Chien-Yang Chiu

Label-free single-molecule detection of DNA-hybridization kinetics with a carbon nanotube field-effect transistor

Single-molecule measurements of biomolecules can provide information about the molecular interactions and kinetics that are hidden in ensemble measurements. However, there is a requirement for techniques with improved sensitivity and time resolution for use in exploring biomolecular systems with fast dynamics. Here, we report the detection of DNA hybridization at the single-molecule level using a carbon nanotube field-effect transistor. By covalently attaching a single-stranded probe DNA sequence to a point defect in a carbon nanotube, we are able to measure two-level fluctuations in the conductance of the nanotube in the presence of a complementary DNA target. The kinetics of the system are studied as a function of temperature, allowing the measurement of rate constants, melting curves and activation energies for different sequences and target concentrations. The kinetics demonstrate non-Arrhenius behaviour, in agreement with DNA hybridization experiments using fluorescence correlation spectroscopy. This technique is label-free and could be used to probe single-molecule dynamics at microsecond timescales.

Reticulated Heterojunctions for Photovoltaic Devices

An organic semiconductor device is formed by the self-assembly on a transparent electrode surface. The donor (see picture; dibenzotetrathienocoronene, yellow layer) deposits as supramolecular cables, and the acceptor (C60, orange) subsequently infiltrates this network. This network provides a donor–acceptor interface that is interwoven at the nanoscale. When incorporated into a solar cell, the active layer provides large increases in power conversion efficiencies.

Shape-shifting in contorted dibenzotetrathienocoronenes

We detail a general method for the synthesis of dibenzotetrathienocoronenes and elucidate their solid state structures in crystals and co-crystals. The contorted dibenzotetrathienocoronene (c-DBTTC) is a tetrathiophene-fused version of the previously studied contorted hexabenzocoronenes (c-HBC). The synthesis detailed here is simple and provides easy access to this important class of materials. We have found that these materials display molecular flexibility and tunable supramolecular self-assembly properties in the solid state by shifting molecular conformations between two different conformations. Depending on the conditions under which a c-DBTTC-containing material crystallizes, the c-DBTTC adopts either the “up-down” or the “butterfly” conformation. When grown from the vapor phase, crystals of the unsubstituted c-DBTTC show the molecule only in the up-down conformation, and it packs into dense crystals containing columnar arrays with close intracolumnar packing. The packing is controlled by the inherent molecular corrugation of the three-dimensional core and sulfur–sulfur interactions. When grown as co-crystals with electron acceptors from solution, the butyl-substituted c-DBTTC either adopts the butterfly conformation when the electron acceptor is small enough to be completely enveloped (TCNQ) or the up-down conformation when the electron acceptor is relatively large (C60). When grown from organic solvent crystals of the butyl-substituted c-DBTTC contain molecules of the solvent as the only guest, and we observe both conformations of the c-DBTTC. Controlling the supramolecular structure is the key to developing these materials for electronic applications.

Debye Screening in Single-Molecule Carbon Nanotube Field-Effect Sensors

Point-functionalized carbon nanotube field-effect transistors can serve as highly sensitive detectors for biomolecules. With a probe molecule covalently bound to a defect in the nanotube sidewall, two-level random telegraph noise (RTN) in the conductance of the device is observed as a result of a charged target biomolecule binding and unbinding at the defect site. Charge in proximity to the defect modulates the potential (and transmission) of the conductance-limiting barrier created by the defect. In this Letter, we study how these single-molecule electronic sensors are affected by ionic screening. Both charge in proximity to the defect site and buffer concentration are found to affect RTN amplitude in a manner that follows from simple Debye length considerations. RTN amplitude is also dependent on the potential of the electrolyte gate as applied to the reference electrode; at high enough gate potentials, the target DNA is completely repelled and RTN is suppressed.

Bending contorted hexabenzocoronene into a bowl

This article describes the synthesis of a new type of bowl-shaped polycyclic aromatic hydrocarbon. These bowls are formed by joining the proximal carbons of contorted hexabenzocoronenes. These methods begin to tap a wealth of structural diversity available from these core structures. The bowl-shaped hydrocarbons more easily accept electrons than their contorted hexabenzocoronene precursors and associate strongly with C70.

Unusual Molecular Conformations in Fluorinated, Contorted Hexabenzocoronenes

Fluorinated, contorted hexabenzocoronenes (HBCs) have been synthesized in a facile manner via Suzuki-Miyaura coupling of fluorinated phenyl boronic acids followed by photocyclization and Scholl cyclization. In addition to the molecular conformation observed in previous HBC derivatives, close-contact fluorine-fluorine intramolecular interactions result in a metastable conformation not previously observed. Heating the metastable HBCs above 100 °C irreversibly converts them to the stable conformation, suggesting that the metastable conformation arises from a kinetically arrested state during cyclization.

Nanostructured electrodes for organic bulk heterojunction solar cells: Model study using carbon nanotube dispersed polythiophene-fullerene blend devices

We test the feasibility of using nanostructured electrodes in organic bulk heterojunctionsolar cells to improve their photovoltaic performance by enhancing their charge collection efficiency and thereby increasing the optimal active blend layer thickness. As a model system, small concentrations of single wall carbon nanotubes are added to blends of poly(3-hexylthiophene): [6,6]-phenyl-C61-butyric acid methyl ester in order to create networks of efficient hole conduction pathways in the deviceactive layer without affecting the light absorption. The nanotube addition leads to a 22% increase in the optimal blend layer thickness from 90 nm to 110 nm, enhancing the short circuit current density and photovoltaic device efficiency by as much as ∼10%. The associated incident-photon-to-current conversion efficiency for the given thickness also increases by ∼10% uniformly across the device optical absorption spectrum, corroborating the enhanced charge carrier collection by nanostructured electrodes.

Ultra-sensitive carbon nanotubes for single-molecule detection of DNA hybridization kinetics using conductance-based correlation spectroscopy

We present a label-free single-molecule based sensing platform using a carbon nanotube field-effect transistor. By point functionalizing a carbon nanotube through an electrochemical oxidation reaction, the conductance becomes sensitive and chemically reactive at a single point to which we can covalently attach a probe DNA molecule. Two-level fluctuations appear in the conductance of the carbon nanotube when it is immersed in a liquid buffer solution containing complementary target DNA. We show that the autocorrelation of the conductance can be used to extract DNN hybridization kinetics. The results are comparable to the one extracted through a hidden Markov model.

Charge sensing using point-functionalized carbonnanotube transistors for single-molecule detection

We have demonstrated that carbon-nanotube field-effect transistors act as highly sensitive single-molecule detectors when point functionalized. The hybridization kinetics of two complementary strands of DNA are associated with two-level fluctuations in the conductance of the nanotube to which the DNA is bound. We have studied the temperature dependence of the nanotube conductance and shown that the transport mechanism is consistent with Frenkel Poole emission, in which negatively charged DNA modulates a tunnel barrier at the point functionalized defect site. These transistors represent an important potential sensing platform for label-free single-molecule diagnostics.