Kinetically stable sub-50 nm fluorescent block copolymer nanoparticles <i>via</i> photomediated RAFT dispersion polymerization for cellular imaging

Tkachenko, Vitalii; Kunemann, Philippe; Malval, Jean‐Pierre; Petithory, Tatiana; Pieuchot, Laurent; Vidal, Loı̈c; Chemtob, Abraham

doi:10.1039/d1nr04934h

Cited by 5 publications

(6 citation statements)

References 72 publications

(59 reference statements)

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“…Instead of OEGMA repeat units, its acrylic analogue, OEGA, was used here for designing copolymers with well-defined molecular characteristics (all components belong to the “family” of acrylates) (Table ). The glass temperature of POEGA ( T g POEGA ∼ 209 K) is slightly lower than that of POEGMA ( T g POEGMA ∼ 213 K; Figure ) while keeping the same EO side group length. It is well documented in the literature , that the dominant factor that governs the segmental dynamics and the associated T g in comb-like polymers is the (EO) side group length due to the internal plasticization effect (e.g., faster backbone dynamics by the incorporation of short and very mobile side groups).…”

Section: Resultsmentioning

confidence: 94%

Grafted Copolymer Electrolytes Based on the Poly(acrylic acid-co-oligo ethylene glycol acrylate) (P(AA-co-OEGA)) Ion-Conducting and Mechanically Robust Block

Pipertzis

Kafetzi

Giaouzi

et al. 2022

ACS Appl. Polym. Mater.

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A series of completely amorphous polymer brushes composed of grafted copolymer electrolytes based on the ioncontaining block of poly(acrylic acid-co-oligo ethylene glycol acrylate) (P(AA-co-OEGA)) doped with LiCF 3 SO 3 (LiTf) or LiN(SO 2 CF 3 ) (LiTFSI) and the glassy polystyrene (PS) block are synthesized and studied with respect to the structural, thermomechanical, and ion conduction properties. The incorporation of some AA units into the ion-conducting phase provides a trade-off between increased mechanical stability and anion/cation complexation. Consequently, the P(AA-co-OEGA) block can be engineered to simultaneously support ion conduction while exhibiting enhanced mechanical stability. Between the two anions ([Tf − ] vs [TFSI − ]), it is the latter that better supports the Li-ion transport. Diblock copolymer electrolytes doped with the larger anion ([TFSI − ]) suppress ion complexation and give rise to superior ion conduction properties (by about 2 orders of magnitude), as compared to that of the smaller anion ([Tf − ]). Overall, the PS-b-P(AA-co-OEGA)/LiTFSI diblock-random copolymer electrolyte with salt concentration, r = 0.08 (r is defined as the molar ratio of Li ions to EO units), best combines the required mechanical stability (storage modulus, G′ ∼ 10 8 Pa) with a relatively high dc-conductivity (σ dc ∼ 10 −6 S•cm −1 ) at an ambient temperature (for application as solid polymer electrolytes (SPEs) in Li-ion batteries). This work suggests routes toward further improving the mechanical stability via the random incorporation of acids into the ion-containing block of nanophase-separated electrolytes.

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Section: Resultsmentioning

confidence: 94%

Grafted Copolymer Electrolytes Based on the Poly(acrylic acid-co-oligo ethylene glycol acrylate) (P(AA-co-OEGA)) Ion-Conducting and Mechanically Robust Block

Pipertzis

Kafetzi

Giaouzi

et al. 2022

ACS Appl. Polym. Mater.

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“…The PISA library for micelle-crosslinked hydrogels was subsequently extended to alcoholic systems (Figures S19–S24 and Table S4). As shown in Figure a–d and Figure S25, typical alcoholic PISA of methacrylates (benzyl methacrylate, BzMA; , lauryl methacrylate, LMA), styrenics (styrene, St), and acrylates (benzyl acrylate, BzA) were all confirmed feasible to the preparation of micellar crosslinkers and micelle-crosslinked tough and ultrastretchable hydrogels. In view of the broad scope of PISA library, the development of micelle-crosslinked hydrogels would therefore be greatly promoted.…”

Section: Results and Discussionmentioning

confidence: 99%

Polymerization-Induced Self-Assembly Toward Micelle-Crosslinked Tough and Ultrastretchable Hydrogels

et al. 2022

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As a promising class of tough and ultrastretchable hydrogels, micellecrosslinked hydrogels have been restrained by the scarcity of micellar crosslinkers with a high concentration, controlled nanostructure, and uniform size distribution. Herein, polymerization-induced self-assembly (PISA) was demonstrated to be a general and powerful platform for micellar crosslinkers, affording micelle-crosslinked hydrogels with tailorable chemical structures, mechanics, and functionality. Poly(N,N-dimethylacrylamide)-b-poly(diacetone acrylamide) (PDMAc-b-PDAAM) micellar crosslinkers with a controlled nanostructure and uniform size distribution were prepared via PISA and onestep post-polymerization modification at high concentrations. Copolymerization of these micellar crosslinkers with acrylamide generated tough and ultrastretchable hydrogels, whose mechanical properties were found correlated with the concentration, nanostructure, and chemical composition of the micelles. The energy dissipation mechanism of these micelle-crosslinked hydrogels was analyzed via cyclic mechanical tests and stress relaxation experiments. The general feasibility of PISA toward micelle-crosslinked hydrogels was verified by systematic evaluation of both aqueous (including 2-methoxyethyl acrylate, tetrahydro-2-furanylmethyl acrylate, and 4-hydroxybutyl acrylate) and alcoholic (including benzyl methacrylate, lauryl methacrylate, styrene, and benzyl acrylate) PISA formulations, producing hydrogels with diverse chemical structures, mechanics, and functionalities depending on the micellar crosslinkers. The modularity of this strategy was further demonstrated by the fabrication of fluoro-functionalized hydrogels with fluoro-containing micellar crosslinkers. This strategy has significantly enlarged the scope and application of micelle-crosslinked hydrogels.

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“…More recently, poly ((oligo(ethylene glycol) acrylate) -b- poly(benzyl acrylate) (POEGA -b- PBzA) NPs had been fabricated by photo-mediated RAFT-PISA (Fig. 11 A) [ 143 ]. Notably, sub-50-nm spherical NPs were successfully obtained by the adjustment of chain length (Fig.…”

Section: Biomedical Applicationsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Polymerization-Induced Self-Assembly for Efficient Fabrication of Biomedical Nanoplatforms

et al. 2023

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Amphiphilic copolymers can self-assemble into nano-objects in aqueous solution. However, the self-assembly process is usually performed in a diluted solution (<1 wt%), which greatly limits scale-up production and further biomedical applications. With recent development of controlled polymerization techniques, polymerization-induced self-assembly (PISA) has emerged as an efficient approach for facile fabrication of nano-sized structures with a high concentration as high as 50 wt%. In this review, after the introduction, various polymerization method-mediated PISAs that include nitroxide-mediated polymerization-mediated PISA (NMP-PISA), reversible addition-fragmentation chain transfer polymerization-mediated PISA (RAFT-PISA), atom transfer radical polymerization-mediated PISA (ATRP-PISA), and ring-opening polymerization-mediated PISA (ROP-PISA) are discussed carefully. Afterward, recent biomedical applications of PISA are illustrated from the following aspects, i.e., bioimaging, disease treatment, biocatalysis, and antimicrobial. In the end, current achievements and future perspectives of PISA are given. It is envisioned that PISA strategy can bring great chance for future design and construction of functional nano-vehicles.

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Kinetically stable sub-50 nm fluorescent block copolymer nanoparticles via photomediated RAFT dispersion polymerization for cellular imaging

Abstract: Self-assembled block copolymer nanoparticles (NPs) have emerged as a major potential nanoscale vehicle for fluorescence bioimaging purpose. Crucial to their practical implementation is to prepare with high yields NPs possessing...

Cited by 5 publications

References 72 publications

Grafted Copolymer Electrolytes Based on the Poly(acrylic acid-co-oligo ethylene glycol acrylate) (P(AA-co-OEGA)) Ion-Conducting and Mechanically Robust Block

Grafted Copolymer Electrolytes Based on the Poly(acrylic acid-co-oligo ethylene glycol acrylate) (P(AA-co-OEGA)) Ion-Conducting and Mechanically Robust Block

Polymerization-Induced Self-Assembly Toward Micelle-Crosslinked Tough and Ultrastretchable Hydrogels

Polymerization-Induced Self-Assembly for Efficient Fabrication of Biomedical Nanoplatforms

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