Graphene oxide-polyamine preprogrammable nanoreactors with sensing capability for corrosion protection of materials.

Corrosion is one of the major issues for sustainable manufacturing globally. The annual global cost of corrosion is US$2.5 trillion (approximately 3.4% of the world's GDP). The traditional ways of corrosion protection (such as barriers or inhibiting) are either not very effective (in the case of barrier protection) or excessively expensive (inhibiting). Here, we demonstrate a concept of nanoreactors, which are able to controllably release or adsorb protons or hydroxides directly on corrosion sites, hence, selectively regulating the corrosion reactions. A single nanoreactor comprises a nanocompartment wrapped around by a pH-sensing membrane represented, respectively, by a halloysite nanotube and a graphene oxide/polyamine envelope. A nanoreactor response is determined by the change of a signaling pH on a given corrosion site. The nanoreactors are self-assembled and suitable for mass-line production. The concept creates sustainable technology for developing smart anticorrosion coatings, which are nontoxic, selective, and inexpensive.

Numerical study of homogeneous nanodroplet growth.

We investigate the axisymmetric homogeneous growth of 10-100 nm water nanodroplets on a substrate surface. The main mechanism of droplet growth is attributed to the accumulation of laterally diffusing water monomers, formed by the absorption of water vapour in the environment onto the substrate. Under assumptions of quasi-steady thermodynamic equilibrium, the nanodroplet evolves according to the augmented Young-Laplace equation. Using continuum theory, we model the dynamics of nanodroplet growth including the coupled effects of disjoining pressure, contact angle and monomer diffusion. Our numerical results show that the initial droplet growth is dominated by monomer diffusion, and the steady late growth rate of droplet radius follows a power law of 1/3, which is unaffected by the substrate disjoining pressure. Instead, the disjoining pressure modifies the growth rate of the droplet height, which then follows a power law of 1/4. We demonstrate how spatial depletion of monomers could lead to a growth arrest of the nanodroplet, as observed experimentally. This work has further implications on the growth kinetics, transport and phase transition of liquids at the nanoscale.

Electron beam manipulation of nanoparticles.

We report on electron beam manipulation and simultaneous transmission electron microscopy imaging of gold nanoparticle movements in an environmental cell. Nanoparticles are trapped with the beam and move dynamically toward the location with higher electron density. Their global movements follow the beam positions. Analysis on the trajectories of nanoparticle movements inside the beam reveals a trapping force in the piconewton range at the electron density gradient of 10(3)-10(4) (e·nm(-2)·s(-1))·nm(-1). Multiple nanoparticles can also be trapped with the beam. By rapidly converging the beam, we further can "collect" nanoparticles on the membrane surface and assemble them into a cluster.

Direct observation of stick-slip movements of water nanodroplets induced by an electron beam.

Dynamics of the first few nanometers of water at the interface are encountered in a wide range of physical, chemical, and biological phenomena. A simple but critical question is whether interfacial forces at these nanoscale dimensions affect an externally induced movement of a water droplet on a surface. At the bulk-scale water droplets spread on a hydrophilic surface and slip on a nonwetting, hydrophobic surface. Here we report the experimental description of the electron beam-induced dynamics of nanoscale water droplets by direct imaging the translocation of 10- to 80-nm-diameter water nanodroplets by transmission electron microscopy. These nanodroplets move on a hydrophilic surface not by a smooth flow but by a series of stick-slip steps. We observe that each step is preceded by a unique characteristic deformation of the nanodroplet into a toroidal shape induced by the electron beam. We propose that this beam-induced change in shape increases the surface free energy of the nanodroplet that drives its transition from stick to slip state.

Imaging protein structure in water at 2.7 nm resolution by transmission electron microscopy.

We demonstrate an in situ transmission electron microscopy technique for imaging proteins in liquid water at room temperature. Liquid samples are loaded into a microfabricated environmental cell that isolates the sample from the vacuum with thin silicon nitride windows. We show that electron micrographs of acrosomal bundles in water are similar to bundles imaged in ice, and we determined the resolution to be at least 2.7 nm at doses of ∼35 e/Å(2). The resolution was limited by the thickness of the window and radiation damage. Surprisingly, we observed a smaller fall-off in the intensity of reflections in room-temperature water than in 98 K ice. Thus, our technique extends imaging of unstained and unlabeled macromolecular assemblies in water from the resolution of the light microscope to the nanometer resolution of the electron microscope. Our results suggest that real-time imaging of protein dynamics is conceptually feasible.

Molecular diagnostics for personal medicine using a nanopore.

Semiconductor nanotechnology has created the ultimate analytical tool: a nanopore with single molecule sensitivity. This tool offers the intriguing possibility of high-throughput, low cost sequencing of DNA with the absolute minimum of material and preprocessing. The exquisite single molecule sensitivity obviates the need for costly and error-prone procedures like polymerase chain reaction amplification. Instead, nanopore sequencing relies on the electric signal that develops when a DNA molecule translocates through a pore in a membrane. If each base pair has a characteristic electrical signature, then ostensibly a pore could be used to analyze the sequence by reporting all of the signatures in a single read without resorting to multiple DNA copies. The potential for a long read length combined with high translocation velocity should make resequencing inexpensive and allow for haplotyping and methylation profiling in a chromosome.

Nanopore Sequencing: Electrical Measurements of the Code of Life.

Sequencing a single molecule of deoxyribonucleic acid (DNA) using a nanopore is a revolutionary concept because it combines the potential for long read lengths (>5 kbp) with high speed (1 bp/10 ns), while obviating the need for costly amplification procedures due to the exquisite single molecule sensitivity. The prospects for implementing this concept seem bright. The cost savings from the removal of required reagents, coupled with the speed of nanopore sequencing places the $1000 genome within grasp. However, challenges remain: high fidelity reads demand stringent control over both the molecular configuration in the pore and the translocation kinetics. The molecular configuration determines how the ions passing through the pore come into contact with the nucleotides, while the translocation kinetics affect the time interval in which the same nucleotides are held in the constriction as the data is acquired. Proteins like α-hemolysin and its mutants offer exquisitely precise self-assembled nanopores and have demonstrated the facility for discriminating individual nucleotides, but it is currently difficult to design protein structure ab initio, which frustrates tailoring a pore for sequencing genomic DNA. Nanopores in solid-state membranes have been proposed as an alternative because of the flexibility in fabrication and ease of integration into a sequencing platform. Preliminary results have shown that with careful control of the dimensions of the pore and the shape of the electric field, control of DNA translocation through the pore is possible. Furthermore, discrimination between different base pairs of DNA may be feasible. Thus, a nanopore promises inexpensive, reliable, high-throughput sequencing, which could thrust genomic science into personal medicine.