Cardiovascular diseases are responsible for a large number of severe disability cases and deaths worldwide. Strong research in this field has been extensively carried out, in particular for the associated complications, such as the occlusion of small-diameter (<6 mm) vessels. Accordingly, in the present research, two random copolyesters of poly(butylene 2,5-furandicarboxylate) (PBF) and poly(butylene isophthalate) (PBI), were successfully synthesized via two-step melt polycondensation and were thoroughly characterized from molecular, thermal, and mechanical perspectives. The copolymeric films displayed a peculiar thermal behavior, being easily processable in the form of films, although amorphous, with T_g close to room temperature. Their thermal stability was high in all cases, and from the mechanical point of view, the materials exhibited a high ultimate strength, together with values of elastic moduli tunable with the chemical composition. The long-term stability of these materials under physiological conditions was also demonstrated. Cytotoxicity was assessed using a direct contact assay with human umbilical vein endothelial cells (HUVECs). In addition, hemocompatibility was tested by evaluating the adhesion of blood components (such as the adsorption of human platelets and fibrinogen). As a result, a proper chemical design and, in turn, both the solid-state and functional properties, are pivotal in regulating cell behavior and opening new frontiers in the tissue engineering of soft tissues, including vascular tissues.

In order to envisage new solutions for complications associated with cardiovascular diseases, including the occlusion of small vessels, a family of random copolymers of poly(butylene trans-1,4-ciclohexanedicarboxylate) (PBCE), containing Pripol moiety, namely, poly(butylene trans-1,4-ciclohexaendicarboxylate/Pripol), were successfully synthesized. The copolymers display reduced crystallinity and stiffness compared with PBCE, exhibiting elastic modulus values that are comparable to those of materials previously investigated for similar applications. The stability of the materials under physiological conditions was demonstrated over an extended time. Cytotoxicity was confirmed by a direct contact assay with human umbilical vein endothelial cells (HUVECs), and blood compatibility was established by the absence of any change in the values of activated prothrombin time and activated partial thromboplastin time, in addition to the low adhesion of blood components. The results demonstrated that the ad hoc design is pivotal in regulating solid state and functional properties, thereby facilitating the development of innovative materials for vascular tissue engineering.

Autologous grafts remain the clinical gold standard for vascular reconstruction; however, their use is limited by donor site morbidity, poor availability, and long‐term failure. Synthetic alternatives, while effective in large‐caliber vessels, fail in small‐diameter applications (<6 mm) due to thrombosis, intimal hyperplasia, and biomechanical mismatch. In this context, tissue‐engineered vascular grafts (TEVGs) emerge as a solution, requiring biomaterials that closely replicate the structural, mechanical, and hemocompatible properties of native vessels. Aliphatic polyesters such as polylactic acid, polyglycolic acid, and poly(ε‐caprolactone) are extensively studied but show poor endothelialization and mechanical deficiency. In contrast, poly(butylene trans‐1,4‐cyclohexanedicarboxylate) (PBCE) attracts interest for its biocompatibility, thermal stability, and processability. Its copolymerization with Pripol 1009, a commercial fatty diacid, enables modulation of mechanical properties and degradation rate, two of the key parameters for vascular engineering. In this work, electrospun scaffolds based on these copolymers are fabricated in flat and tubular formats and characterized in terms of morphology, mechanical behavior, hemocompatibility, and endothelialization potential. Certain formulations display mechanical properties comparable to native vessels, support endothelialization and smooth muscle cell adhesion, and do not trigger coagulation pathways in in vitro assays. These results identify PBCE/Pripol copolymers as promising candidates for next‐generation TEVGs, bridging the gap between synthetic reliability and biological performance in small‐diameter vascular applications.