Humidity-induced formation of water channels in supramolecular assemblies of wedge-shaped amphiphiles: the effect of the molecular architecture on the channel topology.

In supramolecular assemblies, absorption of water can assist the channel formation, similarly to biological systems and Nafion-like commercial ion-selective membranes. In this work, we investigate humidity-induced formation of water channels in wedge-shaped amphiphilic molecules, namely sodium 4'-[3'',4'',5''-tris(alkyloxy)benzoyloxy]azobenzene-4-sulfonates. The studied molecules contain a polar sulfonate group at the tip and a hydrophobic periphery composed of alkyl chains of two different lengths. Upon increasing the relative humidity (RH) the amount of absorbed water significantly increases for the mesogen with dodecyl chains as compared to the one with octyl groups. In the former case, water sorption is accompanied by a considerable enhancement of ionic conductivity and a phase transition. In particular, an increase of RH induces a transition from a lamellar to a columnar phase resulting in the formation of 1D water channels running along the axis of the supramolecular columns. For the compound with shorter alkyl chains the lamellar phase exists in the entire RH-range exhibiting pronounced swelling at high RH-values and thereby forming a 2D water channel structure. NMR diffusometry was used to address the different molecular motions in the lyotropic mesophases of the studied amphiphiles.

Blending of reactive prepolymers to control the morphology and polarity of polyglycidol based microgels.

The compartmentalization of microgels is a challenging task for synthetic polymer chemistry. Although the complexation with low molecular weight compounds or the use of microfluidic techniques offer attractive possibilities for other length scales, it is difficult to implement compartments in the mesoscale range of 10-100 nm. Herein we show how simple blending of reactive prepolymers is suitable to design new microgel morphologies with tailored compartments. We use poly(EEGE)-block-poly(AGE) as crosslinkable, pro-hydrophilic prepolymer in blends with varying amounts of crosslinkable, yet hydrophobic poly(THF-stat-AllylEHO) or inert and hydrophobic polystyrene, and crosslink the allyl functional prepolymer(s) in a thiol-ene click-type reaction after miniemulsification. Our strategy shows how arrested versus free nanophase separation can be used to control easily the morphology and polarity of microgel particles.

The heterogeneity of segmental dynamics of filled EPDM by (1)H transverse relaxation NMR.

Residual second moment of dipolar interactions M(2) and correlation time segmental dynamics distributions were measured by Hahn-echo decays in combination with inverse Laplace transform for a series of unfilled and filled EPDM samples as functions of carbon-black N683 filler content. The fillers-polymer chain interactions which dramatically restrict the mobility of bound rubber modify the dynamics of mobile chains. These changes depend on the filler content and can be evaluated from distributions of M(2). A dipolar filter was applied to eliminate the contribution of bound rubber. In the first approach the Hahn-echo decays were fitted with a theoretical relationship to obtain the average values of the (1)H residual second moment and correlation time <τ(c)>. For the mobile EPDM segments the power-law distribution of correlation function was compared to the exponential correlation function and found inadequate in the long-time regime. In the second approach a log-Gauss distribution for the correlation time was assumed. Furthermore, using an averaged value of the correlation time, the distributions of the residual second moment were determined using an inverse Laplace transform for the entire series of measured samples. The unfilled EPDM sample shows a bimodal distribution of residual second moments, which can be associated to the mobile polymer sub-chains (M(2) ≅ 6.1 rad (2) s(-2)) and the second one associated to the dangling chains M(2) ≅ 5.4 rad(2) s(-2)). By restraining the mobility of bound rubber, the carbon-black fillers induce diversity in the segmental dynamics like the apparition of a distinct mobile component and changes in the distribution of mobile and free-end polymer segments.

Distributions of transverse relaxation times for soft-solids measured in strongly inhomogeneous magnetic fields.

The single-sided NMR-MOUSE sensor that operates in highly inhomogeneous magnetic fields is used to record a CPMG (1)H transverse relaxation decay by CPMG echo trains for a series of cross-linked natural rubber samples. Effective transverse relaxation rates 1/T(2,short) and 1/T(2,long) were determined by a bi-exponential fit. A linear dependence of transverse relaxation rates on cross-link density is observed for medium to large values of cross-link density. As an alternative to multi-exponential fits the possibility to analyze the dynamics of soft polymer network in terms of multi-exponential decays via the inverse Laplace transformation was studied. The transient regime and the effect of the T(1)/T(2) ratio in inhomogeneous static and radiofrequency magnetic fields on the CPMG decays were studied numerically using a dedicated C++ program to simulate the temporal and spatial dependence of the CPMG response. A correction factor T(2)/T(2,eff) is derived as a function of the T(1)/T(2) ratio from numerical simulations and compared with earlier results from two different well logging devices. High-resolution T(1)-T(2) correlations maps are obtained by two-dimensional Laplace inversion of CPMG detected saturation recovery curves. The T(1)-T(2) experimental correlations maps were corrected for the T(1)/T(2) effect using the derived T(2)/T(2,eff) correction factor.

Surface UV aging of elastomers investigated with microscopic resolution by single-sided NMR.

Depth profiles taken from the surface of UV irradiated natural rubber sheets have been measured with microscopic resolution using a Profile NMR-MOUSE. An NMR observable related to the sum of the spin echoes in the Carr-Purcell-Meiboom-Gill pulse sequence was used to characterize the cross-link density changes produced by the action of UV radiation in each sheet. The aging process was investigated as function of irradiation time and penetration depth. An exponential attenuation law with a space dependent absorption coefficient describes the change in the NMR observable with penetration depth. An Avrami model is used to describe the dependence of the absorption coefficient on the aging time. The method can be applied to investigate the effect of various aging agents on the surfaces of elastomers.

Study of order and dynamic processes in tendon by NMR and MRI.

Tendons are composed of a parallel arrangement of densely packed collagen fibrils that results in unique biomechanical properties of strength and flexibility. In the present review we discuss several advanced magnetic resonance spectroscopy (MRS) and imaging (MRI) techniques that have allowed us to better understand the biophysical properties of tendons and ligaments. The methods include multiple quantum and T(2) filtering combined with NMR and MRI techniques. It is shown in detail how these techniques can be used to extract a number of useful parameters: 1) the (1)H-(1)H and (1)H-(2)H dipolar interactions; 2) the proton exchange rates between water and collagen, and between water molecules; 3) the distribution of fibril orientations; and 4) the anisotropy of diffusion. It is shown that relaxation data as a function of angular dependence can be obtained in vivo using mobile NMR sensors. Finally, this article describes how double quantum filtered (DQF) MRI can be used to image and monitor the healing process in injured tendons.

Self-diffusion measurements by a mobile single-sided NMR sensor with improved magnetic field gradient.

A simple and fast method of measuring self-diffusion coefficients of protonated systems with a mobile single-sided NMR sensor is discussed. The NMR sensor uses a magnet geometry that generates a highly flat sensitive volume where a strong and highly uniform static magnetic field gradient is defined. Self-diffusion coefficients were measured by Hahn- and stimulated echoes detected in the presence of the uniform magnetic field gradient of the static field. To improve the sensitivity of these experiments, a Carr-Purcell-Meiboom-Gill pulse sequence was applied after the main diffusion-encoding period. By adding the echo train the experimental time was strongly shortened, allowing the measurement of complete diffusion curves in less than 1min. This method has been tested by measuring the self-diffusion coefficients D of various organic solvents and poly(dimethylsiloxane) samples with different molar masses. Diffusion coefficients were also measured for n-hexane absorbed at saturation in natural rubber with different cross-link densities. The results show a dependence on the concentration that is in good agreement with the theoretical prediction. Moreover, the stimulated-echo sequence was successfully used to measure the diffusion coefficient as a function of the evolution time in systems with restricted diffusion. This type of experiment proves the pore geometry and gives access to the surface-to-volume ratio. It was applied to measure the diffusion of water in sandstones and sheep Achilles tendon. Thanks to the strong static gradient G(0), all diffusion coefficients could be measured without having to account for relaxation during the pulse sequence.

Self-diffusion anisotropy of water in sheep Achilles tendon.

The principal values of the diffusion tensor of free water in the pores of sheep Achilles tendon were determined. For this purpose, the azimuthally angular dependence of the self-diffusion coefficient was measured using a radiofrequency tilt coil and pulsed-field-gradient stimulated-echo (PFGSE) NMR. Combining the PFGSE with multiple acquisitions of Hahn echoes using the Carr-Purcell-Meiboom-Gill pulse sequence reduced the measuring time. The diffusion measurements revealed two diffusion process characterized by a fast and a slow effective diffusion coefficient. A model which describes the stimulated-echo amplitude, encoded by the water diffusion and magnetization transfer, was used for evaluation of the fast diffusion coefficients. The fast diffusion process characterizes the water molecules in pores surrounding the collagen fibrils. The diffusion coefficients characterizing the fast process show a well-defined anisotropy. The principal values of the diffusion tensors were determined assuming the elongated pores to be oriented parallel to the tendon fibrils and thus the orientation distribution function of the pores followed that of the collagen fibrils. The average aspect ratio of pores was estimated from the principal values of the water diffusion tensor and is suitable to characterize quantitatively the changes in tendon morphology due to healing or aging. The methods in this investigation can also be applied to measurements of the diffusion anisotropy using ex situ NMR sensors.

Molecular dynamic heterogeneity of confined lipid films by 1H magnetization-exchange nuclear magnetic resonance.

The molecular dynamic heterogeneity of monolayer to submonolayer thin lecithin films confined to submicron cylindrical pores were investigated by 1H magnetization exchange nuclear magnetic resonance. In this experiment a z-magnetization gradient was generated by a double-quantum dipolar filter. The magnetization-exchange decay and buildup curves were interpreted with the help of a theoretical model based on the approximation of a one-dimensional spin-diffusion process in a three-domain morphology. The dynamic heterogeneity of the fatty acid chains and the effects of the surface area per molecule, the diameter of the pores, and the temperature were characterized with the help of local spin-diffusion coefficients. The effect of various parameters on the molecular dynamics of the mobile region of the fatty acid chains was quantified by introducing an ad hoc Gaussian distribution function of the 1H residual dipolar couplings. For the lipid films investigated in this study, the surface induced order and the geometrical confinement affect the chain dynamics of the entire molecule. Therefore, each part of the chain independently reflects the effect of surface coverage, pore size, and temperature.

Multispin moments edited by multiple-quantum NMR: application to elastomers.

The spin system response to the five-pulse sequence used for measurements of double-quantum and triple-quantum buildup curves is evaluated in the initial excitation/reconversion regime. The multispin dipolar network that is present also in many soft solids like elastomers was considered. It is proved rigorously that the relevant quantity for analysis of double-quantum build-up curves in the initial regime is the second van Vleck moment. The higher-order moments edited by double-quantum as well as higher-order coherences in the multiple-quantum build-up experiments are different from van Vleck moments. These results can be applied to compare (1)H residual moments edited by double-quantum and triple-quantum experiments with those measured by other NMR methods. The sensitivity of multiple-quantum coherences to the changes in the values of residual dipolar couplings for cross-linked natural rubber under uniaxial elongation is also discussed. Under such conditions (1)H second van Vleck moments were measured for different elongation ratios of a cross-linked natural rubber. Moreover, (1)H triple-quantum edited moments were also measured for the same sample under uniaxial compression. The dependence of the second van Vleck moment and the time of the maximum of the double-quantum buildup curve on the cross-link density of natural rubber measured at low magnetic field was also investigated.

Complex morphology of melt-spun nylon-6 fibres investigated by 1H double-quantum-filtered NMR spin-diffusion experiments.

The complex morphology of high-speed melt-spun nylon-6 fibres hydrated with D2O was investigated using 1H double-quantum-filtered spin-diffusion NMR experiments. The magnetisation exchange from selected crystalline domains along the fibrils and interfibrils was simulated with the help of a three-dimensional solution of a spin-diffusion equation approximated by a product of one-dimensional analytical NMR signals, which correspond to a lamellar morphology. This allows to measure the sizes of crystalline and less-mobile amorphous domains along the fibrils, as well as the diameter of the fibrils and interfibril distances. A series of nylon-6 fibres with extreme values of winding speed and draw ratio was investigated. The changes detected in the domain size along the fibrils and interfibrils show the same trend in the data obtained from wide-angle X-ray diffraction and small-angle X-ray scattering.

Enhanced sensitivity to residual dipolar couplings of elastomers by higher-order multiple-quantum NMR.

The homonuclear and heteronuclear residual dipolar couplings in elastomers reflect changes in the cross-link density, temperature, the uniaxial and biaxial extension or compression as well as the presence of penetrant molecules. It is shown theoretically that for an isolated methyl group the relative changes in the intensity of the homonuclear double-quantum buildup curves in the initial time regime due to variation of the residual dipolar coupling strength is less sensitive than the changes in the triple-quantum filtered NMR signal when considering the same excitation/reconversion time. For a quadrupolar nucleus with spin I=2 the sensitivity enhancement was simulated for four-quantum, triple-quantum, and double-quantum buildup curves. In this case the four-quantum build-up curve shows the highest sensitivity to changes of spin couplings. This enhanced sensitivity to the residual dipolar couplings was tested experimentally by measuring 1H double-quantum, triple-quantum, and four-quantum buildup curves of differently cross-linked natural rubber samples. In the initial excitation/reconversion time regime, where the residual dipolar couplings can be measured model free, the relative changes in the intensity of the four-quantum buildup curves are about five times higher than those of the double-quantum coherences. For the first time proton four-quantum coherences were recorded for cross-linked elastomers.

Order parameters of the orientation distribution of collagen fibers in Achilles tendon by 1H NMR of multipolar spin states.

The angular distribution function of collagen fibrils in a sheep Achilles tendon was investigated by (1)H NMR of multipolar spin states represented by dipolar-encoded longitudinal magnetization and double-quantum filtered signals. For the first time the angular distribution function based on the Legendre moment expansion is used. Order parameters were obtained from the anisotropy of (1)H residual dipolar couplings of bond water, which were determined model-free from the excitation efficiency of the multipolar spin states and from double-quantum filtered line splitting. The orientation distribution function of collagen fibrils in Achilles tendon measured from the anisotropy of the residual dipolar couplings is characterized by the average values of beta0 = 1.8+/-0.2 degrees and order parameters [P2] = 0.93+/-0.04, [P4] = 0.78+/-0.04 and [P6] = 0.58+/-0.04. The order of many biological tissues in the presence of ageing, injuries or regeneration can be quantified by the order parameters of the angular distribution function.

Parameter maps of 1H residual dipolar couplings in tendon under mechanical load.

Proton multipolar spin states associated with dipolar encoded longitudinal magnetization (DELM) and double-quantum (DQ) coherences of bound water are investigated for bovine and sheep Achilles tendon under mechanical load. DELM decay curves and DQ buildup and decay curves reveal changes of the 1H residual dipolar couplings for tendon at rest and under local compression forces. The multipolar spin states are used to design dipolar contrast filters for NMR 1H images of heterogeneous tendon. Heterogeneities in tendon samples were artificially generated by local compression parallel and perpendicular to the tendon plug axis. Quotient images obtained from DQ-filtered images by matched and mismatched excitation/reconversion periods are encoded only by the residual dipolar couplings. Semi-quantitative parameter maps of the residual dipolar couplings of bound water were obtained from these quotient images using a reference elastomer sample. This method can be used to quantify NMR imaging of injured ordered tissues.

Self-diffusion measurements by a constant-relaxation method in strongly inhomogeneous magnetic fields.

The simple pulse sequence thetax-tau1-2thetay-tau1+tau2-2thetay-tau2-Hahn echo used to measure the self-diffusion coefficient D under constant-relaxation condition, i.e., for tau1+tau2=const. was investigated in the presence of strongly inhomogeneous static as well as radiofrequency magnetic fields. The encoding of the Hahn-echo amplitude by the pulse flip angle and diffusion was evaluated by taking into account the spatial distribution of the off-resonance field, the strength and orientation of the local field gradients, and the pulse flip angles by a computer simulation program. As input files, this program uses maps of static and radiofrequency fields, and the D coefficient can be evaluated from the time dependence of the Hahn-echo amplitude. The method was applied to a mobile one-sided NMR sensor, NMR-MOUSE with a bar magnet by measuring D for a series of liquids with different viscosities. The method was shown to be particularly useful for measuring D of solvents in elastomers without the need for measurements of the transverse relaxation rates. The self-diffusion coefficient of toluene in a series of crosslinked natural rubber samples was measured and correlated with the crosslink density. Finally, the method was applied to measure the diffusion anisotropy of free water in bovine Achilles tendon.

Domain sizes in heterogeneous polymers by spin diffusion using single-quantum and double-quantum dipolar filters.

1H spin-diffusion experiments employing a double-quantum (DQ) dipolar filter were performed for the characterization of the microdomain structure of heterogeneous samples. For this purpose the NMR spin-diffusion process was analysed based on a model morphology of three different domains with arbitrary sizes, diffusivities, and filter efficiency. General analytical solutions for z magnetization source and sink were obtained valid for a one-dimensional lamellar morphology in the full range of spin-diffusion times. These solutions of the spin-diffusion equations were used for determining the crystalline, interface, and amorphous domain sizes in polystyrene-poly(ethylene oxide) (PS-PEO) and poly(hydroxyethylmethacrylate)-poly(ethylene oxide) (PHEMA-PEO). The DQ dipolar filter has a good efficiency for PS-PEO but is only partially efficient in filtering the signal of the mobile domains in the PHEMA-PEO diblock copolymer. The domain sizes measured by the DQ filter method are compared to those obtained using the traditional dipolar filter creating z magnetization in the mobile domains.

Anisotropy of collagen fiber orientation in sheep tendon by 1H double-quantum-filtered NMR signals.

The anisotropy of the angular distribution of collagen fibrils in a sheep tendon was investigated by 1H double-quantum (DQ) filtered NMR signals. Double-quantum build-up curves generated by the five-pulse sequence were measured for different angles between the direction of the static magnetic field and the axis of the tendon plug. Proton residual dipolar couplings determined from the DQ build-up curves in the initial excitation/reconversion time regime which mainly represent the bound water are interpreted in terms of a model of spin-1/2 pairs with their internuclear axes oriented on average along the fibril direction in the presence of proton exchange. The angular distribution of collagen fibrils around the symmetry axis of the tendon measured by the anisotropy of the residual dipolar couplings was described by a Gaussian function with a standard deviation of 12 degrees +/-1 degrees and with the center of the distribution at 4 degrees +/-1 degrees. The existence of this distribution is directly reflected in the finite value of the residual dipolar couplings at the magic angle, the value of the angular contrast, and the oscillatory behavior of the DQ build-up curves. The 1H residual dipolar couplings were also measured from the doublets recorded by the DQ-filtered signals. From the angular dependence of the normalized splitting the angular distribution of the collagen fibrils was evaluated using a Gaussian function with a standard deviation of 19 degrees +/-1 degrees and with the center of distribution at 2 degrees +/-1 degrees. The advantages and disadvantages of these approaches are discussed.

Solid-state NMR spectroscopy under periodic modulation by fast magic-angle sample spinning and pulses: a review.

Fast magic-angle spinning (MAS) holds promise for new approaches to pulsed high-resolution NMR in solids where homogeneous interactions dominate. Prerequisite for developing new pulse methods is the understanding of signal encoding by spin interactions under MAS conditions and of interferences between MAS and pulses. This review discusses corresponding strategies and techniques in a coherent way with particular concentration on homonuclear decoupling techniques for line-narrowing in solids.

Segmental anisotropy in strained elastomers detected with a portable NMR scanner.

Single-side NMR is particularly suitable for measurements of segmental anisotropy induced in elastomers by uniaxial forces or local strain. Proton transverse nuclear magnetic relaxation was investigated with the NMR-MOUSE by recording the Hahn-echo decay in cross-linked natural rubber bands. This provided information on the dependence of the Hahn-echo decay on the angle between the direction of the uniaxial stretching force and the axis Z defined direction perpendicular to the magnet pole faces of the NMR-scanner. The anisotropy effect on the Hahn-echo decay is correlated with the extension ratio, and it is more evident in the liquid-like regime of the decay. A weaker segmental anisotropy is detected by 1H solid- and Hahn-echo decays recorded by multi-pulse sequences. A qualitative understanding of the angular dependence is obtained by an analytical theory of the Hahn-echo decay adapted to the case of stretched elastomers and to strongly inhomogeneous magnetic fields. Using angular-dependent 1H residual second van Vleck moments and correlation times reported previously [P.T. Callaghan and E.T. Samulski, Macromolecules 30, 113 (1997)] from stretched natural rubber bands the segmental anisotropy measured in inhomogeneous magnetic fields by the Hahn-echo decay was numerically simulated. As an example of a macroscopic distribution of local segmental anisotropy, 1H Hahn-echo decays were measured by the NMR-MOUSE sensor in a stretched cross-linked natural rubber plate with a circular cut in the center.

NMR of multipolar spin states excitated in strongly inhomogeneous magnetic fields.

The possibility of exciting and filtering various multipolar spin states in proton NMR like dipolar encoded longitudinal magnetization (LM), double-quantum (DQ) coherences, and dipolar order (DO) in strongly inhomogeneous static and radio-frequency magnetic fields is investigated. For this purpose pulse sequences which label and manipulate the multipolar spin states in a specific way were implemented on the NMR-MOUSE (mobile universal surface explorer). The performance of the pulse sequences was also tested in homogeneous fields on a solid-state high-field NMR spectrometer. The theoretical justification of these procedures was shown for a rigid two-spin 1/2 system coupled by dipolar interactions. Dipolar encoded longitudinal magnetization decay curves, double-quantum and dipolar-order buildup curves, as well as double-quantum decay curves were recorded with the NMR-MOUSE for natural rubber samples with different crosslink density. The possibility of using these multipolar spin states for investigations of strained elastomers by NMR-MOUSE is also shown. These curves give access to quantitative values of the ratio of the total residual dipolar couplings of the protons in the series of samples which are in good agreement with those measured in homogeneous fields.