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Previous 31P cross-polarization and differential cross-polarization magic angle spinning (CP/MAS and DCP/MAS) solid-state NMR spectroscopy studies of native bone and of the isolated crystals of the calcified matrix synthesized by osteoblasts in cell culture identified and characterized the major PO4-3 phosphate components of the mineral phase. The isotropic and anisotropic chemical shift parameters of the minor HPO4-2 component in bone mineral and in mineral deposited in osteoblast cell cultures were found to differ significantly from those of brushite, octacalcium phosphate, and other synthetic calcium phosphates. However, because of in vivo and in vitro evidence that phosphoproteins may play a significant role in the nucleation of the solid mineral phase of calcium phosphate in bone and other vertebrate calcified tissues, the focus of the current solid-state 31P NMR experiments was to detect the possible presence of and characterize the phosphoryl groups of phosphoproteins in bone at the very earliest stages of bone mineralization, as well as the possible presence of calcium-phosphoprotein complexes. The present study demonstrates that by far the major phosphate components identified by solid-state 31P NMR in the very earliest stages of mineralization are protein phosphoryl groups which are not complexed with calcium. However, very small amounts of calcium-complexed protein phosphoryl groups as well as even smaller, trace amounts of apatite crystals were also present at the earliest phases of mineralization. These data support the hypothesis that phosphoproteins complexed with calcium play a significant role in the initiation of bone calcification. [ABSTRACT FROM AUTHOR]

Presents a study that investigated the demographic basis of differences in the size structure of coral reef fishes in the Great Barrier Reef in Queensland. Spatial analysis of the demographic patterns of Chlorurus sordidus and Scarus frenatus; Differences in the growth profile of the reef fishes; Assessment of the age structure of the reef fishes.

Background: The risk of femoral neck fracture progressively increases with age. However, the reasons behind this consistent increase in the fracture risk can't be completely justified by the decrease in the bone mineral density. The objective of this study was to analyze the correlation between various bone structural features and age., Study Design & Methods: A total of 29 consecutive patients who suffered an intracapsular hip fracture and underwent joint replacement surgery between May 2012 and March 2013 were included in this study. A 2 cm × 1 cm Ø cylindrical trabecular bone sample was collected from the femoral heads and preserved in formaldehyde. Bone mineral density (BMD), microarchitecture, organic content and crystallography were analyzed using a Dual-energy X-ray absorptiometry scan, micro-CT scan, and high resolution magic-angle-spinning-nuclear magnetic resonance (MAS-NMR), respectively. Statistical correlations were made using Spearman´s or Pearson´s correlation tests depending on the distribution of the continuous variables., Results: The mean patient age was 79.83 ± 9.31 years. A moderate negative correlation was observed between age and the hydrogen content in bone ( 1 H), which is an indirect estimate to quantify the organic matrix (r = -0.512, p = 0.005). No correlations were observed between BMD, trabecular number, trabecular thickness, phosphorous content, apatite crystal size, and age (r = 0.06, p = 0.755; r = -0.008, p = 0.967; r = -0.046, p = 0.812; r = -0.152, p = 0.430, respectively). A weak positive correlation was observed between Charlson´s comorbidity index (CCI) and c-axis of the hydroxiapatite (HA) crystals (r = -0.400, p = 0.035)., Conclusion: The femoral head relative protein content progressively decreases with age. BMD was not correlated with other structural bone parameters and age. Patients with higher comorbidity scores had larger HA crystals. The present results suggest that the progressive increase in the hip fracture risk in elderly patients could be partially explained by the lower bone protein content in this age group., Competing Interests: Declaration of Competing Interest All authors declare no conflict of interest in relation to the content of this study., (Copyright © 2020 Elsevier Ltd. All rights reserved.)

Objectives: Susceptibility artefacts from dental materials may compromise MRI diagnosis. However, little is known regarding MRI artefacts of dental material samples with the clinical shapes used in dentistry. The present phantom study aims to clarify how pulse sequences and sequence parameters affect MRI artefacts caused by metal-ceramic restorations., Methods: A phantom consisting of nickel-chromium metal-ceramic restorations (i.e. dental crowns and fixed bridges) and cylindrical reference specimens immersed in agar gel was imaged in 1.5 and 3.0 T MRI scanners. Gradient echo (GRE), spin echo (SE) and ultrashort echo time (UTE) pulse sequences were used. The artefact area in each image was automatically calculated from the pixel values within a region of interest. Mean values for similar pulse sequences differing in one parameter at a time were compared. A comparison between mean artefact area at 1.5 and 3.0 T, and from GRE and SE was also carried out. In addition, a parametric correlation between echo time (TE) and artefact area was performed., Results: A significant correlation was found between TE and artefact area in GRE images. Higher receiver bandwidth significantly reduced artefact area in SE images. UTE images yielded the smallest artefact area at 1.5 T. In addition, a significant difference in mean artefact area was found between images at 1.5 and 3.0 T field strengths (p = 0.028) and between images from GRE and SE pulse sequences (p = 0.005)., Conclusions: It is possible to compensate the effect of higher field strength on MRI artefacts by setting optimized pulse sequences for scanning patients with metal-ceramic restorations.

Apatite particles prepared from natural phosphate rock and grafted with nitrilotris(methylene)triphosphonate (NTP) were evaluated for Pb 2+ and Zn 2+ sorption from aqueous solutions. Sorption capacities as high as 640 mg.g -1 and 300 mg.g -1 could be obtained for the highest organic content (10 wt%). Analysis of the sorption isotherms using Langmuir, Freundlich and Dubinin-Kaganer-Radushkevich models revealed that Pb 2+ ions have a larger affinity for apatite (sorption energy ≈ 8 kJ.mol -1 ) than for NTP so that organo-modified surfaces led to a heterogenous adsorption process. In contrast, Zn 2+ interacts weakly (sorption energy ≈ 1 kJ.mol -1 ) and similarly with the mineral surface and the organic moieties following a homogenous sorption process. Such an association of organic metal ligands with reactive apatite surfaces within porous materials appears as a promising strategy to obtain efficient adsorbents at low cost and limited environmental impact.

We visualized inhomogeneous local magnetic field (internal magnetic field) gradients arising from susceptibility contrast between an array of cylindrical glass tubes (solid matrix) and surrounding water (pore fluids) in a uniform applied magnetic field. MRI was performed to determine the spatially resolved decay rates due to diffusion in the internal magnetic field which were proportional to the strength of local gradient. We also spatially resolved the interference pattern of the cross-terms between the internal and the applied field gradient in order to extract the orientation of the internal field gradient. These experimental results were found to be consistent with the theoretical calculations. This work demonstrates a simple yet representative case for visualizing the strength and orientation of the local susceptibility induced magnetic field gradients in porous media.

Characterization of the very early calcium phosphate (CaP) crystals deposited in bone or in osteoblast cell cultures has been hampered by the overwhelming presence of organic matrix components and cells that obscure spectral analyses. We have overcome this problem using isolated protein-free crystals and have obtained new data including 31P nuclear magnetic resonance (NMR) spectra for the first time from mineral crystals deposited during osteoblast calcification in culture. Crystals were isolated from cultures at two time points: (a) at first calcium accumulation (day 8-10) and (b) after 60 days of culture, to assess maturational changes. The analyses show that the chemical composition overall and short range order of the early and mature crystals are characteristic of the apatite crystals found in young embryonic chick bone in vivo. No mineral phase other than apatite was detected by any of the methods used. 31P NMR spectroscopy identified the HPO4 groups as those present in bone apatite. Similar to bone apatites, no OH groups were detected by Fourier transform infrared (FTIR) spectroscopy. The temporal maturational changes in composition and structure of the mineral phase were difficult to assess because of the continuous deposition of crystals throughout culturing. The pathway of the maturational changes observed were similar to those occurring in chick bone in vivo and synthetic apatite crystals in vitro although to a much smaller extent.

It is shown that solid-state phosphorus-31 nuclear magnetic resonance imaging can be used to measure quantitatively the mass of hydroxyapatite (HA), a synthetic calcium phosphate used as an orthopedic implant material, in the presence of bone. A three-dimensional projection reconstruction technique was used to produce solid-state images from 998 free induction decays sampled in the presence of a fixed amplitude field gradient whose direction was varied uniformly over the unit sphere. Chemical selection is achieved using T1 contrast, as the synthetic calcium phosphate has a shorter T1 (1.8 sec at 4.7 T) compared with the bone (approximately 15 sec at 4.7 T in vivo, 42 sec ex vivo). Experimental results demonstrating the linear relationship between image intensity and HA density in phantoms containing HA and silicon (IV) oxide, and HA and bone are shown. Chemically pure images of bone mineral and synthetic HA have been computed from images of New Zealand White rabbits acquired in vivo at two different recycle times. The technique can be used to follow noninvasively the resorption and remodeling of calcium phosphate implants in vivo.

Until now, orthodontic diagnosis and treatment planning has been based on hard tissue relationships and on the Angle paradigm that considers ideal dental occlusion 'nature's intended ideal form'. In this view, the clinician and nature are partners in seeking the ideal. In the modern biological model, variation is accepted as the natural form; ideal occlusion is the exception rather than the rule, and the orthodontist and nature are often adversaries. The orthodontist's task is to achieve the occlusal and facial outcomes that would most benefit that individual patient, whose esthetic concerns are often paramount. Because the soft tissues largely determine the limitations of orthodontic treatment, from the perspectives of function and stability, as well as esthetics, the orthodontist must plan treatment within the patient's limits of soft tissue adaptation and soft tissue contours. This emerging soft tissue paradigm in diagnosis and treatment planning places greater emphasis on clinical examination of soft tissue function and esthetics than has previously been the case, and new information in these areas is required.

Linear and cyclic polysiloxanes and extracts (free polymer) from a silicone gel-filled implant are used to investigate the reactivity of silicones in vivo. Aqueous emulsions of polysiloxanes and controls (without polysiloxanes) are injected once (day 0, approximately 10% w/v) or six times (starting at day 0, every 14 days, approximately 3% w/v) in the right thigh of rats and the popliteal and lumbar lymph nodes are harvested (3 rats per time point and compound investigated) at 2, 16, 30, 44, 58 and 72 days after the injection. 29Si NMR spectroscopy is used to detect and evaluate the presence of polysiloxanes and their metabolites in the lymph nodes. In addition to the resonance associated with the polysiloxane injected (approximately -20 ppm), the NMR spectra of lymph nodes show new resonances that are attributed to partially hydrolyzed polysiloxanes (-5 to -15 ppm) and silica (-90 to - 120 ppm). These resonances are not present in polysiloxanes emulsions before injection or in the lymph nodes of controls. Our results demonstrate that all polysiloxanes and extracts from silicone gel-filled implants are biotransformed in the lymph nodes, but high molecular weight polymer degrades at a slower rate than oligomers.

Multinuclear three-dimensional solid-state MRI of bone, tooth, and synthetic calcium phosphates is demonstrated in vitro and in vivo with a projection reconstruction technique based on acquisition of free induction decays in the presence of fixed amplitude magnetic field gradients. Phosphorus-31 solid-state MRI provides direct images of the calcium phosphate constituents of bone substance and is a quantitative measurement of the true volumetric bone mineral density of the bone. Proton solid-state MRI shows the density of bone matrix including its organic constituents, which consist principally of collagen. These solid-state MRI methods promise to yield a biological picture of bone richer in information concerning the bone composition and short range-crystalline order than the fluid-state images provided by conventional proton MRI or the density images produced by radiologic imaging techniques. Three-dimensional solid-state projection reconstruction MRI should be readily adaptable to both human clinical use and nonmedical applications for a variety of solids in materials science.

A fundamental goal of orthodontics is to improve the smile, but no objective criteria exist to assess the lip-teeth relationship, establish objectives of treatment or measure treatment outcome. Here we propose a method to digitally measure the smile characteristics of orthodontic patients. Specifically, the 'posed smile' is measured. By definition the posed smile is voluntary and not elicited by an emotion. It can be a learned greeting or a signal of appeasement and can be sustained. The posed smile is reliably repeatable. The multimedia computer program for smile measurement we developed was based on studies of the utility of the smile photograph and the assessment of the lip-teeth characteristics of the posed smile in treated and untreated patients. On the computer screen a grid, or smile mesh, employs horizontal and vertical lines to measure eleven attributes of a smile. Not all orthodontically 'well-treated' patients with exemplary plaster casts exhibit desirable anterior tooth display while smiling. We suggest that the photographic analysis of an unstrained posed smile might be a standard orthodontic record.

An adiabatic demagnetization in the rotating frame (ADRF) differential cross polarization (DCP), or inversion recovery cross polarization (IRCP), technique has been developed to study synthetic calcium phosphates and bone mineral. ADRF of the protons followed by a remagnetization of the phosphorus-31 spins results in an equalization of the dipolar and phosphorus Zeeman nuclear spin temperatures. By shifting the phase of the phosphorus RF by 180 degrees during the forward cross polarization it is possible to invert the temperature of this reservoir and initiate reverse cross polarization. Transient Strombotne-Hahn oscillations were observed on inverting the temperature. The presence of these oscillations complicates the determination of a null point on the basis of cross polarization times. It is necessary to shift the phase of the RF only after a Zeeman spin temperature can be defined, and to use an RF field strength that is slightly smaller than the equivalent S-spin local dipolar field in order to produce a zero crossing after the transient oscillations have decayed.

Orthodontists have traditionally viewed structural discrepancies as the major limitation of treatment. In reality, it is the soft tissues that more closely determine therapeutic modifiability. The boundaries of dental compensation for an underlying jaw discrepancy are established by pressures exerted on the teeth by the lips, cheeks, and tongue; limitations of the periodontal attachment; neuromuscular influences on mandibular position; and the contours of the soft tissue facial mask. The ability of the soft tissues to adapt to changes in tooth-jaw relationships are far narrower than the anatomic limits in correcting occlusal relationships. The tolerances for soft tissue adaptation from equilibrium, periodontal, and facial balance standpoints are in the range of 2 to 3 mm for expansion of the mandibular arch and even less for changes in condylar position. Thus, analysis of the soft tissues is the critical step in orthodontic decision making, and this can only be accomplished through physical examination of the patient. Although quantitative measurements cannot be rigorously applied, guidelines for soft tissue assessment, with particular emphasis on facial esthetics, are proposed. From this perspective, a contemporary philosophy of orthodontic practice is offered, with general indications and contraindications for nonextraction, extraction, and surgical treatment.

Proton NMR spectroscopy has proven useful in the detection of cancer in lymph node tissue. However, due to the high fat content of this type of tissue, 2D 1H COSY measurements (requiring acquisition times of 4-5 h or longer) are necessary to obtain the spectral information necessary for diagnosis. T2-filtered proton magic-angle spinning (MAS) NMR spectroscopy provides 1D spectra of lymph nodes in approximately 20 min with sufficient spectral resolution allowing for identification of changes in cellular chemistry due to the presence of malignant cells. MAS data from lymph nodes of five control and six rats with mammary adenocarcinoma (R13762) demonstrated increases in the signal intensity of resonances associated primarily with lactate (delta = 4.12 ppm) P < 0.0004, creatines/lysine (delta = 3.04 ppm) P < 0.0032, and glutamate/ glutamine (delta = 2.36 ppm) P < 0.0002 in metastatic compared with normal lymph nodes. The infiltration of lymph nodes by malignant cells is an important prognostic factor for many cancers. The rapid assessment of node tissue without the introduction of sampling errors (inherent in currently employed histological procedures) would allow postoperative therapy decisions to be made more efficiently.

Multinuclear nuclear magnetic resonance (NMR) spectroscopy (29Si, 13C, 1H) is used to characterize the aging process of silicone rubber-based biomaterials in a rat model. 1H NMR relaxation measurements (spin-lattice, T1, and spin-spin, T2, relaxation times) were performed to better understand the molecular dynamics of polysiloxane chains in implants. After 1 year of implantation in animals, changes in the 1H T2 relaxation times and the NMR spectra were observed in polydimethylsiloxane, Silastic sheets and chin implants, while these measurements remain unchanged in finger joints. Very small amounts of fat were detected in all types of silicone rubber implants at the end of the implantation period. This work shows that free silicone migrates from the implants to adjacent tissues and distant sites, such as spleen or liver, and is chemically modified.

Chemically selective solid state phosphorus-31 nuclear magnetic resonance (NMR) imaging of the mineral phase of bone and synthetic calcium phosphate models for bone mineral is demonstrated with microscopy-scale (about 5 mm field of view) apparatus at 6.0 T magnetic field strength. Pixel-by-pixel linear combination of image data from multiple radio frequency (RF) pulse sequences, chosen to develop contrast between chemical constituents of interest in the mineral, generates derived images showing the distribution of individual constituents. The technique combines the noninvasive character of magnetic resonance imaging (MRI) with the ability of solid state NMR spectroscopy to characterize subtle chemical variations in bone mineral, as well as to measure the amount of mineral. These methods are, in principle, extensible to larger dimensional scales suitable for live animal subjects or human limbs.

Orthodontic treatment planning is an interactive process in which the patient or parent and the orthodontist serve as co-decision makers. As in most partnerships, there is a natural tension between the orthodontist and the patient because of differences in their frames of reference. The orthodontist generally is influenced more by the objective findings (the problem list), whereas patients are guided more by subjective issues related to their perceived needs, desires, and values. The art of careful probing and listening to the patient as part of the treatment planning process is an essential skill. One of the most difficult situations in contemporary orthodontics is presented by the patient with a jaw discrepancy for which the alternative treatments are orthodontic camouflage through dental compensation or surgical-orthodontic correction. Computer imaging to simulate the probable treatment outcomes can facilitate communication about these alternatives by eliminating misconceptions. Full disclosure and the consideration of all viable treatment alternatives have great benefits from a risk management standpoint, in addition to their bioethical merits.

The detailed chemical composition and microstructure of freshly deposited bone mineral, and how these properties change with maturation of the mineral, have been studied intensively and still remain controversial. For example, current analytical technology is inadequate for the unambiguous characterization of the monohydrogen phosphate ions in bone mineral. Using a differential cross polarization/magic angle spinning solid state nuclear magnetic resonance spectroscopy technique, we suppress the dominant orthophosphate (PO4-3) signal to reveal the spectra of the minor phosphate constituents. This method depends upon differences in the cross polarization time constants for phosphorus-31 nuclei in protonated and non-protonated phosphate ions. It is now possible for the first time to directly measure both the proportion of acid phosphate (HPO4-2) as well as the parameters which characterize its isotropic and anisotropic chemical shift. In bone from three species at several developmental stages, we have found a single type of acid phosphate species, identical in all of the specimens examined. The phosphorus-31 isotropic chemical shift of this acid phosphate group in bone mineral corresponds precisely with that of acid phosphate in octacalcium phosphate, and not with that of brushite. In contrast, the bone acid phosphate anisotropic chemical shift parameters are close to those of brushite, and differ significantly from those of octacalcium phosphate. The orthophosphate resonances of bone mineral, synthetic hydroxyapatite and synthetic octacalcium phosphate share identical chemical isotropic shifts, and similar chemical shift anisotropies. The implication of these results is that the intimate structure of the acid phosphate group in bone mineral is unique, and that none of the common synthetic calcium phosphates accounts well for all of the observed solid state phosphorus-31 NMR properties of bone mineral.

In vivo 1H NMR chemical shift imaging (CSI), 1H NMR localized spectroscopy (STEAM) and multinuclear NMR spectroscopy (29Si, 13C, 1H) were used to characterize the aging process of silicone gel-filled implants in a rat model after long-term implantation. Although no significant changes could be observed in the implants or surrounding tissue by in vivo 1H chemical shift imaging, in vivo 1H localized spectroscopy of the livers from the longer term population revealed the presence of silicone. Ex vivo 29Si spectroscopy of the liver, spleen, and the capsule formed around the 9 and 12 month implants clearly demonstrated and confirmed for the first time that a significant amount of free silicone migrates from silicone gel-filled implants. Also, these results show that silicones are not metabolically inert, and their biodegradation in tissue and within the implant can be monitored after 9 and 12 months by changes in the 29Si chemical shifts seen in corresponding ex vivo spectra. The NMR findings are supported by those obtained by atomic absorption spectroscopy. Silicone aging changes not only the chemical composition of the gel, but also its proton T2 relaxation times, which increase with long implantation times. The three dimensional structure of the gel disintegrates (i.e., polymer chain rupture), increasing the molecular mobility of the polymer and, consequently, its protons T2 values. The relaxation data we obtained reflect this in vivo degradation, especially in the case of implant rupture. Additionally, small concentrations of fat in the silicone gel were found within the implants. The presence of these lipophilic substances also might increase the T2 values (plasticizer effect). These findings may assist in evaluating the implant integrity and disease symptoms related to their presence in humans.

1H NMR localized spectroscopy (STEAM) can assess unambiguously the presence of free chemically unchanged silicone in animal tissue after injection of silicone oil. Although the signal-to-noise ratio obtained in 1H imaging is sufficient to detect the distribution of relatively large amounts of silicone in vivo, the specificity of silicone detection can be improved by using 1H localized spectroscopy techniques. The sensitivity of the STEAM experiments is sufficient to detect silicone at a concentration of 0.5% in a voxel of 27 mm3. Preliminary results from rats with silicone gel-filled implants show no detectable amounts of silicone in sites such as lymph nodes, the liver or the spleen, 3 or 6 months after implantation.