Porous PCL Research Articles

Fast and affordable detection of PKU disease using iron (III) chloride-based solutions and porous PCL biosensors at higher prediction rates

Fast and affordable detection of PKU disease using iron (III) chloride-based solutions and porous PCL biosensors at higher prediction rates

Fabrication of Vascular Grafts Using Poly(ε-Caprolactone) and Collagen-Encapsuled ADSCs for Interposition Implantation of Abdominal Aorta in Rhesus Monkeys.

The production of small-diameter artificial vascular grafts continues to encounter numerous challenges, with concerns regarding the degradation rate and endothelialization being particularly critical. In this study, porous PCL scaffolds were prepared, and PCL vascular grafts were fabricated by 3D bioprinting of collagen materials containing adipose-derived mesenchymal stem cells (ADSCs) on the internal wall of the porous PCL scaffold. The PCL vascular grafts were then implanted in the abdominal aorta of Rhesus monkeys for up to 640 days to analyze the degradation of the scaffolds and regeneration of the aorta. Changes in surface morphology, mechanical properties, crystallization property, and molecular weight of porous PCL revealed a similar degradation process of PCL in PBS at pH 7.4 containing Thermomyces lanuginosus lipase and in situ in the abdominal aorta of rhesus monkeys. The contrast of in vitro and in vivo degradation provided valuable reference data for predicting in vivo degradation based on in vitro enzymatic degradation of PCL for further optimization of PCL vascular graft fabrication. Histological analysis through hematoxylin and eosin (HE) staining and fluorescence immunostaining demonstrated that the PCL vascular grafts successfully induced vascular regeneration in the abdominal aorta over the 640-day period. These findings provided valuable insights into the regeneration processes of the implanted vascular grafts. Overall, this study highlights the significant potential of PCL vascular grafts for the regeneration of small-diameter blood vessels.

Unique Crystallization Characteristics of Pickering High Internal Phase Emulsion Templated Porous Constructs.

To study the crystallization behavior of polymeric chains under the influence of porosity, the thermal properties of various nonporous and porous poly(ε-caprolactone) (PCL) based constructs were investigated. Porous cross-linked PCL nanocomposite constructs were fabricated utilizing in situ polymerization of CL-based surfactant-free Pickering high internal phase emulsions (HIPEs), stabilized using modified fumed silica nanoparticles (mSiNP) at a minimal concentration of 0.6 wt %. The corresponding nanocomposite constructs exhibited polyhedral pore morphology with significant pore roughness due to the presence of mSiNP. DSC thermograms of nonporous constructs illustrated diminished crystallization temperature and kinetics upon cross-linking and inclusion of mSiNP which confirmed suppressed mobility of polymer chains. Further introduction of porosity led to substantial supercooling, resulting in crystallization temperatures as low as -24 °C. Changes in the crystal structure of various nonporous and porous constructs were also studied using XRD. The crystallization behavior of porous constructs was finally evaluated using Jeziorny, Ozawa, and Mo theories under nonisothermal conditions. Significant deviation from the theoretical model, as observed in the case of porous constructs, implied a complex crystallization mechanism that eventually was not only controlled by the chain immobility due to cross-linking but also heterogeneity present in the wall thickness of the constructs. The unique melting-crystallization phenomenon observed in such constructs may further be expanded to other systems of high heat capacity for utilization as energy storage materials.

Bone-targeted lipoplex-loaded three-dimensional bioprinting bilayer scaffold enhanced bone regeneration.

Clinical bone-morphogenetic protein 2 (BMP2) treatment for bone regeneration, often resulting in complications like soft tissue inflammation and ectopic ossification due to high dosages and non-specific delivery systems, necessitates research into improved biomaterials for better BMP2 stability and retention. To tackle this challenge, we introduced a groundbreaking bone-targeted, lipoplex-loaded, three-dimensional bioprinted bilayer scaffold, termed the polycaprolactone-bioink-nanoparticle (PBN) scaffold, aimed at boosting bone regeneration. We encapsulated BMP2 within the fibroin nanoparticle based lipoplex (Fibroplex) and functionalized it with DSS6 for bone tissue-specific targeting. 3D printing technology enables customized, porous PCL scaffolds for bone healing and soft tissue growth, with a two-step bioprinting process creating a cellular lattice structure and a bioink grid using gelatin-alginate hydrogel and DSS6-Fibroplex, shown to support effective nutrient exchange and cell growth at specific pore sizes. The PBN scaffold is predicted through in silico analysis to exhibit biased BMP2 release between bone and soft tissue, a finding validated by in vitro osteogenic differentiation assays. The PBN scaffold was evaluated for critical calvarial defects, focusing on sustained BMP2 delivery, prevention of soft tissue cell infiltration and controlled fiber membrane pore size in vivo. The PBN scaffold demonstrated a more than eight times longer BMP2 release time than that of the collagen sponge, promoting osteogenic differentiation and bone regeneration in a calvarial defect animal. Our findings suggest that the PBN scaffold enhanced the local concentration of BMP2 in bone defects through sustained release and improved the spatial arrangement of bone formation, thereby reducing the risk of heterotopic ossification.

Hierarchical Hybrid Coatings with Drug-Eluting Capacity for Mg Alloy Biomaterials.

A hierarchical hybrid coating (HHC) comprising a ceramic oxide layer and two biodegradable polymeric (polycaprolactone, PCL) layers has been developed on Mg3Zn0.4Ca cast alloy in order to provide a controlled degradation rate and functionality by creating a favorable porous surface topography for cell adhesion. The inner, ceramic layer formed by plasma electrolytic oxidation (PEO) has been enriched in bioactive elements (Ca, P, Si). The intermediate PCL layer sealed the defect in the PEO layer and the outer microporous PCL layer loaded with the appropriate active molecule, thus providing drug-eluting capacity. Morphological, chemical, and biological characterizations of the manufactured coatings loaded with ciprofloxacin (CIP) and paracetamol (PAR) have been carried out. In vitro assays with cell lines relevant for cardiovascular implants and bone prosthesis (endothelial cells and premyoblasts) showed that the drug-loaded coating allows for cell proliferation and viability. The study of CIP and PAR cytotoxicity and release rate indicated that the porous PCL layer does not release concentrations detrimental to the cells. However, complete system assays revealed that corrosion behavior and increase of the pH negatively affects cell viability. H2 evolution during corrosion of Mg alloy substrate generates blisters in PCL layer that accelerate the corrosion locally in crevice microenvironment. A detailed mechanism of the system degradation is disclosed. The accelerated degradation of the developed system may present interest for its further adaptation to new cancer therapy strategies.

An in vitro characterization of a PCL-fibrin scaffold for myocardial repair

Each year in the United States approximately 10,000 babies are born with a complex congenital heart defect (CHD) requiring surgery in the first year of after birth. Several of these operations require the implantation of a full-thickness heart patch; however, the current patch materials available to pediatric heart surgeons are exclusively non-living and non-degradable, which do not grow with the patient and are prone to fail due to an inability to integrate with the heart. In this work, the goal was to develop a full-thickness, tissue engineered myocardial patch (TEMP) that is made from biodegradable components, strong enough to withstand the mechanical forces of the heart wall, and able to integrate with the heart and drive neotissue formation. Here, a thick and porous electrospun PCL scaffold filled with high-salt PEGylated fibrin was developed. The scaffold was found to be mechanically sufficient for heart wall repair. Vascular cells were able to infiltrate more than halfway through the scaffold in static culture within three weeks. The scaffold maintained pluripotent stem cells for at least four days, supports viable iPSC-derived cardiomyocytes, and fostered tissue thickening in vitro. The TEMP developed here and tested in vitro is promising for the repair of structural CHD and will next be assessed in situ.

Solid-state blending for the preparation of porous eco-friendly PCL membranes: Potential for filtration applications

Cryomilling is a promising method for fabricating polymeric blend and composite powder raw materials for various subsequent manufacturing processes. In this study, biodegradable porous membranes were fabricated from poly (ε-caprolactone) (PCL) using the cryomilling/hot pressing/porogen leaching approach. Powder mixtures of six different model compositions were compounded by cryomilling; thereafter, films were fabricated by hot-pressing. Poly (ethylene-oxide) (PEO) and salt were utilized as eco-friendly porogens in these mixtures, which were dissolved in water to introduce porosity in the films. Wood sawdust (WSD) and alum were investigated as fillers potentially capable of manipulating the hydrophilicity, mechanical and antimicrobial properties of the membranes. The morphological, hydrophilicity, mechanical, and filtration efficiency properties were explored and compared to those of commercial laboratory microfiltration (MF) membranes. SEM analysis revealed dense membrane skins for all compositions, along with lamellar porous structures. Mean pore radius ranged from 0.15 to 0.21 μm, which is within the MF pore size range. Water contact angle measurements averaged 70° and decreased with the addition of WSD and alum, indicating increased hydrophilicity. Tensile test results showed a decrease in mechanical properties, with higher porosities and with the addition of WSD. Adding alum (≥10 wt%) resulted in embrittled membranes. Filtration performance was evaluated in terms of pure water flux and turbidity reduction for textile wastewater, and it compared favorably to commercial membranes. In conclusion, this study has successfully introduced a new facile and versatile membrane fabrication approach.

Fabrication of Porous Hydrophilic CN/PANI Heterojunction Film for High-Efficiency Photocatalytic H2 Evolution

The modulation of surface wettability and morphology are essential to optimize the photocatalytic H2 evolution activity of graphitic carbon nitride (CN)-based photocatalysts. In this work, the porous hydrophilic CN/PANI heterojunction film was prepared via interfacial polymerization and loaded on a porous PCL substrate. The construction of the type-II CN/PANI heterojunction enabled an overall spectrum response and the efficient separation and transportation of photoexcited charge carriers. The fabricated CN/PANI solid-state film in comparison with its powder counterpart elevated the utilization efficiency and maintained the long-term stability of photocatalyst. The porous morphology and hydrophilic surface increased the surface area and enhanced the surface wettability, favoring water-molecule adsorption and activation. The as-prepared CN/PANI heterojunction film exhibited photocatalytic H2 production activity up to 3164.3 μmol·h−1·g−1, which was nearly 16-fold higher than that of pristine CN (569.1 μmol·h−1·g−1).

Electrospun Nisin-Loaded Poly(ε-caprolactone)-Based Active Food Packaging

Packaging for fresh fruits and vegetables with additional properties such as inhibition of pathogens grown can reduce food waste. With its biodegradability, poly(ε-caprolactone) (PCL) is a good candidate for packaging material, especially in the form of an electrospun membrane. The preparation of nonwoven fabric of PCL loaded with food additive, antimicrobial nisin makes them an active packaging with antispoilage properties. During the investigation of the nonwoven fabric mats, different concentrations of nisin were obtained from the solution of PCL via the electrospinning technique. The obtained active porous PCL loaded with varying concentrations of nisin inhibited the growth of Staphylococcus aureus and Escherichia coli. Packages made of PCL and PCL/nisin fibrous mats demonstrated a prolongation of the fruits’ freshness, improving their shelf life and, consequently, their safety.

Osteogenic and Angiogenic Synergy of Human Adipose Stem Cells and Human Umbilical Vein Endothelial Cells Cocultured in a Modified Perfusion Bioreactor

ABSTRACT Synergistic promotion of angiogenesis and osteogenesis in bone tissue-engineered constructs remains a crucial clinical challenge, which might be overcome by simultaneous employment of superior techniques including coculture systems, differentiation-stimulated factors, combinatorial scaffolds and bioreactors. Current study investigated the effect of flow perfusion along with coculture of human adipose stem cells (hASCs) and human umbilical vein endothelial cells (HUVECs) on osteogenic and angiogenic differentiation. Pre-treated hASCs with 1,25-dihydroxyvitamin D3 were seeded onto poly(lactic-co-glycolic acid)/β-tricalcium phosphate/polycaprolactone (PLGA/β-TCP/PCL) scaffold with/without HUVECs, and cultured for 14 days within a flask or modified perfusion bioreactor. Analysis of osteogenic and angiogenic gene expression, alkaline phosphatase (ALP) activity and ALP staining indicates a synergistic effect of perfusion flow and coculture system on osteogenic and angiogenic differentiation. The advantage of modified perfusion bioreactor is its five-branch flow distributor which directly connect to the porous PCL hollow fibers embedded in the 3D scaffold to improve flow and flow-induced shear stress uniformity. Dynamic coculture increased VEGF165 by 6-fold, VEGF189 by 2-fold, and Endothelin-1 by 4-fold, relative to dynamic monoculture. Static coculture enhanced osteogenic and angiogenic differentiation, compared with static monoculture. Although dynamic coculture is in preference to static coculture due to significant increase in ALP activity and promoted angiogenic marker expression. Our finding is the first to indicate that the modified perfusion bioreactor combined with the beneficial cell-cell crosstalk in pre-treated hASC/HUVEC cocultures provides a synergy between osteogenic and angiogenic differentiation of the accumulation of cells, suggesting that it represents a promising approach for regeneration of critical-sized bone defects.

Reconstruction of Ultra-thin Alveolar-capillary Basement Membrane Mimics.

Alveolar-capillary basement membrane (BM) is ultra-thin (<2 µm) extracellular matrix that maintains integral epithelial-endothelial cell layers. In vitro reconstructions of alveolar-capillary barrier supported on synthetic scaffolds closely resembling the fibrous and ultra-thin natural BM are essential in mimicking the lung pathophysiology. Although BM topology and dimensions are well known to significantly influence cellular behavior, conventionally used BM mimics fail to recreate this natural niche. To overcome this, electrospun ultra-thin 2 µm poly(caprolactone) (PCL) nanofibrous mesh is used to establish an alveolar-capillary barrier model of lung endothelial/epithelial cells. Transepithelial electrical resistance (TEER) and permeability studies reveal integral tight junctions and improved mass transport through the highly porous PCL meshes compared to conventional dense membranes with etched pores. The chemotaxis of neutrophils is shown across the barrier in presence of inflammatory response that is naturally impeded in confined regions. Conventional requirement of 3 µm or larger pore size can lead to barrier disruption due to epithelial/endothelial cell invasion. Despite high porosity, the interconnected BM mimic prevents barrier disruption and allows neutrophil transmigration, thereby demonstrating the physiological relevance of the thin nanofibrous meshes. It is envisioned that these bipolar cultured barriers would contribute to an organ-level in vitro model for pathological disease, environmental pollutants, and nanotoxicology.

Inner strut morphology is the key parameter in producing highly porous and mechanically stable poly(ε-caprolactone) scaffolds via selective laser sintering

Selective laser sintering (SLS) is an established method to produce dimensionally accurate scaffolds for tissue engineering (TE) applications, especially in bone. In this context, the FDA-approved, biodegradable polymer poly(ε-caprolactone) (PCL) has been suggested as a suitable scaffold material. However, PCL scaffold mechanical stability – an attribute of particular importance in the field of bone TE – was not considered as a primary target for SLS process parameters optimization so far. Here, we investigated the influence of SLS process parameters on the sintered scaffolds with the aim of producing highly porous (>70% porosity) PCL scaffolds with sub-mm geometrical features for bone TE. Specifically, we studied the influence of laser power, beam compensation and laser beam diameter on the dimensional accuracy and mechanical stiffness of the produced PCL scaffolds. We found that the ratio between the diameter of the molten cross-section within scaffold struts and the outer strut diameter (including partially sintered particles) depended on the SLS process parameters. By maximizing this ratio, the mechanical stability could be optimized. The comparison with in silico predictions of scaffold mechanical stiffness revealed that the diameter of the molten cross-section within struts and not the strut diameter controlled the mechanical behaviour of the scaffold. These observations should be considered when evaluating the quality of the sintering process based on dimensional accuracy, especially for features <1 mm. Based on these findings, we suggested an approach to evaluate the sintering outcome and to define SLS process parameters that enable the production of highly porous scaffolds that are both dimensionally accurate and mechanically stable. Moreover, the cytocompatibility of PCL scaffolds was evaluated by elution tests with primary human mesenchymal stromal cells. No evidence of cytotoxicity was found in any of the investigated scaffolds, confirming the suitability of SLS as production technique of PCL scaffolds for bone TE over a wide range of SLS process parameters.

Solvent evaporation induced fabrication of porous polycaprolactone scaffold via low-temperature 3D printing for regeneration medicine researches

Liquid deposition modeling (LDM) is an evolving three-dimensional (3D) printing approach that mainly utilizes polymer solutions to enable the fabrication of biomedical scaffolds under mild conditions. A deep understanding of the rheological properties of polymer printing inks and the features of yielded scaffolds are critical for a successful LDM based fabrication of biomedical scaffolds. In this work, polymer printing inks comprised of Poly(epsilon-caprolactone) (PCL), sodium chloride (NaCl), and trichloromethane (CHCl3) were prepared. The rheological properties, including extrudability (shear stress, viscosity, and shear-thinning) and self-supporting ability (viscosity) of all printing inks were analyzed. Then printing performance was evaluated by measuring the die-swell ratio, 2D, and 3D printing fidelities. Finally, a series of porous PCL scaffolds were fabricated using printing inks comprised of different feed ratios (20:80, 40:60, 50:50, 60:40, and 80:20) of NaCl to PCL, and the porosity, mechanical properties, degradation behaviors, and biocompatibility were discussed. The results suggested that the printing ink formulation is greatly affected the printing performances. The increasing NaCl content in printing inks reduced shear force for extrusion, enhanced the shear-thinning behavior, increased the curing time. The dropping temperature and solvent evaporation both enhanced the self-supporting ability of the printing inks and solvent evaporation is a critical factor for the curing of the printing inks. The further evaluation demonstrated that the obtained fabricated porous PCL scaffolds were endowed with good biocompatibility and controllable porosity, mechanical features, and in vitro degradation behavior related to the NaCl content in the printing inks. This study built a fabricating method of porous polymer scaffolds by 3D printing at low temperatures for regeneration medicine researches.

Breathable Materials and Hybrid Nanocomposites with Antimicrobial Activity Based on Porous Poly(ε‐Caprolactone) Obtained via Environmental Crazing

AbstractStructural modification of poly(ε‐caprolactone) (PCL) allows the fabrication of new functional materials obtained via the PCL films/fibers stretching in ethanol by the crazing mechanism. Atomic force microscopy, X‐ray scattering, and differential scanning calorimetry are employed to study the evolution of PCL structure. It is shown that ethanol plasticizes the polymer being deformed, and the stretching of PCL films/fibers occurs with formation of a fibrillar‐porous structure in the interlamellar space. The obtained porous matrices have pore size below 50 nm and bulk porosities of 28% and 48% for fibers and films, respectively. Thermal stabilization of the PCL films’ porous structure made it possible to obtain breathable materials with a vapor permeability of 625–652 g m−2 per day. The resulting porous PCL fibers and films can be used as matrices for the incorporation of useful additives and preparation of functional nanocomposites (NCs), biodegradable surgical suture, packaging, covering, and textile vapor‐permeable materials. Hybrid NCs with antibacterial and fungicidal activities are obtained on the basis of the porous PCL matrices and functional components (5% silver, 1% brilliant green, 28% Betadine, etc.) incorporated into them.

Fabrication of emulsion-templated macroporous poly(ε-caprolactone) towards highly effective and sustainable oil/water separation

A facile synthetic chemical strategy was descripted to produce porous poly(ϵ-caprolactone) (PCL) towards to a highly selective, reusable and degradable oil absorbent. The porous PCL was synthesized by organocatalyzed ring-opening polymerization (ROP) of ϵ-caprolactone (CL) in a tetradecane-in-CL high internal phase emulsion (HIPE). In this method, methanesulfonic acid (MSA) was used as an organocatalyst, and the block copolymer pluronic F127 acted as both emulsifier of the emulsion and initiator for the ROP of CL at a mild condition (37 °C). The molecular structure of copolymers could be tailored by changing the emulsifier concentration. The resulting polymers exhibited a controllable open-cell macroporous structure with HIPE as templates, and could be completely degraded. Absorption experiments showed the porous polymers absorbed gasoline, diesel, olive oil, or tetradecane from the water-oil mixture within 30 s, and the oils could be recovered simply by a centrifugation process at 3000 rpm. The absorbent had a full preservation of both the porous morphology and the absorption capacity in the performed six absorption/desorption cycles. These materials proved effective as oil absorbents for oil/water separation with not only a noticeable selectivity and recyclability performance, but also unprecedented safe disposability thanks to its degradability.

Novel poly(ε-caprolactone) scaffolds comprised of tailored core/shell-structured filaments using 3D plotting technique

This study presents a novel type of poly(ε-caprolactone) (PCL) scaffold comprised of tailored core/shell-structured filaments. The scaffold can be produced using a nonsolvent-induced phase separation phenomenon during the 3D plotting of PCL solutions in a coagulation bath. Specifically, a mixture of water and ethanol was employed as the nonsolvent, in order to tailor the phase separation behavior of a PCL/acetone solution. The addition of water to ethanol allowed for the creation of dense shells due to the fast exchange between acetone and water during the early stage of the 3D plotting process, while in the cores a number of micropores were formed. In addition, the thickness of the dense shell increased with an increase in water content in the water/ethanol mixture, increasing the mechanical properties (i.e., tensile strength, modulus, and strain at failure) of the porous PCL scaffolds with tailored core/shell-structured filaments remarkably.

One-pot porogen free method fabricated porous microsphere-aggregated 3D PCL scaffolds for bone tissue engineering.

Three-dimensional (3D) scaffolds with interconnected, hierarchically structured pores, and biomimetic nanostructures are desirable for tissue engineering, where preparation with a facile and biocompatible strategy remains challenging. In the present work, an innovative porous microspheres-aggregated 3D PCL scaffold with macropores, micropores, and nanofibrous-like structures was fabricated through a one-pot thermally induced phase separation (TIPS) method without the use of any porogen or specific instruments. Importantly, the porosity, pore size, and mechanical properties of our scaffolds were tailorable through tuning of the polymer concentration. Interestingly, the bioactivity of our 3D PCL scaffolds was significantly improved, as abundant apatite-like layers were formed on the 3D porous scaffolds, while no obvious apatite was observed on the 2D flat PCL film. Moreover, the high surface area attributed to the hierarchical macro/micro/nanostructure enabled our 3D porous scaffold to serve as a drug delivery depot for sustained release of both small molecule drug (phenamil) and protein (BMP2). In addition to sustained drug release, the hierarchical structure and high mechanical properties also contribute to significantly improving BMP2-induced osteogenic differentiation. In summary, we developed a novel PCL porous scaffold through a facile, one-pot TIPS method and demonstrated its promising potential application in large bone defect repair.

Optimizing Integrated Electrode Design for Irreversible Electroporation of Implanted Polymer Scaffolds.

Irreversible electroporation (IRE) is an emerging technology for non-thermal ablation of solid tumors. This study sought to integrate electrodes into microporous poly(caprolactone) (PCL) scaffolds previously shown to recruit metastasizing cancer cells in vivo in order to facilitate application of IRE to disseminating cancer cells. As the ideal parallel plate geometry would render much of the porous scaffold surface inaccessible to infiltrating cells, numerical modeling was utilized to predict the spatial profile of electric field strength within the scaffold for alternative electrode designs. Metal mesh electrodes with 0.35mm aperture and 0.16mm wire diameter established electric fields with similar spatial uniformity as the parallel plate geometry. Composite PCL-IRE scaffolds were fabricated by placing cylindrical porous PCL scaffolds between two PCL dip-coated stainless steel wire meshes. PCL-IRE scaffolds exhibited no difference in cell infiltration in vivo compared to PCL scaffolds. In addition, upon application of IRE in vivo, cells infiltrating the PCL-IRE scaffolds were successfully ablated, as determined by histological analysis 3 days post-treatment. The ability to establish homogeneous electric fields within a biomaterial that can recruit metastatic cancer cells, especially when combined with immunotherapy, may further advance IRE technology beyond solid tumors to the treatment of systemic cancer.

Fabrication of hierarchically porous superhydrophilic polycaprolactone monolith based on nonsolvent-thermally induced phase separation.

Monoliths with a continuous porous structure are of great interest due to high transfer efficiency and large surface area in environmental and tissue engineering fields. This study demonstrated a facile method to prepare PCL monoliths with hierarchically porous structure by nonsolvent-thermally induced phase separation. A suitable mixed solvent mixture using ethanol as nonsolvent reduced the amount of dioxane and provided PCL monoliths with three levels of structures. The monolith structure was easily controlled by changing the fabrication parameters, such as the nonsolvent, the temperature of phase separation, the concentration of the PCL. Finally, the superhydrophilic monolith was easily obtained by polydopamine surface modification. The easy way of fabrication of a hierarchically porous PCL monolith with superhydrophilicity will find applications such as in tissue engineering and purification.

Chondrogenic phenotype in responses to poly(ɛ-caprolactone) scaffolds catalyzed by bioenzymes: effects of surface topography and chemistry

Biodegradable poly(ε-caprolactone) (PCL) has been increasingly investigated as a promising scaffolding material for articular cartilage tissue repair. However, its use can be limited due to its surface hydrophobicity and topography. In this study, 3D porous PCL scaffolds fabricated by a fused deposition modeling (FDM) machine were enzymatically hydrolyzed using two different biocatalysts, namely Novozyme®435 and Amano lipase PS, at varied treatment conditions in a pH 8.0 phosphate buffer solution. The improved surface topography and chemistry of the PCL scaffolds were anticipated to ultimately boost the growth of porcine articular chondrocytes and promote the chondrogenic phenotype during cell culture. Alterations in surface roughness, wettability, and chemistry of the PCL scaffolds after enzymatic treatment were thoroughly investigated using several techniques, e.g., SEM, AFM, contact angle and surface energy measurement, and XPS. With increasing enzyme content, incubation time, and incubation temperature, the surfaces of the PCL scaffolds became rougher and more hydrophilic. In addition, Novozyme®435 was found to have a higher enzyme activity than Amano lipase PS when both were used in the same enzymatic treatment condition. Interestingly, the enzymatic degradation process rarely induced the deterioration of compressive strength of the bulk porous PCL material and slightly reduced the molecular weight of the material at the filament surface. After 28 days of culture, both porous PCL scaffolds catalyzed by Novozyme®435 and Amano lipase PS could facilitate the chondrocytes to not only proliferate properly, but also function more effectively, compared with the non-modified porous PCL scaffold. Furthermore, the enzymatic treatments with 50 mg of Novozyme®435 at 25 °C from 10 min to 60 min were evidently proven to provide the optimally enhanced surface roughness and hydrophilicity most significantly favorable for induction of chondrogenic phenotype, indicated by the greatest expression level of cartilage-specific gene and the largest production of total glycosaminoglycans.