Validity of NMR pore-size analysis of cultural heritage ancient building materials containing magnetic impurities.

NMR relaxation time distributions, obtained with laboratory and portable devices, are utilized to characterize the pore-size distributions of building materials coming from the Roman remains of the Greek-Roman Theatre of Taormina. To validate the interpretation of relaxation data in terms of pore-size distribution, comparison of results from standard and in situ NMR experiments with results of the mercury intrusion porosimetry (MIP) has been made. Although the pore-size distributions can be obtained by NMR in terms of either longitudinal (T(1)) or transverse (T(2)) relaxation times distributions, the shorter duration of the T(2) measurement makes it, in principle, preferable, although the determination of T(2) distributions is not necessarily an easy alternative to finding T(1) distributions. Among other things, the T(1) distribution is almost independent of the inhomogeneity of the magnetic field, while the T(2) distribution is strongly influenced by it. This paper was aimed at answering two questions: what are the validity limits to interpret NMR data in terms of pore-size distributions and whether the portable device can successfully be applied as a non-destructive and non-invasive tool for in situ NMR analysis of building materials, particularly those of Cultural Heritage interest.

Water absorption kinetics in different wettability conditions studied at pore and sample scales in porous media by NMR with portable single-sided and laboratory imaging devices.

NMR relaxation time distributions of water (1)H obtained by a portable single-sided surface device have been compared with MRI internal images obtained with a laboratory imaging apparatus on the same biocalcarenite (Lecce Stone) samples during capillary water uptake. The aim of this work was to check the ability of NMR methods to quantitatively follow the absorption phenomenon under different wettability conditions of the internal pore surfaces. Stone wettability changes were obtained by capillary absorption of a chloroform solution of Paraloid PB72, a hydrophobic acrylic resin frequently used to protect monuments and buildings, through one face of each sample. Both relaxation and imaging data have been found in good quantitative agreement each other and with masses of water determined by weighing the samples. In particular the Washburn model of water capillary rise applied to the imaging data allowed us to quantify the sorptivity in both treated and untreated samples. Combining relaxation and imaging data, a synergetic improvement of our understanding of the water absorption kinetics at both pore and sample scales is obtained. Since relaxation data have been taken over the course of time without interrupting the absorption process, simply by keeping the portable device on the surface opposite to the absorption, the results show that the single-sided NMR technique is a powerful tool for in situ evaluation of water-repellent treatments frequently used for consolidation and/or protection of stone artifacts.

The role of water coordination in binary mixtures. A study of two model amphiphilic molecules in aqueous solutions by molecular dynamics and NMR.

Two binary aqueous mixtures which contain the small amphiphilic molecules TMAO (trimethylamine-N-oxide) and TBA (tert-butyl alcohol) have been investigated by molecular dynamics simulations and NMR chemical shift and self-diffusion measurements. TMAO is an osmolyte, while TBA is a monohydrate alcohol. Both possess bulky hydrophobic groups and polar heads, namely, NO in TMAO and OH in TBA. The hydrophilic/hydrophobic content of these isosteric molecules strongly modulates the structure and dynamics of the hydration shell, which is thought to be responsible for the effects observed on proteins and phospholipids. Simulation results, especially on hydrogen-bond networking, spatial correlations, and self-diffusivity, are consistent with NMR data and agree well with previous numerical studies on similar solutions. The methods employed allow the elucidation of the microscopic features of the solutions. For TBA solutions, the hydration shell is found to have a low density and a large spatial spread, and thus, above the molar fraction of 0.03, reduction of hydrophobic hydration drives self-aggregation of the solute. This effect does not take place in TMAO solutions, where the hydration shell is more compact and stable, maintaining its structure over a wider range of solute concentrations.

Determination of moisture fraction in wood by mobile NMR device.

A mobile NMR probe has been used as a non-destructive and non-invasive tool for water content analysis on wood samples. The porosity index, express as the fraction of the sensitivity volume of the probe occupied by water, is here proposed as an alternative to the moisture content index, namely the amount of water mass with respect to the mass of dried sample. In principle the method can be applied to any kind of porous media that has not detectable proton signal from the rigid matrix as, for instance, in building materials. In wood, where proton signal can be detected also from cellulose and others macromolecular components, some considerations and artifices are here proposed for eliminating this contribution. The method has allowed performing moisture volume fraction analysis on wood samples characterized by different wood species, cutting and moisture contents. The NMR data of moisture detection as volume fraction have successfully been compared with those obtained by the gravimetric method.

A low-resolution non-invasive NMR characterization of ancient paper.

The use of a portable NMR device allows a non-invasive investigation of the paper in order to assess the state of conservation of books and documents of historical or artistic interest. The NMR investigation has been found mainly on relaxation measurements whose results seem compatible with different relaxation rates in crystalline and amorphous cellulose domains. By a simplified physical picture based on spin-diffusion it appears possible to detect the alteration of the crystalline/amorphous cellulose balance and therefore to get information on some deterioration processes of paper. The use of a portable NMR device shows great potentiality because of its safe and simple in situ approach to Cultural Heritage documents. In this work, we present a research carried out on a 17th century manuscript.

Self-diffusion coefficient by single-sided NMR.

It is presented a novel method for the measure of the self-diffusion coefficient. The method exploits the fixed gradient of an open magnet, as that used in single-sided NMR, and it does not use prior information on T(2). The approach presented in this paper can be practiced also on the fringe field of superconducting magnets and it is based on the construction of the ratios between echoes taken at different interpulses separation in a Carr-Purcell-Meiboom-Gill pulse sequence. The determination of the self-diffusion coefficient facilitates the estimate of T(2) because the transverse relaxation results almost influenced by the molecular diffusion effect, also at the shorter interpulses time, when it is measured in field strongly inhomogeneous.

Spin interaction filter in solid-state NMR Imaging.

In the tilted rotating frame (TRF), the transverse relaxation time T(2rho) depends strongly on the orientation of TRF with respect to the usual rotating frame. In the spin space, the relative orientation of the two reference frames modifies the contribution of various spin interactions to T(2rho) relaxation. Since the orientation of the frames and, to some extent, the role of the spin Hamiltonians in TRF are controllable experimentally, the T(2rho) relaxation can be made sensitive to molecular mechanisms related to the selected spin interaction. In this paper, the realization of a contrast Hamiltonian-dependent in solid-state NMR Imaging is proved. The solid-state imaging approach is based on the magic angle in the rotating frame. Some results on simple solid polymers are presented.

Proton MRI of (13)C distribution by J and chemical shift editing.

The sensitivity of (13)C NMR imaging can be considerably favored by detecting the (1)H nuclei bound to (13)C nuclei via scalar J-interaction (X-filter). However, the J-editing approaches have difficulty in discriminating between compounds with similar J-constant as, for example, different glucose metabolites. In such cases, it is almost impossible to get J-edited images of a single-compound distribution, since the various molecules are distinguishable only via their chemical shift. In a recent application of J-editing to high-resolution spectroscopy, it has been shown that a more efficient chemical selectivity could be obtained by utilizing the larger chemical shift range of (13)C. This has been made by introducing frequency-selective (13)C pulses that allow a great capability of indirect chemical separation. Here a double-resonance imaging approach is proposed, based on both J-editing and (13)C chemical shift editing, which achieves a powerful chemical selectivity and is able to produce full maps of specific chemical compounds. Results are presented on a multicompartments sample containing solutions of glucose and lactic and glutamic acid in water.

In vivo detection of 13C-enriched glucose metabolites in mouse brain by T-SEDOR imaging.

Protons J-coupled to 13C were selectively detected in the mouse head by in vivo 1H NMR imaging based on Twin Spin Echo DOuble Resonance (T-SEDOR) excitation. This pulse sequence combines a good chemical specificity with high sensitivity, requires no solvent pre-saturation and is well adapted to the imaging modality. 1H T-SEDOR maps of the mouse head allowed detection of areas of preferential accumulation of 13C-enriched compounds, upon repeated injections of uniformly 13C-labelled glucose, which induced hyperglycemia. The results demonstrated the feasibility, both in time scale and metabolite concentration, of applying T-SEDOR MRI for in vivo mapping brain areas characterized by enhanced rates of glucose uptake and/or accumulation of its metabolites.

Double-resonance J-edited (1)H-NMR detection of 6-(13)C-D-2-deoxyglucose uptake in glioma cells.

The C6 methylene protons were selectively detected in (1)H-NMR spectra of intact glioma cells incubated with 6-(13)C-D-2-deoxyglucose (6-(13)C-2dG), a (13)C-enriched glucose analog that is suitable for monitoring glucose utilization in brain tumors. Spectral editing via (1)H-(13)C scalar coupling was performed with twin spin-echo double resonance (T-SEDOR), a pulse sequence which combines chemical specificity and high sensitivity, requires no solvent pre-saturation, and can easily be adapted to imaging protocols. This work demonstrates the suitability of the pulse sequence for monitoring 6-(13)C-2dG uptake in living cells in vitro, in spite of line-broadening and the occurrence of other strong signals in the spectral region of interest (3.5-4.4 ppm).

The spin coherence relaxation in the rotating frame as a microscopy parameter for strongly coupled spin systems.

The transverse relaxation time in the rotating frame T2rho is proposed as an effective parameter to get specific contrast in solid state imaging. Several peculiarities make T2rho an interesting candidate to map dynamics and structure in solids: the effect of the secular spin interaction can be controlled by the experimenter and therefore the relaxation associated with the nonsecular terms, which is particularly sensitive to very slow dynamics, can be observed. In this paper we present preliminary results obtained on polymers and prove the capability of the MARF Imaging, enhanced by a filter based on rotary echo refocusing, to produce images of solids contrasted by T2rho.

13C imaging by double resonance scalar-coupling editing.

The two-dimensional FT Imaging of 13C-glucose obtained with twin spin-echo double resonance sequence is presented. The images have been obtained by a doubly tuned surface coil on samples containing water and 13C-enriched glucose in water. It is shown, both theoretically and experimentally, that the whole editing capability of the twin spin-echo double resonance imaging sequence is also preserved in the presence of the radiofrequency field inhomogeneity produced by the surface coil. As in an efficient selective irradiation method, the enhancement in the signal-to-noise ratio with respect to the direct 13C detection, depends on the number of protons J-coupled to 13C.

T1rho space dependence in rigid polymers by effective radio frequency gradient.

An extension of the solid-state nuclear magnetic resonance (NMR) imaging based on magic angle in the rotating frame (MARF) line narrowing approach is presented. The modified magic angle in the rotating frame imaging sequence is able to yield T1rho maps of large band polymers with remarkable contrast sensitivity and without contrast parameter alteration referable to the narrowing procedure. This last feature is examined closely in order to outline the actual effectiveness of the method. Further experimental details, especially regarding probe coil design, recently improved, are discussed and some new results are presented.

Immiscible fluids permeability by T1 imaging.

Soil pollution by hydrocarbon compounds is an important part of the more general pollution problem. Some analogies with research problems encountered in studies of oil reservoirs in rocks suggested to us the opportunity to study the pollution dynamics by imaging the spatial distribution of the pollutant in a wet soil model by an NMR imaging technique. Some preliminary results using T1-weighted imaging are reported here.

Spin-lattice relaxation in murine tumors after in vivo treatment with interferon alpha/beta or tumor necrosis factor alpha.

1H NMR spin-lattice relaxation times (T1) were measured in vitro and in vivo in Friend leukemia cell tumors during subcutaneous tumor growth in syngeneic mice and after in vivo administration of either purified murine interferon alpha/beta (IFN) or recombinant tumor necrosis factor alpha (TNF). Untreated tumors exhibited monoexponential T1 relaxation independently of tumor age at least until Day 16 after implantation. Histological examinations showed that under these conditions tumors were highly homogeneous and substantially free of necrotic areas. Peritumoral administrations of either IFN or TNF did not significantly alter the tumor relaxation properties at early stages of inhibition of tumor growth. The longitudinal relaxation decay became instead clearly biexponential at later stages (more than 7 days of IFN treatment or 2 days after TNF administration). While the T1 relaxation behavior could be unequivocally correlated with the presence of necrotic areas in these tumors, it could not be considered as an early marker of the altered growth capability, induced by administration of either IFN or TNF.

Modified crossed-ellipse radiofrequency coil for MRI.

New coil geometries obtained by computer simulations from the crossed-ellipse rf coil are reported. These geometries with elliptical transverse section improve the signal-to-noise ratio with respect to the classic ellipse and saddle coils. The increase of signal-to-noise ratio is mainly due to the reduction of coil losses and to the better B1 efficiency and distribution.