How does a tiny terminal alkynyl end group drive fully hydrophilic homopolymers to self-assemble into multicompartment vesicles and flower-like complex particles?

Liu, Tingting; Tian, Wei; Zhu, Yunqing; Bai, Yang; Yan, Hongxia; Du, Jianzhong

doi:10.1039/c4py00501e

Cited by 50 publications

(73 citation statements)

References 63 publications

(85 reference statements)

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“…The driving forces for supramolecular chemistry are noncovalent interaction ranging from host-guest interaction [11], hydrogen bonding [12], van der Waals interaction [13], π─π stacking [14], electrostatic interactions [15] and hydrophobic effect [16]. Table 1 summarizes most of this noncovalent interaction, as well as of its structuredetermining properties [17].…”

Section: Introductionmentioning

confidence: 99%

Supramolecular Materials Based on Ionic Self‐Assembly: Structure, Property, and Application

Shen¹,

Yuan²,

Xin³

2017

Molecular Self-Assembly in Nanoscience and Nanotechnology

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The technique of ionic self-assembly (ISA), on the basis of electrostatic interactions, is a powerful tool to create new material nanostructures and chemical objects due to its advantages of facility, reliability, cost saving, flexibility, and universality. It has attracted great attention because of its promising applications in catalysis, drug delivery, and molecular detection. This review focuses on recent advances in the construction of self-assemblies with different morphologies on the basis of ISA strategy and its applications. The ISA method provides an opportunity to generate complex and hierarchical assemblies with tunable properties, which is regarded as a very promising case of supramolecular chemistry.

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Section: Introductionmentioning

confidence: 99%

Supramolecular Materials Based on Ionic Self‐Assembly: Structure, Property, and Application

Shen¹,

Yuan²,

Xin³

2017

Molecular Self-Assembly in Nanoscience and Nanotechnology

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“…Typically, mPEG 43 -Br (2.00 g, 0.98 mmol), NaN 3 (1.27 g, 19.52 mmol) and ScCl (1.68 mg, 0.01 mmol) were dissolved in 15 mL distilled water, and the mixture was stirred at 60 8C overnight. After reaction, the mixture was extracted by CH 2 Cl 2 (3 3 50 mL).…”

Section: Methodsmentioning

confidence: 99%

“…The CH 2 Cl 2 solution was dried over anhydrous MgSO 4 , filtered, concentrated, and precipitated into cold diethyl ether. Finally, mPEG 43 Synthesis of Alkynyl-Terminated Poly(2-phenyl-5-ethyl-5-acryloxymethyl-1,3-dioxacyclohexane) (5, PDAEP-Alk) via RAFT Polymerization A typical procedure employed for the preparation of PDAEPAlk (5) by RAFT polymerization was described as follows. Into a Schlenk tube, 4 (14.60 mg, 0.047 mmol), HEDPA (420 mg, 1.52 mmol), AIBN (0.77 mg, 0.0047 mmol), and 1 mL dioxane were added.…”

Section: Methodsmentioning

confidence: 99%

“…The reaction mixture was washed successively with saturated NaHCO 3 solution and water, dried over anhydrous MgSO 4 , filtered, concentrated, and precipitated into cold diethyl ether. After filtration, mPEG 43 -Br was obtained as a white solid. Yield: 50-85%.…”

Section: Methodsmentioning

confidence: 99%

“…The typical procedure for preparation of mPEG 43 -N 3 was given as below. BIBB (0.35 mL, 2.80 mmol) was added dropwise to a solution of mPEG 43 (3.80 g, 2.00 mmol) and TEA (0.39 mL, 2.80 mmol) in 15 mL of anhydrous CH 2 Cl 2 at 0 8C. After 1 h, the mixture was warmed to room temperature, and stirred overnight.…”

Section: Methodsmentioning

confidence: 99%

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Amphiphilic diblock copolymers bearing pendant aromatic acetal groups: Synthesis and tunable pH‐triggered assembly/disassembly transition behavior

Zhang

Fan

Zhang

et al. 2015

J. Polym. Sci. Part A: Polym. Chem.

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A novel aromatic acetal-based acid-labile monomer 2-phenyl-5-ethyl-5-acryloxymethyl-1,3-dioxacyclohexane (HEDPA) was synthesized and polymerized by reversible addition fragmentation chain transfer (RAFT) polymerization using alkynyl functional chain transfer agent (CTA-Alk). Afterward, a series of amphiphilic diblock copolymers composed of fixed hydrophobic poly(2-phenyl-5-ethyl-5-acryloxymethyl-1,3-dioxacyclohexane) (PDAEP) segments and various lengths of hydrophilic mPEG segments were prepared through click reaction between alkynyl-terminated PDAEP and azido-terminated mPEG. The self-assembly behaviors of the diblock copolymers were investigated by dynamic light scattering (DLS), transmission electron microscopy (TEM), fluorescence spectroscopy, and 1 H NMR. These results indicated that the diblock copolymers could self-assemble into nano-sized micelles with PDAEP cores and PEG coronas in aqueous solution. DLS, fluorescence spectroscopy and UV-vis spectroscopy were used to monitor the pH-triggered assembly/disassembly transition of the micelles. These results showed that the assembly/disassembly transition behaviors of the diblock copolymers micelles can be adjusted by changing the lengths of the mPEG segments.

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Facile Fabrication of Robust Organic Counterion‐Induced Vesicles: Reversible Thermal Behavior for Optical Temperature Sensor and Synergistic Catalyst upon Removal of Amine

Zhang

Pang

et al. 2015

Adv Funct Materials

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A general concept of organic counterion‐directed molecular strategy for thepreparation of robust vesicles is developed. Functional amphiphilic ammonium salts (L1‐L3) bearing readily available oligo‐ethyleneglycol‐based ligand 1 and single‐tailed fatty amines self‐assemble into vesicles with controllable sizes in aqueous media. The organic counterion‐induced vesicles (OCIVs) are characterized by dynamic light scattering, transmission electron microscopy, and acid triggered release of hydrophilic drug (DOX·HCl). The introduction of organic counterion not only plays an important role in vesicle construction, but also endows the material with greatly practical values. By virtue of alkynyl groups attached on the organic ligand, the OCIVs can be easily cross‐linked via thiol‐ene reaction to generate a robust material. Importantly, the cross‐linked OCIVs exploit reversible temperature‐dependant size change, which can be repeated over 10 times without appreciable size fluctuating. Based on the unique property, a robust luminescence temperature sensor with a useful detection range of 35–70 °C is developed. Besides, removing the amines buried in the polymerized OCIVs under acidic condition, the resulting carboxylic acid‐functionalized material is found to have unusual efficiency as “nanozyme” for acetal hydrolysis, which exhibits over 20‐fold rate acceleration compared with that catalyzed by 1 or benzoic acid.

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How does a tiny terminal alkynyl end group drive fully hydrophilic homopolymers to self-assemble into multicompartment vesicles and flower-like complex particles?

Abstract: We report an unusual self-assembly behavior driven by a tiny terminal alkynyl end group in fully hydrophilic homopolymers which form multicompartment vesicles and flower-like nanoparticles in aqueous solution.

Cited by 50 publications

References 63 publications

Supramolecular Materials Based on Ionic Self‐Assembly: Structure, Property, and Application

Supramolecular Materials Based on Ionic Self‐Assembly: Structure, Property, and Application

Amphiphilic diblock copolymers bearing pendant aromatic acetal groups: Synthesis and tunable pH‐triggered assembly/disassembly transition behavior

Facile Fabrication of Robust Organic Counterion‐Induced Vesicles: Reversible Thermal Behavior for Optical Temperature Sensor and Synergistic Catalyst upon Removal of Amine

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