Eric J. Olson

Rates of DNA-Mediated Electron Transfer Between Metallointercalators

Ultrafast emission and absorption spectroscopies were used to measure the kinetics of DNA-mediated electron transfer reactions between metal complexes intercalated into DNA. In the presence of rhodium(III) acceptor, a substantial fraction of photoexcited donor exhibits fast oxidative quenching (>3 × 1010 per second). Transient-absorption experiments indicate that, for a series of donors, the majority of back electron transfer is also very fast (∼1010 per second). This rate is independent of the loading of acceptors on the helix, but is sensitive to sequence and π stacking. The cooperative binding of donor and acceptor is considered unlikely on the basis of structural models and DNA photocleavage studies of binding. These data show that the DNA double helix differs significantly from proteins as a bridge for electron transfer. On-Line References and Notes

Getting more out of a Job plot: determination of reactant to product stoichiometry in cases of displacement reactions and n:n complex formation.

The method of continuous variation (often referred to as Jobs method) is an easy and common method for the determination of the reactant stoichiometry of chemical equilibria. The traditional interpretation of Job plots has been limited to complex association equilibria of the type nA + mB ⇌ A(n)B(m), while little focus has been placed upon displacement type reactions (e.g., A + B ⇌ C + D), which can give Job plots that look quite similar. We developed a novel method that allows the user to accurately distinguish between 1:1 complex association, 2:2 complex association, and displacement reactions using nothing more than a pocket calculator. This method involves preparing a Job plot of the system under investigation (using regularly spaced mole fractions), normalizing the measured quantities (such as the concentration of A(n)B(m) or C for the above reactions) to their maximum value (i.e., at mole fraction 0.5), and determining the sum of the normalized values. This sum is then compared with theoretically predicted normalized sum values that depend on the nature of the equilibrium. The relationship between, on the one hand, the sum of the normalized values and, on the other hand, the reaction equilibrium constant and the concentration of the stock solutions used for the preparation of the Job plot is also explored. The use of this new technique for the interpretation of Job plots permits users to readily determine information that can be obtained otherwise only with laborious additional experiments, as illustrated by the analysis of four Job plots taken from the literature.

SnSe2 field-effect transistors with high drive current

SnSe2 field-effect transistors fabricated using mechanical exfoliation are reported. Substrate-gated devices with source-to-drain spacing of 0.5 μm have been fabricated with drive current of 160 μA/μm at T = 300 K. The transconductance at a drain-to-source voltage of Vds = 2 V increases from 0.94 μS/μm at 300 K to 4.0 μS/μm at 4.4 K, while the field-effect mobility increases from 8.6 cm2/Vs at 300 K to 28 cm2/Vs at 77 K. The conductance at Vds = 50 mV shows an activation energy of only 5.5 meV, indicating the absence of a significant Schottky barrier at the source and drain contacts.

Graphene-Based Quantum Capacitance Wireless Vapor Sensors

A wireless vapor sensor based on the quantum capacitance effect in graphene is demonstrated. The sensor consists of a metal-oxide-graphene variable capacitor (varactor) coupled to an inductor, creating a resonant oscillator circuit. The resonant frequency is found to shift in proportion to water vapor concentration for relative humidity (RH) values ranging from 1% to 97% with a linear frequency shift of 5.7 kHz/%RH ± 0.3 kHz/%RH. The capacitance values extracted from the wireless measurements agree with those determined from capacitance-voltage measurements, providing strong evidence that the sensing arises from the variable quantum capacitance in graphene. These results represent a new sensor transduction mechanism and pave the way for graphene quantum capacitance sensors to be studied for a wide range of chemical and biological sensing applications.

Interaction of a weakly acidic dinitroaromatic with alkylamines: avoiding the Meisenheimer trap.

Polynitroaromatics are well-known to form anionic σ-complexes (Meisenheimer complexes). The formation of such complexes was assumed in the past to explain the blue color of solutions of 2,4-dinitrotoluene (DNT) and amines. However, this work shows that caution is warranted to avoid the hasty misidentification of Meisenheimer complexes. (1)H NMR spectra exhibit no significant shifts in the positions of the DNT protons, indicating that the majority of DNT species in solutions of DNT and amines retain their aromaticity. Density functional calculations on DNT-ethylamine complexes suggest that Meisenheimer complexes are sufficiently high in free energy so that they make up only a very small fraction of the full equilibrium population. While principal component analysis of the UV/vis spectra of the DNT-amine solutions reveals that only one absorbing species of significant concentration is formed, quantitative fits of Jobs plots show that 1:1 association of DNT with the amines alone cannot explain the visible absorption spectra. Instead, the Jobs plots can be accurately interpreted by deprotonation of DNT, with the amines acting as bases. The deprotonation equilibria lie far on the side of the unreacted DNT, preventing the detection by NMR of the deprotonated minority species that gives the solutions their strong blue color. The analysis of systems with DNT and n-butylamine, diethylamine, triethylamine, or benzylamine provides a consistent pK(a) of DNT in dimethyl sulfoxide of 15.3 ± 0.2.

Capacitive Sensing of Intercalated H2O Molecules Using Graphene

Understanding the interactions of ambient molecules with graphene and adjacent dielectrics is of fundamental importance for a range of graphene-based devices, particularly sensors, where such interactions could influence the operation of the device. It is well-known that water can be trapped underneath graphene and its host substrate; however, the electrical effect of water beneath graphene and the dynamics of how the interfacial water changes with different ambient conditions has not been quantified. Here, using a metal-oxide-graphene variable-capacitor (varactor) structure, we show that graphene can be used to capacitively sense the intercalation of water between graphene and HfO2 and that this process is reversible on a fast time scale. Atomic force microscopy is used to confirm the intercalation and quantify the displacement of graphene as a function of humidity. Density functional theory simulations are used to quantify the displacement of graphene induced by intercalated water and also explain the observed Dirac point shifts as being due to the combined effect of water and oxygen on the carrier concentration in the graphene. Finally, molecular dynamics simulations indicate that a likely mechanism for the intercalation involves adsorption and lateral diffusion of water molecules beneath the graphene.

NEW METHOD FOR FABRICATING ULTRA-NARROW METALLIC WIRES

An improved, cryogenic shadowed evaporation technique has been developed to produce ultra‐narrow metallic wires. It has been used to create wires of Pd with widths less than 15 nm and as long as 800 nm. Arrays of wires covering areas as large as 6400 μm2 have been made. This method, which can be extended to other materials and structures, is presently limited by the grain size of the ‘‘template’’ material, and therefore holds promise for even finer linewidths.

Time Resolved Electron Transfer Studies Between Metallointercalators in DNA

Ultrafast studies on the rates of DNA-mediated forward and reverse electron transfer between photoexcited [Ru(phen)2dppz]2+ and various acceptors are reported. We also present the first results that resolve the ultrafast emission decay of the so-called “light-switch” molecule [Ru(phen)2dppz]2+ in aqueous solution, distinguishing the diverse photophysical mechanisms of [Ru(phen)2dppz]2+.