High failure rates of the Spectron EF stem at a minimum of 10 year's follow-up.

We prospectively followed 112 hips, undergoing THA with a Spectron EF stem. At mean follow-up of 11.2years, 21 patients had died. We obtained radiological follow-up in 99% and clinical follow-up in 100% of the surviving 91 hips. Fifty-four percent demonstrated osteolysis in at least one Gruen zone. Twenty-two hips required revision for all causes, with a further five stems radiologically loose. With endpoint being stem revision for aseptic loosening or radiological failure, survivorship at 11years was 0.783. We believe the addition of a rougher surface finish has contributed to the high levels of osteolysis and stem failure seen with the Spectron EF.

A long-lasting guided bone regeneration membrane from sequentially functionalised photoactive atelocollagen.

The fast degradation of collagen-based membranes in the biological environment remains a critical challenge, resulting in underperforming Guided Bone Regeneration (GBR) therapy leading to compromised clinical results. Photoactive atelocollagen (AC) systems functionalised with ethylenically unsaturated monomers, such as 4-vinylbenzyl chloride (4VBC), have been shown to generate mechanically competent materials for wound healing, inflammation control and drug delivery, whereby control of the molecular architecture of the AC network is key. Building on this platform, the sequential functionalisation with 4VBC and methacrylic anhydride (MA) was hypothesised to generate UV-cured AC hydrogels with reduced swelling ratio, increased proteolytic stability and barrier functionality for GBR therapy. The sequentially functionalised atelocollagen precursor (SAP) was characterised via TNBS and ninhydrin colourimetric assays, circular dichroism and UV-curing rheometry, which confirmed nearly complete consumption of collagen's primary amino groups, preserved triple helices and fast (< 180 s) gelation kinetics, respectively. Hydrogel's swelling ratio and compression modulus were adjusted depending on the aqueous environment used for UV-curing, whilst the sequential functionalisation of AC successfully generated hydrogels with superior proteolytic stability in vitro compared to both 4VBC-functionalised control and the commercial dental membrane Bio-Gide®. These in vitro results were confirmed in vivo via both subcutaneous implantation and a proof-of-concept study in a GBR calvarial model, indicating integrity of the hydrogel and barrier defect, as well as tissue formation following 1-month implantation in rats. STATEMENT OF SIGNIFICANCE: Collagen-based membranes remain a key component in Guided Bone Regeneration (GBR) therapy, but their properties, e.g. proteolytic stability and soft tissue barrier functionality, are still far from optimal. This is largely attributed to the complex molecular configuration of collagen, which makes chemical accessibility and structure-function relations challenging. Here, we fabricated a UV-cured hydrogel network of atelocollagen, whereby triple helices were sequentially functionalised with two distinct ethylenically unsaturated monomers. The effects of the sequential functionalisation and UV-curing on the macroscopic properties, degradation behaviour and GBR capability were investigated in vitro and in vivo. The results highlight the key role of the sequential functionalisation and provide important insights for the design of future, longer-lasting resorbable membranes for GBR therapy.

Distribution of enamel crystallite orientation through an entire tooth crown studied using synchrotron X-ray diffraction.

The biomineralization of human dental enamel has resulted in a highly anisotropic and heterogeneous distribution of hydroxyapatite crystallites, which in combination with its high mineral content has resulted in one of the most durable and hardest tissues in the human body. In this study, we used position-sensitive synchrotron X-ray diffraction to quantify the spatial variation in the direction and magnitude of the preferred orientation of enamel crystallites across a whole tooth crown. Two-dimensional synchrotron X-ray diffraction images were collected with 300 µm spatial resolution over a series of six sequential tooth sections obtained from a single maxillary first premolar and were analyzed using Rietveld refinement. Both the magnitude and the direction of the crystallite orientation were found to have a high spatial heterogeneity. Areas of high crystallite alignment were directed perpendicular to the biting surfaces, which is thought to meet the functional requirements of mastication. The results may assist in our understanding of the structure-function relationship and of the evolutionary development of enamel.

Development and characterisation of dental composites containing anisotropic fluorapatite bundles and rods.

OBJECTIVES: To develop dental composites incorporating fluorapatite (FA) crystals as a secondary filler and to characterise degree of conversion, key mechanical properties and fluoride release. METHODS: FA rod-like crystals and bundles were hydrothermally synthesised and characterised by scanning electron microscopy/energy dispersive X-ray spectroscopy (SEM/EDS), X-ray diffraction (XRD) and 19F MAS-NMR. Composites were formulated containing BisGMA/TEGDMA/BisEMA and barium-aluminium-silicate glass (0FA). FA crystals were incorporated at 10 (10FA), 20 (20FA), 30 (30FA) and 40wt% (40FA) maintaining a filler content of 80wt% (63-67vol%). Degree of conversion (DC), flexural strength (FS), flexural modulus (FM), fracture toughness (K1C), Vickers hardness (HV) and 2-body wear were measured. Fluoride release was measured in neutral and acidic buffers. RESULTS: XRD and 19F MAS-NMR confirmed that only FA was formed, whilst SEM revealed the presence of single rods and bundles of nano-rods. DC ranged between 56-60% (p>0.05). FA composites showed lower FM and lower FS (p<0.05), but comparable wear resistance and HV (p>0.05) to 0FA. 30FA and 40FA showed similar K1C to 0FA (p>0.05), with SEM showing evidence of toughening mechanisms, whereas 10FA and 20FA showed lower K1C (p<0.05). FA containing composites released fluoride that was proportional to the amount of FA incorporated (p<0.05) but only under acidic conditions. SIGNIFICANCE: The addition of FA to the experimental composites reduced strength and stiffness but not the DC, hardness or wear rate. 30FA and 40FA had a higher K1C compared to other FA groups. Fluoride release occurred under an accelerated acidic regime, suggesting potential as a bioactive 'smart' composite.

Post-fatigue fracture resistance of premolar teeth restored with endocrowns: An in vitro investigation.

OBJECTIVES: To evaluate the post-fatigue load-to-failure and failure modes of endodontically treated premolar teeth restored with endocrowns fabricated from different CAD/CAM materials. MATERIALS AND METHODS: A total of 60 extracted human, single-rooted premolar teeth were endodontically treated and sectioned horizontally 2 mm above the cementoenamel junction. Sectioned teeth were restored using two reconstruction designs: endocrowns (Cendo) or post-crowns (Cpost) (n = 30 p/g). In each group, reconstructions were fabricated from 3 different CAD/CAM substrates (n = 10 p/g); a resin-based composite (Cera), a lithium disilicate glass ceramic (LiSi) and a monolithic, translucent zirconia (Zir). Additional 10 intact teeth were used as control. Restored teeth were subjected to dynamic fatigue test (10-50 N, 600,000 cycles) and thermocycling (5-55 °C, 1500 cycles). Load-to-failure and failure mode was determined following application of a static, 45° oblique compressive load on each specimen. One-way and Two-way analysis of variance (ANOVA), Tukey's post hoc and chi-square tests were used to determine statistically significant interactions among experimental and control groups. RESULTS: All specimens survived the mechanical and thermal fatigue tests. A statistically significant interaction between reconstruction design and material type was observed (p  <  0.001). CpostZir and CendoCera groups exhibited significantly higher post-fatigue load-to-failure when compared to other materials of the same reconstruction design (p ≤ 0.001). The highest frequency of catastrophic failures was observed with Zir reconstructions in both designs. Intact teeth exhibited significantly higher load-to-failure when compared to all groups (p ≤ 0.042) except CpostZir (p = 0.345). CONCLUSION: Single piece, CAD/CAM resin composite endocrowns can present a reliable option for restoring endodontically treated premolar teeth. CLINICAL SIGNIFICANCE: Endocrowns can be as effective as post-crowns provided appropriate preparation; material selection; and bonding protocols are utilized. Clinicians need to be cautious when prescribing zirconia endocrowns to restore premolar teeth owing to the low fracture resistance and high risk of catastrophic failures.

Cement penetration after patella venting.

There is a high rate of patellofemoral complications following total knee arthroplasty. Optimization of the cement-bone interface by venting and suction of the tibial plateau has been shown to improve cement penetration. Our study was designed to investigate if venting the patella prior to cementing improved cement penetration. Ten paired cadaver patellae were allocated prior to resurfacing to be vented or non-vented. Bone mineral density (BMD) was measured by DEXA scanning. In vented specimens, a 1.6 mm Kirschner wire was used to breach the anterior cortex at the center. Specimens were resurfaced with standard Profix instrumentation and Versabond bone cement (Smith and Nephew PLC, UK). Cement penetration was assessed from Faxitron and sectioned images by a digital image software package (ImageJ V1.38, NIH, USA). Wilcoxon rank sum test was used to assess the difference in cement penetration between groups. The relationship between BMD and cement penetration was analyzed by Pearson correlation coefficient. There was a strong negative correlation between peak BMD and cement penetration when analyzed independent of experimental grouping (r(2)=-0.812, p=0.004). Wilcoxon rank sum testing demonstrated no significant difference (rank sum statistic W=27, p=0.579) in cement penetration between vented (10.53%+/-4.66; mean+/-std dev) and non-vented patellae (11.51%+/-6.23; mean+/-std dev). Venting the patella using a Kirschner wire does not have a significant effect on the amount of cement penetration achieved in vitro using Profix instrumentation and Versabond cement.

Deformation and retentive force following in vitro cyclic fatigue of cobalt-chrome and aryl ketone polymer (AKP) clasps.

OBJECTIVE: To compare the retention force of individual clasps made from cobalt chromium (CoCr) or new aryl ketone polymer (AKP) material, Ultaire™ AKP, following prolonged fatigue testing along ideal and non-ideal paths of removal and to assess 3D deformation of the active and passive clasp tips. METHODS: CoCr and AKP clasps were manufactured in their standard, respective processes, digitally scanned prior to testing, then cycled 15,000 times over an e.max analogue crown in artificial saliva. Retentive load was measured in situ, as a function of cycles. Clasps were rescanned to assess deformation and along with their antagonists subjected to SEM to assess localised wear. RESULTS: Distortion of the CoCr clasps was consistently larger than Ultaire™ AKP clasps, irrespective of removal path. CoCr clasps had significantly higher retentive forces than AKP clasps, for both removal paths. Ultaire™ AKP clasps showed a lower but relatively constant retentive force. The non-ideal path of removal affected retentive forces for both clasp materials. SEM showed localised removal of glaze for e.max crowns used with CoCr clasps. SIGNIFICANCE: Ultaire™ AKP clasps showed significantly less permanent deformation and lower retentive force than CoCr clasps. Unlike CoCr, the Ultaire™ AKP clasps did not work harden, nor had as large a reduction in retentive force and accompanying permanent deformation; the retentive force for the Ultaire™ AKP clasps was consistent over 15,000 cycles of fatigue mimicking prolonged clinical use. The AKP material was more robust; showing minimal deformation even in non-ideal paths of removal, as many patients would routinely use.

Intracoronal stress transfer through enamel following RBC photopolymerisation: A synchrotron X-ray study.

OBJECTIVES: To measure the spatial distribution of crystallographic strain in tooth enamel induced by the photo-polymerisation of a dimethacrylate resin based composite cavity restoration. METHODS: Six sound first premolar teeth, allocated into two groups (n=3), were prepared with mesio-occlusal distal cavities. The enamel was machined at the point of maximum convexity on the outer tooth to create a vertical fin of thickness 100µm and 0.5mm depth to allow for synchrotron X-ray diffraction measurements. 2D diffraction patterns were used to determine crystallite orientation and quantify changes in the hydroxyapatite crystal lattice parameters, before and after photo-polymerisation of a composite material placed in the cavity, to calculate strain in the respective axis. The composite was photo-polymerised with either relatively high (1200mWcm-2, group 1) or low (480mWcm-2, group 2) irradiances using LED or quartz halogen light sources, respectively. A paired t-test was used to determine significant differences in strain between irradiance protocols at ɑ=0.001. RESULTS: Photo-polymerisation of the composite in the adjacent cavity induced significant changes in both the crystallographic c and a axes of the enamel measurement area. However the magnitude of strain was low with ∼0.1% difference before and after composite photo-polymerisation. Strain in enamel was not uniformly distributed and varied spatially as a function of crystallite orientation. Increased alignment of crystallites perpendicular to the cavity wall was associated with higher c axis strain. Additionally, strain was significantly greater in the c (p<0.001) and a axis (p<0.001) when using a high irradiance photo-polymerisation protocol. SIGNIFICANCE: Although cuspal deflection is routinely measured to indirectly assess the 'global' effect of composite shrinkage on the tooth-restoration complex, here we show that absolute strains generated in enamel are low, indicating strain relief mechanisms may be operative. The use of low irradiance protocols for photo-polymerisation resulted in reduced strain.

2D mapping of texture and lattice parameters of dental enamel.

We have used synchrotron X-ray diffraction to study the texture and the change in lattice parameter as a function of position in a cross section of human dental enamel. Our study is the first to map changes in preferred orientation and lattice parameter as a function of position within enamel across a whole tooth section with such high resolution. Synchrotron X-ray diffraction with a micro-focused beam spot was used to collect two-dimensional (2D) diffraction images at 150 microm spatial resolution over the entire tooth crown. Contour maps of the texture and lattice parameter distribution of the hydroxyapatite phase were produced from Rietveld refinement of diffraction patterns generated by azimuthally sectioning and integrating the 2D images. The 002 Debye ring showed the largest variation in intensity. This variation is indicative of preferred orientation. Areas of high crystallite alignment on the tooth cusps match the expected biting surfaces. Additionally we found a large variation in lattice parameter when travelling from the enamel surface to the enamel-dentine junction. We believe this to be due to a change in the chemical composition within the tooth. The results provide a new insight on the texture and lattice parameter profiles within enamel.

Development of custom-built bone scaffolds using mesenchymal stem cells and apatite-wollastonite glass-ceramics.

There is a clinical need for new bone replacement materials that combine long implant life with complete integration and appropriate mechanical properties. We have used human mesenchymal stem cells (MSCs) to populate porous apatite-wollastonite (A-W) glass-ceramic scaffolds produced by the layer manufacturing technique, selective laser sintering, to create custom-built bone replacements. Confocal and scanning electron microscopy were used to determine optimal seeding densities and to demonstrate that MSCs adhered and retained viability on the surface of A-W scaffolds over a culture period of 21 days. We found a significant increase in the number of MSCs growing on the scaffolds over 7 days. Using bromodeoxyuridine incorporation we demonstrated that MSCs proliferated on the scaffolds. Using real-time PCR we analyzed the expression of the osteogenic markers alkaline phosphatase, collagen type-I, Cbfa-1, osteocalcin, osteonectin, and osteopontin by MSCs cultured in the absence of osteogenic supplements. The expression of the osteogenic markers by MSCs was equivalent to or significantly greater on A-W scaffolds than on tissue culture plastic. We also identified significantly higher alkaline phosphatase activity on A-W compared to a commercial calcium phosphate scaffold. These results indicate for the first time the biocompatibility and osteo-supportive capacity of A-W scaffolds and their potential as patient-specific bone replacement materials.

Biological evaluation of an apatite-mullite glass-ceramic produced via selective laser sintering.

The biological performance of a porous apatite-mullite glass-ceramic, manufactured via a selective laser sintering (SLS) method, was evaluated to determine its potential as a bone replacement material. Direct contact and extract assays were used to assess the cytotoxicity of the material. A pilot animal study, implanting the material into rabbit tibiae for 4 weeks, was also carried out to assess in vivo bioactivity. The material produced by SLS did not show any acute cytotoxic effects by either contact or extract methods. There was no evidence of an apatite layer forming on the surface of the material when soaked in SBF for 30 days, suggesting that the material was unlikely to exhibit bioactive behaviour in vivo. It is hypothesized that the material was unable to form an apatite layer in SBF due to the fact that this glass-ceramic was highly crystalline and the fluorapatite crystal phase was relatively stable in SBF, as were the two aluminosilicate crystal phases. There was thus no release of calcium and phosphorus and no formation of silanol groups to trigger apatite deposition from solution within the test time period. Following implantation in rabbit tibiae for 4 weeks, bone was seen to have grown into the porous structure of the laser-sintered parts, and appeared to be very close to, or directly contacting, the material surface. This result may reflect the local environment in vivo compared to that artificially found with the in vitro SBF test and, furthermore, confirms previous in vivo data on these glass-ceramics.

Thirty-five percent carbamide peroxide application causes in vitro demineralization of enamel.

OBJECTIVES: The objective of this in vitro study was to investigate whether a high concentration 'in-office' bleaching agent affected the mineral content of enamel and dentin. METHODS: A commercially available 35% carbamide peroxide bleaching agent was applied for 2h to sectioned teeth (n=11). Specimens were then immersed in artificial saliva at 37 degrees C for a further 24h to simulate the oral environment. Tomographic images of these sections were obtained (micro-CT 80, Scanco, Switzerland) prior to and post-bleach application. Eight three-dimensional regions of interest (ROI), starting from the enamel surface extending to the dentinoenamel junction, were selected for each section. The hydroxyapatite equivalent mineral concentrations (g/cm(3)) of the ROIs were calculated. Any changes in mineral content as a consequence of the bleaching procedure were calculated in relation to each ROI. RESULTS: There was a significant reduction in the mineral content of enamel specimens post-bleach application extending to a depth of 250microm (paired t-test, p<0.05); this reduction in mineral content was greatest in the ROI's closest to the tooth surface. There was, however, no significant difference in the mineral content of dentin as a consequence of bleaching. SIGNIFICANCE: This in vitro study has shown that significant demineralization of enamel occurred following bleaching with 35% carbamide peroxide. The concept that 'in-office' bleaching is a non-destructive cosmetic procedure should be reconsidered.

The use of confocal microscopy to assess surface roughness of two milled CAD-CAM ceramics following two polishing techniques.

OBJECTIVE: To assess the effects of two polishing techniques on the surface roughness of a commercial and experimental dental ceramic for use in a chairside CAD-CAM system. METHODS: A standard onlay was reproduced fifteen times in each of the two materials. Each stub was retained and examined using confocal microscopy in reflection mode. Five random samples of each were polished with Sof-Lex aluminium oxide discs, five polished with diamond impregnated polishing wheels and five left in the as-machined state. Surface roughness parameters were measured for each material group in each condition and statistical analyses carried out to determine the efficacy of the polishing techniques for each material. RESULTS: The as-machined surfaces of both materials had a statistically similar surface finish. Polishing with Sof-Lex discs was effective at reducing surface roughness of both materials. Whilst the polishing wheels were effective in reducing surface roughness for the commercial material, there was no statistically significant difference in the surface roughness of the experimental material in the as-machined or wheel polished states. SIGNIFICANCE: Although Sof-Lex discs were effective in reducing surface roughness of the two materials examined in this study, wheel polishing should not be used to reduce surface roughness of the experimental material. This will need to be taken into consideration in any future clinical studies of this material.

An investigation of the constituent elements and modes of fracture of in vivo fractured metallic posts.

OBJECTIVES: The objective of this investigation was to determine the materials used in metallic post and core construction and investigate and the modes of failure that occurred resulting in post fracture. METHODS: Eighty-five fractured metal posts were clinically retrieved over a 5-year period. The tooth with the fractured post, and relevant clinical details were recorded. Investigation of the fractured posts was undertaken to determine their constituent elements and modes of fracture using scanning electron microscopy (SEM) and energy-dispersive X-ray analysis (EDX). RESULTS: The results showed that 77% of the posts were cast and 23% wrought. The modes of fracture were ductile (67%) or brittle (52%) although some posts exhibited both within the same specimen. In addition, evidence of fatigue was present in 20% of posts and porosity in 48%. CONCLUSIONS: A large variety of materials were used in the construction of post and cores although low-gold silver-palladium alloy most commonly encountered. Their failure was predominantly ductile in nature although a significant amount of brittle fracture was also noted. Porosity within castings also appeared to be a contributory factor in some cases and this was particularly evident in high-palladium castings. Evidence of fatigue was noted in a minority of posts.

An approach to understanding tribological behaviour of dental composites through volumetric wear loss and wear mechanism determination; beyond material ranking.

OBJECTIVE: To investigate the fundamental wear mechanisms of six resin-based composite (RBC) formulations during short-term in vitro wear testing. MATERIALS: RBC materials were condensed into rectangular bar-shaped specimens and light irradiated using the ISO 4049 specimen manufacture and irradiation protocol. Wear testing (n=10 specimens for each RBC) was performed on a modified pin-on-plate wear test apparatus and wear facets were analysed for wear volume loss using a white light profilometer. The wear tested RBC specimens and their corresponding antagonists were analysed using scanning electron microscopy (SEM) and energy-dispersive X-ray spectroscopy (EDS), respectively to determine the wear mechanism. RESULTS: Data generated using the profilometer showed variations in the mean total wear volume (mm3) between the RBCs tested (p<0.05). Abrasive wear was evident in all RBCs investigated with varying degrees of damage. Material transfer/deposition of the filler particles on the corresponding antagonists was evident in two RBC materials (Filtek Supreme and Kalore) indicative of a further adhesive wear mechanism. CONCLUSION: It is proposed that the approach employed to use a combination of measurement and analytical techniques to quantify the wear facet volume (profilometry), wear trough (SEM) and material transfer (EDS) provides more useful information on the wear mechanism and the tribology of the system rather than relying on a simple wear ranking for the RBC materials as is routinely the case in dental research studies.

Physicochemical and Antibacterial Characterization of a Novel Fluorapatite Coating.

Peri-implantitis remains the major impediment to the long-term use of dental implants. With increasing concern over the growth in antibiotic resistance, there is considerable interest in the preparation of antimicrobial dental implant coatings that also induce osseointegration. One such potential coating material is fluorapatite (FA). The aim of this study was to relate the antibacterial effectiveness of FA coatings against pathogens implicated in peri-implantitis to the physicochemical properties of the coating. Ordered and disordered FA coatings were produced on the under and upper surfaces of stainless steel (SS) discs, respectively, using a hydrothermal method. Surface charge, surface roughness, wettability, and fluoride release were measured for each coating. Surface chemistry was assessed using X-ray photoelectron spectroscopy and FA crystallinity using X-ray diffraction. Antibacterial activity against periodontopathogens was assessed in vitro using viable counts, confocal microscopy, and scanning electron microscopy (SEM). SEM showed that the hydrothermal method produced FA coatings that were predominately aligned perpendicular to the SS substrate or disordered FA coatings consisting of randomly aligned rodlike crystals. Both FA coatings significantly reduced the growth of all examined bacterial strains in comparison to the control. The FA coatings, especially the disordered ones, presented significantly lower charge, greater roughness, and higher area when compared to the control, enhancing bacteria-material interactions and therefore bacterial deactivation by fluoride ions. The ordered FA layer reduced not only bacterial viability but adhesion too. The ordered FA crystals produced as a potential novel implant coating showed significant antibacterial activity against bacteria implicated in peri-implantitis, which could be explained by a detailed understanding of their physicochemical properties.

Reinforcement of poly(methyl methacrylate) denture base with glass flake.

OBJECTIVES: Since the introduction of poly(methyl methacrylate) as a denture base material, it has suffered from having relatively poor mechanical properties. Many methods of improving its strength and toughness have been investigated. Most of these have not been adopted due to: increased cost, the need for specialist processing equipment or increased laboratory time due to more complicated procedures. Glass flake has been used as a reinforcing agent in many industrial polymers, but is as yet untested with denture base acrylic materials. The aim of this study is to evaluate the effect of adding glass flake to denture base acrylic powder on the fracture toughness of the set material. METHODS: Glass flake was added in 5, 10 or 20% w/w to Trevalon denture base powder. The material was mixed, flasked, packed and processed in a manner typical for a denture base material. Fracture toughness was determined using a double torsion test technique. RESULTS: The addition of glass flake gave up to a 69% increase in fracture toughness compared to plain Trevalon material. The addition of 5% glass flake lead to an improvement in fracture toughness that was statistically significant compared to both plain Trevalon and the 10 and 20% groups. SIGNIFICANCE: The significant improvement in fracture toughness of a denture base acrylic material using glass flake is an extremely promising result. Other mechanical properties will require testing before glass flake can be recommended as a reinforcing agent for denture base acrylic materials.

Thermal conductivity through various restorative lining materials.

OBJECTIVES: Traditional teaching has advocated the placement of insulating materials under restorations to protect against 'thermal shock'. Often this involves placement of a thick zinc-oxide eugenol cement lining. The purpose of this in vitro study was to assess the heat transfer through four lining materials and dentine and to relate these findings to the temperature exposures that may be experienced in the oral environment. METHODS: Two 'traditional' linings, zinc oxide eugenol cement (ZNOE) and calcium hydroxide paste (CAOH), and two more contemporary materials, a resin modified glass polyalkenoate (RMGP) and dentine bonding system (DBS) were studied in addition to dentine itself. Seven samples of each material were tested by utilising a Lees' Disc apparatus. Incorporation of thermocouples allowed heat transfer through the sample to be recorded. Thermal conductivity (J/m/s/ degrees C) was calculated for individual samples and a mean value obtained for each material. One way ANOVA and post hoc Tukey's tests were applied to the data obtained. RESULTS: In ascending order of thermal conductivity, DBS

Multi-scale mechanical characterization of highly swollen photo-activated collagen hydrogels.

Biological hydrogels have been increasingly sought after as wound dressings or scaffolds for regenerative medicine, owing to their inherent biofunctionality in biological environments. Especially in moist wound healing, the ideal material should absorb large amounts of wound exudate while remaining mechanically competent in situ. Despite their large hydration, however, current biological hydrogels still leave much to be desired in terms of mechanical properties in physiological conditions. To address this challenge, a multi-scale approach is presented for the synthetic design of cyto-compatible collagen hydrogels with tunable mechanical properties (from the nano- up to the macro-scale), uniquely high swelling ratios and retained (more than 70%) triple helical features. Type I collagen was covalently functionalized with three different monomers, i.e. 4-vinylbenzyl chloride, glycidyl methacrylate and methacrylic anhydride, respectively. Backbone rigidity, hydrogen-bonding capability and degree of functionalization (F: 16 ± 12-91 ± 7 mol%) of introduced moieties governed the structure-property relationships in resulting collagen networks, so that the swelling ratio (SR: 707 ± 51-1996 ± 182 wt%), bulk compressive modulus (Ec: 30 ± 7-168 ± 40 kPa) and atomic force microscopy elastic modulus (EAFM: 16 ± 2-387 ± 66 kPa) were readily adjusted. Because of their remarkably high swelling and mechanical properties, these tunable collagen hydrogels may be further exploited for the design of advanced dressings for chronic wound care.

Wet-spinnability and crosslinked fibre properties of two collagen polypeptides with varied molecular weight.

The formation of naturally derived materials with wet stable fibrous architectures is paramount in order to mimic the features of tissues at the molecular and microscopic scale. Here, we investigated the formation of wet-spun fibres based on collagen-derived polypeptides with comparable chemical composition and varied molecular weight. Gelatin and hydrolysed fish collagen (HFC) were selected as widely available linear amino-acidic chains of high and low molecular weight, respectively, and functionalised in the wet-spun fibre state in order to preserve the material geometry in physiological conditions. Wet-spun fibre diameter and morphology were dramatically affected depending on the polypeptide molecular weight, wet-spinning solvent (i.e. 2,2,2-trifluoroethanol and dimethyl sulfoxide) and coagulating medium (i.e. acetone and ethanol), resulting in either bulky or porous internal geometry. Dry-state tensile moduli were significantly enhanced in gelatin and HFC samples following covalent crosslinking with activated 1,3-phenylenediacetic acid (Ph) (E: 726±43-844±85MPa), compared to samples crosslinked via intramolecular carbodiimide-mediated condensation reaction (E: 588±38MPa). Resulting fibres displayed a dry diameter in the range of 238±18-355±28µm and proved to be mechanically stable (E: 230kPa) following equilibration with PBS, whilst a nearly complete degradation was observed after 5-day incubation in physiological conditions.