Morphogenic effect of common solvent in the self-assembly behavior of amphiphilic PEO-b-PLA

Simonutti, Roberto; Bertani, Daniela; Ferrario, Silvia; Manzone, D.; Mauri, Michele; Gregori, Maria; Orlando, Antonina; Masserini, Massimo

doi:10.1016/j.polymer.2021.123511

Cited by 14 publications

(11 citation statements)

References 56 publications

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“…The obtainment of large self-assembled nanoparticles for Lco-PILs and Cco-PILs can be ascribed to the predominantly hydrophobic segments and minorly hydrophilic segments, because the hydrophilic segments are too short to balance the elastic and interface energy of the solvophobic segments by solvation so that the relative energy minima can be reached by arrangement to large nanoparticles. [26][27][28][29] To note, no internal structure was observed for these two nanoassemblies by cryo-TEM (Figure 3C,F), and the observed size difference between Lco-PILs and Cco-PILs nanoassemblies in the cryo-TEM survey is in agreement with the results from the TEM analysis. DMSO was next used as well as the 2 nd good solvent to carry out the self-assembly of co-PILs, and its solvent effect was investigated on the co-PILs' self-assembly behaviors.…”

Section: Resultssupporting

confidence: 83%

“…For self-assembly of amphiphilic diblock copolymers bearing predominantly hydrophobic segments, the spherical aggregates were generally transitioned from spherical micelles. [26][27][28][29] Based on the results of CGMD simulations, we speculate that the spherical aggregates are formed by transitioning from micelles, which formed by enriched hydrophobic counter anions in the core and enriched hydrophilic counter anions in the corona, showing gradient block-like structures (Scheme 1). Such distribution differences of counter anions can be evidenced by the varied contrast of the selfassembled coPIL nanoparticles observed in the Cryo-TEM images (Figure 2C,F).…”

Section: Resultsmentioning

confidence: 99%

“…The smaller diameter range for both Lco‐PILs and Cco‐PILs nanoassemblies than that obtained in DMF as the starting good solvent, may be ascribed to the different polymer‐solvent interaction and the polarity of the solvent, which were reported to have a distinct influence on the self‐assembly process. [ 26,27,30 ] Alternatively, the bimodal distribution in DMF but monomodal distribution in DMSO for Lco‐PILs nanoassemblies also can be attributed to the difference of polymer‐solvent interaction and the polarity of the solvent. [ 26,27,30 ] These data also indicate that the cyclic topology plays indeed a significant role in co‐PILs’ self‐assembly behavior, which may be ascribed to the restriction of co‐PILs’ chain stretch by the loop.…”

Section: Resultsmentioning

confidence: 99%

“…[ 26,27,30 ] Alternatively, the bimodal distribution in DMF but monomodal distribution in DMSO for Lco‐PILs nanoassemblies also can be attributed to the difference of polymer‐solvent interaction and the polarity of the solvent. [ 26,27,30 ] These data also indicate that the cyclic topology plays indeed a significant role in co‐PILs’ self‐assembly behavior, which may be ascribed to the restriction of co‐PILs’ chain stretch by the loop.…”

Section: Resultsmentioning

confidence: 99%

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Topological Effects on Cyclic Co‐Poly(ionic liquid)s Self‐Assembly

Tang

Ren

Kochovski

et al. 2022

Macro Chemistry & Physics

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Topological geometry of poly(ionic liquid)s (PILs), such as brush-like, knot-like, hyperbranched and randomly coiled, often exerts a strong influence on their self-assembly behaviors. As a primary topological form, the cyclic topology-derived effects have not been investigated on PILs, which concerns synergy of charges and zero chain end. Herein, linear and cyclic poly(ionic liquid) copolymers (co-PILs) with randomly distributed counter anions of B(Ph) 4 − and Br − by a template method in combination with a follow-up partial anion exchange is prepared. The self-assembly phenomena of linear and cyclic co-PILs are studied in selective solvents, where the hydrophobic counter anions B(Ph) 4 − and hydrophilic counter anions Br − aggregated to form cores and corona in the assembled nanospheres, showing the average size of cyclic co-PILs nanospheres is 46.2% smaller (≈120 nm) than linear co-PILs nano-assemblies (≈176 nm). Based on the CGMD simulations, the authors speculate that the spherical aggregates are formed by transitioning from micelles with gradient block-like structures, which formed by enriched hydrophobic counter anions in the core and enriched hydrophilic counter anions in the corona. These results indicate a novel synergy of topology effects and dynamic anion movements, as revealed by cyclic co-PIL self-assembly in this work.

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Section: Resultssupporting

confidence: 83%

Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

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Topological Effects on Cyclic Co‐Poly(ionic liquid)s Self‐Assembly

Tang

Ren

Kochovski

et al. 2022

Macro Chemistry & Physics

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“…In fact, the size distributions of both drug-free and PAX-loaded TPGS 2000 - b -PCL nanocarriers showed bimodal size distribution ( Figure S7 ), which may suggest either nanoparticle aggregation or formation of a mixed population, e.g., micelles and polymersomes. However, further studies (e.g., atomic force microscopy and cryogenic TEM) are needed to verify the possibility of presence of mixed morphologies [ 54 , 56 , 62 ].…”

Section: Resultsmentioning

confidence: 99%

Design and Development of D‒α‒Tocopheryl Polyethylene Glycol Succinate‒block‒Poly(ε-Caprolactone) (TPGS−b−PCL) Nanocarriers for Solubilization and Controlled Release of Paclitaxel

et al. 2021

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The objective of this study was to synthesize and characterize a set of biodegradable block copolymers based on TPGS-block-poly(ε-caprolactone) (TPGS-b-PCL) and to assess their self-assembled structures as a nanodelivery system for paclitaxel (PAX). The conjugation of PCL to TPGS was hypothesized to increase the stability and the drug solubilization characteristics of TPGS micelles. TPGS-b-PCL copolymer with various PCL/TPGS ratios were synthesized via ring opening bulk polymerization of ε-caprolactone using TPGS, with different molecular weights of PEG (1–5 kDa), as initiators and stannous octoate as a catalyst. The synthesized copolymers were characterized using 1H NMR, GPC, FTIR, XRD, and DSC. Assembly of block copolymers was achieved via the cosolvent evaporation method. The self-assembled structures were characterized for their size, polydispersity, and CMC using dynamic light scattering (DLS) technique. The results from the spectroscopic and thermal analyses confirmed the successful synthesis of the copolymers. Only copolymers that consisted of TPGS with PEG molecular weights ≥ 2000 Da were able to self-assemble and form nanocarriers of ≤200 nm in diameter. Moreover, TPGS2000-b-PCL4000, TPGS3500-b-PCL7000, and TPGS5000-b-PCL15000 micelles enhanced the aqueous solubility of PAX from 0.3 µg/mL up to 88.4 ug/mL in TPGS5000-b-PCL15000. Of the abovementioned micellar formulations, TPGS5000-b-PCL15000 showed the slowest in vitro release of PAX. Specifically, the PAX-loaded TPGS5000-b-PCL15000 micellar formulation showed less than 10% drug release within the first 12 h, and around 36% cumulative drug release within 72 h compared to 61% and 100% PAX release, respectively, from the commercially available formulation (Ebetaxel®) at the same time points. Our results point to a great potential for TPGS-b-PCL micelles to efficiently solubilize and control the release of PAX.

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Investigation of morphology and structure of drug‐loaded PLA‐b‐PEO‐b‐PLA polymeric micelle: A dissipative particle dynamics simulations study

Liu,

Lin,

Wang

et al. 2024

J Biomed Mater Res

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The dissipative particle dynamics (DPD) simulation was used to study the morphologies and structures of the paclitaxel‐loaded PLA‐b‐PEO‐b‐PLA polymeric micelle. We focused on the influences of PLA block length, PLA‐b‐PEO‐b‐PLA copolymer concentration, paclitaxel drug content on morphologies and structures of the micelle. Our simulations show that: (i) with the PLA block length increase, the self‐assemble structure of PLA‐b‐PEO‐b‐PLA copolymers with paclitaxel vary between onion‐like structure (core‐middle layer‐shell) to spherical core‐shell structure. The PEO shell thins and the size of the PLA core increases. The onionlike structures are comprised of the PEO hydrophilic core, the PLA hydrophobic middle layer, and the PEO hydrophilic shell, the distribution of the paclitaxel drug predominantly occurs within the hydrophobic intermediate layer; (ii) The system forms a spherical core‐shell structure when a small amount of the drug is added, and within a certain range, the size of the spherical structure increases as the drug amount increases. When the drug contents (volume fraction) cdrug = 10%, it can be observed that the PLA4‐b‐PEO19‐b‐PLA4 spherical structures connect to form rod‐shaped structures. With the length of PLA block NPLA = 8, as the paclitaxel drug concentrations cdrug = 4%, PEO has been insufficient to completely encapsulate the PLA and paclitaxel drug beads. To enhance drug loading capacity while maintaining stability of the system in aqueous solution, the optimal composition for loading paclitaxel is PLA4‐b‐PEO19‐b‐PLA4; the drug content is not higher than 4%; (iii) The paclitaxel‐loaded PLA4‐b‐PEO19‐b‐PLA4 micelle undergo the transition from onionlike (core‐middle layer‐shell) to spherical (core‐shell) to rod‐shaped and lamellar structure as the PLA4‐b‐PEO19‐b‐PLA4 copolymer concentration increases from ccp = 10% to 40%.

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Morphogenic effect of common solvent in the self-assembly behavior of amphiphilic PEO-b-PLA

Cited by 14 publications

References 56 publications

Topological Effects on Cyclic Co‐Poly(ionic liquid)s Self‐Assembly

Topological Effects on Cyclic Co‐Poly(ionic liquid)s Self‐Assembly

Design and Development of D‒α‒Tocopheryl Polyethylene Glycol Succinate‒block‒Poly(ε-Caprolactone) (TPGS−b−PCL) Nanocarriers for Solubilization and Controlled Release of Paclitaxel

Investigation of morphology and structure of drug‐loaded PLA‐b‐PEO‐b‐PLA polymeric micelle: A dissipative particle dynamics simulations study

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