Jin He

Translocation of Single-Stranded DNA through Single-Walled Carbon Nanotubes

Carbon Nanotube Bridge for DNA Transport The nanoporosity of carbon nanotubes has been exploited in the control of molecular transport—for example, in creating membranes. Liu et al. (p. 64) fabricated devices in which one single-walled carbon nanotube connects two fluid reservoirs. In some of these devices, apparently those in which the nanotube is metallic, the ionic conductivity is anomalously higher than that expected from the bulk resistivity of the electrolyte. This high conductivity was exploited for the transport of single-stranded DNA, which was accompanied by large but transient increases in the ion current. Transfer of DNA by electrophoresis through some carbon nanotubes is accompanied by giant current pulses. We report the fabrication of devices in which one single-walled carbon nanotube spans a barrier between two fluid reservoirs, enabling direct electrical measurement of ion transport through the tube. A fraction of the tubes pass anomalously high ionic currents. Electrophoretic transport of small single-stranded DNA oligomers through these tubes is marked by large transient increases in ion current and was confirmed by polymerase chain reaction analysis. Each current pulse contains about 107 charges, an enormous amplification of the translocated charge. Carbon nanotubes simplify the construction of nanopores, permit new types of electrical measurements, and may open avenues for control of DNA translocation.

Identifying single bases in a DNA oligomer with electron tunnelling

It has been proposed that single molecules of DNA could be sequenced by measuring the physical properties of the bases as they pass through a nanopore. Theoretical calculations suggest that electron tunnelling can identify bases in single-stranded DNA without enzymatic processing, and it was recently experimentally shown that tunnelling can sense individual nucleotides and nucleosides. Here, we report that tunnelling electrodes functionalized with recognition reagents can identify a single base flanked by other bases in short DNA oligomers. The residence time of a single base in a recognition junction is on the order of a second, but pulling the DNA through the junction with a force of tens of piconewtons would yield reading speeds of tens of bases per second.

Electronic signatures of all four DNA nucleosides in a tunneling gap.

Nucleosides diffusing through a 2 nm electron-tunneling junction generate current spikes of sub-millisecond duration with a broad distribution of peak currents. This distribution narrows 10-fold when one of the electrodes is functionalized with a reagent that traps nucleosides in a specific orientation with hydrogen bonds. Functionalizing the second electrode reduces contact resistance to the nucleosides, allowing them to be identified via their peak currents according to deoxyadenosine > deoxycytidine > deoxyguanosine > thymidine, in agreement with the order predicted by a density functional calculation.

Switching of a photochromic molecule on gold electrodes: single-molecule measurements

We have studied the electronic changes caused by light-induced isomerization of a photochromic molecule between an open state (that absorbs in the UV to become closed) and a closed state (that absorbs in the visible to become open). Data obtained using a newly developed repetitive break junction method are interpreted in terms of single-molecule resistances of 526 +/- 90 M Omega in the open form and 4 +/- 1 M Omega in the closed form when the molecule is bound between two gold contacts via dithiol linkages. The corresponding ratio of open to closed resistance is in close agreement with the results of ab initio calculations, though the measured resistances are about half of the calculated values. Optical spectroscopy indicates that the photoisomerization occurs in both directions on small gold particles, evaporated thin gold films, and in the break junction experiments.

Solution synthesis of ultrathin single-crystalline SNS nanoribbons for photodetectors via phase transition and surface processing

We report the solution-phase synthesis and surface processing of ~2-5 μm long single-crystalline IV-VI tin(II) sulfide (SnS) ultrathin nanoribbons, with thicknesses down to 10 nm, and their use in single nanoribbon based photodetectors. The SnS nanoribbons grow via a metastable-to-stable phase transition from zinc blende (ZB) nanospheres to orthorhombic nanoribbons; dual-phase intermediate heterostructures with zinc blende nanosphere heads and orthorhombic nanoribbon tails were observed. Exchange of long, insulating organic oleylamine ligands by short, inorganic HS(-) ligands converts the organic SnS nanoribbons into completely inorganic, hydrophilic structures. Field-effect transistor (FET) devices were made from single SnS nanoribbons, both before and after ligand exchange, which exhibit p-type semiconductor behavior. The SnS single nanoribbon based photodetector devices showed highly sensitive and rapid photocurrent responses to illumination by blue, green, and red light. The switching behavior of photocurrent generation and annihilation is complete within approximately 1 ms and exhibits high photoconductivity gains (up to 2.3 × 10(4)) and good stability. The ON/OFF ratio of the photodetector can be engineered to 80 (4 nA/50 pA) using a small drain current (10 mV) for the all inorganic SnS nanoribbons. This work paves the way for the colloidal growth of low-cost, environmentally benign, single-crystalline narrow band gap semiconductor nanostructures from abundant elements for applications in photodetectors and other nanoscale devices.

Tunnelling readout of hydrogen-bonding-based recognition

Hydrogen bonding has a ubiquitous role in electron transport1,2 and in molecular recognition, with DNA base-pairing being the best known example.3 Scanning tunneling microscope (STM) images4 and measurements of the decay of tunnel-current as a molecular junction is pulled apart by the STM tip, 5 are sensitive to hydrogen-bonded interactions. Here we show that these tunnel-decay signals can be used to measure the strength of hydrogen bonding in DNA basepairs. Junctions that are held together by three hydrogen bonds per basepair (e.g., guanine-cytosine interactions) are stiffer than junctions held together by two hydrogen bonds per basepair (e.g., adenine-thymine interactions). Similar, but less-pronounced, effects are observed on the approach of the tunneling probe, implying that hydrogen-bond dependent attractive forces also have a role in determining the rise of current. These effects provide new mechanisms for making sensors that transduce a molecular recognition event into an electronic signal.

Improved charge transport of Nb-doped TiO2 nanorods in methylammonium lead iodide bromide perovskite solar cells

Nb-doped rutile nanorod-based methylammonium lead iodide bromide (MAPbI3−xBrx) perovskite solar cells have been developed by integrating an excellent photon-active perovskite sensitizer with the superior electron transporting rutile nanorods. It is found that there are two distinct stages in the formation of the perovskite materials prepared using non-stoichiometric mixed halide precursors, namely the orange colored bromine-rich transient state formed at 105 °C and the dark brown colored iodine-rich crystallized state formed at 155 °C. Optical, compositional, and crystalline properties of the perovskite samples at the two stages are studied by using UV-vis spectroscopy, energy-dispersive X-ray spectroscopy, and X-ray diffraction. The mixed halide materials undergo a transition from an intermediate cubic phase to a well-crystallized tetragonal perovskite phase through complicated diffusion, evaporation, and intercalation processes. Furthermore, a well-crystallized mixed halide perovskite is integrated with Nb-doped rutile nanorods and undoped rutile nanorods to fabricate perovskite solid state solar cells. Perovskite solar cells with Nb-doped rutile nanorods have significantly improved performance including the increased short circuit current and open circuit voltage compared to perovskite solar cells with undoped rutile nanorods. The overall power conversion efficiency enhancement of the device with Nb-doped rutile nanorods is over 50% compared with an undoped nanorod-based device, which is attributed to the superior charge collection efficiency of the Nb-doped rutile nanorods as evidenced by the electrochemical impedance measurement.

Measuring single molecule conductance with break junctions.

Single-molecule conductance measurements made under potential control provide a critical link between chemical and molecular electronic data. These measurements are made possible by the STM break-junction method introduced recently, but questions remain about its reliability. Here we report the use of a logarithmic current-to-voltage converter to examine a wide range of currents in an STM break junction study of octanedithiol, clearly showing both the gold-quantum wire regime and the single molecule conductance regime. We find two sets of molecular currents that we tentatively ascribe to different bonding geometries of the molecules in the break junction.

Origin of Giant Ionic Currents in Carbon Nanotube Channels

Fluid flow inside carbon nanotubes is remarkable: transport of water and gases is nearly frictionless, and the small channel size results in selective transport of ions. Very recently, devices have been fabricated in which one narrow single-walled carbon nanotube spans a barrier separating electrolyte reservoirs. Ion current through these devices is about 2 orders of magnitude larger than predicted from the bulk resistivity of the electrolyte. Electroosmosis can drive these large excess currents if the tube both is charged and transports anions or cations preferentially. By building a nanofluidic field-effect transistor with a gate electrode embedded in the fluid barrier, we show that the tube carries a negative charge and the excess current is carried by cations. The magnitude of the excess current and its control by a gate electrode are correctly predicted by the Poisson-Nernst-Planck-Stokes equations.

Self-assembly of core-satellite gold nanoparticles for colorimetric detection of copper ions

Molecule-coated nanoparticles are hybrid materials which can be engineered with novel properties. The molecular coating of metal nanoparticles can provide chemical functionality, enabling assembly of the nanoparticles that are important for applications, such as biosensing devices. Herein, we report a new self-assembly of core-satellite gold nanoparticles linked by a simple amino acid l-Cysteine for biosensing of Cu(2+). The plasmonic properties of core-satellite nano-assemblies were investigated, a new red shifted absorbance peak from about 600 to 800 nm was found, with specific wavelength depending on ratios with assembly of large and small gold nanoparticles. The spectral features obtained using surface-enhanced Raman spectroscopy (SERS) provided strong evidence for the assembly of the Cu(2+) ions to the L-Cysteine molecules leading to the successful formation of the core-satellite Cu(l-Cysteine) complex on the gold surfaces. In addition, a linear relationship between the concentration of mediating Cu(2+) and absorbance of self-assembled gold nanoparticles (GNPs) at 680 nm was obtained. These results strongly address the potential strategy for applying the functionalized GNPs as novel biosensing tools in trace detections of certain metal ions.