Self-diffusion study of poly (ethylene oxide)-poly (propylene oxide)-poly (ethylene oxide) block copolymers in aqueous solution

The self-diffusion of poly (ethylene oxide)-poly (propylene oxide)-poly (ethylene oxide) block copolymers dissolved in deuterated water was investigated by means of pulsed field gradient NMR (PFG-NMR). The polymer forms micelles in the solution and, with increasing temperature, clouding and phase demixing occurs. The self-diffusion coefficient indicates the association of the polymer molecules in the vicinity of the cloud point because of its maximum with increasing temperature. Above the cloud point, two kinds of diffusing species are observed due to phase separation. The faster diffusing species is attributed to the polymer-poor phase. The self-diffusion coefficient of the polymer-rich phase species decreases with increasing temperature above the cloud point due to further association and dehydration. The correlation length of the diffusing associates, calculated from the self-diffusion coefficient and the viscosity by means of the Stokes-Einstein equation is nearly independent of temperature and concentration up to 30 wt-% polymer concentration. The correlation length is about 1.4 nm. It shows a slight maximum at the cloud point.     

Effect of the structure of ethylene oxide-propylene oxide block copolymers on their interaction with biological membranes

Partition coefficients of ethylene oxide-propylene oxide block copolymers between the lipid phase and water have been estimated via equilibrium dialysis. It has been shown that for the triblock copolymer (Pluronic L61), the partition coefficient is 45 ± 9, while for the diblock copolymer (REP), this parameter is as high as 78 ± 17. The effect of the copolymers on the permeation of the charged organic ion carboxyfluorescein across the lecithin bilayer membrane changes in the same direction. Even though the triblock copolymer binding is weaker, it shows a stronger effect on the rate of transbilayer migration of lipids and on the permeation of the uncharged substance (doxorubicin). The incorporation of cholesterol into the membrane decreases its sensitivity to the action of copolymers; however, the character of changes induced by both copolymers remains invariable. The experimental data of this study indicate that the triblock structure of amphiphilic macromolecules is responsible for their higher ability to disturb lipid bilayer membranes.     

水溶性聚合物和两亲聚合物:12.环氧乙烷-环氧丙烷无规共聚醚结构与性能的关系

来用连续加料法,以二元醇-KOH为引发剂合成一组不同组成的环氧乙烷-环氧丙烷无规共聚醚,并用核磁共振、红外光谱、示差扫描量热计和热失重等方法对其本体聚合物,用浊点和表面张力测定的方法对其水溶液,进行系统的表征。     

Synthesis and properties of segmented block copolymers based on mixtures of poly(ethylene oxide) and poly(tetramethylene oxide) segments

The synthesis and characterisation of segmented block copolymers based on mixtures of hydrophilic poly(ethylene oxide) and hydrophobic poly(tetramethylene oxide) polyether segments and monodisperse crystallisable bisester tetra-amide segments are reported. The PEO length was varied from 600 to 8000 g/mol and the PTMO length was varied from 650 to 2900 g/mol. The influence of the polyether phase composition on the thermal mechanical and the elastic properties of the resulting copolymers was studied.The use of high melting monodisperse tetra-amide segments resulted in a fast and almost complete crystallisation of the rigid segment. The copolymers had only one polyether glass transition temperature, which suggests that the amorphous polyether segments were homogenously mixed. Thermal analysis of the copolymers showed one polyether melting temperature that was lower than in the case of ideal co-crystallisation between the two polyether segments. However, at PEO or PTMO lengths larger than 2000 g/mol two polyether melting temperatures were observed. The copolymer with the best low temperature properties was based on a mixture of PEO and PTMO segments, both having a molecular weight of 1000 g/mol, at a weight ratio of 30/70.     

Full separation of oligomers in block copolymers of ethylene oxide and propylene oxide

In this study di‐ and triblock copolymers of ethylene oxide (EO) and propylene oxide (PO) are analyzed by using CAP for one block and adsorption for the other block. This gives a complete picture of EO‐ and PO‐based block copolymer with respect to the oligomers of both blocks. A full resolution of the individual oligomers can be achieved for both blocks up to an average molecular weight of 1000–1500 of each block.     

Thermoreversible gelation of poly(ethylene oxide) biodegradable polyester block copolymers. II

Poly(ethylene oxide)-b-poly(L-lactic acid) (PEO-PLLA) diblock copolymers were synthesized via a ring opening polymerization from poly(ethylene oxide) and l -lactide. Stannous octoate was used as a catalyst in a solution polymerization with toluene as the solvent. Their physicochemical properties were investigated by using infrared spectroscopy, ¹H-NMR spectroscopy, gel permeation chromatography, and differential scanning calorimetry, as well as the observational data of gel-sol transitions in aqueous solutions. Aqueous solutions of PEO-PLLA diblock copolymers changed from a gel phase to a sol phase with increasing temperature when their polymer concentrations are above a critical gel concentration. As the PLLA block length increased, the gel-sol transition temperature increased. For comparison, diblock copolymers of poly(ethylene oxide)-b-poly(l -lactic acid-co-glycolic acid) [PEO-P(LLA/GA)] and poly(ethylene oxide)-b-poly(dl -lactic acid-co-glycolic acid) [PEO-P(DLLA/GA)] were synthesized by the same methods, and their gel-sol transition behaviors were also investigated. The gel-sol transition properties of these diblock copolymers are influenced by the hydrophilic/hydrophobic balance of the copolymer, block length, hydrophobicity, and stereoregularity of the hydrophobic block of the copolymer. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 2207–2218, 1999     

Self-aggregation and phase behavior of poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) block copolymers in aqueous solution

The phase behavior and aggregation properties of block copolymers of poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) (Pluronics, poloxamers) in aqueous solution have recently attracted much attention. Both experimental and theoretical studies are reviewed, not comprehensively, but with the focus on studies, partly cooperative, partly independent, performed by groups in Uppsala (light scattering and fluorescence), Roskilde (rheology and calorimetry), Risø (SANS), Graz (x-ray and speed of sound), and Lund (theoretical model calculations).The phase behavior of these copolymers is similar in many respects to that of conventional nonionic surfactants, with the appearance of hexagonal, cubic, and lamellar liquid crystalline phases at high concentrations. In the isotropic solution phase the critical concentration for micelle formation is strongly temperature dependent, and at a given concentration the monomer to micelle transition occurs gradually over a broad temperature range, partly due to the broad size polydispersity of both the PO- and EO-blocks. For some Pluronic copolymers a transition from globular to long rod-like micelles occurs above a transition temperature, resulting in a strong and sudden increase of viscosity and viscoelasticity of the solution.Size and aggregation numbers have been determined for the globular micelles in some cases, and also the rod-like micelles have been characterized. NMR and fluorescence measurements have provided further information on the properties of the micellar core and mantle. In combination, results from different measurements on the same Pluronics material indicate that the aggregation number of the micelles increases with the temperature, whereas the hydrodynmic radius varies much less. The PEO-mantle of the micelles seems to contract with increasing temperature. The core appears to contain appreciable amounts of PEO in addition to PPO (and also some water). The segregation between core and mantle is not as distinct as in normal micelles, a conclusion which is in line with the predictions from the model calculations.     

Synthesis and aqueous solution properties of functionalized and thermoresponsive poly(D,L-lactide)/polyether block copolymers

Tri- and pentablock amphiphilic copolymers containing hydrophobic poly(D,L-lactide) block(s) and hydrophilic polyethers were synthesized in order to obtain new precursor architectures suitable for drug delivery systems. Polyglycidol-6-poly(ethylene oxide)-b-poly(D,L-lactide) possess high hydroxyl functionality provided by the linear polyglycidol block. Thus very stable hydroxyl functionalized micelles in aqueous media were obtained. On the other hand poly(D,L-lactide)-b-poly(ethylene oxide)-b-poly(propylene oxide)-b-poly(ethylene oxide)-b-poly(D,L-lactide) form temperature sensitive aggregates. The copolymers obtained were analyzed by SEC and NMR, and their aqueous solution properties were followed by cloud point measurements and determination of critical micellization temperature. TEM was used for particles visualization.     

Novel double hydrophilic block copolymers based on poly(p‐hydroxystyrene) derivatives and poly(ethylene oxide)

The synthesis of three series of double hydrophilic block copolymers (DHBCs), consisting of poly(ethylene oxide) as the neutral water soluble block and a second polyelectrolyte block of variable chemistry, is described. The synthetic scheme involves the anionic polymerization of poly(p‐tert‐butoxystyrene‐b‐ethylene oxide) (PtBOS‐PEO) amphiphilic block copolymer precursors followed by the acidic hydrolysis of the hydrophobic poly(p‐tert‐butoxystyrene) (PtBOS) block to an annealed anionic polyelectrolyte poly(p‐hydroxystyrene) (PHOS) block. The PHOS block was subsequently transformed into a high charge density annealed cationic polyelectrolyte namely poly[3,5‐bis(dimethylaminomethylene) hydroxystyrene] (NPHOS), via aminomethylation. Finally, the NPHOS block was transformed into a quenched polyelectrolyte, namely quaternized poly[3,5‐bis(dimethylaminomethylene) hydroxystyrene] (QNPHOS) block by reaction with CH₃I. The solution properties of the different series of the above block polyelectrolyte copolymers have been investigated using static, dynamic and electrophoretic light scattering, turbidimetry, and fluorescence spectroscopy. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 5790–5799, 2007     

Effect of phenol on the aggregation characteristics of an ethylene oxide-propylene oxide triblock copolymer P65 in aqueous solution

The effects of phenol on the micellization, micellar growth, and phase separation of a poly(ethylene oxide)-block-poly(propylene oxide)-block-poly(ethylene oxide) (PEO-PPO-PEO) amphiphilic copolymer (Pluronic P65: EO19 PO30 EO19) in aqueous solution have been studied by cloud point, viscosity, dynamic light scattering (DLS), differential scanning calorimetry (DSC), fluorescence spectroscopy, and small-angle neutron scattering (SANS). Various concentrations of P65 have been chosen to estimate the effect of phenol on different concentration regions of P65. Phenol interacts quite differently at low concentrations (0-2%) than at high concentrations (2-10%) of P65, as per the observation that phenol is more predominant at smaller concentrations of P65. A marked decrease in the cloud points of the P65 solutions is observed in presence of phenol. The critical micelle temperature (CMT) of P65 shows a synergistic effect of phenol on P65 aggregates. Micellar transitions, phase separation, and aggregation behaviours like micellization and micellar growth in the presence of phenol have been observed by combining viscometry, DLS, DSC, and CP. DLS shows that the effect of phenol is predominant at high temperatures. SANS shows a high increase in axial ratio and aggregation numbers in the presence of phenol at fixed concentrations of P65. Fluorescence data illustrate that addition of phenol makes micelles polar but at the same time its favours aggregation. Water-soluble phenol (present in low concentrations) forms aggregates with P65, which can be separated by cloud point extraction, making this study interesting for separation of phenol from the phenol-water system.     

Hydrophilic segmented block copolymers based on poly(ethylene oxide) and monodisperse amide segments

Segmented block copolymers based on poly(ethylene oxide) (PEO) flexible segments and monodisperse crystallizable bisester tetra‐amide segments were made via a polycondensation reaction. The molecular weight of the PEO segments varied from 600 to 4600 g/mol and a bisester tetra‐amide segment (T6T6T) based on dimethyl terephthalate (T) and hexamethylenediamine (6) was used. The resulting copolymers were melt‐processable and transparent. The crystallinity of the copolymers was investigated by differential scanning calorimetry (DSC) and Fourier Transform infrared (FTIR). The thermal properties were studied by DSC, temperature modulated synchrotron small angle X‐ray scattering (SAXS), and dynamic mechanical analysis (DMA). The elastic properties were evaluated by compression set (CS) test. The crystallinity of the T6T6T segments in the copolymers was high (>84%) and the crystallization fast due to the use of monodisperse tetra‐amide segments. DMA experiments showed that the materials had a low T_g, a broad and almost temperature independent rubbery plateau and a sharp flow temperature. With increasing PEO length both the PEO melting temperature and the PEO crystallinity increased. When the PEO segment length was longer than 2000 g/mol the PEO melting temperature was above room temperature and this resulted in a higher modulus and in higher compression set values at room temperature. The properties of PEO‐T6T6T copolymers were compared with similar poly(propylene oxide) and poly(tetramethylene oxide) copolymers. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 4522–4535, 2007     

Micellisation and gelation of diblock copolymers of ethylene oxide and propylene oxide in aqueous solution, the effect of P-block length

The aqueous solution properties of five diblock copolymers prepared by sequential anionic copolymerisation (i.e. E₁₀₂P₃₇, E₁₀₄P₅₂, E₉₂P₅₅, E₁₀₄P₆₀ and E₉₈P₇₃ where E denotes oxyethylene and P denotes oxypropylene) were studied across a wide range of concentration. The techniques used to study micellisation and micellar properties in dilute solution were static and dynamic light scattering, surface tension, and eluent gel-permeation chromatography. The gelation of concentrated solutions was also investigated. As expected, the critical micelle concentration (CMC) was lowered and the association number of the micelles was increased by an increase in P-block length. In contrast, the critical gel concentration was unchanged, consistent with the constant E-block length leading to micelles with essentially identical E-block fringes. Comparison of the CMCs of the diblock copolymers with those of triblock E_mP_nE_m copolymers with the same P-block length shows the diblock copolymers to micellise more efficiently. A similar comparison of the CMCs of the diblock copolymers with those of E_mB_n copolymer (B denotes oxybutylene) shows the hydrophobicity of a P unit to be one-sixth that of a B unit. The possibility is explored of correlating the limiting association number of a spherical micelle with the hydrophobe block length of its constituent copolymer. Of the five copolymers, only dilute solutions of E₉₈P₇₃ were predominantly micellar at both room temperature and body temperature, and this copolymer must be a prime candidate in any consideration of the potential application of E_mP_n copolymers in the solubilisation and controlled release of drugs.     

Associative block copolymers comprising poly(N‐isopropylacrylamide) and poly(ethylene oxide) end‐functionalized with a fluorophilic or hydrophilic group. Synthesis and aqueous solution properties

A series of block copolymers comprising poly(N‐isopropylacrylamide) (PNIPAM) and poly(ethylene oxide) (PEO) end‐functionalized with a quaternary ammonium group (R_Q) was synthesized by free‐radical polymerization of N‐isopropylacrylamide with well‐defined R_QPEO macroazoinitiators. The radical termination occurred mainly by disproportionation, as confirmed by combining the data from size exclusion chromatography (SEC) and rheology measurements. The copolymers denoted R_QE_xN_y differ in type of the terminal group [F_Q = C₈F₁₇(CH₃)₂N⁺ or M_Q = (CH₃)₃N⁺] and in the length of the PEO (E_x; x = 4, 6, or 10 K) and PNIPAM (N_y; y = 7 or 17–19 K) blocks. The type of the terminal group determined the behavior of the block copolymers in the dilute and semidilute regime. Self‐assembled species formed by both F_Q and M_Q modified block copolymers were detected by static light scattering measurements at 25 °C and above the lower critical solution temperature (LCST). The LCST of the block copolymers depended on the type of the R_Q group and the length of the blocks. F_Q‐modified copolymers form elastic gels below and above the LCST. It was inferred that the F_Q groups and the PNIPAM blocks form segregated microdomains that serve as junctions to maintain a viscoelastic network. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 5736–5744, 2004     

Effects of stereocomplexation on the physicochemical behavior of PLA/PEG block copolymers in aqueous solution

A series of polylactide/poly(ethylene glycol) (PLA/PEG) block copolymers were synthesized by ring‐opening polymerization of L ‐ or D ‐lactide in the presence of mono‐ or di‐hydroxyl PEG. The effects of stereocomplexation on the physicochemical behavior of PLA/PEG copolymers in aqueous solution were investigated by varying the degree of stereocomplexation or PLLA/PEG to PDLA/PEG ratio. In mixture solutions of insoluble and soluble copolymers, stereocomplexation strongly affects the solubility of the copolymers. In mixture solutions of soluble copolymers, both the size and aggregation number (N_agg) of the aggregates vary as a function of the degree of stereocomplexation. It is suggested that the size variation of the aggregates with increasing the degree of stereocomplexation is dependent on N_agg changes which are determined by two effects: the self‐adjusting of the aggregates so as to minimize the free energy and thus to increase the N_agg, and the kinetics of aggregation which tend to form more aggregates and thus to decrease the N_agg. Combination of the two opposite effects well explains the diverse variations of N_agg and size of the aggregates as a function of the degree of stereocomplexation. © 2012 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2012     

Effect of incorporated CdS nanoparticles on the crystallinity and morphology of poly(styrene‐b‐ethylene oxide) diblock copolymers

Surface‐modified CdS nanoparticles selectively dispersed in hexagonally packed poly(ethylene oxide) (PEO) cylinders of poly(styrene‐b‐ethylene oxide) (PSEO) block copolymers were prepared. The photoluminescence and ultraviolet–visible characteristics of the presynthesized CdS nanoparticles in N,N‐dimethylformamide and in PEO domains of the PSEO block copolymers were determined. Because of strong interactions between the CdS nanoparticles and PEO chains, as shown by Fourier transform infrared spectroscopy, the incorporation of the CdS nanoparticles prevented the PEO cylinders from properly crystallizing; this was confirmed by differential scanning calorimetry and wide‐angle X‐ray diffraction measurements. The intercylinder distance between the swollen and reduced‐crystallinity CdS/PEO cylinders in turn increased, as confirmed by small‐angle X‐ray scattering and transmission electron microscopy. At a high CdS concentration (43 wt % or 8.3 vol % with respect to PEO), however, the hexagonally packed cylindrical nanostructure of the PSEO diblock copolymers was destroyed. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 1220–1229, 2005     

Effect of bovine serum albumin on the micellization of poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) block copolymers in aqueous solutions by fluorescence spectroscopy

Effect of bovine serum albumin (BSA) on the temperature-dependent association behavior of poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) (PEO-PPO-PEO) block copolymers was investigated using pyrene fluorescence spectroscopy. The critical micellization temperature (CMT) of pluronics in aqueous solution was increased by the addition of BSA. A closed association model was used to obtain the standard free energies (△G0), enthalpies (△H 0), and entropies (△S 0) of micellization. The standard enthalpy and entropy of micellization for pluronic polymers in water were decreased with an increase of the BSA content. The more PPO component in the pluronic polymer, the higher the changed values of micellization enthalpy and entropy. The hydrophobic part of the pluronics, PPO, was responsible for the interaction between pluronics and BSA. Hydrophobic interaction between PPO and BSA was correlated to the alternation of the PPO-PPO interaction by the addition of BSA, which would shift the CMT toward higher temperature and alter the thermodynamic parameters of micellization for pluronics in aqueous solutions.     

Effect of stereocomplex formation between enantiomeric poly(l,l-lactide) and poly(d,d-lactide) blocks on self-organization of amphiphilic poly(lactide)-block-poly(ethylene oxide) copolymers in dilute aqueous solution

The effect of crystallization of a hydrophobic poly(lactide) block on the self-organization of biocompatible and biodegradable amphiphilic poly(lactide)-block-poly(ethylene oxide) (PLA-b-PEO) copolymers in a dilute aqueous solution has been investigated. It was demonstrated that the co-crystallization of poly(L,L-lactide) [P(L,L)LA] and poly(d,d-lactide) [P(d,d)LA] chains under equimolar mixing of P(L,L)LA₄₆-b-PEO₁₁₃ and P(d,d)LA₅₆-b-PEO₁₁₃ copolymers resulted in the formation of stable and spontaneously water-redispersible stereocomplex micelles with semicrystalline P(L,L)LA/P(d,d)LA cores. It was shown that the P(L,L)LA₄₆ / P(d,d)LA₅₆-b-PEO₁₁₃ stereo-complex micelles produced by dialysis can be potential vehicles for the anticancer agent oxaliplatin     

Hydroxyl end-capped macromers of N-vinyl-2-pyrrolidinone as precursors of amphiphilic block copolymers

Telechelic N-vinyl-2-pyrrolidinone (NVP) oligomers terminated by hydroxyl groups were prepared by radical polymerization in the presence of functional chain transfer agents. Then hydroxy-terminated poly(NVP) was used as initiator in the ring opening polymerization of ε-caprolactone (ε-CL). Experiments were performed either under basic conditions or by using SnOct₂ or ZnEt₂ as catalyst. The resulting amphiphilic AB-type block copolymers were thoroughly characterized by spectroscopic and thermal techniques. These data and fractionation in protic solvents indicated that the copolymerization products are constituted by a mixture of copolymers with a wide composition range. The water-soluble copolymer fractions formed micelles and nanoaggregates that showed an appreciable capacity of loading piroxicam, a hydrophobic non-steroidal anti-inflammatory drug. Contact angle measurements, atomic force microscopy, and surface plasmon resonance measurements indicated that the surface of films prepared from the insoluble fractions does not have antiopsonizing properties in spite of their high hydrophilicity.