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Biomedical subjects

Neal R Armstrong

Publications and source records attributed to Neal R Armstrong.

11 recordsLinked to original sources
PubMed2006

Small molecule chemisorption on indium-tin oxide surfaces: enhancing probe molecule electron-transfer rates and the performance of organic light-emitting diodes.

Indium-tin oxide (ITO) surfaces have been modified by chemisorption of carboxylic acid functionalized small molecules: ferrocene dicarboxylic acid (1), 3-thiophene acetic acid (2), and 6-{4-[{4'-[[4-(5-carboxy-pentyloxy)-phenyl]-(4-methoxy-phenyl)-amino]-biphenyl-4-yl}-(4-methoxy-phenyl)-amino]-phenoxy}-hexanoic acid (p-OMe)2-TPD-(C5-COOH)2) (3). Voltammetrically determined surface coverages of 1-3 increased in two stages, the first stage completing in minutes, the latter stage taking several hours. Electron-transfer rate coefficients, kS, for the probe molecule ferrocene in acetonitrile likewise increased in two stages with increasing surface coverages of 1, 2, and 3. Fourier transform infrared spectroscopy of In2O3 powders, exposed for long periods to ethanol solutions of each modifier, confirmed the formation of indium oxalate-like surface species. X-ray photoelectron spectroscopy of carboxy-terminated alkanethiol-modified gold surfaces, exposed to these same In2O3(powder)/small molecule modifier solutions, showed the capture of trace levels of indium as a result of the chemisorption of these small molecules, suggesting that slow etching of the ITO surface also occurs during the chemisorption event. Conventional aluminum quinolate/bis-triarylamine organic light-emitting diodes (OLEDs) created on ITO surfaces modified with 1, 2, and 3, with and without an overlayer of PEDOT:PSS (a poly(thiophene)/poly(stryenesulfonate) ITO modifier), showed leakage currents lowered by several orders of magnitude and an increase in OLED device efficiency.

Acetates↗
PubMed2006

Dendritic arrays of [Re6(mu3-Se)8]2+ core-containing clusters: exploratory synthesis and electrochemical studies.

The reaction between the previously reported site-differentiated cluster solvate [Re(6)(mu(3)-Se)(8)(PEt(3))(5)(MeCN)](SbF(6))(2) (1) with pyridyl-based ditopic ligands 4,4'-trimethylenedipyridine (2), 1,2-bis(4-pyridyl)ethane (3), and (E)-1,2-bis(4-pyridyl)ethene (4) afforded cluster complexes of the general formula [Re(6)(mu(3)-Se)(8)(PEt(3))(5)(L)](SbF(6))(2) (5-7), where L represents one of the pyridyl-based ligands. Reacting these cluster complex-based ligands with the fully solvated cluster complex [Re(6)(mu(3)-Se)(8)(MeCN)(6)](SbF(6))(2) (8) produced dendritic arrays of the general formula {Re(6)(mu(3)-Se)(8)[Re(6)(mu(3)-Se)(8)(PEt(3))(5)(L)](6)}(SbF(6))(14) (9-11), each featuring six circumjacent [Re(6)(mu(3)-Se)(8)(PEt(3))(5)](2+) units bridged to a [Re(6)(mu(3)-Se)(8)](2+) core cluster by the pyridyl-based ligands. Electrochemical studies using a thin-layer electrochemical cell revealed cluster-based redox events in these cluster arrays. For 9 (L = 2), one reversible oxidation event corresponding to the removal of 7 electrons was observed, indicating noninteraction or extremely weak interactions between the clusters. For 10 (L = 3), two poorly resolved oxidation waves were found. For 11 (L = 4), two reversible oxidation events, corresponding respectively to the removal of 1 and 6 electrons, were observed with the 1-electron oxidation event occurring at a potential 150 mV more positive than the 6-electron oxidation. These electrochemical studies suggest intercluster coupling in 11 via through-bond electronic delocalization, which is consistent with electronic spectroscopic studies of this same molecule.

Journal Article↗
PubMed2006

Potential-modulated, attenuated total reflectance spectroscopy of poly(3,4-ethylenedioxythiophene) and poly(3,4-ethylenedioxythiophene methanol) copolymer films on indium-tin oxide.

We report the first application of a potential-modulated spectroelectrochemical ATR (PM-ATR) instrument utilizing multiple internal reflections at an optically transparent electrode to study the charge-transfer kinetics and electrochromic response of adsorbed films. A sinusoidally modulated potential waveform was applied to an indium-tin oxide (ITO) electrode while simultaneously monitoring the optical reflectivity of thin (2-6 equivalent monolayers) copolymer films of poly(3,4-ethylenedioxythiophene) (PEDOT) and poly(3,4-ethylenedioxythiophene methanol) (PEDTM), previously characterized in our laboratory. At high modulation frequencies the measured response of the polymer film is selective toward the fastest electrochromic processes in the film, presumably those occurring within the first adsorbed monolayer. Quantitative determination of the electrochromic switching rate, derived from the frequency response of the attenuated reflectivity, shows a linear decrease in the rate, from 11 x 10(3) s(-1) to 3 x 10(3) s(-1), with increasing proportions of PEDTM in the copolymer, suggesting that interactions between the methanol substituent on EDTM and the ITO surface slow the switching process by limiting the rate of conformational change in the polymer film.

Journal Article↗
PubMed2006

Characterization of proton transport across a waveguide-supported lipid bilayer.

Cellular energy transduction processes are often driven by transmembrane ion gradients, and numerous artificial biomembrane systems have been developed that allow for chemically or light-induced charge transport into/out of liposomes. Liposomal architectures, however, are not readily interfaced to a solid-state transducer. Formation of an ion gradient across a planar-supported membrane, "wired" to a substrate electrode, may ultimately allow utilization of the potential energy to drive other electrochemical processes. Described here is a novel conductive polymer/planar waveguide assembly that provides for highly sensitive transduction of proton transport across a planar-supported lipid bilayer (PSLB). A quinone proton shuttle is embedded in the PSLB, which is coupled to the planar optical waveguide electrode through a pH-sensitive, self-assembled conductive polymer film. Interfacial potential and absorbance changes in the conductive polymer film provide for sensitive characterization of transmembrane proton transport. The general and flexible nature of this architecture makes it adaptable to many different types of transmembrane transport chemistries, particularly light-activated systems.

Acrylic Resins↗
PubMed2005

Covalently bound hole-injecting nanostructures. Systematics of molecular architecture, thickness, saturation, and electron-blocking characteristics on organic light-emitting diode luminance, turn-on voltage, and quantum efficiency.

Hole transporting materials are widely used in multilayer organic and polymer light-emitting diodes (OLEDs, PLEDs, respectively) and are indispensable if device electroluminescent response and durability are to be truly optimized. This contribution analyzes the relative effects of tin-doped indium oxide (ITO) anode-hole transporting layer (HTL) contact versus the intrinsic HTL materials properties on OLED performance. Two siloxane-based HTL materials, N,N'-bis(p-trichlorosilylpropyl)-naphthalen-1-yl)-N,N'-diphenyl-biphenyl-4,4'-diamine (NPB-Si(2)) and 4,4'-bis[(p-trichlorosilylpropylphenyl)phenylamino]biphenyl (TPD-Si(2)), are designed and synthesized. They have the same hole transporting triarylamine cores as conventional HTL materials such as 1,4-bis(1-naphthylphenylamino)biphenyl (NPB) and N,N-diphenyl-N,N-bis(3-methylphenyl)-1,1-biphenyl)-4,4-diamine (TPD), respectively. However, they covalently bind to the ITO anode, forming anode-HTL contacts that are intrinsically different from those of the anode to TPD and NPB. Applied to archetypical tris(8-hydroxyquinolato)aluminum(III) (Alq)-based OLEDs as (1) the sole HTLs or (2) anode-NPB HTL interlayers, NPB-Si(2) and TPD-Si(2) enhance device electroluminescent response significantly versus comparable devices based on NPB alone. In the first case, OLEDs with 36 000 cd/m(2) luminance, 1.6% forward external quantum efficiency (eta(ext)), and 5 V turn-on voltages are achieved, affording a 250% increase in luminance and approximately 50% reduction in turn-on voltage, as compared to NPB-based devices. In the second case, even more dramatic enhancement is observed (64 000 cd/m(2) luminance; 2.3% eta(ext); turn-on voltages as low as 3.5 V). The importance of the anode-HTL material contact is further explored by replacing NPB with saturated hydrocarbon siloxane monolayers that covalently bind to the anode, without sacrificing device performance (30 000 cd/m(2) luminance; 2.0% eta(ext); 4.0 V turn-on voltage). These results suggest new strategies for developing OLED hole transporting structures.

Journal Article↗
PubMed2005

Electrochemically tunable surface-plasmon-enhanced diffraction gratings and their (bio-)sensing applications.

Electrochemistry was combined with surface-plasmon-enhanced diffraction (ESPD) to investigate a redox-switchable polymer grating and its (bio-)sensing applications. Patterned arrays of polyaniline (PANI)/ poly(styrenesulfonate) (PSS) were fabricated by the combination of electropolymerization and micromolding in capillaries (MIMIC) and were used as an optical grating for surface-plasmon-enhanced diffraction experiments. The diffraction efficiency (DE) could be tuned by changes in the applied potential, and by changes in the pH of the surrounding solution (dielectric medium). The response of the DE to the pH depends strongly on the redox state of the PANI/PSS grating. If the polymer grating is mainly in its reduced state, the DE shows a linear dependence on the pH. The DE of the PANI/PSS grating can also be modulated by an electrocatalytic event: by keeping PANI/PSS in its oxidized form, the addition of beta-nicotinamide adenine dinucleotide (NADH) increases the DE with the increase of NADH concentration, which points to the possibility of the use of ESPD technologies for biosensing.

Aniline Compounds↗
PubMed2005

High-performance hole-transport layers for polymer light-emitting diodes. Implementation of organosiloxane cross-linking chemistry in polymeric electroluminescent devices.

This contribution describes an organosiloxane cross-linking approach to robust, efficient, adherent hole-transport layers (HTLs) for polymer light-emitting diodes (PLEDs). An example is 4,4'-bis[(p-trichlorosilylpropylphenyl)phenylamino]biphenyl (TPDSi(2)), which combines the hole-transporting efficiency of N,N-diphenyl-N,N-bis(3-methylphenyl)-1,1-biphenyl)-4,4-diamine) (TPD, prototypical small-molecule HTL material) and the strong cross-linking/densification tendencies of organosilanol groups. Covalent chemical bonding of TPDSi(2) to PLED anodes (e.g., indium tin oxide, ITO) and its self-cross-linking enable fabrication of three generations of insoluble PLED HTLs: (1) self-assembled monolayers (SAMs) of TPDSi(2) on ITO; (2) cross-linked blend networks consisting of TPDSi(2) + a hole transporting polymer (e.g., poly(9,9-dioctylfluorene-co-N-(4-(3-methylpropyl))diphenylamine), TFB) on ITO; (3) TPDSi(2) + TFB blends on ITO substrates precoated with a conventional PLED HTL, poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonate) (PEDOT-PSS). PLED devices fabricated using these new HTLs exhibit comparable or superior performance vs comparable devices based on PEDOT-PSS alone. With these new HTLs, current efficiencies as high as approximately 17 cd/A and luminances as high as approximately 140,000 cd/m(2) have been achieved. Further experiments demonstrate that not only do these HTLs enhance PLED anode hole injection but they also exhibit significantly greater electron-blocking capacity than PEDOT-PSS. The present organosiloxane HTL approach offers many other attractions such as convenience of fabrication, flexibility in choosing HTL components, and reduced HTL-induced luminescence quenching, and can be applied as a general strategy to enhance PLED performance.

Journal Article↗
PubMed2005

Determination of molecular anisotropy in thin films of discotic assemblies using attenuated total reflectance UV-visible spectroscopy.

We report here an investigation of absorbance anisotropy in highly ordered, single bilayer (ca. 5.6 nm) Langmuir-Blodgett (LB) thin films of discotic liquid-crystalline phthalocyanines, using a recently introduced broad-band attenuated total reflectance (ATR) spectroscopic technique, capable of measuring dichroism in such films in the UV--visible optical region down to absorbances of ca. 0.003 absorbance units. On the basis of the ATR measurements of LB-deposited films, a thorough treatment was established to determine the ensemble average of the Cartesian components and the associated optical anisotropy of transition dipoles in the molecular film. In an effort to recover order parameters of molecular orientation, those results were interpreted with a circular dipole model, which is the expected model for the isolated molecule based on symmetry properties. We measured a strong dipole component normal to the film plane that cannot be explained in terms of a truly circular model, indicating that the molecular transition dipoles were perturbed upon aggregation. The utility of the experimental approach was further demonstrated by (a) investigating the effect of substrate modifiers (methyl- and phenyl-terminated silanes) on the ordering within the phthalocyanine film and (b) the effect of water immersion and re-annealing of the thin film on molecular ordering and optical anisotropy.

Journal Article↗
PubMed2004

LB films of rodlike phthalocyanine aggregates: specular X-ray reflectivity studies of the effect of interface modification on coherence and microstructure.

We present here X-ray specular reflectivity (XRR) characterization of the ordering of Langmuir-Blodgett films of the liquid crystalline phthalocyanine (Pc) 2,3,9,10,16,17,23,34-octakis(2-benzyloxyethoxy)copper(II) phthalocyanine, 1, on Si(100) wafers with a native oxide layer and these same substrates modified with monolayers of varying percentages of methyl- and phenyl-terminated silanes. The central copper atom in these Pc's provides for high contrast in X-ray reflectivity for single-bilayer films of 1. The XRR data are modeled as arising from multiple layers of organic material, above and below the rows of copper atoms in the aligned Pc cores; variations in the total thickness of these films, and the spacing between the rows of copper atoms, are attributed to changes in the interaction with the substrate, and changes in the Pc orientation and side chain packing. The most pronounced effect on these parameters comes from variations in the ratio of the phenyl-silane versus methyl-silane content of the substrate modifiers and annealing of these films past their crystalline (K) --> liquid crystalline (LC) mesophase transition temperature. Transfer of multiple bilayers of this Pc leads to additional changes in the thickness of each layer, eventually forming a hexagonal close-packed array, reminiscent of bulk fibers of this material, as revealed by X-ray diffraction (XRD).

Journal Article↗
PubMed2003

Broadband coupling into a single-mode, electroactive integrated optical waveguide for spectroelectrochemical analysis of surface-confined redox couples.

A single-mode, electroactive waveguiding platform capable of measuring spectroelectrochemical responses of surface-adsorbed redox-active molecules over a broad spectral bandwidth has been created. This new planar waveguide spectrometer is a combination of the previously developed electroactive integrated optical waveguide (EA-IOW; Dunphy, D. R.; Mendes, S. B.; Saavedra, S. S.; Armstrong, N. R. Anal. Chem. 1997, 69, 3086-3094) with a recently reported simplified approach to broadband coupling (Bradshaw, J. T.; Mendes, S. B.; Saavedra, S. S. Anal. Chem. 2002, 74, 1751-1759). With the use of a commercially available prism as an incoupling element, the EA-IOW can now guide visible light from at least 500 to 700 nm, improving upon its previously demonstrated monochromatic nature. Coupling profiles of various laser lines along with transmission spectra of narrow band-pass filters at various potentials are used to demonstrate the optical characteristics of this broadband EA-IOW and to compare its response to that of a conventional transmission instrument. Assessment of spectral resolution, performed by measuring the fwhm of various laser lines, ranges from 0.6 to 0.8. To demonstrate the capabilities of this technology, we show the acquisition of absorbance spectra of two different adsorbates, cytochrome c and ferrocenedicarboxylic acid, as a function of applied potential. Subtleties in the redox chemistries of adsorbed molecules, which were difficult to monitor with a monochromatic waveguide, are readily apparent when using the broadband coupling scheme.

Electrochemistry↗