Characterization and demulsification of poly(ethylene oxide)-block-poly(propylene oxide)-block-poly(ethylene oxide) copolymers

Four poly(ethylene oxide)-block-poly(propylene oxide)-block-poly(ethylene oxide) copolymers with different molecular weights and PPO/PEO composition ratios were synthesized. The characterization of the PEO-PPO-PEO triblock copolymers was studied by surface tension measurement, UV-vis spectra, and surface pressure method. These results clearly showed that the CMC of PEO-PPO-PEO was not a certain value but a concentration range, in contrast to classical surfactant, and two breaks around CMC were reflected in both surface tension isotherm curves and UV-vis absorption spectra. The range of CMC became wider with increasing PPO/PEO composition ratio. Surface pressure Pi-A curves revealed that the amphiphilic triblock copolymer PEO-PPO-PEO molecule was flexible at the air/water interface. We found that the minimum area per molecule at the air/water interface increased with the proportion of PEO chains. The copolymers with the same mass fractions of PEO had similar slopes in the isotherm of the Pi-A curve. From the demulsification experiments a conclusion had been drawn that the dehydration speed increased with decreased content of PEO, but the final dehydration rate of four demulsifiers was approximate. We determined that the coalescence of water drops resulted in the breaking of crude oil emulsions from the micrograph.     

Maghemite nanoparticles protectively coated with poly(ethylene imine) and poly(ethylene oxide)-block-poly(glutamic acid)

Superparamagnetic iron oxide particles (SPIO) of maghemite were prepared in aqueous solution and subsequently stabilized with polymers in two layer-by-layer deposition steps. The first layer around the maghemite core is formed by poly(ethylene imine) (PEI), and the second one is formed by poly(ethylene oxide)-block-poly(glutamic acid) (PEO-PGA). The hydrodynamic diameter of the particles increases stepwise from D(h) = 25 nm (parent) via 35 nm (PEI) to 46 nm (PEI plus PEO-PGA) due to stabilization. This is accompanied by a switching of their zeta-potentials from moderately positive (+28 mV) to highly positive (+50 mV) and finally slightly negative (-3 mV). By contrast, the polydispersity indexes of the particles remain constant (ca. 0.15). M?ssbauer spectroscopy revealed that the iron oxide, which forms the core of the particles, is only present as Fe(III) in the form of superparamagnetic maghemite nanocrystals. The magnetic domains and the maghemite crystallites were found to be identical with a size of 12.0 +/- 0.5 nm. The coated maghemite nanoparticles were tested to be stable in water and in physiological salt solution for longer than 6 months. In contrast to novel methods for magnetic nanoparticle production, where organic solvents are necessary, the procedure proposed here can dispense with organic solvents. Magnetic resonance imaging (MRI) experiments on living rats indicate that the nanoparticles are useful as an MRI contrast agent.     

Synthesis and characterization of a poly(para-phenyleneethynylene)-block-poly(ethylene oxide) rod-coil block copolymer

The synthesis of the poly(para-phenyleneethynylene)-block-poly(ethylene oxide) block copolymer (PPE-b-PEO) ( 1 ) via condensation of endfunctionalized poly(para-phenyleneethynylene) (PPE) ( 5 ) and poly(ethylene oxide) monomethyl ether (PEO) is reported. This is achieved by the initial synthesis of a PPE homopolymer with quantitative terminal functionalization, as proven by ¹H NMR and field desorption mass spectrometry (FD-MS). Reaction of the latter with PEO affords the block copolymer 1 , which was characterized by ¹H NMR spectroscopy, FD-MS and gel permeation chromatography (GPC). Furthermore it is shown that matrix assisted laser desorption ionization-time of flight mass spectrometry (MALDI-TOF-MS) is a suitable method to investigate PPE-b-PEO with respect to molecular weights and copolymer composition.     

Association of poly(4-hydroxystyrene)-block-poly(ethylene oxide) in aqueous solutions: block copolymer nanoparticles with intermixed blocks

Association behavior of diblock copolymer poly(4-hydroxystyrene)-block-poly(ethylene oxide) (PHOS-PEO) in aqueous solutions and solutions in water/tetrahydrofuran mixtures was studied by static, dynamic, and electrophoretic light scattering, (1)H NMR spectroscopy, transmission electron microscopy, and cryogenic field-emission scanning electron microscopy. It was found that, in alkaline aqueous solutions, PHOS-PEO can form compact spherical nanoparticles whose size depends on the preparation protocol. Instead of a core/shell structure with segregated blocks, the PHOS-PEO nanoparticles have intermixed PHOS and PEO blocks due to hydrogen bond interaction between -OH groups of PHOS and oxygen atoms of PEO and are stabilized electrostatically by a fraction of ionized PHOS units on the surface.     

Self-consistent field modeling of poly(ethylene oxide) adsorption onto silica: the multiple roles of electrolytes

In technological applications, it is increasingly important to understand and predict interfacial phenomena. Using a self-consistent field model within the Scheutjens-Fleer discretization scheme, we have developed a molecularly realistic model of the adsorption of poly(ethylene oxide) (PEO) onto silica from an aqueous solution. The bulk solution consists of water, PEO, 1:1 electrolyte, protons, and hydroxyl ions. The solvent quality is good below and becomes poor above a threshold ionic strength (of around 1 M). The silica surface features a number of silanol groups that have an affinity for PEO (by means of H bonding) when these groups are not dissociated. In line with experimental data, the surface changes from adsorbing to nonadsorbing at a sufficiently high pH. Even though PEO is uncharged, there is a complex effect of the ionic strength on the interfacial characteristics. For example, we report a non-monotonic behavior of the adsorbed amount as a function of ionic strength. Going from a low to a high ionic strength at a neutral or slightly basic pH, the adsorbed amount initially decreases as the surface affinity decreases (caused by the reduction of adsorption sites when, as a result of screening, the surface is increasingly charged) but then increases as a result of a reduction in solvent quality. These results indicate that molecularly realistic models can reveal much richer interfacial behavior than anticipated from generic models. The predictions follow many experimental findings.     

Complexes of poly(ethylene oxide)-block-poly(L-glutamate) and diminazene

Nanoparticles with a mean hydrodynamic radius of 16 nm and low polydispersity (P.I. = 0.1) were spontaneously formed by the complexation of poly(ethylene oxide)-block-poly(L-glutamate) (PEO-b-PLGlu) with diminazene. Only one of two possible binding sites of each diminazene molecule was involved in complexation. As determined by UV-vis difference spectra measurements, the complex binding constant is on the order of 1-2 x 10(4) M(-1). Circular dichroism measurements showed that the highly water-soluble diminazene can induce and stabilize the alpha-helical secondary structure of a PLGlu block.     

Colloidal aqueous dispersion of polyaniline nanotubes grafted non-covalently with poly(ethylene oxide)-block-poly(acrylic acid) copolymer

Polyaniline (PANI) nanotubes were prepared by oxidative polymerization of aniline in the presence of two structure-directing agents—salicylic acid (SA) and sodium dodecyl sulfate (SDS). When using only SA, mainly aggregated nanotube dendrites or coral-like structures have been obtained. Addition of a very small amount of the surfactant SDS, much less than the critical micelle concentration, results in substantial reduction of the aggregated nanotube morphology on the account of isolated PANI nanotubes, which is the favorable structure from the point of view of further modification. In order to make the isolated nanotubes water dispersible, their surface was modified by complex formation (non-covalent grafting) with hydrophilic poly(ethylene oxide)-block-poly(acrylic acid) copolymer. These water-dispersible PANI nanotubes might be good candidates for some biochemical and biomedical applications.     

Influence of metalation on the morphologies of poly(ethylene oxide)-block-poly(4-vinylpyridine) block copolymer micelles

Micellization of a poly(ethylene oxide)-block-poly(4-vinylpyridine) (PEO45-b-P4VP28) copolymer in water during metalation (incorporation of gold compounds and gold nanoparticle formation) with three types of gold compounds, NaAuCl4, HAuCl4, and AuCl3, was studied using dynamic light scattering (DLS) and transmission electron microscopy (TEM). The transformations of the PEO45-b-P4VP28 block copolymer micelles in water were found to depend on a number of parameters including the thermal history of the as-prepared block copolymer, the type of the metal compound, and the metal loading. For the HAuCl4-filled PE045-b-P4VP28 micelles, the subsequent reduction with hydrazine hydrate results in a significant fraction of rodlike micelles, suggesting that slow nucleation (confirmed by the formation of the large gold nanoparticles) and facilitated migration of gold ions yields the ideal conditions for sphere-to-rod micellar transition.     

Interaction between poly (ethylene oxide) and silica nanoparticles in dilute solutions

A mixed system that includes poly(ethylene oxide) (PEO) and silica (SiO2) nanoparticles is prepared using two mixing methods. The interaction between PEO and the SiO2 nanoparticles in the dilute basic solution is investigated using the dynamic light scattering (DLS) and isothermal titration calorimetry (ITC) techniques. The DLS results show qualitatively that SiO2 nanoparticles interact with both random coils and aggregates of PEO through hydrogen bonding, and PEO-SiO2 complexes are formed. The degree of disaggregation of aggregates of PEO is readily adjusted by changing the concentration of SiO2 nanoparticle suspensions. Moreover, the ITC results also certify quantitatively the interaction between PEO and SiO2 nanoparticle, and give the evidence of formation of PEO-SiO2 complex.     

Restricted self-diffusion in an aqueous solution of poly(ethylene oxide) poly(propylene oxide) poly(ethylene oxide) triblock copolymer

 The self-diffusion behavior of a triblock copolymer (PEO–b– PPO–b–PEO) in an aqueous solution of 20% (m/m) was investigated during a temperature-induced phase transition from liquid to gel state using pulsed field gradient NMR and static light scattering. The measured self-diffusivity shows a strong dependence on the observation time in the gel phase indicating the existence of diffusion barriers in the size range of about 0.6 μm. Additional static light-scattering measurements show a structure in the same size range of several hundred nanometers, which is far above molecular or micellar sizes and thus, has to be caused by larger clusters. The similarity in the space scales suggests that the restriction of molecular propagation is correlated with the grain boundaries between the domains of the poly-crystalline structure formed by the arranged micelles. Received: 28 October 1996 Accepted: 21 March 1997     

Synthesis and characterization of poly(ethylene oxide)/polylactide/poly(ethylene oxide) triblock copolymer

Poly(ethylene oxide/polylactide/poly(ethylene oxide) (PEO/PL/PEO) triblock copolymers, in which each block is connected by an ester bond, were synthesized by a coupling reaction between PL and PEO. Hydroxyl‐terminated PLs with various molecular weights were synthesized and used as hard segments. Hydroxyl‐terminated PEOs were converted to the corresponding acid halides via their acid group and used as a soft segment. Triblock copolymers were identified by Fourier transform infrared spectroscopy, ¹H NMR, and gel permeation chromatography. Differential scanning calorimetry (DSC) and X‐ray diffractometry of PEO/PL/PEO triblock copolymers suggested that PL and PEO blocks were phase‐separated and that the crystallization behavior of the PL block was markedly affected by the presence of the PEO block. PEO/PL/PEO triblock copolymers with PEO 0.75k had two exothermic peaks (by DSC), and both peaks were related to the crystallization of PL. According to thermogravimetric analysis, PEO/PL/PEO triblock copolymer showed a higher thermal stability than PL or PEO. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 2545–2555, 2002     

Interaction of poly(ethylene oxide) with fumed silica

Interaction of poly(ethylene oxide) (PEO, 600 kDa) with fumed silica A-300 (SBET = 316 m2/g) was investigated under different conditions using adsorption, infrared (IR), thermal analysis (TG-DTA), AFM, and quantum chemical methods. The studied dried silica/PEO samples were also carbonized in a flow reactor at 773 K. The structural characteristics of fumed silica, PEO/silica, and pyrocarbon/fumed silica were investigated using nitrogen adsorption-desorption at 77.4 K. PEO adsorption isotherm depicts a high affinity of PEO to the fumed silica surface in aqueous medium. PEO adsorbed in the amount of 50 mg per gram of silica (PEO monolayer corresponds to CPEO approximately 190 mg/g) can disturb approximately 70% of isolated surface silanols. However, at the monolayer coverage, only 20% of oxygen atoms of PEO molecules take part in the hydrogen bonding with the surface silanols. An increase in the PEO amount adsorbed on fumed silica leads to a diminution of the specific surface area and contributions of micro- (pore radius R < 1 nm) and mesopores (1 < R < 25 nm) to the pore volume but contribution of macropores (R > 25 nm) increases with CPEO. Quantum chemical calculations of a complex of a PEO fragment with a tripple bond SiOH group of a silica cluster in the gas phase and with consideration for the solvent (water) effect show a reduction of interaction energy in the aqueous medium. However, the complex remains strong enough to provide durability of the PEO adsorption complexes on fumed silica; i.e., PEO/fumed silica nanocomposites could be stable in both gaseous and liquid media.     

Monolayer-protected gold nanoparticles by the self-assembly of micellar poly(ethylene oxide)-b-poly(epsilon-caprolactone) block copolymer

A study is presented of the preparation of gold nanoparticles incorporated into biodegradable micelles. Poly(ethylene oxide)-b-poly(epsilon-caprolactone) (PEO-b-PCL) copolymer was synthesized by ring-opening polymerization, and the hydroxyl end group of the PCL block was modified with thioctic acid using dicyclohexyl carbodiimide as the coupling reagent. The PEO-b-PCL-thioctate ester (TE) thus obtained was used in a later step to form monolayer protected gold nanoparticles via the thioctate spacer. Gold nanoparticles stabilized with the PEO-b-PCL block (named Au/Block (x/y), where x/y is the mole feed ratio between HAuCl4 and PEO-b-PCL-TE) were prepared and analyzed. Au/Block (1/1), Au/Block (2/1), and Au/Block (3/1) nanoparticles were found to form stable dispersions in the organic solvents commonly used to dissolve the unlabeled block copolymer. The average diameter of the nanoparticles was determined by transmission electron microscopy (TEM) and found to be 6+/-2 nm. Au/Block (4/1) nanoparticle dispersions in organic solvents, on the other hand, were not stable and produced large gold clusters (50-100 nm). Cluster formation was attributed to the low grafting density of the block copolymer, which facilitates agglomeration. For Au/Block (12/1), along the same trend, only an insoluble product was isolated. Micelles in water were prepared by the slow addition of the dilute Au/Block solution in dimethylformamide into a large excess of water with vigorous stirring. Au/Block (1/1) and Au/Block (2/1) formed nanosized structures of 5-7 nm. TEM images of stained Au/Block (1/1) micelles, made in water, clearly showed the formation of core-shell structures. Au/Block (3/1) micelles, on the other hand, were not stable and large agglomerates a few microns in size were observed. The study focuses on the synthesis, characterization, and aggregation behavior of gold-loaded PEO-b-PCL block copolymer micelles, a potential system for drug delivery in conjunction with tissue and subcellular localization studies.     

Selective adsorption of poly(ethylene oxide) onto a charged surface mediated by alkali metal ions

Using a surface force balance, we have measured normal and shear interactions between mica surfaces across pure water and across 0.1 M aqueous solutions of LiNO3, NaNO3, KNO3, and CsNO3, both prior to adding polymer and following addition of 1.5 x 10(-4) w/w poly(ethylene oxide) (PEO, Mw = 170 kD) and overnight incubation. Our results reveal that while the PEO adsorbs strongly from the KNO3 and CsNO3 solutions, unexpectedly it does not adsorb at all from the LiNO3 and NaNO3 salt solutions. We attribute this to the different nature of the hydration layers about the alkali metal ions: these favor liganding to the negatively charged mica surface of the etheric -O- group on the ethylene oxide monomer for the case of the more weakly hydrated K+ and Cs+, but not for the case of Na+ or Li+ with their more strongly bound water. A simple model relating the electrostatic energy changes occurring upon such liganding to the experimentally measured hydration energies of the different alkali metal ions supports this attribution.     

Preparation and characterization of self-assembled nanoparticles formed by poly(ethylene oxide)-block-poly(epsilon-caprolactone) copolymers with long poly(epsilon-caprolactone) blocks in aqueous solutions

Aqueous solutions of self-assembled nanoparticles formed by biocompatible diblock copolymers of poly(epsilon-caprolactone)-block-poly(ethylene oxide) (PCL-PEO) with the same molar mass of the PEO block (5000 g mol-1) and three different molar masses of the PCL block (5000, 13 000, and 32 000 g mol-1) have been prepared by a fast mixing the copolymer solution in a mild selective solvent, tetrahydrofuran (THF)/water, with an excess of water, that is, by quenching the reversible micellization equilibrium, and a subsequent removal of THF by dialysis of the water-rich solution against water. The prepared nanoparticles have been characterized by static and dynamic light scattering and atomic force microscopy imaging. It was found that stable monodisperse nanoparticles are formed only if the initial mixed solvent contained 90 vol % THF. The results show that the prepared nanoparticles are spherical vesicles with relatively thick hydrophobic walls, that is, spherical core/shell nanoparticles with the hollow core filled with the solvent.     

Monitoring solute interactions with poly(ethylene oxide)-modified colloidal silica nanoparticles via fluorescence anisotropy decay

The fluorescence-based nanosize metrology approach, proposed recently by Geddes and Birch (Geddes, C. D.; Birch, D. J. S. J. Non-Cryst. Solids 2000, 270, 191), was used to characterize the extent of binding of a fluorescent cationic solute, rhodamine 6G (R6G), to the surface of silica particles after modification of the surface with the hydrophilic polymer poly(ethylene oxide) (PEO) of various molecular weights. The measurement of the rotational dynamics of R6G in PEO solutions showed the absence of strong interactions between R6G and PEO chains in water and the ability of the dye to sense the presence of polymer clusters in 30 wt % solutions. Time-resolved anisotropy decays of polymer-modified Ludox provided direct evidence for distribution of the dye between bound and free states, with the bound dye showing two decay components: a nanosecond decay component that is consistent with local motions of bound probes and a residual anisotropy component due to slow rotation of large silica particles. The data showed that the dye was strongly adsorbed to unmodified silica nanoparticles, to the extent that less than 1% of the dye was present in the surrounding aqueous solution. Addition of PEO blocked the adsorption of the dye to a significant degree, with up to 50% of the probe being present in the aqueous solution for Ludox samples containing 30 wt % of low molecular weight PEO. The addition of such agents also decreased the value and increased the fractional contribution of the nanosecond rotational correlation time, suggesting that polymer adsorption altered the degree of local motion of the bound probe. Atomic force microscopy imaging studies provided no evidence for a change in the particle size upon surface modification but did suggest interparticle aggregation after polymer adsorption. Thus, this redistribution of the probe is interpreted as being due to coverage of particles with the polymer, resulting in lower adsorption of R6G to the silica. The data clearly show the power of time-resolved fluorescence anisotropy decay measurements for probing the modification of silica surfaces and suggest that this method should prove useful in characterization of new chromatographic stationary phases and nanocomposite materials.     

Temperature-dependent aggregation and disaggregation of poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) block copolymer in aqueous solution

Aggregation and disaggregation of poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) (PEO-PPO-PEO) block copolymers, Pluronics P103 and P104, in aqueous solutions during a heating and cooling cycle were investigated by dynamic laser scattering (DLS) and 1H NMR spectroscopy. Temperature hysteresis was observed by DLS when cooling the copolymer aqueous solutions because larger aggregates existed at temperatures lower than critical micellization temperature (CMT), but no temperature differences were observed by NMR. This phenomenon was explained as the forming of water-swollen micelles at temperatures lower than CMT during the cooling process.     

Self-assembly of poly(ethylene oxide)-block-poly(acrylic acid) induced by CaCl2: mechanistic study

The interaction between CaCl 2 and double hydrophilic block copolymer, poly(ethylene oxide) 45- block-poly(acrylic acid) 70, PEO 45- b-PAA 70, was investigated. At a stoichiometric ratio of Ca2+:COO (-) = 0.5, Ca2+ ions were bound to COO (-) groups on PAA segments via electrostatic interaction. Small particles of 4-8 nm in diameter were observed, suggesting the formation of coil-like polymeric globule induced by charge neutralization. At Ca2+:COO (-) >or= 2.5, monodispersed aggregates of average hydrodynamic diameter of 52.0 +/- 7.4 nm were produced. The ISE, ITC, surface tension and fluorescence spectroscopic data confirmed that the formation of these aggregates is not the result of interaction between excess Ca2+ ions and the polymer, but rather it is due to changes in the water activity that triggers the structural rearrangement of Ca2+/PEO 45- b-PAA 70 complex.     

Reversible aggregation of polystyrene-block-poly(2-vinylpyridine)-block-poly(ethylene oxide) block copolymer micelles in acidic aqueous Solutions

Micelles of polystyrene-block-poly(2-vinylpyridine)-block-poly(ethylene oxide) (PS-PVP-PEO) were studied in acidic aqueous solutions by static and dynamic light scattering, alkalimetric titration, fluorescence correlation spectroscopy, and after deposition on a mica surface by atomic force microscopy. The PS-PVP-PEO micelles prepared by dialysis in ternary 1,4-dioxane-methanol-acidic water mixtures have a very low association number and show a strong tendency to form aggregates. The aggregation, which is promoted at low pH, seems to be fully reversible. Possible mechanisms of the aggregation are discussed. Atomic force microscopy scans of PS-PVP-PEO micelles deposited on a mica surface reveal the formation of micellar aggregates and support the general concept of aggregation upon changes in conditions and deterioration of the stability of small micelles.