Oligo(rU)_(15)对SDS/DEAB混合胶束向囊泡转化的诱导作用

囊泡是由表面活性剂分子分散在水中形成的具有密闭双分子层结构的球形或者椭球形的分子有序组合体,在生物学、材料学、化学和医药学等领域具有极为重要和广泛的应用~([1-4]).     

Facilitation effect of oligonucleotide on vesicle formation from single‐chained cationic surfactant—Dependences of oligonucleotide sequence and size and surfactant structure

The interaction between DNA and surfactant has both biological and technological significances. Recently, we reported for the first time that oligo d(C)₂₅ can induce single‐chained cationic surfactant molecules to aggregate into vesicles. In this article, we studied systematically the formation of vesicles from traditional single‐chained cationic surfactant molecules in the presence of a series of oligonucleotides and found that the facilitation efficiency of oligonucleotide on vesicle formation depends on its size and base composition. Oligo d(T)_n cannot induce vesicle formation, whereas the other oligonucleotides can. Moreover, the oligonucleotide with a bigger size or with a hairpin structure favors vesicle formation more, and the increases in the size of the head group and/or the length of the alkyl group of surfactant decrease the facilitation efficiency of oligonucleotide. Since so far, there is very limited report about the vesicle formation in DNA/single‐chained cationic surfactant solution, this study could be expected to increase the efficiency and applicability for DNA/amphiphile system. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 434–449, 2009     

Effect of oligonucleotide conformation on its facilitation efficiency on negatively charged micelle‐to‐vesicle transition

In our previous article, we reported for the first time that the oligonucleotides composed of one nucleotide species, for example, oligo d(A)_n, oligo d(C)_n, and oligo d(T)_n, could facilitate negatively charged sodium dodecyl sulfate/dodecyl triethyl ammonium bromide mixed micelles to transform to vesicles. In this study, we will report the facilitation ability of self‐complementary hairpin‐structured oligonucleotides, oligo d(A_nCT_n) and oligo d(AT)_nACT(AT)_n (or oligo d(AT)_nC(AT)_n), on micelle‐to‐vesicle transition. It is found that the facilitation behavior of hairpin‐structured oligonucleotide is different from that of the oligonucleotide comprising one base species, and the facilitation efficiency of hairpin‐structured oligonucleotide is closely dependent on the sequence of bases A and T; oligo d(A_nCT_n) is more efficient than oligo d(AT)_nACT(AT)_n (or oligo d(AT)_nC(AT)_n). Moreover, oligo d(A_nCT_n) is more efficient than oligo d(A)_n, oligo d(C)_n, and oligo d(T)_n. Since so far, there is very limited report about the facilitation effect of oligonucleotide and DNA on vesicle formation as well as the role of their conformation in their interaction with surfactant, this study should be expected to provide some helpful information for the application of DNA/amphiphile system. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 852–860, 2010     

Kinetics of thermo-induced micelle-to-vesicle transitions in a catanionic surfactant system investigated by stopped-flow temperature jump

The kinetics of thermo-induced micelle-to-vesicle transitions in a catanionic surfactant system consisting of sodium dodecyl sulfate (SDS) and dodecyltriethylammonium bromide (DEAB) were investigated by the stopped-flow temperature jump technique, which can achieve T-jumps within ～2-3 ms. SDS/DEAB aqueous mixtures ([SDS]/[DEAB] = 2/1, 10 mM) undergo microstructural transitions from cylindrical micelles to vesicles when heated above 33 °C. Upon T-jumps from 20 °C to final temperatures in the range of 25-31 °C, relaxation processes associated with negative amplitudes can be ascribed to the dilution-induced structural rearrangement of cylindrical micelles and to the dissolution of non-equilibrium mixed aggregates. In the final temperature range of 33-43 °C the obtained dynamic traces can be fitted by single exponential functions, revealing one relaxation time (τ) in the range of 82-440 s, which decreases with increasing temperature. This may be ascribed to the transformation of floppy bilayer structures into precursor vesicles followed by further growth into final equilibrium vesicles via the exchange and insertion/expulsion of surfactant monomers. In the final temperature range of 45-55 °C, vesicles are predominant. Here T-jump relaxations revealed a distinctly different kinetic behavior. All dynamic traces can only be fitted with double exponential functions, yielding two relaxation times (τ(1) and τ(2)), exhibiting a considerable decrease with increasing final temperatures. The fast process (τ(1)～ 5.2-28.5 s) should be assigned to the formation of non-equilibrium precursor vesicles, and the slow process (τ(2)～ 188-694 s) should be ascribed to their further growth into final equilibrium vesicles via the fusion/fission of precursor vesicles. In contrast, the reverse vesicle-to-micelle transition process induced by a negative T-jump from elevated temperatures to 20 °C occurs quite fast and almost completes within the stopped-flow dead time (～2-3 ms).     

Effects of salt and temperature on single‐chained cationic surfactant/oligodeoxynucleotide vesicle formation

Recently, we found oligodeoxynucleotide could induce single‐chained cationic surfactant to organize into vesicles. In this article, we will report the effects of NaCl and temperature on the surfactant/oligodeoxynucleotide vesicle formation. A moderate content of NaCl can facilitate vesicle formation and high content of NaCl makes vesicle degraded. The enhanced hydrophobic interaction between surfactant and oligodeoxynucleotide with NaCl plays a key role for facilitating vesicle formation. Moreover, surfactant/oligodeoxynucleotide vesicles tend to aggregate at high temperature and the change is irreversible. However, the presence of NaCl makes this change reversible. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

A Femtosecond Study of Solvation Dynamics and Anisotropy Decay in a Catanionic Vesicle: Excitation‐Wavelength Dependence

The structure and dynamics of a catanionic vesicle are studied by means of femtosecond up‐conversion and dynamic light scattering (DLS). The catanionic vesicle is composed of dodecyl‐trimethyl‐ammonium bromide (DTAB) and sodium dodecyl sulphate (SDS). The DLS data suggest that 90 % of the vesicles have a diameter of about 400 nm, whereas the diameter of the other 10 % is about 50 nm. The dynamics in the catanionic vesicle are compared with those in pure SDS and DTAB micelles. We also study the dynamics in different regions of the micelle/vesicle by varying the excitation wavelength (λ_ex) from 375 to 435 nm. The catanionic vesicle is found to be more heterogeneous than the SDS or DTAB micelles, and hence, the λ_ex‐dependent variation of the solvation dynamics is more prominent in the first case. The solvation dynamics in the vesicle and the micelles display an ultraslow component (2 and 300 ps, respectively), which arises from the quasibound, confined water inside the micelle, and an ultrafast component (<0.3 ps), which is due to quasifree water at the surface/exposed region. With an increase in λ_ex, the solvation dynamics become faster. This is manifested in a decrease in the total dynamic solvent shift and an increase in the contribution of the ultrafast component (<0.3 ps). At a long λ_ex (435 nm), the surface (exposed region) of a micelle/vesicle is probed, where the solvation dynamics of the water molecules are faster than those in a buried location of the vesicle and the micelles. The time constant of anisotropy decay becomes longer with increasing λ_ex, in both the catanionic vesicle and the ordinary micelles (SDS and DTAB). The slow rotational dynamics (anisotropy decay) in the polar region (at long λ_ex) may be due to the presence of ionic head groups and counter ions.     

Micellar structure and mechanical properties of block copolymer‐modified epoxies

Amphiphilic block copolymers provide a unique means for toughening epoxy resins because they can self‐assemble into different inclusion shapes before epoxy curing. The two examples reported here are spherical micelles and vesicles, which form in blends containing epoxy and symmetric or asymmetric poly(ethylene oxide)–poly(ethylene‐alt‐propylene) (PEO–PEP) block copolymer with PEO volume fractions of 0.5 and 0.26, respectively. The vesicles and spherical micelles were characterized by transmission electron microscopy and small‐angle X‐ray scattering (SAXS), respectively. SAXS data from the spherical micelles were fit to the Percus–Yevick model for a liquid‐like packing of spheres with hard‐core interactions. Mechanical properties of spherical‐micelle‐modified and vesicle‐modified epoxies in the dilute limit are compared. The glass‐transition temperature and Young's (storage) modulus were tested with dynamic mechanical spectroscopy, and compact‐tension experiments were performed to determine the critical plane‐strain energy release rate for fracture. Vesicles were most effective in improving the epoxy fracture resistance. © 2001 John Wiley & Sons, Inc. J Polym Sci Part B: Polym Phys 39: 2996–3010, 2001     

Vesicle formation induced by layered double hydroxides in the catanionic surfactant solution composed of sodium dodecyl sulfate and dodecyltrimethylammonium bromide

In this paper, it is reported that positively charged Mg₃Al layered double hydroxide (LDH) nanoparticles can induce the spontaneous formation of vesicles in micelle solution of sodium dodecyl sulfate (SDS) and dodecyltrimethylammonium bromide (DTAB) with a mass ratio of 8:2. The formation of vesicles was demonstrated by negative-staining transmission electron microscopy observations. The size of the vesicles increased with the increase in the concentration of Mg₃Al-LDH nanoparticles. A composite of LDH nanoparticles encapsulated in vesicles was formed. A possible mechanism of LDH-induced vesicle formation was suggested. The positively charged LDH surface attracts negatively charged micelles or free amphiphilic molecules, which facilitates their aggregation into bilayer patches. These bilayer patches connect to each other and finally close to form vesicles. It was also found that an adsorbed compound layer of SDS and DTAB micelles or molecules on the LDHs surface played a key role in vesicle formation.     

Reversible Switching of a Micelle‐to‐Vesicle Transition by Compressed CO2

The study of the micelle‐to‐vesicle transition (MVT) is of great importance from both theoretical and practical points of view. Herein, we studied the effect of compressed CO₂ on the aggregation behavior of dodecyltrimethylammonium bromide (DTAB)/sodium dodecyl sulfate (SDS) mixed surfactants in aqueous solution by means of direct observation, turbidity and conductivity measurements, steady‐state fluorescence, time‐resolved fluorescence quenching (TRFQ), fluorescence quantum yield, and template methods. Interestingly, all these approaches showed that compressed CO₂ could induce the MVT in the surfactant system, and the vesicles returned to the micelles simply by depressurization; that is, CO₂ can be used to switch the MVT reversibly by controlling pressure. Some other gases, such as methane, ethylene, and ethane, could also induce the MVT of the surfactant solution. A possible mechanism is proposed on the basis of the packing‐parameter theory and thermodynamic principles. It is shown that the mechanism of the MVT induced by a nonpolar gas is different from the MVT induced by polar and electrolyte additives.     

囊泡形成和破坏的动力学

利用停流装置研究了十二烷基硫酸钠(SDS)和十二烷基三甲基溴化铵(DTAB)复配形成囊泡的过程和囊泡破坏过程的动力学性质, 并结合动态光散射技术和电子透射显微镜探索囊泡形成和囊泡破坏过程的机理. 动态光散射和电子透射显微镜的研究结果表明囊泡的形成过程主要包括四个阶段: 混合胶团→柔性的长棒状聚集体→“非平衡囊泡”→平衡囊泡, 而与其对应的粒度分散度则呈现“单分散性→多分散性”的周期性变化规律. 此外, 动力学结果表明囊泡形成过程很长, 但其活化能不大, 这意味着囊泡形成过程的控制步骤可能不是活化能控制. 而相对于囊泡的形成, 囊泡的破坏过程是十分迅速的.     

Ultrafast FRET to Study Spontaneous Micelle‐to‐Vesicle Transitions in an Aqueous Mixed Surface‐Active Ionic‐Liquid System

The spontaneous micelle‐to‐vesicle transition in an aqueous mixture of two surface‐active ionic liquids (SAILs), namely, 1‐butyl‐3‐methylimidazolium n‐octylsulfate ([C₄mim][C₈SO₄]) and 1‐dodecyl‐3‐methylimidazoium chloride ([C₁₂mim]Cl) is described. In addition to detailed structural characterization obtained by using dynamic light scattering, transmission electron microscopy (TEM), and cryogenic TEM techniques, ultrafast fluorescence resonance energy transfer (FRET) from coumarin 153 (C153) as a donor (D) to rhodamine 6G (R6G) as an acceptor (A) is also used to study micelle–vesicle transitions in the present system. Structural transitions of SAIL micelles ([C₄mim][C₈SO₄] or [C₁₂mim]Cl micelles) to mixed SAIL vesicles resulted in significantly increased D –A distances, and therefore, increased timescale of FRET. In [C₄mim][C₈SO₄] micelles, FRET between C153 and R6G occurs on an ultrafast timescale of 3.3 ps, which corresponds to a D –A distance of about 15 Å. As [C₄mim][C₈SO₄] micelles are transformed into mixed micelles upon the addition of a 0.25 molar fraction of [C₁₂mim]Cl, the timescale of FRET increases to 300 ps, which suggests an increase in the D –A distance to 31 Å. At a 0.5 molar fraction of [C₁₂mim]Cl, unilamellar vesicles are formed in which FRET occurs on multiple timescales of about 250 and 2100 ps, which correspond to D –A distances of 33 and 47 Å. Although in micelles and mixed micelles the obtained D –A distances are well correlated with their radius, in vesicles the obtained D –A distance is within the range of the bilayer thickness.     

Spontaneous Formation of Biocompatible Vesicles in Aqueous Mixtures of Amino Acid‐Based Cationic Surfactants and SDS/SDBS

The spontaneous formation of vesicles by six amino acid‐based cationic surfactants and two anionic surfactants (sodium dodecylbenzene sulfonate (SDBS) and sodium dodecyl sulfate (SDS)) is reported. The head‐group structure of the cationic surfactants is minutely altered to understand their effect on vesicle formation. To establish the regulatory role of the aromatic group in self‐aggregation, both aliphatic and aromatic side‐chain‐substituted amino acid‐based cationic surfactants are used. The presence of aromaticity in any one of the constituents favors the formation of vesicles by cationic/anionic surfactant mixtures. The formation of vesicles is primarily dependent on the balance between the hydrophobicity and hydrophilicity of both cationic and anionic surfactants. Vesicle formation is characterized by surface tension, fluorescence anisotropy, transmission electron microscopy, dynamic light scattering, and phase diagrams. These vesicles are thermally stable up to 65 °C, determined by temperature‐dependent fluorescence anisotropy. According to the MTT assay, these catanionic vesicles are nontoxic to NIH3T3 cells, thus indicating their wider applicability as delivery vehicles to cells. Among the six cationic surfactants examined, tryptophan‐ and tyrosine‐based surfactants have the ability to reduce HAuCl₄ to gold nanoparticles (GNPs), which is utilized to obtain in‐situ‐synthesized GNPs entrapped in vesicles without the need for any external reducing agent.     

A new model to study the phase transition from microstructures to nanostructures in ionic/ionic surfactants mixture

The phase behavior and aggregate structures of mixtures of the oppositely charged surfactants cetyltrimethyl ammonium bromide (CTAB) and sodium dodecyl sulfate (SDS) are explored at high dilution by pulsed field gradient stimulated echo (PFG-STE) NMR. The aggregation numbers and hydrodynamic radii of vesicles and mixed micelles were determined by a combination of viscosity and self-diffusion coefficient measurements. The average size of the mixed micelles was larger than that of micelles containing uniformly charged head groups. Analysis of the variations of the self-diffusion coefficient and viscosity with changing concentration of CTAB or SDS in the cationic-rich and anionic-rich regions revealed a phase transition from vesicles to mixed micelles. Differences in the lengths of the CTAB and SDS hydrophobic chains stabilize vesicles relative to other microstructures (e.g., liquid crystalline and precipitate phase), and vesicles form spontaneously over a wide range of compositions in both cationic-rich and anionic-rich solutions. The results obtained from conductometry measurements confirmed this transition. Finally, according to the capacitor model, a new model was developed for estimating the surface potentials and electrostatic free energy (g(elec)). Then we investigated the variations of electrostatic and transfer free energy in phase transition between mixed micelle and vesicle.     

Physicochemical studies on hydrophobic PEO‐PPO‐PEO triblock copolymer micelles in SDS micellar environment

The shape, size, aggregation, hydration, and correlation times of water insoluble PEO‐PPO‐PEO triblock copolymer micelles with sodium dodecylsulfate (SDS) micelles were investigated using transport studies and dynamic light scattering technique. From the conductance of micellar solutions of the polymer in 25 mM SDS and 5 mM NaCl, the hydration of polymer micelles were determined using the principle of obstruction of electrolyte migration by the polymer. The asymmetry of the micellar particles of polymer and polymer‐SDS mixed micellar systems in 5 mM NaCl and their average axial ratios were calculated using intrinsic viscosity and hydration data obeying Simha–Einstein equation. Hydration number and micellar sizes were variable with temperature. The shape of the polymer micelles has been ellipsoidal rather than spherical. The micellar volume, hydrodynamic radius, radius of gyration, diffusional coefficients as well as translational, rotational and effective correlation times have been calculated from the absolute values of the axes. The partial molal volume of polymer micelles has also been determined and its comparison with the molar volume of pure polymer suggested a volume contraction due to immobilization of the water phase by the hydrophilic head groups of the polymer. The thermodynamic activation parameters for viscous flow favor a more ordered water structure around polymer micelles at higher temperatures. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 2410–2420, 2007     

Design and proof of reversible micelle‐to‐vesicle multistimuli‐responsive morphological regulations

Multistimuli‐responsive precise morphological control over self‐assembled polymers is of great importance for applications in nanoscience as drug delivery system. A novel pH, photoresponsive, and cyclodextrin‐responsive block copolymer were developed to investigate the reversible morphological transition from micelles to vesicles. The azobenzene‐containing block copolymer poly(ethylene oxide)‐b‐poly(2‐(diethylamino)ethyl methacrylate‐co‐6‐(4‐phenylazo phenoxy)hexyl methacrylate) [PEO‐b‐P(DEAEMA‐co‐PPHMA)] was synthesized by atom transfer radical polymerization. This system can self‐assemble into vesicles in aqueous solution at pH 8. On adjusting the solution pH to 3, there was a transition from vesicles to micelles. The same behavior, that is, transition from vesicles to micelles was also realizable on addition of β‐cyclodextrin (β‐CD) to the PEO‐b‐P(DEAEMA‐co‐PPHMA) solution at pH 8. Furthermore, after β‐CD was added, alternating irradiation of the solution with UV and visible light can also induce the reversible micelle‐to‐vesicle transition because of the photoinduced trans‐to‐cis isomerization of azobenzene units. The multistimuli‐responsive precise morphological changes were studied by laser light scattering, transmission electron microscopy, and UV–vis spectra. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Revisit to the formation mechanism of exfoliated montmorillonite/PMMA nanocomposite latex through soap‐free emulsion polymerization

Soap‐free emulsion polymerization of methyl methacrylate (MMA) in the aqueous suspension of montmorillonite (MMT) was able to fabricate the exfoliated MMT/PMMA nanocomposite latex. Because neither MMA nor substantial quantity of potassium persulfide (KPS) initiator could be individually absorbed into the interlayer region of MMT, the polymerizing ionic radicals in water phase were considered as a major component to diffuse into the gallery of MMT. They have been observed to organize into disk‐like micelles in the interlayer regions to exfoliate MMT. The diffusion of the polymerizing ionic radicals was further supported by using sodium dodecyl sulfate (SDS) surfactant as a model compound to diffuse into the gallery of MMT. The exfoliation of MMT was almost completed before micellization stage was over. After exfoliation, the disk‐like micelles became a polymerization loci for monomers. Because the disk‐like micelles in numbers were substantially over the commonly formed spherical micelles in the typical soap‐free emulsion polymerization, the conversion rate of MMA to MMT/PMMA nanocomposite latex was faster. Based on the above experimental observation, a justified exfoliation mechanism of MMT was proposed. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 459–466, 2009     

Coarse‐grained molecular dynamics simulation study on spherical and tube‐like vesicles formed by amphiphilic copolymers

Molecular‐level understanding of the vesicular structure and formation process is beneficial for potential vesicle applications, especially in drug delivery. In this article, coarse‐grained molecular dynamics simulation was used to study the self‐assembly behavior of amphiphilic poly(acrylic acid)‐b‐polystyrene copolymers in water at different concentrations and PS/PAA block ratios. It was found that various spherical and tube‐like vesicles formed at PS/PAA 3:3 and 4:2. For spherical vesicles, analysis of vesicular structure indicated that the cavity size was influenced by copolymer concentration and wall thickness by the block ratio. Tube‐like vesicle was formed via the fusion of two spherical vesicles, and a key factor for this morphology is polymer movements between inner and outer layer. This simulation study identifies the key factors governing vesicle formation and structure, and provides a guidance to design and prepare various vesicles for wide applications in drug delivery. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2017 , 55, 1220–1226     

Size,Charge, and Stability of Fully Serine‐Based Catanionic Vesicles: Towards Versatile Biocompatible Nanocarriers

Vesicles based on mixed cationic and anionic surfactants (catanionic vesicles) offer a number of advantageous colloidal features over conventional lipid‐based vesicles, namely spontaneity in formation, long‐term stability, and easy modulation of size and charge. If biocompatibility is added through rational design of the chemical components, the potential for biorelated applications further emerges. Here, we report for the first time on two catanionic vesicle systems in which both ionic amphiphiles are derivatized from the same amino acid—serine—with the goal of enhancing aggregate biocompatibility. Phase behavior maps for a mixture with chain length symmetry, 12Ser/12‐12Ser, and another with asymmetry, 16Ser/8‐8Ser, are presented, for which regions of vesicles, micelles, and coexisting aggregates are identified. For the asymmetric mixture, detailed phase behavior and microstructure characterization have been carried out based on surface tension, light microscopy, cryo‐SEM, cryo‐TEM, and dynamic light scattering analysis. Vesicles are found with tunable mean size, pH, and zeta potential. Changes in aggregate shape with varying composition and the effect of preparation methods and aging on vesicle features and stability have been investigated in detail. The results are discussed in the light of self‐assembly models and related catanionic systems reported before. A versatile system of robust vesicles is thus presented for potential applications.     

Control of block copolymer morphology: An example of selective morphology induced by self‐assembly formation condition

An example case of selective morphology by simply varying pH and heating profile based on a diblock copolymer, i.e., poly(N‐isopropylacrylamide) (PNIPAAM) and poly[2‐(dimethylamino)ethyl acrylate] (PDMAEA) is reported. A variation of pH induces an aggregation of the block copolymers in either micelles or vesicles. In a subsequent step, temperature variation triggers the formation of vesicular structures. This demonstrates not only the temperature but also the heating rate that tunes the nanostructures from micelles to vesicles. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2009     

Construction of temperature responsive hybrid crosslinked self‐assemblies based on PEG‐b‐P(MMA‐co‐MPMA)‐b‐PNIPAAm triblock copolymer: ATRP synthesis and thermoinduced association behavior

A novel amphiphilic thermosensitive poly(ethylene glycol)₄₅‐b‐poly(methyl methacrylate₄₆‐co‐3‐(trimethoxysilyl)propyl methacrylate)₂‐b‐poly(N‐isopropylacrylamide)₄₂₉ (PEG₄₅‐b‐P(MMA₄₆‐co‐MPMA₂)‐b‐PNIPAAm₄₂₉) triblock copolymer was synthesized via consecutive atom transfer radical polymerization techniques. The thermoinduced association behavior of the resulting triblock copolymers in aqueous medium was further investigated in detail by ¹H NMR, transmission electron microscopy, and dynamic light scattering. The results showed that at the temperature (25 °C) below the LCST, PEG₄₅‐b‐P(MMA₄₆‐co‐MPMA₂)‐b‐PNIPAAm₄₂₉ triblock copolymers self‐assembled into the core crosslinked micelles with the hydrophobic P(MMA‐co‐MPMA) block constructing a dense core, protected by the mixed soluble PEG and PNIPAAm chains acting as a hydrophilic shell simultaneously. With an increase in temperature, the resulting core‐shell micelles converted into a new type of micelles with the hydrophilic PEG chains stretching out from the hydrophobic core through the collapsed PNIPAAm shell. On the other hand, at the temperature (40 °C) above the LCST, such triblock copolymers formed the crosslinked vesicles with the hydrophobic PNIPAAm and P(MMA‐co‐MPMA) blocks constructing a membrane core and the soluble PEG chains building the hydrophilic lumen and the shell. On further decreasing the temperature, the resulting vesicles underwent transformation from the shrunken to the expanded status, leading to the formation of swollen vesicles with enlarged size. This study is believed to present the first formation of two types of hybrid crosslinked self‐assemblies by thermoinduced regulation. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011