Does the addition of vitamin E to conventional UHMWPE improve the wear performance of hip acetabular cups? Micro-Raman characterization of differently processed polyethylene acetabular cups worn on a hip joint simulator.

In knee replacements, vitamin E-doped ultra-high molecular weight polyethylene (UHMWPE) shows a better wear behavior than standard UHMWPE. Therefore, different sets of polyethylene (PE) acetabular cups, i.e. standard UHMWPE and cross-linked polyethylene irradiated with 50 kGy and 75 kGy, were compared, at a molecular level, with vitamin E-doped UHMWPE to evaluate their wear performance after being tested on a hip joint simulator for five million cycles. Unworn control and worn acetabular cups were analyzed by micro-Raman spectroscopy to gain insight into the effects of wear on the microstructure and phase composition of PE. Macroscopic wear was evaluated through mass loss measurements. The data showed that the samples could be divided into two groups: 1) standard and vitamin E-doped cups (mass loss of about 100 mg) and 2) the cross-linked cups (mass loss of about 30-40 mg). Micro-Raman spectroscopy disclosed different wear mechanisms in the four sets of acetabular cups, which were related to surface topography data. The vitamin E-doped samples did not show a better wear behavior than the cross-linked ones in terms of either mass loss or morphology changes. However, they showed lower variation at the morphological level (lower changes in phase composition) than the UHMWPE cups, thus confirming a certain protecting role of vitamin E against microstructural changes induced by wear testing.

Does the addition of vitamin E to conventional UHMWPE improve the wear performance of hip acetabular cups? Micro-Raman characterization of differently processed polyethylene acetabular cups worn on a hip joint simulator

In knee replacements, vitamin E-doped ultra-high molecular weight polyethylene (UHMWPE) shows a better wear behavior than standard UHMWPE. Therefore, different sets of polyethylene (PE) acetabular cups, i.e. standard UHMWPE and cross-linked polyethylene irradiated with 50 kGy and 75 kGy, were compared, at a molecular level, with vitamin E-doped UHMWPE to evaluate their wear performance after being tested on a hip joint simulator for five million cycles. Unworn control and worn acetabular cups were analyzed by micro-Raman spectroscopy to gain insight into the effects of wear on the microstructure and phase composition of PE. Macroscopic wear was evaluated through mass loss measurements. The data showed that the samples could be divided into two groups: 1) standard and vitamin E-doped cups (mass loss of about 100 mg) and 2) the cross-linked cups (mass loss of about 30-40 mg). Micro-Raman spectroscopy disclosed different wear mechanisms in the four sets of acetabular cups, which were related to surface topography data. The vitamin E-doped samples did not show a better wear behavior than the cross-linked ones in terms of either mass loss or morphology changes. However, they showed lower variation at the morphological level (lower changes in phase composition) than the UHMWPE cups, thus confirming a certain protecting role of vitamin E against microstructural changes induced by wear testing.

Properties of BioRoot RCS, a tricalcium silicate endodontic sealer modified with povidone and polycarboxylate.

AIM: To evaluate the chemical and physical properties of a tricalcium silicate root canal sealer containing povidone and polycarboxylate (BioRoot RCS), a calcium silicate MTA-based sealer containing a salicylate resin (MTA Fillapex), a traditional eugenol-containing sealer (Pulp Canal Sealer) and an epoxy resin-based root canal sealer (AH Plus). METHODOLOGY: Calcium release, pH, setting time, water sorption, volume of open pores, volume of impervious portion, apparent porosity and weight loss were measured. The ability to nucleate calcium phosphates (CaP) after ageing 28 days in a simulated body fluid was evaluated using ESEM-EDX and micro-Raman spectroscopy. Data were statistically analysed (P = 0.05) using one-way anova (setting time, radiopacity, solubility, water sorption, porosity) or two-way anova (ion release tests). RESULTS: BioRoot RCS had a final setting time of 300 min and adequate radiopacity (5.2 mm Al). It demonstrated the highest (P < 0.05) and more prolonged ability to release calcium ions (721 ppm at 3 h) and to increase the pH (11-12) (P < 0.05); B-type carbonated apatite deposits were found on aged BioRoot RCS (biointeractivity-related CaP-forming ability). A final setting time of 270 min and good calcium release (17.4 ppm at 3 h) were measured for MTA Fillapex; apatite deposits were present on aged samples. No calcium release and no alkalizing activity were measured for Pulp Canal Sealer and AH Plus; no CaP nucleation was detected on aged Pulp Canal Sealer, and some apatite deposits were found on aged AH Plus (chemi/physisorption-related CaP-deposition). Higher and significantly different (P < 0.05) porosity, water sorption and solubility were measured for the two calcium silicate sealers, especially for BioRoot RCS. CONCLUSIONS: BioRoot RCS had bioactivity with calcium release, strong alkalizing activity and apatite-forming ability, and adequate radiopacity.

Properties of NeoMTA Plus and MTA Plus cements for endodontics.

AIM: To test a novel calcium silicate cement mixed with a water-based gel (NeoMTA Plus) with regard to chemical-physical properties and apatite-forming ability. METHODOLOGY: NeoMTA Plus (Avalon Biomed Inc. Bradenton, FL, USA; lot. 2014090301) and a commercial MTA-based material with similar properties (MTA Plus, Prevest Denpro Limited, Jammu, India; lot. 41001) were tested for ion-releasing ability, initial and final setting times, radiopacity, open and impervious porosity and apparent porosity, water sorption, weight loss, solubility, ability to nucleate calcium phosphates (CaP) after immersion in HBSS (Hank's Balanced Salt Solution) by ESEM-EDX and micro-Raman spectroscopy. The results were analysed statistically with the anova test (P  <  0.05). RESULTS: NeoMTA Plus had a prolonged setting time (315 min) and a satisfactory radiopacity (3.76 mm Al). Calcium and hydroxyl ion release was significantly greater and more prolonged in comparison with MTA Plus (P < 0.05). Both NeoMTA Plus and MTA Plus had high values of open porosity and solubility. ESEM-EDX and micro-Raman confirmed the ability to nucleate calcium phosphates on their surface after immersion in HBSS. CONCLUSION: NeoMTA Plus is a new calcium silicate-based cement for root filling with an adequate radiopacity and prolonged setting time. The ion release and CaP-forming ability could increase stability of the root filling and promote endodontic and periodontal tissue regeneration, enhancing the bioactivity and biocompatibility of the material.

Micro-topography and reactivity of implant surfaces: an in vitro study in simulated body fluid (SBF).

The creation of micro-textured dental implant surfaces possessing a stimulating activity represents a challenge in implant dentistry; particularly, the formation of a thin, biologically active, calcium-phosphate layer on their surface could help to strengthen the bond to the surrounding bone. The aim of the present study was to characterize in terms of macrostructure, micro-topography and reactivity in simulated body fluid (SBF), the surface of titanium (Ti) implants blasted with TiO2 particles, acid etched with hydrofluoric acid, and activated with Ca and Mg-containing nanoparticles. Sandblasted and acid-etched implants were analyzed by ESEM-EDX (environmental scanning electron microscope with energy dispersive X-ray system) to study the micromorphology of the surface and to perform elemental X-ray microanalysis (microchemical analyses) and element mapping. ESEM-EDX analyses were performed at time 0 and after a 28-day soaking period in SBF Hank's balanced salt solution (HBSS) following ISO 23317 (implants for surgery­in vitro evaluation for apatite-forming ability of implant materials). Microchemical analyses (weight % and atomic %) and element mapping were carried out to evaluate the relative element content, element distribution, and calcium/phosphorus (Ca/P) atomic ratio. Raman spectroscopy was used to assess the possible presence of impurities due to manufacturing and to investigate the phases formed upon HBSS soaking. Micro-morphological analyses showed a micro-textured, highly rough surface with microgrooves. Microchemical analyses showed compositional differences among the apical, middle, and distal thirds. The micro-Raman analyses of the as-received implant showed the presence of amorphous Ti oxide and traces of anatase, calcite, and a carbonaceous material derived from the decomposition of an organic component of lipidic nature (presumably used as lubricant). A uniform layer of Ca-poor calcium phosphates (CaPs) (Ca/P ratio <1.47) was observed after soaking in HBSS; the detection of the 961 cm⁻¹ Raman band confirms this finding. These implants showed a micro-textured surface supporting the formation of CaPs when immersed in SBF. These properties may likely favor bone anchorage and healing by stimulation of mineralizing cells.

Formaldehyde replacement with glyoxylic acid in semipermanent hair straightening: a new and multidisciplinary investigation.

OBJECTIVE: Formaldehyde is an effective and popular semipermanent hair straightener, but the severe consequences for human health due to its toxicity have prompted the search for safer alternatives. Different carbonyl compounds, including glyoxylic acid, have recently been proposed as promising candidates. Despite the interest in this topic, there is a lack of information about the interactions between hair keratin and straightener agents. This study addresses this issue to gain new insights useful in the development of new products for safe, semipermanent hair deformation. METHODS: The possible reactions occurring between carbonyl groups and nucleophilic sites on amino acid residues belonging to the keratin were investigated using as model compounds some aldehydes and amino acid derivatives. Raman and IR analyses on yak hair subjected to the straightening treatment with glyoxylic acid in different conditions were carried out. Scanning electron microscope (SEM) analyses were carried out on yak and curly human hair after each step of the straightening procedure. RESULTS: The reactions between aldehydes and N-α-acetyl-L-lysine revealed the importance of the carbonyl electrophilicity and temperature to form imines. Raman and IR analyses on yak hair subjected to the straightening treatment evidenced rearrangements in the secondary structure distribution, conformational changes to the disulphide bridges, a decrease of the serine residues and formation of imines. It was also indicated that straightening produced major conformational rearrangements within the hair fibre rather than on the cuticle. CONCLUSION: This investigation revealed the role played by the electrophilicity of the carbonyl on the straightener agent and of the temperature, closely related to the dehydration process. Raman and IR studies indicated the involvement of imine bonds and the occurrence of a sequence of conformational modifications during the straightening procedure. SEM analyses showed the effectiveness of the treatment at the cuticular level.

The predicted relative risk of premature ovarian failure for three radiotherapy modalities in a girl receiving craniospinal irradiation.

In girls and young women, irradiation of the ovaries can reduce the number of viable ovarian primordial follicles, which may lead to premature ovarian failure (POF) and subsequently to sterility. One strategy to minimize this late effect is to reduce the radiation dose to the ovaries. A primary means of reducing dose is to choose a radiotherapy technique that avoids irradiating nearby normal tissue; however, the relative risk of POF (RRPOF) due to the various therapeutic options has not been assessed. This study compared the predicted RRPOF after craniospinal proton radiotherapy, conventional photon radiotherapy (CRT) and intensity-modulated photon radiotherapy (IMRT). We calculated the equivalent dose delivered to the ovaries of an 11-year-old girl from therapeutic and stray radiation. We then predicted the percentage of ovarian primordial follicles killed by radiation and used this as a measure of the RRPOF; we also calculated the ratio of the relative risk of POF (RRRPOF) among the three radiotherapies. Proton radiotherapy had a lower RRPOF than either of the other two types. We also tested the sensitivity of the RRRPOF between photon and proton therapies to the anatomic position of the ovaries, i.e., proximity to the treatment field (2 ≤ RRRPOF ≤ 10). We found that CRT and IMRT have higher risks of POF than passive-scattering proton radiotherapy (PRT) does, regardless of uncertainties in the ovarian location. Overall, PRT represents a lower RRPOF over the two other modalities.

Retrieval analysis of three generations of Biolox® femoral heads: spectroscopic and SEM characterisation.

Wear and osteolysis continue to be the major reasons for revision surgery in Total Hip Arthroplasty. The introduction of the ceramic-on-ceramic bearings eliminates the problem of polyethylene wear debris. During the last 40 years, three generations of Biolox® ceramics were developed (Biolox®, Biolox® forte, and Biolox® delta), each better than the previous from the density, grain size and purity point of view. We conducted a retrieval study on 15 Biolox® femoral heads (Biolox®, Biolox® forte, and Biolox® delta) articulating against liners of the same type. Surface properties and residual stress were assessed using SEM, fluorescence and Raman spectroscopy. At SEM examination, the Biolox® delta retrievals showed a lower wear than the previous generations. The fluorescence measurements suggested different wear mechanisms in the three sets of retrievals. Micro-cracking was predominant in Biolox®, while in Biolox® forte and Biolox® delta a wider range of residual stress values was observed upon wear. Surface polishing was observed only in Biolox® and Biolox® forte. Raman spectroscopy of Biolox® delta femoral heads showed a progressive improvement in material composition. Wear induced a tetragonal to monoclinic transformation. The Raman results on the retrievals, here reported for the first time, allowed to validate the in vitro ageing protocols proposed in the literature to simulate the effects of the in vivo wear.

Poster - Thur Eve - 36: Out-of-Field dose in craniospinal irradiation.

The risk of radiotherapy induced secondary cancer depends on the integral dose delivered to the patient where the dose delivered within the radiation field is accounted for, as well as dose to out-of-field organs from scattered and leakage radiation. While commercial treatment planning systems allow accurate determination of in-field dose, they are generally not capable of accurate out-of-field dose prediction. Secondary cancer risk is especially an issue in craniospinal treatments where involved patients are often children or young adults. In this work we therefore propose a mathematical model that accurately predicts out-of-field dose for patients treated by craniospinal irradiation at the American University of Beirut Medical Center. An anthropomorphic phantom was imaged, planned and treated, with thermoluminescent dosimeters inserted in the phantom at in-field and out-of-field locations. The measurements showed that our treatment planning system calculated accurately (within 2%) dose inside the field, but did not perform well at points just outside the field edge and consistently underestimated the dose at points further away from the field edge. From the out-of-field measured data, a model was developed that predicts out-of-field dose at a point in the patient based on the distance of that point to the treatment field edge. The developed model is of the double-gaussian type; it contains parameters that can be tuned to make it applicable in other centers where linac geometry and treatment techniques may differ.

SU-E-T-257: Risk of Radiogenic Second Cancer after Photon and Proton Craniospinal Irradiation.

PURPOSE: To compare proton and photon therapies in terms of the risks of second cancers for a pediatric medulloblastoma patient receiving craniospinal irradiation (CSI). METHODS: Two CSI treatment plans with 23.4 Gy or Gy (RBE) prescribed dose were computed for a 4-year-old boy withmedulloblastoma: a three-field 6-MV photon therapy plan and a four-field proton therapy plan. The primary doses for both plans were determined using a commercial treatment planning system. Stray radiation doses for proton therapy were determined from Monte Carlo simulations, and stray radiation doses for photon therapy were determined from measured data. The dose-risk model based on Biological Effects of Ionization Radiation VII report was used to estimate risk of second cancer. RESULTS: Baseline predictions of the relative risk of each organ were always less for proton CSI than for photon CSI after various follow-up years for the patient. The lifetime risks of the incidence of second cancer after proton CSI and photon CSI were 7.7% and 92%, respectively, and the ratio of lifetime risk was 0.083. Uncertainty analysis revealed the qualitative findings of this study were insensitive to any plausible changes of dose-risk models and mean neutron radiation weighting factor. CONCLUSIONS: Proton therapy confers lower predicted risk of second cancer for the pediatric medulloblastoma patient compared with photon therapy.

Mobile or fixed unicompartmental knee prostheses? In-vitro wear assessments to solve this dilemma.

The unicompartmental knee prosthesis is an attractive alternative to total knee arthroplasty. Current UKP devices can be subdivided into two groups based on different design principles: fixed bearing knees, where the ultra-high molecular weight polyethylene meniscal component snap or press fits into the tibial tray, and mobile bearing designs which facilitate movement of the insert relative to the tray. The present study was aimed at comparing the in-vitro wear behaviour of fixed and mobile unicompartmental knee menisci under two configurations: the femoral components were cemented into a custom-made metallic block or, as a novelty of the present study, into a synthetic femur (i.e. under conditions which should better reproduce the in-vivo behaviour). Analyses were performed using a displacement-control knee wear simulator with "three-plus-one" stations. All the kinematics tests were set in accordance with the ISO 14243-1,2,3. Fixed and mobile polyethylene menisci showed a different wear behaviour: the fixation-frame influenced directional load transfer through each component in a qualitative and quantitative way. In fact, gravimetric results showed that under the metal block holder fixation, mobile components worn more than fixed components (weight losses of 8.7±2.0 mg and 2.6±1.09 mg, respectively); on the other hand, under the synthetic femur configuration, differences in wear behaviour were less pronounced and mobile menisci underwent a slightly lower weight loss than fixed components (4.5±2.2 mg vs. 6.7±1.4 mg). This different trend was explained in relation to the kinematic schemes of the two fixation methods. Raman spectroscopy, used to evaluate the UHMWPE crystallinity changes induced by mechanical stress, showed that mobile menisci specimens were more affected than the fixed components in both their superior and inferior surfaces, independent of the fixation-frame. In conclusion, if tested under conditions which should better reproduce the in-vivo behaviour, mobile UKPs did not show a worse wear behaviour than fixed components in terms of weight losses, although UHMWPE changes at the molecular scale could be detrimental.

Fluoride-containing nanoporous calcium-silicate MTA cements for endodontics and oral surgery: early fluorapatite formation in a phosphate-containing solution.

AIM: To test the chemical-physical properties and apatite-forming ability of experimental fluoride-doped calcium silicate cements designed to create novel bioactive materials for use in endodontics and oral surgery. METHODOLOGY: A thermally treated calcium silicate cement (wTC) containing CaCl(2) 5%wt was modified by adding NaF 1%wt (FTC) or 10%wt (F10TC). Cements were analysed by environmental scanning electron microscopy with energy-dispersive X-ray analysis, IR and micro-Raman spectroscopy in wet conditions immediately after preparation or after ageing in a phosphate-containing solution (Dulbecco's phosphate-buffered saline). Calcium and fluoride release and pH of the storage solution were measured. The results obtained were analysed statistically (Tukey's HSD test and two-way anova). RESULTS: The formation of calcium phosphate precipitates (spherulites) was observed on the surface of 24 h-aged cements and the formation of a thick bone-like B-type carbonated apatite layer (biocoating) on 28 day-aged cements. The rate of apatite formation was FTC>F10TC>wTC. Fluorapatite was detected on FTC and F10TC after 1 day of ageing, with a higher fluoride content on F10TC. All the cements released calcium ions. At 5 and 24 h, the wTC had the significantly highest calcium release (P<0.001) that decreased significantly over the storage time. At 3-28 days, FTC and F10TC had significantly higher calcium release than wTC (P<0.05). The F10TC had the significantly highest fluoride release at all times (P<0.01) that decreased significantly over storage time. No significant differences were observed between FTC and wTC. All the cements had a strong alkalinizing activity (OH(-) release) that remained after 28 days of storage. CONCLUSIONS: The addition of sodium fluoride accelerated apatite formation on calcium silicate cements. Fluoride-doped calcium silicate cements had higher bioactivity and earlier formation of fluorapatite. Sodium fluoride may be introduced in the formulation of mineral trioxide aggregate cements to enhance their biological behaviour. F-doped calcium silicate cements are promising bone cements for clinical endodontic use.

Apatite-forming ability (bioactivity) of ProRoot MTA.

AIM: Apatite-forming ability, considered as an index of bioactivity (bond-to-bone ability), was tested on ProRoot MTA cement after immersion in phosphate-containing solution (DPBS). METHODOLOGY: Disk samples were prepared and immersed in DPBS for 10 min, 5 h, 1 and 7 days. The cement surface was studied by attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy, by micro-Raman spectroscopy and by environmental scanning electron microscope with energy dispersive X-ray (ESEM-EDX) analyses. The pH of the storage solution was also investigated. RESULTS: Spectroscopic analyses revealed calcium phosphate bands after 5-h immersion in DPBS. After 1 day, an even coating composed of apatite spherulites (0.1-0.8 micron diameter) was observed by ESEM/EDX. After 7 days, its thickness had increased. Apatite nucleation had already occurred after 5-h immersion. At this time, the presence of portlandite (i.e. Ca(OH)(2) , calcium hydroxide) on the cement surface was also observed; at longer times, this component was released into the medium, which underwent a remarkable pH increase. CONCLUSIONS: The study confirms the ability of ProRoot MTA to form a superficial layer of apatite within hours. The excellent bioactivity of ProRoot MTA might provide a significant clinical advantage over the traditional cements used for root-end or root-perforation repair.

Wear behaviour in total ankle replacement: a comparison between an in vitro simulation and retrieved prostheses.

BACKGROUND: To minimise wear of the meniscal component in total ankle replacement, a three-component artificial joint has recently been developed. This new prosthesis has convex spherical tibial and anticlastic talar metal components with non-anatomic but ligament-compatible shapes in the sagittal plane, and a fully conforming ultra-high-molecular-weight-polyethylene meniscal component inserted in between. The in vitro wear of meniscal components can be assessed using a four-station joint simulator. The study was aimed at comparing wear patterns obtained in vitro with those observed in implant retrievals with the same design. METHODS: The wear tests were run in a joint wear simulator at a frequency of 1.1 Hz for two million cycles. Three bearings within corresponding metal components were subjected to flexion/extension (range 0-58 degrees), anterior-posterior translation (0-5.2 mm), internal-external rotation (-1.9 degrees to +5.7 degrees), and a maximum axial load of 2.6 KN. These conditions were taken from the most recent findings in ankle joint mechanics. Three prostheses of the same type were harvested from patients due to replacement failures not associated with the device, 24, 24 and 9 months, respectively, after implantation. The in vitro worn components and the three retrievals were analysed by using a scanning electron microscope, a Coordinate Measuring Machine, and micro-Raman spectroscopy. FINDINGS: Visual and microscopic observations, analyses, and Raman crystallinity-based measurements showed similarity between the patterns generated experimentally in the wear simulator and those seen in retrievals with similar wear life. INTERPRETATION: A joint wear simulator like the one used in this study, once configured properly, appears to be suitable to assess wear rates also in total ankle prostheses.

Effect of head surface roughness and sterilization on wear of UHMWPE acetabular cups.

The impact of femoral head surface roughness on wear of gamma-irradiation sterilized (3 MRad in nitrogen, crosslinked) and nonsterilized (not crosslinked) UHMWPE acetabular cups has been evaluated. Gravimetric wear testing was performed in a hip joint simulator for 2 x 10(6) cycles. CoCrMo heads were used with different surface roughness (R(a) = 15 nm and R(a) = 400 nm). The surface roughness after wear test was unchanged for the roughened heads, whereas the initially smooth heads showed a few scratches. The roughened heads increased the wear of the acetabular cups 2-fold. The gamma-irradiated cups tested against rough heads underwent the highest wear. The absorption of water was highest for the gamma-irradiated cups (0.0204% compared to 0.0031% after 85 days). Raman spectroscopy showed small but significant crystallinity changes in the wear zone, where the gamma-irradiated cups with the most extensive abrasion increased in crystallinity, whereas the nonsterilized cups underwent a crystallinity decrease.

Intercomparision of Monte Carlo Radiation Transport Codes MCNPX, GEANT4, and FLUKA for Simulating Proton Radiotherapy of the Eye.

Monte Carlo simulations of an ocular treatment beam-line consisting of a nozzle and a water phantom were carried out using MCNPX, GEANT4, and FLUKA to compare the dosimetric accuracy and the simulation efficiency of the codes. Simulated central axis percent depth-dose profiles and cross-field dose profiles were compared with experimentally measured data for the comparison. Simulation speed was evaluated by comparing the number of proton histories simulated per second using each code. The results indicate that all the Monte Carlo transport codes calculate sufficiently accurate proton dose distributions in the eye and that the FLUKA transport code has the highest simulation efficiency.

Chemical and physical properties of sulfated silk fabrics.

Silk fabrics were treated with chlorosulphonic acid in pyridine for different times. The amount of sulfur bound to silk increased during the first 2 h of reaction and then reached a plateau. The amino acidic pattern of sulfated silk remained essentially unchanged for short reaction times (< or =2 h). Longer reaction times resulted in drastic changes in the concentration of Asp, Glu, and Tyr. Surface morphology and texture of silk fabrics changed upon sulfation. Warp and weft yarns became progressively thinner, and deposits of foreign material appeared on the fiber surface. Changes were more evident at longer reaction times (> or =2 h). Spectroscopic analyses performed by FT-IR and FT-Raman showed the appearance of new bands attributable to various vibrations of sulfated groups. The IR bands at 1049 and 1014 cm-1, due to organic sulfate salts, were particularly intense. Bands assigned to alkyl sulfates and sulfonamides appeared in the 1300-1180 cm-1 range. Organic covalent sulfates displayed a weak but distinct IR band at 1385 cm-1. Both IR and Raman spectra revealed that silk fibroin mainly bound sulfates through the hydroxyl groups of Ser and Tyr, while involvement of amines could not be proved. Changes observed in the amide I and II range indicated an increase of the degree of molecular disorder of sulfated silk. Accordingly, the I850/I830 intensity ratio between the two Tyr bands at 850-830 cm-1 increased from 1.41 to 1.52, indicating a more exposed state of Tyr residues in sulfated silk. TGA, DSC, and TG analyses showed that sulfated silk attained a higher thermal stability. A thermal transition attributable to sulfated silk fibroin fractions appeared at about 260 degrees C in the DSC thermograms.

In vitro bioactivity of poly(epsilon-caprolactone)-apatite (PCL-AP) scaffolds for bone tissue engineering: the influence of the PCL/AP ratio.

Porous poly(epsilon-caprolactone) (PCL) is used as long-term bioresorbable scaffold for bone tissue engineering. The bone regeneration process can be enhanced by addition of carbonated apatites (AP). This study was aimed at evaluating the influence of the PCL/AP ratio on the in vitro degradation and bioactivity of PCL-AP composites. To this purpose, PCL-AP samples were synthesised with the following PCL/AP weight/weight ratios: 50/50, 60/40 and 75/25. Vibrational IR and Raman spectroscopies coupled to thermogravimetry (TG) and differential scanning calorimetry (DSC) were used to investigate the in vitro degradation mechanism in different media: 0.01 M NaOH solution (pH=12), saline phosphate buffer at pH 7.5 (SPB), esterase in SPB and simulated body fluid (SBF) at pH 7.5. The latter medium was used to evaluate the bioactivity of the composites. A control PCL sample was analysed before the addition of the AP component. As regards the untreated samples, the method of synthesis utilised for preparing the composite was found to enhance the crystallinity degree. The AP component revealed to be constituted of a B-type carbonated hydroxyapatite with a 3% carbonate content. After 28 days of treatment, the samples showed different degradation patterns and extents depending on the degradation medium, the starting PCL crystallinity and composite composition. Weight measurements, Raman and TG analyses revealed deposition of an apatitic phase on all the composites immersed in SBF. Therefore, all the samples displayed a good bioactivity; the sample which showed the most pronounced apatitic deposition was 50/50, i.e. that containing the highest amount of AP.

Advanced nanocomposite materials for orthopaedic applications. I. A long-term in vitro wear study of zirconia-toughened alumina.

The use of ceramic-on-ceramic (alumina- and zirconia-based) couplings in hip joint prostheses has been reported to produce lower wear rates than other combinations (i.e., metal-on-polyethylene and ceramic-on-polyethylene). The addition of zirconia into an alumina matrix (zirconia-toughened alumina, ZTA) has been reported to result in an enhancement of flexural strength, fracture toughness, and fatigue resistance. The development of new processing routes in nonaqueous media has allowed to obtain high-density ZTA nanocomposites with a very homogeneous microstructure and a significantly smaller and narrower particle-size distribution of zirconia than conventional powder mixing methods. The aim of the present study was to set up and validate a new ZTA nanocomposite by testing its biocompatibility and wear behavior in a hip-joint simulator in comparison with commercial alumina and experimental alumina specimens. The primary osteoblast proliferation onto ZTA nanocomposite samples was found to be not significantly different from that onto commercial alumina samples. After 7 million cycles, no significant differences were observed between the wear behaviors of the three sets of cups. In this light, it can be affirmed that ZTA nanocomposite materials can offer the option of improving the lifetime and reliability of ceramic joint prostheses.