Dynamics of Micelles of Polyethyleneoxide-Polypropyleneoxide-Polyethyleneoxide Block Copolymers in Aqueous Solutions

The dynamics of the micelles of five triblock poly(ethyleneoxide)-poly(propyleneoxide)-poly(ethyleneoxide) copolymers, the Pluronics P104 (EO27PO61EO27), P84 (EO19PO43EO19), P65 (EO18PO29EO18), P85 (EO26PO40EO26), and P103 (EO17PO60EO17), have been investigated using two chemical relaxation methods: the temperature-jump and the ultrasonic relaxation (absorption). In the frequency range investigated (0.5-50 MHz), the ultrasonic absorption spectra (absorption vs frequency plots) consisted in tails of relaxation curves, indicating characteristic times much longer than 0.3 μs for the exchange of copolymers between micelles and intermicellar solution. Absorption measurements at a fixed frequency yielded the critical micellization temperature of the solutions. The temperature-jump results obtained in this study together with those from a previous one for the copolymers L64 (EO13PO30EO13) and PF80 (EO73PO27EO73) (B. Michels et al., Langmuir 13, 3111, 1997) showed that the relaxation time associated with the formation/breakup of micelles becomes longer upon increasing copolymer molecular weight at constant composition. This time also increased when decreasing the length of the hydrophilic block at fixed hydrophobic block length or increasing the length of the hydrophobic block at fixed hydrophilic block length, similar to conventional surfactants. The dynamics of block copolymers micelles in aqueous solution are discussed. Copyright 1999 Academic Press.     

Micelles from PEO-PPO-PEO block copolymers as nanocontainers for solubilization of a poorly water soluble drug hydrochlorothiazide

The effect of molecular characteristics of EO-PO triblock copolymers viz. Pluronic(?) P103 (EO(17)PO(60)PEO(17)), P123 (EO(19)PO(69)EO(19)), and F127 (EO(100)PO(65)EO(100)) on micellar behavior and solubilization of a diuretic drug, hydrochlorothiazide (HCT) was investigated. The critical micellization temperatures (CMTs) and size for empty as well as drug loaded micelles are reported. The CMTs and micelle size depended on the hydrophobicity and molecular weight of the copolymer; a decrease in CMT and increase in size was observed on solubilization. The solubilization of the drug hydrochlorothiazide (HCT) in the block copolymer nanoaggregates at different temperatures (28, 37, 45°C), pH (3.7, 5.0, 6.7) and in the presence of added salt (NaCl) was monitored by using UV-vis spectroscopy and solubility data were used to calculate the solubilization characteristics; micelle-water partition coefficient (P) and thermodynamic parameters of solubilization viz. Gibbs free energy (ΔG(s)°), enthalpy (ΔH(s)°) and entropy (ΔS(s)°). The solubility of the drug in copolymer increases with the trend: P103>P123>F127. The solubilized drug decreased the cloud point (CP) of copolymers. Results show that the drug solubility increases in the presence of salt but significantly enhances with the increase in the temperature and at a lower pH in which drug remains in the non-ionized form.     

On the binding of calcium by micelles composed of carboxy-modified pluronics measured by means of differential potentiometric titration and modeled with a self-consistent-field theory

We perform differential potentiometric titration measurements for the binding of Ca2+ ions to micelles composed of the carboxylic acid end-standing Pluronic P85 block copolymer (i.e., CAE-85 (COOH-(EO)26-(PO)39-(EO)26-COOH)). Two different ion-selective electrodes (ISEs) are used to detect the free calcium concentration; the first ISE is an indicator electrode, and the second is a reference electrode. The titration is done by adding the block copolymers to a known solution of Ca2+ at neutral pH and high enough temperature (above the critical micellization temperature CMT) and various amount of added monovalent salt. By measuring the difference in the electromotive force between the two ISEs, the amount of Ca2+ that is bound by the micelles is calculated. This is then used to determine the binding constant of Ca2+ with the micelles, which is a missing parameter needed to perform molecular realistic self-consistent-field (SCF) calculations. It turns out that the micelles from block copolymer CAE-85 bind Ca2+ ions both electrostatically and specifically. The specific binding between Ca2+ and carboxylic groups in the corona of the micelles is modeled through the reaction equilibrium -COOCa+ <==> -COO- + Ca2+ with pKCa = 1.7 +/- 0.06.     

Effect of structure of PEO-PPO-PEO copolymers on reverse micelle formation induced by compressed CO2

The micellization of PEO-PPO-PEO block copolymers in p-xylene has been studied in the presence of CO2. With the application of CO2, some copolymers with suitable molecular weights and EO ratios can form reverse micelles with critical micellization pressure up to 5.8 MPa. For the copolymers with the same length of PO block, higher EO ratios facilitate reverse micelle formation. For the copolymers with the same composition, higher molecular weight is favorable to form reverse micelles. With the suitable composition and molecular weight, the critical micelle pressure (CMP) of copolymers decreases with the increase in the lengths of PEO and PPO blocks due to the hydrophilic and folding effects, respectively. Both the EO ratios and the molecular weights are important for the formation of reverse micelle. The reverse micelle solution can solubilize water with W0 (molar ratio of water to EO segment) up to 3.3.     

聚乙二醇-聚乳酸共聚物胶束溶液的冷冻干燥及胶束体外释药动力学研究

合成了一系列亲水、疏水链段质量比例不同的聚乙二醇-聚乳酸(PEG-PLA)嵌段共聚物胶束, 并以两性霉素B为模型药物制备了载药胶束. 为获得稳定性良好的、可长期储存的载药胶束剂型, 对胶束进行了冷冻干燥. 使用不同浓度的糖类(包括甘露糖、海藻糖、葡萄糖)、泊洛沙姆188 (Pluronic F68)、聚乙二醇作为冻干保护剂, 以冻干产品的重分散性、冻干前后胶束的粒径及多分散性为指标评价各种保护剂的保护效果. 结果发现, 当嵌段聚合物中聚乳酸链段的质量百分比小于或等于聚乙二醇时, 糖类、Pluronic F68和PEG均可以起到有效的冻干保护作用; 而对于聚乳酸链段质量比例较大的共聚物胶束, 只有PEG和Pluronic F68能够起到较好的冻干保护作用. 对载药胶束体外释放研究表明, 聚合物胶束的体外释放缓慢, 符合一级动力学特征.     

Effects of block size of pluronic polymers on the water structure in the corona region and its effect on the electron transfer reactions

Effects of constituent block size of triblock copolymers on the nature of the water molecules in the corona region of their micelles have been investigated using time-resolved fluorescence measurements. The physical nature of the water molecules in the micellar corona region of the block copolymer, Pluronic F88 ([ethylene oxide (EO)]103-[propylene oxide (PO)]39-EO103), has been studied using a solubilized coumarin dye. Solvent reorientation time and rotational correlation time have been measured and compared with another block copolymer, Pluronic P123 (EO20-PO70-EO20), which has a different composition of the constituent PO and EO blocks. It is noted that due to the presence of larger number of EO blocks in F88 as compared with P123, the corona region of the former micelle is more hydrated than that of the latter. The solvent reorientation time and rotational correlation time are found to be relatively shorter for F88 as compared with P123. This indicates that the water molecules in the corona of the F88 micelle are more labile than those of P123, which is also supported from the estimated number of water molecules associated with each EO unit, measured from the size of each type of micelle and its aggregation number. To understand the effect of block size on the chemical reactions in these microheterogeneous media, electron transfer reactions have been carried out between different coumarin acceptors and N, N-dimethylaniline donor. The electron transfer results obtained in F88 micelles have been compared with those obtained in P123, and the results are rationalized on the basis of the relative hydration of the two triblock copolymer micelles.     

PHOTOLUMINESCENT PROPERTIES OF OCTADECYLRHODAMINE B IN MICELLES OF LOW-MOLECULAR-WEIGHT DETERGENTS AND WATER-SOLUBLE TRIBLOCK COPOLYMERS

The fluorescence intensity, lifetime and degree of polarization of octadecylrhodamine B (ORB) have been measured in order to examine the usefulness of this molecule as a probe of micelle properties for low-molecular-weight detergents and water-soluble triblock copolymers. The surfactants examined are hexadecyltrimethylammonium chloride (HTAC), Triton X-100 (TX-100), sodium dode-cylsulfate (SDS), sodium tetradecylsulfate (STS), and Pluronic L64 (ethylene oxide [EO]₁₃ propylene oxide₃₀ EO₁₃, L64). The fluorescence intensity and degree of polarization of ORB show drastic increases at the critical micelle concentrations (CMC) of HTAC, TX-100 and L64, indicating that ORB is cooperatively incorporated into the micelles upon micellization. This feature demonstrates the validity of ORB as a probe for detecting micelle formation of these surfactants. However, in the case of SDS and STS, the fluorescence intensity starts to rise at concentrations far below the CMC, and the degree of polarization does not show significant changes at the CMC. The details of the interactions between ORB and the anionic surfactants have been unclear. These facts imply that some caution is needed for the applications of ORB to the systems containing anionic surfactants. The local viscosity of L64 micelles has been determined by polarization and lifetime measurements. The structure of the block copolymer micelles and the locations of the probe in the micelles are discussed in terms of the viscosity data.     

Interaction of ethylene oxide-propylene oxide copolymers with ionic surfactants studied by calorimetry: random versus block copolymers

The present study used calorimetric techniques to follow the interaction of random and block ethylene oxide (EO)-propylene oxide (PO) copolymers with ionic surfactants. Features such as the intensity of the interaction (evaluated through their critical aggregation concentrations) and the profile of the isothermal titration calorimetry (ITC) curves were comparatively analyzed for random and block copolymers with similar composition (number of EO and PO units). Random copolymers displayed an interaction similar to that observed with other hydrophilic homopolymers with the additional characteristic that the intensity of the interaction increased with the increase in the copolymer hydrophobicity (as determined by its PO content), revealing that these copolymers display an intermediate behavior between PEO and PPO. For nonaggregated block copolymers (unimers) with large enough EO blocks (molar mass above 2000 g mol-1), ITC curves revealed that the anionic surfactant sodium dodecylsulfate (SDS) interacts with the PO and EO blocks almost independently, being more favorable with the PO block, which controls the critical aggregation concentration (cac) value. Effects of temperature and of the nature of the ionic surfactants on their interaction with these copolymers were found to agree with the previously reported trends.     

Room temperature sphere-to-rod growth and gelation of PEO-PPO-PEO triblock copolymers in aqueous salt solutions

The effects of NaCl and KF on the sphere-to-rod micellar growth behavior of triblock copolymers having two different compositions, (EO)20(PO)70(EO)20 (P123) and (EO)26(PO)40(EO)26 (P85), have been studied by dynamic light scattering (DLS), small angle neutron scattering (SANS) and dilute solution viscometry. NaCl can effectively tune the sphere-to-rod growth temperature of the micelles of both these copolymers and induce micellar growth down to the room temperature and below. The growth behavior is found to be dependent on the composition of the copolymer as P123 being more hydrophobic shows the room temperature growth in the presence of ethanol at significantly lesser NaCl concentration than the less hydrophobic copolymer P85. DLS studies depict for the first time the growth driven transition of the copolymer solutions from dilute to semi-dilute regime as a function of copolymer and salt concentrations. KF can also induce room temperature growth of the P123 micelles at lesser salt concentration than NaCl but it fails to induce any such growth of the P85 micelles. A pseudo-binary temperature-concentration phase diagram on 15% copolymer solutions shows the variation of the sphere-to-rod transition temperature and the cloud point of the copolymer solutions as a function of salt concentration.     

Apparent Specific Volume Measurements of Poly(ethylene oxide), Poly(butylene oxide), Poly(propylene oxide), and Octadecyl Chains in the Micellar State as a Function of Temperature

Apparent specific densities of aqueous solutions of the diblock copolymers C18(EO)100, C18(EO)20, and (EO)92(BO)18 and the triblock copolymers (EO)25(PO)40(EO)25 and (EO)21(PO)47(EO)21 in the micellar state have been measured over a temperature range from 10 to 90 degrees C at concentrations between 1% and 5%, using an oscillating tube densitometer. From these measurements, apparent specific volumes of poly(ethylene oxide) (PEO), poly(propylene oxide) (PPO), poly(butylene oxide) (PBO), and octadecane in the micellar state have been determined. The composition of the block copolymers was checked by NMR spectroscopy. Results were compared with published data for the polymers and bulk values for octadecane, respectively. The apparent specific density of PEO chains in the dissolved state was also measured for PEG4600 solutions at different concentrations and compared with results in the micellar state. The results presented in the paper are crucial in connection with analysis and modeling of small-angle X-ray scattering (SAXS) data from polymer and block copolymer micellar systems. PEO and PPO have a relatively low apparent partial specific volume in water at low temperatures. It is associated with water molecules making strong hydrogen bonds with the oxygen atoms on the polymer backbone. These water molecules gradually become disordered when the temperature is increased and the polymer apparent specific volume increases. For PBO in the micellar cores of PBO-PEO block copolymer micelles and in PNiPAM microgels, pronounced temperature dependence with the same origin is also found. The application of the derived results for the apparent specific volume of PEO for deriving contrast factors is demonstrated and the results are used in the analysis of SAXS data for semidilute solutions of PEG4600 in a broad temperature range.     

Effect of acid on the aggregation of poly(ethylene xide)-poly(propylene oxide)-poly(ethylene oxide) block copolymers

The acid effect on the aggregation of poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) block copolymers EO(20)PO(70)EO(20) has been investigated by transmission electron microscopy (TEM), particle size analyzer (PSA), Fourier transformed infrared, and fluorescence spectroscopy. The critical micellization temperature for Pluronic P123 in different HCl aqueous solutions increases with the increase of acid concentration. Additionally, the hydrolysis degradation of PEO blocks is observed in strong acid concentrations at higher temperatures. When the acid concentration is low, TEM and PSA show the increase of the micelle mean diameter and the decrease of the micelle polydispersity at room temperature, which demonstrate the extension of EO corona and tendency of uniform micelle size because of the charge repulsion. When under strong acid conditions, the aggregation of micelles through the protonated water bridges was observed.     

Effect of SDS on the self-assembly behavior of the PEO-PPO-PEO triblock copolymer (EO)20(PO)70(EO)20

The mixed micellar system comprising the poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide)-based triblock copolymer (EO)(20)(PO)(70)(EO)(20) (P123) and the anionic surfactant sodium dodecyl sulfate (SDS) has been investigated in aqueous media by small-angle neutron scattering (SANS) and viscosity measurements. The aggregation number of the copolymer in the micelles decreases upon addition of SDS, but a simultaneous enhancement in the degree of micellar hydration leads to a significant increase in the micellar volume fraction at a fixed copolymer concentration. This enhancement in the micellar hydration leads to a marked increase in the stability of the micellar gel phase until it is destroyed at very high SDS concentration. Mixed micellar systems with low and intermediate SDS concentrations form the micellar gel phase in much wider temperature and copolymer concentration ranges than the pure copolymer micellar solution. A comparison of the observed results with those for the copolymers (EO)(26)(PO)(40)(EO)(26) (P85) and (EO)(99)(PO)(70)(EO)(99) (F127) suggests that the composition of the copolymers plays a significant role in determining the influence of SDS on the gelation characteristics of the aqueous copolymer solutions. Copolymers with high PO/EO ratios show an enhancement in the stability of the gel phase, whereas copolymers with low PO/EO ratios show a deterioration of the same in the presence of SDS.     

Interactions between poloxamers in aqueous solutions: micellization and gelation studied by differential scanning calorimetry, small angle X-ray scattering, and rheology

Poloxamers F88 (EO97PO39EO97) and P85 (EO27PO39EO27) are triblock copolymers of ethylene oxide (EO) and propylene oxide (PO), which have the same hydrophobic PO block. We studied aqueous solutions of these two copolymers by the conjoint use of differential scanning calorimetry (DSC), rheology, and small-angle X-ray scattering (SAXS). The results showed that the temperature-induced micellization of aqueous solutions of F88 and P85 was a progressive process followed by gelation for sufficiently concentrated samples. Gelation was due to the ordered packing of micelles under a hexagonal compact (HC) structure for P85 and a body-centered cubic (BCC) phase for F88. Importantly, the phase diagram of F88/P85 mixtures in water was elucidated and showed the destabilization of the HC phase upon addition of small amounts of F88.     

Mixed block copolymer aggregates with tunable temperature behavior

A block copolymer of propylene oxide (PO) and ethoxyethyl glycidyl ether (EEGE), (PO)(2)(EEGE)(6)(PO)(2), that has been found to possess lower critical solution temperature properties in water in the temperature range below 20 degrees C was mixed at 1:0.1, 1:1, and 1:10 weight ratios with commercially available Pluronic (L64 or P85) block copolymers. The cooperative association of the copolymers in aqueous solution was studied by dynamic light scattering over a wide temperature range (5-60 degrees C). At lower temperatures, the systems containing either L64 or P85 behave similarly irrespective of the composition: three species corresponding to (PO)(2)(EEGE)(6)(PO)(2) unimers, Pluronic-dominated mixed micelles, and large (50-60 nm in radius) composite (PO)(2)(EEGE)(6)(PO)(2)/Pluronic aggregates were identified. At a certain temperature, which is composition-dependent, the systems phase-separate [(PO)(2)(EEGE)(6)(PO)(2)/L64 1:0.1], enter an interval of instability [(PO)(2)(EEGE)(6)(PO)(2)/L64 1:1 and 1:10], or rearrange by dissociation of the large composite particles [(PO)(2)(EEGE)(6)(PO)(2)/P85]. The presence of a Pluronic micellar peak in the relaxation time distribution at lower temperatures, the dimensions of the composite particles, and the different behavior of the systems at elevated temperatures are discussed. A possible application of the thermosensitive mixtures in delivery/release of active substances is suggested.     

Influence of a hydrophobic diol on the micellar transitions of Pluronic P85 in aqueous solution

Micellization behavior of an amphiphilic ethylene oxide-propylene oxide-ethylene oxide tri-block copolymer Pluronic P85 [(EO)(26)(PO)(39)-(EO)(26)] in aqueous solution and in the presence of a hydrophobic C(14)diol (also known as Surfynol104) was examined by physico-chemical methods such as viscometry, cloud point (CP) and scattering techniques viz. dynamic light scattering (DLS) and small angle neutron scattering (SANS). The addition of diol decreases the cloud point and gelation temperature of aqueous Pluronic P85 copolymer solution. DLS and SANS measurements of the polymer in aqueous solution indicated micellar growth and sphere to rod transition in the presence of diol. Surfynol 104 is a sparingly water soluble diol surfactant with a solubility of approximately 0.1 wt%. However, up on addition to Pluronic solution, diol gets incorporated in the block copolymer micelles and leads to structural transition of the micelles. An increase in the temperature and the presence of added sodium chloride in the solution further enhances this effect. The addition of hydrophobic C(14)diol increases the hydrodynamic size and aggregation numbers of the micellar system. The micellar parameters for the copolymer in the presence of C(14)diol are reported at different temperatures and added sodium chloride concentrations.     

Improved micellar hydration and gelation characteristics of PEO-PPO-PEO triblock copolymer solutions in the presence of LiCl

LiCl-induced changes in the micellar hydration and gelation characteristics of aqueous solutions of the two triblock copolymers F127 (EO(100)PO(70)EO(100)) and P123 (EO(20)PO(70)EO(20)) (where EO represents the ethylene oxide block and PO represents the propylene oxide block) have been studied by small-angle neutron scattering (SANS) and viscometry. The effect of LiCl was found to be significantly different from those observed for other alkali metal chloride salts such as NaCl and KCl. This can be explained on the basis of the complexation of hydrated Li(+) ions with the PEO chains in the micellar corona region. The interaction between the chains and the ions is more significant in the case F127 because of its larger PEO block size, and therefore, micelles of this copolymer show an enhanced degree of hydration in the presence of LiCl. The presence of the hydrated Li(+) ions in the micellar corona increases the amount of mechanically trapped water there and compensates more than the water molecules lost through the dehydration of the PEO chains in the presence of the Cl(-) ions. The enhancement in micellar hydration leads to a decrease in the minimum concentration required for the F127 solution to form a room-temperature cubic gel phase from 18% to 14%. Moreover, for both copolymers, the temperature range of stability of the cubic gel phase also increases with increasing LiCl concentration, presumably because of the ability of the Li(+) ions to reduce micellar dehydration with increasing temperature. Viscosity studies on a poly(ethylene glycol) (PEG) homopolymer with a size equivalent to that of the PEO block in F127 (4000 g/mol) also suggest that the dehydrating effect of the Cl(-) ion on the PEG chain is compensated by its interaction with the hydrated Li(+) ions.     

Molecular implications in the nanoencapsulation of the anti-tuberculosis drug rifampicin within flower-like polymeric micelles

Tuberculosis (TB) is the second most deadly infectious disease behind the Human Immunodeficiency Virus (HIV). An effective pharmacotherapy has been available for more than 5 decades. However, the length of the treatment and the pill burden result in low patient compliance and adherence to the regimens. Nanotechnologies can overcome these basic technological drawbacks. The present work explored the molecular implications governing the encapsulation and water solubilization of RIF within flower-like micelles of poly(epsilon-caprolactone)-b-poly(ethylene glycol)-poly(epsilon-caprolactone) (PCL-PEG-PCL) block copolymers. Ten derivatives of different molecular weight and hydrophobic/hydrophilic caprolactone/ethylene oxide ratio (CL/EO) were synthesized by a fast and high-yield Microwave-Assisted Polymer Synthesis (MAPS) technique; CL/EO values are determined by taking the ratios of the number of repeating units in the PCL and the PEG segments. The aggregation behavior of the copolymers was thoroughly investigated by means of surface tension (critical micellar concentration), dynamic light scattering (size, size distribution and zeta potential) and transmission electron microscopy (morphology). In general, the greater the central PEG segment, the larger the micelles formed. The physical stability was intimately associated with the molecular weight and the composition. Then, the encapsulation of RIF in the different copolymer families was evaluated, and the physical stability of the drug-loaded aggregates characterized. The micellar size appears as the most crucial property, this phenomenon being primarily controlled by the molecular weight of the PEG central block. Having expressed this, sufficiently high CL/EO ratios (and long PCL segments) are also demanded to attain stable micellar systems with cores that are large enough to host the bulky RIF molecule.     

Interaction between cationic, anionic, and non-ionic surfactants with ABA block copolymer Pluronic PE6200 and with BAB reverse block copolymer Pluronic 25R4

The interaction in aqueous solution between either the normal block copolymer poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide): Pluronic PE6200 [(EO)(11)-(PO)(28)-(EO)(11)], or the reverse block copolymer poly(propylene oxide)-poly(ethylene oxide)-poly(propylene oxide): Pluronic 25R4 [(PO)(19)-(EO)(33)-(PO)(19)] and the surfactants sodium decylsulfate, C(10)OS, decyltrimethyl ammonium bromide, C(10)TAB, and pentaethylene glycol monodecyl ether, C(10)E(5), was investigated and the aggregation behavior of these surfactants with Pluronics was compared. Surface tension measurements show that Pluronics in their non-aggregated state better interact with the anionic surfactant C(10)OS than with cationic and non-ionic ones. The presence of the two Pluronics induces the same lowering of the aggregation number of C(10)OS as shown by fluorescence quenching measurements. The number of polymer chains necessary to bind each C(10)OS aggregate has been estimated to be approximately 6 for PE6200 and approximately 2 for 25R4. Furthermore, this surfactant also induces the same increment in the gyration radius of the polymers as revealed by viscosimetry. Calorimetric results have been reasonably reproduced by applying a simple equilibrium model to the aggregation processes.     

荧光探针法研究PEO-PPO嵌段共聚物胶束的特性

利用十六烷基罗丹明Ｂ作为主要荧光探针，研究了水溶性嵌段共聚物Ｐｌｕｒｏｎｉｃ Ｆ－６８在水溶液中的胶束化行为，研究表明，Ｐｌｕｒｏｎｉｃ－Ｆ－６８形成胶束的监界胶束浓度与温度有极大关系，随温度的升高，其ＣＭＣ值急剧下降，并且温度对胶束的性质也有很大，影响温度升高可导致胶束的微观粘度增大，表现出很强的负粘－温效应，并发现引起这种负粘－温效应的主要原因是Ｐｌｕｒｏｎｉｃ Ｆ－６８分子中聚环氧乙烷（ＰＥ     

Synthesis and micellar behavior of poly(vinyl alcohol-<Emphasis Type="Italic">b</Emphasis>-styrene) copolymers containing PVA blocks with different syndiotacticity

Poly(vinyl alcohol-b-styrene) (poly(VA-b-St)) diblock copolymers with different syndiotacticity of poly(vinyl alcohol) (PVA) block were synthesized via consecutive telomerization, atom transfer radical polymerization, and saponification. These amphiphilic block copolymeric micelles were prepared by dialysis against water. Dynamic light scattering and transmission electron micrograph measurements confirmed the formation of a micelles, and the size of a micelle was less than 100 nm and increased with the molecular weight of polystyrene (PS) block. From the fluorescence emission spectrum measurements using pyrene as a fluorescence probe, the copolymers formed micelles with critical micelle concentration (CMC) in the range of 0.125–4.47 mg/l. The CMC values increase with decrease of the molecular weight of the PS block and increase of the syndiotacticity of PVA block. Kinetic stability study of micelles showed increased stability for block copolymers containing PVA block with higher syndiotacticity.