Fabrication of Phenanthroline Modified Graphene Nanosheets Decorated with Palladium Nanoparticles.

Palladium nanoparticles decorated modified reduced graphene oxide (RGO) composite was synthesized by a two-step process using 1,10-Phenanthroline (PHEN) as bridging agent. Firstly, the graphene oxide (GO) was non-covalently modified with the PHEN molecules through π-π interaction between two components. Then, the modified GO was complexed with Pd precursor and subsequently reduced from Pd2+ to Pd0 using NaBH4 to yield Pd dispersed modified RGO sheets. The structure and morphology of the resulting composites were characterized by FTIR, TGA, EDX, FESEM, HRTEM and XRD measurements. XPS results revealed that the reduction of Pd2+ to metal-lic Pd was successfully achieved, while the HRTEM and FESEM micrographs suggested that the Pd nanoparticles were well-dispersed on the functionalized graphene sheets.

Synthesis and properties of an ionic conducting material: in-situ preparation of poly(2-ethynyl-N-iodopyridinium iodide) and its electro-optical and electrochemical properties.

Poly(2-ethynyl-N-iodopyridinium iodide) [PEIPI] was easily prepared via in-situ uncatalyzed polymerization of 2-ethynylpyridine by using iodine. The activated acetylenic bond of 2-ethynyl-N-iodopyridinium iodide formed at the initial reaction time was assumed to be susceptible to linear polymerization, followed by an identical propagation step that contains the produced macroanion and quaternized monomeric species. The polymer structure was characterized by various instrumental methods to have the conjugated polymer backbone system bearing the designed substituents. The electro-optical and electrochemical properties of polymer were studied. The UV-visible spectrum of PEIPI showed a characteristic absorption peak in the visible region up to 800 nm. The PL emission spectrum of PEIPI shows two peaks at 515 and 550 nm. The cyclic voltammetry of PEIPI exhibited irreversible electrochemical behavior between the oxidation and reduction peaks.

Synthesis and characterization of an ionic conjugated polymer: poly[2-ethynyl-N-(2-furoyl)pyridinium chloride].

A new ionic polyacetylene derivative with furoyl substituents was prepared by the uncatalyzed polymerization of 2-ethynylpyridine by using 2-furoyl chloride in high yield. The polymer structure was characterized by such instrumental methods as NMR, IR, and UV-visible spectroscopies to have a polyacetylene backbone system with the N-(2-furoyl)pyridinium chloride. The electro-optical and electrochemical properties of poly[2-ethynyl-N-(2-furoyl)pyridinium chloride [PEFPC] were studied. The photoluminescence spectrum showed that the PL peak is at 578 nm corresponding to the photon energy of 2.15 eV. The cyclovoltammograms of PEFPC exhibited the irreversible electrochemical behaviors between the oxidation and reduction peaks. The oxidation current density of polymer versus the scan rates is approximately linear relationship in the range of 30 mV/sec-150 mV/sec. It was found that the kinetics of redox process is controlled by the reactant diffusion process from the oxidation current density of PEFPC versus the scan rates.

Uncatalyzed synthesis and characterization of a water-soluble polyacetylene: poly[2-ethynyl-N-(propylsulfonate)pyridinium betaine].

A new ionic conjugated polymer was prepared by the activated polymerization of 2-ethynylpyridine with the ring-opening of 1,3-propanesultone without any additional initiator or catalyst. This polymer was characterized by various instrumental methods to have conjugated polymer backbone system with pendant N-propylsulfonate functional groups. The photoluminescence spectrum of polymer showed that the PL peak is located at 552 nm corresponding to the photon energy of 2.25 eV. The cyclovoltammograms of polymer exhibited the irreversible electrochemical behaviors between the oxidation and reduction peaks. The oxidation current density of polymer versus the scan rates is approximately linear relationship in the range of 30-120 mV/sec. It was found that the kinetics of the redox process is almost controlled by the reactant diffusion process from the oxidation current density of polymer versus the scan rates.

Synthesis and characterization of phenylpyridine-based iridium(III) complex for solution-processed phosphorescent organic light-emitting diode.

A novel main ligand 2-(2,4-dimethoxyphenyl)-5-trifluoromethylpyridine (MeO2CF3ppy) and its complex bis[2-(2,4-dimethoxy-phenyl)-5-trifluoromethyl pyridinato-N,C2]iridium acetylacetonate (MeO2CF3ppy)2Ir(acac) was synthesized. 2,4-Dimethoxy and 5-trifluoromethyl group were incorporated into main ligand to tune luminescence color. The phosphorescence organic light-emitting diodes (PhOLEDs) based on this complex with the configuration of ITO/PEDOT:PSS (40 nm)/PVK:CBP:Ir(III) complex (50 nm)/BCP (20 nm)/LiF (0.7 nm)/Al (100 nm) were fabricated. The solution-processed PhOLEDs based on (MeO2CF3ppy)2Ir(acac) exhibited a maximum quantum efficiency of 4.18% and luminance efficiency 9.04 cd/A with CIE coordinate of (0.32, 0.64).

Preparation and characterization of graphene/poly(diphenylamine) composites.

Nanocomposites of graphene nanosheets and poly(diphenylamine) (graphene-PDPA) were synthesized via the in-situ oxidative polymerization of diphenylamine in a sulphuric acid medium. First, graphite oxide (GO) was prepared by oxidation of natural graphite using the modified Hummer's method and subsequently reduced using hydrazine monohydrate. The as-prepared graphene sheets were noncovalently grafted with PDPA using ammonium peroxydisulphate as an oxidant. During the polymerization, graphene sheets were homogeneously dispersed in the PDPA matrix. The formation of the hybrid material was confirmed by FTIR, XPS, TGA, HRTEM, FESEM and XRD measurements. XPS analysis revealed the removal of oxygen functionality from the GO surface after reduction and the bonding structure of the reduced hybrids. In addition, the nanocomposites showed better thermal properties due to the intrinsic property of the graphene sheets.

Fabrication and characterization of graphene/poly(p-phenylenediamine) hybrids.

Graphene nanosheets functionalized with poly(p-phenylenediamine) (PPDA) were prepared via the in-situ chemical oxidative polymerization using potassium persulphate as a catalyst. Graphene nanosheets were previously prepared by chemical reduction of exfoliated graphite oxide. The structure and morphology of the composite material were characterized by FTIR, XPS, HRTEM, FESEM and XRD, while the thermal and electrical properties were measured by TGA and a four-probe method. FESEM and HRTEM observations indicated that the graphene sheets were encapsulated in the PPDA matrix. Furthermore, the nanocomposites exhibited improved conductivity and thermal stability as compared with pure PPDA.

Noncovalent grafting of poly(3-octylthiophene) at the edges of the graphene nanosheets.

Noncovalent functionalization of graphene was carried out via in-situ oxidative polymerization of poly(3-octylthiophene) (P3OT). First, graphene sheets were prepared by a modified Hummer's method and subsequently reduced with hydrazine monohydrate. The structure and morphology of the composites were investigated by using FTIR, XPS, EDX, TGA, HRTEM, FESEM and XRD measuments. The results obtained from spectroscopic studies confirm the reduction of graphite oxide to graphene. UV-Vis and photoluminescence spectroscopies were also used to prove the doping function of the graphene in the composites. Dispersion stability indicates the good mixing between graphene and the polymer due to pi-pi interaction between two components. Scanning electron microscopy results suggest that the graphene sheets were well dispersed in the polymer matrix. The UV-Vis spectra of graphene/P3OT composites show a red shift by a few nanometers, while the emission spectra show a small blue shift. However, the nanocomposites retained the photoluminescence property of as synthesized P3OT.

Chemical modification of polyhedral oligomeric silsesquioxanes by functional polymer via azide-alkyne click reaction.

A series of poly(methylmethacrylate-co-2-hydroxyethylmethacrylate)/polyhedral oligomeric silsesquioxanes (P(MMA-co-HEMA)/POSS) nanocomposites were synthesized by the combination of ATRP and click chemistry. The hybrid nanocomposites were characterized by FT-IR, 1H-NMR, GPC, SEM, XRD, DSC, and TGA analyses. The loading of POSS in the nanocomposites was calculated using 1H-NMR data. TGA measurements suggested that the incorporation of POSS into polymer matrices enhanced decomposition temperature as well as char yield of the polymeric materials. The glass transition temperature linearly increased with the increase of POSS loading plausibly because of the aggregation of POSS nanoparticles and the dipole-dipole interaction between POSS and P(MMA-co-HEMA) segments.

Facile Fabrication of NIR-Responsive Alginate/CMC Hydrogels Derived through IEDDA Click Chemistry for Photothermal-Photodynamic Anti-Tumor Therapy.

Novel chemically cross-linked hydrogels derived from carboxymethyl cellulose (CMC) and alginate (Alg) were prepared through the utilization of the norbornene (Nb)-methyl tetrazine (mTz) click reaction. The hydrogels were designed to generate reactive oxygen species (ROS) from an NIR dye, indocyanine green (ICG), for combined photothermal and photodynamic therapy (PTT/PDT). The cross-linking reaction between Nb and mTz moieties occurred via an inverse electron-demand Diels-Alder chemistry under physiological conditions avoiding the need for a catalyst. The resulting hydrogels exhibited viscoelastic properties (G' ~ 492-270 Pa) and high porosity. The hydrogels were found to be injectable with tunable mechanical characteristics. The ROS production from the ICG-encapsulated hydrogels was confirmed by DPBF assays, indicating a photodynamic effect (with NIR irradiation at 1-2 W for 5-15 min). The temperature of the ICG-loaded hydrogels also increased upon the NIR irradiation to eradicate tumor cells photothermally. In vitro cytocompatibility assessments revealed the non-toxic nature of CMC-Nb and Alg-mTz towards HEK-293 cells. Furthermore, the ICG-loaded hydrogels effectively inhibited the metabolic activity of Hela cells after NIR exposure.

Synthesis and properties of a water-soluble ionic conjugated polymer with carboxylic acids.

A new water-soluble ionic conjugated polymer, poly[N-(carboxymethyl)-2-ethynylpyridinium bromide], was prepared by the activated polymerization of 2-ethynylpyridine by using bromoacetic acid. This polymerization proceeded well in mild reaction conditions without any additional initiator or catalyst. The polymer structure was characterized by various instrumental methods to have a conjugated polymer backbone system with the designed functional groups. The photoluminescence spectrum of polymer showed that the PL peak is located at 603 nm corresponding to the photon energy of 2.06 eV. The cyclovoltammograms of polymer exhibited the irreversible electrochemical behaviors between the oxidation and reduction peaks. The oxidation current density of polymer versus the scan rates is approximately linear relationship in the range of 30 mV/sec-150 mV/sec. It was found that the kinetics of the redox process of polymer is almost controlled by the reactant diffusion process from the oxidation current density of polymer versus the scan rates.

Poly(glycidyl methacrylate-acrylonitrile)-based polymeric electrolytes for dye-sensitized solar cell applications.

Poly(glycidyl methacrylate-acrylonitrile) P(GMA-AN) copolymer was synthesized and used as a polymer electrolyte in dye-sensitized solar cells (DSSCs). P(GMA-AN)-based polymer electrolyte is obtained by adding 1-methyl-3-propylimidazolium iodide (PMII) as a room temperature ionic liquid (RTIL), tetrabutylammonium iodide (TBAI), iodide (I2) as the source of redox couple (I3(-)/I(-)) in order to improve the power conversion efficiency (PCE) by addition of optimized plasticizer contents such as ethylene carbonate (EC) and propylene carbonate (PC) in an acetonitrile solvent. These polymer electrolyte results revealed that more stable photovoltaic performance such as PCE of 4.97% with enhanced short-circuit current density (J(SC), 10.42 mA/cm2) and open circuit voltage (V(OC), 0.75 V) and fill factor (FF) of 0.63 under standard light intensity of 100 mW/cm2, irradiation of AM 1.5 sunlight. It is expected that these polymer electrolyte is an attractive alternative to liquid electrolytes for the fabrication of the long term stable DSSCs.

Synthesis and characterization of TiO2/poly(methyl methacrylate) nanocomposites via surface thiol-lactam initiated radical polymerization.

An approach to the surface modification of TiO2 nanoparticles was described based on the thiol functionalization of TiO2 followed by thiol-lactam initiated radical polymerization (TLIRP) of methyl methacrylate (MMA). FT-IR, XRD and XPS analyses confirmed the grafting of the polymer on the TiO2 surface. TGA analysis revealed superior thermal stability of PMMA-g-TiO2 compared with PMMA. TEM measurements and time-dependent phase monitoring suggested much higher colloidal stability of PMMA-g-TiO2 than TiO2 in toluene. The controlled nature of the TLIRP of MMA from the surface of TiO2 was determined by GPC analysis.

Low-temperature processing method of preparing for transparent graphene oxide electrode film with better electrical properties.

Graphene oxide films were prepared by a facile ball milling process. The milling time and the amount of the acryl type polymer dispersion agent were controlled to obtain well dispersed graphene oxide solution in ethanol. Consequently, the transparent and conducting graphene oxide film which had 69% transmittance and 1.5 x 10(6) ohm/sq surface resistance was produced by bar coating the solution on a PET substrate. The electrical property of the graphene oxide film could be further improved to 2.1 x 10(5) ohm/sq by hydrazine vapor reduction.

Multi-stimuli responsive hydrogels derived from hyaluronic acid for cancer therapy application.

One of the most promising strategies for the controlled release of therapeutic molecules is stimuli-responsive and biodegradable hydrogels developed from natural polymers. However, current strategies to development stimuli-responsive hydrogels lack precise control over drug release profile and use cytotoxic materials during preparation. To address these issues, multi-stimuli responsive hydrogels derived from hyaluronic acid and diselenide based cross-linker were developed for the controlled release of doxorubicin (DOX). Hydrogels were rapidly formed via an inverse electron demand Diels-Alder click chemistry and encapsulated DOX/indocyanine green (ICG) in their porous networks. The hydrogels showed a rapid release of DOX in acidic (pH 5), reducing (10 mmol DTT), and oxidizing medium (0.5% H2O2), and after NIR irradiation. The in vitro experiments demonstrated that hydrogels were highly cytocompatible and the DOX-loaded hydrogels induced similar anti-tumor effect as compared to that of the free-DOX. Furthermore, DOX + ICG loaded hydrogels increased the antitumor efficacy of DOX after NIR irradiation.

Fast Absorbent and Highly Bioorthogonal Hydrogels Developed by IEDDA Click Reaction for Drug Delivery Application.

In this work, we engineered highly biocompatible and fast absorbent injectable hydrogels derived from norbornene (Nb)-functionalized hyaluronic acid (HA-Nb) and a water-soluble cross-linker possessing tetrazine (Tz) functional groups on both ends of polyethylene glycol (PEG-DTz). The by-product (nitrogen gas) of the inverse electron demand Diels−Alder (IEDDA) cross-linking reaction carved porosity in the resulting hydrogels. By varying the molar ratio of HA-Nb and PEG-DTz (Nb:Tz = 10:10, 10:5, 10:2.5), we were able to formulate hydrogels with tunable porosity, gelation time, mechanical strength, and swelling ratios. The hydrogels formed quickly (gelation time < 100 s), offering a possibility to use them as an injectable drug delivery system. The experimental data showed rapid swelling and a high swelling ratio thanks to the existence of PEG chains and highly porous architectures of the hydrogels. The hydrogels were able to encapsulate a high amount of curcumin (~99%) and released the encapsulated curcumin in a temporal pattern. The PEG-DTz cross-linker, HA-Nb, and the resulting hydrogels showed no cytotoxicity in HEK-293 cells. These fast absorbent hydrogels with excellent biocompatibility fabricated from HA-Nb and the IEDDA click-able cross-linker could be promising drug carriers for injectable drug delivery applications.

Nanodomain development of semifluorinated diblock copolymeric thin films via solvent vapor annealing.

The effect of solvent vapor annealing on the morphological change of poly(ethylene oxide)-b-poly(1H,1H dihydrofluorooctyl methacrylate) (PEO-b-PFOMA) micellar thin films has been studied. The time development of the nanodomain structure in PEO(5k)-b-PFOMA(10k) thin films was investigated with the vapor treatment of perfluoroalkanes. The block copolymeric thin film was initially cast from chloroform which is a good solvent for PEO. The as-cast film which has disordered morphology can be changed to ordered cylindrical morphology and at last to highly ordered morphology consisting of PEO spherical domains and PFOMA continuous phase by varying the annealing time.

Synthesis and properties of diblock copolymers containing poly(3-hexylthiophene) and poly(fluorooctyl methacrylate).

This study reports the synthesis of regioregular poly(3-hexylthiophene)-b-poly(1H,1H-dihydro perfluorooctyl methacrylate) (P3HT-b-PFOMA) block copolymers by atom transfer radical polymerization of FOMA using P3HT macroinitiators. The P3HT macroinitiator was previously prepared by chemical modification of hydroxy terminated P3HT The block copolymers were characterized by 1H-NMR, 13C-NMR, GPC, DSC, TGA and TEM. The block copolymers are able to self-assemble into phase separated micellar thin film morphology from chloroform.

Synthesis and characterization of a polyacetylene derivative with phenylazobenzene moieties.

A new polyacetylene derivative was prepared by the activated polymerization of 2-ethynylpyridine by using 4-(phenylazo)benzoyl chloride without any additional initiator or catalyst in high yield. The chemical structure of poly[2-ethynyl-N-(4-(phenylazo)benzoyl) pyridinium chloride [PEPABPC] was characterized by such instrumental methods as NMR, IR, and UV-visible spectroscopies to have a conjugated polymer backbone system with the designed azobenzene moieties. The electrooptical and electrochemical properties of PEPABPC were studied. The photoluminescence spectrum showed that the PL peak is at 597 nm corresponding to the photon energy of 2.07 eV. The cyclovoltammograms of PEPABPC exhibited the irreversible electrochemical behaviors between the oxidation and reduction peaks. The oxidation current density of PEPABPC versus the scan rates is approximately linear relationship in the range of 30 mV/sec-150 mV/sec. It was found that the the kinetics of the redox process of this polymer is controlled by the reactant diffusion process from the oxidation current density of PEPABPC versus the scan rates.

Synthesis and properties of poly(4-vinylpyridine-co-styrene) with pendant azobenzonitrile moieties.

A new ionic polymer, poly(4-vinylpyridine-co-styrene) [PVPS] with pendant azobenzonitrile moieties was prepared by the polymeric reaction of PVPS and 4-[4-(8-bromooctyloxy)phenylazo]benzonitrile. The polymer structure was characterized by various instrumental methods to have a PVPS backbone system with the designed azobenzonitrile moieties. The electrochemical and electro-optical properties were studied. The polymer showed two oxidation and reduction response properties in a polymer unit and two electrochemical processes were included in the irreversible redox steps. The plot of the oxidation current density of polymer versus the scan rate showed approximately a linear relationship in the range of 30 mV/sec 150 mV/sec. The exponent of scan rate, when we apply power law to our data, was found to be 0.35. The absorption spectrum showed a characteristic absorption peak at 365 nm.