Graphene Oxide/Cholesterol-Substituted Zinc Phthalocyanine Composites with Enhanced Photodynamic Therapy Properties.

In the present work, cholesterol (Chol)-substituted zinc phthalocyanine (Chol-ZnPc) and its composite with graphene oxide (GO) were prepared for photodynamic therapy (PDT) applications. Briefly, Chol-substituted phthalonitrile (Chol-phthalonitrile) was synthesized first through the substitution of Chol to the phthalonitrile group over the oxygen bridge. Then, Chol-ZnPc was synthesized by a tetramerization reaction of Chol-phthalonitrile with ZnCl2 in a basic medium. Following this, GO was introduced to Chol-ZnPc, and the successful preparation of the samples was verified through FT-IR, UV-Vis, 1H-NMR, MALDI-TOF MS, SEM, and elemental analysis. Regarding PDT properties, we report that Chol-ZnPc exhibited a singlet oxygen quantum yield (Φ∆) of 0.54, which is slightly lower than unsubstituted ZnPc. Upon introduction of GO, the GO/Chol-ZnPc composite exhibited a higher Φ∆, about 0.78, than that of unsubstituted ZnPc. Moreover, this enhancement was realized with a simultaneous improvement in fluorescence quantum yield (ΦF) to 0.36. In addition, DPPH results suggest low antioxidant activity in the composite despite the presence of GO. Overall, GO/Chol-ZnPc might provide combined benefits for PDT, particularly in terms of image guidance and singlet oxygen generation.

Cost-Effective Control of Molecular Weight in Ultrasound-Assisted Emulsion Polymerization of Styrene.

This paper focuses on the determination of economically most feasible conditions to obtain polystyrene with various target molecular weights through ultrasound-assisted emulsion polymerization. Briefly, batch polymerizations of styrene have been performed by ultrasound-assisted emulsion polymerization process using different reaction feed compositions. Polymerization rates were calculated using the monomer conversions at various reaction times. Also, molecular weights of the synthesized polymers, as well as the Mark-Houwink constants, were determined by intrinsic viscosity and gel permeation chromatography measurements. It was found that the polydispersity index of the polymers is ranging from 1.2 to 1.5, and the viscosity average molecular weights are in between 100000-1500000 g/mol depending on the reaction conditions. Finally, model equations were also developed for response variables, and the most economical ways of reaching various target molecular weights were interpreted by response surface methodology based multi objective optimization.

High-performance thermoelectric materials based on ternary TiO2/CNT/PANI composites.

In the present work, we report the fabrication of high-performance thermoelectric materials using TiO2/CNT/PANI ternary composites. We showed that a conductivity of ∼2730 S cm-1 can be achieved for the binary CNT (70%)/PANI (30%) composite, which is the highest recorded value for the reported CNT/PANI composites. We further demonstrated that the Seebeck coefficient of CNT/PANI composites could be enhanced by incorporating TiO2 nanoparticles into the binary CNT/PANI composites, which could be attributed to lower carrier density and the energy scattering of low-energy carriers at the interfaces of TiO2/a-CNT and TiO2/PANI. The resulting TiO2/a-CNT/PANI ternary system exhibits a higher Seebeck coefficient and enhanced thermoelectric power. Further optimization of the thermoelectric power was achieved by water treatment and by tuning the processing temperature. A high thermoelectric power factor of 114.5 µW mK-2 was obtained for the ternary composite of 30% TiO2/70% (a-CNT (70%)/PANI (30%)), which is the highest reported value among the reported PANI based ternary composites. The improvement of thermoelectric performance by incorporation of TiO2 suggests a promising approach to enhance power factor of organic thermoelectric materials by judicial tuning of the carrier concentration and electrical conductivity.

Tailoring the Diameters of Polyaniline Nanofibers for Sensor Application.

Size control has been successfully achieved in inorganic materials, but it still remains a challenge in organic polymers due to their polydispersity. We here report a facial approach to tailor the diameter of polyaniline (PANI) nanofibers in a range of 200-30 nm via temperature-controlled polymerization from room temperature to -192 °C. It is shown that the formation of PANI nanofibers was directed by the self-assembly of an amphiphilic aniline-glutamic acid complex, which formed micelles with different sizes at various temperatures during polymerization. The size-dependent properties of the resulting PANI nanofibers, such as molecular weights, optical properties, crystallinity, and electron conductivity, have been discussed. Most importantly, we showed a more than 3 magnitude increase in the conductivities of doped PANI nanofibers with a decrease in the diameter from 150 to 30 nm. A homemade sensing device was constructed, and it is shown that PANI nanofibers with smaller diameters exhibit a much faster response than those of larger-sized fibers or bulk PANIs due to their large surface area and high intrinsic conductivities.