The influence of polylactide/hydroxyapatite composite material crystallinity on the polymer structure degradation rate

Introduction Assessment of biological characteristics of polylactide/hydroxyapatite (PLLA/HA) biodegradable materials is requiered to specify indications for the use of PLLA/HA composite implants in clinical practice.

The present study was aimed to measure the kinetics of calcium and phosphate release from PLLA and its dependence on polymer structure crystallinity.

Material and methods Four types of biodegradable materials were studied in vitro. Samples of type 1 and type 3 made of crystalline PLLA after annealing contained 25 % and 50 % of HA mass fraction, respectively. Samples of type 2 and type 4 made of amorphous PLLA (without annealing) contained 25 % and 50 % of HA mass fraction, respectively. In every group, 6 samples were tested. The samples were incubated in an aqueous medium at 37 °C for 52 weeks. The rate of PLLA degradation was assessed by the accumulation of lactate monomer in the hydrolysate. The concentrations of calcium ions and phosphate ions were determined for assessment the HA hydrolysis rate. The degree of crystallinity of the polymer matrix was evaluated by scanning calorimetry.

Results The hydrolysis of PLLA and HA in the samples was not simultaneous. The PLLA was hydrolyzed first followed by HA hydrolysis. By the moment of complete hydrolysis of PLLA, there was only 15 % of hydrolyzed HA. The release of calcium ions occurred from the sixth week of incubation for all tested samples, that of phosphate ions from the third week. The total amount of the released calcium ions and phosphate ions decreased in the line: material 3 > material 4 > material 1 > material 2. Calcium ions in the hydrolysates were detected up to 42 weeks of incubation, phosphate ions up to the 52nd week.

Conclusion Higher crystallinity of PLLA achieved by annealing results in increased rate of hydrolysis of HA from PLLA matrix. Biological activity of PLLA/HA implants can be determined by degree of polymer crystallinity and saturation with HA.

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