Reduced staining from a chlorhexidine mouthwash: A randomized clinical trial.

PURPOSE: To investigate the stain preventing ability of a new chlorhexidine mouthwash while maintaining efficacy using a randomized clinical trial design. METHODS: 98 subjects were enrolled and completed a 4-week clinical study that evaluated the effectiveness of the new mouthwash on plaque, gingivitis, and staining as compared to a commercially available chlorhexidine mouthwash. A subset of 62 subjects was evaluated for the effectiveness of the mouthwashes against plaque bacteria. RESULTS: After 4 weeks of use, the new chlorhexidine mouthwash reduced staining by 42.6% (P< 0.05) as compared to the commercially available mouthwash. The two mouthwashes were equivalent with regards to their effect on gingivitis, plaque, and plaque bacteria. CLINICAL SIGNIFICANCE: A new mouthwash, containing 0.12% chlorhexidine gluconate, has been developed that delivers stain reduction while maintaining equivalent efficacy to a commercially available chlorhexidine mouthwash with regards to gingivitis, plaque, and plaque bacteria. These findings should be considered by dental practitioners when making recommendations to patients whose teeth stain easily and need an anti-gingivitis and anti-plaque mouthwash.

Thermally Stable Metallic Nanoparticles Prepared via Core-Cross-linked Block Copolymer Micellar Nanoreactors.

Thermally stable metallic nanoparticles (MNPs) are highly desirable for the melt processing of polymer nanocomposites. However, due to the high surface energy penalty and decreased melting temperature, MNPs are easy to agglomerate and lose their unique properties if there is no protection or confinement layer. In this work, we report a facile and efficient way to synthesize thermally stable MNPs using core-cross-linked polystyrene-b-poly(4-vinylpyridine) (PS-b-P4VP) reverse micelles as nanoreactors. From infrared results, gold, silver, and palladium ions exhibited distinctive coordination to the 4VP groups with varying chelation strengths. Compared to the non-cross-linked micelles, 1,4-dibromobutane (DBB)-cross-linking of the P4VP cores provided several advantages. First, it prevented severe swelling of the P4VP cores caused by the reducing agents and subsequent merger of swollen micelles. Second, the quaternized P4VP with hydrophilicity enhanced the uptake speed of precursor metal ions into the cores. Third, the cross-linked cores greatly stabilized the MNPs against the high-temperature environment (e.g., 110 °C for 40 h in toluene). In addition, the solubility of the reducing agents also played an important role. Anhydrous hydrazine could swell the P4VP cores and concentric core-shell particle morphology was obtained. On the contrary, triethylsilane could not swell the P4VP cores and thus eccentric core-shell particle morphology was observed. Only the concentric core-shell MNPs exhibited good thermal stability, whereas the eccentric core-shell MNPs did not. This work suggested that these thermally stable MNPs could be good candidates for the melt processing of functional polymer nanocomposites.

In Situ Characterization of Binary Mixed Polymer Brush-Grafted Silica Nanoparticles in Aqueous and Organic Solvents by Cryo-Electron Tomography.

We present an in situ cryo-electron microscopy (cryoEM) study of mixed poly(acrylic acid) (PAA)/polystyrene (PS) brush-grafted 67 nm silica nanoparticles in organic and aqueous solvents. These organic-inorganic nanoparticles are predicted to be environmentally responsive and adopt distinct brush layer morphologies in different solvent environments. Although the self-assembled morphology of mixed PAA/PS brush-grafted particles has been studied previously in a dried state, no direct visualization of microphase separation was achieved in the solvent environment. CryoEM allows the sample to be imaged in situ, that is, in a frozen solvated state, at the resolution of a transmission electron microscope. Cryo-electron tomograms (cryoET) were generated for mixed PAA/PS brush-grafted nanoparticles in both N,N-dimethylformamide (DMF, a nonselective good solvent) and water (a selective solvent for PAA). Different nanostructures for the mixed brushes were observed in these two solvents. Overall, the brush layer is more compact in water, with a thickness of 18 nm, as compared with an extended layer of 27 nm in DMF. In DMF, mixed PAA/PS brushes are observed to form laterally separated microdomains with a ripple wavelength of 13.8 nm. Because of its lower grafting density than that of PAA, PS domains form more or less cylindrical or truncated cone-shaped domains in the PAA matrix. In water, PAA chains are found to form a more complete shell around the nanoparticle to maximize their interaction with water, whereas PS chains collapse into the core of surface-tethered micelles near the silica core. The cryoET results presented here confirm the predicted environmentally responsive nature of PAA/PS mixed brush-grafted nanoparticles. This experimental approach may be useful for the design of future mixed brush-grafted nanoparticles for nano- and biotechnology applications.

Environmentally responsive self-assembly of mixed poly(tert-butyl acrylate)-polystyrene brush-grafted silica nanoparticles in selective polymer matrices.

Environmentally responsive self-assembly of nearly symmetric mixed poly(tert-butyl acrylate) (PtBA, 22.2 kDa)/polystyrene (PS, 23.4 kDa) brushes grafted onto 67 nm silica nanoparticles in selective homopolymer matrices [PtBA for the grafted PtBA chains and poly(cyclohexyl methacrylate) (PCHMA) for the grafted PS chains] was investigated using both conventional transmission electron microscopy (TEM) and electron tomography (i.e., 3D TEM). A variety of self-assembled phase morphologies were observed for the mixed brushes in selective polymer matrices with different molecular weights, and these can be explained by entropy-driven wet- and dry-brush theories. In a low molecular weight selective matrix, the wet-brush regime was formed with the miscible chains stretching out and the immiscible chains collapsing into isolated domains. In contrast, when the molecular weight of the selective matrix was higher than that of the compatible grafted polymer chains, the dry-brush regime was formed with the mixed brushes exhibiting the unperturbed morphology. In addition to the molecular weight, the size of nanoparticles (or the substrate curvature) was also observed to play an important role. For small particles (core size less than 50 nm), the wet brush-like morphology with a surface-tethered micellar structure was observed. Finally, the wet- and dry-brush regimes also significantly affected the dispersion of mixed brush particles in selective polymer matrices.

Dual Roles of Polymeric Capping Ligands in the Surface-Protected Etching of Colloidal Silica.

In this work, we reveal the dual roles of polymeric capping ligands in the hollowing of silica nanospheres during their surface-protected etching. We first show that polymeric capping ligands, if they have a stronger interaction with the surface Si-OH groups than water, can reduce the condensation of the silica network, allowing the diffusion of OH- ions through the shell to dissolve the inner silica. Also, the polymeric ligands can passivate the surface silica, making it less likely to be dissolved by OH- ions. The combination of these two roles ensures highly selective etching of the interior of the colloidal silica spheres, making the surface-protected etching a robust process for the synthesis of hollow silica nanoshells. Our insight into the specific roles of the ligands is expected to elucidate the impact of polymeric ligands on the colloidal chemistry of silica, particularly in its condensation and etching behaviors, and offer new opportunities in the design of silica and other oxide-based nanostructures.

The Role of Field Electron Emission in Polypropylene/Aluminum Nanodielectrics Under High Electric Fields.

Polymer/metallic particle nanocomposites or nanodielectrics can exhibit colossal dielectric constants with a relatively low dissipation factor under low electric fields and thus seem to be promising for high-energy density dielectric capacitors. To study this possibility, this work focused on the dielectric performance and loss mechanisms in polypropylene (PP)/aluminum nanoparticle (nAl NP) composites under high electric fields. Phosphonic acid-terminated poly(ethylene-co-1-butene) was grafted to the Al2O3 surface layer on the nAl NPs in order to achieve reasonable dispersion in the PP matrix. The dielectric breakdown study showed that the breakdown strength decreased to nearly 1/20 that of the neat PP film as the nAl content increased to 25.0 vol %. The leakage current study revealed three electronic conduction mechanisms in the PP/100 nm nAl nanocomposites, namely, ohmic conduction at low fields, hopping conduction at intermediate fields, and Fowler-Nordheim (FN) field electron emission above a critical field, depending on the filler content. Compared to the 100 nm nAl NPs, smaller (e.g., 18 nm) nAl NPs needed a much higher electric field to exhibit FN field electron emission. It was the FN electron tunneling that induced a substantial reduction in breakdown strength for the PP/nAl nanocomposites. Meanwhile, electron-tunneling injected space charges (electrons) from nAl NPs into the PP matrix, and internal electronic conduction led to significant dielectric nonlinearity at high poling fields. Although polymer/metallic NP composites are not suitable for high-field electric applications, they can be good candidates for electrical switches and quantum tunneling composites operated at relatively low electric fields.

Self-Stratified Antimicrobial Acrylic Coatings via One-Step UV Curing.

We designed and synthesized a novel quaternary ammonium methacrylate compound (QAC-2) bearing a perfluoroalkyl tail on one end and an acrylic moiety on the other. Via one-step UV curing of QAC-2 and methyl methacrylate (MMA) with ethylene glycol dimethacrylate (EGDMA) as the cross-linker, we obtained cross-linked coatings with excellent antimicrobial property, as demonstrated by the total kill against both Gram-negative Escherichia coli (E. coli) and Gram-positive Staphylococcus epidermidis (S. epidermidis) at a QAC-2 concentration as low as ∼0.06 mol % (∼0.4 wt %) relative to MMA, which was substantially lower than the QAC amount needed in the coatings containing QACs with a hydrocarbon tail. A zone of inhibition test confirmed that the antimicrobial effect was on the basis of contact killing and there was no leaching of antimicrobial species from the cross-linked coating. The high antimicrobial potency in QAC-2-containing films was the consequence of strong surface enrichment of the fluorinated QAC, as confirmed by X-ray photoelectron spectroscopy (XPS).

Truncated Wedge-Shaped Nanostructures Formed from Lateral Microphase Separation of Mixed Homopolymer Brushes Grafted on 67 nm Silica Nanoparticles: Evidence of the Effect of Substrate Curvature.

Mixed poly(tert-butyl acrylate) (PtBA)/polystyrene (PS) brushes with controlled molecular weights and narrow polydispersities were synthesized from asymmetric difunctional initiator (Y-initiator)-functionalized 67 nm silica nanoparticles by sequential surface-initiated atom transfer radical polymerization of tBA at 75 °C and nitroxide-mediated radical polymerization of styrene at 120 °C in the presence of a free initiator in each polymerization. The Y-initiator-functionalized nanoparticles were prepared by the immobilization of a triethoxysilane-terminated Y-initiator onto the surface of 67 nm silica particles via an ammonia-catalyzed hydrolysis and condensation process. Transmission electron microscopy studies showed that mixed PtBA/PS brushes grafted on 67 nm silica nanoparticles with comparable molecular weights for the two polymers underwent lateral microphase separation after being cast from CHCl3 and annealed with CHCl3 vapor, producing distinct truncated wedge-shaped nanostructures. In contrast, under the same conditions, mixed PtBA/PS brushes grafted on 160 nm silica particles self-assembled into nanodomains with a more uniform width. This suggests that the truncated wedge-shaped nanostructures formed by mixed brushes on 67 nm silica nanoparticles originated from a higher substrate curvature.