Carbon-nanotube field-effect transistors for resolving single-molecule aptamer-ligand binding kinetics.

Small molecules such as neurotransmitters are critical for biochemical functions in living systems. While conventional ultraviolet-visible spectroscopy and mass spectrometry lack portability and are unsuitable for time-resolved measurements in situ, techniques such as amperometry and traditional field-effect detection require a large ensemble of molecules to reach detectable signal levels. Here we demonstrate the potential of carbon-nanotube-based single-molecule field-effect transistors (smFETs), which can detect the charge on a single molecule, as a new platform for recognizing and assaying small molecules. smFETs are formed by the covalent attachment of a probe molecule, in our case a DNA aptamer, to a carbon nanotube. Conformation changes on binding are manifest as discrete changes in the nanotube electrical conductance. By monitoring the kinetics of conformational changes in a binding aptamer, we show that smFETs can detect and quantify serotonin at the single-molecule level, providing unique insights into the dynamics of the aptamer-ligand system. In particular, we show the involvement of G-quadruplex formation and the disruption of the native hairpin structure in the conformational changes of the serotonin-aptamer complex. The smFET is a label-free approach to analysing molecular interactions at the single-molecule level with high temporal resolution, providing additional insights into complex biological processes.

Assessing the Thickness-Permeation Paradigm in Nanoporous Membranes.

Driven by the need of maximizing performance, membrane nanofabrication strives for ever thinner materials aiming to increase permeation while evoking inherent challenges stemming from mechanical stability and defects. We investigate this thickness rationale by studying viscous transport mechanisms across nanopores when transitioning the membrane thickness from infinitely thin to finite values. We synthesize double-layer graphene membranes containing pores with diameters from ∼6 to 1000 nm to investigate liquid permeation over a wide range of viscosities and pressures. Nanoporous membranes with thicknesses up to 90 nm realized by atomic layer deposition demonstrate dominance of the entrance resistance for aspect ratios up to one. Liquid permeation across these atomically thin pores is limited by viscous dissipation at the pore entrance. Independent of thickness and universal for porous materials, this entrance resistance sets an upper bound to the viscous transport. Our results imply that membranes with near-ultimate permeation should feature rationally selected thicknesses based on the target solute size for applications ranging from osmosis to microfiltration and introduce a proper perspective to the pursuit of ever thinner membranes.

Failure mechanism of the polymer infiltration of carbon nanotube forests.

Polymer melt infiltration is one of the feasible methods for manufacturing filter membranes out of carbon nanotubes (CNTs) on large scales. Practically, however, its process suffers from low yields, and the mechanism behind this failure is rather poorly understood. Here, we investigate a failure mechanism of polymer melt infiltration of vertical aligned (VA-) CNTs. In penetrating the VA-CNT interstices, polymer melts exert a capillarity-induced attractive force laterally on CNTs at the moving meniscus, leading to locally agglomerated macroscale bunches. Such a large configurational change can deform and distort individual CNTs so much as to cause buckling or breakdown of the alignment. In view of membrane manufacturing, this irreversible distortion of nanotubes is detrimental, as it could block the transport path of the membranes. The failure mechanism of the polymer melt infiltration is largely attributed to steric hindrance and an energy penalty of confined polymer chains. Euler beam theory and scaling analysis affirm that CNTs with low aspect ratio, thick walls and sparse distribution can maintain their vertical alignment. Our results can enrich a mechanistic understanding of the polymer melt infiltration process and offer guidelines to the facile large-scale manufacturing of the CNT-polymer filter membranes.

Understanding the interaction between energetic ions and freestanding graphene towards practical 2D perforation.

We report experimentally and theoretically the behavior of freestanding graphene subjected to bombardment of energetic ions, investigating the capability of large-scale patterning of freestanding graphene with nanometer sized features by focused ion beam technology. A precise control over the He(+) and Ga(+) irradiation offered by focused ion beam techniques enables investigating the interaction of the energetic particles and graphene suspended with no support and allows determining sputter yields of the 2D lattice. We found a strong dependency of the 2D sputter yield on the species and kinetic energy of the incident ion beams. Freestanding graphene shows material semi-transparency to He(+) at high energies (10-30 keV) allowing the passage of >97% He(+) particles without creating destructive lattice vacancy. Large Ga(+) ions (5-30 keV), in contrast, collide far more often with the graphene lattice to impart a significantly higher sputter yield of ∼50%. Binary collision theory applied to monolayer and few-layer graphene can successfully elucidate this collision mechanism, in great agreement with experiments. Raman spectroscopy analysis corroborates the passage of a large fraction of He(+) ions across graphene without much damaging the lattice whereas several colliding ions create single vacancy defects. Physical understanding of the interaction between energetic particles and suspended graphene can practically lead to reproducible and efficient pattern generation of unprecedentedly small features on 2D materials by design, manifested by our perforation of sub-5 nm pore arrays. This capability of nanometer-scale precision patterning of freestanding 2D lattices shows the practical applicability of focused ion beam technology to 2D material processing for device fabrication and integration.

Ultimate permeation across atomically thin porous graphene.

A two-dimensional (2D) porous layer can make an ideal membrane for separation of chemical mixtures because its infinitesimal thickness promises ultimate permeation. Graphene--with great mechanical strength, chemical stability, and inherent impermeability--offers a unique 2D system with which to realize this membrane and study the mass transport, if perforated precisely. We report highly efficient mass transfer across physically perforated double-layer graphene, having up to a few million pores with narrowly distributed diameters between less than 10 nanometers and 1 micrometer. The measured transport rates are in agreement with predictions of 2D transport theories. Attributed to its atomic thicknesses, these porous graphene membranes show permeances of gas, liquid, and water vapor far in excess of those shown by finite-thickness membranes, highlighting the ultimate permeation these 2D membranes can provide.

Enhanced charge transport kinetics in anisotropic, stratified photoanodes.

The kinetics of charge transport in mesoporous photoanodes strongly constrains the design and power conversion efficiencies of dye sensitized solar cells (DSSCs). Here, we report a stratified photoanode design with enhanced kinetics achieved through the incorporation of a fast charge transport intermediary between the titania and charge collector. Proof of concept photoanodes demonstrate that the inclusion of the intermediary not only enhances effective diffusion coefficients but also significantly suppresses charge recombination, leading to diffusion lengths two orders of magnitude greater than in standard mesoporous titania photoanodes. The intermediary concept holds promise for higher-efficiency DSSCs.