Crystallinity Of PCL Research Articles

Reinforcement and Controlling the Stability of Poly(ε-caprolactone)-Based Polymeric Materials via Reversible and Movable Cross-Links Employing Cyclic Polyphenylene Sulfide.

Due to its biodegradation ability, poly(ε-caprolactone) (PCL) is a suitable alternative for packaging materials; however, its biodegradation can also lead to instability in its usage. Cyclic polyphenylene sulfide (7U) has been shown to form rotaxane structures with PCL by simple blending to generate the π-π stacking effect and movable cross-link. A 2-fold increase in toughness and no decrease in Young's modulus for the PCL-based polyurethane with 7U are observed. The rotaxane structures mainly exist in the amorphous regions and have no impact on the crystallinity of PCL. Under the catalysis of lipase in aqueous solution, the stability of PCL is improved due to the 7U's suppression of the attack from the enzymes on PCL. After dissolution of the PCL films in the organic solvent, the dispersion of 7U and the breakage of the cross-links lead to little suppression on degradation during the catalysis of lipase. Thus, the controlled stability of PCL using 7U can prolong the life span of the biodegraded PCL materials.

Shape Memory Polymer Bioglass Composite Scaffolds Designed to Heal Complex Bone Defects.

An off-the-shelf scaffold with requisite properties could enable the viable treatment of irregular craniomaxillofacial bone defects. Notably, the scaffold should be conformally fitting, innately bioactive, and bioresorbable. In prior work, we developed a series of shape memory polymer (SMP) scaffolds based on cross-linked poly(ε-caprolactone) (PCL). These were capable of "self-fitting" into complex bone defects when exposed to temperatures above the melt transition of the constituent PCL, either linear-PCL-diacrylate (linear-PCL-DA, Tm ∼55 °C) or star-PCL-tetraacrylate (star-PCL-TA, Tm ∼45 °C) for the potential to improve tissue safety. To achieve favorably increased degradation rates versus PCL-only scaffolds, semi-interpenetrating networks (semi-IPNs) were formed by including linear- or star-poly(l-lactic acid) (PLLA). A potential limitation of these self-fitting scaffolds is the lack of bioactivity, which is essential to osteoinductivity and osseointegration. Herein, analogous composite scaffolds were formed with 45S5 bioglass (BG) to impart bioactivity. The solvent-cast particulate leaching fabrication method was adapted to introduce BG to the fused salt template, resulting in composites with BG concentrated on the pore wall surfaces rather than within pore struts. Composite scaffolds with good pore wall integrity were produced with 2.5, 5, and 10 wt % BG. All composite scaffolds exhibited non-brittle behavior and did not fracture with 85% strain. For semi-IPN composite scaffolds, PLLA crystallinity was lost, and mechanical properties were not appreciably altered versus the non-BG controls. Sufficient retention of PCL crystallinity led to excellent shape memory behavior. The inclusion of 5 and 10 wt % BG led to hydroxyapatite mineralization after 1 day of exposure to simulated body fluid, as well as increased rates of in vitro degradation.

Candida Antarctica Lipase B-assisted top-down visualization of surface morphology of poly(ε-caprolactone)/poly(ethylene oxide) blend films

A series of enzymatic degradation experiments were designed to examine the surface morphology of phase separated poly(ε-caprolactone) (PCL)/poly(ethylene oxide) (PEO) blend films. Candida antarctica Lipase B (CALB), previously reported to have superior degradation selectivity when used at low concentrations, was utilized to selectively dissect interlamellar amorphous PCL chains and therefore to reveal the crystalline region of PCL phase. Water soluble PEO can be simultaneously removed by the CALB aqueous solutions, allowing one to envision the topological features of phase separated PCL/PEO films with various blend ratios. The transition of phase-separated PCL/PEO from nucleation and growth to spinodal decomposition was fully mapped out, along with the spatial distribution and surface morphological features of the crystalline PCL phase. The morphological characteristics of PCL/PEO blend films were further correlated to their reported physicochemical properties, demonstrating the impact of microscopic structures on the macroscopic properties of given semicrystalline polymer systems.

Ultraviolet encryption information storage using hydrophobic poly(ε-caprolactone)/carbon quantum dot composite film

Luminescent poly(ε-caprolactone)/nitrogen-doped carbon quantum dots (PCL/N-CQDs) film with the function of information protection and encryption was realized based on the fluorescent N-CQDs. The N-CQDs were synthesized from citric acid with urea as a dopant for the enhancement of fluorescent properties. The facilely prepared composite film retained the hydrophobic nature of PCL and achieved the enhanced mechanical property. The appropriate crystallization temperature and degree of crystallinity of PCL provide the film with opaque characteristics at room temperature, rendering it an ideal carrier for carrying information. The information encryption and decryption are achieved through ionoprinting technique, exploiting the ability of Fe3+ ions to quench the fluorescence of N-CQDs, allowing for the encryption of designed information on the film’s surface. With its opaque, hydrophobic, and photoluminescent properties, the PCL/N-CQDs composite film holds significant promise for applications in information encryption.

Thermal analysis of crystallization reveals subtle interactions in pristine graphene-polycaprolactone nanocomposites

In this study, we investigate the melting behavior and crystallization of nanocomposites of poly(ε-caprolactone) (PCL), a biodegradable polymer, with pristine graphene, an economically feasible filler widely available from natural sources. Nanocomposites with pristine graphene loads between 0.01 and 5 wt% were prepared via solvent casting and primarily probed by Differential Scanning Calorimetry (DSC). Conventional DSC shows that the presence of graphene increases PCL crystallinity. Non-isothermal crystallization was studied using Mo's model, whereas other parameters as Activation Energy and Nucleation Activity were obtained. It is shown that graphene increases crystallization rates acting as nucleant, with no signatures of retardant effects. Compared with other classic nano-loads, like ad-hoc modified bentonite also analyzed for comparison, pristine graphene is more effective as nucleant, which indicates that it is better dispersed in PCL. Analysis by Self Successive Annealing (SSA), also carried out by DSC, reveals that graphene hinders the formation of crystals with lamellar thickness above 7.3 nm, as found in regular PCL. It may indicate that molecular interactions between PCL and pristine graphene disrupts the movement of polymeric chains, consequently limiting lamellar growth. Evidence of such interaction is found by Infrared and Raman spectroscopies that reveal broadening of the carbonyl peak of PCL and alteration of G and D' bands of graphene.

Polycaprolactone/ atorvastatin nanocomposite - A supplier for 3D printing and drug delivery systems

Atorvastatin (ATV) exhibits pleiotropic effects on bone tissue and cardiovascular diseases, among others. Improving ATV's effectiveness requires enhancing its bioavailability, possibly through prolonged drug release. This study produced polycaprolactone/ATV nanocomposites through Hot Melting Extrusion (HME) at 69 °C. HME altered the crystallinity of both ATV and PCL. The resulting filament can be employed in 3D printing near the polymer's melting temperature, preventing ATV thermal degradation. ATV release is extended for both the filament and the produced scaffold (2mgATV/g scaffold). Results indicate this filament's potential as a valuable resource for 3D printing personalized products aimed at ATV release.

Investigation of the Effects of Chain Extender on Material Properties of PLA/PCL and PLA/PEG Blends: Comparative Study between Polycaprolactone and Polyethylene Glycol.

This study investigated the effect of the Joncryl concentration on the properties of polylactide/poly(ε-caprolactone) (PLA/PCL) and PLA/poly(ethylene glycol) (PEG) blends. The addition of Joncryl influenced the properties of both PLA-based blends. In the blend of PLA/PCL blends, the addition of Joncryl reduced the size of PCL droplets, which implies the compatibility of the two phases, while PLA/PEG blends showed a co-continuous type of morphology at 0.1% and 0.3 wt.% of Joncryl loading. The crystallinity of PCL and PEG was studied on both PLA/PCL and PLA/PEG blend systems. In both scenarios, the crystallinity of the blends decreased upon the addition of Joncryl. Thermal stabilities were shown to depend on the addition of Joncryl. The toughness increased when 0.5 wt.% of Joncryl was added to both systems. However, the stiffness of PLA/PCL decreased, while the stiffness of PLA/PEG increased with the increasing concentration of Joncryl. This study provides new insight into the effect of chain extenders on the compatibility of PLA-based blends.

Nanofibrous hybrid scaffolds based on PCL-borosilicate system by a green sol-gel process

Tissue regeneration is yet a critical issue, and to mimic the natural extracellular matrix (ECM) innovative scaffolds need to be developed to ensure the functional and safe repair of the damaged organs or tissues. Hybrid biomaterials based on the combination of a biodegradable polymer and bioactive glasses (BGs) are potential candidates for tissue engineering (TE), since they exhibit tailored physical, biological, and mechanical properties, as well as controlled degradation behavior. Thus, the main purpose of this research was to develop by electrospinning (ES) a hybrid nanofibrous membrane composed of a synthetic polymeric matrix (PCL) and a boron and calcium silicate glass, formed via in situ sol-gel, and based on a non-aqueous and green fabrication route. Formic acid (FA) and glacial acetic acid (AA) were used as green solvents to dissolve the PCL. Different compositions were prepared: neat PCL and PCL/SiO2–B2O3–CaO with different sol-gel aging times and green solvent systems. All prepared hybrid solutions, except the composition with only AA, were spinnable. Structural features of the hybrids were assessed by ATR-FTIR spectroscopy, which confirmed the presence of siloxane (Si–O–Si) bonds of silica and carbonyl (CO) bonds characteristic of PCL polymer as well as intermolecular hydrogen-bonding interactions between the carbonyls of PCL and the silanol hydroxyls (Si–OH) of silica networks. Boron (B–O–B) and borosiloxane (B–O–Si) bonds were not visible due to the overlapping of PCL bands in the spectra. Only the solid state 11B NMR technique allowed to find peaks assigned to trigonal BO3 and tetrahedral BO4 groups, which evidence the boron linkages to silica. Thermal analysis showed a change in the crystallinity of PCL with the incorporation of inorganic domains, confirming the formation of chemical interactions between the polymer and the inorganic part. Microstructure and chemical analysis, by SEM/EDS, showed a homogenous distribution of Ca and Si elements into the fibers, as well as an increase of the fiber diameter with the incorporation of boron and calcium silicate glass in the PCL. The developed compositions of PCL/boron and calcium-containing silicate were feasible to electrospin into fibrous meshes, proving its potential for further design of multicomponent nanofibrous microstructures closer to extra cellular matrix architectures.

Enzymatic PCL-grafting to NH2-end grouped silica and development of microspheres for pH-stimulated release of a hydrophobic model drug

This study set out to evaluate novel PCL-based silica containing nanohybrids as the polymer matrix in a hydrophobic drug-loaded microsphere system. Nanohybrids were synthesized by PCL-grafting to NH2-end grouped silica by in situ enzymatic ring opening polymerization of ε-caprolactone. Molecular weight and monomer conversion, PCL grafting percentage, thermal properties and crystallinity of the nanohybrids were determined by 1H NMR, TGA, DSC and XRD. Synthesized nanohybrids had low crystallinity percentage (32 and 39 %) and molecular weight (4800 and 8700 g/mol), promising for controlled drug release applications. The nanohybrids were used for fabrication of trans-chalcone-loaded microspheres by O/W single emulsion solvent evaporation. Mean particle diameter of the microspheres were between 15 and 30 µm. The result of release studies showed that optimum microsphere formulations (AP4 and A2, respectively) had 61 and 64 % encapsulation efficiency. One of the more significant findings to emerge from this investigation is that TC release was extended to 16 and 37 days, in a controlled manner. TC release was significantly enhanced in acidic pH media (pH 3.6 and 5.6) indicating pH-dependent release from nanohybrid microspheres; releasing 80–100 % of the loaded drug in 4–14 days. Drug/polymer interactions and molecular structures were investigated by FT-IR spectroscopy and DSC analysis. According to the results obtained, enzymatically synthesized nanohybrids have potential for pH-dependent release of the model drug, trans-chalcone.

Crystallization Behavior of Poly(ε-Caprolactone)-Hollow Glass Microspheres Composites for Rotational Molding Technology

Composites suitable for rotational molding technology based on poly(ε-caprolactone) (PCL) and filled with hollow glass microspheres (HGM) or functionalized hollow glass microspheres (HGMf) were prepared via melt-compounding. The functionalization of glass microspheres was carried out by a silanization treatment in order to improve the compatibility between the inorganic particles and the polymer matrix and achieve a good dispersion of glass microspheres in the matrix and an enhanced filler–polymer adhesion. The crystallization behavior of materials was studied by DSC under isothermal and non-isothermal conditions and the nucleating effect of the glass microspheres was proven. In particular, the presence of silanized glass microspheres promoted faster crystallization rates and higher nucleation activity, which are enhanced by 75% and 50%, respectively, comparing neat PCL and the composite filled with 20 wt% HGMf. The crystalline and supermolecular structure of PCL and composites crystallized from the melt was evaluated by WAXD and SAXS, highlighting differences in terms of crystallinity index and structural parameters as a function of the adopted crystallization conditions.

Renewable rice straw cellulose nanofibril reinforced poly(ε-caprolactone) composite films

In this study, cellulose nanofibrils (CNFs) fabricated from rice straw were utilized to reinforce poly(ε-caprolactone) (PCL), and the structure and properties of these CNF/PCL composite films were analyzed by morphology observation and the measurements of X-ray diffraction (XRD), differential scanning calorimeter (DSC), thermogravimetric analyzer (TGA), mechanical property and water absorption. The experimental results revealed that in PCL matrix, CNF exhibits a homogeneous distribution at low content, but shows some aggregates at high content. The incorporated CNF doesn't change the crystal type, crystallinity and melting temperature of PCL, but accelerates the crystallization of PCL due to its heterogeneous nucleating agent effect. Compared with PCL film, the CNF/PCL composite films show obvious improvement of tensile strength and Young's modulus with the increments of 7.5% at 10% CNFs and 76% at 15% CNFs respectively. However, after the CNF content exceeds 10%, the tensile strength of the composite films begins to decrease, and high loading of CNFs also causes remarkable negative influences on the thermal stability and hydrophobicity of the composite films. The straw CNFs reinforced PCL composite films can be employed in packaging and biomedical applications.

Melt electrowriting reinforced composite membrane for controlled drug release

An in-house built hybrid manufacturing device, combining the pros of melt electrowriting (MEW) and melt electrospinning (MES), is firstly proposed to produce a reinforced nonwoven fabric applied in drug delivery systems. MEW is used to print regular PCL lattice, followed by the deposition of a PCL nonwoven fabric loaded with drugs, forming a MEW/MES composite scaffold. Tensile test results suggest that after combining with MEW lattice, the strength of the composite scaffold can have a two-fold improvement and the elongation to break can increase up to 900%. Solvent vapor annealing is applied to adjust drug release rate through controlling the crystallinity of PCL. Although the increased crystallinity restrained drug release, a shish-kebab-shaped fiber structure formed by the annealing facilitates drug release. This MEW-based hybrid printing method can greatly enhance the freedom of making complex scaffold and extend to other nanotechnologies to fabricate reinforced scaffold as well.

Development of Flexible Nanocomposites Based on Poly(ε-caprolactone) for Tissue Engineering Application: The Contributing Role of Poly(glycerol succinic acid) and Polypyrrole

Poly(ε-caprolactone) (PCL), a semi-crystalline polyester, has been widely used for tissue engineering and regenerative medicine applications due to its favorable mechanical properties, biocompatibility, and long-term biodegradation. Despite desirable physical and chemical characteristics, PCL shows low hydrophilicity, thus constraining its utility for biomedical applications. Here, we report the synthesis and characterization of elastomeric PCL/poly(glycerol succinate) (PGSu) blends and their nanocomposites with improved surface wettability and tunable mechanical properties, and controlled biodegradation. Also, the effect of the polypyrrole (PPy) coating layer on the properties of scaffolds was investigated. By tailoring the surface and bulk properties of scaffolds using a change in PCL to PGSu ratio, adding nano-hydroxyapatite (n-HA) as a filler, and deposition of PPy on the scaffolds, it is possible to engineer scaffolds with customized degradation and mechanical properties. The addition of PGSu and n-HA increased hydrophilicity of the PCL matrix, developed its mechanical performance, and enhanced in-vitro cell metabolic activity. It was shown that Young’s modulus of PCL-PGSu-based scaffolds could be tuned from about 11.5 MPa to 4.5 MPa by altering the amount of PGSu and n-HA within the PCL network. The crystallinity of PCL was also considerably influenced by PGSu and n-HA. Moreover, deposition of PPy on the scaffolds resulted in a desirable antibacterial activity and electrical conductivity of about 5*10-2 S/cm. As expected, the rate of degradation increased with an increase in PGSu concentration. At the same time, the PPy coating layer delayed the degradation process, indicating that the biodegradation rate of the PCL matrix can be regulated. PCL-PGSu-based scaffolds also supported cell viability and proliferation, where PPy coating significantly improved cell viability. Therefore, the synthesized scaffolds can be used for a range of tissue engineering applications.

Suitability of EtO sterilization for polydopamine-coated, self-fitting bone scaffolds

Irregularly shaped craniomaxillofacial (CMF) defects may be advantageously treated by “self-fitting” shape memory polymer (SMP) scaffolds, namely those prepared from poly(ε-caprolactone)diacrylate (PCL-DA) networks and PCL-DA/poly(L-lactic acid) (PLLA) (75:25 wt%) semi-interpenetrating polymer networks (semi-IPNs). In addition to achieving good scaffold-tissue contact, a polydopamine (PD) coating can be leveraged to enhance bioactivity for improved osseointegration. Sterilization with ethylene oxide (EtO) represents a logical choice due to its low operating temperature and humidity. Herein, for the first time, the impact of EtO sterilization on the material properties of PD-coated SMP scaffolds was systematically assessed. Morphological features (i.e., pore size and pore interconnectivity), and in vitro bioactivity were preserved as were PCL crystallinity, PLLA crystallinity, and crosslinking. These latter features led to sustained shape memory properties, and compressive modulus. EtO-sterilized, PD-coated scaffolds displayed similar in vitro degradation behaviors versus analogous non-sterilized scaffolds. This included maintenance of compression modulus following 28 days of exposure to non-accelerated degradation conditions.

Molecular Brushes with a Polyimide Backbone and Poly(ε-Caprolactone) Side Chains by the Combination of ATRP, ROP, and CuAAC.

An approach to the synthesis of the novel molecular brushes with a polyimide (PI) backbone and poly(ε-caprolactone) (PCL) side chains was developed. To obtain such copolymers, a combination of various synthesis methods was used, including polycondensation, atom transfer radical polymerization (ATRP), ring opening polymerization (ROP), and Cu (I)-catalyzed azide-alkyne Huisgen cycloaddition (CuAAC). ATRP of 2-hydroxyethyl methacrylate (HEMA) on PI macroinitiator followed by ROP of ε-caprolactone (CL) provided a “brush on brush” structure PI-g-(PHEMA-g-PCL). For the synthesis of PI-g-PCL two synthetic routes combining ROP and CuAAC were compared: (1) polymer-analogous transformations of a multicenter PI macroinitiator with an initiating hydroxyl group separated from the main chain by a triazole ring followed by ROP of CL, or (2) a separate synthesis of macromonomers with the desirable functional groups (polyimide with azide groups and PCL with terminal alkyne groups), followed by a click reaction. Results showed that the first approach allows to obtain graft copolymers with a PI backbone and relatively short PCL side chains. While the implementation of the second approach leads to a more significant increase in the molecular weight, but unreacted linear PCL remains in the system. Obtained macroinitiators and copolymers were characterized using 1H NMR and IR spectroscopy, their molecular weight characteristics were determined by SEC with triple detection. TGA and DSC were used to determine their thermal properties. X-ray scattering data showed that the introduction of a polyimide block into the polycaprolactone matrix did not change the degree of crystallinity of PCL.

Triple one‐way and two‐way shape memory poly(ethylene‐co‐vinyl acetate)/poly(ε‐caprolactone) immiscible blends

AbstractTriple one‐way and two‐way shape memory polymers (1W‐SMPs and 2W‐SMPs) are highly desirable for many practical applications due to the multiple shape transformation. In this work, the blend with co‐continuous structure is fabricated based on poly(ethylene‐co‐vinyl acetate) (EVA) and poly(ε‐caprolactone) (PCL), which shows excellent triple one‐way and two‐way shape memory properties. It is found that the blends have two independent crystallization peaks and two independent melting peaks. With the increase of dicumyl peroxide (DCP) content, the crystallization temperature, melting temperature, and crystallinity of both EVA and PCL in the blends gradually decreases. The blends show great dual and triple one‐way shape memory property, and the phenomena of elongation induced by oriented crystallization and contraction induced by melting are clearly seen. Moreover, the blends exhibit remarkable and recyclable triple two‐way shape memory performance, with an average shape recovery magnitude of 97.3% and an average actuation magnitude of 50.6%. In terms of the excellent triple one‐way and two‐way shape memory performance, the EVA/PCL blends may have potential applications in the fields of soft robotics, actuators, and cranes. The new preparation method of triple 2W‐SMPs can be used to fabricate other triple 2W‐SMPs with commercial polymers.

Highly crystalline PCL ultrathin films as thermally switchable biomaterial coatings

Semi-crystalline oligomers are explored as functionalized thermoswitchable coatings for modification of biomaterials surface. Highly crystalline oligo(ε-caprolactone) (OCL) films are prepared at the air–water interface by the Langmuir technique, which consist of tightly packed single crystals. Their morphology and melting temperature can be tuned by the chemical structure of the OCL end-groups (hydroxy or methacrylate) and by the crystallization temperature (12 or 21 °C) as physical parameter. This demand of high crystallite density and adjustable morphology of coatings is not met by conventional methodologies for preparing thin films, e.g., spin coating, spray coating, or solvent evaporation. The high crystallinity reduces the enzymatic degradation rate of the films on both water and solid surfaces. The high density of methacrylate end-groups at the crystal surfaces enables post-functionalization, which was demonstrated using fluorescein dimethacrylate as chemically linked label. The thermoswitching behavior (melting and recrystallization) of fluorescein functionalized, highly crystalline OCL films shows temperature-dependent distribution of the chemically linked fluorescein moieties, which are accumulated on the surfaces of crystals, and homogeneously dispersed when the crystals are molten. Thermally switchable highly crystalline films are relevant for cell substrates modulating adhesion at the biointerface or for coatings as barrier layer influencing the degradation rate.Graphic abstract

Cellulose nanocrystal effect on crystallization kinetics and biological properties of electrospun polycaprolactone

Mechanical properties of tissue engineering nanofibrous scaffolds are of importance because they not only determine their ease of application, but also influence the environment for cell growth and proliferation. Cellulose nanocrystals (CNCs) are natural renewable nanoparticles that have been widely used for manipulating nanofibers' mechanical properties. In this article, cellulose nanoparticles were incorporated into poly(caprolactone) (PCL) solution, and composite nanofibers were produced. Ozawa-Flynn-Wall (OFW) methodology and X-ray diffraction were used to investigate the effect of CNC incorporation on PCL crystalline structure and its biological properties. Results showed that CNC incorporation up to 1% increases the crystallization activation energy and reduces the crystal volume, while these factors remain constant above this critical concentration. MTT assay and microscopic images of seeded cells on the nanofiber scaffolds indicated increased cell growth on the samples containing CNC. This behavior could be attributed to their greater hydrophilicity, which was confirmed using parallel exponential kinetics (PEK) model fitting to results obtained from dynamic vapor sorption (DVS) studies. Superior performance of CNC containing samples was also confirmed by in vivo implantation on full-thickness wounds. The wound area faded away more rapidly in these samples. H&E and Masson's trichrome staining showed better regeneration and more developed tissues in wounds treated with PCL-CNC1% nanofibers.

Controlling the crystallinity and solubility of functional PCL with efficient post-polymerisation modification

Varying the size of an alkyl side-chain group, installed by thiol–ene addition of alkylthiols to poly(ε-allyl caprolactone), the semi-crystallinity and lipophilicity of functional PCLs could be modulated to achieve divergent physico-chemical properties.

Physical structure contributions in pH degradation of PEO-b-PCL films

Poly(ethylene oxide)-block-poly(ε-caprolactone) (PEO-b-PCL) is an intriguing candidate for hydrophobic drug encapsulation and controlled release into the body as a biocompatible, amphiphilic block copolymer. In this study, a variety of characterization techniques, including DSC, NMR, and SEM, were employed to investigate the degradation of PEO-b-PCL films within aqueous environments. Previous work has shown that the degradation of these films is accelerated in both basic and acidic environments; however, it is important to develop a better understanding of degradation rate as it relates to the physical structure of the films. To this end, the degree of crystallinity of each block within PEO-b-PCL films was manipulated intentionally by varying the molecular weight and rate of cooling from melt. The data indicated that molecular weight, cooling rate, and pH all have substantial effects on the rate of degradation of the films and on the composition of the degradation products over time. In general, increasing the mass fraction or degree of crystallinity of PCL leads to slower degradation. Further, crystallization of the PEO block hinders buffer penetration, slowing degradation, while a higher mass fraction of amorphous PEO accelerates the erosion of these films. This insight can help inform efforts to fine-tune the encapsulation and delivery of hydrophobic pharmaceutical compounds.