Greatly Enhanced Accessibility and Reproducibility of Worm‐like Micelles by In Situ Crosslinking Polymerization‐Induced Self‐Assembly

Zhang, Wenjian; Chang, Zi-Xuan; Bai, Wei

doi:10.1002/ange.202211792

Cited by 4 publications

(6 citation statements)

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“…44 The diameters of these micelles closely aligned with the theoretical value of 12.6 nm, supporting the proposed self-assembly mechanism (Figure S6). Such microstructures have been reported 45 to exhibit excellent capability in drug delivery to cells, as the worm-like structure enhances the probability that the particle can pass through the cell membrane. Additionally, worm-like micelles exhibit extended circulation time in the bloodstream, with micelle disassembly into smaller spherical particles resulting in faster clearance.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

Dextran Macroinitiator for Synthesis of Polysaccharide-b-Polypeptide Block Copolymers via NCA Ring-Opening Polymerization

Wang,

Tang,

Kou

et al. 2024

Biomacromolecules

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Synthesis of polysaccharide-b-polypeptide block copolymers represents an attractive goal because of their promising potential in delivery applications. Inspired by recent breakthroughs in N-carboxyanhydride (NCA) ring-opening polymerization (ROP), we present an efficient approach for preparation of a dextran-based macroinitiator and the subsequent synthesis of dextran-b-polypeptides via NCA ROP. This is an original approach to creating and employing a native polysaccharide macroinitiator for block copolymer synthesis. In this strategy, regioselective (2,2,6,6-tetramethylpiperidin-1-yl)oxyl (TEMPO) oxidation of the sole primary alcohol located at the C-6 position of the monosaccharide at the nonreducing end of linear dextran results in a carboxylic acid. This motif is then transformed into a tetraalkylammonium carboxylate, thereby generating the dextran macroinitiator. This macroinitiator initiates a wide range of NCA monomers and produces dextran-b-polypeptides with a degree of polymerization (DP) of the polypeptide up to 70 in a controlled manner (Đ < 1.3). This strategy offers several distinct advantages, including preservation of the original dextran backbone structure, relatively rapid polymerization, and moisture tolerance. The dextran-b-polypeptides exhibit interesting self-assembly behavior. Their nanostructures have been investigated by dynamic light scattering (DLS) and transmission electron microscopy (TEM), and adjustment of the structure of block copolymers allows self-assembly of spherical micelles and worm-like micelles with varied diameters and aspect ratios, revealing a range of diameters from 60 to 160 nm. Moreover, these nanostructures exhibit diverse morphologies, including spherical micelles and worm-like micelles, enabling delivery applications.

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Section: ■ Results and Discussionmentioning

confidence: 99%

Dextran Macroinitiator for Synthesis of Polysaccharide-b-Polypeptide Block Copolymers via NCA Ring-Opening Polymerization

Wang,

Tang,

Kou

et al. 2024

Biomacromolecules

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“…It has been widely reported that the polymer concentration has an important influence on the morphology evolution in the PISA process. ,, Higher concentration results in a higher frequency of inelastic collision between the nano-objects, which facilitates the morphology evolution. In consideration of this aspect, RAFT dispersion copolymerization of MAEAC and MAEB targeted to PEG 45 - b -P(MAEAC 0.6 - co -MAEB 0.4 ) 150 block copolymers with identical compositions was carried out at different polymer concentrations.…”

Section: Resultsmentioning

confidence: 99%

“…Polymerization-induced self-assembly (PISA), which effectively simplifies the procedure of producing polymeric nano-objects and allows preparing polymeric nano-objects in concentrated solution, has been demonstrated to be a powerful strategy. − Recently, fabrication of polymeric nanotubes by PISA in a highly efficient manner has been reported by several groups. − For example, O’Reilly and co-workers reported the preparation of polymeric nanotubes by polymerization-induced one-dimensional (1D) fusion of spherical vesicles in an aqueous ring-opening metathesis PISA formulation . The formation of nanotubes was attributed to the high glass-transition temperature ( T g ) and the rigid backbone of the poly(norbornene) core-forming blocks.…”

Section: Introductionmentioning

confidence: 99%

“…In an alcoholic PISA case with poly(2,3,4,5,6-pentafluorostyrene) (PPFS) as the core-forming block, the authors found that formation of polymeric nanotubes is favored when T p is close to the solvated glass-transition temperature ( T sg ) of the PPFS blocks . Notwithstanding these elegant works, − the formation of polymeric nanotubes is still an unusual phenomenon, and spherical vesicles are preferred in most of the reported PISA literature studies. − Moreover, fabrication of polymeric nanotubes with an adjustable aspect ratio has rarely been reported …”

Section: Introductionmentioning

confidence: 99%

“…In a typical PISA process, chain extension of the solvophilic stabilizers generates amphiphilic block copolymers, which concurrently induces self-assembly of the resultant block copolymers. ,, Spherical micelles are usually formed at the initial stage, and the growth of the solvophobic blocks results in the alteration of the packing parameter ( P = v / a o l ) of the resultant block copolymers, which drives morphology evolution of the corresponding nano-objects from spherical micelles to wormlike micelles to spherical vesicles and then to the inverse structures. , It has been widely accepted that spherical micelles are formed at P ≤ 1/3, wormlike micelles are favored at 1/3 < P ≤ 1/2, spherical vesicles are generated at 1/2 < P < 1, and inverse structures are produced at P > 1. According to the theoretical prediction of packing parameters, it seems that polymeric nanotubes cannot be produced by the self-assembly of block copolymers, which may be the reason that only a handful of works have reported the preparation of polymeric nanotubes to date.…”

Section: Introductionmentioning

confidence: 99%

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Polymerization-Induced Self-Assembly with Assistance of Aromatic Interactions Facilitates the Formation of Polymeric Nanotubes

2023

Self Cite

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Polymerization-induced self-assembly (PISA) has been demonstrated to be a powerful strategy for producing polymeric nano-objects. Polymeric nanotubes with hollow and anisotropic structures have attracted great interest in materials science. However, according to the theoretical prediction of the packing parameter, polymeric nanotubes are hard to be produced by the self-assembly of block copolymers, which may be due to the lack of directionality of solvophobic interactions. Herein, we demonstrate that aromatic interactions between the solvophobic blocks facilitate the formation of polymeric nanotubes. Polymeric nanotubes with a remarkable length (>11 μm) are generated in the reversible addition−fragmentation chain transfer (RAFT) dispersion polymerization of the aromatic monomer 2-(methacryloyloxy) ethyl anthracene-9-carboxylate (MAEAC) using poly(ethylene glycol) as the macro RAFT agent (PEG 45 -CPADB). When the aromatic interactions of the membrane-forming blocks are weakened by high temperature or copolymerization of MAEAC with a weakly aromatic monomer 2-(methacryloyloxy)ethyl benzoate (MAEB), spherical nano-objects instead of nanotubes tend to be produced. The concentration of polymer chains also plays a vital role in the formation of polymeric nanotubes. The aspect ratio of the polymeric nanotubes can be adjusted by controlling the polymer concentration without varying the polymer composition, and polymeric nanotubes with a larger aspect ratio tend to be generated at higher concentrations of block copolymers. The formation of polymersomes with different aspect ratios for a given polymer provides significant opportunities to investigate the shape-determined performances of the polymersomes while eliminating the influence of polymer composition.

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Synergistic Effect of Hydroxyl and Carboxyl Groups on Promoting Nanoparticle Occlusion within Calcite

Zhang

Xiong

et al. 2023

Small

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defluoridation, [7] optoelectronics, [8] biomimetic synthesis, [2,9] and property regulation in magnetization, band gap, and chemical stability. [10] However, it has been a great challenge to efficiently occlude nanoparticles into inorganic host crystals because the crystallization of the latter phase is favorable for excluding impurities rather than incorporation. [11] Over the past decade, tremendous efforts have been placed in elucidating the fundamental design rules that determine efficient nanoparticle occlusion within inorganic crystals. [12] Owing to the large difference in surface energy, the guest nanoparticles are not compatible with the growing host crystals. Nonetheless, surface-modification of the guest nanoparticles with suitable polymers has been proven to be a feasible way to minimize this surface energy difference. [1b] Notably, only those polymers with required composition and functionality can drive nanoparticle occlusion. For example, the polymer chain density on the surface of the nanoparticles has played a key role in facilitating the efficient occlusion of sulfate-based copolymer nanoparticles within calcite (CaCO 3 ) crystals. [12d] On the other hand, polymer chain length has to be sufficiently long enough to achieve uniform occlusion. [12b] Otherwise, no occlusion or non-uniform occlusion occurred. [13] In term of chemical functionality, systematic investigation has revealed that carboxylate group has strong affinity with calcite and exhibits a superior performance (compared with phosphate, sulfate or sulfonate groups, etc.) in promoting nanoparticle occlusion within calcite crystals. [14] So far as we are aware, poly(methacrylic acid) is the most studied and well-established polymer that was used to drive polymeric nanoparticle occlusion into calcite crystals. [1b,4a] Unfortunately, as a weak polyelectrolyte, polycarboxylate cannot maintain colloidal stability at a high concentration of metal ions (e.g., calcium ions in the case of CaCO 3 host crystals). As a result, the concentration of the precursor ions must be kept at a very low level (typically below 1.5 mM) in order to achieve uniform nanoparticle occlusion. [4a] Obviously, this intrinsic drawback significantly limits the application of polycarboxylate in promoting nanoparticle occlusion. To solve this issue, we herein introduce multiple functionalities into the polymer stabilizer of the guest nanoparticles, aiming to endow such nanoparticles with both colloidal stability and outstanding capability in driving nanoparticle occlusion. To this end, three types of polymers with comparable mean degree of polymerization (DP) Direct occlusion of guest nanoparticles into host crystals enables the straightforward preparation for various of nanocomposite materials with emerging properties. Therefore, it is highly desirable to elucidate the 'design rules' that govern efficient nanoparticle occlusion. Herein, a series of stericallystabilized nanoparticles are rationally prepared, where the surface stabilizer chains of such nanoparticles...

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Greatly Enhanced Accessibility and Reproducibility of Worm‐like Micelles by In Situ Crosslinking Polymerization‐Induced Self‐Assembly

Cited by 4 publications

References 85 publications

Dextran Macroinitiator for Synthesis of Polysaccharide-b-Polypeptide Block Copolymers via NCA Ring-Opening Polymerization

Dextran Macroinitiator for Synthesis of Polysaccharide-b-Polypeptide Block Copolymers via NCA Ring-Opening Polymerization

Polymerization-Induced Self-Assembly with Assistance of Aromatic Interactions Facilitates the Formation of Polymeric Nanotubes

Synergistic Effect of Hydroxyl and Carboxyl Groups on Promoting Nanoparticle Occlusion within Calcite

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