Ionic Liquid-Stabilized Titania Quantum Dots Applied in Adhesive Resin.

Quantum dots (QDs; 1 to 10 nm) were recently synthesized by sol-gel and used as nonagglomerated nanoparticles in adhesive resin. The sol-gel process presented a low yield and resulted in a liquid product without stability. In this study, an imidazolium ionic liquid (IL; 1- n-butyl-3-methylimidazolium tetrafluoroborate, BMI.BF4) was used as stabilizing agent to synthesize titanium dioxide QDs (TiO2QDs/BMI.BF4) via a chemical route. The product was isolated as powder after washing, centrifuging, and drying. An experimental adhesive resin was formulated by mixing methacrylate monomers and a photoinitiator system. The TiO2QDs/BMI.BF4 powder was incorporated at 2.5 (G2.5%) and 5 (G5%) wt% in the adhesive resin, and one group remained without TiO2QDs/BMI.BF4 powder as the control (Gctrl). The TiO2QDs/BMI.BF4 powder was analyzed by micro-Raman spectroscopy, thermogravimetry, and transmission electron microscopy. The dispersion of TiO2QDs/BMI.BF4 powder was analyzed in the polymerized adhesive resin with transmission electron microscopy and fluorescence microscopy. The adhesive resins were evaluated for immediate and long-term antibacterial activity, cytotoxicity, polymerization behavior, degree of conversion, softening in solvent, immediate and long-term microtensile bond strength, and fracture pattern. The TiO2QDs/BMI.BF4 powder showed peaks of anatase and rutile and 26 wt% of BMI.BF4. TiO2QDs/BMI.BF4 presented a minimum size of 1.19 nm, a maximum size of 7.11 nm, and a mean ± SD size of 3.54 ± 1.08 nm. TiO2QDs/BMI.BF4 was dispersed in the adhesive resin without agglomeration, presenting intermittent luminescence by blinking. The addition of any tested concentration of TiO2QDs/BMI.BF4 powder provided immediate and long-term antibacterial activity without cytotoxic effect against the pulp fibroblasts. Furthermore, compared with Gctrl, G2.5% showed reliable polymerization behavior and degree of conversion without differences for softening in solvent with maintenance of bond adhesion to tooth immediately and over time. Thus, the incorporation of 2.5 wt% of TiO2QDs/BMI.BF4 in adhesive resin showed reliable physical, chemical, and biological properties.

Study on the chiral recognition of the enantiomers of ephedrine derivatives with neutral and sulfated heptakis(2,3-O-diacetyl)-beta-cyclodextrins using capillary electrophoresis, UV, nuclear magnetic resonance spectroscopy and mass spectrometry.

The enantiomers of methylephedrine, pseudoephedrine and ephedrine showed a different migration behavior in capillary electrophoresis in the presence of beta-cyclodextrin (beta-CD), heptakis(2,3-O-diacetyl)-beta-cyclodextrin and heptakis(2,3-O-diacetyl-6-sulfato)-beta-cyclodextrin (HDAS). Utilizing UV, MS and NMR spectroscopy, in particular rotating frame Overhauser experiments, an attempt was made to elucidate the chiral recognition mechanism. In the case of the neutral CDs 1:1 complexes were formed with ephedrine and methylephedrine characterized by the inclusion of the phenyl ring in the cavity and the side chain pointing out of the wider rim. In contrast, manifold complexes were formed with HDAS, which on average are characterized by an upside down inclusion of the phenyl ring in the cavity and the side chain pointing out of the narrow rim. This complex geometry is likely be stabilized by an ion-ion interaction between the positively charged nitrogens of the ephedrine derivatives and the negative charges of HDAS. In addition, an attachment of the ligand to the outside of HDAS and other complex stoichiometries are also possible.

Characterization of polyalkylvinyl ether phases by solid-state and suspended-state nuclear magnetic resonance investigations.

Pure organic polyalkvlvinyl ether phases were synthesized by suspension polymerization using different ratios and compositions of n-butylvinyl ether (C4VE) and n-octadecylvinyl ether (C18VE) with triethylene glycol divinyl ether or divinylbenzene as crosslinkers, respectively. These phases were investigated by means of solid-state 13C cross-polarization magic angle spinning nuclear magnetic resonance (NMR) spectroscopy and 1H high-resolution magic angle spinning (HR MAS) NMR spectroscopy in suspended-state. A comparison of these two methods showed the substantial advantages of 1H HR MAS NMR measurements. Structure elucidation was achieved using a 2D H,H-COSY NMR experiment performed under MAS conditions enabling full peak assignment of the 1H NMR spectra of these phases. The dynamic behavior of the polyalkylvinyl ether phases was determined by employing temperature-dependent measurements of spin-lattice relaxation times (T1) as well as accumulation of a 2D wide line separation NMR spectrum.