Biomedical subjects

James E Whitten

Publications and source records attributed to James E Whitten.

4 recordsLinked to original sources

PubMed2006

Conjugated polymers in an arene sandwich.

A series of poly(p-arylene butadiynylene)s containing zero, one, and two co-facial pi-pi interactions per repeat unit were synthesized and characterized. A surprisingly selective and high-yielding Diels-Alder cycloaddition of anthracene and nonsymmetric, sterically hindered anhydrides proved essential to generating the cofacial arene-containing monomers. Single-crystal X-ray structures display nearly parallel cofacial arenes that are within the van der Waals contact distances. The precursor molecules with cofacial arenes undergo reversible one- and two-electron oxidations to the radical cation and dication in CH2Cl2. The anhydrides were converted to N-alkyl imides to increase the solubility. High-molecular weight poly(p-arylene butadiynylene)s were prepared via Pd/Cu(I)/benzoquinone oxidative coupling of the diacetylene monomers. The resulting polymers are highly emissive in solution and thin films. The ionization potentials were measured using ultraviolet photoelectron spectroscopy with thin films. Last, fluorescence measurements of polymer thin films during continuous irradiation indicate that the most hindered polymer is more resistant to photobleaching.

Journal Article↗

PubMed2006

Template-directed adsorption of block copolymers on alkanethiol-patterned gold surfaces.

Functionalized alkanethiols have been self-assembled on gold to modify the wetting properties of the surface and promote or hinder the adsorption of block copolymers containing both hydrophobic and hydrophilic blocks. X-ray photoelectron spectroscopy (XPS) studies of spin-coated polyethylene-block-poly(ethylene oxide) (PE-b-PEO) copolymers on 16-mercaptohexadecanoic acid (MHDA)-, octadecanethiol (ODT)-, and 1H,1H,2H,2H-perfluorodecanethiol (PFDT)-covered surfaces have been performed. In the case of an 80 wt % PEO block copolymer, spin-coating on a gold surface precovered with MHDA results in a polymer film thick enough to completely attenuate Au 4f photoelectrons; spin-coating on the more hydrophobic ODT and PFDT monolayers leads to significantly thinner polymer films and incomplete attenuation of the gold photoelectrons. The opposite results are observed when a 20 wt % PEO block copolymer is used. Angle-resolved XPS studies of the 80 wt % PEO block copolymer spin-coated onto an MHDA-covered surface indicate that the PE blocks of the polymer segregate to the near-surface region, oriented away from the hydrophilic carboxylic acid tails of the monolayers; the surface concentration of PE is further enhanced by annealing at 90 degrees C. Microcontact printing and dip-pen nanolithography have been used to pattern gold surfaces with MHDA, and the surfaces have been backfilled with ODT or PFDT, such that the unpatterned regions of the surface are covered with hydrophobic monolayers. In the case of backfilling with PFDT, spin-coating the 80 wt % PEO copolymer onto these patterned surfaces and subsequent annealing results in the block copolymer preferentially adsorbing on the MHDA-covered regions and forming well-defined patterns that mimic the MHDA pattern, as determined by scanning electron microscopy and atomic force microscopy. Significantly worse patterning, characterized by micron-sized polymer droplets, results when the surface is backfilled with ODT instead of PFDT. Using PFDT and MHDA, polymer features having widths as small as 500 nm have been formed. These studies demonstrate a novel method to pattern block copolymers with nanoscale resolution.

Journal Article↗

PubMed2005

High ionization potential conjugated polymers.

We report the synthesis of a series of poly(p-phenylene ethynylene)s (PPEs) with high ionization potentials and associated high excited-state electron affinities. Their photophysical properties were investigated using steady-state and time-resolved fluorescence techniques. The ionization potentials of the polymer thin films were determined using ultraviolet photoelectron spectroscopy (UPS), and those with the highest ionization potentials displayed high sensitivity for the detection of electron-donating aromatic compounds. The effects of sterics, chemical structure, and electronic properties on the polymers' sensory responses were investigated by fluorescence quenching experiments in both solution and solid thin films. In addition, we report that in some cases the excited-state charge-transfer complexes (exciplexes) of the PPEs with analytes were observed. These latter effects provide promising opportunities for the formation of sensitive and selective chemical sensors.

Journal Article↗

PubMed2005

Peroxidase-catalyzed in situ polymerization of surface orientated caffeic acid.

Nanoscale surface patterning and polymerization of caffeic acid on 4-aminothiophenol-functionalized gold surfaces has been demonstrated with dip pen nanolithography (DPN). The diphenolic moiety of caffeic acid can be polymerized by biocatalysis with laccase or horseradish peroxidase. In the present study, the DPN patterned features were polymerized in situ through the use of the peroxidase. Using samples prepared by DPN, microcontact printing, and adsorption on macroscopic substrates, the products were characterized by electrostatic force microscopy (EFM), MALDI-TOF, X-ray photoelectron spectroscopy (XPS), UV-vis, and FT-IR. The in situ surface polymerization resulted in the formation of a quinone structure, while the phenyl ester formed in bulk polymerization reactions was not detected. A different coupling site was observed when comparing the polymers obtained from solution (bulk) vs the surface DPN reactions. The structural differences were attributed to surface-induced pre-organization and orientation of the monomers prior to the enzymatic polymerization step. The results of this study expand the application of DPN technology to surface modification and surface chemistry reactions wherein stereo-regularity and regioselectivity can be exploited.

Alloys↗