Controlling polylactide stereocomplex (sc-PLA) self-assembly: From microspheres to nanoparticles

Michalski, Adam; Makowski, Tomasz; Biedroń, Tadeusz; Brzeziński, Marek; Biela, Tadeusz

doi:10.1016/j.polymer.2016.03.049

Cited by 39 publications

(40 citation statements)

References 48 publications

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“…When a stereocomplex is prepared with the application of medium molecular weight PLAs then the microparticle morphology depends strongly on the nature of the polymer end groups, as we have recently found . Our study indicated that such factors as stereocomplexation conditions and the PLA architecture as well as terminal group interactions can influence microparticle morphology in the case of the stereocomplexation of star and star‐linear PLAs containing terminal −OH and −COOH groups …”

Section: Introductionsupporting

confidence: 65%

“…The dependence of stereocomplex morphology on different parameters was first studied for simple linear PLA containing one −OH and only one −COOH terminal group (PLA‐(COOH) 1 ). During preliminary experiments it was found that the microparticle size depends only slightly on solution concentration (this dependence was checked earlier for another system); thus 10 wt% solutions were used for all stereocomplexations. Figure presents the dependence of stereocomplex morphology on different parameters.…”

Section: Resultsmentioning

confidence: 90%

“…It is known that stereocomplex morphology depends on stereocomplex formation conditions . (Micro)nanospheres or fibrillary (micro)nanoparticles or particles with worm‐like morphology have recently been obtained as a result of stereocomplexation performed with the application of linear and star medium molecular weight PLAs with −COOH and −OH end groups . The particle size depended on the solvent type and polymer concentration.…”

Section: Resultsmentioning

confidence: 99%

“…Microspheres of star PLA with −OH groups precipitated from 5 − 20 wt% solutions in THF as 1.5 − 3.5 µm microparticles (smaller particles in less concentrated solution). On precipitation from dioxane, a stereocomplex from star PLLA‐COOH/linear PDLA‐IL (IL, ionic liquid group) in the form of 0.4 µm nanospheres was formed …”

Section: Resultsmentioning

confidence: 99%

“…The synthesis of spherical microparticles by crystallization from the solvent depends strongly on the nature of the solvent and crystallization conditions and only at precisely selected conditions can highly regular microparticles be obtained. When a stereocomplex is prepared with the application of medium molecular weight PLAs then the microparticle morphology depends strongly on the nature of the polymer end groups, as we have recently found .…”

Section: Introductionmentioning

confidence: 99%

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Spontaneous formation of polylactide stereocomplex microspheres containing metal ions

2016

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Linear poly(l‐lactides) (PLLAs) and poly(d‐lactides) (PDLAs) with Mn in the range 2000 − 4300 containing a different number and placement of carboxyl groups were obtained via cationic ring‐opening polymerization and post‐polymerization functionalization. PLA stereoisomers (PLLA‐(COOH)x and PDLA‐(COOH)x, where x = 1 − 3) were used for the investigation of stereocomplexation in solution performed in the presence of metal cations such as Ca2+, Mg2+, Zn2+, Fe3+. Spherical microparticles with a diameter in the range 0.7 − 3.0 µm were obtained in all cases which was confirmed on the basis of scanning electron microscopy (SEM) analysis. The microsphere size and homogeneity were analyzed depending on the stereocomplexation conditions and the molecular weight as well as the number of carboxyl end groups in the PLLA and PDLA used for stereocomplexation. The PLA microspheres obtained were analyzed by Fourier transform IR spectroscopy, wide angle X‐ray spectroscopy and energy‐dispersive X‐ray spectroscopy methods which confirmed the presence of metal cations inside. The application of regular microspheres with metal ions as drug delivery systems is considered. © 2016 Society of Chemical Industry

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Section: Introductionsupporting

confidence: 65%

Section: Resultsmentioning

confidence: 90%

Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Spontaneous formation of polylactide stereocomplex microspheres containing metal ions

2016

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Ionic and Coordination Ring‐Opening Polymerization

Penczek¹,

Biela²,

Cypryk³

et al. 2022

Macromolecular Engineering

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This article provides the up‐to‐date and comprehensive review (over 700 citations) of all the important subjects of the ring‐opening polymerization (ROP) methods of polymers syntheses. This is the method of synthesis of several important classes of polymers that cannot be prepared in a different way (e.g., polyethers). It also complements known methods of polycondensation and ROP often is the method of choice. ROP is particularly important in syntheses of the biodegradable polymers‐polylactide and poly(ε‐caprolactone), discussed in details. Applications of these polymers, as well as polysiloxanes in biomedical applications are irreplaceable in the modern medicine. Either as bulk polymers or as nano‐ and microspheres, described In this article separately. There are sections in the present version that were not presented in the previous editions. This is description of polyoxazolines, polymers with phosphorus atoms in the chains, as well as mentioned above polysiloxanes an microspheres. We introduced also section describing novel analytical methods, particularly useful in studies of polymers with various architectures (star shape, multibranched etc.). Besides the synthetic aspects of ROP, this article describes thermodynamics and kinetic features of the living/controlled polymerizations, particularly by activated monomer mechanism and importance of dormant polymers in precision syntheses of desired structures.

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Reversible Supramolecular Polylactides Gels Obtained via Stereocomplexation

Michalski

Socka

Brzeziński

et al. 2018

Macro Chemistry & Physics

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In this paper, stereocomplexation is used as a driving force for the formation of 3D polymer networks by hydrogen bonding cross‐linking between complementary enantiomeric polylactides (PLAs). Thus, the formation of the gels after the mixing of equimolar solutions of l‐ and d‐star‐shaped PLAs in the biocompatible N‐methyl‐2‐pyrrolidone (NMP) is observed. The utility of star‐shaped polymers facilitates the cross‐linking of macromolecules by increasing the number of functional end groups. Moreover, the well‐established reaction with succinic anhydride is used to functionalize the star‐shaped PLAs with carboxylic functions. These end groups have a significant impact on the viscosity and stability of the resulting PLA gels. Importantly, the formation of the supramolecular gel is reversible, and it can return to sol upon heating. These results demonstrate that the gel formation is a result of a synergic interaction of the PLA functional end groups and stereocomplexation. These novel stereocomplex gels have potential for biomedical applications due to the biocompatibility of both components: PLA and NMP.

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Controlling polylactide stereocomplex (sc-PLA) self-assembly: From microspheres to nanoparticles

Cited by 39 publications

References 48 publications

Spontaneous formation of polylactide stereocomplex microspheres containing metal ions

Spontaneous formation of polylactide stereocomplex microspheres containing metal ions

Ionic and Coordination Ring‐Opening Polymerization

Reversible Supramolecular Polylactides Gels Obtained via Stereocomplexation

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