Cracks emanating from slipping inclusions near a bone-implant interface.

It has been hypothesized that mechanical fracture at the bone-cement-implant interface is the initial cause for loosening of orthopedic implants. Previous investigators have observed cracks to emanate from methacrylate beads, apparently acting as inclusions within the cement. It is believed that the bond between these inclusions and the surrounding matrix breaks prior to emanation of radial cracks from the inclusion. An analytical model is developed for radial cracks emanating from circular inclusions that allow slip along their interface. The solution to the interaction of a single dislocation and a slipping inclusion is used as a Green's Function to model the crack. The Mode I stress intensity factors are calculated for arbitrary orientations of the crack and for varying relative stiffness of the matrix and the inclusion to test feasibility of crack growth.     

Early cement damage around a femoral stem is concentrated at the cement/bone interface

This study aimed to improve understanding of the mechanical aspects of cemented implant loosening. After aggressive fatigue loading of stem/cement/femur constructs, micro-cracks and stem/bone micro-motions were quantified to answer three research questions: Are cracks preferentially associated with the stem/cement interface, the cement/bone interface or voids? Is cement damage dependent on axial position? Does cement damage correlate with micro-motion between the stem and the bone? Eight Charnley Cobra stems were implanted in cadaveric femora. Six stem/cement/femur constructs were subjected to "stair-climbing" loads for 300 kcycles at 2Hz. Loads were normalized by construct stiffness to avoid fracture. Two additional constructs were not loaded. Transverse sections were cut at 10mm intervals, stained with a fluorescent dye penetrant and examined using epi-fluorescence stereomicroscopy. Crack lengths and cement areas were recorded for 9 sections per specimen. Crack length-density was calculated by dividing summed crack length by cement mantle area. To isolate the effect of loading, length-density data were offset by the baseline length-density measured in the non-loaded specimens. Significantly more cracks were associated with the interdigitated area (35.1%+/-11.6%) and the cement/bone interface (31.0%+/-6.2%) than with the stem/cement interface (11.0%+/-5.2%) or voids (6.1%+/-4.8%) (p<0.05). Load-induced micro-crack length-density was significantly dependent on axial position, increasing proximally (p<0.001). Micro-motions were small, all stems rotated internally. Cement damage did not correlate with micro-motion.     

A model of tension and compression cracks with cohesive zone at a bone-cement interface

This paper gives an insight about compression and tension cracks as encountered at a bone-cement interface. Within the context of continuum theory of fracture, an analytical solution is presented for the problem of a bimaterial interface edge crack under uniaxial tension or compression, assuming no tangential slip along the crack faces since cement pedicles penetrate into the cancellous bone several millimeters. Also essential to the solution are cohesive zone effects that account for a strengthening mechanism over the crack faces. The solution provides a methodological framework for quantifying the influence of the cohesive zone on the magnitude of the stress singularity. Mode I crack tip stress intensity factors are calculated at different stages of the loading and unloading phases under uniaxial tension or compression. Finally, an inelastic mechanism is presented that gives theoretical support to explain the formation of interfacial compression cracks, a phenomenon that was not previously appreciated and that arises from the rigid cement being forced into the more compliant cancellous bone.     

A crack model of a bone cement interface

This paper is concerned with the fracture mechanics of a bone-cement interface that includes a cohesive zone effect on the crack faces. This accounts for the experimentally observed strengthening mechanism due to the mechanical interlock between the crack faces. Edge crack models are developed where the cohesive zone is simulated by a continuous or a discrete distribution of linear or nonlinear springs. It is shown that the solution obtained by assuming a homogeneous material is fairly close to the exact solution for the bimaterial interface edge crack problem. On the basis of that approximation, the analysis is conducted for the problem of two interacting edge cracks, one at the interface, and the other one in the cement. The small crack that was observed to initiate in the cement, close to the bone-cement interface, does not affect much the mode I stress-intensity factor at the tip of the interface crack. However it may grow, leading to a catastrophic breakdown of the cement. The analysis and following discussion point out an interdependency between bone-cement interface strength and cement strength not previously appreciated. The suggested crack models provide a framework for quantifying the fracture mechanisms at the bone-cement interface.     

Cracks emanating from a fluid filled void loaded in compression: application to the bone-implant interface

Loosening of orthopedic implants is believed to be caused, in part, by fracture at the bone-cement interface. This loosening occurs even in regions where the interfacial load is primarily compressive. A model is developed whereby cracks can radiate from an elliptical fluid filled void. The incompressible fluid is allowed to penetrate into the cracks when the system is loaded compressively. The mode I stress intensity factor is calculated to test the feasibility of crack growth, and a numerical scheme which uses piecewise quadratic polynomials is used to solve the resulting singular integral equations. The results show the combinations of parameters for which cracks are likely to grow.     

The behavior of the micro-mechanical cement-bone interface affects the cement failure in total hip replacement

In the current study, the effects of different ways to implement the complex micro-mechanical behavior of the cement-bone interface on the fatigue failure of the cement mantle were investigated. In an FEA-model of a cemented hip reconstruction the cement-bone interface was modeled and numerically implemented in four different ways: (I) as infinitely stiff, (II) as infinitely strong with a constant stiffness, (III) a mixed-mode failure response with failure in tension and shear, and (IV) realistic mixed mode behavior obtained from micro-FEA models. Case II, III, and IV were analyzed using data from a stiff and a compliant micro-FEA model and their effects on cement failure were analyzed. The data used for Case IV was derived from experimental specimens that were tested previously. Although the total number of cement cracks was low for all cases, the compliant Case II resulted in twice as many cracks as Case I. All cases caused similar stress distributions at the interface. In all cases, the interface did not display interfacial softening; all stayed the elastic zone. Fatigue failure of the cement mantle resulted in a more favorable stress distribution at the cement-bone interface in terms of less tension and lower shear tractions. We conclude that immediate cement-bone interface failure is not likely to occur, but its local compliancy does affect the formation of cement cracks. This means that at a macro-level the cement-bone interface should be modeled as a compliant layer. However, implementation of interfacial post-yield softening does seems to be necessary.     

The use of XFEM to assess the influence of intra-cortical porosity on crack propagation

This study aimed at using eXtended finite element method (XFEM) to characterize crack growth through bone’s intra-cortical pores. Two techniques were compared using Abaqus: (1) void material properties were assigned to pores; (2) multiple enrichment regions with independent crack-growth possibilities were employed. Both were applied to 2D models of transverse images of mouse bone with differing porous structures. Results revealed that assigning multiple enrichment regions allows for multiple cracks to be initiated progressively, which cannot be captured when the voids are filled. Therefore, filling pores with one enrichment region in the model will not create realistic fracture patterns in Abaqus-XFEM.     

An α-Helical Core Encodes the Dual Functions of the Chlamydial Protein IncA

Chlamydia is an intracellular bacterium that establishes residence within parasitophorous compartments (inclusions) inside host cells. Chlamydial inclusions are uncoupled from the endolysosomal pathway and undergo fusion with cellular organelles and with each other. To do so, Chlamydia expresses proteins on the surface of the inclusion using a Type III secretion system. These proteins, termed Incs, are located at the interface between host and pathogen and carry out the functions necessary for Chlamydia survival. Among these Incs, IncA plays a critical role in both protecting the inclusion from lysosomal fusion and inducing the homotypic fusion of inclusions. Within IncA are two regions homologous to eukaryotic SNARE (soluble N-ethylmaleimide-sensitive factor attachment receptor) domains referred to as SNARE-like domain 1 (SLD1) and SNARE-like domain 2 (SLD2). Using a multidisciplinary approach, we have discovered the functional core of IncA that retains the ability to both inhibit SNARE-mediated fusion and promote the homotypic fusion of Chlamydia inclusions. Circular dichroism and analytical ultracentrifugation experiments show that this core region is composed almost entirely of α-helices and assembles into stable homodimers in solution. Altogether, we propose that both IncA functions are encoded in a structured core domain that encompasses SLD1 and part of SLD2.     

Direct evidence of "damage accumulation" in cement mantles surrounding femoral hip stems retrieved at autopsy: cement damage correlates with duration of use and BMI

The "damage accumulation" phenomenon has not been quantitatively demonstrated in clinical cement mantles surrounding femoral hip stems. We stained transverse sections of 11 postmortem retrieved femoral hip components fixed with cement using fluorescent dye-penetrant and quantified cement damage, voids, and cement-bone interface gaps in epifluorescence and white light micrographs. Crack density (Cr.Dn), crack length-density (Cr.Ln.Dn), porosity, and cement-bone interface gap fraction (c/b-gap%) were calculated, normalized by mantle area. Multiple regression tests showed that cement damage (Cr.Ln.Dn. & Cr.Dn.) was significantly positively correlated (r(2)=0.98, p<0.001) with "duration of use" and body mass index ("BMI") but not cement mantle "porosity". There were significant interactions: "duration of use"*"BMI" was strongly predictive (p<0.005) of Cr.Dn.; and "duration of use"*"porosity" was predictive (p=0.04) of Cr.Ln.Dn. Stem related cracks accounted for approximately one fifth of Cr.Dn and one third of Cr.Ln.Dn. The mean c/b-gap% was 13.8% but it did not correlate (r(2)=0.01, p=0.8) with duration of use. We concluded that duration-dependent fatigue damage accumulation occurred during in vivo use. BMI strongly influenced cement crack length and the rate of new crack formation over time. Voids did not increase the rate of crack initiation but appeared to have promoted crack growth over time. Although not progressive, substantial bone resorption at the cement-bone interface appeared to be common.     

In vitro interface and cement mantle analysis of different femur stem designs

The aim of this study is to define stem design related factors causing both gaps in the metal-bone cement interface and cracks within the cement mantle. Six different stem designs (Exeter; Lubinus SP II; Ceraver Osteal; Mueller-straight stem; Centega; Spectron EF) (n=15 of each design) were cemented into artificial femur bones. Ten stems of each design were loaded, while five stems served as an unloaded control. Physiologically adapted cyclical loading (DIN ISO 7206-4) was performed with a hip simulator. After loading both interfaces and the bone cement itself were analysed regarding gaps and cracks in the cement mantle. Significant differences between the stem designs concerning gaps in the metal-bone cement interface and cracks in the cement mantle became apparent. Additionally, a high correlation between gaps in the metal-bone cement interface and cracks within the cement mantle could be proven. Gaps in the metal-bone cement interface but no cracks within the cement mantle were seen in the unloaded specimens. Differences between the unloaded control groups and the cyclical loaded stems regarding the longitudinal extension and width of gaps in the metal-bone cement interface were obvious. The designs of cemented femoral stems have an influence on both the quality of the metal-bone cement contact and the failure rate of the cement mantle. Less interface gaps and less cement defects were found with anatomically formed, collared, well-rounded stem designs without undercuttings.     

The role of the lamellar interface during torsional yielding of human cortical bone

Fragility fractures are a result of alterations in bone quantity, tissue properties, applied loads, or a combination of these factors. The current study addresses the contribution of cortical bone tissue properties to skeletal fragility by characterizing the shear damage accumulation processes which occur during torsional yielding in normal bone. Samples of human femoral cortical bone were loaded in torsion and damaged at a post-yield twist level. The number of microcracks within osteons, interstitial tissue, and along cement lines were assessed using basic fuchsin staining. Damage density measures (number of cracks/mm2) were correlated with stiffness degradation and changes in relaxation. Damaged samples exhibited a wide variation in total microcrack density, ranging from 1.1 to 43.3 cracks/mm2 with a mean density of 19.7 +/- 9.8 cracks/mm2. Lamellar interface cracks comprised more than 75% of the total damage, indicating that the lamellar interface is weak in shear and is a principal site of shear damage accumulation. Damage density was positively correlated with secant stiffness degradation, but only explained 22% of the variability in degradation. In contrast, damage density was uncorrelated with the changes in relaxation, indicating that a simple crack counting measure such as microcrack density was not an appropriate measure of relaxation degradation. Finally, a nonuniform microcrack density distribution was observed, suggesting that internal shear stresses were redistributed within the torsion samples during post-yield loading. The results suggested that the lamellar interface in human cortical bone plays an important role in torsional yielding by keeping cracks physically isolated from each other and delaying microcrack coalescence in order to postpone the inevitable formation of the fatal crack.     

Carbon nanotubes in blends of polycaprolactone/thermoplastic starch

Despite the importance of polymer–polymer multiphase systems, very little work has been carried out on the preferred localization of solid inclusions in such multiphase systems. In this work, carbon nanotubes (CNT) are dispersed with polycaprolactone (PCL) and thermoplastic starch (TPS) at several CNT contents via a combined solution/twin-screw extrusion melt mixing method. A PCL/CNT masterbatch was first prepared and then blended with 20 wt% TPS. Transmission and scanning electron microscopy images reveal a CNT localization principally in the TPS phase and partly at the PCL/TPS interface, with no further change by annealing. This indicates a strong driving force for the CNTs toward TPS. Young's model predicts that the nanotubes should be located at the interface. X-ray photoelectron spectroscopy (XPS) of extracted CNTs quantitatively confirms an encapsulation by TPS and reveals a covalent bonding of CNTs with thermoplastic starch. It appears likely that the nanotubes migrate to the interface, react with TPS and then are subsequently drawn into the low viscosity TPS phase. In a low shear rate/low shear stress internal mixer the nanotubes are found both in the PCL phase and at the PCL/TPS interface and have not completed the transit to the TPS phase. This latter result indicates the importance of choosing appropriate processing conditions in order to minimize kinetic effects. The addition of CNTs to PCL results in an increase in the crystallization temperature and a decrease in the percent crystallinity confirming the heterogeneous nucleating effect of the nanotubes. Finally, DMA analysis reveals a dramatic decrease in the starch rich phase transition temperature (∼26 °C), for the system with nanotubes located in the TPS phase.     

Optical Fiber-Based Surface-Enhanced Raman Scattering Sensor Using Au Nanovoid Arrays

Plasmonic properties of gold nanovoid array substrates for fiber-based surface-enhanced Raman scattering (SERS) sensing are studied numerically and experimentally. In the nanovoid arrays, each void has openings on both sides, bottom hole facing the fiber tip for introducing incident light and collecting scattered light and the top hole exposed to the analyte solution for interrogating analyte molecules in the voids. Electromagnetic field modes are confined strongly in and around these nanovoids, acting as localized plasmon resonators. The enhanced electric field extends hundreds of nanometers into the voids, resulting in a large SERS-active zone several orders of magnitude larger than nanoparticle-based structures. The effect of structural parameters of the nanovoid arrays, including void diameter, Au film thickness, and bottom hole diameter, on electric field confinement in the voids is investigated using three-dimensional finite difference time domain simulation. Au nanovoid arrays are fabricated using a scalable, inexpensive nanosphere lithography fabrication method. The largest SERS signal is realized by tuning the localized plasmon resonance peak of Au nanovoid arrays to the laser excitation wavelength. Multiplexed detection capability with the fiber-based SERS sensor using Au nanovoid arrays is demonstrated by measuring the Raman spectrum of a mixture solution of diethylthiatricarbocyanine and crystal violet.     

Scalable Fabrication of Efficient Perovskite Solar Modules on Flexible Glass Substrates

Perovskite materials are good candidates for flexible photovoltaic applications due to their strong absorption and low‐temperature processing, but efficient flexible perovskite modules have not yet been realized. Here, a record efficiency flexible perovskite solar module is demonstrated by blade coating high‐quality perovskite films on flexible Corning Willow Glass using additive engineering. Ammonium chloride (NH₄Cl) is added into the perovskite precursor solution to retard the nucleation which prevents voids formation at the interface of perovskite and glass. The addition of NH₄Cl also suppresses the formation of PbI₂ and reduces the trap density in the perovskite films. The implementation of NH₄Cl enables the fabrication of single junction flexible perovskite solar devices with an efficiency of 19.72% on small‐area cells and a record aperture efficiency of 15.86% on modules with an area of 42.9 cm². This work provides a simple way to scale up high‐efficiency flexible perovskite modules for various applications.     

The structure of polyunsaturated lipid bilayers important for rhodopsin function: a neutron diffraction study

The structure of oriented 1-stearoyl-2-docosahexaenoyl-sn-glycero-3-phosphocholine bilayers with perdeuterated stearoyl- or docosahexaenoyl hydrocarbon chains was investigated by neutron diffraction. Experiments were conducted at two different relative humidities, 66 and 86%. At both humidities we observed that the polyunsaturated docosahexaenoyl chain has a preference to reside near the lipid water interface. That leaves voids in the bilayer center that are occupied by saturated stearoyl chain segments. This uneven distribution of saturated- and polyunsaturated chain densities is likely to result in membrane elastic stress that modulates function of integral receptor proteins like rhodopsin.     

Failure prediction of the total hip prosthesis system

The mechanical failure of the prosthesis-cement-femur system is analyzed by using a two-dimensional finite element model. The strain energy density (SED) criterion is applied to locate potential failure sites in the PMMA and prosthesis stem for five different prosthesis positions.

Medial and lateral failure sites in the proximal regions of the cement are found to be the most sensitive to prosthesis position. According to the SED criterion, these are the weakest regions of the cement. Additional bilateral failure sites are also located at the distal end of the prosthesis, but are less likely to fail. The overall structural integrity of the total hip system is found to be adequate for the ideal case considered herein. In practice, the combination of energy concentration coupled with imperfections such as voids and cracks in the cement are potential sites of failure initiation.

On the basis of clinical evidence on cement and prosthesis stem fracture, local reductions in the cement elastic modulus were introduced into the finite element model in order to model cement defects. The bilateral reduction of modulus by 40% in the cement adjacent to the distal portion of the prosthesis stem can lead to an increase of the strain energy density by 19%.     

Molecular interaction between organophosphorus acid anhydrolase and diisopropylfluorophosphate

Organophosphorus acid anhydrolases (OPAA; E.C.3.1.8.2) are a class of enzymes that hydrolyze a variety of toxic acetylcholinesterase-inhibiting organophosphorus (OP) compounds, including pesticides and fluorine-containing chemical nerve agents. In this paper, subphase conditions have been optimized to obtain stable OPAA Langmuir films, and the diisopropylfluorophosphate (DFP) hydrolysis reaction catalyzed by OPAA in aqueous solution and at the air-water interface was studied. OPAA-DFP interactions were investigated utilizing different spectroscopic techniques, that is, circular dichroism and fluorescence in aqueous solution and infrared reflection absorption spectroscopies at the air-water interface. The characterization of OPAA and its secondary structure in aqueous solution and as a monolayer at the air-water interface in the absence and in the presence of DFP dissolved in aqueous solution or in the aqueous subphase demonstrated significantly distinctive features. The research described herein demonstrated that OPAA can be used in an enzyme-based biosensor for DFP detection.     

CASTp: Computed Atlas of Surface Topography of proteins

Computed Atlas of Surface Topography of proteins (CASTp) provides an online resource for locating, delineating and measuring concave surface regions on three-dimensional structures of proteins. These include pockets located on protein surfaces and voids buried in the interior of proteins. The measurement includes the area and volume of pocket or void by solvent accessible surface model (Richards' surface) and by molecular surface model (Connolly's surface), all calculated analytically. CASTp can be used to study surface features and functional regions of proteins. CASTp includes a graphical user interface, flexible interactive visualization, as well as on-the-fly calculation for user uploaded structures. CASTp is updated daily and can be accessed at http://cast.engr.uic.edu.     

The Structure of Polyunsaturated Lipid Bilayers Important for Rhodopsin Function: A Neutron Diffraction Study

The structure of oriented 1-stearoyl-2-docosahexaenoyl-sn-glycero-3-phosphocholine bilayers with perdeuterated stearoyl- or docosahexaenoyl hydrocarbon chains was investigated by neutron diffraction. Experiments were conducted at two different relative humidities, 66 and 86%. At both humidities we observed that the polyunsaturated docosahexaenoyl chain has a preference to reside near the lipid water interface. That leaves voids in the bilayer center that are occupied by saturated stearoyl chain segments. This uneven distribution of saturated- and polyunsaturated chain densities is likely to result in membrane elastic stress that modulates function of integral receptor proteins like rhodopsin.     

Structure and energy of fusion stalks: the role of membrane edges

Fusion of lipid bilayers proceeds via a sequence of distinct structural transformations. Its early stage involves a localized, hemifused intermediate in which the proximal but not yet the distal monolayers are connected. Whereas the so-called stalk model most successfully accounts for the properties of the hemifused intermediate, there is still uncertainty about its microscopic structure and energy. We reanalyze fusion stalks using the theory of membrane elasticity. In our calculations, a short (cylindrical micelle-like) tether connects the two proximal monolayers of the hemifused membranes. The shape of the stalk and the length of the tether are calculated such as to minimize the overall free energy and to avoid the formation of voids within the hydrocarbon core. Our free energy expression is based on three internal degrees of freedom of a perturbed lipid layer: thickness, splay, and tilt deformations. Based on exactly the same model, we compare fusion stalks with and without the ability included to form sharp edges at the interfacial region between the hydrocarbon core and the polar environment. Requiring the interface to be smooth everywhere, our detailed calculations recover previous results: the stalk energies are far too high to account for the experimental observation of fusion intermediates. However, if we allow the interface to be nonsmooth, we find a remarkable reduction of the stalk free energy down to more realistic values. The corresponding structure of a nonsmooth stalk exhibits sharp edges at the transition regions between the bilayer and tether parts. In addition to that, a corner is formed at each of the two distal monolayers. We discuss the mechanism how membrane edges reduce the energy of fusion stalks.