Temperature-dependent structure and dynamics of highly-branched poly(N-isopropylacrylamide) in aqueous solution.

Small-angle neutron scattering (SANS) and neutron spin-echo (NSE) have been used to investigate the temperature-dependent solution behaviour of highly-branched poly(N-isopropylacrylamide) (HB-PNIPAM). SANS experiments have shown that water is a good solvent for both HB-PNIPAM and a linear PNIPAM control at low temperatures where the small angle scattering is described by a single correlation length model. Increasing the temperature leads to a gradual collapse of HB-PNIPAM until above the lower critical solution temperature (LCST), at which point aggregation occurs, forming disperse spherical particles of up to 60 nm in diameter, independent of the degree of branching. However, SANS from linear PNIPAM above the LCST is described by a model that combines particulate structure and a contribution from solvated chains. NSE was used to study the internal and translational solution dynamics of HB-PNIPAM chains below the LCST. Internal HB-PNIPAM dynamics is described well by the Rouse model for non-entangled chains.

Interfacial characteristics and determination of cohesive and adhesive strength of plasma-coated hydroxyapatite via nanoindentation and microscratch techniques.

We investigate the chemical composition and mechanical properties of plasma-deposited hydroxyapatite on grit-blasted Ti-6Al-4V coupons as models of typical prosthetic hip implants. Nanoindentation is used to extract the mechanical properties of the hydroxyapatite (HA) coating and to evaluate the behavior of the material as a function of distance from the interface. A microscratch technique was used to determine parameters of cohesive and adhesive failure of the material that are critical in determining the functionality of these biomedical devices. This delamination method has not been studied in detail before and is usually considered to be unsuitable because of the thickness of the HA and the roughness of the substrate. However, through cross-section analysis of the scratch test, we can determine the point at which the HA delaminates from the substrate. It was concluded that spallation occurs locally, and there is no evidence of gross spallation, indicating that the coating is well adhered to the substrate.

Interface induced crystal structures of dioctyl-terthiophene thin films.

Temperature dependent structural and morphological investigations on semiconducting dioctyl-terthiophene (DOTT) thin films prepared on silica surfaces reveals the coexistence of surface induce order and distinct crystalline/liquid crystalline bulk polymorphs. X-ray diffraction and scanning force microscopy measurements indicate that at room temperature two polymorphs are present: the surface induced phase grows directly on the silica interface and the bulk phase on top. At elevated temperatures the long-range order gradually decreases, and the crystal G (340 K), smectic F (348 K), and smectic C (360 K) phases are observed. Indexation of diffraction peaks reveals that an up-right standing conformation of DOTT molecules is present within all phases. A temperature stable interfacial layer close to the silica-DOTT interface acts as template for the formation of the different phases. Rapid cooling of the DOTT sample from the smectic C phase to room temperature results in freezing into a metastable crystalline state with an intermediated unit cell between the room temperature crystalline phase and the smectic C phase. The understanding of such interfacial induced phases in thin semiconducting liquid crystal films allows tuning of crystallographic and therefore physical properties within organic thin films.

Effect of cross-linking and hydration on microscale flat punch indentation contact to collagen-hyaluronic acid films in the viscoelastic limit.

The properties of the extracellular matrix (ECM) have profound impact upon cell behaviour. As an abundant protein in mammals, collagen is a desirable base material to engineer an ECM tissue scaffold, but its structural weakness generally requires molecular crosslinking or incorporation of additional ECM-based macromolecules such as glycosaminoglycans. We have performed microscopic indentation to test collagen films under dry and aqueous conditions prepared with different levels of physical and chemical crosslinking. Our technique isolates intrinsic properties of the poro-viscoelastic matrix in a regime minimizing the influence of drainage hydrodynamics and allows direct measurement of the effect of hydrating a specific sample. A doubling of the effective stress-strain stiffness under crosslinking could be directly correlated to structural changes in X-ray diffraction spectra, while electron microscopy revealed possible fibril bridging mechanisms explaining observed toughness. Overall, an intrinsic viscoelastic stress-strain response of collagen under various conditions of cross-linking was observed for both dry and wet conditions, with the latter most affected by indentation rate. Under creep testing, a three order of magnitude increase in dynamic compliance and factor three reduction in relaxation time was found going from the dry to hydrated state. When fitted to a simple viscoelastic model, crosslinking showed a tendency to decrease relaxation time in both states, but reduced dynamic compliance only in the hydrated case. This suggests a reduced role of virtual crosslinks under hydration. This is the first study reporting consistent mechanical testing of dry and hydrated ECM-derived biomaterials, accessing the intrinsic material mechanics under in vivo-like conditions. STATEMENT OF SIGNIFICANCE: This manuscript presents new insights into the effect of crosslinking on mechanical properties of dry and hydrated collagen intended for tissue scaffolding applications. A novel microscopic indentation technique allowed testing of the poro-viscoelastic matrix isolated in a regime minimizing the influence of drainage hydrodynamics, so direct comparison of the effect of hydration on the intrinsic material behaviour to could be made. A variety of experimental techniques including X-ray diffraction, infrared spectroscopy, and scanning electron and atomic force microscopy were used to augment the mechanical testing. The results of creep testing were numerically analysed using a four-component viscoelastic model. This is the first mechanical testing of dry and hydrated ECM-derived biomaterials, accessing the intrinsic material mechanics under in vivo-like conditions.

Characteristics, interactions and coating adherence of heterogeneous polymer/drug coatings for biomedical devices.

With this rise in surgical procedures it is important to focus on the mobility and safety of the patient and reduce the infections that are associated with hip replacements. We examine the mechanical properties of gentamicin sulphate as a model antimicrobial layer for titanium-alloy based prosthetic hips to help prevent methicillin-resistant Staphylococcus aureus infection after surgery. A top layer of poly(lactic-co-glycolic acid) is added to maintain the properties of the gentamicin sulphate as well as providing a drug delivery system. Through the use of nanoindentation and micro-scratch techniques it is possible to determine the mechanical and adhesive properties of this system. Nanoindentation determined the modulus values for the poly(lactic-co-glycolic acid) and gentamicin sulphate materials to be 8.9 and 5.2GPa, respectively. Micro-scratch established that the gentamicin sulphate layer is strongly adhered to the Ti alloy and forces of 30N show no cohesive or adhesive failure. It was determined that the poly(lactic-co-glycolic acid) is ductile in nature and delaminates from the gentamicin sulphate layer of at 0.5N.

Mechanical properties of self-assembled chitin nanofiber networks.

Chitin nanofibers are structural components of the insect cuticle, the exoskeleton of crabs, and mollusk shells. Chitin nanofibers have found broad use in biomedical applications. Here, we study structure-properties-processing relationships of 3 nm chitin nanofiber networks self-assembled from a chitin hexafluoroisopropanol solution.