Photosensitization of bioinspired thymine-containing polymers.

Here, we report a sensitization study on a family of water-soluble photopolymers based on thymine. The goal of this study was to determine whether the presence of sensitizer molecules would promote photocrosslinking/immobilization of the polymers using low-energy irradiation (520 nm) as compared to the UV irradiation (approximately 280 nm) necessary for the standard photoinduced process to take place. With the aid of Eosin Y Spirit Soluble (EY) as a sensitizer, water-soluble polystyrene copolymers of vinylbenzylthymine-vinylbenzyltriethylammonium chloride (VBT-VBA) were immobilized after exposure to visible irradiation. By exciting the sensitizer molecule in the presence of VBT copolymers at a wavelength where absorption by the latter does not occur, the triplet state of the sensitizer is generated in high yields, and consequently, polymer photocross-linking takes place. UV-vis spectroscopy has been used to study the effect of irradiation dose, copolymer composition, and sensitizer concentration on the photoreactivity of VBT polymers. These studies demonstrate the feasibility of using Eosin Y as a sensitizer to achieve the thymine photodimer formation, resulting in immobilization of VBT-VBA-EY films on PET substrate. This provides complementary information on photoinduced immobilization of VBT-VBA films that are crucial for developing new classes of environmentally benign materials and new energy-saving methods.

Effect of pH on the viscosity of titanium dioxide aqueous dispersions with carboxylic acids.

Dispersions of titanium dioxide nanoparticles with terephthalic acid, isophthalic acid, salicylic acid, benzoic acid, and pyridine-2,5-dicarboxylic acid were prepared by aqueous grinding. The pH of the dispersions was adjusted by adding either HCl or NaOH, and the viscosity of the dispersions was measured. It was found that the viscosity of the system depends strongly on pH. The qualitative interpretation of the results based on the DLVO theory is presented. The evidence of the effect of bridging interactions on the viscosity of titanium dioxide-dicarboxylic acid dispersions is discussed.

OH, HO2, and ozone gaseous diffusion coefficients.

The diffusion of OH, HO2, and O3 in He, and of OH in air, has been investigated using a coated-wall flow tube reactor coupled to a chemical ionization mass spectrometry. The diffusion coefficients were determined from measurements of the loss of the reactive species to the flow tube wall as a function of pressure. On the basis of the experimental results, D(OH-He) = 662 +/- 33 Torr cm2 s-1, D(OH-air) = 165 +/- 20 Torr cm2 s-1, D(HO2-He) = 430 +/- 30 Torr cm2 s-1, and D(O3-He) = 410 +/- 25 Torr cm2 s-1 at 296 K. We show that the measured values for OH and HO2 are in better agreement with measured values of their polar analogues (H2O and H2O2) compared with measured values of their nonpolar analogues (O and O2). The measured value for OH in air is 25% smaller than that for O (the nonpolar analogue). The difference between the measured value for HO2 and O2 (the nonpolar analogue) in air is expected to be even larger. Also we show that calculations of the diffusion coefficients based on Lennard-Jones potentials are in excellent agreement with the measurements. This gives further confidence that these calculations can be used to estimate accurate diffusion coefficients for conditions where laboratory data currently do not exist.

Photo-cross-linked immobilization of polyelectrolytes for enzymatic construction of conductive nanocomposites.

Horseradish peroxidase has been demonstrated to catalyze the oxidative polymerization of aniline to form conductive polyaniline. This process is facilitated by the presence of a macromolecular template with sulfonic acid groups that provide a unique environment for the formation of the conducting polymer. Here we report the use of a photo-cross-linkable thymine-based polymer with phenylsulfonate groups as a templating substrate. This allows for an aqueous-based environmentally benign photopatterning of a conductive material. A description and results of this process are presented.