Fabrication of pH and thermal dual-responsive hyperbranched copolymer grafted magnetic graphene oxide via surface-initiated RAFT-SCVP for controlled release of DOX

Kohestanian, Mohammad; Keshavarzi, Nahid; Pourjavadi, Ali; Rahmani, Fatemeh

doi:10.1016/j.mtcomm.2023.105504

Cited by 4 publications

(4 citation statements)

References 49 publications

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“…Figure a shows the 1 H NMR spectra of CEPA, HEMA, and CEPEMA, confirming the successful synthesis of this CTM with high purity. It should be noted that trithiocarbonate-based CTMs with a methacryloyl R-group and a thioalkyl Z-group have rarely been reported. − Very recently, Despres et al reported a detailed investigation on solution RAFT-SCVP using a CTM with a similar structure. We then conducted a kinetic study of RAFT solution polymerization of CEPEMA and 2-(dimethylamino)ethyl methacrylate (DMAEMA) in ethanol with a [CEPEMA]/[DMAEMA] ratio of 1/1 (Figure S1).…”

Section: Resultsmentioning

confidence: 99%

Chain Architecture as an Orthogonal Parameter to Tune Morphologies of Polymer Assemblies: Efficient Synthesis and Self-Assembly of Linear-Branched Block Copolymers via RAFT Dispersion Polymerization

Li,

Yan

et al. 2024

Macromolecules

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Although the formation of linear block copolymers and the assemblies from polymerization-induced self-assembly (PISA) has been widely investigated, the controlled introduction of branching in the block copolymers and therefore the morphological control of block copolymer assemblies via PISA are virtually unexplored. Herein, a diverse set of linear-branched macromolecular chain transfer agents (macro-CTAs) with similar molecular chemical compositions but with different linear chain lengths or branching degrees were synthesized by a two-stage selfcondensing vinyl polymerization (SCVP) of 2-(dimethylamino)ethyl methacrylate (DMAEMA) in ethanol. Performing reversible addition−fragmentation chain transfer (RAFT) dispersion polymerization of benzyl methacrylate (BzMA) in ethanol using these linear-branched macro-CTAs led to the formation of linearbranched block copolymer assemblies. Effects of the structure of linear-branched macro-CTAs on the morphology of linear-branched block copolymer assemblies were investigated in detail. It was found that increasing the linear chain length or decreasing the degree of branching of linear-branched macro-RAFT agents favored the formation of colloidally stable polymer assemblies but with lowerorder morphologies. Besides branching in the stabilizer block, the introduction of branching in the core-forming block was also achieved by adding a chain transfer monomer (CTM) into the RAFT dispersion polymerization. Computer simulations of the synthesis of linear-branched block copolymer assemblies were performed, demonstrating similar morphological transitions in our PISA experiments. We expect that this study not only provides an efficient strategy for controlled synthesis of linear-branched block copolymers and the assemblies but also provides valuable insights into the PISA process of linear-branched (or branched) block copolymers.

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Section: Resultsmentioning

confidence: 99%

Chain Architecture as an Orthogonal Parameter to Tune Morphologies of Polymer Assemblies: Efficient Synthesis and Self-Assembly of Linear-Branched Block Copolymers via RAFT Dispersion Polymerization

Li,

Yan

et al. 2024

Macromolecules

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“…Other advances involving RAFT towards this polymer architecture, include its expansion to bulk [101], surface-initiated [102][103][104] polymerization, polymerization-induced self-assembly [89,105], combination with ring-opening polymerization [106] or even flow chemistry. Specifically, using flow chemistry is a promising method for improving SCVP.…”

Section: Hyperbranched Copolymersmentioning

confidence: 99%

Using RAFT Polymerization Methodologies to Create Branched and Nanogel-Type Copolymers

Skandalis,

Sentoukas,

Selianitis

et al. 2024

Materials

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This review aims to highlight the most recent advances in the field of the synthesis of branched copolymers and nanogels using reversible addition-fragmentation chain transfer (RAFT) polymerization. RAFT polymerization is a reversible deactivation radical polymerization technique (RDRP) that has gained tremendous attention due to its versatility, compatibility with a plethora of functional monomers, and mild polymerization conditions. These parameters lead to final polymers with good control over the molar mass and narrow molar mass distributions. Branched polymers can be defined as the incorporation of secondary polymer chains to a primary backbone, resulting in a wide range of complex macromolecular architectures, like star-shaped, graft, and hyperbranched polymers and nanogels. These subcategories will be discussed in detail in this review in terms of synthesis routes and properties, mainly in solutions.

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“…Among R-transmers, acrylates, − , (meth)acrylamides, , and styrene − derivatives have been considered as polymerizable groups. Concerning methacrylate derivatives, dithiobenzoate-based R-transmers with a phenyl Z-group have been reported. − Trithiocarbonate-based R-transmers displaying a methacryloyl moiety and a thioalkyl or a thioaryl Z-group − have been rarely reported. Most often, HBP structures and properties were discussed, considering that all thiocarbonylthio-moieties of the R-transmer create branching points.…”

Section: Introductionmentioning

confidence: 99%

“…This work provides rational knowledge and quantification on the percentage of thiocarbonylthio group of a novel methacrylic-based R-transmer that creates branching points thanks to high-resolution NMR spectroscopy. This approach allows a deeper understanding of HBP structures, when most reported studies − consider that all thiocarbonylthio-moieties of R-transmer create branching points.…”

Section: Introductionmentioning

confidence: 99%

Investigating the Reactivity of a Novel Methacrylic Transmer in Solution RAFT-SCVP and Its Impact on the Structure of the Resulting Hyperbranched Polymers

Despres,

Fabre,

Legeay

et al. 2024

Macromolecules

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A novel methacrylic-based R-transmer, named 2-(methacryloyloxy)ethyl 4-cyano-4-(((propylthio)carbonothioyl)thio)pentanoate, was synthesized, and its reactivity (propagation versus reversible chain transfer) in reversible addition–fragmentation chain transfer self-condensing vinyl polymerization (RAFT-SCVP) with methyl methacrylate (MMA) was studied to apprehend its impact on hyperbranched polymers (HBP) structure. The resulting HBP were characterized by nuclear magnetic resonance (NMR) spectroscopy, size exclusion chromatography (SEC) and differential scanning calorimetry (DSC) to determine, respectively, their composition and degree of branching (DB), number average molecular weight (Mn ) and dispersity (Đ), and glass transition temperature (T g). Homopolymers of methacrylic-based R-transmer and copolymers with MMA were considered to study the reactivity of the methacrylic-based R-transmer with different initial molar ratios [MMA]0/[R-transmer]0 through kinetic studies and its consequences on HBP macromolecular characteristics and thermal properties. By varying the [MMA]0/[R-transmer]0 ratio from 1:1 to 100:1, HBP with increasing Mn (from 6,400 to 14,900 g mol–1) and T g values (from 36.1 to 87.9 °C), decreasing Đ values (from 4.07 to 1.71) and DB values (from 0.30 to 0.03) were obtained.

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Fabrication of pH and thermal dual-responsive hyperbranched copolymer grafted magnetic graphene oxide via surface-initiated RAFT-SCVP for controlled release of DOX

Cited by 4 publications

References 49 publications

Chain Architecture as an Orthogonal Parameter to Tune Morphologies of Polymer Assemblies: Efficient Synthesis and Self-Assembly of Linear-Branched Block Copolymers via RAFT Dispersion Polymerization

Chain Architecture as an Orthogonal Parameter to Tune Morphologies of Polymer Assemblies: Efficient Synthesis and Self-Assembly of Linear-Branched Block Copolymers via RAFT Dispersion Polymerization

Using RAFT Polymerization Methodologies to Create Branched and Nanogel-Type Copolymers

Investigating the Reactivity of a Novel Methacrylic Transmer in Solution RAFT-SCVP and Its Impact on the Structure of the Resulting Hyperbranched Polymers

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