Tightly Bound PMMA on Silica Has Reduced Heat Capacities.

The heat capacities of very small adsorbed amounts of poly(methyl methacrylate) on high-surface-area silica (Cab-O-Sil) were measured using temperature-modulated differential scanning calorimetry (TMDSC) using a quasi-isothermal method and interpreted via different models. The composition-dependent heat capacities of the adsorbed samples were measurably less than those predicted with a simple mixture model. A two-state model, composed of tightly and loosely bound polymer, fits the data better with heat capacities of the tightly bound polymer found to be 70-80% (glassy region) and 70-94% (rubbery region) of that of the bulk polymer at the same temperatures. The amount of tightly bound polymer was estimated to be about 1.2 mg/m2 (about 1 nm thickness) in both the glassy and rubbery regions, consistent with heat flow measurements. The data sets were also extensive enough to model them with a more detailed layered gradient model, including a nonzero heat capacity for the polymer at zero adsorbed amount, which increased based on an exponential growth function to bulk polymer value of the heat capacity away from the surface. More importantly, this gradient model mimicked the experimental dependence on adsorbed amounts in the tightly bound adsorbed amount region (approximately 1 mg/m2). This model provided, for the first time, an experimental estimate of the heat capacity of the polymer adsorbed closest to the surface. The fractional heat capacity of the adsorbed polymer closest to the silica surface, relative to bulk polymer, increased with temperature from 0.3 (well below) to 0.8 (well above the bulk Tg). It was also possible to estimate the exponential growth parameter of the development from the initial heat capacities to the bulk heat capacity as 0.4 to 0.6 mg/m2, identifying a distance scale (0.3 to 0.5 nm) consistent with the notion of a transition from tightly bound to loosely bound polymer.

Dynamics of Cetyltrimethylammonium Bromide Head Groups in Bulk by Solid-State Deuterium NMR Spectroscopy.

Variable temperature, solid-state deuterium (2H) NMR spectroscopy has been used to probe the rather complex head group dynamics of the surfactant cetyltrimethylammonium bromide- d9 (CTAB- d9) in bulk. Heating and cooling runs were made as the surfactant underwent supercooling. 2H NMR line shape simulations were used to identify the hierarchy of the molecular motions of CTAB as a function of temperature. Fast continuous methyl rotations about the N-Cmethyl axes and 3-fold jumps about the main chain C-N axis were present at all of the temperatures from -40 to 120 °C. With heating, the spectra were consistent with CTAB molecules starting 180° flips about the hydrocarbon chain molecular axis around 0 °C, which continued to flip with increasing flip rates up to 80 °C. At 90 °C, the flips changed to rotation of the CTAB molecules about the hydrocarbon chain axis and that rotation continued to 120 °C. Comparison of spectra of bulk CTAB at different temperatures from heating and cooling runs revealed that the rotation about the long axis of the hydrocarbon chains started at around 90 °C on heating, however, it does not freeze out until between 70 and 80 °C because of supercooling.

Cationic surfactant blocks radical-inhibiting sites on silica.

Surfactant-catalyzed room-temperature radical polymerization of methyl methacrylate (MMA) was conducted in the presence of fumed silica nanoparticles and water. Three types of surfactants, cationic (CTAB), nonionic (Triton X-100) or anionic (SDS), were used to catalyze the decomposition of the initiator, 2,2'-azobisisobutyronitrile (AIBN). The surfactant-catalyzed decomposition rate constant for AIBN at room temperature was found to be independent of the surfactant type. However, the rates of polymerization of the MMA emulsion gels at room temperature were found to depend on the types of surfactant with: cationic>nonionic>anionic. An inhibition period was observed for the polymerizations with nonionic and anionic surfactants. The radical-inhibition was likely due to the reactions between the radicals and the silanol groups on fumed silica. This inhibition can be reduced by using cationic surfactants to block these surface silanols.

Surface Properties of Silane-Treated Diatomaceous Earth Coatings: Effect of Alkyl Chain Length.

Modification of diatomaceous earth (DE) was performed using alkyltrimethoxysilanes of different chain lengths (C3, C8, C12, C16, and C18), and their resultant properties were determined. The thermal properties of these alkyltrimethoxysilane-treated DE powders were probed using thermogravimetric analysis and temperature-modulated differential scanning calorimetry, and the surface/porosity was studied using nitrogen adsorption and electron microscopy. Crystallinity of the hydrocarbon tails occurred when the chain lengths were C12 or larger, and the adsorbed hydrocarbon amounts were 1.6 mg/m2 or more. The wettability of functionalized DE-containing surfaces was studied using water contact angle measurements. At larger adsorbed amounts of 2.2 mg/m2 or more, the treated DE formed superhydrophobic coatings (with water contact angles ≥150°) with a polyurethane binder. These coatings required a minimum of 30% particle loadings, which allowed the DE particles to dominate the surface. At loadings larger than approximately 50%, there was a decrease in the contact angles corresponding to a reduction in roughness on the surface. Samples with adsorbed amounts less than 2.2 mg/m2 or chain lengths shorter than C12 were only hydrophobic. These results were in agreement with scanning electron microscopy and Brunauer-Emmett-Teller specific surface area and pore volume measurements.

A three-dimensional in vitro model to demonstrate the haptotactic effect of monocyte chemoattractant protein-1 on atherosclerosis-associated monocyte migration.

Monocyte transendothelial migration is a multi-step process critical for the initiation and development of atherosclerosis. The chemokine monocyte chemoattractant protein-1 (MCP-1) is overexpressed during atheroma and its concentration gradients in the extracellular matrix (ECM) is critical for the transendothelial recruitment of monocytes. Based on prior observations, we hypothesize that both free and bound gradients of MCP-1 within the ECM are involved in directing monocyte migration. The interaction between a three-dimensional (3D), cell-free, collagen matrix and MCP-1; and its effect on monocyte migration was measured in this study. Our results showed such an interaction existed between MCP-1 and collagen, as 26% of the total MCP-1 added to the collagen matrix was bound to the matrix after extensive washes. We also characterized the collagen-MCP-1 interaction using biophysical techniques. The treatment of the collagen matrix with MCP-1 lead to increased monocyte migration, and this phenotype was abrogated by treating the matrix with an anti-MCP-1 antibody. Thus, our results indicate a binding interaction between MCP-1 and the collagen matrix, which could elicit a haptotactic effect on monocyte migration. A better understanding of such mechanisms controlling monocyte migration will help identify target cytokines and lead to the development of better anti-inflammatory therapeutic strategies.

Low-temperature polymerization of methyl methacrylate emulsion gels through surfactant catalysis.

Poly(methyl methacrylate) (PMMA)/silica/cetyltrimethylammonium bromide (CTAB) composites were prepared through surfactant catalyzed free radical polymerizations at 40 °C. Fumed silica particles controlled the morphology of the polymeric composites producing porous structures. The internal structures of the porous composite were determined using temperature-modulated differential scanning calorimetry (TMDSC). The fumed silica particles were encapsulated by an incompletely covered CTAB monolayer, with a crystallization temperature, T(C,CTAB)=76 °C, and a mixed PMMA/CTAB shell, with T(C,CTAB)=63 °C. The fumed silica surfaces acted as inhibitors for PMMA free radical polymerizations. Much of the PMMA formed in the composites was adsorbed on the silica, as evidenced by its elevated glass transition temperature compared to bulk. The enhanced decomposition of the initiator was catalyzed by CTAB and resulted in free radical polymerization of PMMA at 40 °C, which is considerably lower than the temperatures normally used for PMMA synthesis by free radical means with thermal initiation. These lowered polymerization temperatures allow energy efficient production of composites, which can incorporate temperature sensitive materials.

PS/CTAB/silica composites from room temperature polymerization of high internal phase emulsion gels.

Polystyrene (PS)/cetyltrimethylammonium bromide (CTAB)/silica composites were prepared by CTAB-catalyzed in-situ polymerization of high internal phase emulsion gels (HIPE gels) at room temperature. The room temperature approach in HIPE gels yielded mono-dispersed PS/CTAB/silica spherical composite particles with sizes of 121 and 155nm. The complex microscopic internal structures of these particles were determined with the use of temperature-modulated differential scanning calorimetry (TMDSC). CTAB, in particular, was identified in different environments within the composite particles based on its different crystallization temperatures observed on cooling: a thin layer at the surface of the fumed silica (TC,CTAB=74°C), multilayers (TC,CTAB=82°C), and a mixed PS/CTAB shell (TC,CTAB=65°C). The amounts of each component were estimated from the enthalpies of the crystallization. The PS/CTAB mixed shell contained CTAB on the surface of the particle plus internal CTAB domains.

Segmental dynamics in poly(methyl acrylate) on silica: effect of surface treatment.

The effect of surface treatment on the dynamics of adsorbed poly(methyl acrylate) (PMA) was studied using deuterium NMR and temperature-modulated differential scanning calorimetry (TMDSC). The solid-state deuterium NMR experiments were performed using PMA-d(3), deuterated on the methyl group. The line shape changes for PMA-d(3) were followed as a function of temperature and compared for the polymer on untreated silica, organically modified (treated) silica (reacted with hexamethyltrisilazane), and in bulk. The dynamics of PMA-d(3) on treated silica was found to be intermediate between that of the polymer adsorbed on untreated silica and that of the bulk polymer, i.e., the treated silica caused a restriction on the dynamics of the polymer as compared to bulk, but not as dramatically as that on untreated silica. Similar to the dynamics on untreated silica, the dynamics on treated silica showed a broad heterogeneity with a superposition of more-mobile and less-mobile components. Two molecular mass samples were also studied (38 and 77 kDa) with the molecular mass dependence on the treated or untreated silica being weaker than that in bulk. The TMDSC thermograms of the samples were consistent with the NMR results, with the glass transition region for the PMA-d(3) on the treated silica being in between that of the bulk and that on the untreated silica.

Segmental dynamics of poly(methyl acrylate)-d3 adsorbed on anopore: a deuterium NMR study.

The segmental dynamics of poly(methyl acrylate-d3) (PMA-d3) adsorbed in the pores of anopore membranes has been investigated using deuterium NMR over the temperature range 25-80 degrees C. The onset of the NMR glass-transition temperature (Tg) for the adsorbed samples was approximately 15 degrees C higher than that for the bulk sample. The adsorbed polymer contained segments with restricted mobility (glassy), even at the highest temperatures studied, at which the bulk polymer showed only mobile segments. The spectra from samples with different adsorbed amounts of PMA-d3, between 1.1 and 4.2 mg/m2, were similar in their temperature-dependent mobilities. Neither was there much difference in the spectra of PMA-d3 on anopore samples with pore sizes of 0.2 and 0.02 microm. However, for a solvent-washed sample with an adsorbed amount of 0.7 mg/m2, additional restriction in PMA-d3 mobility was observed.

Segmental dynamics in poly(methyl acrylate) on silica: molecular-mass effects.

The effect of molecular mass on the segmental dynamics of poly(methyl acrylate) (PMA) adsorbed on silica was studied using deuterium quadrupole-echo nuclear magnetic resonance (NMR) and modulated differential scanning calorimetry. Samples adsorbed on silica (all about 1.5 mg PMA/m2 silica) were shown to have more restricted segmental mobility, and higher Tg's, than the corresponding bulk PMA samples. Around the glass-transition region, adsorbed samples exhibited segmental mobility, which could be classified as heterogeneous due to a superposition of more-mobile and less-mobile components present in the deuterium NMR spectra. This heterogeneity was consistent with a motional gradient with more-mobile segments near the polymer-air interface and the less-mobile species near the polymer-silica interface. The mobility of the adsorbed 77 kDa PMA sample was the lowest among the four different molecular-mass samples studied. Samples studied with masses both larger and smaller than 77 kDa had larger mobile-component fractions in the adsorbed polymer. The additional mobility was attributed to the presence of either longer tail and loop conformations in the higher molecular-mass samples or the inherent mobility of the tails in the lower molecular-mass samples on the surface.

A comparative study of the properties of polar and nonpolar solvent/solute/polystyrene solutions in microwave fields via molecular dynamics.

The influence of an applied microwave field on the dynamics of methylamine-dichloromethane (DCM) mixtures bound within atactic polystyrene (a-PS) over a range of polymer densities from 30 to 94 wt % polymer was examined using atomistic molecular dynamics simulations. This study is an extension of previous studies on methylamine transport in relatively polar polystyrene solutions of methanol and dimethylformamide [M. J. Purdue et al., J. Chem. Phys. 124, 204904 (2006)]. A direct comparison is made across the three types of polystyrene solutions. Consideration is given to both solvent and reagent transport within the polymer solutions under zero-field conditions and in an external electromagnetic field in the canonical ensemble (NVT) at 298.0 K. Various frequencies up to 10(4) GHz and a rms electric field intensity of 0.1 VA were applied. The simulation studies were validated by comparison of the simulated zero-field self-diffusion coefficients of DCM in a-PS with those obtained using pulsed-gradient spin-echo NMR spectrometry. Athermal effects of microwave fields on solute transport behavior within polymer solutions are discussed.

Room-temperature decomposition of 2,2'-azobis(isobutyronitrile) in emulsion gels with and without silica.

The decomposition of 2,2'-azobis(isobutyronitrile) (AIBN) at room temperature was studied in emulsion gels, with and without silica, using UV/visible spectroscopy. The emulsion gels consisted of toluene, AIBN, an aqueous solution of a surfactant (either hexadecyltrimethylammonium bromide, CTAB, or sodium dodecyl sulfate, SDS), and, in some cases, fumed silica. The AIBN compositions were determined in the opaque emulsion gels by converting them to transparent microemulsions. The decomposition rate constants for AIBN were determined to be 3.7 x 10(-8) s(-1) (+/-0.6 x 10(-8) s(-1)) for the emulsion gels and 10.2 x 10(-8) s(-1) (+/-1.3 x 10(-8) s(-1)) for the silica-containing emulsion gels. These rate constants were significantly greater than that in toluene solution, which, by our technique, is below our measurement threshold (effectively 0).

Molecular dynamics of polystyrene solutions in microwave fields.

Equilibrium and nonequilibrium molecular dynamics simulation techniques were used to assess the influence of an applied microwave field on the dynamics of methylamine-methanol and methylamine-dimethylformamide (DMF) solutions bound within atactic polystyrene over a range of polymer densities from 35 to 96 wt % polymer. Atomistically detailed systems were studied, ranging from 3000 to 10 644 particles, using previously established potential models. Structural and dynamical properties were determined in the canonical (NVT) ensemble at 298 K. The simulated DMF self-diffusion coefficients in polystyrene solutions were compared with the zero-field experimental results established with pulsed-gradient spin-echo NMR spectrometry. A simulated external microwave field, with a rms electric field intensity of 0.1 VA, was applied to these systems and the simulated dynamical results over field frequencies up to 10(4) GHz were compared with the zero-field values. Simulated evidence of athermal effects on the diffusive characteristics of these mixtures is reported.

Thermal Analysis of Adsorbed Poly(methyl methacrylate) on Silica.

Modulated differential scanning calorimetry has been used to quantify the glass transitions of small adsorbed amounts of poly(methyl methacrylate) (PMMA) on silica. While a relatively narrow, single glass transition was found for bulk PMMA, broader two-component transitions were found for the adsorbed polymer. A two-state model based on loosely bound polymer (glass transition similar to bulk) and more tightly bound polymer (glass transition centered around 156 degrees C) was used to interpret the thermograms. On the basis of this model, the amount of tightly bound polymer was found to be approximately 1.3 mg/m2, corresponding to a 1.1 nm thick layer. The change in heat capacity for the tightly bound polymer at the glass transition temperature was estimated to be about 16% of that of the bulk polymer.

Molecular mass and dynamics of poly(methyl acrylate) in the glass-transition region.

The segmental dynamics of bulk poly(methyl acrylate) (PMA) were studied as a function of molecular mass in the glass-transition region using 2H NMR and modulated differential scanning calorimetry (MDSC). Quadrupole-echo 2H NMR spectra were obtained for four samples of methyl-deuterated PMA-d3 with different molecular masses. The resulting spectra were fit using superpositions of simulated spectra generated from the MXQET simulation program, based on a model incorporating nearest-neighbor jumps from positions on the vertices of a truncated icosahedron (soccer-ball shape). The lower molecular-mass samples, influenced by the presence of more chain ends, showed more heterogeneity (broader distribution) and lower glass transitions than the higher molecular-mass samples. The MDSC experiments on both protonated and deuterated samples showed behavior consistent with the NMR results, but temperature shifted due to the different frequency range of the measurements in terms of both the position and breadth of the glass transition as a function of molecular mass.

Synthesis of polyaniline-gold nanocomposites using "grafting from" approach.

Polyaniline-gold nanocomposites containing polyaniline nanostructures attached to well-dispersed uniform-size gold nanoparticles were obtained using a surface initiation approach.