Biomedical subjects

D E Demco

Publications and source records attributed to D E Demco.

At least 19 recordsLinked to original sources

PubMed2006

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.

Achilles Tendon↗

PubMed2005

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.

Aluminum Oxide↗

PubMed2005

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.

Achilles Tendon↗

PubMed2005

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.

Journal Article↗

PubMed2004

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.

Caprolactam↗

PubMed2004

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.

Algorithms↗

PubMed2003

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.

Achilles Tendon↗

PubMed2003

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.

Journal Article↗

PubMed2003

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.

Achilles Tendon↗

PubMed2003

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.

Algorithms↗

PubMed2003

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.

Achilles Tendon↗

PubMed2002

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.

Magnetic Resonance Spectroscopy↗

PubMed2001

Double-quantum-filtered NMR signals in inhomogeneous magnetic fields.

The possibility of exciting and detecting proton NMR double-quantum coherences in inhomogeneous static and radiofrequency magnetic fields was investigated. For this purpose specialized pulse sequences which partially refocus the strongly inhomogeneous evolution of the spin system and generate double-quantum buildup and decay curves were implemented on the NMR MOUSE (mobile universal surface explorer). The theoretical justification of the method was developed for the simple two-spin-1/2 system. The performances of the same pulse sequences were also tested on a solid-state high-field NMR spectrometer. It was shown that DQ decay curves have a better signal-to-noise ratio in the initial time regime than DQ buildup curves. The double-quantum buildup and decay curves were recorded for a series of cross-linked natural rubber samples. These curves give access to quantitative values of the ratio of proton total residual dipolar couplings which are in good agreement with those measured in homogeneous fields. A linear dependence of these ratios on the sulfur-accelerator content was found.

Journal Article↗

PubMed2001

Dipolar and J encoded DQ MAS spectra under rotational resonance.

A two-dimensional (2D) double-quantum (DQ) experiment under rotational resonance (R(2)) conditions is introduced for evaluating dipolar couplings in rotating solids. The contributions from the R(2)-recoupled dipolar interaction and the J coupling can be conveniently separated in the resulting 2D R(2)-DQ spectrum, so that the unknown dipolar coupling can readily be extracted, provided that the values of the involved J coupling constants are known. Since the measured parameters are integral intensity ratios between suitably chosen absorption peaks in the 2D spectrum, the proposed method is characterized by a reduced sensitivity to relaxation parameters. The effect of rotor-modulated terms, including chemical shift anisotropy, is efficiently averaged out by synchronizing the excitation/reconversion time with the rotor period. All of these features are demonstrated theoretically by the example of two model systems, namely, isolated spin-pairs and a three-spin system. The results of the theoretical models are applied to both (13)C and (1)H nuclei to extract dipolar couplings in uniformly (13)C labeled L-alanine and a crosslinked natural rubber.

Journal Article↗

PubMed1999

Heteronuclear double-quantum MAS NMR spectroscopy in dipolar solids.

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

Magnetic Resonance Spectroscopy↗

PubMed1999

1H NMR imaging of residual dipolar couplings in cross-linked elastomers: dipolar-encoded longitudinal magnetization, double-quantum, and triple-quantum filters.

Contrastfilters for NMR imaging of residual 1H dipolar couplings of elastomers are introduced based on dipolar-encoded longitudinal magnetization, as well as double- and triple-quantum coherences. The spin response is discussed in the initial excitation time regime for methylene, methyl, and methine protons applicable to poly(isoprene) and other elastomers, taking into account the hierarchy of dipolar couplings and the associated editing features of multiple-quantum experiments. The efficiency of these filters is investigated for a series of cross-linked poly(isoprene) samples. Spatially resolved dipolar-encoded longitudinal magnetization decays and double-quantum and triple-quantum buildup curves are presented for a phantom made of poly(isoprene) with different cross-link densities. Two-dimensional images representing residual dipolar couplings are presented using dipolar-encoded longitudinal magnetization, double-quantum, and triple-quantum contrast filters. Images from dipolar-encoded longitudinal magnetization and triple-quantum coherences show the highest resolution and contrast, respectively.

Algorithms↗

PubMed1999

Proton residual dipolar couplings by NMR magnetization exchange in cross-linked elastomers: determination and imaging.

Proton nuclear magnetic resonance (NMR) magnetization exchange is used to investigate residual dipolar couplings in a series of cross-linked poly(styrene-cobutadiene) elastomers. A new model for the dipolar unit is used for the evaluation of the signal decay in magnetization exchange experiments. It takes into account an extended residual dipolar coupling network along the polymer chain. It is shown that in the regime of short mixing times, information about the residual dipolar coupling between methine and methylene protons can be obtained which is not affected by other inter- and intramolecular dipolar couplings. The dynamic order parameter of methine-methylene protons is measured and correlated with cross-link density. This study certifies the quality of a filter for magnetization from residual dipolar couplings which exploit magnetization exchange. The filter can be used to generate contrast in NMR images of heterogeneous elastomers. The first proton NMR parameter image of a dynamic order parameter is presented for a phantom made from poly(styrene-cobutadiene) samples with different cross-link densities.

Algorithms↗

PubMed1998

Resolution enhancement in multiple-quantum MAS NMR spectroscopy.

Two techniques for resolution and sensitivity enhancement are introduced in multiple-quantum (MQ) MAS spectroscopy of rigid solids. The first makes use of ultrafast MAS with spinning frequencies of up to 35 kHz, while the second combines MAS at moderately fast spinning frequencies of about 13 kHz with multiple-pulse (MP) dipolar decoupling. For the latter approach, a semiwindowless WHH-4 sequence is applied during the MQ evolution period (MQ dimension) and/or detection period (single-quantum dimension). In the MQ dimension, the MP sequence has to be supplemented by two bracketing pulses in order to preserve the order and the intensities of the evolving MQ coherences. Double-quantum 1H NMR spectra of l-alanine recorded using both decoupling techniques are shown and compared to each other. Triple-quantum 1H NMR spectra under ultrafast MAS conditions are also presented.

Alanine↗