Non-invasive spatial tissue discrimination in ancient mummies and bones in situ by portable nuclear magnetic resonance

Rühli, Frank J; Böni, Thomas; Perlo, Juan; Casanova, Federico; Baias, Maria; Egarter, Eduard; Blümich, Bernhard

doi:10.1016/j.culher.2007.03.002

Cited by 54 publications

(34 citation statements)

References 14 publications

Supporting

Mentioning

Contrasting

Unclassified

Order By: Relevance

“…Indeed, 23 Na is a spin 3/2 quadrupolar nucleus of 100% natural abundance, and many 23 Na solid state NMR studies of inorganic materials have been reported. 51 In addition, 23 Na MRI has been used to analyse the structure of biological tissues like mummified bone and cartilage, 61,62 and it has recently been shown that the local environment of sodium in synthetic carbonated apatites can be studied by 23 Na solid state NMR. 63 In 2005, in a review on ''Solid State NMR Studies of Bone'', 24 Kolodziejski concluded that ''quadrupolar nuclei like 23 Na and…”

Section: àmentioning

confidence: 99%

Probing the calcium and sodium local environment in bones and teeth using multinuclear solid state NMR and X-ray absorption spectroscopy

Laurencin

Wong

Chrzanowski

et al. 2010

Phys. Chem. Chem. Phys.

110

View full text Add to dashboard Cite

International audienceDespite the numerous studies of bone mineral, there are still many questions regarding the exact structure and composition of the mineral phase, and how the mineral crystals become organised with respect to each other and the collagen matrix. Bone mineral is commonly formulated as hydroxyapatite, albeit with numerous substitutions, and has previously been studied by 31P and 1H NMR, which has given considerable insight into the complexity of the mineral structure. However, to date, there has been no report of an NMR investigation of the other major component of bone mineral, calcium, nor of common minority cations like sodium. Here, direct analysis of the local environment of calcium in two biological apatites, equine bone (HB) and bovine tooth (CT), was carried out using both 43Ca solid state NMR and Ca K-edge X-ray absorption spectroscopy, revealing important structural information about the calcium coordination shell. The 43Ca diso in HB and CT is found to correlate with the average Ca–O bond distance measured by Ca K-edge EXAFS, and the 43Ca NMR linewidths show that there is a greater distribution in chemical bonding around calcium in HB and CT, compared to synthetic apatites. In the case of sodium, 23Na MAS NMR, high resolution 3Q-MAS NMR, as well as 23Na{31P} REDOR and 1H{23Na} R3-HMQC correlation experiments give the first direct evidence that some sodium is located inside the apatite phase in HB and CT, but with a greater distribution of environments compared to a synthetic sodium substituted apatite (Na-HA)

show abstract

Section: àmentioning

confidence: 99%

Probing the calcium and sodium local environment in bones and teeth using multinuclear solid state NMR and X-ray absorption spectroscopy

Laurencin

Wong

Chrzanowski

et al. 2010

Phys. Chem. Chem. Phys.

110

View full text Add to dashboard Cite

show abstract

“…This sequence offers a solution to the long-standing problem of MR imaging of solids (2). In addition to biomedical applications, this approach may be applied to the study of geological samples (29), archaeological artifacts (30,31), and granular physics (32,33), to name but a few examples. Very generally, quadratic echo imaging represents the ultimate limit of Hamiltonian design: The entire internal Hamiltonian is removed, and the desired external Hamiltonian is added to drive the coherent evolution of a quantum system.…”

Section: Discussionmentioning

confidence: 99%

Phosphorus-31 MRI of hard and soft solids using quadratic echo line-narrowing

Frey

Michaud

VanHouten

et al. 2012

Proc. Natl. Acad. Sci. U.S.A.

View full text Add to dashboard Cite

Magnetic resonance imaging (MRI) of solids is rarely attempted. One of the main reasons is that the broader MR linewidths, compared to the narrow resonance of the hydrogen ( 1 H) in free water, limit both the attainable spatial resolution and the signal-to-noise ratio. Basic physics research, stimulated by the quest to build a quantum computer, gave rise to a unique MR pulse sequence that offers a solution to this long-standing problem. The "quadratic echo" significantly narrows the broad MR spectrum of solids. Applying field gradients in sync with this line-narrowing sequence offers a fresh approach to carry out MRI of hard and soft solids with high spatial resolution and with a wide range of potential uses. Here we demonstrate that this method can be used to carry out three-dimensional MRI of the phosphorus ( 31 P) in ex vivo bone and soft tissue samples.bone mineral | cell membranes M agnetic resonance imaging (MRI) has become an invaluable tool for clinical medicine, fundamental biomedical research, the physical sciences, and engineering (1). Typically, MRI detects only the signal from free water, using just a single nuclear isotope ( 1 H). Extending the reach of MRI to the study of other elements, and to hard or soft solids, opens new frontiers of discovery. One example is phosphorus ( 31 P), which is abundant in both bone mineral and cell membranes, so 31 P MRI of tissues is, in principle, possible. In practice, however, the slower motion of 31 P in those environments (compared to 1 H in water) results in much broader MR spectra (Fig. S1), limiting both the attainable spatial resolution and the signal-to-noise ratio (2). In this paper, we describe the use of a pulse sequence to narrow the 31 P MR spectrum of solids to that of a liquid (3), making high-resolution imaging possible. This line-narrowing MR sequence was discovered in the course of basic research (3-6) initiated by Kane's proposal (7) to build a quantum computer using phosphorus spins in silicon. Applying field gradients in synch with this sequence, we have obtained high-resolution 3D MR images of the 31 P in a variety of ex vivo animal bone samples. This is a unique probe of a key element in bone mineral, which complements existing assessments of bone quality. Using the same approach, we have obtained 3D MR images of 31 P in several ex vivo soft tissues.Bone is a composite material (8), containing approximately 45% bone mineral by volume (9). Bone mineral is similar to calcium hydroxyapatite (i.e., Ca 10 ðOHÞ 2 ðPO 4 Þ 6 Þ, but it is less crystalline, and it has a unique stoichiometry (10). The spatial distribution, composition, and quantity of bone mineral are primarily responsible for the compressive strength and stiffness of bone (8-10). While a few 31 P MRI studies have successfully targeted in vivo (10-12) and ex vivo (10, 13, 14, 15) bone, the broad MR spectra have limited the achievable spatial resolution to no better than 0.5 mm (15) and more typically in the range of 2 mm. There is currently a great need to probe the internal compositi...

show abstract

“…Non-destructive, in situ, low-field unilateral nuclear magnetic resonance (NMR) has been successfully applied to assess the condition of objects of cultural significance when sampling was not possible. To date, several studies have been undertaken in order to evaluate the porosity, the detachment of paint, and salt efflorescence in wall paintings [30][31][32]; to determine the state of degradation of paper [33][34][35][36]; the followup on consolidation treatments of porous building materials and wall paintings [36][37][38][39][40]; to study of the absorption and diffusion of water in acrylic paint films [41]; and to characterize stains on paper supports [42]. Moreover, depth profiling using the NMR MOUSE Ò has been applied in the non-invasive spatial tissue discrimination in the ancient mummies and bones [26] and, more recently, to study of the stratigraphy of ancient wall paintings and mosaics [39,40].…”

Section: Characterization and Identification Of Protein-based Bindersmentioning

confidence: 99%

In Situ Unilateral 1H-NMR Studies of the Interaction Between Lead White Pigments and Collagen-Based Binders

et al. 2011

View full text Add to dashboard Cite

The lead white pigment, 2PbCO 3 ÁPb(OH) 2 , is thought to play a critical role in the degradation of paint in illuminated manuscripts. Cracking, flaking, and separation of paint films containing lead white on parchment and other works of art have been reported, and have been attributed to the interaction of the pigment with the binding media. A previous study by Fourier transform infrared spectroscopy showed lead white to induce a change in the state of hydration of protein-based binders, though the mechanism of this process is still not well understood. In this work, we apply in situ 1 H unilateral nuclear magnetic resonance (NMR) to explore the nature of the interaction between lead white and collagen-based binders while at the same time we evaluate the feasibility of applying unilateral 1 H-NMR to assess the condition of the paint in medieval-illuminated manuscripts and to follow up the effectiveness of consolidation treatments. Carr, Purcell, Meiboom, and Gill (CPMG) measurements reveal that the addition of lead white to binders derived from collagen, such as bone, rabbit skin or fish glues, increases the T 2eff relaxation constant of these binders. This effect is more pronounced at low relative humidity. The increase in T 2eff suggests that the pigment induces a change in the protein that leads

show abstract

Non-invasive spatial tissue discrimination in ancient mummies and bones in situ by portable nuclear magnetic resonance

Cited by 54 publications

References 14 publications

Probing the calcium and sodium local environment in bones and teeth using multinuclear solid state NMR and X-ray absorption spectroscopy

Probing the calcium and sodium local environment in bones and teeth using multinuclear solid state NMR and X-ray absorption spectroscopy

Phosphorus-31 MRI of hard and soft solids using quadratic echo line-narrowing

In Situ Unilateral 1H-NMR Studies of the Interaction Between Lead White Pigments and Collagen-Based Binders

Contact Info

Product

Resources

About