a strongly restricted mobility of the guest in the cavity, while no residual interaction was observed for encaged dichloromethane. In order to rationalize this unexpected result, we performed single crystal X‐ray diffraction studies, which confirmed that both guest molecules indeed were present inside the cryptophane cavity, with a certain level of disorder. To improve the insight in the dynamics, we performed a 13C NMR spin‐lattice relaxation study for the dichloromethane guest in solution. The system was characterized by chemical exchange, which was slow on the chemical shift time scale but fast with respect to the relaxation rates. Despite these disadvantageous conditions, we demonstrated that the data could be analyzed and that the results were consistent with an isotropic reorientation of dichloromethane within the cryptophane cavity. Copyright © 2015 The Authors. Magnetic Resonance in Chemistry published by John Wiley & Sons Ltd.

Characterization and mapping of dipolar interactions within macromolecules in tissues using a combination of DQF, MT and UTE MRI

This study shows that by combining a double-quantum filtered magnetization transfer (DQF-MT) with an ultra-short TE (UTE) MRI that it is possible to obtain contrast between tissue compartments based on the following characteristics: (a) the residual dipolar coupling interaction within the biomacromolecules, which depends on their structure, (b) residual dipolar interactions within water molecules, and (c) the magnetization exchange rate between biomacromolecules and water. The technique is demonstrated in rat-tail specimens, where the collagenous tissue such as tendons and the annulus pulposus of the disc are highlighted in these images, and their macromolecular properties along with those of bones and muscles can be characterized. DQF-MT UTE MRI also holds promise because collagenous tissues that are typically invisible in conventional MRI experiments produce significant signal intensities using this approach.

Ultra High-Resolution NMR: Sustained Induction Decays of Long-Lived Coherences

Long-lived coherences (LLCs) in homonuclear pairs of chemically inequivalent spins can be excited and sustained during protracted radio frequency irradiation periods that alternate with brief windows for signal observation. Fourier transformation of the sustained induction decays recorded in a single scan yields NMR spectra with line-widths in the range 10 < Δν < 100 mHz, even in moderately inhomogeneous magnetic fields. The resulting doublets, which are reminiscent of J-spectra, allow one to determine the sum of scalar and residual dipolar interactions in partly oriented media. The signal intensity can be boosted by several orders of magnitude by "dissolution" dynamic nuclear polarization (DNP).

Spectroscopic, thermal and X-ray structural study of the antiparasitic and antiviral drug nitazoxanide

Nitazoxanide [2-(acetyloxy)- N-(5-nitro-2-thiazolyl)benzamide, NTZ] is a potent antiparasitic and antiviral agent recently approved. The anti-protozoal activity of NTZ is believed to be due to interference with the pyruvate:ferredoxin oxidoreductase (PFOR) enzyme dependent electron transfer reaction. As drug–enzyme interactions are governed by the three-dimensional stereochemistry of both participants, the crystal structure of NTZ was determined for the first time to identify the conformational preferences that may be related to biological activity. NTZ crystallizes as the carboxamide tautomer in the orthorhombic system, space group Pna2 1 with the following parameters at 100(2) K: a = 14.302(2) Å, b = 5.2800(8) Å, c = 33.183(5) Å, V = 2505.8(6) Å 3, Z = 8, D x = 1.629 g cm −3, R = 0.0319, wR 2 = 0.0799 for 5121 reflections. In addition, the spectroscopic and thermal properties were determined and related to the molecular structure. The 13C CPMAS NMR spectra showed resolved signals for each carbon of NTZ, some signals being broad due to residual dipolar interaction with quadrupolar 14N nuclei. In particular, the resonance at about 127 ppm showed multiplicity, indicating more than one molecule in the asymmetric unit and this is consistent with the crystallographic data. The DSC and TG data revealed that NTZ shows a single DSC melting peak with extrapolated onset at 201 °C which is accompanied by a TG weight loss, indicating that NTZ melts with decomposition.

Echo planar correlated spectroscopic imaging: Implementation and pilot evaluation in human calf in vivo

Exploiting the speed benefits of echo-planar imaging (EPI), the echo-planar spectroscopic imaging (EPSI) sequence facilitates recording of one spectral and two to three spatial dimensions faster than the conventional magnetic resonance spectroscopic imaging (MRSI). A novel four dimensional (4D) echo-planar correlated spectroscopic imaging (EP-COSI) was implemented on a whole body 3 T MRI scanner combining two spectral with two spatial encodings. Similar to EPSI, the EP-COSI sequence used a bipolar spatial read-out train facilitating simultaneous spatial and spectral encoding, and the conventional phase and spectral encodings for the other spatial and indirect spectral dimensions, respectively. Multiple 2D correlated spectroscopy (COSY) spectra were recorded over the spatially resolved volume of interest (VOI) localized by a train of three slice-selective radiofrequency (RF) pulses (90°-180°-90°). After the initial optimization using phantom solutions, the EP-COSI data were recorded from the lower leg of eight healthy volunteers including one endurance trained volunteer. Pilot results showed acceptable spatial and spectral quality achievable using the EP-COSI sequence. There was a detectable separation of cross peaks arising from the skeletal muscle intramyocellular lipids (IMCLs) and extramyocellular lipids (EMCLs) saturated and unsaturated pools. Residual dipolar interaction between the N-methylene and N-methyl protons of creatine/phosphocreatine (Cr/PCr) was also observed in the tibialis anterior region.

Study of the residual dipolar coupling by 1H NMR MAS technique. Effect of the grafting ratio on interface polymer grafted on silica

1H NMR permits some approaches to a monomer unit scale of the macromolecular grafted on the solid. In the case of poly(ethylene) grafted on silica, the magic angle spinning technique confirms, by narrowing of the central line and apparition of side bands, the existence of the residual dipolar interaction, which reveals the high monomer unit concentration at the surface. The study of the side bands permits calculation of the physical parameter: the second moment, which gives in turn an indication of the evolution of the monomer unit concentration on the surface. This behavior has been studied as a function of molecular weight of the chains and grafting ratio. A fair agreement is obtained for the second moment and the linewidth, giving a consistent picture by two independent techniques: magnetic relaxation and magic angle spinning.

Determination of residual dipolar interaction from transverse 1H NMR relaxation in elastomers

The formula expressing the proton transverse magnetization decay for elastomers is reconsidered. It is improved by incorporating the relaxation contribution. The spin–spin relaxation times T 2 are estimated from spin–lattice relaxation times in the laboratory frame T 1 and spin–lattice relaxation times in the rotating frame T 1ρ measured at the low static magnetic field. The improved formula together with distributed residual dipolar couplings is applied to several samples of elastomers, and residual dipolar couplings are estimated. A good correlation between a swelling ratio and the residual dipolar coupling is obtained.

Efficient heteronuclear dipolar decoupling in NMR of static solid samples using phase-wiggled two-pulse phase modulation

A new scheme using phase-wiggled two-pulse phase modulation (PW-TPPM) is proposed for efficient heteronuclear dipolar decoupling in nuclear magnetic resonance (NMR) of static solid samples. The two pulses within each TPPM element have different alternating phase angles so that these elements become phase-wiggled. It is derived theoretically that such phase wiggling causes a resonance for additional averaging of the residual heteronuclear dipolar interactions and thus significantly improves decoupling efficiency in stationary solids. A static 15N-acetyl-valine crystal sample and a 15N-labeled helical peptide sample aligned in hydrated phospholipid bilayers were used to illustrate the advantages of this new scheme.

An isotropic chemical shift–chemical shift anisotropic correlation experiment using discrete magic angle turning

An isotropic–anisotropic shift 2D correlation spectroscopy is introduced that combines the advantages of both magic angle turning (MAT) and magic angle hopping (MAH) technologies. In this new approach, denoted DMAT for “discrete magic angle turning”, the sample rotates clockwise followed by an anticlockwise rotation of exactly the same amount with each rotation less or equal than 360° but greater than 240°, with the rotation speed being constant only for times related to the evolution dimension. This back and forth rotation is repeated and synchronized with a special radio frequency (RF) pulse sequence to produce an isotropic–anisotropic shift 2D correlation spectrum. For any spin-interaction of rank-2 such as chemical shift anisotropy, isotropic magnetic susceptibility interaction, and residual homo-nuclear dipolar interaction in biological fluid samples, the projection along the isotropic dimension is a high resolution spectrum. Since a less than 360° sample rotation is involved, the design potentially allows for in situ control over physical parameters such as pressure, flow conditions, feed compositions, and temperature so that true in situ NMR investigations can be carried out.

Interaction of Hydronium Ion with Dibenzo-18-crown-6: NMR, IR, and Theoretical Study

Interaction of dibenzo-18-crown-6 (DBC) with H 3O (+) (HP) in nitrobenzene- d 5 and dichloromethane- d 2 was studied by using (1)H and (13)C NMR spectra and relaxations, FTIR spectra, and quantum chemical DFT calculations. NMR shows that the DBC*HP complex is in a dynamic equilibrium with the reactants, the equilibrium constant K being 0.66 x 10 (3), 1.16 x 10 (4), and 1.03 x 10 (4) L x mol (-1) in CD 2Cl 2, nitrobenzene, and acetonitrile, respectively. The complex appears to have a C 2 v symmetry in NMR, but FTIR combined with DFT normal mode calculations suggest that such high symmetry is only apparent and due to exchange averaging of the structure. FTIR spectra as well as energy-optimized DFT calculations show that the most stable state of the complex in solution is that with three linear hydrogen bonds of HP with one CH 2-O-CH 2 and two Ar-O-Ar oxygen atoms. The structure is similar to that found in solid state but adopts a somewhat different conformation in solution. The dynamics of exchange between bound and free DBC was studied by NMR transverse relaxation. It was found to be too fast to give reproducible results when measured with the ordinary CPMG sequence or its variant DIFTRE removing residual static dipolar interaction, but it could be established by rotating-frame measurements with high intensity of the spin-lock field. The correlation time of exchange was found to be 5.6 x 10 (-6) and 3.8 x 10 (-6) s in dichloromethane and nitrobenzene, respectively. Such fast exchange can be explained by cooperative assistance of present water molecules.

Order Parameters and Distribution in the Smectic Layer of Probe Molecules Dissolved in Ferroelectric Liquid Crystalline Mixtures

For a few types of relatively small probe molecules with different sizes and geometrical anisotropies, alignment-induced 13 C chemical shifts or spacings in the multiplet due to the residual dipolar interaction are measured in the anisotropic S A and S C * phases of ferroelectric liquid crystals. On the basis of the simplified motional model, the orientational order parameter and the tilt angle are determined for the probes and compared with those of the liquid crystal itself. The tilt angles of the probes are fairly similar to those of liquid crystals. Various types of temperature variations of the orientational order are discussed in terms of the mobility and spatial distribution of the probe molecules in the smectic layers in relation to the expulsion of the probes from the rigid core region in the liquid crystal.

Collagen Fibers as a Chiral Agent: A Demonstration of Stereochemistry Effects

The collagen is the most common protein in mammalians. Thus its interaction with small molecules and particularly amino acids is of interest. Owing to the high degree of order of collagen fibers in a tendon, the 1H-1H and 1H-13C dipolar interactions and the 2H quadrupolar interaction of small molecules interacting with it do not average to zero. In the present work we report that these residual interactions for alanine in intact tendons are significantly different for the l and d enantiomers meaning that the collagen in its native state acts as a chiral agent. The different l/d ratios for each of the residual interactions along the different vectors in the alanine molecule and the similarly transferred NOE from the collagen to the l and d enantiomers indicate that the main source of the different residual dipolar and quadrupolar interactions is the stereochemistry of the binding and not the amounts of bound molecules.

Magic sandwich echo relaxation mapping of anisotropic systems

The main objective of this article was (i) to refocus the residual dipolar and quadrupolar interactions in anisotropic tissues employing magic sandwich echo (MSE) imaging and to compare the results with that of conventional spin-echo (SE) imaging, and (ii) to quantify MSE relaxation and dispersion characteristics in bovine Achilles tendon and compare with spin-lattice relaxation time constant in the rotating frame (T(1rho)). Magic sandwich echo weighted images are approximately 75-100% higher in signal-to-noise ratio than the corresponding T(2)-weighted images. Magic sandwich echo relaxation times varied from 13+/-2 to 19+/-3 ms (mean+/-S.D.), depending upon the structural location of tendon. T(2) relaxation times only varied from 4+/-1 to 10+/-3 ms (mean+/-S.D.) on the same corresponding locations. Magic sandwich echo provides approximately 100% enhancement in relaxation times compared to T(2). Preliminary results based on bovine Achilles tendon and cartilage specimens suggest that the MSE technique has potential for refocusing residual dipolar as well as quadrupolar interactions in anisotropic systems and yields higher intensities than conventional SE imaging as well as T(1rho)-encoded imaging, especially at low-burst pulse amplitudes (250 and 500 Hz).

Multinuclear NMR and MRI studies of the maturation of pig articular cartilage

The maturation of pig articular cartilage was followed by (2)H in-phase double quantum filtered (IP-DQF) spectroscopic MRI, (1)H T(2) MRI, and (23)Na DQF and triple quantum filtered MRS. The results all lead to the conclusion that the order and density of the collagen fibers in articular cartilage increase from birth to maturity. At birth, both (2)H IP-DQF signal and (1)H T(2) were homogeneous throughout the cartilage and their values independent of the orientation of the plug relative to the magnetic field. At maturation, the (2)H IP-DQF spectrum near the bone is composed of two pairs of quadrupolar split satellites and the (1)H T(2) relaxation is biexponential, indicating the presence of two groups of collagen fibers. The (2)H satellites are orientation dependent, indicating that the two groups of fibers are well ordered at maturation. The fast component of (1)H T(2) is also orientation dependent and thus we have concluded that this component results from residual dipolar interaction, while the slow T(2) component in mature cartilage, as well as the T(2) relaxation in immature cartilage, is governed by other mechanisms.

Suppression of undesired peaks due to residual intermolecular dipolar interactions in liquid NMR

Residual intermolecular dipolar interactions may result in undesired spectral features on highly concentrated samples in liquid NMR. Although homonuclear decoupling can be employed to suppress the interactions, it may cause a strong irradiation peak, which obscures the nearby peaks. In order to overcome this shortcoming, a modified CRAZED sequence with three radio-frequency pulses was proposed. The analytical expression derived from the dipolar field treatment was employed to select proper flip angles and phase cycling. Theoretical predictions, experimental observations, and computer simulations demonstrated that the new method effectively suppresses the undesired peaks due to residual dipolar effects.

Water in tendon: Orientational analysis of the free induction decay

The orientation dependence of the free induction decay (FID) of 1H NMR water signal in ex vivo bovine digital flexor tendon at the native level of hydration is reported. Residual dipolar coupling due to the overall tissue anisotropy produces a 6:1 change in the signal intensity as an angle between the long axis of a specimen and the external magnetic field is changed from the "magic angle" of 54.7 degrees to 0 degrees. The strength of residual dipolar interactions between water protons was estimated by orientational analysis of the signal intensity to be equal to 780 Hz. Apparent signal maxima are observed at orientations 8-13 degrees away from 54.7 degrees due to an inhomogeneous contribution to the decay. A small fraction of total water in tendon is detectable at all orientations and exhibits a shift in the precession frequency. It is hypothesized that this water fraction resides in the interconnecting gaps at the ends of collagen molecules. The gaps have a disordered environment that allows for a zero time average of dipolar interactions. Measured frequency and phase shifts are interpreted as signatures of the bulk magnetic susceptibility effect due to geometry of the cavity formed by adjacent gaps at the ends of the collagen molecules. The multiexponentiality of the FID decay is hypothesized to be due to the exchange between orientationally restricted water structured along the length of the collagen molecule and disordered water in the cavity.

NMR OBSERVATION OF THE SPIN-LATTICE AND SPIN-SPIN RELAXATION IN SOME POLIBUTADIENES WITH DIFFERENT VINYL CONTENTS

Some polybutadienes with different vinyl contents were observed by NMR methods in order to disclose the influence of the microstructure of the polymeric chains on the relaxation of the longitudinal and transverse magnetization. The relaxation process is correlated with the dynamic properties of the polymeric chains. The residual dipolar interaction determined by the rigidity of the polymeric chains is observed by the pseudo-solid echo method and is associated with the vinyl contents of the samples.