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Biomedical subjects

Steven P Armes

Publications and source records attributed to Steven P Armes.

At least 19 recordsLinked to original sources
PubMed2007

Surface ATRP of hydrophilic monomers from ultrafine aqueous silica sols using anionic polyelectrolytic macroinitiators.

A convenient two-step route was developed to prepare new anionic ATRP macroinitiators from near-monodisperse poly(2-hydroxyethyl methacrylate) precursors by partial esterification with 2-bromoisobutyryl bromide, followed by esterification of the remaining hydroxyl groups using excess 2-sulfobenzoic acid cyclic anhydride. These new macroinitiators can be electrostatically adsorbed onto ultrafine cationic Ludox CL silica sols; subsequent surface polymerization of various hydrophilic monomers in aqueous solution at room temperature afforded a range of polymer-grafted ultrafine silica sols. The resulting sterically stabilized particles were characterized by dynamic light scattering, transmission electron microscopy, aqueous electrophoresis, FTIR spectroscopy, and elemental microanalyses.

Journal Article↗
PubMed2006

Facile synthesis of highly biocompatible poly(2-(methacryloyloxy)ethyl phosphorylcholine)-coated gold nanoparticles in aqueous solution.

Diblock copolymers comprising a highly biocompatible poly(2-(methacryloyloxy)ethyl phosphorylcholine) (PMPC) block and a poly(2-(dimethylamino)ethyl methacrylate) (PDMA) block were evaluated for the synthesis of sterically stabilized gold nanoparticles in aqueous solution. The PDMA block becomes partially protonated on addition of HAuCl4, and the remaining nonprotonated tertiary amine groups reduce the AuCl4- counterion to zerovalent gold in situ. This approach results in the adsorption of the PDMA block onto the gold nanoparticle surface while the PMPC chains serve as a stabilizing block, producing highly biocompatible gold sols in aqueous solution at ambient temperature without any external reducing agent. The size and shape of gold nanoparticles could be readily controlled by tuning synthesis parameters such as the block composition and the relative and absolute concentrations of the PMPC-PDMA diblock copolymer and HAuCl4. These highly biocompatible gold sols have potential biomedical applications.

Biocompatible Materials↗
PubMed2006

Characterizing the pH-responsive behavior of thin films of diblock copolymer micelles at the silica/aqueous solution interface.

The pH-responsive behavior of cationic diblock poly(2-(dimethylamino)ethyl methacrylate)-block-poly(2-(diethylamino)ethyl methacrylate) copolymer micelles adsorbed at the silica/aqueous solution interface has been characterized. The micellar morphology of this copolymer, initially adsorbed at pH 9, can be dramatically altered by lowering the solution pH. The original micelle-like morphology of the adsorbed copolymer chains at pH 9 completely disappears as the pH is decreased to 4, and a brush-like layer structure is produced. This change results from protonation of the copolymer chains: the subsequent electrostatic repulsions within the film drive the copolymer chains to expand into the aqueous phase. Returning the solution pH from 4 to 9 causes this brush-like layer to collapse, with atomic force microscopy images suggesting degradation of the film. Hence, the pH-responsive behavior of the copolymer film exhibits irreversible morphological changes. Measurements of the adsorbed/desorbed amounts of the copolymer film were conducted using both a quartz crystal microbalance with dissipation monitoring (QCM-D) and optical reflectometry (OR). After an initial rinse at both pH values, the OR adsorbed mass becomes almost constant during subsequent pH cycling, whereas the corresponding QCM-D adsorbed mass changes significantly but reversibly in response to the solution pH. Since the QCM-D measures a bound mass that moves in tandem with the surface, the discrepancy with the OR data is due to changes in the amount of bound water in the copolymer film as a result of the pH-induced changes in surface morphology. The larger effective mass observed at pH 4 suggests that the brush-like layer contains much more entrapped water than the micellar films at pH 9. The pH dependence of the contact angle of the adsorbed film is consistent with the changes observed using the other techniques, regardless of whether the solution pH is altered in situ or the aqueous solution is completely replaced. In fact, comparison of these two approaches provides direct evidence of the exposure of adsorbed micelle core blocks to the solution during pH cycling and the concomitant impact upon all the other measurements.

Journal Article↗
PubMed2006

pH-responsive diblock copolymer micelles at the silica/aqueous solution interface: Adsorption kinetics and equilibrium studies.

The adsorption behavior of two examples of a weakly basic diblock copolymer, poly(2-(dimethylamino)ethyl methacrylate)-block-poly(2-(diethylamino)ethyl methacrylate) (PDMA-PDEA), at the silica/aqueous solution interface has been investigated using a quartz crystal microbalance with dissipation monitoring and an optical reflectometer. Dynamic and static light scattering measurements have also been carried out to assess aqueous solution properties of such pH-responsive copolymers. In alkaline solution, core-shell micelles are formed above the critical micelle concentration (cmc) by both copolymers, whereas the chains are molecularly dissolved (as unimers) at all concentrations in acidic solution. As a result, the adsorption behavior of PDMA-PDEA diblock copolymers on silica is strongly dependent on both the copolymer concentration and the solution pH. Below the cmc at pH 9, the cationic PDMA-PDEA copolymers adsorb as unimers and the conformation of the adsorbed polymer is essentially flat. At concentrations just above the cmc, the initial adsorption of copolymer onto the silica is dominated by the unimers due to their faster diffusion compared to the much larger micelles. Rearrangement of the adsorbed unimers and/or their subsequent displacement by micelles from solution is then observed during an equilibration period, and the final adsorbed mass is greater than that observed below the cmc. At concentrations well above the cmc, the much higher proportion of micelles in solution facilitates more effective competition for the surface at all stages of the adsorption process and no replacement of initially adsorbed unimers by micelles is evident. However, the adsorbed layer undergoes gradual rearrangement after initial adsorption. This relaxation is believed to result from a combination of further copolymer adsorption and swelling of the adsorbed layer.

Journal Article↗
PubMed2006

Effects of copolymer concentration and chain length on the pH-responsive behavior of diblock copolymer micellar films.

The pH-responsive behavior of adsorbed diblock copolymer films of PDMA-PDEA (poly(2-(dimethylamino)ethyl methacrylate)-block-poly(2-(diethylamino)ethyl methacrylate)) on silica has been characterized using a quartz crystal microbalance with dissipation monitoring (QCM-D), an optical reflectometer (OR) and an atomic force microscope (AFM). The copolymer was adsorbed at pH 9 from various copolymer concentrations; QCM-D measurements indicate that the level of desorption when rinsed at pH 9 depends on the initial copolymer concentration. The adsorbed films produced at pH 9 generally have low charge densities; adjusting the solution pH to 4 results in a significant protonation of the constituent copolymers and a related interfacial structural change for the copolymer film. OR studies show no significant change during pH cycling, while QCM-D measurements indicate that the adsorbed mass and dissipation alter dramatically in response to the solution pH. The difference between the QCM-D adsorbed masses and dissipation values at pH 4 and 9 were found to be dependent on the initial copolymer concentration. This is due to differences in the initial conformations within the adsorbed copolymer layers at pH 9. The effect of the PDMA chain length on the pH-responsive behavior has also been studied; both the QCM-D adsorbed mass and dissipation of PDMA54-PDEA24 (shorter PDMA block) at pH 4 and 9 were observed to be greater than those of PDMA9X-PDEA2Y (longer PDMA block). This suggests that the normal extension of the adsorbed PDMA54-PDEA24 copolymer films is more significant than that of the PDMA9X-PDEA2Y films on silica.

Hydrogen-Ion Concentration↗
PubMed2006

Stimulus-responsive particulate emulsifiers based on lightly cross-linked poly(4-vinylpyridine)-silica nanocomposite microgels.

Lightly cross-linked poly(4-vinylpyridine)-silica nanocomposite microgel particles have been recently reported to act as pH-responsive particulate emulsifiers [Fujii, S.; Read, E. S.; Armes, S. P.; Binks, B. P. Adv. Mater. 2005, 17, 1014]. In this work, the synthesis and performance of such nanocomposite microgel particles are studied in more detail. Scanning electron microscopy, dynamic light scattering, nitrogen microanalyses, thermogravimetric analysis, aqueous electrophoresis, and acid-base titration were used to characterize the nanocomposites in terms of their particle size and morphology, polymer and silica contents, surface compositions, and critical swelling pH, respectively. Depending on the polarity of the oil phase and the purity of the nanocomposite particles, either oil-in-water or water-in-oil emulsions could be prepared at pH 8-9, but not at pH 2-3. These emulsions were characterized in terms of their emulsion type, mean droplet diameter, and morphology using electrical conductivity, light diffraction, and both electron and optical microscopy. In some cases, rapid demulsification could be induced by lowering the solution pH: addition of acid led to protonation of the 4-vinylpyridine residues, which imparted cationic microgel character to the nanocomposite particles. Cross-linking of the nanocomposite microgel particles is essential for their optimum performance as a pH-responsive emulsifier, but unfortunately it is not sufficient to allow recycling.

Journal Article↗
PubMed2006

Long-range structural order, moiré patterns, and iridescence in latex-stabilized foams.

We describe the facile production of highly stable foams stabilized solely by micrometer-sized, sterically stabilized polystyrene (PS) latex particles. Such foams can survive for more than one year in the wet state and remain intact after drying. In contrast, foams stabilized with either sodium dodecyl sulfate or poly(N-vinylpyrrolidone) were destroyed after removal of the aqueous phase. Scanning electron microscopy studies reveal hexagonally close-packed arrays of PS particles within the dried foam, which suggests high colloid stability for the PS particles prior to their adsorption at the air-water interface. Localized moiré patterns are observed by optical microscopy due to the formation of well-defined latex bilayers with exquisite long-range order. Moreover, the dried foams are highly iridescent in bright transmitted light, which may offer potential applications in security inks and coatings.

Journal Article↗
PubMed2006

Comparison of the adsorption of cationic diblock copolymer micelles from aqueous solution onto mica and silica.

The similarities and differences in the adsorption behavior of diblock poly(2-(dimethylamino)ethyl methacrylate)-b-poly(2-(diethylamino)ethyl methacrylate) (XqPDMA-PDEA, where X refers to a mean degree of quaternization of the PDMA of either 0, 10, 50, or 100 mol%) copolymers at the mica/ and silica/aqueous solution interfaces have been investigated. These diblock copolymers form core-shell micelles with the PDEA chains located in the cores and the more hydrophilic PDMA chains forming the cationic micelle coronas at pH 9. These micelles adsorb strongly onto both mica and silica due to electrostatic interactions. In situ atomic force microscopy (AFM) has demonstrated that the mean spacing and the dimension of the adsorbed micelles depend on both the substrate and the mean degree of quaternization of the PDMA blocks. In particular, the morphology of the adsorbed nonquaternized 0qPDMA-PDEA copolymer micelles is clearly influenced by the substrate type: these micelles form a disordered layer on silica, while much more close-packed, highly ordered layers are obtained on mica. The key reasons for this difference are suggested to be the ease of lateral rearrangement for the copolymer micelles attached to the solid substrates and the relative rates of relaxation of the coronal PDMA chains.

Journal Article↗
PubMed2006

Polystyrene-silica nanocomposite particles via alcoholic dispersion polymerization using a cationic azo initiator.

Submicrometer-sized polystyrene-silica nanocomposite particles have been prepared by alcoholic dispersion polymerization of styrene using commercial alcoholic silica sols of 13 or 22 nm diameter as the sole stabilizing agent. The key to the formation of colloidally stable nanocomposite particles is the selection of a cationic azo initiator (use of nonionic or anionic initiators leads either to the formation of silica-stabilized polystyrene latex particles with very low silica contents or to the precipitation of polystyrene, respectively). Neither surface modification of the silica sol nor the addition of surfactant or polymeric stabilizers is required for successful nanocomposite syntheses. The purified polystyrene-silica nanocomposite particles have relatively narrow particle size distributions, with mean diameters ranging from 331 to 464 nm as judged by disk centrifuge photosedimentometry. Thermogravimetric analyses indicated mean silica contents of 13-26 wt. %, depending on the synthesis conditions. Calcination of the polystyrene-silica nanocomposite particles leads to the formation of hollow silica shells, which indicates a well-defined core-shell morphology for the original nanocomposite particles.

Journal Article↗
PubMed2006

Reversible activation of diblock copolymer monolayers at the interface by pH modulation, 1: Lateral chain density and conformation.

This study focuses on the design of chemically regulated surfaces that allow for reversible control of the interactions between biological matter (cells and proteins) and planar substrates. As a tunable interlayer, we use a monolayer of a near-monodisperse poly[2-(dimethylamino)ethyl methacrylate-block-methyl methacrylate] (PDMAEMA-PMMA) diblock copolymer. Owing to the relatively large fraction (50%) of the hydrophobic PMMA block, this copolymer forms a stable Langmuir monolayer at the air/water interface. Both in situ and ex situ film balance experiments suggest that the hydrophilic PDMAEMA block adsorbs to the air/water interface in its uncharged state (pH 8.5), but stretches into the subphase in its charged state (pH 5.5). Optimization of the preparation protocols enables us to fabricate stable, homogeneous diblock copolymer films on hydrophobized substrates via Langmuir-Schaefer transfer at well-defined lateral chain densities. Ellipsometry and X-ray reflectivity studies of the transferred films confirm that the film thickness can be systematically regulated by the lateral chain densities. The transferred copolymer films remain stable in water for about a week, suggesting that they are promising materials for the creation of pH-controlled solid substrates for the support of biological matter such as proteins and cells.

Adsorption↗
PubMed2006

Reversible activation of diblock copolymer monolayers at the interface by pH modulation, 2: Membrane interactions at the solid/liquid interface.

A monolayer of the pH-responsive poly[2-(dimethylamino)ethyl methacrylate-block-methyl methacrylate] diblock copolymer [PDMAEMA-PMMA] was transferred from the air/water interface to a silicon substrate for evaluation as a tunable interlayer between biological material and solid substrates. Specular neutron reflectivity experiments revealed that the weak polyelectrolyte PDMAEMA chains at the solid/liquid interface can be reversibly activated by pH modulation. The thickness, scattering length density, and surface roughness of the polymer film can be systematically controlled by pH titration. As a simple model of plasma membranes, a lipid bilayer was deposited onto the polymer film. The membrane-substrate interaction was characterized by neutron reflectivity experiments, demonstrating that the membrane-substrate distance could be reversibly regulated by pH titration. These results confirm the potential of stimuli-responsive polymers for precise control of cell-surface interactions.

Biocompatible Materials↗
PubMed2006

Efficient synthesis of sterically stabilized pH-responsive microgels of controllable particle diameter by emulsion polymerization.

Emulsion polymerization of 2-vinylpyridine (2VP) in the presence of divinylbenzene (DVB) cross-linker, a cationic surfactant, and a hydrophilic macromonomer, monomethoxy-capped poly(ethylene glycol) methacrylate (PEGMA), at around neutral pH and 60 degrees C afforded near-monodisperse, sterically stabilized latexes at approximately 10% solids. Judicious selection of the synthesis parameters enabled the mean latex diameter to be varied over an unusually wide range for one-shot batch syntheses. Scanning electron microscopy studies confirmed near-monodisperse spherical morphologies, with mean weight-average particle diameters ranging from 370 to 970 nm depending on the initiator, polymeric stabilizer, and surfactant concentrations. Particle sizing studies were also conducted using disk centrifuge photosedimentometry and dynamic light scattering and gave similar data. These lightly cross-linked latexes acquired cationic microgel character at low pH, as expected. The critical pH for this latex-to-microgel transition was around pH 4.1 at 1.0 wt % DVB, which is significantly lower than the pKa of 4.92 estimated for linear P2VP homopolymer by acid titration. 1H NMR and aqueous electrophoresis studies indicated that substantial swelling occurred at low pH due to protonation of the 2VP groups, while dynamic light scattering (DLS) studies indicated volumetric swelling ratios of up to 3 orders of magnitude, depending on the initial latex diameter. Systematic variation of the degree of cross-linking led to a monotonic decrease in the pKa values of the P2VP latexes (as judged by acid titration) and also the critical swelling pH (as judged by visual inspection). This was attributed to the increasingly branched nature of the P2VP chains in their swollen microgel form. Preliminary studies of the kinetics of acid-induced swelling were also conducted using the pH jump method in conjunction with a stopped-flow apparatus. These P2VP latexes swell significantly faster than P2VP latexes described in the literature and the characteristic time scales observed in the present study are much closer to those predicted by the Tanaka equation.

Journal Article↗
PubMed2006

Effects of pH and salt concentration on oil-in-water emulsions stabilized solely by nanocomposite microgel particles.

Aqueous dispersions of lightly cross-linked poly(4-vinylpyridine)/silica nanocomposite microgel particles are used as a sole emulsifier of methyl myristate and water (1:1 by volume) at various pH values and salt concentrations at 20 degrees C. These particles become swollen at low pH with the hydrodynamic diameter increasing from 250 nm at pH 8.8 to 630 nm at pH 2.7. For batch emulsions prepared at pH 3.4, oil-in-water (o/w) emulsions are formed that are stable to coalescence but exhibit creaming. Below pH 3.3, however, these emulsions are very unstable to coalescence and rapid phase separation occurs just after homogenization (pH-dependent). The pH for 50% ionization of the pyridine groups in the particles in the bulk (pK(a)) was determined to be 3.4 by acid titration measurements of the aqueous dispersion. Thus, the charged swollen particles no longer adsorb at the oil-water interface. For continuous emulsions (prepared at high pH with the pH then decreased abruptly or progressively), demulsification takes place rapidly below pH 3.3, implying that particles adsorbed at the oil-water interface can become charged (protonated) and detached from the interface in situ (pH-responsive). Furthermore, at a fixed pH of 4.0, addition of sodium chloride to the aqueous dispersion increases the degree of ionization of the particles and batch emulsions are significantly unstable to coalescence at a salt concentration of 0.24 mol kg(-1). The degree of ionization of such microgel particles is a critical factor in controlling the coalescence stability of o/w emulsions stabilized by them.

Journal Article↗
PubMed2006

Phosphorylcholine-based pH-responsive diblock copolymer micelles as drug delivery vehicles: light scattering, electron microscopy, and fluorescence experiments.

The micellization behavior of a diblock copolymer comprising a highly hydrophilic and biocompatible poly(2-methacryloyloxyethyl phosphorylcholine) (PMPC) corona-forming block and a pH-sensitive poly(2-(diisopropylamino)ethyl methacrylate) (PDPA) core-forming block (PMPC-b-PDPA) has been studied by static and dynamic light scattering (SDLS), transmission electron microscopy (TEM), and potentiometry. Self-assembly of PMPC-b-PDPA copolymers with two different DPA volume fractions (phi(DPA)) leads to narrowly distributed and structurally distinct spherical micelles, as evidenced by their molecular weight (M(w,mic)), aggregation number (N(agg)), hydrodynamic radius (R(H)), corona width (W), and core radius (R(c)). The excellent potential of these pH-responsive micelles as nanosized drug delivery vehicles was illustrated by the encapsulation of dipyridamole (DIP), a model hydrophobic drug that dissolves in acid solutions and becomes insoluble above pH 5.8, which is comparable to the pK(a) of the PDPA block. The influence of micelle structure (namely M(w,mic), N(agg), R(H), W, and R(c)) on drug loading content, drug loading efficiency, partition coefficient, and release kinetics was investigated and confirmed by fluorescence spectroscopy studies. The maximum dipyridamole loadings within PMPC(30)-b-PDPA(30) (R(H) = 14.0 nm; W = 4.8 nm; R(c) = 9.2 nm) and PMPC(30)-b-PDPA(60) (R(H) = 27.1 nm; W = 11.0 nm; R(c) = 16.1 nm) micelles were 7 and 12% w/w(p), respectively. This preferential solubilization of DIP into micelles formed by copolymer chains having longer core-forming blocks (i.e., possessing larger core volumes) reflects the larger partition coefficient (K(V)) of DIP between the aqueous phase and PMPC(30)-b-PDPA(60) micelles (K(V) = 5.7 x 10(4)) compared to PMPC(30)-b-PDPA(30) micelles (K(V) = 1.1 x 10(4)). This enhanced ability of PMPC(30)-b-PDPA(60) aggregates to entrap/stabilize small hydrophobic molecules also produces slower release kinetics. Rapid release can be triggered by lowering the pH to induce micellar dissociation.

Dipyridamole↗
PubMed2005

pH-sensitive vesicles based on a biocompatible zwitterionic diblock copolymer.

Highly biocompatible pH-sensitive diblock copolymer vesicles were prepared from the self-assembly of a biocompatible zwitterionic copolymer, poly[2-(methacryloyloxy)ethyl phosphorylcholine-block-2-(diisopropylamino)ethyl methacrylate], PMPC-b-PDPA. Vesicle formation occurred spontaneously by adjusting the solution pH from pH 2 to above 6, with the hydrophobic PDPA chains forming the vesicle walls. Transmission electron microscopy (TEM), dynamic laser light scattering (DLS), and UV-visible absorption spectrophotometry were used to characterize these vesicles. Gold nanoparticle-decorated vesicles were also obtained by treating the vesicles with HAuCl4, followed by NaBH4.

Biocompatible Materials↗
PubMed2005

pH triggered release of protective poly(ethylene glycol)-b-polycation copolymers from liposomes.

Triggered release of adsorbed polymers from liposomes enables protection against immune recognition during circulation and subsequent intracellular delivery of DNA. Polycationic blocks, poly[2-(dimethylamino) ethyl methacrylate] (DMAEMA) (0.8, 3.1, 4.9, or 9.8 kg/mol) or polylysine (K) (3 kg/mol), act as anchors for poly(ethylene glycol) (PEG) (2 or 5 kg/mol) protective blocks. In addition, a copolymer with 15 strictly alternating blocks of PEG (2 kg/mol) and cationic amine sites was evaluated as a protective coating. Incorporation of 1,2-dioleoyl-3-dimethylammonium-propane, a titratable lipid with a pKa of approximately 6.7, allows the liposome's net charge to increase as the pH shifts from 7.4 in the bloodstream to 5.5 in the endosome. The increased net liposome cationicity results in decreased cationic polymer adsorption. The EMPEG113-DMAEMA31 and EMPEG113-DMAEMA62 association constants decrease from 3.1 and 6.2 (mg/m(2))/(mg/ml) at pH 7.4 to 1.7 and 3.2 (mg/m(2))/(mg/ml) at pH 5.5, respectively. However, EMPEG45-DMAEMA5, EMPEG45-DMAEMA20, and EMPEG45-N-DP15 did not show a strong response to changes in pH. Cationic polymer adsorption exceeds calculated values for liposome neutralization, resulting in adsorption profiles in the brush regime.

Adsorption↗