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.     

pH-responsive behavior of selectively quaternized diblock copolymers adsorbed at the silica/aqueous solution interface

The desorption and subsequent pH-responsive behavior of selectively quaternized poly(2-(dimethylamino)ethyl methacrylate)-block-poly(2-(diethylamino)ethyl methacrylate) (PDMA-PDEA) films at the silica/aqueous solution interface has been characterized. The copolymer films were prepared at pH 9, where micelle-like surface aggregates are spontaneously formed on silica. The subsequent rinse with a copolymer-free electrolyte solution adjusted to pH 9 causes partial desorption of the weakly or non-quaternized copolymers, but negligible desorption for the highly quaternized copolymers. Further rinsing with a pH 4 electrolyte solution results in additional desorption and extension (swelling) of the remaining adsorbed copolymer film normal to the interface. This pH-responsive behavior is reversible for two pH cycles (9-4-9-4) as monitored by both quartz crystal microbalance with dissipation monitoring (QCM-D) and also zeta potential measurements. The magnitude of the pH-responsive behavior depends on the mean degree of quaternization of the PDMA block. Moreover, a combination of contact angle data, zeta potential measurements and in situ atomic force microscopy (AFM) studies indicates that the pH-responsive behavior is influenced not only by the number of cationic binding sites on the adsorbed copolymer chains but also by the adsorbed layer structure.     

Adsorption characteristics of zwitterionic diblock copolymers at the silica/aqueous solution interface

The adsorption of a zwitterionic diblock copolymer, poly(2-(diethylamino)ethyl methacrylate)-block-poly(methacrylic acid) (PDEA59-PMAA50), at the silica/aqueous solution interface has been characterised as a function of pH. In acidic solution, this copolymer forms core-shell micelles with the neutral PMAA chains being located in the hydrophobic cores and the protonated PDEA chains forming the cationic micelle coronas. In alkaline solution, the copolymer forms the analogous inverted micelles with anionic PMAA coronas and hydrophobic PDEA cores. The morphology of the adsorbed layer was observed in situ using soft-contact atomic force microscopy (AFM): this technique suggests the formation of a thin adsorbed layer at pH 4 due to the adsorption of individual copolymer chains (unimers) rather than micelle aggregates. This is supported by the remarkably low dissipation values and the relatively low degrees of hydration for the adsorbed layers, as estimated using a combination of quartz crystal microbalance with dissipation monitoring (QCM-D) and optical reflectometry (OR). In alkaline solution, analysis of the adsorption data suggests a conformation for the adsorbed copolymers where one block projects normal to the solid/liquid interface; this layer consists of a hydrophobic PDEA anchor block adsorbed on the silica surface and an anionic PMAA buoy block extending into the solution phase. Tapping mode AFM studies were also carried out on the silica surfaces after removal from the copolymer solutions and subsequent drying. Interestingly, in these cases micelle-like surface aggregates were observed from both acidic and alkaline solutions. The lateral dimension of the aggregates seen is consistent with the corresponding hydrodynamic diameter of the copolymer micelles in bulk solution. The combination of the in situ and ex situ AFM data provides evidence that, for this copolymer, micelle aggregates are only seen in the ex situ dry state as a result of the substrate withdrawal and drying process. It remains unclear whether these aggregates are caused by micelle deposition at the surface during the substrate withdrawal from the solution or as a result of unimer rearrangements at the drying front as the liquid recedes from the surface.     

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.     

Adsorption characteristics of monomeric/gemini surfactant mixtures at the silica/aqueous solution interface

The adsorption of the monomeric/gemini surfactant mixtures at the silica/aqueous solution interface has been characterized on the basis of quartz crystal microbalance with dissipation monitoring (QCM-D) and atomic force microscopy (AFM) data. The gemini surfactant employed in this study was cationic 1,2-bis(dodecyldimethylammonio)ethane dibromide (12-2-12). This surfactant was mixed with monomeric surfactants (dodecyltrimethylammonium bromide (DTAB), hexadecyltrimethylammonium bromide (HTAB), and octaoxyethylenedodecyl ether (C(12)EO(8))) in the presence of an added electrolyte (NaBr). The key finding in our current study is that the addition of the gemini surfactant (12-2-12) makes significant impact on the adsorption properties even when the mole fraction of 12-2-12 is quite low in the surfactant mixtures. This is suggested by the experimental results that (i) the QCM-D adsorption isotherms measured for the monomeric/gemini surfactant mixtures shift to the region of lower surfactant concentrations compared with the monomeric single systems; (ii) the adsorbed layer morphology largely depends on the mole fraction of 12-2-12 in the surfactant mixtures, and the increased 12-2-12 mole fraction results in the less curved surface aggregates; and (iii) the addition of 12-2-12 yields a relatively rigid adsorbed layer when compared with the layer formed by the monomeric single systems. These adsorption properties result from the fact that the more favorable interaction of 12-2-12 with the silica surface sites drives the overall surfactant adsorption in these mixtures, which is particularly obvious in the region of low surfactant concentrations and at the 12-2-12 low mole fractions. We believe that this knowledge should be important when considering the formulation of gemini surfactants into various chemical products.     

Adsorption equilibrium and kinetics on N-lauroyl-N-methylglucamide at air/water interface

The adsorption equilibrium and kinetics of N-lauroyl-N-methylglucamide (MEGA-12) aqueous solution were studied. The critical micelle concentration, the maximum surface excess, and the minimum area per molecule of MEGA-12 were obtained as 2.48 × 10⁻⁴ mol/l, 4.883 × 10⁻⁶ mol/m², and 0.34 nm², respectively. The adsorption kinetics of MEGA-12 was studied by the maximum bubble pressure method. The result shows that in the initial stage or at small MEGA-12 concentrations, the adsorption process is diffusion-controlled; however, it changes to become adsorption-controlled at the end of the process. The effects of temperature, inorganic salts, alcohols, and ionic liquid on the adsorption kinetics were also discussed. The text was submitted by the authors in English.     

Adsorption kinetics at the solid/solution interface: statistical rate theory at initial times of adsorption and close to equilibrium

The kinetics of solute adsorption at the solid/solution interface has been studied by statistical rate theory (SRT) at two limiting conditions, one at initial times of adsorption and the other close to equilibrium. A new kinetic equation has been derived for initial times of adsorption on the basis of SRT. For the first time a theoretical interpretation based on SRT has been provided for the modified pseudo-first-order (MPFO) kinetic equation which was proposed empirically by Yang and Al-Duri. It has been shown that the MPFO kinetic equation can be derived from the SRT equation when the system is close to equilibrium. On the basis of numerically generated points ( t, q) by the SRT equation, it has been shown that we can apply the new equation for initial times of adsorption in a larger time range in comparison to the previous q vs radical t linear equation. Also by numerical analysis of the generated kinetic data points, it is shown that application of the MPFO equation for modeling of whole kinetic data causes a large error for the data at initial times of adsorption. The results of numerical analysis are in perfect agreement with our theoretical derivation of the MPFO kinetic equation from the SRT equation. Finally, the results of the present theoretical study were confirmed by analysis of an experimental system.     

Adsorption and precipitation processes at cadmium oxide/sodium sulfate aqueous solution interface

The results of experimental studies of the adsorption of ions at the cadmium oxide/electrolyte solution interface are presented. On the basis of kinetic changes in the concentration of cadmium, hydroxide, and sulfate ions in the solution, the processes occurring in this system are discussed. It was found that cadmium oxide is transformed into the hexagonal form of cadmium hydroxide. The surface charge data for cadmium oxide/aqueous Na₂SO₄ are presented.     

Local mobility and structure of cationic amphiphilic diblock copolymer micelles in aqueous solutions

The local mobility and organization of micelles formed by the cationic diblock copolymer PS-poly(N-ethyl-4-vinylpyridinium bromide) in dilute aqueous solutions is studied by spin-probe ESR spectroscopy. Micelles composed of a hydrophobic PS core and a lyophilizing polyelectrolyte corona are prepared by two methods: dialysis from a nonselective solvent and direct dispersion of the diblock copolymer in water under long-term heating. Velocity-sedimentation studies and static and dynamic light-scattering measurements show that the micelles obtained by dialysis have smaller mean hydrodynamic sizes and weight-average molecular masses and are less polydisperse than micelles prepared by direct dispersion. The ESR spectra of spin probes localized in micelles of both types are found to be identical. This finding suggests that their local structure is independent of the dispersion procedure and molecular-mass characteristics. Probes are localized in the outer layer of the PS core near the core/shell boundary, and their local mobility is a factor of ∼2 higher than the local mobility of probes in the phase of the solid PS. It is inferred that the structure of the outer layer of the PS core in micelles is looser than the structure of PS in the solid phase. The localization sites of spin probes are partially penetrated by water.     

Adsorption kinetics at air/solution interface studied by maximum bubble pressure method

A general dynamic surface adsorption equation (t) for maximum bubble pressure method was derived by solving Ficks diffusion equation for the bubbles under different initial and boundary conditions. Different from the planar surface adsorption(Ward-Tordai equation), the derived dynamic surface adsorption (t) for the short time consists of two terms, one of them reflects the geometric effect caused by the spherical bubble surface. This kind of effect was discussed.The equilibrium surface tension _eq and the dynamic surface tension (t) of aqueous C₁₀E₈ (CH₃(CH₂)₉(OCH₂CH₂)₈OH) solution at temperature 25 °C were measured by means of Wilhelmy plate method and maximal bubble pressure method respectively. In the region of t0 (short time limits) a good agreement of experimental results with the theory was reached and the adsorption was controlled by diffusion. However, for the long time limits, a mixed diffusion-kinetics controlled process was proved.     

Adsorption and phase transition of alkanol and fluoroalkanol at electrified mercury/aqueous solution interface

The adsorption behavior and the phase transition of alkanol and fluoroalkanol at the electrified mercury/aqueous solution interface were investigated by the interfacial tension measurements and the thermodynamic analysis. In the alkanol system, it is found that the phase transitions in low interfacial densities occur: the ones from the zero adsorption to the gaseous or the expanded state and the gaseous to the expanded state at the electrified interface depending on the electrostatic nature as well as the concentration in the bulk phase. These phase transitions were verified by the thermodynamic equations derived by the assumption of coexistence of two phases at the electrified interface. Furthermore the distribution of ionic species in the interfacial region is discussed on the basis of dependence of the interfacial charge density of solution phase on an applied potential. Fluoroalkanol, on the other hand, was practically not adsorbed at the electrified interface within this experimental condition. The zero adsorption of fluoroalkanol molecules suggests the driving force of the adsorption may be the interaction hydrophobic group of alcohol molecule and mercury.     

Synthesis and aqueous solution properties of a well-defined thermo-responsive schizophrenic diblock copolymer

We report only the second example of a thermo-responsive 'schizophrenic' diblock copolymer surfactant: unlike the original (meth)acrylamide-based example reported by Laschewsky and co-workers (J. Am. Chem. Soc., 2002, 124, 3787), this new methacrylate-based diblock copolymer is near-monodisperse, readily synthesized in high yield and exhibits a broad temperature range between the two micelle transitions.     

Diffusion-controlled adsorption kinetics at the air/solution interface

 To describe diffusion-controlled adsorption, the diffusion equation is solved under different initial and boundary conditions by means of a Laplace transformation. By solving this equation, it has been found that the solution, which Ward and Tordai used, is only applicable for x>0; therefore, it is incorrect if the derivation is made at x = 0. Ward and Tordai did not notice this and the first derivation was made at x = 0 in order to get the dynamic surface adsorption, Γ(t). In this paper, an accurate solution, which is applicable for x≥ 0, is given and the expression for Γ(t) is obtained. Furthermore the relationship between the dynamic surface tension and Γ(t) is derived. As an example, the dynamic surface tensions of an aqueous octyl-β-d-glucopyranosid solution were measured by means of the maximum bubble pressure method. By using the derived theory it has been proved that the controlling mechanism of the adsorption process of this surfactant at the long-time-adsorption limits changes as a function of the bulk concentration; only at dilute concentration is it controlled by diffusion. Received: 26 July 1999/Accepted in revised form: 16 September 1999     

Twinning and growth kinetics of lamellar grains in a diblock copolymer solution

The initial stages of growth of the lamellar phase in a block copolymer solution were observed with polarizing optical microscopy (POM). Measurements were made on a poly(styrene‐b‐isoprene) diblock copolymer with block molecular weights of 15 and 13 kg/mol, respectively, dissolved in dioctyl phthalate with 70% polymer by volume. Upon cooling from above the order–disorder transition temperature, 89.5 °C, to temperatures from 87.5 to 88.5 °C, four distinct types of grain were observed: ellipsoidal single grains, twinned ellipsoidal grains, 2‐fold twinned grains, and spherulites. The relative populations were distributed as 50% single ellipsoids, 25% twinned ellipsoids, 10% 2‐fold twinned grains, and 15% spherulites. These grain types cover a range of lamellae orientation. For example, the surface of a 2‐fold twinned grain is composed of lamellar edges, whereas the spherulite surface is composed of lamellar planes. The specific grain types that arise give insight into the thermodynamic and kinetic forces governing lamellae ordering. Furthermore, growth front velocities of individual grains were measured after rapid quenches from above T_ODT. These results were compared to the predictions of Goveas and Milner. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 405–412, 2005     

Molecular weight dependence of diblock copolymer segregation at a polymer/polymer interface

Utilizing forward recoil spectrometry (FRES), we have determined the segregation isotherm which describes the interfacial excess z_i^* of diblock copolymers of poly (d₈-styrene-b-2-vinylpyridine) (dPS-PVP) at the interface between the homopolymers PS and PVP as a function of ?_∞, the volume fraction of diblock copolymer remaining in the host homopolymer. All the samples were analyzed after annealing at temperatures and times sufficient to achieve equilibrium segregation. The effect of the degree of polymerization of both the diblock copolymers and the host homopolymers on the segregation isotherm is investigated. When the degree of polymerization of the homopolymer is much larger than that of the diblock copolymer, the normalized interfacial excess (z_i^*/R_g), where R_g is the radius of gyration of an isolated block copolymer chain, is a universal function of that portion of the block copolymer chemical potential due to chain stretching. The existence of such a universal function is predicted by theory and its form is in good agreement with self-consistent mean field calculations. Using these results, one can predict important aspects of the block copolymer segregation (e.g., the saturation interfacial excess) without recourse to the time-consuming numerical calculations. © 1994 John Wiley & Sons, Inc.     

Crystallization of micelles and matrix in dilute diblock copolymer/homopolymer solutions

The crystallization, morphology, and crystalline structure of dilute solid solutions of tetrahydrofuran–methyl methacrylate diblock copolymer (PTHF-b-PMMA) in poly(ethylene oxide) (PEO) and PTHF have been studied with differential scanning calorimetry (DSC), X-ray, and optical microscopy. This study provides a new insight into the crystallization behavior of block copolymers. For the dilute PTHF-b-PMMA/PEO system containing only 2 to 7 wt % of PTHF content, crystallization of the PTHF micellar core was detected both on cooling and on heating. Compared the crystallization of the PTHF in the dilute solutions with that in the pure copolymer, it was found that the crystallizability of the PTHF micellar core in the solution is much greater than that of the dispersed PTHF microdomain in the pure copolymer. The stronger crystallizability in the solution was presumably due to a softened PMMA corona formed in the solution of the copolymer with PEO. However, the “soft” micelles formed in the solution (meaning that the glass transition temperatures (T_g) of the micelle is lower than the T_m of the matrix phase) showed almost no effects on the spherulitic morphology of the PEO component, compared with that of the pure PEO sample. In contrast, significant effects of the micelles with a “hard” PMMA core (meaning that the T_g of the core is higher than the T_m of the PTHF homopolymer) on the nucleation, crystalline structure, and spherulitic morphology were observed for the dilute PTHF-b-PMMA/PTHF system. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 2961–2970, 1998     

Adsorption of cetyltrimethylammonium bromide at the silica gel/water interface

The adsorption isotherms of cetyltrimethylammonium ion (CTA+) together with that of the Br counterion on silica gel, and the effects of pH and added salts (NaF, NaCl and NaBr) have been systematically determined at 25°C. Electrophoretic mobilities of the silica gel particles have also been measured in the same conditions. The adsorption isotherm of CTA⁺ consists of four regions. Region I, at low concentrations of surfactant, the adsorption results primarily from electrostatic force between CTA⁺ and the negatively charged silica surface. Region II (first plateau), at medium concentrations, the adsorption is due to both the electrostatic force and the specific attraction (vdW forces) between CTA⁺ and the surface. Region III, characterized by an abrupt increase in the slope of the isotherm when the concentration reaches a particular point known as hemimicelle concentration (HMC). The abrupt increase in the adsorption is due to the hydrophobic interaction between hydrocarbon chains. Region IV (second plateau), at or above CMC, the limiting adsorption is reached as the micelle is not adsorbed. Based on this model, the experimental results can be explained reasonably. The results show that the HMC is about half of the CMC. According to the assumption that each adsorbed CTA⁺ ion in the first plateau is an active center for surface aggregation, the average aggregation number of hemimicelle have been calculated.     

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.