Early bloodmaterial interfacial events and capillary transport on nanoparticle modified nanofibers

Electrospun poly(ε-caprolactone) (PCL)nanofibrous mats are widely considered for blood-contacting wound dressings and small-diameter vascular applications; however, their intrinsic hydrophobicity limits rapid wetting and controlled interaction with blood. In this work, we modulate the interfacial response of PCL nanofibers by incorporating oxide-shelled silicon nanoparticles (SiNPs) synthesized by pulsed laser ablation in liquid, a ligand-free approach that avoids organic stabilizers and preserves surface reactivity. Two composite architectures were designed: SiNPs embedded within the fiber bulk (PAC1,4,16) and SiNPs preferentially exposed at the fiber surface (SPAC1,4,16), with systematically increasing nanoparticle loadings. Structural characterization confirmed the retention of a homogeneous fibrous morphology and the targeted nanoparticle distribution. The dynamic interaction with whole blood was quantified using time-resolved contact-angle measurements, complemented by top-view optical microscopy and three-dimensional profilometry of dried droplets. Pristine PCL remained strongly hydrophobic whereas a hydrophilic PCL functionalized with APTES showed rapid spreading. Incorporation of SiNPs within the fiber volume led to only a moderate enhancement of wettability, and dried droplets retained compact morphologies with limited spreading. In contrast, surface-decorated mats displayed a sharp, concentration-dependent transition toward highly wettable behavior: for SPAC16, the contact angle fell below 20, droplet profiles became markedly flattened, and microscopy revealed extended plasma-rich regions surrounding a red-cell-rich core, indicative of pronounced phase separation within the nanofibrous network.