Kinetics and the Theoretical Aspects of Drug Release from PLA/HAp Thin Films

Dieser Beitrag ist mit Zustimmung des Rechteinhabers aufgrund einer (DFG geförderten) Allianz- bzw. Nationallizenz frei zugänglich.This publication is with permission of the rights owner freely accessible due to an Alliance licence and a national licence (funded by the DFG, German Research Foundation) respectively.The theory of dissolution kinetics of gentamicin from polylactic acid-hydroxyapatite thin film composites is spotlighted with the combination of diffusion and polymer degradation modeling. The use of various mathematical models, characterizing diffusion, dissolution or/and erosion prevalence as well as a mix of dissolution-diffusion rate processes were employed in order to compare theory with experimental data. A number of factors influence the release kinetics of gentamicin from medical drug release systems and devices. It is difficult to have a single mathematical model that takes all these factors into account. It is shown that the degradation of the polymer matrix plays the biggest role in the release kinetics of polymer-ceramics thin film composites. It was also observed that multistage drug release form these devices depends also on the degradation kinetics of the polymer matrix. The effect of pH and device sizes were not studied but could also be of interest in future studies

Functionalisation of Ti6Al4V and hydroxyapatite surfaces with combined peptides based on KKLPDA and EEEEEEEE peptides

Surface modifications are usually performed on titanium alloys to improve osteo-integration and surface bioactivity. Modifications such as alkaline and acid etching, or coating with bioactive materials such as hydroxyapatite, have previously been demonstrated. The aim of this work is to develop a peptide with combined titanium oxide and hydroxyapatite binders in order to achieve a biomimetic hydroxyapatite coating on titanium surfaces. The technology would also be applicable for the functionalisation of titanium and hydroxyapatite surfaces for selective protein adsorption, conjugation of antimicrobial peptides, and adsorption of specialised drugs for drug delivery. In this work, functionalisation of Ti6Al4V and hydroxyapatite surfaces was achieved using combined titanium-hydroxyapatite (Ti-Hap) peptides based on titanium binder (RKLPDA) and hydroxyapatite binder (EEEEEEEE) peptides. Homogeneous peptide coatings on Ti6Al4V surfaces were obtained after surface chemical treatments with a 30 wt % aqueous solution of H2O2 for 24 and 48 hours. The treated titanium surfaces presented an average roughness of Sa=197 nm (24 h) and Sa=128 nm (48 h); an untreated mirror polished sample exhibited an Sa of 13 nm. The advancing water contact angle of the titanium oxide layer after 1 hour of exposure to 30 wt % aqueous solution of H2O2 was around 65°, decreasing gradually with time until it reached 35° after a 48 hour exposure, suggesting that the surface hydrophilicity increased over etching time. The presence of a lysine (L) amino acid in the sequence of the titanium binder resulted in fluorescence intensity roughly 16 % higher compared with the arginine (R) amino acid analogue and therefore the lysine containing titanium binder was used in this work. The Ti-Hap peptide KKLPDAEEEEEEEE (Ti-Hap1) was not adsorbed by the treated Ti6Al4V surfaces and therefore was modified. The modifications involved the inclusion of a glycine spacer between the binding terminals (Ti-Hap2) and the addition of a second titanium binder (KKLPDA) (Ti-Hap3 and Ti-Hap4). The Ti-Hap peptide aptamer which exhibited the strongest intensity after the titanium dip coating was KKLPDAKKLPDAEEEEEEEE (Ti-Hap4). On the other hand, hydroxyapatite surfaces, exhibiting an average roughness of Sa=1.42 µm, showed a higher fluorescence for all peptides compared with titanium surfaces

Assessment by finite element analysis of the impact of osteoporosis and osteoarthritis on hip resurfacing

Hip resurfacing is proposed as an alternative to total hip replacement (THR) for treatment of osteoarthritis (OA), especially for younger, heavier and more active sufferers. There is however, concern with regards to the incidence of post operative femoral neck fractures. We have investigated, with finite element models, the changes in stress and strain in the femoral neck following hip resurfacing. We have included several different bone material property values representing normal, elderly, osteoarthritic and osteoporotic bone. We have also modelled two different hip implant orientations. We have shown that hip resurfacing may increase the magnitude of stress and strain in the femoral neck, especially in osteoporotic bone. We have also shown that the superolateral offset associated with the valgus orientation, not the valgus orientation itself, may be what reduces the stress and strain in the neck and leads to lower incidence of fracture

Conversion of Marine Structures to Calcium Phosphate Materials: Mechanisms of Conversion Using Two Different Phosphate Solutions

Marine structure, coralline materials were converted to calcium phosphate using two different phosphate solutions. The aim was to study the conversion mechanisms under acidic and basic environment at moderate conditions of temperature. Crystal growth and morphology of converted corals were characterized by XRD and SEM respectively. The results suggested that under acidic conditions (H3PO4), dissolution and precipitation control and direct the crystal formation and morphology in which transition from plate like to rod like hydroxyapatite structure was favoured. Metastable phase such as monetite formed and transformed to HAp during reaction. During the first hour of the dissolution a monetite and hydroxyapatite mixture precipitates and then the full conversion to hydroxyapatite is observed. On the other hand, under basic conditions (NH4)2HPO4, just diffusional surface conversion of the calcium carbonate structure of coralline materials to hydroxyapatite and a very small amount of tri-calcium phosphate is observed. The mechanism can be classified as the solid-state topotactic ion-exchange reaction mechanism

Conversion of snail shells (Achatina achatina) acclimatized in Benin to calcium phosphate for medical and engineering use

Most methods for producing calcium phosphates involve synthetic calcium and phosphates sources. However, it has recently been proposed that calcium phosphate can be produced with bio-based calcium sources such as nacre, coral, and cuttlefish bones. One specific source of bio-based calcium is found in the Achatina snail shell, which becomes a waste product after flesh consumption. The present work aimed to assess the effectiveness of Achatina snail shells and to study the conversion kinetics in both acid and alkaline environment rich in phosphate ions. It was observed that in acidic conditions, the calcium released by the dissolution of the aragonite precipitates with the phosphate ions of reaction medium induces brushite formation which is rapidly converted into monetite. In alkaline conditions, calcium released from aragonite reacts with surrounding phosphates and carbonate ions and induces carbonated apatite precipitation. Regardless of the source of calcium used in the presence of phosphate, the conversion is carried out according to complex phenomena that involve topotactic transformation or dissolution-precipitation mechanisms

Antibiotic Containing Poly Lactic Acid/Hydroxyapatite Biocomposite Coatings for Dental Implant Applications

The biodegradable and biocompatible antibiotic containing thin film composites are very appropriate biomaterials as coating materials for dental implants because of their adjustable drug loading and release rates for the prevention of implant related infections. Coralline hydroxyapatite (HAp) was loaded with gentamicin antibiotics and combined with a biodegradable polylactic acid (PLA) to form thin film composites. PLA-HAp, PLA-Gentamicin (GM) and PLA-HAp-GM composites were produced, and their dissolution studies were carried out in phosphate buffered saline under SINK conditions. It was observed that the coatings could be efficiently applied to titanium dental implants and the drug release rates can be efficiently controlled

Conversion of Calcified Algae (Halimeda sp) and Hard Coral (Porites sp) to Hydroxyapatite

Calcium phosphate materials can be produced using a number of wet methods that are based on hydrothermal or co-precipitation methods that might use acidic or basic chemical environments. In our previously published works, we have investigated calcium phosphates such as monetite, hydroxyapatite, and whitlockite which were successfully produced by mechano-chemical methods and/or hydrothermal treatments from a range of marine shells and corals which were obtained from the Great Barrier Reef. The aim of the current work was to analyze and compare the mechanisms of conversion of one hard coral species and one calcified algae species from the Great Barrier Reef

Comparative study of coral conversion, Part 3: Intermediate products in the first half an hour

Different methods to produce calcium phosphate materials have been well established and are currently used by both scientific and industrial community. While other new and more economical production techniques are under development, the actual reactions mechanisms involve in these techniques are not well understood. Understanding what really happen during reaction will pave a way to tune the final product for well-defined morphology and purity. We focused into improving in-depth understanding of the reaction mechanisms and the intermediates products participating in the reaction of coralline materials with orthophosphoric and ammonium phosphate solutions under mechano-chemical reaction technique. The results suggest that within 30 minutes of reaction under ammonium phosphate solution only HAp phase is produced through solid-state iron exchange reaction. On the other hand, under orthophosphoric acid solution, intermediate phases such as octacalcium phosphate (OCP) and monetite form and convert to hydroxyapatite HAp at different times. Other phase that formed as an intermediate was identified as brushite. It was also observed that pH plays a big role in the formation of these phases due to their different pH stability. The results also confirm our previous hypothesis that under orthophosphoric acid phosphate solution the reaction mechanism is dissolution-recrystallization while under ammonium phosphate solution is solid-state topotactic ion exchange reaction mechanism. It is envisaged that there are possibilities of the formation of intermediate products within or before the first 5 minutes of reaction

Adsorption of Textile Dyes on the Shells of Snails Achatina achatina and Lanistes varicus Acclimatized in Benin: Influence of Their Heating Treatment

The characterization of the shells of snails Achatina achatina and Lanistes varicus indicates that they contain calcium carbonate (98%) essentially aragonite, and organic matter (2%). The heating at 500°C during three hours (3 h) has destroyed their constitutive organic matter, converted the aragonite form completely into the calcite and reduced their specific surfaces. The effects of these modifications have been revealed in the adsorption in aqueous environment of methylene blue (MB) and methyl orange (MO) which are respectively cationic and anionic dyes. The results showed that the sorption of these dyes on the raw shells is more important than the heated shells. The methylene blue has more affinity for shells than methyl orange. Between these two types of snails, the shells of Lanistes varicus have a higher capacity of adsorption. This sorption of the methylene blue is more in relationship with the Freundlich model ( for EG and for EA) comparatively to Langmuir model If the shells of these snails were calcined before using for the cicatrizing of the human cutaneous wounds in Benin. In the case of the sorption of organic molecule, it will be necessary to avoid submitting them to a preliminary heat treatment

In vitro bioactivity and stem cells attachment of three-dimensionally ordered macroporous bioactive glass incorporating iron oxides

Three-dimensionally ordered macroporous bioactive SiO2-CaO-Na2O-P2O5 glass (3DOM-BG) is synthesized by using the sol-gel method. After an in vitro test in simulated body fluid (SBF), the hydroxyapatite (HAp) crystalline phase is clearly formed on its surface as confirmed by X-ray diffractometry (XRD) and Raman spectroscopy. Magnetic 3DOM-BG/Fe samples are synthesized by partial substitution of SiO2 with iron oxide. Whilst the HAp layer is not confirmed, energy dispersive spectroscopy (EDS), Fourier transform infrared spectroscopy (FTIR) and XRD analysis reveal calcium phosphate layer on the surface of 3DOM-BG/Fe samples after the SBF soaking. The growth of HAp-like layer is slower with increasing iron oxides. The initial mechanism that thought to induce bone formation is reduced due to the replacement of Ca2+ with Fe ions in the glass network. The formation of HAp-like layer is modified by the sedimentation of Ca and P while the nonmagnetic 3DOM-BG forms the calcium phosphate by the ionic exchange following the Hench mechanism. The adult human adipose tissue-derived stem cells (hADSCs) can be closely attached and well spread on the flat-plate of all 3DOM-BG/Fe and 3DOM-BG. Without detectable cytotoxicity possibly induced by iron oxides, the osteoblast can be grown and proliferated. In addition to these bioactivity and biocompatibility, porous structures can allow their possible use in targeted drug delivery and magnetic properties of 3DOM-BG/Fe can essentially be implemented in hyperthermia therapy