Phase transfer of highly monodisperse iron oxide nanocrystals with Pluronic F127 for biomedical applications

Iron oxide nanoparticles made from the thermal decomposition method are highly uniform in all respects (size, shape, composition and crystallography), making them ideal candidates for many bioapplications. The surfactant coating on the as-synthesized nanoparticles renders the nanoparticles insoluble in aqueous solutions. For biological applications nanoparticles must be water soluble. Here we demonstrate the phase transfer of our nanoparticles with the biocompatible copolymer Pluronic F127. Transmission electron microscopy, Fourier transform infrared spectroscopy and dynamic light scattering indicate that the nanoparticles are coated discretely. Magnetic measurements show that the nanoparticles remain superparamagnetic with saturation magnetization ∼96% of the maximum theoretical value.     

Effect of Pluronic F127 on the pore structure of macrocellular biodegradable polylactide foams

Thermally induced phase separation technique was utilized to fabricate biodegradable poly(l ‐lactic acid) (PLLA) macrocellular foams which were capable of being applied in tissue engineering. The block copolymer Pluronic F127 composed of (polyethyleneoxide)‐(polypropyleneoxide)‐(polyethyleneoxide) [(PEO)‐(PPO)‐(PEO)] was used as a porogen. Water/dioxane mixtures with different volume ratios were used as solvents. The addition of Pluronic F127 could induce an appearance of large pores (50–200 μm) besides small pores (10–20 μm) or a change from a solid–liquid phase separation to a liquid–liquid phase separation. The role of Pluronic F127 depends on the water/dioxane ratios in the PLLA/dioxane/water system. The X‐ray diffraction patterns and porosity measurement results showed that Pluronic F127 was crystallized and existed on the pore wall. The effect of Pluronic F127 on changing pore structure is attributed to the occurrence of the interaction of the lipophilic PPO blocks in Pluronic F127 with PLLA clews, consequently, this results in PLLA aggregation and early phase separation on cooling. Copyright © 2004 John Wiley & Sons, Ltd.     

Capillary flow behavior of worm‐like micelles studied by small‐angle X‐ray scattering and small angle light scattering

A novel capillary flow device has been developed and applied to study the orientation of worm‐like micelles, among other systems. Small‐angle X‐ray scattering (SAXS) data from micelles formed by a Pluronic block copolymer in aqueous salt solution provides evidence for the formation of worm‐like micelles, which align under flow. A transition from a rod‐like form factor to a less persistent conformation is observed under flow. Flow alignment of worm‐like micelles formed by the low molar mass amphiphile system cetyl pyridinium chloride+sodium salicylate is studied for comparative purposes. Here, inhomogenous flow at the micron scale is revealed by streaks in the small‐angle light scattering pattern perpendicular to the flow direction. Copyright © 2006 John Wiley & Sons, Ltd.     

苯在Pluronic F127和P123胶束水溶液中的增溶动力学

发展了不分离胶束的增溶动力学数据分析模型,以此考察苯在F127和P123胶束水溶液中的增溶动力学行为.实验发现,这二种胶束增溶苯的速度较快,温度升高进一步促进了增溶.     

Mono- and Di-valent Salts as Modifiers of PEO-PPO-PEO Block Copolymer Interactions with Silica Nanoparticles in Aqueous Dispersions

Colloidal stabilization of nanoparticle dispersions is central to applications including coatings, mineral extraction, and dispersion of oil spills in oceanic environments, which often involves oil-mineral-aggregates (OMAs). We have an ongoing interest in the modulation of amphiphile micellization and adsorption behavior in aqueous colloidal dispersions in the presence of various additives. Here we evaluate the effect of added salts CaCl₂, MgCl₂, and NaCl on the micellization and adsorption behavior of the poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) triblock copolymer Pluronic P105 (EO₃₇PO₅₆EO₃₇). In 0.10 wt% silica nanoparticle (10.6 nm average diameter) dispersion, adsorbed block copolymer layer formation begins at a critical surface micelle concentration (csmc) of 0.02 wt%, well below the critical micellization concentration of Pluronic P105 in water. Dye solubilization experiments demonstrate an increase in the csmc upon addition of each salt. Each added salt reaches a level of maximum effectiveness in its ability to disfavor Pluronic P105 adsorption at the silica surface. These peak levels occur at concentrations of 0.005, 0.03, and 0.05 M for CaCl₂, MgCl₂, and NaCl, respectively, in the presence of 0.10 wt% silica nanoparticles. We explain these results in the context of an electrostatic displacer mechanism and discuss possible connections to OMA-dispersant formation.     

Sieving properties of end group‐halogenated Pluronic polymer matrix in DNA separation under nondenaturing CE analysis

CE‐SSCP analysis is a well‐established DNA separation method that is based on variations in mobility caused by sequence‐induced differences in the conformation of single‐stranded DNA. The resolution of CE‐SSCP analysis was improved by using a Pluronic polymer matrix, and it has been successfully applied in various genetic analyses. Because the Pluronic polymer forms a micellar cubic structure in the capillary, it provides a stable internal structure for high‐resolution CE‐SSCP analysis. We hypothesized that formation of micellar cubic structure is influenced by the end hydroxyl group of the Pluronic polymer, which affords structural stability through hydrogen bonding. To test this hypothesis, the hydroxyl group was halogenated to eliminate the hydrogen bonding without disturbing the polarity of polymer matrix. CE‐SSCP resolution of two DNA fragments with a single base difference was significantly worse in the halogenated polymer matrices due to band broadening. The viscoelastic properties of control (which has hydroxyl group), chlorinated, and brominated F108 solution upon heating were also investigated by rheological experiments, and we found that gelation was significantly associated with resolution. In this series of experiments, the effect of the hydroxyl group in Pluronic polymer matrix on separation resolution of CE‐SSCP analysis was demonstrated.     

Cinnamoyl Pluronic F127 as a Stimuli-Sensitive Amphiphile

Cinnamoyl Pluronic F127 (CP F127) was prepared by reacting cinnamoyl chloride and Pluronic F127. On the ¹H NMR spectrum of CP F127, 1.2 moiety of cinnamoyl group was found to be attached to one molecule of CP F127. Using pyrene as a fluorescence probe, it was found that not only Pluronic F127 but also CP F127 could be readily assembled into micelles, and the critical micelle concentration was around 0.015 mg/ml and 0.03 mg/ml, respectively. Pluronic F127 in aqueous solution (2% w/v) could form no particles in 10–20°C, but particles (ca. 30 nm in diameter) were detected on a dynamic light scattering machine in 25–40°C possibly due to the thermal micellization. However, CP F127 was assembled into particles (ca. 230 nm) even in the lower temperature range, possibly because of the intermolecular hydrophobic interaction of the cinnamoyl group. The particle size of CP F127 strongly depended on the medium temperature and UV irradiation time. CP F127 was a good emulsifier for the preparation of O/W emulsions. The oil droplet size markedly increased upon UV irradiation (254 nm, 6 W), possibly because of the photo-dimerization of cinnamoyl group, but it was little affected by the temperature change (10–40°C).     

Effect of pharmaceuticals on thermoreversible gelation of PEO-PPO-PEO copolymers

Pluronic F127, a triblock copolymer of poly(ethylene oxide) (PEO) and poly(propylene oxide) (PPO), has generated considerable interest as a drug delivery vehicle due to its ability to gel at physiological temperatures. This work examines the gelation behavior of Pluronic F127 in the presence of a series of hydrophobic pharmaceuticals, to determine whether there is any correlation between gelation and physicochemical parameters of drug solutes. The study includes the local anesthetics dibucaine, lidocaine, and tetracaine; the pharmaceutical additives methyl paraben, ethyl paraben, and propyl paraben; the anti-cancer agents paclitaxel and baccatin III; and the anti-inflammatory agent sulindac. The results indicate that the presence of local anesthetics and pharmaceutical additives allows F127 solutions to form gels at lower copolymer concentrations; local anesthetics and pharmaceutical additives also shift gelation down to a lower gelation temperature. This behavior is strongly dependent on drug solubility; poorly soluble drugs (paclitaxel, baccatin III, sulindac) do not change the lower gelation temperature or minimum F127 concentration for gelation. An equation relating the decrease in gelation temperature to drug solubility is presented, and the equation fits the data well. The results have significant positive implications on the toxicity and economic issues related to use of Pluronic F127 in drug delivery.     

Pluronic嵌段共聚物F127和P123胶束对萘、蒽、芘的增溶

35℃时F127和P123在ccm后可生成内核PO成分分别为92.7%和94.5%的胶束,后者胶束内核体积为前者的2.8倍.稠环芳烃和空胶束的第一步缔合平衡常数K₁值均随萘、蒽、芘顺序逐渐增大.萘、蒽、芘在每个F127和P123胶束中的增溶量均随胶束内核体积增大而线性增加,每个PO基团对应的增溶量比十二烷基磺酸胶束内核中相同体积对应的增溶量约大近2倍.Pluronic胶束除与稠环芳烃间具有强相互作用力外,所形成的大内核是导致大增溶量的重要因素.     

Direct determination of residual Pluronic F-68 in in-process samples from monoclonal antibody preparations by high performance liquid chromatography

A simple and sensitive high performance liquid chromatography (HPLC) method was developed to determine residual Pluronic F-68 (PF-68) in in-process samples of monoclonal antibody (MAb) preparations. The method permits the direct injection of proteinaceous samples after simple sample dilution and is able to quantitate as low as 50 mg/L of PF-68 in the presence of up to approximately 30 g/L of protein. The PF-68 molecule was separated on a restricted access reversed phase column using a step gradient and then measured by an evaporative light scattering detector (ELSD). The method was successfully applied to demonstrate PF-68 clearance in MAb purification processes. A modified colorimetric method using liquid-liquid extraction and cobalt thiocyanate to derivatize PF-68 is also described. The results obtained by both the HPLC and colorimetric methods were compared. In addition to its ease of use and simplicity, the HPLC method had better accuracy and higher throughput than the colorimetric method.