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We describe the rational design of oligothiophene semiconductors to facilitate solution-based fabrication of environmentally stable organic field-effect transistors (OFETs). Ultrathin films of α,ω-distyryl quaterthiophene (DS4T), pentathiophene (DS5T), and sexithiophene (DS6T) were prepared via solution processing to probe the effect of styryl end groups, oligomer length, and thin film structure on air stability. These films were prepared via solution deposition and thermal annealing of precursors featuring thermally labile ester solubilizing groups. A detailed study of the thin film structure was performed using atomic force microscopy (AFM), near-edge X-ray absorption fine structure (NEXAFS) spectroscopy, and grazing incidence X-ray diffraction (GIXD). Functional OFETs were obtained for DS5T and DS6T and have, respectively, hole mobilities of 0.051 and 0.043 cm2/(V s) and on/off ratios of 1 × 105 to 1 × 106, whereas DS4T OFETs failed to function because of poor film continuity. The effect of both short-...

Bipolar transport polymers have been developed as host materials for electroluminescent devices by incorporating both electron-transporting and hole-transporting functionalities into copolymers. Two different copolymers having the same molecular weight (Mn ∼ 30 kg/mol) and the same fraction of electron-transporting monomers (fOXA = 0.50) have been synthesized in the form of random and diblock copolymers, respectively. The effect of molecular structure and film morphology of these bipolar polymers on device performance has been studied. For the diblock copolymers, pronounced phase segregation forming different nanomorphologies has been observed by modern microscopic techniques, which is not observed for the random counterparts under the same thin film preparation conditions. The results of single-layer polymer light emitting diodes (PLEDs) show that the nanophase separation morphology of diblock copolymers has a significant effect on device performance: lowering charge transport and facilitating the hole−...

Hydrogen adsorption using a series of nanoporous synthetic polymers has been studied. Promising results were obtained during the screening of commercially available porous polymer beads; of the polymers considered, hypercrosslinked Hypersol-Macronet MN200 resin exhibited the highest adsorption capacity for hydrogen. This initial success triggered the development of our own high surface area hypercrosslinked materials. Subjecting gel-type and macroporous vinylbenzyl chloride-based precursors swollen in dichloroethane to a Friedel−Crafts reaction catalyzed by iron trichloride afforded beads with surface areas of 1 930 and 1 300 m2/g, respectively, as calculated using the BET equation. The former polymer reversibly stores up to 1.5 wt % H2 at a pressure of 0.12 MPa and a temperature of 77.3 K. The initial heat of adsorption of hydrogen molecules onto this polymer is 6.6 kJ/mol.

Symmetrical α,ω-substituted quarter-(T4), penta-(T5), sexi-(T6), and heptathiophene (T7) oligomers containing thermally removable aliphatic ester solubilizing groups were synthesized, and their UV−vis and thermal characteristics were compared. Spun-cast thin films of each oligomer were examined with atomic force microscopy and near-edge X-ray absorption fine structure spectroscopy to evaluate the ability of the material to self-assemble from a solution-based process while maintaining complete surface coverage. Films of the T5−T7 oligomers self-assemble into crystalline terraces after thermal annealing with higher temperatures required to affect this transformation as the size of the oligomers increases. A symmetrical α,ω-substituted sexithiophene (T6-acid) that reveals carboxylic acids after thermolysis was also prepared to evaluate the effect of the presence of hydrogen-bonding moieties. The charge transport properties for these materials evaluated in top-contact thin film transistor devices were found t...

Natural photosynthetic systems collect sunlight using a vast array of light-harvesting chromophores that channel the absorbed energy to a single reaction center. Recently, it has been realized that dendritic macromolecules can exhibit similar properties, though on a more modest scale. The preparation of dendritic structures and assemblies composed of numerous light-collecting chromophores that transfer their energy to a single energy ‘sink’ at the core has been achieved in a number of diverse and creative ways. These novel structures are being used as model systems in light-emitting diodes, signal amplifiers, fluorescent sensors, frequency converters, and other photonic devices.

The thin film microstructure development of functionalized oligothiophenes with branched, thermally removable groups at each end of conjugated cores with five, six, and seven thiophene rings was monitored during their thermal conversion from solution processible precursors to insoluble semiconductor products. The change in end group character provides a comparison of branched vs linear end group functionalization in oligothiophenes. Near edge X-ray absorption fine structure (NEXAFS) spectroscopy confirmed that branched alpha-, omega-substitutions of the precursors strongly influenced the packing of the conjugated core. The quinque- and sexithiophene precursors oriented perpendicular to the substrate, whereas the septithiophene precursor oriented parallel to the substrate, providing one of the first examples of length dependence in oligothiophene orientation. This dependence may be due to a packing mismatch between the conjugated cores and the branched end groups. The convertible septithiophene exhibits four distinct microstructures as it converts from precursor to product that correlate strongly with its field-effect hole mobility in field-effect transistors. The extent of septithiophene order and the surface-relative orientation of its ordered phases clearly influence field-effect transistor performance.

High molecular weight (MW) polymers have shown promise in terms of improving the properties and the efficacy of low MW therapeutics. However, new systems that are highly biocompatible, are biodegradable, have well-defined MW, and have multiple functional groups for drug attachment are still needed. The biological evaluation of a library of eight polyester dendrimer-poly(ethylene oxide) (PEO) bow-tie hybrids is described here. The group of evaluated polymers was designed to include a range of MWs (from 20000 to 160000) and architectures with the number of PEO arms ranging from two to eight. In vitro experiments revealed that the polymers were nontoxic to cells and were degraded to lower MW species at pH 7.4 and pH 5.0. Biodistribution studies with (125)I-radiolabeled polymers showed that the high MW carriers (40000) exhibited long circulation half-lives. Comparison of the renal clearances for the four-arm versus eight-arm polymers indicated that the more branched polymers were excreted more slowly into the urine, a result attributed to their decreased flexibility. Due to their essentially linear architecture that does not provide for good isolation of the iodinated phenolic moieties, the polymers with "two arms" were rapidly taken up by the liver. The biodistributions of two long-circulating high MW polymers in mice bearing subcutaneous B16F10 tumors were evaluated, and high levels of tumor accumulation were observed. These new carriers are therefore promising for applications in drug delivery and are also useful for improving our understanding of the effect of polymer architecture on pharmacokinetic properties.

A novel porous polymer was microfabricated to serve as a porous plug for a new device, the porous plug electro-osmotic pump (pp-EOP). The plug eliminates any back pressure effects while enhances electro-osmotic flow in a channel. The pp-EOP was batch fabricated by surface micromachining on top of a silicon wafer. The pp-EOP device is driven by a periodic, zero-average injected current signal at low frequencies producing bubble-free electro-osmotic flow with reversible net movement. Testing of the device produced an average water-air interface velocity of 1.8 /spl mu/m/s at 0.8 Hz. The velocity was increased to 4.8 and to 13.9 /spl mu/m/s by necking the channel size.

A novel approach to thermoresponsive polymeric membranes based on molded monolithic sheets of macroporous polymers has been demonstrated. The macroporous sheet prepared from glycidyl methacrylate ethylene dimethacrylate is functionalized either by free-radical grafting of N-isopropylacrylamide, or, better, by copolymerization of N-isopropylacrylamide onto the vinylated surface of the pores of the polymer sheet. The macroporous polymers modified with poly(N-isopropylacrylamide) were shown to be thermoresponsive. Changes in the temperature of a flow system incorporating the modified macroporous material were accompanied by significant changes in the backpressure required to effect flow. This study confirms the feasibility of thermoresponsive membranes for water purification.

Crosslinked bead polymers containing vinylpyridine units were prepared by pearl copolymerization of monomer mixtures containing various percentagesof 4-vinylpyridine, styrene, and di-vinylbenzene. The polymers were functionalized by reaction with hydrogen bromide and bromine, and the resulting poly-(vinylpyridinium hydrobromide perbromide) resins, which were stable for long periods of time, were used to brominate a number of alkenes and ketones. In most cases, the brominated products were obtained in excellent yields and could be separated from the polymeric by-product by a simple filtration. The polymeric reagent could be fully regenerated after use without loss of activity.

The use of the t-BOC protecting group for the preparation of an organic soluble derivative of poly(vinyl alcohol) is reported. Poly(vinyl-t-butyl carbonate) can be obtained by free-radical polymerization of the monomer using peroxide or azo initiators at 90–120°C. The t-BOC polymer is thermolyzed cleanly to poly(vinyl alcohol) with evolution of carbon dioxide and 2-methyl-propene when heated to 210–220°C. The t-BOC polymer may be useful for imaging processes involving acid-catalyzed thermolysis.

The kinetics of phase-transfer catalysis using glycidyl methacrylate-ethylene dimethacrylate resins modified with pendant quaternary butylammonium groups have been studied. In contrast to expectations based on currently proposed mechanisms, the activity of polymeric catalysts is not improved through modifications that balance the hydrophilic and hydrophobic properties of the material. It is believed that much of the activity of the polymeric catalysts derives from the swelling of the polymer in both aqueous and organic phases. This enhances not only the rate of diffusion of both reagents to the vicinity of the catalytically active groups but also the ability of reactive groups to oscillate between the two phases. Both swelling and diffusion are restricted severely as the percentage of crosslinking is increased. This restriction is of particular importance with macroporous resins. Comparison of kinetic data obtained with various polymers suggests that gel polymers with very small bead sizes and therefore high external surface areas provide much higher reactivities than their macroporous counterparts.

Crosslinked polystyrene resins containing thiol or hydroxyl functionalities on a fraction of their aromatic rings were prepared by reaction of crosslinked polystyryllithium with elemental sulphur or oxygen followed by reduction of the resulting polymer. Similarly, resins containing hydroxymethyl or thiomethyl functional groups were prepared from chloromethylated polystyrene by displacement of chloride in procedures involving three phase systems and the use of a phase transfer catalyst. The degree of functionalization could be controlled easily and the sulphur containing polymers were free of disulphide bonds.

Several new reactive polymers containing various nitrogen functionalities have been prepared in bead form and tested as catalysts or ligands for reactive moieties in organic synthesis. In particular polymers containing 4-dialkylaminopyridine pendant groups show good to excellent catalytic activities depending on their structure and their microenvironment. Best results are obtained on polystyrene backbones when the catalytic species are removed from the styrene rings by a three carbon spacer. Poly-benzimidazole resins prepared by precipitation polymerization are good ligands for transition metal catalysts used in the catalytic hydrogenation of nitro compounds or olefinic double-bonds. The PBI resins can also be used to prepare a polymeric oxidizing reagent through the binding of Cr(VI); the reagent oxidizes alcohols to the corresponding carbonyls while spent Cr(II) or Cr(III) remains anchored to the polymer. Other polymers containing chiral amino-alcohol pendant groups show useful properties as chiral auxiliaries in the asymmetric reduction of ketones using polymer-complexed lithium aluminium hydride.

An efficient synthetic route to pure, high molecular weight poly(p-hydroxystyrene) is reported. The route involves synthesis of a new monomer, p-tert-butoxycarbonyloxystyrene, polymerization by radical initiation or by cationic initiation in liquid SO2, followed by thermolysis or acidolysis of the tert-butoxycarbonyl protecting group. Porous, crosslinked resin beads containing the nucleophilic, phenol pendant group have been prepared in a similar fashion from the precursor terpolymer of p-tert-butoxycarbonyloxystyrene, styrene and divinylbenzene. The utility of this resin for solid-phase synthesis has been demonstrated.

Functionalized crosslinked polystyrene resins have received much attention recently due to their numerous possible applications in chemistry and biochemistry. Three types of insoluble polymers with various degrees of cross-linking and different physical properties are used frequently as starting materials in the functional!zation reactions; these are popcorn polymers, solvent swellable beads and macroreticular beads. The reactions used in the chemical modification of these polymers are reviewed with emphasis on those reactions which introduce versatile, easily transformed functional groups which may serve to anchor the more specific functionalities of many special use resins. The following reactions of crosslinked polystyrene resins are reviewed: halogenation, chloromethylation, metalation, formylation, acylation, carboxylation, phosphination, nitration, amination and the introduction of hydroxyl, anhydride and sulfur containing functional groups. Finally, the analytical problems encountered in the characterization of the functionalized resins are reviewed.

This paper describes the design and preparation of a negative tone, oxygen etch resistant DUV photoresist. This two-component resist system is composed of an oxygen plasma etch resistant matrix resin, poly(trimethylsilylmethylstyrene), and a monomeric radical generator such as trichlorobenzene or 3,3'-diazidodiphenylsulfone.