Tendon attaches to bone across a functionally graded interface, “the enthesis”. A gradient of mineral content is believed to play an important role for dissipation of stress concentrations at mature fibrocartilaginous interfaces. Surgical repair of injured tendon to bone often fails, suggesting that the enthesis does not regenerate in a healing setting. Understanding the development and the micro/nano-meter structure of this unique interface may provide novel insights for the improvement of repair strategies. This study monitored the development of transitional tissue at the murine supraspinatus tendon enthesis, which begins postnatally and is completed by postnatal day 28. The micrometer-scale distribution of mineral across the developing enthesis was studied by X-ray micro-computed tomography and Raman microprobe spectroscopy. Analyzed regions were identified and further studied by histomorphometry. The nanometer-scale distribution of mineral and collagen fibrils at the developing interface was studied using transmission electron microscopy (TEM). A zone (∼20 µm) exhibiting a gradient in mineral relative to collagen was detected at the leading edge of the hard-soft tissue interface as early as postnatal day 7. Nanocharacterization by TEM suggested that this mineral gradient arose from intrinsic surface roughness on the scale of tens of nanometers at the mineralized front. Microcomputed tomography measurements indicated increases in bone mineral density with time. Raman spectroscopy measurements revealed that the mineral-to-collagen ratio on the mineralized side of the interface was constant throughout postnatal development. An increase in the carbonate concentration of the apatite mineral phase over time suggested possible matrix remodeling during postnatal development. Comparison of Raman-based observations of localized mineral content with histomorphological features indicated that development of the graded mineralized interface is linked to endochondral bone formation near the tendon insertion. These conserved and time-varying aspects of interface composition may have important implications for the growth and mechanical stability of the tendon-to-bone attachment throughout development.
Aliphatic epoxy composites with multifunctional polyhedral oligomeric silsesquioxane (POSS) ((C 6H5CHCHO)4(Si8O12)(CHdCHC6H5)4) nanophases (epoxy/POSS 95/5 and 75/25) and epoxy blends with the prepolymer of ladderlike polyphenylsilsesquioxane (PPSQ) (95/5, 90/10, and 85/15) were prepared by solution casting and then curing. These composites and blends were studied by dynamic mechanical thermal analysis (DMTA) and mechanical testing. The POSS units incorporated into the epoxy network are well dispersed in the composite, probably on the molecular scale, even at high POSS content (25 wt %) based on TEM observations. However, the aliphatic epoxy/PPSQ blends exhibit good miscibility only at low PPSQ content (e10 wt %). Phase separation was clearly observed when the PPSQ content was 15%. Incorporation of the POSS macromer into this epoxy network by curing at upper temperatures of 120 and 150 °C broadened the temperature range of glass transition of the resulting composites but has almost no influence on their T g (the tan δ peak temperature). The Tg of epoxy/PPSQ blends containing e10 wt % PPSQ increased slightly with increasing PPSQ content. However, the Tg of epoxy/PPSQ 85/15 is lower than that of the neat epoxy resin because cross-linking density is reduced in the blend. Inclusion of PPSQ into the epoxy resin has no effect on the width of their glass transition range. The storage moduli E′ of both epoxy/POSS composites and epoxy/PPSQ blends at T > Tg are higher than those of neat epoxy resin and increase with the POSS or PPSQ content, improving their thermal dimensional stability. The flexural modulus of the epoxy resin is raised by POSS incorporation or PPSQ addition. Modification of the epoxy resin's flexural modulus is larger for composites with molecularly dispersed POSS than for those containing PPSQ. The magnitude of this increase goes up as more POSS or PPSQ was added. But, the flexural strengths of epoxy/POSS nanocomposites and epoxy/PPSQ blends are lower than that of neat epoxy.
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