Synthesis and self-assembly of CO<sub>2</sub>-responsive dendronized triblock copolymers

Huo, Meng; Ye, Qiquan; Che, Hailong; Sun, Mengzhen; Yuan, Jinying; Wei, Yen

doi:10.1039/c5py00868a

Cited by 15 publications

(12 citation statements)

References 59 publications

(63 reference statements)

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“…Phosphotungstic acid (PTA) (analytical grade) was purchased from Beijing Chemical Co. and was dissolved in water to form 0.5 wt % solution. 4-(4-Cyanopentanoic acid) dithiobenzoate (CPADB) was synthesized before and used directly . Poly( N , N -dimethylaminoethyl methacrylate) (PDMA 33 ) ( M n,NMR = 5.5 kDa, M n,SEC = 5.3 kDa, Đ = 1.23) macro-CTA was synthesized according to the procedure reported before .…”

Section: Methodsmentioning

confidence: 99%

“…4-(4-Cyanopentanoic acid) dithiobenzoate (CPADB) was synthesized before and used directly. 62 Poly(N,N-dimethylaminoethyl methacrylate) (PDMA 33 ) (M n,NMR = 5.5 kDa, M n,SEC = 5.3 kDa, Đ = 1.23) macro-CTA was synthesized according to the procedure reported before. 55 BzMA and FHEMA were passed through an alumina column to remove the inhibitors.…”

Section: ■ Experimental Sectionmentioning

confidence: 99%

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Tailoring the Multicompartment Nanostructures of Fluoro-Containing ABC Triblock Terpolymer Assemblies via Polymerization-Induced Self-Assembly

Huo

Zeng

et al. 2017

Macromolecules

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Polymer self-assembly has been one of the most important strategies for preparation of multicompartment micelles (MCMs). However, the traditional self-assembly techniques are constrained by limited common solvent, complex kinetic factors, low solids content, etc. Polymerization-induced self-assembly (PISA) is a novel technique for preparation of polymer assemblies at high solids content and has been exploited to produce MCMs. Nevertheless, the morphology evolution of the MCMs obtained through PISA has not yet been well understood. Herein, we study the compartmentalization behaviors of a series of MCMs constituted by poly(N,N-dimethylaminoethyl methacrylate)-b-poly(benzyl methacrylate)-b-poly(2-perfluorohexylethyl methacrylate) (PDMA-b-PBzMA-b-PFHEMA) triblock terpolymers, which were synthesized by seeded reversible addition–fragmentation chain transfer (RAFT) dispersion polymerization of FHEMA using PDMA-b-PBzMA micelles, wormlike micelles, or vesicles as the seeds. Because of the strong incompatibility between PBzMA and PFHEMA, MCMs with abundant compartmentalized nanostructures were produced. Phosphotungstic acid- and RuO4-stained TEM images of these MCMs indicate that their morphologies are controlled by both the DPs of PBzMA and PFHEMA. Our results suggest that PISA could serve as a reliable platform for revealing the compartmentalization behaviors of polymeric assemblies.

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Section: Methodsmentioning

confidence: 99%

Section: ■ Experimental Sectionmentioning

confidence: 99%

Tailoring the Multicompartment Nanostructures of Fluoro-Containing ABC Triblock Terpolymer Assemblies via Polymerization-Induced Self-Assembly

Huo

Zeng

et al. 2017

Macromolecules

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“…AIBN was purified and stored at −20 °C before use. 4-(4-Cyanopentanoic acid) dithiobenzoate (CPADB) was prepared before and stored in the vacuum drier before use …”

Section: Methodsmentioning

confidence: 99%

“…4-(4-Cyanopentanoic acid) dithiobenzoate (CPADB) was prepared before and stored in the vacuum drier before use. 62 All the 1 H NMR spectra were recorded using a 400 MHz JEOL JNM-ECA 400 spectrometer. The fluoro-containing triblock copolymers were characterized using a mixture of CDCl 3 and CF 2 ClCFCl 2 as the solvent.…”

Section: ■ Experimental Sectionmentioning

confidence: 99%

Morphology Evolution of Polymeric Assemblies Regulated with Fluoro-Containing Mesogen in Polymerization-Induced Self-Assembly

et al. 2017

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Mesogen-containing amphiphilic block copolymers have shown extremely abundant self-assembly behaviors because of the liquid crystalline (LC) alignment within the assemblies. However, development of an understanding of the self-assembly behaviors of these amphiphilic LC polymers is still constrained by the low assembly concentration and complex kinetic effects. Polymerization-induced self-assembly (PISA) is a powerful technique to prepare polymer assemblies at high solids content with good repeatability. Taking advantage of PISA, we systematically study the self-assembly behaviors of a series of mesogen-containing triblock copolymers poly(2-dimethylaminoethyl methacrylate)-b-poly(benzyl methacrylate)-b-poly(2-perfluorooctylethyl methacrylate) (PDMA-b-PBzMA-b-PFMA), which are prepared by seeded reversible addition–fragmentation chain transfer dispersion polymerization of FMA with PDMA-b-PBzMA micelles or vesicles as the seeds. When PDMA-b-PBzMA micelles are used, the morphology of the PDMA-b-PBzMA-b-PFMA assemblies evolves from spheroid to phase-segregated sphere, followed by phase-segregated spheroid, and eventually to cylinder, while the assemblies undergo a vesicle-to-micelle transition with a framboidal intermediate when PDMA-b-PBzMA vesicles are used as the seeds. These spherical micelles further fuse to cylinders or large spheres depending on the DPs of PBzMA and PFMA blocks. The LC ordering of the PFMA blocks is examined by differential scanning calorimetry and X-ray diffraction; the microphase segregation between PFMA and PBzMA blocks is studied with TEM and atomic force microscopy. These experiments evince that the formation of the ellipsoidal and cylindrical micelles is driven by the LC alignment of PFMA blocks, while the microphase segregation between PFMA and PBzMA blocks complicates the ultimate morphology through modulating the size of PFMA nanodomains. The interplay of the hydrophobic interaction among PBzMA blocks, lipophobic interaction, and LC ordering of PFMA blocks thus generates the above self-assembly behaviors.

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“…DMAEMA and BzMA were passed through a short alkaline alumina column before use to remove the inhibitor. 4-Cyanopentanoic acid dithiobenzoate (CPADB) was prepared as described previously . 2-(4-Vinylphenyl)ethene-1,1,2-triyl)tribenzene (TPE) was prepared according to the literature .…”

Section: Experimental Sectionmentioning

confidence: 99%

Polymer Assemblies with Nanostructure-Correlated Aggregation-Induced Emission

Huo¹,

Ye²,

Che³

et al. 2017

Macromolecules

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The correlation of aggregation-induced emission (AIE) to the nanostructure of polymer assemblies was investigated. A series of AIE-active PDMA-b-P(BzMA-TPE) [PDMA: poly( N , N -dimethylaminoethyl methacrylate); P(BzMA-TPE): poly[benzyl methacrylate-co-1-ethenyl-4-(1,2,2-triphenylethenyl)benzene]] assemblies with controlled nanostructures were prepared via polymerization-induced self-assembly of BzMA and TPE, an AIEgen, in the presence of PDMA macro-chain-transfer agents. We found that the fluorescence intensity and fluorescent quantum yield increase in the order of vesicles > wormlike micelles > spherical micelles. For spherical micelles and vesicles, the AIE effect strengthens with increase in micellar size and wall thickness, respectively. As the AIE effect indicates the packing compactness of the AIEgens, the discovered structure-correlated emission can be attributed to the stress variation of polymer chains in the aggregates. AIE is therefore potentially useful as a probe for the investigation and understanding of nanostructure and evolution process of polymer self-assemblies.

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Synthesis and self-assembly of CO₂-responsive dendronized triblock copolymers

Abstract: Dendronized amphiphilic block copolymers POEGMA-b-P(Gn)-b-PDEAEMA were synthesized, and their self-assembly behavior could be regulated by the dendron generation, the type of common solvent, and CO2-stimulus.

Cited by 15 publications

References 59 publications

Tailoring the Multicompartment Nanostructures of Fluoro-Containing ABC Triblock Terpolymer Assemblies via Polymerization-Induced Self-Assembly

Tailoring the Multicompartment Nanostructures of Fluoro-Containing ABC Triblock Terpolymer Assemblies via Polymerization-Induced Self-Assembly

Morphology Evolution of Polymeric Assemblies Regulated with Fluoro-Containing Mesogen in Polymerization-Induced Self-Assembly

Polymer Assemblies with Nanostructure-Correlated Aggregation-Induced Emission

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Synthesis and self-assembly of CO2-responsive dendronized triblock copolymers

Abstract: Dendronized amphiphilic block copolymers POEGMA-b-P(Gn)-b-PDEAEMA were synthesized, and their self-assembly behavior could be regulated by the dendron generation, the type of common solvent, and CO2-stimulus.

Cited by 15 publications

References 59 publications

Tailoring the Multicompartment Nanostructures of Fluoro-Containing ABC Triblock Terpolymer Assemblies via Polymerization-Induced Self-Assembly

Tailoring the Multicompartment Nanostructures of Fluoro-Containing ABC Triblock Terpolymer Assemblies via Polymerization-Induced Self-Assembly

Morphology Evolution of Polymeric Assemblies Regulated with Fluoro-Containing Mesogen in Polymerization-Induced Self-Assembly

Polymer Assemblies with Nanostructure-Correlated Aggregation-Induced Emission

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Synthesis and self-assembly of CO₂-responsive dendronized triblock copolymers