Biological application of multi-component nanowires in hybrid devices powered by F-1-ATPase motors

In this paper, construction of hybrid device by integrating nanowires with F1-ATPase motors is described. The nickel nanowires and multi-segment nanowires, including gold and nickel, were fabricated by electrochemical deposition in nanoporous templates. The nickel nanowires functionalized by biotinylated peptide can be assembled directly onto F1-ATPase motors to act as the propellers. If the multicomponent nanowires, including gold and nickel, were selectively functionalized by the thiol group modified ssDNA and the synthetic peptide, respectively, the biotinylated F1- ATPase motors can be attached to the biotinylated peptide on nickel segment of the nanowires. Then, the multi-component nanowires can also be used as the propellers, and one may observe the rotations of the multi-component nanowires driven by F1-ATPase motors. Therefore, introduction of multiple segments along the length of a nanowire can lead to a variety of multiple chemical functionalities, which can be selectively bound to cells and special biomolecules. This method provides an insight for the construction of other hybrid devices with its controlling arrangement of different biomolecule on designed nanometer scale structures.

Template-free electrochemical nanofabrication of polyaniline nanobrush and hybrid polyaniline with carbon nanohorns for supercapacitors.

Polyaniline (PANI) nanobrushes were synthesized by template-free electrochemical galvanostatic methods. When the same method was applied to the carbon nanohorn (CNH) solution containing aniline monomers, a hybrid nanostructure containing PANI and CNHs was enabled after electropolymerization. This is the first report on the template-free method to make PANI nanobrushes and homogeneous hybrid soft matter (PANI) with carbon nanoparticles. Raman spectroscopy was used to analyze the interaction between CNH and PANI. Electrochemical nanofabrication offers simplicity and good control when used to make electronic devices. Both of these materials were applied in supercapacitors and an improvement capacitive current by using the hybrid material was observed.

Functionalization of Si(111) surfaces and the formation of mixed monolayers for the covalent attachment of molecular catalysts in photoelectrochemical devices

The functionalization of silicon surfaces with molecular catalysts for proton reduction is an important part of the development of a solar-powered, water-splitting device for solar fuel formation. The covalent attachment of these catalysts to silicon without damaging the underlying electronic properties of silicon that make it a good photocathode has proven difficult. We report the formation of mixed monolayer-functionalized surfaces that incor- porate both methyl and vinylferrocenyl or vinylbipyridyl (vbpy) moieties. The silicon was functionalized using reaction conditions analogous to those of hydrosilylation, but instead of a H-terminated Si surface, a chlorine-terminated Si precursor surface was used to produce the linked vinyl-modified functional group. The functionalized surfaces were characterized by time-resolved photoconductivity decay, X-ray photoelectron spectroscopy (XPS), electro- chemical, and photoelectrochemical measurements. The functionalized Si surfaces were well passivated, exhibited high surface coverage and few remaining reactive Si atop sites, had a very low surface recombination velocity, and displayed little initial surface oxidation. The surfaces were stable toward atmospheric and electrochemical oxidation. The surface coverage of ferrocene or bipyridine was controllably varied from 0 up to 30% of a monolayer without loss of the underlying electronic properties of the silicon. Interfacial charge transfer to the attached ferrocene group was relatively rapid, and a photovoltage of 0.4 V was generated upon illumination of functionalized n-type silicon surfaces in CH₃CN. The immobilized bipyridine ligands bound transition metal ions, and thus enabled the assembly of metal complexes on the silicon surface. XPS studies demonstrated that [Cp∗Rh(vbpy)Cl]Cl, [Cp∗Ir(vbpy)Cl]Cl, and Ru(acac)₂vbpy were assembled on the surface. For the surface prepared with iridium, x-ray absorption spectroscopy at the Ir L_III edge showed an edge energy and post-edge features virtually identical to a powder sample of [Cp∗Ir(bipy)Cl]Cl (bipy is 2,2 ́-bipyridyl). Electrochemical studies on these surfaces confirmed that the assembled complexes were electrochemically active.

DNA-Mediated Charge Transport Devices for Protein Detection

Detection of biologically relevant targets, including small molecules, proteins, DNA, and RNA, is vital for fundamental research as well as clinical diagnostics. Sensors with biological elements provide a natural foundation for such devices because of the inherent recognition capabilities of biomolecules. Electrochemical DNA platforms are simple, sensitive, and do not require complex target labeling or expensive instrumentation. Sensitivity and specificity are added to DNA electrochemical platforms when the physical properties of DNA are harnessed. The inherent structure of DNA, with its stacked core of aromatic bases, enables DNA to act as a wire via DNA-mediated charge transport (DNA CT). DNA CT is not only robust over long molecular distances of at least 34 nm, but is also especially sensitive to anything that perturbs proper base stacking, including DNA mismatches, lesions, or DNA-binding proteins that distort the π-stack. Electrochemical sensors based on DNA CT have previously been used for single-nucleotide polymorphism detection, hybridization assays, and DNA-binding protein detection. Here, improvements to (i) the structure of DNA monolayers and (ii) the signal amplification with DNA CT platforms for improved sensitivity and detection are described.

First, improvements to the control over DNA monolayer formation are reported through the incorporation of copper-free click chemistry into DNA monolayer assembly. As opposed to conventional film formation involving the self-assembly of thiolated DNA, copper-free click chemistry enables DNA to be tethered to a pre-formed mixed alkylthiol monolayer. The total amount of DNA in the final film is directly related to the amount of azide in the underlying alkylthiol monolayer. DNA monolayers formed with this technique are significantly more homogeneous and lower density, with a larger amount of individual helices exposed to the analyte solution. With these improved monolayers, significantly more sensitive detection of the transcription factor TATA binding protein (TBP) is achieved.

Using low-density DNA monolayers, two-electrode DNA arrays were designed and fabricated to enable the placement of multiple DNA sequences onto a single underlying electrode. To pattern DNA onto the primary electrode surface of these arrays, a copper precatalyst for click chemistry was electrochemically activated at the secondary electrode. The location of the secondary electrode relative to the primary electrode enabled the patterning of up to four sequences of DNA onto a single electrode surface. As opposed to conventional electrochemical readout from the primary, DNA-modified electrode, a secondary microelectrode, coupled with electrocatalytic signal amplification, enables more sensitive detection with spatial resolution on the DNA array electrode surface. Using this two-electrode platform, arrays have been formed that facilitate differentiation between well-matched and mismatched sequences, detection of transcription factors, and sequence-selective DNA hybridization, all with the incorporation of internal controls.

For effective clinical detection, the two working electrode platform was multiplexed to contain two complementary arrays, each with fifteen electrodes. This platform, coupled with low density DNA monolayers and electrocatalysis with readout from a secondary electrode, enabled even more sensitive detection from especially small volumes (4 μL per well). This multiplexed platform has enabled the simultaneous detection of two transcription factors, TBP and CopG, with surface dissociation constants comparable to their solution dissociation constants.

With the sensitivity and selectivity obtained from the multiplexed, two working electrode array, an electrochemical signal-on assay for activity of the human methyltransferase DNMT1 was incorporated. DNMT1 is the most abundant human methyltransferase, and its aberrant methylation has been linked to the development of cancer. However, current methods to monitor methyltransferase activity are either ineffective with crude samples or are impractical to develop for clinical applications due to a reliance on radioactivity. Electrochemical detection of methyltransferase activity, in contrast, circumvents these issues. The signal-on detection assay translates methylation events into electrochemical signals via a methylation-specific restriction enzyme. Using the two working electrode platform combined with this assay, DNMT1 activity from tumor and healthy adjacent tissue lysate were evaluated. Our electrochemical measurements revealed significant differences in methyltransferase activity between tumor tissue and healthy adjacent tissue.

As differential activity was observed between colorectal tumor tissue and healthy adjacent tissue, ten tumor sets were subsequently analyzed for DNMT1 activity both electrochemically and by tritium incorporation. These results were compared to expression levels of DNMT1, measured by qPCR, and total DNMT1 protein content, measured by Western blot. The only trend detected was that hyperactivity was observed in the tumor samples as compared to the healthy adjacent tissue when measured electrochemically. These advances in DNA CT-based platforms have propelled this class of sensors from the purely academic realm into the realm of clinically relevant detection.

Chemical and Electrochemical Behavior of Graphene-Covered Silicon Photoanodes

This dissertation describes efforts over the last five years to develop protective layers for semiconductor photoelectrodes based on monolayer or few-layer graphene sheets. Graphene is an attractive candidate for a protective layer because of its known chemical inertness, transparency, ease of deposition, and limited number of electronic states. Monolayer graphene was found to effectively inhibit loss of photocurrent over 1000 seconds at n-Si/aqueous electrolyte interfaces that exhibit total loss over photocurrent over 100 seconds. Further, the presence of graphene was found to effect only partial Fermi level pinning at the Si/graphene interface with respect to a range of nonaqueous electrolytes. Fluorination of graphene was found to extend the stability imparted on n-Si by the monolayer sheet in aqueous Fe(CN)₆^3-/4- electrolyte to over 100,000 seconds. It was demonstrated that the stability of the photocurrent of n-Si/fluorinated graphene/aqueous electrolyte interfaces relative to n-Si/aqueous electrolyte interfaces is likely attributable to the inhibition of oxidation of the silicon surface.

This dissertation also relates efforts to describe and define terminology relevant to the field of photoelectrochemistry and solar fuels production. Terminology describing varying interfaces employed in electrochemical solar fuels devices are defined, and the research challenges associated with each are discussed. Methods for determining the efficiency of varying photoelectrochemical and solar-fuel-producing cells from the current-voltage behavior of the individual components of such a device without requiring the device be constructed are described, and a range of commonly employed performance metrics are explored.

Characterization and fabrication of zinc oxide nanowire devices

In this paper, we demonstrate an approach for the local synthesis of ZnO nanowires (ZnO NWs) and the potential for such structures to be incorporated into device applications. Three network ZnO NW devices are fabricated on a chip by using a bottom-up synthesis approach. Microheaters (defined by standard semiconductor processing) are used to synthesize the ZnO NWs under a zinc nitrate (Zn(NO3)2·6H2O) and hexamethylenetetramine (HMTA, (CH2)6·N4) solution. By controlling synthesis parameters, varying densities of networked ZnO NWs are locally synthesized on the chip. The fabricated networked ZnO NW devices are then characterized using UV excitation and cyclic voltammetry (CV) experiments to measure their photoresponse and electrochemical properties. The experimental results show that the techniques and material systems presented here have the potential to address interesting device applications using fabrication methods that are fully compatible with standard semiconductor processing. © 2013 IEEE.

Use of vertically-aligned carbon nanotube array to enhance the performance of electrochemical capacitors

In the domain of energy storage, electrochemical capacitors have numerous applications ranging from hybrid vehicles to consumer electronics, with very high power density at the cost of relatively low energy storage. Here, we report an approach that uses vertically aligned carbon nanotube arrays as electrodes in electrochemical capacitors. Different electrolytes were used and multiple parameters of carbon nanotube array were compared: carbon nanotube arrays were shown to be two to three times better than graphite in term of specific capacitance, while the surface functionalization was demonstrated to be a critical factor in both aqueous and nonaqueous solutions to increase the specific capacitance. We found that a maximum energy density of 21 Wh/kg at a power density of 1.1 kW/kg for a hydrophilic electrode, could be easily achieved by using tetraethylammonium tetrafluoroborate in propylene carbonate. These are encouraging results in the path of energy-storage devices with both high energy density and power density, using only carbon-based materials for the electrodes with a very long lifetime, of tens of thousands of cycles. © 2011 IEEE.

Solution-processable highly efficient yellow- and red-emitting phosphorescent organic light emitting devices from a small molecule bipolar host and iridium complexes

A bipolar transport compound, 2,5-bis(4-(9-(2-ethylhexyl)-9H-carbazol-3-yl) phenyl)-1,3,4-oxadiazole (CzOXD), incorporating both electron-and hole-transport functionalities, was synthesized and fully characterized by H-1 NMR, C-13 NMR, elemental analysis and mass spectrometry. Its thermal, electrochemical, electronic absorption and photoluminescent properties were studied

Multifunctional metallophosphors with anti-triplet–triplet annihilation properties for solution-processable electroluminescent devices

With the goal to provide organometallic triplet emitters with good hole-injection/hole-transporting properties, highly amorphous character for simple solution-processed organic light-emitting diodes, and negligible triplet-triplet (T-T) annihilation, a series of new phosphorescent cyclometalated Ir-III and Pt-II complexes with triphenylamine-anchored fluorenylpyridine dendritic ligands were synthesized and characterized. The photophysical, thermal, electrochemical and electroluminescent properties of these molecules are reported.

Biomolecule-nanoparticle hybrids for electrochemical biosensors

Inorganic nanoparticles (NPs) with attractive electronic, optical, magnetic, thermal and catalytic properties have attracted great interest due to their important applications in physics, chemistry, biology, medicine, materials science and interdisciplinary fields. Biomolecule-NP hybrid systems, which combine recognition and catalytic properties of biomolecules with electronic, optical, magnetic and catalytic properties of NPs, are particularly new materials with synergistic properties originating from the components of the hybrid composites. The biomolecule-NP hybrid system has excellent prospects for interfacing biological recognition events with electronic signal transduction so as to design a new generation of bioelectronic devices with high sensitivity.

Capillary electrophoresis and microchip capillary electrophoresis with electrochemical and electrochemiluminescence detection

Recent advances and key strategies in capillary electrophoresis and microchip CE with electrochemical detection (ECD) and electrochemiluminescence (ECL) detection are reviewed. This article consists of four main parts: CE-ECD; microchip CE-ECD; CE-ECL; and microchip CE-ECL. It is expected that ECD and ECL will become powerful tools for CE microchip systems and will lead to the creation of truly disposable devices. The focus is on papers published in the last two years (from 2005 to 2006).

Electrochemical and electrogenerated chemiluminescence of clay nanoparticles/Ru(bpy)(3)(2+) multilayer films on ITO electrodes

The electrochemical and electrogenerated chemiluminescence of Ru(bpy)(3)(2+) immobilized in {clay/Ru(bpy)(3)(2+)}(n) multilayer films by layer-by-layer assembly were investigated. The stable multilayer films of clay and Ru(bpy)(3)(2+) were assembled by alternate adsorption of negatively charged clay platelets and positively charged Ru(bpy)(3)(2+) from their aqueous dispersions. UV-vis spectroscopy, quartz crystal microbalance (QCM), cyclic voltammetry, and electrogenerated chemiluminescence (ECL) were used to monitor the immobilization of Ru( bpy)(3)(2+) and the regular growth of the {clay/Ru( bpy)(3)(2+)}(n) multilayer films. The multilayer films modified electrode was used for the ECL detection of tripropylamine ( TPA) and oxalate. The proposed novel immobilized method exhibited good stability, reproducibility and high sensitivity for the determination of TPA and oxalate, which mainly resulted from the contributing of clay nanoparticles with appreciable surface area, special structural features and unusual intercalation properties.

Highly efficient electroluminescence from green-light-emitting electrochemical cells based on Cu-I complexes

The complexes [Cu(dnpb)(DPEphos)](+)(X-) (dnpb and DPEphos are 2,9-di-n-butyl-1,10-phenanthroline and bis[2-(diphenyl-phosphino)phenyl]ether, respectively, and X- is BF4-, ClO4-, or PF6-) can form high quality films with photoluminescence quantum yields of up to 71 +/- 7%. Their electroluminescent properties are studied using the device-structure indium tin oxide (ITO)/complex/metal cathiode. The devices emit green light efficiently, with an emission maximum of 523 nm, and work in the mode of light-emitting electrochemical cells. The response time of the devices greatly depends on the driving voltage, the counterions, and the thickness of the complex film. After pre-biasing at 25 V for 40 s, the devices turn on instantly, with a turn-on voltage of ca. 2.9 V. A current efficiency of 56 cd A(-1) and an external quantum efficiency of 16% are realised with Al as the cathode. Using a low-work-function metal as the cathode can significantly enhance the brightness of the device almost without affecting the turn-on voltage and current efficiency. With a Ca cathode, a brightness of 150 cd m(-2) at 6 V and 4100 cd m(-2) at 25 V is demonstrated. The electroluminescent performance of these types of complexes is among the best so far for transition metal complexes with counterions.

Fabrication of integrated microelectrodes for electrochemical detection on electrophoresis microchip by electroless deposition and micromolding in capillary technique

A new method for the fabrication of an integrated microelectrode for electrochemical detection (ECD) on an electrophoresis microchip is described. The pattern of the microelectrode was directly made on the surface of a microscope slide through an electroless deposition procedure. The surface of the slide was first selectively coated with a thin layer of sodium silicate through a micromolding in capillary technique provided by a poly(dimethylsiloxane) (PDMS) microchannel; this left a rough patterned area for the anchoring of catalytic particles. A metal layer was deposited on the pattern guided by these catalytic particles and was used as the working electrode. Factors influencing the fabrication procedure were discussed. The whole chip was built by reversibly sealing the slide to another PDMS layer with electrophoresis microchannels at room temperature. This approach eliminates the need of clean room facilities and expensive apparatus such as for vacuum deposition or sputtering and makes it possible to produce patterned electrodes suitable for ECD on microchip under ordinary chemistry laboratory conditions. Also once the micropattern is ready, it allows the researchers to rebuild the electrode in a short period of time when an electrode failure occurs. Copper and gold microelectrodes were fabricated by this technique. Glucose, dopamine, and catechol as model analytes were tested.