The effect of temperature and pressure on polycaprolactone morphology

Baptista, Cameron; Azagury, Aharon; Shin, Hyeseon; Baker, Christopher M.; Ly, Eileen; Lee, Rachel; Mathiowitz, Edith

doi:10.1016/j.polymer.2020.122227

Cited by 50 publications

(25 citation statements)

References 35 publications

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“…Two main reflexes were observed: at 21.4 corresponding to (110) lattice of PCL, and, at 23.7 corresponding to (200) one. 31 The reflex at 22.0 corresponding to (111) lattice of PCL was present in XRD of the PCL scaffold and disappeared with the addition of PVP.…”

Section: Resultsmentioning

confidence: 99%

Enhanced properties of poly(ε‐caprolactone)/polyvinylpyrrolidone electrospun scaffolds fabricated using 1,1,1,3,3,3‐hexafluoro‐2‐propanol

Goreninskii

Danilenko

Bolbasov

et al. 2021

J of Applied Polymer Sci

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Poly(ε‐caprolactone)/polyvinylpyrrolidone (PCL/PVP) scaffolds with various composition were fabricated from 1,1,1,3,3,3‐hexafluoro‐2‐propanol (HFIP) solution using the same electrospinning parameters in order to reveal the effect of polymer ratio on the material properties. The obtained materials were characterized using scanning electron microscopy, contact angle measurements, X‐ray diffraction, Fourier‐transformed infrared spectroscopy, and tensile testing. The strengthening effect of PVP was observed: Young modulus of PCL/PVP scaffold with 50/50 polymer ratio was found at 105.4 ± 8.4 MPa which is six times higher comparing to those of PCL scaffold. PVP‐containing scaffolds were extremely hydrophilic with PVP concentration of 5 wt% (vs. 25 wt% in previous reports) leading to full wetting of the material. in vitro studies showed an improved viability of HeLa cells cultured with the composites containing higher concentrations of PVP. Owing to the application of HFIP, PCL‐based materials were loaded with cyclophosphamide for the first time and the PVP‐containing materials demonstrated the intensified initial release of the model compound. Utilizing HFIP for the fabrication of PCL/PVP scaffolds significantly widens their application for drug delivery systems due to a good solubility of proteins, drugs, and other biologically active compounds in this solvent.

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Section: Resultsmentioning

confidence: 99%

Enhanced properties of poly(ε‐caprolactone)/polyvinylpyrrolidone electrospun scaffolds fabricated using 1,1,1,3,3,3‐hexafluoro‐2‐propanol

Goreninskii

Danilenko

Bolbasov

et al. 2021

J of Applied Polymer Sci

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“…Also, X‐ray diffraction (XRD) of hydrogel at 50 wt% polymer confirms that PCL cores are amorphous, judging from the absence of sharp diffractions at either 2 θ (°) = 21–22 or 24 ( Figure a). [ 27 ] We speculate that the considerably longer PCBMA midblocks, with DP 3–4 times higher than the PCL blocks, shapes the PCL cores into spheres with large surface curvature due to significant excluded volume repulsion between the PCBMA chains. The discontinuity of spherical domains can suppress the PCL crystallization, as it must occur individually and be initiated from the homogeneous nucleation, [ 28 ] which is consistent with the previous observation of PCL crystallization in cylindrical nanoconfinements.…”

Section: Resultsmentioning

confidence: 99%

Antifreeze and Rheological Properties of Injectable Triblock Copolymer Hydrogels with Supramolecular Junctions

Choi

Kim

Mun

et al. 2021

Macromol. Rapid Commun.

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ABC triblock copolymers composed of hydrophobic poly(𝝐-caprolactone) (PCL), zwitterionic poly(carboxybetaine methacrylate) midblock, and P(PEGMA-UPy 0.15 ) containing supramolecular ureidopyrimidinone moieties, poly(𝝐-caprolactone-block-carboxybetaine methacrylate-block-[poly(ethylene glycol) methyl ether methacrylate-co-(𝜶-methacryloyl-𝝎-(6-(3-(6-methyl-4-oxo-1,4-dihydropyrimidin-2-yl)ureido)hexylcarbamoyloxy)poly(ethylene glycol))]), are investigated to achieve multifunctional antifreeze hydrogels. The PCL and P(PEGMA-UPy 0.15 ) blocks induce the formation of physical network with a hierarchical nanostructure comprising hydrophobic PCL cores and supramolecular junctions, respectively. The super-hydrophilic nature of polyzwitterion midblocks and the confinement effect of the supramolecular junctions enhance the antifreeze performance, where the majority of water molecules remains supercooled below sub-zero temperature. The hydrogel relaxation characterized over a wide range of timescale reveals that the facile dynamics of the supramolecular junctions lead to the self-healing and injectability of the hydrogels. In conjunction with the biodegradable PCL cores, the antifreeze and rheological characteristics of the triblock copolymer hydrogels provide significant potential to use for cryo-preservable and bio-injectable drug storage and delivery.

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“…Pressure-induced liquid crystallinity is simply a consequence of the reduced molar volume (relative to the isotropic state) that characterizes fluids having a long-range orientational order. The same phenomenon can be used to induce LC in thermotropic polyesters such as PLLA or polycaprolactone [ 21 , 22 , 23 ]. Mesophases have been induced in non-mesogenic PLLA by pressing at a controlled temperature.…”

Section: Introductionmentioning

confidence: 99%

“…Mesophases have been induced in non-mesogenic PLLA by pressing at a controlled temperature. This process was also accompanied by the formation of multiple morphologies [ 23 , 24 , 25 ]. The formation mechanism of the mesophase obtained by pressing is likely related to the limited degrees of freedom of polymer chains at temperatures close to the glass transition temperature ( T g ).…”

Section: Introductionmentioning

confidence: 99%

Nematic-to-Isotropic Phase Transition in Poly(L-Lactide) with Addition of Cyclodextrin during Abiotic Degradation Study

Rydz

Duale

Janeczek

et al. 2022

IJMS

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Poly(L-lactide) is capable of self-assembly into a nematic mesophase under the influence of temperature and mechanical stresses. Therefore, subsequent poly(L-lactide) films were obtained and characterized, showing nematic liquid crystal properties both before and after degradation. Herein, we present that, by introducing β-cyclodextrin into the polymer matrix, it is possible to obtain a chiral nematic mesophase during pressing, regardless of temperature and time. The obtained poly(L-lactide) films exhibiting liquid crystal properties were subjected to degradation tests and the influence of degradation on these properties was determined. Thermotropic phase behavior was investigated using polarized optical microscopy, X-ray diffraction, and differential scanning calorimetry. The degradation process demonstrated an influence on the liquid crystal properties of pressed polymer films. The colored planar texture of the chiral nematic mesophase, which was not observed prior to degradation in films without the addition of β-cyclodextrin, appeared after incubation in water as a result of the entrapment of degradation products in the polymer matrix. These unusual tailor-made properties, obtained in liquid crystals in (bio)degradable polymers using a simple method, demonstrate the potential for advanced photonic applications.

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The effect of temperature and pressure on polycaprolactone morphology

Cited by 50 publications

References 35 publications

Enhanced properties of poly(ε‐caprolactone)/polyvinylpyrrolidone electrospun scaffolds fabricated using 1,1,1,3,3,3‐hexafluoro‐2‐propanol

Enhanced properties of poly(ε‐caprolactone)/polyvinylpyrrolidone electrospun scaffolds fabricated using 1,1,1,3,3,3‐hexafluoro‐2‐propanol

Antifreeze and Rheological Properties of Injectable Triblock Copolymer Hydrogels with Supramolecular Junctions

Nematic-to-Isotropic Phase Transition in Poly(L-Lactide) with Addition of Cyclodextrin during Abiotic Degradation Study

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