Melburne C. LeMieux

Self-Sorted, Aligned Nanotube Networks for Thin-Film Transistors

To find use in electronics, single-walled carbon nanotubes need to be efficiently separated by electronic type and aligned to ensure optimal and reproducible electronic properties. We report the fabrication of single-walled carbon nanotube (SWNT) network field-effect transistors, deposited from solution, possessing controllable topology and an on/off ratio as high as 900,000. The spin-assisted alignment and density of the SWNTs are tuned by different surfaces that effectively vary the degree of interaction with surface functionalities in the device channel. This leads to a self-sorted SWNT network in which nanotube chirality separation and simultaneous control of density and alignment occur in one step during device fabrication. Micro-Raman experiments corroborate device results as a function of surface chemistry, indicating enrichment of the specific SWNT electronic type absorbed onto the modified dielectric.

Neuroprotective natural antibodies to assemblies of amyloidogenic peptides decrease with normal aging and advancing Alzheimer's disease

A number of distinct β-amyloid (Aβ) variants or multimers have been implicated in Alzheimers disease (AD), and antibodies recognizing such peptides are in clinical trials. Humans have natural Aβ-specific antibodies, but their diversity, abundance, and function in the general population remain largely unknown. Here, we demonstrate with peptide microarrays the presence of natural antibodies against known toxic Aβ and amyloidogenic non-Aβ species in plasma samples and cerebrospinal fluid of AD patients and healthy controls aged 21–89 years. Antibody reactivity was most prominent against oligomeric assemblies of Aβ and pyroglutamate or oxidized residues, and IgGs specific for oligomeric preparations of Aβ1-42 in particular declined with age and advancing AD. Most individuals showed unexpected antibody reactivities against peptides unique to autosomal dominant forms of dementia (mutant Aβ, ABri, ADan) and IgGs isolated from plasma of AD patients or healthy controls protected primary neurons from Aβ toxicity. Aged vervets showed similar patterns of plasma IgG antibodies against amyloid peptides, and after immunization with Aβ the monkeys developed high titers not only against Aβ peptides but also against ABri and ADan peptides. Our findings support the concept of conformation-specific, cross-reactive antibodies that may protect against amyloidogenic toxic peptides. If a therapeutic benefit of Aβ antibodies can be confirmed in AD patients, stimulating the production of such neuroprotective antibodies or passively administering them to the elderly population may provide a preventive measure toward AD.

Sorted and aligned single-walled carbon nanotube networks for transistor-based aqueous chemical sensors.

Detecting trace amounts of analytes in aqueous systems is important for health diagnostics, environmental monitoring, and national security applications. Single-walled carbon nanotubes (SWNTs) are ideal components for both the sensor material and active signal transduction layer because of their excellent electronic properties and high aspect ratio consisting of entirely surface atoms. Submonolayer arrays, or networks of SWNTs (SWNTnts) are advantageous, and we show that topology characteristics of the SWNT network, such as alignment, degree of bundling, and chirality enrichment strongly affect the sensor performance. To enable this, thin-film transistor (TFT) sensors with SWNTnts were deposited using a one-step, low-cost, solution- based method on a polymer dielectric, allowing us to achieve stable low-voltage operation under aqueous conditions. These SWNT-TFTs were used to detect trace concentrations, down to 2 ppb, of dimethyl methylphosphonate (DMMP) and trinitrotoluene (TNT) in aqueous solutions. Along with reliable cycling underwater, the TFT sensors fabricated with aligned, sorted nanotube networks (enriched with semiconductor SWNTs) showed a higher sensitivity to analytes than those fabricated with random, unsorted networks with predominantly metallic charge transport.

The p75 neurotrophin receptor promotes amyloid-beta(1-42)-induced neuritic dystrophy in vitro and in vivo.

Oligomeric forms of amyloid-β (Aβ) are thought to play a causal role in Alzheimers disease (AD), and the p75 neurotrophin receptor (p75NTR) has been implicated in Aβ-induced neurodegeneration. To further define the functions of p75NTR in AD, we examined the interaction of oligomeric Aβ(1-42) with p75NTR, and the effects of that interaction on neurite integrity in neuron cultures and in a chronic AD mouse model. Atomic force microscopy was used to ascertain the aggregated state of Aβ, and fluorescence resonance energy transfer analysis revealed that Aβ oligomers interact with the extracellular domain of p75NTR. In vitro studies of Aβ-induced death in neuron cultures isolated from wild-type and p75NTR−/− mice, in which the p75NTR extracellular domain is deleted, showed reduced sensitivity of mutant cells to Aβ-induced cell death. Interestingly, Aβ-induced neuritic dystrophy and activation of c-Jun, a known mediator of Aβ-induced deleterious signaling, were completely prevented in p75NTR−/− neuron cultures. Thy1-hAPPLond/Swe × p75NTR−/− mice exhibited significantly diminished hippocampal neuritic dystrophy and complete reversal of basal forebrain cholinergic neurite degeneration relative to those expressing wild-type p75NTR. Aβ levels were not affected, suggesting that removal of p75NTR extracellular domain reduced the ability of excess Aβ to promote neuritic degeneration. These findings indicate that although p75NTR likely does not mediate all Aβ effects, it does play a significant role in enabling Aβ-induced neurodegeneration in vitro and in vivo, establishing p75NTR as an important therapeutic target for AD.

Solution Assembly of Organized Carbon Nanotube Networks for Thin-Film Transistors

Ultrathin, transparent electronic materials consisting of solution-assembled nanomaterials that are directly integrated as thin-film transistors or conductive sheets may enable many new device structures. Applications ranging from disposable autonomous sensors to flexible, large-area displays and solar cells can dramatically expand the electronics market. With a practical, reliable method for controlling their electronic properties through solution assembly, submonolayer films of aligned single-walled carbon nanotubes (SWNTs) may provide a promising alternative for large-area, flexible electronics. Here, we report SWNT network TFTs (SWNTntTFTs) deposited from solution with controllable topology, on/off ratios averaging greater than 10(5), and an apparent mobility averaging 2 cm(2)/V.s, without any pre- or postprocessing steps. We employ a spin-assembly technique that results in chirality enrichment along with tunable alignment and density of the SWNTs by balancing the hydrodynamic force (spin rate) with the surface interaction force controlled by a chemically functionalized interface. This directed nanoscale assembly results in enriched semiconducting nanotubes yielding excellent TFT characteristics, which is corroborated with mu-Raman spectroscopy. Importantly, insight into the electronic properties of these SWNT networks as a function of topology is obtained.

Single functional group interactions with individual carbon nanotubes

Carbon nanotubes display a consummate blend of materials properties that affect applications ranging from nanoelectronic circuits and biosensors to field emitters and membranes. These applications use the non-covalent interactions between the nanotubes and chemical functionalities, often involving a few molecules at a time. Despite their wide use, we still lack a fundamental understanding and molecular-level control of these interactions. We have used chemical force microscopy to measure the strength of the interactions of single chemical functional groups with the sidewalls of vapour-grown individual single-walled carbon nanotubes. Surprisingly, the interaction strength does not follow conventional trends of increasing polarity or hydrophobicity, and instead reflects the complex electronic interactions between the nanotube and the functional group. Ab initio calculations confirm the observed trends and predict binding force distributions for a single molecular contact that match the experimental results. Our analysis also reveals the important role of molecular linkage dynamics in determining interaction strength at the single functional group level.

Lyotropic Liquid-Crystalline Solutions of High-Concentration Dispersions of Single-Walled Carbon Nanotubes with Conjugated Polymers†

The 1D structure of single-walled carbon nanotubes (SWNTs) leads to unique physical properties, which have been investigated extensively. Numerous applications and device prototypes have been demonstrated; however, most have used SWNTs grown in situ by chemical vapor deposition. This limits throughput and choice of substrate owing to the high growth temperatures involved. Solution-based postsynthesis device fabrication, typically involving purification, solubilization, chemical functionalization, cutting, and/ or controlled assembly of SWNTs, is more desirable because of low cost, scalability to large areas, and compatibility with flexible plastic substrates. Unfortunately, SWNTs are not readily soluble, and chemical functionalization strategies for their solubilization usually alter their electronic properties. Furthermore, to take full advantage of the anisotropic charge-transport properties of SWNTs and to enhance their performance in high-strength composite materials, it is necessary to align them over a large area. Noncovalent functionalization of SWNTs is a particularly attractive avenue for dispersion because it enables modification of material properties without altering the chemical structure of the nanotubes. To date, most high-concentration dispersions (>1mg mL ) have been obtained in aqueous solutions by mixing SWNTs with surfactants, doubleor

Nanotubes on display: how carbon nanotubes can be integrated into electronic displays.

Random networks of single-walled carbon nanotubes show promise for use in the field of flexible electronics. Nanotube networks have been difficult to utilize because of the mixture of electronic types synthesized when grown. A variety of separation techniques have been developed, but few can readily be scaled up. Despite this issue, when metallic percolation pathways can be separated out or etched away, these networks serve as high-quality thin-film transistors with impressive device characteristics. A new article in this issue illustrates this point and the promise of these materials. With more work, these devices can be implemented in transparent displays in the next generation of hand-held electronics.

Self-sorted nanotube networks on polymer dielectrics for low-voltage thin-film transistors.

Recent exploitations of the superior mechanical and electronic properties of carbon nanotubes (CNTs) have led to exciting opportunities in low-cost, high performance, carbon-based electronics. In this report, low-voltage thin-film transistors with aligned, semiconducting CNT networks are fabricated on a chemically modified polymer gate dielectric using both rigid and flexible substrates. The multifunctional polymer serves as a thin, flexible gate dielectric film, affords low operating voltages, and provides a platform for chemical functionalization. The introduction of amine functionality to the dielectric surface leads to the adsorption of a network enriched with semiconducting CNTs with tunable density from spin coating a bulk solution of unsorted CNTs. The composition of the deposited CNT networks is verified with Raman spectroscopy and electrical characterization. For transistors at operating biases below 1 V, we observe an effective device mobility as high as 13.4 cm(2)/Vs, a subthreshold swing as low as 130 mV/dec, and typical on-off ratios of greater than 1,000. This demonstration of high performance CNT thin-film transistors operating at voltages below 1 V and deposited using solution methods on polymeric and flexible substrates is an important step toward the realization of low-cost flexible electronics.

Influence of Electrostatic Interactions on Spin-Assembled Single-Walled Carbon Nanotube Networks on Amine-Functionalized Surfaces

Preferential interactions between self-assembled monolayers (SAMs) terminated with amine functional groups and single-walled carbon nanotubes (SWNTs) were exploited to produce nanotube networks (SWNTnts) via spin coating. We provide insight into the mechanisms of this system while simultaneously demonstrating a facile approach toward controllable arrays of SWNTnts. The chirality, density, and alignment of the SWNTnt was heavily influenced by adsorption onto amine-functionalized surfaces that were exposed to varying pH solutions, as evidenced by atomic force microscopy (AFM) and Raman spectroscopy. This pH treatment altered the charge density on the surface, allowing for the examination of the contribution from electrostatic interaction to SWNT adsorption and SWNTnt characteristics. Secondary and tertiary amines with methyl substitutions were utilized to confirm that adsorption and chirality specific adsorption is largely due to the nitrogen lone pair, not the neighboring hydrogen atoms. Thus, the nature of adsorption is predominantly electrostatic and not due to van der Waals forces or localized polarization on the SWNTs. Moreover, the overall density of SWNTnts is different for the various amines, indicating that the accessibility to the lone pair electrons on the nitrogen plays a crucial role in SWNT adsorption. With greater understanding of the amine-SWNT interaction, these findings can be utilized to control SWNTnt formation for the precise integration into electronic devices.