Shape-Controlled Synthesis of Melamine Based Polyamide Materials and Application in Suzuki-Miyaura Coupling Reaction Abstract The shape of the supporters would influence the catalytic performance in Suzuki-Miyaura coupling reaction. To test the hypothesis, this study synthesized polyamides and their corresponding catalysts with different shapes by the template-assisted method using cheap and commercially available melamine and p-phthalic acid as raw materials. The samples were characterized by SEM, XPS, TEM, XRD, FT-IR, TGA and BET surface area and porosity analyzers. After detailed investigation of these polyamides with different shapes and their applications to catalytic reactions, it was established that these polyamides could be recyclable and efficient catalyst supporters towards Suzuki-Miyaura reactions. Supporters’ shape influence the TOF (turnover frequency) value of the catalysts in Suzuki-Miyaura reaction and interaction between Pd active specie and supporters in the heterogeneous catalysts. Polyamides supported Pd catalysts exhibit excellent activity, selectivity and reusability in water medium.

3-Arm PEG Based Amphiphilic Polymer Sorbents for Polar and Non-Polar Liquids Abstract Crosslinked polymer gels are gaining technological and industrial attention due to their sophisticated application features. Herein, a highly effective amphiphilic polymeric network capable of absorbing polar and nonpolar solvents was produced using hydrophilic glycerol ethoxylate, a member of star type polyethylene glycol (s-PEG), and different hydrophobic organosilane monomers by bulk polymerization as utilized under an inert atmosphere. In this context, the preparation of amphiphilic polymeric networks was achieved by the reaction between hydroxyl terminated s-PEG and ethoxysilane terminated organosilane without using any initiator, activator or a catalyst. SEM, FTIR, 13C and 29Si CPMAS NMR and TGA are used for morphological, structural and thermal characterization of the prepared materials. Likewise, the absorption behavior of amphiphilic polymeric networks was determined by measuring their swelling ratios in polar and nonpolar solvents. Because of having a hydrophobic and hydrophilic structure in their 3D polymeric structure, the obtained polymeric networks behave as an organogel in oil medium, while they can prepared as a hydrogel in aqueous medium. The effect of crosslinker’s difference on the swelling capacity of sorbent were researched by comparing different molecular weight of monomers, and it was found that the molecular structure of organosilane monomers had significant influence on the swelling ability of obtained amphiphilic sorbents. By the use of easy preparations, not needing extra agents for the synthesis, having high and quick absorption abilities in organic solvents showed that the resulting amphiphilic sorbent have potential as absorbents for different organic solvents. Also, the degradable features of amphiphilic polymer networks in water open up optimum application opportunities for additional uses, such as with drug delivery agents.

Synthesis and Characterizations of Biodegradable Polyurethane Microspheres with Dexamethasone for Drug Delivery Abstract This manuscript reports on the synthesis of biodegradable polyurethanes (PU) using poly(ε-caprolactone) diol and fabrication of microspheres containing dexamethasone (DEX). Biodegradable PUs with different isocyanate ratios were successfully synthesized using PCL diol as a polyol. The PU with a high isocyanate ratio exhibited a low average molecular weight, high melting point, high Young’s modulus, low tensile strength, low elongation to break, low hydrolytic degradation rate, and fast release profile of DEX. These results can be used to optimize properties so as to be suitable for specific applications. Our next goal is to evaluate the performance of PU microspheres as an injectable cartilage filler through in vitro and in vivo studies. In addition, the biodegradable PUs can be used for tissue-engineered scaffolds using three-dimensional printing.

New One Step Self-assembly Strategy of Large-Area Highly Ordered, Crack-Free 2D Inverse Opal Films of Transition Metal Oxides and Its Application to Fabrication of Bilayer Inverse Opal Films Abstract A new one step method for self-assembly of sacrificial polystyrene (PS) spheres colloidal crystal with a transition metal oxide (TMO) precursor matrix material is developed to fabricate highly ordered, crack-free two-dimensional (2D) TiO2 and 2D WO3 inverse opal (IO) films over a centimeter scale. Opal composite monolayer PS/WO3 and PS/TiO2 films have been successfully generated via simultaneous assembly of polymeric colloidal spheres floating on aqueous TiO2 and WO3 precursor solutions, thereby avoiding the infiltration step of the TMO precursor solution into a preassembled opal template. Large-area crack-free 2D WO3 and 2D TiO2 IO films were subsequently obtained after the removal of the PS opal template by chemical method. Such new strategy avoids the need for liquid infiltration into a preassembled PS opal template and minimizes the associated large cracks and inhomogeneity that often occur during the fabrication of IO films. The obtained PS/WO3 and PS/TiO2 opal composite monolayer films were also used as building blocks for the fabrication of highly ordered bilayer (3D) IO films with homo- and hetero-structure via a bottom-up, layer by layer route, through repeated operations of this new one step self-assembly method. Hence, four types of bilayer IO films were synthesized: homo-structural TiO2 and WO3, hetero-structural TiO2 (bottom layer)/WO3 (top layer) and WO3 (bottom layer)/TiO2 (top layer). The underlying mechanism of multilayer assembly that may account for the formation of large area crack-free multilayer films, is discussed. The electrochromic behavior of these 2D and 3D IO samples was investigated.

Effect of Head Structure on ATP Detection in Polydiacetylene Systems Abstract ATP detection systems were formed using 10,12-pentacosadiynoic acid derivatives that had a tertiary amine group at their end. Ortho, meta, and para derivatives were synthesized and the receptiveness for ATP using these derivatives was characterized. A vesicle did not form with the ortho derivative. The para derivative, did form a vesicle but was unable to detect ATP. Only the meta derivative showed a color change from blue to red upon ATP detection. The size of the vesicle using a meta derivative was larger than that formed when using a para derivative. The meta derivative did not respond with a color change to analogs of ATP. The concentration of ATP that was able to be detected by the naked eye was 100 μM, and that by the UV spectrum was 50 μM. An ATP detection system was developed using polydiacetylene systems in this study.

Poly- l -lactide Polymer-Based Triple Drug-Eluting Stent with Abciximab, Alpha-Lipoic Acid and Sirolimus in Porcine Coronary Restenosis Model Abstract This study evaluated the effect of a novel triple drug-eluting stent containing antithrombotic abciximab, antioxidative alpha-lipoic acid (ALA), and antiproliferative sirolimus in a porcine model. The coronary arteries of pigs were randomized into three groups: triple drug-eluting stent (TES; n=10), sirolimus-eluting stent (SES; n=10), and bare metal stent (BMS; n=10). At 28 days after stent implantation, a histopathologic analysis was performed. There were no significant differences in the injury score. There were significant differences in the neointimal area (2.3±0.6 mm2 in TES vs. 2.5±0.88 mm2 in SES vs. 3.3±0.58 mm2 in BMS, p<0.0001), percent area of stenosis (37.1±9.26% in TES vs. 46.1±15.9% in SES vs. 66.2±10.12% in BMS, p<0.0001), inflammation score (1.0 [range, 0.0-1.0] in TES vs. 1.5 [range, 1.0-2.0] in SES vs. 1.0 [range, 1.0-2.0] in BMS, p<0.05), and fibrin score (2.0 [range, 1.0-2.0] in TES vs. 2.0 [range, 1.0-2.5] in SES vs. 0.0 [range, 0.0-1.0] in BMS, p<0.0001) among the three groups. The occlusion rates using micro-computed tomography showed similar restenosis rates based on histologic analysis (35.4±8.39% in TES vs. 43.4±10.12% in SES vs. 71.4±4.38% in BMS, p<0.0001). TES demonstrated an inhibitory effect on the smooth muscle cells compared to the other stents. It also suppressed inflammation in the stented lesion compared to SES as evidenced by the inflammation score.

Intense Pulsed Light Sintered Core-Shell Nanoparticles for Organic Photovoltaic Devices Abstract A fast and low-cost fabrication process using intense pulsed light sintering of metal nanoparticles was studied. Silver, copper, and four different copper-silver core-shell alloy nanoparticles were synthesized. The composition and resistivity of the sintered metal electrodes were studied. The resistivity of the silver electrode formed through nanoparticle sintering was comparable to that of a conventional solution-processed silver electrode. The performance of the device prepared using the copper nanoparticles only was low due to the oxidation of copper in the air. The current density-voltage (J-V) characteristics of the devices fabricated using the synthesized core-shell nanoparticles revealed that the alloy ratio up to approximately 2 did neither affect the performances nor the lifetime of the devices. As the content of copper increased, the device performance decreased due to the oxidation of copper. Usage of the sintered metal alloy electrodes resulted in the reduction of cost by 33% compared with the conventional silver electrode.

Sequential Symmetry-Breaking Intercolumnar Transformations of a Conjugated Rod Molecule with a Flexible Coil Abstract In this paper, we report distinct symmetry-breaking phase transitions in molecules based on oligo-para-phenylene rods and a poly(ethylene oxide) coil depending on the length of the aromatic rod block The observed phase transitions were characterized by differential scanning calorimetry (DSC) and X-ray scattering methods. Compound 1 with a tetra-para-phenylene rod exhibited a symmetry breaking intercolumnar transition from p2gg to p6mm symmetry. This phase transition was accompanied by an endothermic peak in the DSC profile (first-order transition), suggesting an in-plane twist of the ribbon-like rod domain. On the other hand, 2 with a longer penta-para-phenylene rod exhibited sequential symmetry breaking intercolumnar transitions from c2mm to p2gg to p6mm symmetry. In contrast with 1, the phase transitions were accompanied by no enthalpy change. Therefore, the ribbon-like rod domains were not segmented due to increased inter-rod interactions of the longer aromatic rods. The phase transitions of 2 are attributed to increased thermal motions of the coils, which vary the orientational angle of the aromatic columns in the lattice.

Synthesis of Quinoxaline-Based Small Molecules Possessing Multiple Electron-Withdrawing Moieties for Photovoltaic Applications Abstract Three quinoxaline-based small molecules possessing multiple electron-withdrawing moieties were synthesized by the Suzuki coupling reaction for organic photovoltaic cells (OPVs). The electron-donating triarylamine units were linked to both ends of electron-accepting 2,3-diphenyl quinoxaline (DPQ) derivatives with strong electron-withdrawing trifluoromethyl (CF3) moieties to produce a reference D-A-D type small molecule of CF3Qx-0F. Furthermore, one and two fluorine atoms were additionally introduced to the 6,7-positions ofthe DPQ unit of CF3Qx-0F affording CF3Qx-1F and CF3Qx-2F, respectively. Owingto the significant contribution of the electron-withdrawing CF3 and fluorine units, all inverted-type OPVs based on three small molecules exhibited high open circuit voltages greater than 0.82 V. In addition, the power conversion efficiencies (PCEs) of the devices were gradually improved with increasing number of fluorine atoms. The highest PCE (2.82%) with a Voc of 0.88 V, a short-circuit current of 6.38 mA cm−2, and a fill factor of 50.6% was achieved from the device based on CF3Qx-2F.

3D-Printed Poly Lactic Acid Scaffolds with Tetrapod-Interlocked Structure Containing Dipyridamole Abstract Poly lactic acid (PLA) filament containing dipyridamole (DIP) was prepared and DIP/PLA tetrapod-interlocked scaffold was printed by fused deposition modeling method. Tetrapod-interlocked structure was designed with CAD and translated into G-code with slic3r program. The mechanical property was investigated using universal testing machine. Compressive stress resistance of the tetrapod-interlocked structure was significantly increased. Meanwhile, release profile and osteoblast proliferation ability of tetrapod-interlocked scaffold with DIP was examined. Osteoblast proliferation was increased with the increasing amount of DIP.