Interfacial tension of evaporating emulsion droplets containing amphiphilic block copolymers: effects of solvent and polymer composition

Evaporating droplets of volatile organic solvent containing amphiphilic block copolymers may undergo hydrodynamic instabilities that lead to dispersal of copolymer micelles into the surrounding aqueous phase. As for related phenomena in reactive polymer blends and oil/water/surfactant systems, this process has been ascribed to a nearly vanishing or transiently negative interfacial tension between the water and solvent phases induced by adsorption of copolymer to the interface. In this report, we investigate the influence of the choice of organic solvent and polymer composition for a series of polystyrene-b-poly(ethylene oxide) (PS-PEO) diblock copolymers, by in situ micropipette tensiometry on evaporating emulsion drops. These measurements suggest that the sensitivity to the organic solvent chosen reflects both differences in the bare solvent/water interfacial tension as well as the propensity of the copolymer to aggregate within the organic phase. While instabilities coincident with an approach of the interfacial tension nearly to zero were observed only for copolymers with PEO content greater than 15 wt.%, beyond this point the interfacial behavior and critical concentration needed to trigger surface instability were found to depend only weakly on copolymer composition.     

Wormlike morphology formation and stabilization of "pluronic p123" micelles by solubilization of pentaerythritol tetraacrylate

A transition from spherical to wormlike micelles of a poly(ethylene oxide) 20- block-poly(propylene oxide) 70- block-poly(ethylene oxide) 20 triblock copolymer Pluronic P123 induced by solubilization of a tetrafuctional monomer, Pentaerythritol tetraacrylate (PETA), in aqueous media has been studied. The wormlike micelles shape was locked by UV cross-linking of PETA within the micelles resulting in stabilized polymeric micelles (SPMs). The stability of SPMs in a good solvent for both polyether blocks like THF, and upon dilution below the critical micelle concentration (CMC) of P123 in water was confirmed by dynamic light scattering (DLS) and scanning force microscopy (SFM). Formation of cadmium sulfide (CdS) nanoparticles within the wormlike SPMs was carried out via the reduction of Cd (2+) with NaS and analyzed by transmission electron microscopy (TEM) and UV-vis absorption measurements. A stable water-dispersible hybrid system consisting of CdS quantum dots embedded into the wormlike SPMs was obtained.     

Transparent titanium dioxide/block copolymer modified epoxy-based systems in the long scale microphase separation threshold

Microphase separated epoxy-based materials modified with an amphiphilic poly(styrene-block-ethylene oxide) diblock copolymer (PS-b-PEO) with low amount of PEO-block as well as ternary systems modified with this block copolymer and containing via sol–gel in situ synthesized TiO₂ nanoparticles were prepared and characterized. The obtained results indicate that block copolymer had enough amount of PEO-block in order to achieve microphase separated materials for a high range of PS-b-PEO contents, morphologies changing from spherical micelles to long wormlike micelles passing through vesicles upon increasing copolymer amounts. In the case of 20 wt.% inorganic/organic epoxy-based materials, addition of synthesized TiO₂ nanoparticles into PS-b-PEO-(DGEBA/MCDEA) system led to location of the nanoparticles in PEO-block/epoxy-rich confined between two microphase separated PS-block-rich phases. Designed highly transparent multiphase inorganic/organic epoxy-based materials possess interesting specific properties such as high UV shielding efficiency and high water repellence.     

聚肽接枝共聚物的自组装行为研究

Polymeric micelles of poly(γ-benzyl L-glutamate)(PBLG)-poly(ethylene oxide)(PEO) graft copolymer were prepared by the dialysis method in deionized water. Fluorescence spectroscopy, nuclear magnetic resonance(NMR) and transmission electron microscope(TEM) were used for the investigation of the self-assembly of PBLG-PEO graft copolymer. Fluorescence spectrosco0y measurements suggest that PBLG-PEO graft copolymer associates to form polymeric micelles in water. ^1H NMR measurements further prove that in aqueous medium PBLG-PEO graft copolymer could assemble into polymeric micelles with PBLG segments as the hydrophobic inner core and PEO segments as the hydrophilic shell. The results of the TEM observations show that the polymeric micelles of PBLG-PEO graft copolymer are almost spindly shaped, which are different from the morphology of the spherical micelles formed by PBLG-PEO block copolymer. Polymeric micelles formed by polypeptide copolymer have potential application as drug carrier in controlled-release delivery system.     

Supramolecular self-assembly of multiblock copolymers in aqueous solution

A unique pH-dependent phase behavior from a copolymer micellar solution to a collapsed hydrogel with micelles ordered in a hexagonal phase was observed. Small-angle neutron scattering (SANS) was used to follow the pH-dependent structural evolution of micelles formed in a solution of a pentablock copolymer consisting of poly((diethylaminoethyl methacrylate)-b-(ethylene oxide)-b-(propylene oxide)-b-(ethylene oxide)-b-(diethylaminoethyl methacrylate)) (PDEAEM25-b-PEO100-b-PPO65-b-PEO100-b-PDEAEM25). Between pH 3.0 and pH 7.4, we observed the presence of charged spherical micelles. Increasing the pH of the micelle solution above pH 7.4 resulted in increasing the size of the micelles due to the increasing hydrophobicity of the PDEAEM blocks above their pKa of 7.6. The increase in size of the spherical micelles resulted in a transition to a cylindrical micelle morphology in the pH range 8.1-10.5, and at pH >11, the copolymer solution undergoes macroscopic phase separation. Indeed, the phase separated copolymer sediments and coalesces into a hydrogel structure that consists of 25-35 wt % water. Small-angle X-ray scattering (SAXS) clearly indicated that the hydrogel has a hexagonal ordered phase. Interestingly, the process is reversible, as lowering of the pH below 7.0 leads to rapid dissolution of the solid into homogeneous solution. We believe that the hexagonal structure in the hydrogel is a result of the organization of the cylindrical micelles due to the increased hydrophobic interactions between the micelles at 70 degrees C and pH 11. Thus we have developed a pH-/temperature-dependent, reversible hierarchically self-assembling block copolymer system with structures spanning nano- to microscale dimensions.     

Synthesis and micellization of amphiphilic poly(sebacic anhydride)–poly(ethylene glycol)–poly(sebacic anhydride) block copolymers

Amphiphilic biodegradable block copolymers [poly(sebacic anhydride)–poly(ethylene glycol)–poly(sebacic anhydride)] were synthesized by the melt polycondensation of poly(ethylene glycol) and sebacic anhydride prepolymers. The chemical structure, crystalline nature, and phase behavior of the resulting copolymers were characterized with ¹H NMR, Fourier transform infrared, gel permeation chromatography, and differential scanning calorimetry. Microphase separation of the copolymers occurred, and the crystallinity of the poly(sebacic anhydride) (PSA) blocks diminished when the sebacic anhydride unit content in the copolymer was only 21.6%. ¹H NMR spectra carried out in CDCl₃ and D₂O were used to demonstrate the existence of hydrophobic PSA domains as the core of the micelle. In aqueous media, the copolymers formed micelles after precipitation from water‐miscible solvents. The effects on the micelle sizes due to the micelle preparation conditions, such as the organic phase, dropping rate of the polymer organic solution into the aqueous phase, and copolymer concentrations in the organic phase, were studied. There was an increase in the micelle size as the molecular weight of the PSA block was increased. The diameters of the copolymer micelles were also found to increase as the concentration of the copolymer dissolved in the organic phase was increased, and the dependence of the micelle diameters on the concentration of the copolymer varied with the copolymer composition. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 1271–1278, 2006     

Effect of block length, polydispersity, and salt concentration on PEO-PDEAMA block copolymer structures in dilute solution

A series of poly(ethylene oxide)-block-poly(N,N-diethylaminoethyl methacrylate) (PEO-PDEAMA) block copolymers with relatively high polydispersity (1.36 < PDI < 1.96) have been prepared to determine the effect that polydispersity has on the self-assembly of amphiphilic block copolymers in dilute solution. Because monodisperse macroinitiators were used for the ATRP reactions, the polydispersity resides within the hydrophobic block. By adjusting the relative block lengths, spherical micelles, wormlike micelles, vesicles, or a precipitate is formed. Here, we show that relatively high polydispersity in the block copolymer does not preclude efficient self-assembly. We also discuss the effect of increasing the concentration of NaCl in the systems and show that this can result in a shift from one morphology to another. These shifts are reversible in some cases, but for PEO12-PDEAMA39, this method allows access to giant vesicles of between 500 nm and 1 microm in diameter.     

Polystyrene-poly(ethylene oxide) diblock copolymer: the effect of polystyrene and spreading concentration at the air/water interface

Polystyrene-block-poly(ethylene oxide) (PS-PEO) is an amphiphilic diblock copolymer that undergoes microphase separation when spread at the air/water interface, forming nanosized domains. In this study, we investigate the impact of PS by examining a series of PS-PEO samples containing constant PEO (~17,000 g·mol(-1)) and variable PS (from 3600 to 200,000 g·mol(-1)) through isothermal characterization and atomic force microscopy (AFM). The polymers separated into two categories: predominantly hydrophobic and predominantly hydrophilic with a weight percent of PEO of ~20% providing the boundary between the two. AFM results indicated that predominantly hydrophilic PS-PEO forms dots while more hydrophobic samples yield a mixture of dots and spaghetti with continent-like structures appearing at ~7% PEO or less. These structures reflect a blend of polymer spreading, entanglement, and vitrification as the solvent evaporates. Changing the spreading concentration provides insight into this process with higher concentrations representing earlier kinetic stages and lower concentrations demonstrating later ones. Comparison of isothermal results and AFM analysis shows how polymer behavior at the air/water interface correlates with the observed nanostructures. Understanding the impact of polymer composition and spreading concentration is significant in leading to greater control over the nanostructures obtained through PS-PEO self-assembly and their eventual application as polymer templates.     

聚甲基丙烯酸甲酯接枝聚氧乙烯共聚物溶液性质的研究

采用核磁共振 (NMR)、动态激光光散射 (DLS)、透射电子显微镜 (TEM )等方法研究了规整性聚甲基丙烯酸甲酯接枝聚氧乙烯共聚物溶液性质 ,研究表明两亲接枝共聚物在选择性溶剂中可形成球状胶束 ,溶液的浓度、温度和聚合物结构等因素影响其胶束的大小、形态     

Temperature and concentration effects on supramolecular aggregation and phase behavior for poly(propylene oxide)-b-poly(ethylene oxide)- b-poly(propylene oxide) copolymers of different composition in aqueous mixtures, 1

The phase behavior (temperature vs composition) and microstructure for the two binary systems Pluronic 25R4 [(PO)19(EO)33(PO)19]-water and Pluronic 25R2 [(PO)21(EO)14(PO)21]-water have been studied by a combined experimental approach in the whole concentration range and from 5 to 80 degrees C. The general phase behavior has been identified by inspection under polarized light. Precise phase boundaries have been determined by analyzing 2H NMR line shape. The identification and microstructural characterization of the liquid crystalline phases have been achieved using small-angle X-ray scattering (SAXS). The isotropic liquid solution phases have been investigated by self-diffusion measurements (PGSE-NMR method). 25R2 does not form liquid crystals and is miscible with water in the whole concentration range; with increasing temperature, the mixtures split into water-rich and a copolymer-rich solutions in equilibrium. 25R4 shows rich phase behavior, passing, with increasing copolymer concentration, from a water-rich solution to a lamellar and copolymer-rich solution. A small hexagonal phase, completely encircled in the stability region of the water-rich solution, is also present. In water-rich solutions, at low temperatures and low copolymer concentrations, the copolymers are dissolved as independent macromolecules. With increasing copolymer concentrations an interconnected network of micelles is formed in which micellar cores of hydrophobic poly(propylene oxide) are interconnected by poly(ethylene oxide) strands. In copolymer-rich solutions water is molecularly dissolved in the copolymer. The factors influencing the self-aggregation of Pluronic R copolymers (PPO-PEO-PPO sequence) are discussed, and their behavior in water is compared to that of Pluronic copolymers (PEO-PPO-PEO sequence).     

Effects of block architecture and composition on the association properties of poly(oxyalkylene) copolymers in aqueous solution

A block copolymer of hydrophilic poly(ethylene oxide) and a hydrophobic poly(alkylene oxide) can associate in dilute aqueous solution to form micelles. The results of recent investigations of the micellisation behaviour and micelle properties of such copolymers are described. Copolymers of ethylene oxide with propylene oxide, 1,2‐butylene oxide or styrene oxide are considered, including aspects of their preparation. Experimental methods for determination of critical conditions for micellisation, micelle association number and spherical‐micelle radius are summarised. Effects of temperature, composition, block length and block architecture (diblock, triblock and cyclic‐diblock) are described and, where possible, related to the predictions of theory. Brief consideration is given to the dynamics of micelle formation/dissociation, to cylindrical micelles, and to effects of added salts.     

Effects of salts and ethanol on the population and morphology of triblock copolymer micelles in solution

The morphological changes of micelles composed of triblock copolymer of ethylene oxide and propylene oxide (EO20PO70EO20) in the presence of different inorganic salts and ethanol have been investigated using dynamic light scattering (DLS), rheometry, and cryogenic transmission electron microscopy (cryo-EM). The following salts were studied: KF, KCl, KI, LiCl, and CsCl. In the presence of KF, KCl, and CsCl, spherical and wormlike micelles coexist. LiCl and KI have little influence on the morphology of the micelles, whereas KF has the most pronounced effect. In agreement with the well-known Hoffmeister anion salt series, F- has the strongest effect of the three anions studied (F-, Cl-, I-). In contrast, the effectiveness of the cation type does not follow the original Hoffmeister cation series. The addition of ethanol to the KCl micellar solutions leads to the formation of more or longer wormlike micelles, which start to interact at certain copolymer concentrations depending on the volume fraction of ethanol added. Both the dilute and the semidilute regimes of the wormlike micelles were studied. The length of the micelles reaches a maximum value at around 8-10 vol % ethanol, after which it decreases again. At higher ethanol concentrations (18 vol %), spherical micelles are formed. Conclusions from this study enhance our understanding of the role played by ethanol and salts in the formation of micelle-templated mesoporous materials, such as SBA-15.     

Rheology and phase behavior of poly(n-butyl acrylate)-block-poly(acrylic acid) in aqueous solution

The surface activity and the rheological properties of aqueous solutions of the amphiphilic block copolymer poly(n-butyl acrylate)-block-poly(acrylic acid) (PnBA-b-PAA) were studied as a function of the degree of neutralization, alpha, of the poly(acrylic acid) block. Although the block copolymer spontaneously forms spherical micelles having a stretched PAA corona and a collapsed PnBA core in water for alpha > 0.1, the solutions do not exhibit any surface activity at this degree of neutralization. Cryo-TEM micrographs show that the radii of the hydrophobic core of the largest micelles are as long as the length of the hydrophobic chain. The micelles, however, have a broad size distribution, and on average, as shown by SANS, the micelles are only about half as long. At concentrations as low as 1 wt %, the solutions exhibit highly viscoelastic behavior and have a yield stress value depending on alpha. The globular micelles are highly ordered in the bulk phase, and the viscoelastic properties are a result of the dense packing of the micelles. The addition of salt or cationic surfactants dramatically decreases the viscosity of the solution. The observed properties seem to be due to electrostatic interactions between the PAA chains of the micelles.     

Interaction of amphiphilic block copolymer micelles with surfactants

An out line and summary of literature studies on interactions between different types of amphiphilic copolymer micelles with surfactants has been given. This field of research is still emerging and it is difficult presently to make generalisations on the effects of surfactants on the copolymer association. The effects are found to be varied depending upon the nature and type of hydrophobic (hp) core and molecular architecture of the copolymers and the hydrocarbon chain length and head group of surfactants. The information available on limited studies shows that both anionic and cationic surfactants (in micellar or molecular form) equally interact strongly with the associated and unassociated forms of copolymers. The beginning of the interaction is typically displayed as critical aggregation concentration (CAC), which lies always below the critical micelle concentration of the respective surfactant. The surfactants first bind to the hydrophobic core of the copolymer micelles followed by their interaction with the hydrophilic (hl) corona parts. The extent of binding highly depends upon the nature, hydropobicity of the copolymer molecules, length of the hydrocarbon tail and nature of the head group of the surfactant. The micellization of poly(ethylene oxide) (PEO)–poly(propylene oxide) (PPO)–poly(ethylene oxide) was found to be suppressed by the added surfactants and at higher surfactant concentrations, the block copolymer micelles get completely demicellized. This effect was manifested itself in the melting of liquid crystalline phases in the high copolymer concentrations. However, no such destabilization was found for the micelles of polystyrene (PS)–poly(ethylene oxide) copolymers in water. On the contrary, the presence of micellar bound surfactant associates resulted in to large super micellar aggregates through induced intra micellar interactions. But with the change in the hydrophobic part from polystyrene to poly(butadiene) (PB) in the copolymer, the added surfactants not only reduced the micellar size but also transformed cylindrical micelles to spherical ones. The mixtures in general exhibited synergistic effects. So varied association responses were noted in the mixed solutions of surfactants and copolymers.     

Influence of Mixed Common Solvent on the Co-assembled Morphology of PS-b-PEO and CdS Quantum Dots

The hybrid structures of polystyrene-b-poly(ethylene oxide)(PS-b-PEO) block copolymer and inorganic nanoparticles with good stability and biocompatibility have potential applications in drug delivery and bioimaging. Spherical co-assemblies of PS120-b-PEO318 and oleylamine-capped Cd S quantum dots(QDs) are produced successfully in this work by adding water to a mixed common solvent, such as N,N-dimethylmethanamide(DMF)/chloroform, DMF/tetrahydrofuran(THF), or DMF/toluene. The energy dispersive X-ray(EDX) spectrum indicates that QDs are located at the interface between the core and shell of the spherical co-assemblies. The co-assembly process during water addition is traced by transmission electron microscopy(TEM) and turbidity measurement. Spherical co-assemblies are formed through budding from bilayers of the block copolymer and QDs. The morphology of the co-assemblies is related to the miscibility of the QD-dispersing solvents with water and the morphology changes from a spherical to a vesicle-like structure with DMF/toluene. Increasing THF content in the mixed solvent causes morphological transitions from spherical co-assemblies to multi-branched cylinders and micelles where QDs are located in the central core. Increasing chloroform content yields vesicle-like structures with protruding rods on the surface. The mechanism of the morphological transitions is also discussed in detail.     

Phase behavior of a mixture of poly(isoprene)-poly(oxyethylene) diblock copolymer and poly(oxyethylene) surfactant in water

The phase behavior of a mixture of poly(isoprene)-poly(oxyethylene) diblock copolymer (PI-PEO or C250EO70) and poly(oxyethylene) surfactant (C12EO3, C12EO5, C12EO6, C12EO7, and C12EO9) in water was investigated by phase study, small-angle X-ray scattering, and dynamic light scattering (DLS). The copolymer is not soluble in surfactant micellar cubic (I1), hexagonal (H1), and lamellar (Lalpha) liquid crystals, whereas an isotropic copolymer fluid phase coexists with these liquid crystals. Although the PI-PEO is relatively lipophilic, it increases the cloud temperatures of C12EO3-9 aqueous solutions at a relatively high PI-PEO content in the mixture. Most probably, in the copolymer-rich region, PI-PEO and C12EOn form a spherical composite micelle in which surfactant molecules are located at the interface and the PI chains form an oil pool inside. In the C12EO5/ and C12EO6/PI-PEO systems, one kind of micelles is produced in the wide range of mixing fraction, although macroscopic phase separation was observed within a few days after the sample preparation. On the other hand, small surfactant micelles coexist with copolymer giant micelles in C12EO7/ and C12EO9/PI-PEO aqueous solutions in the surfactant-rich region. The micellar shape and size are calculated using simple geometrical relations and compared with DLS data. Consequently, a large PI-PEO molecule is not soluble in surfactant bilayers (Lalpha phase), infinitely long rod micelles (H1 phase), and spherical micelles (I1 phase or hydrophilic spherical micelles) as a result of the packing constraint of the large PI chain. However, the copolymer is soluble in surfactant rod micelles (C12EO5 and C12EO6) because a rod-sphere transition of the surfactant micelles takes place and the long PI chains are incorporated inside the large spherical micelles.     

Aqueous dispersions of C60 fullerene by use of amphiphilic block copolymers: preparation and nonlinear optical properties

The dispersion of the otherwise insoluble C60 fullerene in water is discussed. Amphiphilic block copolymers, namely, polystyrene-b-polyethylene oxide (PS-PEO), were found to be able to disperse C60 in aqueous solutions, where the polymer forms micelles with a hydrophobic PS core. The preparation protocol of the final solutions was found to play a crucial role in the ability of the block copolymer to disperse the C60 molecules. The C60 containing aggregates were studied using optical spectroscopy, light scattering, and scanning electron microscopy. In addition, their optical limiting action and nonlinear optical properties under visible nanosecond laser excitation were studied and compared with that of C60-toluene solutions.     

Wormlike aggregates from a supramolecular coordination polymer and a diblock copolymer

The formation of wormlike micelles in mixed systems of a supramolecular coordination polymer Zn-L2EO4 and a diblock copolymer P2MVP41-b-PEO205 is investigated by light scattering and Cryo-TEM. By direct mixing at a stoichiometric charge ratio, the above mixtures proved to be capable of formation of spherical micelles with a radius of about 25 nm (Yan et al. Angew. Chem., Int. Ed.; 2007, 46, 1807-1809). Lately, we find wormlike micelles with a hydrodynamic radius >150 nm in a mixture with excess positive charge, that is, a negative charge fraction f- < 0.5. The transformation between wormlike and spherical micelles can be realized by variation of the mixing ratio through different protocols. Upon addition of negatively charged Zn-L2EO4 to a mixture with excess positively charged P2MVP41-b-PEO205, most of the wormlike micelles are transformed into spherical ones; upon addition of positively charged P2MVP41-b-PEO205 to a mixture of pure spherical micelles, wormlike micelles can be produced again. The effect of sample preparation protocol, sample history, and concentration on this transformation process is systematically reported in this article. A possible mechanism for the formation of wormlike micelles is proposed.     

Competitive hydrogen bonding and self‐assembly in poly(2‐vinyl pyridine)‐block‐poly(methyl methacrylate)/poly(hydroxyether of bisphenol A) blends

Blends of poly(2‐vinyl pyridine)‐block‐poly(methyl methacrylate) (P2VP‐b‐PMMA) and poly(hydroxyether of bisphenol A) (phenoxy) were prepared by solvent casting from chloroform solution. The specific interactions, phase behavior and nanostructure morphologies of these blends were investigated by Fourier transform infrared (FTIR) spectroscopy, differential scanning calorimetry (DSC), dynamic light scattering (DLS), atomic force microscopy (AFM), and transmission electron microscopy (TEM). In this block copolymer/homopolymer blend system, it is established that competitive hydrogen bonding exists as both blocks of the P2VP‐b‐PMMA are capable of forming intermolecular hydrogen bonds with phenoxy. It was observed that the interaction between phenoxy and P2VP is stronger than that between phenoxy and PMMA. This imbalance in the intermolecular interactions and the repulsions between the two blocks of the diblock copolymer lead to a variety of phase morphologies. At low phenoxy concentration, spherical micelles are observed. As the concentration increases, PMMA begins to interact with phenoxy, leading to the changes of morphology from spherical to wormlike micelles and finally forms a homogenous system. A model is proposed to describe the self‐assembled nanostructures of the P2VP‐b‐PMMA/phenoxy blends, and the competitive hydrogen bonding is responsible for the morphological changes. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 1894–1905, 2009     

Self-assembly of poly(ethylene oxide)-b-poly(epsilon-caprolactone) copolymers in aqueous solution

The associative behavior of monodisperse diblock copolymers consisting of a hydrophilic poly(ethylene oxide) block and a hydrophobic poly(epsilon-caprolactone) or poly(gamma-methyl-epsilon-caprolactone) block has been studied in aqueous solution. Copolymers have been directly dissolved in water. The solution properties have been studied by surface tension, in relation to mesoscopic analyses by NMR (self-diffusion coefficients), transmission electron microscopy, and small-angle neutron and X-ray scattering. The experimental results suggest that micellization occurs at low concentration (approximately 0.002 wt %) and results in a mixture of unimers and spherical micelles that exchange slowly. The radius of the micelles has been measured (ca. 11 nm), and the micellar substructure has been extracted from the fitting of the SANS data with two analytical models. The core radius and the aggregation number change with the hydrophobic block length according to scaling laws as reported in the scientific literature. The poly(ethylene oxide) blocks are in a moderately extended conformation in the corona, which corresponds to about 25% of the completely extended chain. No significant modification is observed when poly(gamma-methyl-epsilon-caprolactone) replaces poly(epsilon-caprolactone) in the diblocks.