Tuning of the Temperature Window for Unit‐Cell and Pore‐Size Enlargement in Face‐Centered‐Cubic Large‐Mesopore Silicas Templated by Swollen Block Copolymer Micelles

The unit‐cell size and pore diameter as functions of temperature are investigated in the syntheses of FDU‐12 silicas with face‐centered cubic structure templated by Pluronic (PEO‐PPO‐PEO) block copolymer micelles swollen by toluene. The temperature range in which the unit‐cell size and pore size strongly increase as temperature decreases is correlated with the critical micelle temperature (CMT) of the surfactant. While Pluronic F127 affords a wide range of unit‐cell parameters (28–51 nm) and pore diameters (16–32 nm), it renders moderately enlarged pore sizes at 25 °C. The use of Pluronic F108 with higher CMT affords FDU‐12 with very large unit‐cell size (～49 nm) and large pore diameter (27 nm) at 23 °C. Large unit‐cell size (40–41 nm) and pore size (22 nm) were obtained even at 25 °C. The application of Pluronics F87 and F88 with much smaller molecular weights and higher CMTs also allows one to synthesize FDU‐12 with quite large unit‐cell parameters and pore sizes at room temperature. The present work demonstrates that one can judiciously select Pluronic surfactants with appropriate CMT to shift the temperature range in which the pore diameter is readily tunable.     

Pore size engineering in mesoporous silicas using supercritical CO2

In this paper we investigate the use of supercritical carbon dioxide (sc-CO(2)) for synthesizing calcined mesoporous silicas with tunable pore sizes, wall thickness, and d spacings. Small angle neutron scattering was used to probe the controlled swelling of the triblock copolymer surfactant templating agents, P123 (PEO(20)PPO(69)PEO(20)), P85 (PEO(26)PPO(39)PEO(26)), and F127 (PEO(106)PPO(70)PEO(106)), as a function of CO(2) pressure. The transition from the liquid crystal phase to the calcined mesoporous silicas, formed upon condensation and drying, was also studied in detail. Powder X-ray diffraction, transmission electron microscopy, and nitrogen adsorption techniques were used to establish pore diameters, silica wall widths, and the hexagonal packing of the pores within the calcined silicas. Using a direct templating method, the diameters of mesopores and the spacing between the pores could be tuned with a high level of precision. The swelling process was observed to have no detrimental effects on the quality of silica formed, a distinct advantage over conventional swelling techniques, and all of the silicas synthesized in this study were highly ordered over distances of at least 2000 A.     

Microviscosity in poly(ethylene oxide)‐polypropylene oxide‐poly(ethylene oxide) block copolymers probed by fluorescence depolarization kinetics

Triblock copolymers [poly(ethylene oxide) (PEO) and polypropylene oxide (PPO)], Pluronic F127 with 100 PEO blocks on each end, and 65 blocks of PPO in the center were examined in aqueous solution. The “sol” and “gel” phase diagram was determined as a function of concentration and temperature. For further study, the concentration was fixed at 20 wt %, and the temperature dependence of the dynamic viscosity differed from the temperature dependence of fluorescence emission spectra and the microviscosity probed by the fluorescence depolarization kinetics of rhodamine 123 dye, which was dissolved in the continuous hydrophilic phase. The depolarization measurements used single‐photon counting after two‐photon excitation with a Ti‐sapphire femtosecond laser. Although the viscoelastic modulus increased by an order of magnitude when the sol‐to‐gel transition was crossed, the microviscosity of the hydrophilic continuous medium showed only minor changes. At different temperatures the fluorescence lifetime was the same with a single‐exponential time constant, but the fluorescence depolarization displayed a double‐exponential decay. After comparison with fluorescence depolarization of the dye in PPO melt and PEO whose molecular weight and aqueous concentrations were varied, the relative proportions of faster and slower components of the fluorescence depolarization were tentatively attributed to varying ratios of the dye in free solution and associated with micelles. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 2883–2888, 2002     

Preparation of a Macroporous Poly(L‐lactide) Scaffold by Liquid‐Liquid Phase Separation of a PLLA/1,4‐Dioxane/Water Ternary System in the Presence of NaCl

A novel method for preparing regular and highly interconnected macroporous poly(L ‐lactic acid) (PLLA) scaffolds is presented. Scaffolds with pore sizes ranging from 50 to 300 μm were fabricated from a PLLA/1,4‐dioxane/water ternary system via a thermally induced phase separation (TIPS) in the presence of small amounts of NaCl (⩽0.1 wt.‐%). The addition of salt had the following effects. The cloud‐point temperature was raised because of a salt‐out effect. Spinodal decomposition was induced at a higher temperature with a large quench depth. Gelation due to the crystallization of PLLA was prevented to a large extent, which led to the creation of the highly interconnected macropores required for effective cell penetration.     

Effect of chain lengths of PEO-PPO-PEO on small unilamellar liposome morphology and stability: an AFM investigation

The morphology and stability of small unilamellar egg yolk phosphatidylcholine (EggPC) liposomes modified with the Pluronic copolymer (poly (oxyethylene)-poly (oxypropylene)-poly (oxyethylene) (PEO-PPO-PEO)) with different compositions on mica surface have been investigated using atomic force microscopy. Morphology studies reveal significant morphological changes of liposomes upon incorporating the Pluronic copolymer. Bilayers are observed for Pluronic with small hydrophilic (PEO) chain lengths such as L81 [(PEO)2(PPO)40(PEO)2] and L121 [(PEO)4(PPO)60(PEO)4]; bilayer and vesicle coexistence is observed for P85 [(PEO)26(PPO)39.5(PEO)26] and F87 [(PEO)61.1(PPO)39.7(PEO)61.1]; and stable vesicles are observed for F88 [(PEO)103.5(PPO)39.2(PEO)103.5], F127 [(PEO)100(PPO)65(PEO)100], and F108 [(PEO)132.6(PPO)50.3(PEO)132.6]. The micromechanical properties of Pluronic-modified EggPC vesicles were studied by analyzing AFM approaching force curve. The bending modulus (k(c)) of the Pluronic-modified EggPC vesicles increased several-fold compared with that of the pure EggPC vesicles. The significant difference is due to the enhanced rigidity of the EggPC vesicles as a result of the incorporation of PPO molecules and PEO chains. Based on the analysis of onset point by AFM and diameters of vesicles by light scattering, it was concluded that the favorable model to describe the polymer-bilayer interaction is the membrane-spanning model.     

Synthesis, Characteristics and Evaluation of a New Monolithic Silica Column Prepared from Copolymer Pluronic F127

Monolithic silica columns were prepared via a sol–gel process using tri-block copolymer Pluronic F127 as structure-directing reagent. In this reaction, F127 induced phase separation but also acted as a template leading to a continuous structure of silica skeletons and textural pores as well as the formation of mesopores. The morphology of the monolithic materials was studied by scanning electron microscopy. The capability of separation and loading on this column were demonstrated. Phosphatidylcholine was separated from soy lecithin, demonstrating fast and efficient performance when the column was used for normal phase liquid chromatography.     

Phase behavior,crystallization, and nanostructures in thermoset blends of epoxy resin and amphiphilic star‐shaped block copolymers

This article reports thermoset blends of bisphenol A‐type epoxy resin (ER) and two amphiphilic four‐arm star‐shaped diblock copolymers based on hydrophilic poly(ethylene oxide) (PEO) and hydrophobic poly(propylene oxide) (PPO). 4,4′‐Methylenedianiline (MDA) was used as a curing agent. The first star‐shaped diblock copolymer with 70 wt % ethylene oxide (EO), denoted as (PPO‐PEO)₄, consists of four PPO‐PEO diblock arms with PPO blocks attached on an ethylenediamine core; the second one with 40 wt % EO, denoted as (PEO‐PPO)₄, contains four PEO‐PPO diblock arms with PEO blocks attached on an ethylenediamine core. The phase behavior, crystallization, and nanoscale structures were investigated by differential scanning calorimetry, transmission electron microscopy, and small‐angle X‐ray scattering. It was found that the MDA‐cured ER/(PPO‐PEO)₄ blends are not macroscopically phase‐separated over the entire blend composition range. There exist, however, two microphases in the ER/(PPO‐PEO)₄ blends. The PPO blocks form a separated microphase, whereas the ER and the PEO blocks, which are miscible, form another microphase. The ER/(PPO‐PEO)₄ blends show composition‐dependent nanostructures on the order of 10?30 nm. The 80/20 ER/(PPO‐PEO)₄ blend displays spherical PPO micelles uniformly dispersed in a continuous ER‐rich matrix. The 60/40 ER/(PPO‐PEO)₄ blend displays a combined morphology of worm‐like micelles and spherical micelles with characteristic of a bicontinuous microphase structure. Macroscopic phase separation took place in the MDA‐cured ER/(PEO‐PPO)₄ blends. The MDA‐cured ER/(PEO‐PPO)₄ blends with (PEO‐PPO)₄ content up to 50 wt % exhibit phase‐separated structures on the order of 0.5–1 μm. This can be considered to be due to the different EO content and block sequence of the (PEO‐PPO)₄ copolymer. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 975–985, 2006     

The Effects of Salts and Ionic Surfactants on the Micellar Structure of Tri‐Block Copolymer PEO‐PPO‐PEO in Aqueous Solution

The micelles of two poly(ethylene oxide)‐poly(propylene oxide)‐poly(ethylene oxide) (PEO‐PPO‐PEO) block copolymers, P123 and F127 (same mol wt of PPO but different % PEO) in aqueous solution in the absence and presence of salts as well as ionic surfactants were mainly examined by dynamic light scattering (DLS). The study is further supported by cloud point and viscosity measurements. The change in cloud point (CP), as well as the size of micelles in aqueous solution in presence of salts obeys the Hofmeister lyotropic series. Addition of both cationic cetylpyridinium chloride (CPC) and anionic sodium dodecylsulfate (SDS) surfactants in the aqueous solution of P123 show initial decrease of micellar size from 20 nm to nearly 7 nm and then increasing with a double relaxation mode, further in the presence of NaCl this double relaxation mode vanishes. The effect of surfactant on F127, which has much bigger hydrophilic part is different than P123 and have no double relaxation. The relaxation time distributions is obtained using the Laplace inversion routine REPES. Two relaxation modes for P123 are explained on the bases of Pluronic rich mixed micelles containing ionic surfactants and the other smaller, predominantly surfactant rich micelles domains.     

Modification of the lyotropic liquid crystalline microstructure of amphiphilic block copolymers in the presence of cosolvents

This article reviews the results of recent investigations on the macroscopic (phase behavior) and microscopic (microstructure) aspects of the role of cosolvents on the self-assembly of amphiphilic copolymers. A comprehensive account of the systematic studies performed in ternary isothermal systems consisting of a representative poly(ethylene oxide)–poly(propylene oxide)–poly(ethylene oxide) (PEO–PPO–PEO) block copolymer (Pluronic P105, EO₃₇PO₅₈EO₃₇), water and a polar cosolvent (such as glycerol, propylene glycol or ethanol) is presented. The effect of cosolvents on the copolymer phase behavior is quantified in terms of the highest cosolvent/water ratio able to maintain the liquid crystalline structures. The effect of cosolvents on the microstructure of the lyotropic liquid crystals is quantified in terms of the degree of relative swelling per cosolvent content per copolymer content, a parameter that characterizes the given cosolvent and copolymer. The set of correlations on the cosolvent effects on the phase behavior or microstructure to the cosolvent physicochemical characteristics (such as octanol/water partition coefficient or solubility parameter) have led to the development of a hypothesis that accounts for the cosolvent effects on the self-assembly of PEO–PPO–PEO block copolymers and can be used to predict them. The rich structural diversity and the potential for a precise and convenient modification of the lyotropic liquid crystalline microstructure of the PEO–PPO–PEO block copolymers is discussed in comparison to the phase behavior of the low-molecular nonionic surfactants.     

Phase behavior and local dynamics of concentrated triblock copolymer micelles

We report a neutron-scattering study to characterize the ordering and local dynamics of spherical micelles formed by the triblock copolymer polyethylene oxide (PEO)--polypropylene oxide (PPO)--polyethylene oxide (Pluronic) in aqueous solution. The study focuses on two Pluronic species, F68 and F108, that have the same weight fraction of PEO but that differ in chain length by approximately a factor of 2. At sufficiently high concentration, both species undergo a sequence of phase changes with increasing temperature from dissolved chains to micelles with liquid-like order to a cubic crystal phase and finally back to a micelle liquid phase. A comparison of the phase diagrams constructed from small-angle neutron scattering indicates that crystallization is suppressed for shorter chain micelles due to fluctuation effects. The intermediate scattering function I(Q,t)I(Q,0) determined by neutron spin echo displays a line shape with two distinct relaxations. Comparisons between I(Q,t)I(Q,0) for fully hydrogenated F68 chains in D2O and for F68 with deuterated PEO blocks reveal that the slower relaxation corresponds to Rouse modes of the PPO segments in the concentrated micelle cores. The faster relaxation is identified with longitudinal diffusive modes in the PEO corona characteristic of a polymer brush.     

Effect of chain length on binding of fatty acids to Pluronics in microemulsions

We investigated the effect of fatty acid chain length on the binding capacity of drug and fatty acid to Pluronic F127-based microemulsions. This was accomplished by using turbidity experiments. Pluronic-based oil-in-water microemulsions of various compositions were synthesized and titrated to turbidity with concentrated Amitriptyline, an antidepressant drug. Sodium salts of C(8), C(10), or C(12) fatty acid were used in preparation of the microemulsion and the corresponding binding capacities were observed. It has been previously determined that, for microemulsions prepared with sodium caprylate (C(8) fatty acid soap), a maximum of 11 fatty acid molecules bind to the microemulsion per 1 molecule of Pluronic F127 and a maximum of 12 molecules of Amitriptyline bind per molecule of F127. We have found that with increasing the chain length of the fatty acid salt component of the microemulsion, the binding capacity of both the fatty acid and the Amitriptyline to the microemulsion decreases. For sodium salts of C(8), C(10) and C(12) fatty acids, respectively, a maximum of approximately 11, 8.4 and 8.3 molecules of fatty acid molecules bind to 1 Pluronic F127 molecule. We propose that this is due to the decreasing number of free monomers with increasing chain length. As chain length increases, the critical micelle concentration (cmc) decreases, thus leading to fewer monomers. Pluronics are symmetric tri-block copolymers consisting of propylene oxide (PO) and ethylene oxide (EO). The polypropylene oxide block, PPO is sandwiched between two polyethylene oxide (PEO) blocks. The PEO blocks are hydrophilic while PPO is hydrophobic portion in the Pluronic molecule. Due to this structure, we propose that the fatty acid molecules that are in monomeric form most effectively diffuse between the PEO "tails" and bind to the hydrophobic PPO groups.     

Controlled synthesis and association behavior of graft Pluronic in aqueous solutions

Poly(vinyl pyrrolidone) (PVP) was grafted onto Pluronic F127 (PEO-PPO-PEO) to produce novel amphiphilic PVP-g-F127 graft copolymers. A controlled synthesis method was used to graft PVP onto different parts of F127. Two types of graft polymers were obtained: one has PVP grafted onto the PEO part of F127 and the other has PVP grafted onto the PPO part of F127. The association behavior of the two modified polymers was examined using differential scanning calorimetry, surface tension measurements, and dynamic light scattering.     

Shape memory polymers with interconnected nanopores and high mechanical strength

The fabrication of shape memory polymers with both interconnected nanopores and high mechanical strength is challenging. In this work, porous shape memory polymers (PSMPs) were prepared based on the combination of crystallization and phase separation in a ternary blend of poly(l ‐lactic acid)/polyvinyl acetate/poly(ethylene oxide) (i.e., PLLA/PVAc/PEO). The phase separation between the PLLA and PVAc/PEO resulted in bicontinuous structures in microscale including a PLLA‐rich phase and a mixed PVAc/PEO phase. On one hand, the continuous PLLA‐rich phase contributed to the high mechanical strength and shape memory performance, in which tiny crystals and amorphous matrix of PLLA act as the shape fixed phase and reversible phase, respectively. On the other hand, the crystallization of PEO in the miscible PVAc/PEO blend produced submicrometer bicontinuous structures. The interconnected nanopores have been obtained by selective etching of the PEO. Our strategy opens a new avenue for fabricating PSMPs with both interpenetrated channels and high strength. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2018 , 56, 125–130     

Synthesis of micrometer-sized hard silica spheres with uniform mesopore size and textural pores

Micrometer-sized silica spheres were prepared using a new pH-induced rapid colloid aggregation method in water-in-oil (W/O) emulsion separately with F127 and the mixture of Pluronic triblock copolymer (F127, P123, or P105) and PEG20000 as templates. All the mesoporous silica spheres exhibited high surface areas (657-1145 m2/g) and large pore volumes (0.46-2.16 ml/g). Through optimizing the synthetic conditions, hard silica spheres with narrow particle size distribution, uniform pore size, and textural pores were obtained. Finally, the mechanism of this synthetic route is discussed.     

Thermodynamics of temperature-sensitive polyether-modified poly(acrylic acid) microgels

The temperature-induced structural changes and thermodynamics of ionic microgels based on poly(acrylic acid) (PAA) networks bonded with poly(ethylene oxide)-b-poly(propylene oxide)-b-poly(ethylene oxide) (PEO-PPO-PEO) (Pluronic) copolymers have been studied by small-angle neutron scattering (SANS), ultra-small-angle neutron scattering (USANS), differential scanning calorimetry (DSC), and equilibrium swelling techniques. Aggregation within microgels based on PAA and either the hydrophobic Pluronic L92 (average composition, EO8PO52EO8; PPO content, 80%) or the hydrophilic Pluronic F127 (average composition, EO99PO67EO99; PPO content, 30%) was studied and compared to that in the solutions of the parent Pluronic. The neutron scattering results indicate the formation of micelle-like aggregates within the F127-based microgel particles, while the L92-based microgels formed fractal structures of dense nanoparticles. The microgels exhibit thermodynamically favorable volume phase transitions within certain temperature ranges due to reversible aggregation of the PPO chains, which occurs because of hydrophobic associations. The values of the apparent standard enthalpy of aggregation in the microgel suspensions indicate aggregation of hydrophobic clusters that are more hydrophobic than the un-cross-linked PPO chains in the Pluronic. Differences in the PPO content in Pluronics L92 and F127 result in a higher hydrophobicity of the resulting L92-PAA-EGDMAmicrogels and a larger presence of hydrophobic, densely cross-linked clusters that aggregate into supramolecular structures rather than micelle-like aggregates such as those formed in the F127-PAA-EGDMA microgels.     

Dopant-Mediated Interactions in a Lecithin Lamellar Phase

Interactions induced by dopants in a lamellar phase constructed from the lecithin and water are analyzed by the small angle x-ray scattering (SAXS) technique. From SAXS patterns, scattering peak or curve shape changes disclose information on phase structure as well as the interactions between dopant and host matrices. At a certain concentration, two amphiphilic tri-block copolymers (Pluronic P123 and F127) as dopants squeeze themselves into the lecithin bilayers with PPO hydrophobic blocks and produce various effects on the lamellar phase depending on the length of PEO hydrophilic groups. Coexistence of two different lamellar phases is observed in P123-doped systems.     

Effects of poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) triblock copolymers on structure and stability of liposomal dioleoylphosphatidylethanolamine

The effects caused by poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) (PEO-PPO-PEO; Pluronic) copolymers on the structure and stability of dioleoylphosphatidylethanolamine (DOPE) liposomes were studied by means of turbidity, leakage, and cryo-transmission electron microscopy investigations. The results show that by inclusion of Pluronics in the DOPE dispersion it is possible to stabilize the lamellar Lalpha phase and to produce liposomes that are stable and nonleaky at low pH (pH 5). The stabilizing capacity was observed to depend critically on the molecular composition of the Pluronics. Block copolymers with comparably long PPO and PEO segment lengths, such as F127 and F108, most effectively protected DOPE liposomes prepared at high pH from aggregation and subsequent structural rearrangements induced by acidification. A sufficiently long PPO block was found to be the most decisive parameter in order to obtain adequate coverage of the liposome surface at low Pluronic concentrations. Upon increasing the copolymer concentration, however, Pluronics with comparably short PPO and PEO segment lengths, such as F87 and P85, could also be used to stabilize the DOPE liposomes. Essentially the same trends were observed when the Pluronics were added to preformed DOPE liposomes instead of being included in the preparation mixture. In this case the least effective copolymers failed, however, to completely prevent the DOPE liposomes from releasing encapsulated hydrophilic markers.     

Thermosensitive and Dissolution Properties in Nanocomposite Polymer Hydrogels

We investigate the phase transition behavior and dissolution resistant properties of thermo‐sensitive nanocomposite hydrogels made from PEO‐PPO‐PEO triblock copolymer (Pluronic F127) and Laponite silicate nanoparticles. The rapid dissolution properties of F127 copolymer hydrogels usually limit their use as sustained release drug carriers. We overcome this limitation by synergistic combination of nanoparticle gelation characteristics with polymer thermo‐sensitivity. We present a proof of concept that the temperature‐dependent phase transitions can be shifted as a function of hydrogel composition and that the dissolution of the polymer hydrogels as well as the release of a model drug, albumin, can be significantly slowed down by addition of nanoparticles. The dissolution resistant properties generated will prove useful in the future formulation, processing and application of our polymer hydrogels for sustained release drug delivery carriers.

     

Influence of NaCl on the behavior of PEO-PPO-PEO triblock copolymers in solution, at interfaces, and in asymmetric liquid films

The solution behavior of the polymeric surfactant Pluronic F127 (PEO(99)PPO(65)PEO(99)) and its adsorption behavior on aqueous-silica and aqueous-air interfaces, as well as the disjoining pressure isotherms of asymmetric films (silica/aqueous film/air) containing F127, are studied. The interfacial properties of adsorbed F127 layers (the adsorbed amount Gamma and the thickness h) as well as the aqueous wetting film properties [film thickness (h) and refractive indexes] were studied via ellipsometry. The solution properties of F127 were investigated using surface tensiometry and light scattering. The interactions between the air-water and silica-water interfaces were measured with a thin film pressure balance technique (TFB) and interpreted in terms of disjoining pressure as a function of the film thickness. The relations between the behaviors of the asymmetric films, adsorption at aqueous air, and aqueous silica interfaces and the solution behavior of the polymeric surfactant are discussed. Special attention is paid to the influence of the concentrations of F127 and NaCl. Addition of electrolyte lowers the critical micelle concentration, diminishes adsorption on silica, and increases the thickness of the asymmetric film.     

A viscosity-tunable polymer for DNA separation by microchip electrophoresis

A thermo-responsive separation matrix, consisting of Pluronic F127 tri-block copolymers of poly(ethylene oxide) and poly(propylene oxide), was used to separate DNA fragments by microchip electrophoresis. At low temperature, the polymer matrix was low in viscosity and allowed rapid loading into a microchannel under low pressure. With increasing temperatures above 25°C, the Pluronic F127 solution forms a liquid crystalline phase consisting of spherical micelles with diameters of 17–19 nm. The solution can be used to separate DNA fragments from 100 bp to 1500 bp on poly(methyl methacrylate) (PMMA) chips. This temperature-sensitive and viscosity-tunable polymer provided excellent resolution over a wide range of DNA sizes. Separation is based on a different mechanism compared with conventional matrices such as methylcellulose. To illustrate the separation mechanism of DNA in a Pluronic F127 solution, DNA molecular imaging was performed by fluorescence microscopy with F127 polymer as the separation matrix in microchip electrophoresis. Figure Temperature dependence of the viscosity of 20% w/w Pluronic F127 solution in 1xTBE buffer. Dotted approximates resultant curve.