Temperature and hydration dependence of proton MAS NMR spectra in MCM-41: model based on motion induced chemical shift averaging.

The proton MAS NMR spectra in MCM-41 at low hydration levels (less than hydration amounting to one water molecule per surface hydroxyl group) show complex proton resonance peak structures, with hydroxyl proton resonances seen in dry MCM-41 disappearing as water is introduced into the pores and new peaks appearing, representing water and hydrated silanol groups. Surface hydroxyl group-water molecule chemical exchange and chemical shift averaging brought about by a water molecule visiting different surface hydrogen bonding sites have been proposed as possible causes for the observed spectral changes. In this report a simple model based on chemical shift averaging, due to the making and breaking of hydrogen bonds as water molecules move on the MCM-41 surface, is shown to fully reproduce the NMR spectra, both as a function of hydration and temperature. Surface proton-water proton chemical exchange is not required in this model at low hydration levels.

Hydration water dynamics in biopolymers from NMR relaxation in the rotating frame.

Assuming dipole-dipole interaction as the dominant relaxation mechanism of protons of water molecules adsorbed onto macromolecule (biopolymer) surfaces we have been able to model the dependences of relaxation rates on temperature and frequency. For adsorbed water molecules the correlation times are of the order of 10(-5)s, for which the dispersion region of spin-lattice relaxation rates in the rotating frame R(1)(ρ)=1/T(1)(ρ) appears over a range of easily accessible B(1) values. Measurements of T(1)(ρ) at constant temperature and different B(1) values then give the "dispersion profiles" for biopolymers. Fitting a theoretical relaxation model to these profiles allows for the estimation of correlation times. This way of obtaining the correlation time is easier and faster than approaches involving measurements of the temperature dependence of R(1)=1/T(1). The T(1)(ρ) dispersion approach, as a tool for molecular dynamics study, has been demonstrated for several hydrated biopolymer systems including crystalline cellulose, starch of different origins (potato, corn, oat, wheat), paper (modern, old) and lyophilized proteins (albumin, lysozyme).

¹H Nuclear Magnetic Resonance of Lodgepole Pine Wood Chips Affected by the Mountain Pine Beetle.

In this study, wood-water interactions of mountain pine beetle affected lodgepole pine were found to vary with time since death. Based on an analysis of magnetization components and spin-spin relaxation times from 1H NMR, it was determined that the mountain pine beetle attack does not affect the crystalline structure of the wood. Both the amorphous structure and the water components vary with time since death, which could be due to the fungi present after a mountain pine beetle attack, as well as the fact that wood from the grey-stage of attack cycles seasonally through adsorption and desorption in the stand.

Initial investigation on the use of MR spectroscopy and micro-MRI of GAFCHROMIC EBT radiotherapy film.

PURPOSE: This article presents an initial investigation of the efficacy of using 1H MRS and micro-MRI as analysis techniques for irradiated GAFCHROMIC EBT radiotherapy films. METHODS: GAFCHROMIC EBT radiotherapy film was irradiated with 6 MV x rays to known doses ranging from 5 to 1000 cGy. 24 h following irradiation 1H MRS measurements were performed to access the degree of post-irradiation polymer cross-linking. 2D 1H micro-MRI experiments were also performed for film irradiations of 0 and 300 cGy. RESULTS: Linear response of the 1H MRS linewidth to dose in the range from 0 to 400 cGy (R2 = 0.98) was observed. Such linearity is not seen when analyzed under conventional light analysis. The sensitivity of the film, as measured by the slope of the curve between 0 and 400 cGy, is 0.0042 +/- 0.0003 kHz/cGy, demonstrating the sensitivity of the 1H MRS technique used to analyze the film. The film saturates at a dose of approximately 900 cGy. Broadline 1H MRS provides a quantitative measure of the degree of polymerization of the film. CONCLUSIONS: A quantitative measurement of the degree of polymerization of GAFCHROMIC EBT film has been presented using 1H MRS. The saturation of the film at approximately 900 cGy is corroborated by that observed with light analysis. Further MR spectroscopic experiments are needed to investigate the response of the film to dose, allowing for a better understanding of the relationship between polymer cross-linking in the active layer.

Characterization of proteoglycan depletion in articular cartilage using two-dimensional time domain nuclear magnetic resonance.

In vitro proteoglycan (PG) depletion in the 20-40% range (enzymatic PG depletion of normal cartilage in the early osteoarthritis (OA) PG depletion range) was investigated in articular cartilage using 2D time domain NMR relaxation techniques. Spin-lattice relaxation times were measured at low fields (T(1rho)) and at high fields (T(1)) using nonselective and selective excitation pulse sequences. The short relaxation time magnetization components in T(1rho) ( approximately 8% signal) and nonselective T(1) ( approximately 5% signal) experiments were significantly altered with PG degradation. In addition, a magnetization component ( approximately 5% signal) with a "fast " T(1) approximately 7 ms was observed in the T(1) experiment involving selective excitation. This fast T(1) was at least 10 times shorter than the short T(1) in the nonselective experiment and was associated with a strong magnetization exchange mechanism between collagen and PG. The results suggest that T(1rho) and T(1) (nonselective and selective) relaxation based MRI techniques, which focus on the short relaxation time magnetization components, have the potential of detecting molecular abnormalities associated with early OA earlier than single, long relaxation time component approaches.