A homoleptic chromium(iii) carboxylate.

Structurally characterized chromium(iii) carboxylates form clusters with a variety of bridging groups introduced from aqueous reaction conditions. The first homoleptic monomeric chromium(iii) carboxylate has been prepared using an anhydrous salt metathesis synthetic route. The carboxylate groups coordinate the chromium in a bidentate chelate yielding an aliphatic soluble complex. The complex was characterized by a variety of methods including high energy X-ray diffraction, FD-MS, IR and Raman spectroscopy, complemented by DFT modeling.

Plasma surface modification of electrospun fibers for adhesion-based cancer cell sorting.

Personalized cancer therapies drive the need for devices that rapidly and accurately segregate cancer cells from solid tumors. One potential sorting strategy is to segregate populations of cells based on their relative strength of adhesion. To investigate the effect of surface hydrophilicity and cell phenotype on adhesion, primary human breast skin fibroblasts and keratinocytes and MCF-7 breast cancer cells were seeded onto air and CF(4) plasma-treated nanofibers followed by exposure to three shear stresses (200, 275 and 350 dynes per cm(2)) 1 hour after inoculation. No difference in strength of adhesion was measured in either fibroblasts or keratinocytes on either plasma treated-surface: all exhibited >60% of the initial cell count after a 5 minute exposure to 350 dynes per cm(2) of shear stress. In contrast, a significant difference between relative strength of adhesion on air versus CF(4) plasma-treated surfaces was observed for MCF-7 cells: 26% and 6.6% of cells remained on the air and CF(4) plasma-treated surfaces, respectively. The ability to sort this cancer cell line from two non-cancerous primary human cells was evaluated by inoculating a mixture of all three cell types simultaneously onto CF(4) treated nanofibers followed by 1 hour of culture and exposure to 350 dynes per cm(2) shear stress. The majority of MCF-7 cells were removed (0.7% remained) while a majority of fibroblasts and keratinocytes remained adhered (74 and 57%). Post-sorted MCF-7 viability and morphology remained unchanged, preserving the possibility of post-separation and analysis. These data suggest that the plasma treatment of electrospun scaffolds provides a tool useful in sorting cancer cells from a mixed cell population based on adhesion strength.

Local bone formation due to combined mechanical loading and intermittent hPTH-(1-34) treatment and its correlation to mechanical signal distributions.

We evaluated the local response of cortical bone in the rat tibia due to combined treatment with synthetic parathyroid hormone, hPTH-(1-34), and mechanical stimulation by four-point bending. Forty-eight female retired breeder Sprague-Dawley rats were divided into six groups. Mechanically stimulated animals included the following groups: (1) Bend+PTH, (2) Sham+PTH, (3) Bend+Vehicle, (4) Sham+Vehicle. Non-mechanically stimulated animals included a (5) Control group that received neither loading nor injections, and a (6) PTH group that received only hPTH-(1-34) injections. The right limbs of mechanically loaded animals were exposed to a peak force of 50 N for 36 cycles at 2 Hz, three days per week for four weeks, and PTH-treated animals received injections equivalent to 50 microg/kg BW. Fluorochrome labeling was used to measure local formation at 12 sectors about the endocortical periphery. The distributions of endocortical bone formation were compared to the local formation differences between treatment groups and to a variety of potential mechanical stimuli signals. Results indicated that hPTH-(1-34) exerted a potent anabolic effect with near-uniform formation about the endocortical surface, and that localized formation peaks due to bending were further augmented in the presence of hPTH-(1-34) treatment. Correlation of formation patterns to mechanical signal distributions highlighted several candidate signals including the mid-principal stress, the dilatational strain, and the radial gradient of the local radial strain.

A cellular solid model of the lamina cribrosa: mechanical dependence on morphology.

The biomechanics of the optic nerve head (ONH) may underlie many of the potential mechanisms that initiate the characteristic vision loss associated with primary open angle glaucoma. Therefore, it is important to characterize the physiological levels of stress and strain in the ONH and how they may change in relation to material properties, geometry, and microstructure of the tissue. An idealized, analytical microstructural model of the ONH load bearing tissues was developed based on an octagonal cellular solid that matched the porosity and pore area of morphological data from the lamina cribrosa (LC). A complex variable method for plane stress was applied to relate the geometrically dependent macroscale loads in the sclera to the microstructure of the LC, and the effect of different geometric parameters, including scleral canal eccentricity and laminar and scleral thickness, was examined. The transmission of macroscale load in the LC to the laminar microstructure resulted in stress amplifications between 2.8 and 24.5xIOP. The most important determinants of the LC strain were those properties pertaining to the sclera and included Young's modulus, thickness, and scleral canal eccentricity. Much larger strains were developed perpendicular to the major axis of an elliptical canal than in a circular canal. Average strain levels as high as 5% were obtained for an increase in IOP from 15 to 50 mm Hg.

Isotope quantum effects in water around the freezing point.

We have measured the difference in electronic structure factors between liquid H(2)O and D(2)O at temperatures of 268 and 273 K with high energy x-ray diffraction. These are compared to our previously published data measured from 279 to 318 K. We find that the total structural isotope effect increases by a factor of 3.5 over the entire range, as the temperature is decreased. Structural isochoric temperature differential and isothermal density differential functions have been used to compare these data to a thermodynamic model based upon a simple offset in the state function. The model works well in describing the magnitude of the structural differences above approximately 310 K, but fails at lower temperatures. The experimental results are discussed in light of several quantum molecular dynamics simulations and are in good qualitative agreement with recent temperature dependent, rotationally quantized rigid molecule simulations.

Shape adaptation of long bone structures using a contour based approach.

In this work, an approach for mechanically driven shape adaptation of long bone structures is presented which utilizes contour descriptions to track morphological changes at different bone cross sections. A script-based procedure is used to iteratively generate a solid geometry and finite element (FE) model from these contours, perform a stress analysis, and then update the contour shapes using the results of the stress analysis using a prescribed remodeling rule. Because a remeshing operation is performed at each timestep the method is able to effectively simulate large changes in geometry. Several examples of shape adaptation of idealized and geometrically accurate long-bone structures are presented using a variety of remodeling signals and parameters.

Temperature dependence of isotopic quantum effects in water.

The technique of high energy x-ray diffraction has been used to measure the temperature variation of hydrogen versus deuterium isotopic quantum effects on the structure of water. The magnitude of the effect is found to be inversely proportional to the temperature, varying by a factor of 2.5 over the range 6 to 45 degrees C. In addition, the H216O versus H218O effect has been measured at 26 degrees C and the structural difference shown to be restricted to the nearest neighbor molecular interactions. The results are compared to recent simulations and previously measured isochoric temperature differentials; additionally, implications for H/D substitution experiments are considered.

On the spectral similarity of bridging and nonbridging oxygen in tellurites.

We show by high field (17)O solid-state nuclear magnetic resonance (NMR) and by ab initio calculations of both the NMR and the oxygen 1s photoelectron spectra that the oxygen sites in tellurite glasses show no spectroscopic distinction, even when comparing bridging and nonbridging sites. This is remarkable because two such sites differ formally by a full electronic charge, and they are readily distinguished by these same methods in silicates. We argue that this similarity arises from the symmetry breaking that occurs when the original TeO(2) crystal solid forms, due to the pseudo-Jahn-Teller distortion induced by the two additional valence electrons present in Te(IV) as compared to Si(IV).

Anterior scleral canal geometry in pressurised (IOP 10) and non-pressurised (IOP 0) normal monkey eyes.

AIMS: To characterise lamina cribrosa and anterior scleral canal wall architecture in pressurised (IOP 10 mm Hg) and non-pressurised (IOP 0 mm Hg) normal monkey eyes. METHODS: Eight normal eyes from eight monkeys were enucleated before sacrifice and the optic nerve heads (ONH) trephined and immersion fixed in glutaraldehyde (IOP 0). Nine normal eyes from nine monkeys were perfusion fixed in situ with paraformaldehyde at IOP 10 mm Hg (IOP 10), and the ONHs trephined and stored in glutaraldehyde. Each ONH specimen was embedded in glycol methacrylate and cut into vertical or horizontal, 4 micro m thick, serial sections. Within digitised images of every sixth section, anterior laminar position and laminar thickness were measured at nine evenly spaced locations across the scleral canal opening. Additionally, scleral canal diameters at Bruch's membrane (SCD-B) and at the anterior laminar insertion (SCD-ALI) were measured within the 15 middle section images of each vertically sectioned ONH. RESULTS: Anterior laminar position was significantly more anterior (nearer Bruch's membrane) in the IOP 10 eyes, compared with the IOP 0 eyes (116 (+/-95% CI; 2) micro m v 184 (2) micro m, respectively). Also in the IOP 10 eyes, the lamina cribrosa was thinner (195 (2) micro m v 264 (2) micro m) and the scleral canal diameter was larger (SCD-B: 1751 (23) micro m v 1591 (19) micro m; SCD-ALI: 1961 (21) micro m v 1717 (17) micro m), compared with the IOP 0 eyes. CONCLUSION: The anterior scleral canal wall is expanded and the lamina cribrosa is thinned and more tautly stretched within pressurised (perfusion fixed at IOP 10) young monkey eyes, compared with non-pressurised (immersion fixed at IOP 0) young monkey eyes. The constricted scleral canal and the relaxed and thickened lamina in the non-pressurised eyes may represent phenomena that contribute to optic disc swelling in hypotonous eyes.

Posterior scleral thickness in perfusion-fixed normal and early-glaucoma monkey eyes.

PURPOSE: To characterize posterior scleral thickness in the normal monkey eye and to assess the effects of acute (15- to 80-minute) and short-term chronic (3- to 7-week) intraocular pressure (IOP) elevations. METHODS: Both eyes of four normal monkeys (both eyes normal) and four monkeys with early glaucoma (one eye normal and one eye with induced chronic elevation of IOP) were cannulated. In each monkey, IOP was set to 10 mm Hg in the normal eye and 30 or 45 mm Hg in the contralateral eye (normal or early glaucoma) for 15 to 80 minutes. All eight monkeys were perfusion fixed, yielding eight low IOP-normal eyes, four high IOP-normal eyes, and four high IOP-early glaucoma eyes. Posterior scleral thickness was measured histomorphometrically at 15 measurement points within each eye, and the data were grouped by region: foveal, midposterior, posterior-equatorial, and equatorial. RESULTS: Overall, posterior scleral thickness was significantly different in the various regions and among the treatment groups (P < 0.0001). In the low IOP-normal eyes, the posterior sclera was thickest in the foveal region (307 microm) and thinner in the midposterior (199 microm), posterior-equatorial (133 microm), and equatorial (179 microm) regions. In the high IOP-normal and high IOP-early glaucoma eyes, the posterior sclera was thinner both overall and within specific regions, compared with the low IOP-normal eyes. CONCLUSIONS: The posterior sclera in the perfusion-fixed normal monkey eye thins progressively from the fovea to the equator and is thinnest just posterior to the equator. Acute and short-term chronic IOP elevations cause regional thinning within the posterior sclera of some monkey eyes, which significantly increases stresses in the scleral wall.

The optic nerve head as a biomechanical structure: initial finite element modeling.

PURPOSE: To study the relationship between intraocular pressure (IOP) and the IOP-related stress (force/cross-sectional area) it generates within the load-bearing connective tissues of the optic nerve head. METHODS: Thirteen digital, three-dimensional geometries were created representing the posterior scleral shell of 13 idealized human eyes. Each three-dimensional geometry was then discretized into a finite element model consisting of 900 constituent finite elements. In five models, the scleral canal was circular (diameters of 0.50, 1.50, 1.75, 2.00, and 2.56 mm), with scleral wall thickness (0.8 mm) and inner radius (12.0 mm) held constant. In three models, the canal was elliptical (vertical-to-horizontal ratios of 2:1 [2.50 x 1.25 mm], 1.5:1 [2.1 x 1.4 mm], and 1.15:1 [1.92 x 1.67 mm]), with the same constant scleral wall thickness and inner radius. In five additional models, scleral canal size was held constant (1.92 x 1.67 mm), and either scleral wall thickness (three models, 0.5, 1.0, and 1.5 mm) or inner radius (two models, 13.0 and 14.0 mm) was varied. In all models, each finite element was assigned a single isotropic material property, either scleral (modulus of elasticity, 5500 kPa) or axonal (modulus of elasticity, 55 kPa). Maximum stresses within specific regions were calculated at an IOP of 15 mm Hg (2000 Pa). RESULTS: Larger scleral canal diameter, elongation of the canal, and thinning of the sclera increased IOP-related stress for a given level of IOP. For all models, maximum IOP-related stress ranged from 6 x IOP (posterior sclera) to 122 x IOP (laminar trabeculae). For each model, maximum IOP-related stress was highest within the laminar trabecular region and decreased progressively through the laminar insertion, peripapillary scleral, and posterior scleral regions. Varying the inner radius had little effect on the maximum IOP-related stress within the scleral canal. CONCLUSIONS: Initial finite element models show that IOP-related stress within the load-bearing connective tissues of the optic nerve head is substantial even at low levels of IOP. Although the data suggest that scleral canal size and shape and scleral thickness are principal determinants of the magnitude of IOP-related stress within the optic nerve head, models that incorporate physiologic scleral canal and laminar geometries, a more refined finite element model meshwork, and nonisotropic material properties will be required to confirm these results.

Contact analysis of a posterior cervical spine plate using a three-dimensional canine finite element model.

The development of a three-dimensional finite element model of a posteriorly plated canine cervical spine (C3-C6) including contact nonlinearities is described. The model was created from axial CT scans and the material properties were derived from the literature. The model demonstrated sufficient accuracy from the results of a mesh convergence test. Significant steps were taken toward establishing model validation by comparison of plate surface strains with a posteriorly plated canine cervical spine under three-point bending. This model was developed to better characterize the contact pressures at the various interfaces under average physiologic canine loading. The analysis showed that the screw-plate interfaces had the highest values of all the mechanical parameters evaluated.

Stress analysis of halo pin insertion by non-linear finite element modeling.

Halo fixation is associated with a high complication rate. The most common complications are loose pins and pin site infections believed to be exacerbated by loose pins. Although pin designs and the technique of pin insertion have changed little in over 30 years, the pin/skull mechanics are poorly understood. Halo pin insertion was modeled using nonlinear finite element analyses to determine the stress distribution in the human skull underlying and surrounding the point of pin fixation. Model validity was established by comparing pin insertion depth and the profile of the hole generated in the bone to the results of experimental mechanical tests. The region surrounding the pin tip within 1 mm was found to undergo plastic deformation and compressive loading in excess of the compressive yield strength of cortical bone. The implication is that damaged bone in this region is responsible for the high incidence of halo pin loosening. Resorption or migration of bone particles with periodic relief of compression in this region due to daily cyclic forces might result in an enlarged pin site and eventually, a loose pin.

Modeling the biomechanics of the mandible: a three-dimensional finite element study.

Three-dimensional finite element models of a partially edentulated human mandible were generated to calculate the mechanical response to simulated isometric biting and mastication loads. The level of mesh refinement was established via a convergence test and showed that a model with over 30,000 degrees of freedom was required to obtain analysis accuracy. The functional loading cases included muscle loading based on an algorithm that assigns muscle forces in accordance with muscle cross-sectional area, while maintaining static equilibrium. Results were found for isometric application of unilateral and bilateral bite and mastication loading, and two different sets of displacement boundary conditions were imposed at the condyles. The mechanical response is shown in terms of displacements, principal strains, and a new measure called the 'mechanical intensity scalar'. For each load case studied, there was substantial bending in the molar region of the corpus and high tensile strains in the anterior portion of the ramus.

Finite-element model of the human head: scalp potentials due to dipole sources.

Three-dimensional finite-element models provide a method to study the relationship between human scalp potentials and neural current sources inside the brain. A new formulation of dipole-like current sources is developed here. Finite-element analyses based on this formulation are carried out for both a three-concentric-spheres model and a human-head model. Differences in calculated scalp potentials between these two models are studied in the context of the forward and inverse problems in EEG. The effects of the eye orbit structure on surface potential distribution are also studied.

Errors in the orientation of the principal stress axes if bone tissue is modeled as isotropic.

The error in the prediction of the orientation of the principal axes of stress in bone tissue is determined in the case when the tissue is modeled as elastically isotropic rather than as orthotropic, the probable symmetry of bone tissue. Results are two-dimensional and assume the same underlying strain state for both the orthotropic and isotropic cases. The maximum error is 45 degrees, and the typical error is generally significant.

A theoretical study of the influence of bone maturation rate on surface remodeling predictions: idealized models.

The use of a finite element based computational method, RFEM3D, is described for the study of strain-induced bone remodeling. The purpose of the research is to find the potential influence on the predictions of surface bone remodeling when various models for the maturation of newly deposited bone are used. A parameter study is performed using seven hypothetical mechanical descriptions of the bone maturation process. The results show that, theoretically, the process of surface bone maturation may be an efficient mechanism for reducing overload strains in bone, but that differences as a consequence of using any of the proposed maturation rules are rather subtle.

Supercomputer use in orthopaedic biomechanics research: focus on functional adaptation of bone.

The authors describe two biomechanical analyses carried out using numerical methods. One is an analysis of the stress and strain in a human mandible, and the other analysis involves modeling the adaptive response of a sheep bone to mechanical loading. The computing environment required for the two types of analyses is discussed. It is shown that a simple stress analysis of a geometrically complex mandible can be accomplished using a minicomputer. However, more sophisticated analyses of the same model with dynamic loading or nonlinear materials would require supercomputer capabilities. A supercomputer is also required for modeling the adaptive response of living bone, even when simple geometric and material models are use.

Functional adaptation in long bones: establishing in vivo values for surface remodeling rate coefficients.

In this paper we describe a computational means, based on beam theory, for application of the theory of adaptive elasticity to examples of real bone geometries. The results of the animal experiments were taken from the literature, and each documented the temporal evolution of a change in bone shape after a significant change in the mechanical loading environment of the bone. For each of these studies, we establish preliminary estimates of the in vivo values of the surface remodeling rate coefficients--the key parameters in the theory of surface remodeling. Our preliminary parameter estimates are established by comparison of published animal experimental results with surface remodeling theory predictions generated by the computational method.