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A mesostructured nanocomposite was fabricated by using a novel electroactive, polymerizable surfactant as a template in a sol-gel process, and the first example of well-resolved polystyrene with redoxactive functional group synthesized in silicate matrices was provided.
Benzene rings of polystyrene samples are labelled with deuterium oxide and catalytic amount of platinum(iv) oxide under hydrothermal conditions.
A solvent-free route for the photooxygenation of the 5-methoxyoxazoles (1) is described. The substrates were embedded in nanosized polystyrene particles generated by the emulsifier-free emulsion polymerization of styrene with divinylbenzene and porphyrine dyes as cross-polymerizable reagents. From the photooxygenation of , the 1,2,4-dioxazoles (2) were formed and isolated from the reaction cavities by ethanol extraction. From comparison of the substrate conversions, the efficiency of singlet oxygen generation from the porphyrine dyestuff and the stability of the sensitizing material were estimated.
In the asymmetric addition of allyltrichlorosilane to benzaldehyde, polystyrenes with chiral phosphoramide substituents as Lewis base catalysts showed up to 2.4 times better catalytic activity and 1.4 times higher enantioselectivity than the corresponding low-molecular-weight analogues.
Production of porous polystyrene microspheres having dimpled surface structures was demonstrated using amphiphilic and hydrophobic silica particles as structure-directing agents.
The single-step preparation of a polystyrene-bound N-methylthiourea and its use for the hydrogenolysis of bicyclic endoperoxides is described.
Polymer brushes consisting of polystyrene (PS) chains bonded covalently to N-doped multiwalled carbon nanotubes (CNx) were synthesized by a "grafting from" route using nitroxide mediated radical polymerization (NMRP).
The interaction between platelets stirred in suspension and VWF immobilized on polystyrene beads was studied. Platelets aggregated and released ATP in response to stirring with VWF beads. Closer examination of the interaction using transmission electron microscopy revealed that the platelets did not simply aggregate with one another but initially adhered to the beads and spread. Platelets in suspension then bound to the bead-adherent platelets forming layers of platelets associated with each bead. The VWF bead-induced platelet activation was completely inhibited by addition of monoclonal antibody (mAb) to GPIb or GPIIb/IIIa. In addition, the activation response was inhibited in the presence of aspirin, indomethacin or the thromboxane receptor antagonist BM13.177, demonstrating a dependence on an intact cyclo-oxygenase pathway. Platelet function studies were carried out on 30 patients with a history of mild bleeding using conventional optical aggregation and VWF bead-induced platelet activation. 12 patients were abnormal by conventional optical aggregometry, whereas 27 patients showed depressed ATP release in response to VWF beads. The results suggest that easily-bruised patients may have a platelet function defect rather than a vascular-based abnormality and that VWF bead-induced platelet activation is a more sensitive test for detecting platelet dysfunction.
The delta form of crystalline syndiotactic polystyrene is a clathrate molecular compound in which various aromatic molecules are encaged. We have investigated the size, shape, and connectivity of the molecular cavity in the crystal using a molecular dynamics simulation. The effects of the guest species on the cavity structure were investigated in detail. In order to systematically vary the guest structure, various aromatic guests, e.g., benzene, toluene, p-xylene, m-xylene, o and mesitylene were examined. The interstitial spaces between the guests and the polymer chains were analyzed by cluster analysis of the free volumes. The individual cavity volumes into which the guests are clathrated were also evaluated. It was found that the guest molecules can greatly affect not only the cavity size and shape but also the connectivity of the cavities. The transport of small molecules in the crystal is discussed in connection with the cavity structure.
Various characteristics of dewetting of thin polystyrene (PS) films absorbed on highly cross-linked epoxy-coated and silicon oxide covered substrates are studied as a function of PS film thickness (20 h(c1) whereas the spinodal dewetting (SD) occurs through the growth of surface undulations for h h(c2) while the SD mechanism is observed for h<h(c2), where h(c2) is approximately 6R(g). We demonstrate that the highly cross-linked epoxy-coated silicon substrate leads to retardation of the PS film dewetting in comparison to the silicon oxide covered silicon substrate. Moreover, we confirm that the epoxy-coated substrate leads to a significant decrease in the fraction of dewetted area at the apparent equilibrium stage of dewetting due to the anchoring effect of PS molecules caused from the cross-linked networks of the epoxy layer. In contrast the retardation effect of the epoxy-coated substrate on the rate of dewetting is more remarkable for relatively thinner PS films (h< approximately 800 A) than thicker films ( approximately 800<h<1300 A) since the short-range intermolecular interactions are dominant for relatively thin PS films. Thus the highly cross-linked epoxy-coated substrate has a large influence on the kinetics, morphology, and mechanism of dewetting of thin PS films.
Lateral force microscopy (LFM) was used to probe the molecular motions at thin polystyrene film surface. The effect of the applied load on the LFM measurements was investigated by presenting both the LFM results and the surface morphology after several scans over the same area. Depending on the loads, the scanning can be nonperturbative (without alternating the surface morphology) or perturbative (patterning the surface). Temperature-dependent LFM measurements were conducted in order to determine the apparent transitions at the surface. Perturbative scans under high loads (e.g., 150 nN) witnessed that the apparent transitions shifted to low temperatures with an increasing scan rate, while the transitions behaved oppositely under lower loads (1, 10, and 20 nN). The heating effect is suggested to account for the behavior under high loads. According to our results from nonperturbative LFM, the apparent glass transition temperature (T(g)s) is more than 10 K lower than the bulk value. Moreover, rate-dependent LFM measurements were performed under 1 nN in order to detect the surface molecular motions. Time-temperature superposition yields a master curve exhibiting three apparent relaxation peaks. The molecular motions at the surface are discussed on the context of the coupling model.
The reorientation of one small paramagnetic molecule (spin probe) in glassy polystyrene (PS) is studied by high-field electron paramagnetic resonance spectroscopy at two different Larmor frequencies (190 and 285 GHz). Two different regimes separated by a crossover region are evidenced. Below 180 K the rotational times are nearly temperature independent with no apparent distribution. In the temperature range of 180-220 K a large increase of the rotational mobility is observed with the widening of the distribution of correlation times which exhibits two components: (i) a deltalike, temperature-independent component representing the fraction of spin probes w which persist in the low-temperature dynamics; (ii) a strongly temperature-dependent component, to be described by a power distribution, representing the fraction of spin probes 1-w undergoing activated motion over an exponential distribution of barrier heights g(E). Above 180 K a steep decrease of w is evidenced. The shape and the width of g(E) do not differ from the reported ones for PS within the errors. For the first time the large increase of the rotational mobility of the spin probe at 180 K is ascribed to the onset of the fast dynamics detected by neutron scattering at T(f)=175+/-25 K.
Video particle tracking (VPT) and diffusing wave spectroscopy were used to characterize the microrheology of polystyrene sulfonate combs in aqueous solutions. At low frequencies VPT demonstrated predominantly viscous behavior. The manner in which the viscosity scaled as a function of monomer concentration was a sensitive function of the comb architecture. Densely branched combs or combs with long side chains demonstrated entangled polyelectrolyte scaling above the overlap concentration, whereas sparsely branched combs had unentangled polyelectrolyte scaling. A dynamic scaling model was developed for the viscosity of unentangled semidilute solutions of comb polyelectrolytes. Diffusing wave spectroscopy demonstrated Rouse modes (G' approximately G" approximately omega12) for the high-frequency dynamics of the semidilute comb solutions. The form of the high-frequency viscoelasticity was independent of the chain architecture and the modulus scaled as expected for linear flexible polyelectrolytes.
The surface pressure of monolayers of insoluble diblock copolymers has been measured. One of the blocks is made of poly(t-butyl acrylate) (PtBA), and the other one by polystyrene (PS). The interface is a good solvent for PtBA, while it is a poor solvent for PS. For the sake of comparison, monolayers of a PtBA homopolymer (good solvent conditions) and of poly(4-hydroxy styrene) (P4HS) (poor solvent conditions) have been also measured. It has been found that the relative length of the blocks plays an important role on the shape of the surface pressure Pi versus surface concentration Gamma curves and also on the shape of the equilibrium compressibility versus Gamma curves. However, it does not affect the maximum value of Pi reached at high Gamma's. Surprisingly, the ellipsometric thickness of the copolymer monolayers is almost independent of the relative length of the blocks. The dynamics of the monolayers has been studied by step compression and by surface-light scattering techniques. When M(w,PtBA) >> M(w,PS) single exponential relaxations are observed. However, stretched exponentials are obtained for M(w,PS) > or = M(w,PtBA). The relaxation times decrease with increasing Gamma for all the copolymers studied. This is the behavior usually found for poor solvent conditions (P4HS) and opposite to that found for homopolymers under good solvent conditions [PtBA, poly(vinylacetate)]. This means that the solvent quality of the interface does not determine the pressure dependence of tau. The elasticity modulus of the monolayers in the kilohertz range takes values that are similar to those of the high-frequency limit of the relaxation experiments. This means that the relaxation processes have characteristic frequencies below 1 Hz.
A novel method for the continuous monitoring of thermooxidative degradation products of polystyrene by membrane extraction with sorbent interface (MESI) and gas chromatography (GC) is developed. The results are compared with solid-phase microextraction-GC, which can extract gases, vapors, and aerosols. The volatile and semivolatile degradation products are identified by mass spectrometry. The membrane used in the MESI-GC analysis shows a high permeation for volatile aromatic hydrocarbons; a low permeation for corresponding volatile aldehydes; and no permeation for less volatile alcohols, acids, and degradation products with a high molecular weight, thus reducing significantly the number of compounds detected from MESI-GC. Sensitivity of the method depends on the time of trapping, which is limited by the breakthrough of the trap. By heating the trap at fixed intervals of time, consecutive gas chromatograms are obtained.
The glass transition temperature T(g) and the temperature T(alpha) corresponding to the peak in the dielectric loss due to the alpha process have been simultaneously determined as functions of film thickness d through dielectric measurements for polystyrene thin films supported on glass substrate. The dielectric loss peaks have also been investigated as functions of frequency for a given temperature. A decrease in T(g) was observed with decreasing film thickness, while T(alpha) was found to remain almost constant for d>d(c) and to decrease drastically with decreasing d for d<d(c). Here, d(c) is a critical thickness dependent on molecular weight. The relaxation time tau(alpha) of the alpha process, which was measured as the frequency at which the dielectric loss realizes its peak value at a given temperature, was found to have a d dependence similar to that of T(alpha). The relaxation function for the alpha process was obtained by using the observed frequency dependence of the peak profile of the dielectric loss. The exponent beta(KWW), which was obtained from the relaxation functions, decreases as thickness decreases. This suggests that the distribution of relaxation times for the alpha process broadens with decreasing thickness. The thickness dependence of T(g) is directly related to the distribution of relaxation times for the alpha process, not to the relaxation time itself. The value of the thermal expansion coefficient normal to the film surface was found to increase with decreasing film thickness below T(g), but to decrease with decreasing film thickness above T(g). These experimental results are discussed in the context of a three-layer model in which within thin films there are three layers with different mobilities and glass transition temperatures.
X-ray photon correlation spectroscopy and small-angle x-ray scattering measurements are applied to characterize the dynamics and structure of concentrated suspensions of charge-stabilized polystyrene latex spheres dispersed in glycerol, for volume fractions between 2.7% and 52%. The static structures of the suspensions show essentially hard-sphere behavior. The short-time dynamics shows good agreement with predictions for the wave-vector-dependent collective diffusion coefficient, which are based on a hard-sphere model [C. W. J. Beenakker and P. Mazur, Physica A 126, 349 (1984)]. However, the intermediate scattering function is found to violate a scaling behavior found previously for a sterically stabilized hard-sphere suspension [P. N. Segre and P. N. Pusey, Phys. Rev. Lett. 77, 771 (1996)]. Our measurements are parametrized in terms of a viscoelastic model for the intermediate scattering function [W. Hess and R. Klein, Adv. Phys. 32, 173 (1983)]. Within this framework, two relaxation modes are predicted to contribute to the decay of the dynamic structure factor, with mode amplitudes depending on both wave vector and volume fraction. Our measurements indicate that, for particle volume fractions smaller than about 0.30, the intermediate scattering function is well described in terms of single-exponential decays, whereas a double-mode structure becomes apparent for more concentrated systems.
Temporal relaxation of rubbed polystyrene (PS) thin films (50 nm thick) was studied by probing the decay of the optical anisotropy in the sample. Our results show that the relaxation process is characterized by two single-exponential decays plus a temperature-dependent constant. Both relaxations are orders of magnitude faster than the main chain (alpha) relaxation at temperatures well below (>10 degrees C)T(g), with activation energies 3.0 kcal/mol and 5.1 kcal/mol, respectively, either of which are much smaller than that of the alpha relaxation ( approximately 50 kcal/mol). The decay time constants are found to be independent of the sample molecular weights M(w) (=13.7 K to 550 K Daltons, M(w)/M(n)</=1.1) at these temperatures. This shows the local nature of the relaxation modes of rubbed PS.