Yolanda Márquez

Study of Non-Isothermal Crystallization of Polydioxanone and Analysis of Morphological Changes Occurring during Heating and Cooling Processes

Non-isothermal crystallization kinetics of polydioxanone (PDO), a polymer with well-established applications as bioabsorbable monofilar suture, was investigated by Avrami, Mo, and isoconversional methodologies. Results showed Avrami exponents appearing in a relatively narrow range (i.e., between 3.76 and 2.77), which suggested a three-dimensional spherulitic growth and instantaneous nucleation at high cooling rates. The nucleation mechanism changed to sporadic at low rates, with both crystallization processes being detected in the differential scanning calorimetry (DSC) cooling traces. Formation of crystals was hindered as the material crystallized because of a decrease in the motion of molecular chains. Two secondary nucleation constants were derived from calorimetric data by applying the methodology proposed by Vyazovkin and Sbirrazzuoli through the estimation of effective activation energies. In fact, typical non-isothermal crystallization analysis based on the determination of crystal growth by optical microscopy allowed secondary nucleation constants of 3.07 × 105 K2 and 1.42 × 105 K2 to be estimated. Microstructure of sutures was characterized by a stacking of lamellae perpendicularly oriented to the fiber axis and the presence of interlamellar and interfibrillar amorphous regions. The latter became enhanced during heating treatments due to loss of partial chain orientation and decrease of electronic density. Degradation under various pH media revealed different macroscopic morphologies and even a distinct evolution of lamellar microstructure during subsequent heating treatments.

Incorporation of biguanide compounds into poly(GL)-b-poly(GL-co-TMC-co-CL)-b-poly(GL) monofilament surgical sutures

A new biodegradable coating was developed for bioabsorbable monofilament sutures. Specifically, a random copolymer having 35wt-% and 65wt-% of lactide and trimethylene carbonate units showed appropriate flexibility, stickiness and degradation rate, as well as capability to produce a complete and uniform coating. Monofilament sutures of polyglycolide-b-poly(glycolide-co-trimethylene carbonate-co-ε-caprolactone)-b-polyglycolide were loaded with chlorhexidine (CHX) and poly(hexamethylene biguanide) (PHMB) to explore the possibility to achieve antimicrobial activity without adverse cytotoxic effects. To this end, two processes based on single drug adsorption onto the suture surface and incorporation into the coating copolymer were used and subsequently evaluated. Although the second process could be considered more complex, clear benefits were observed in terms of drug loading efficiency, antimicrobial effect and even lack of cytotoxicity. In general, drugs could be loaded in an amount leading to a clear bacteriostatic effect for both Gram-negative and Gram-positive bacteria without causing significant cytotoxicity. Release profiles of PHMB and CHX were clearly different. Specifically, adsorption of the drug onto the fiber surface which prevented complete release was detected for PHMB. This polymer had advantages derived from its high molecular size, which hindered penetration into cells, thus resulting in lower cytotoxicity. Furthermore, bacterial growth kinetics measurements and bacterial adhesion assays showed greater effectiveness of this polymer.