Tag Archives: Mark Ratner

A DNA switch for new electronic applications

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I little dreamed when reading “The Double Helix : A Personal Account of the Discovery of the Structure of DNA” by James Watson that DNA (deoxyribonucleic acid) would one day become just another material for scientists to manipulate. A Feb. 20, 2017 news item on ScienceDaily describes the use of DNA as a material in electronics applications,

DNA, the stuff of life, may very well also pack quite the jolt for engineers trying to advance the development of tiny, low-cost electronic devices.

Much like flipping your light switch at home — only on a scale 1,000 times smaller than a human hair — an ASU [Arizona State University]-led team has now developed the first controllable DNA switch to regulate the flow of electricity within a single, atomic-sized molecule. The new study, led by ASU Biodesign Institute researcher Nongjian Tao, was published in the advanced online journal Nature Communications.

DNA, the stuff of life, may very well also pack quite the jolt for engineers trying to advance the development of tiny, low-cost electronic devices. Courtesy: ASU

A Feb. 20, 2017 ASU news release (also on EurekAlert), which originated the news item, provides more detail,

“It has been established that charge transport is possible in DNA, but for a useful device, one wants to be able to turn the charge transport on and off. We achieved this goal by chemically modifying DNA,” said Tao, who directs the Biodesign Center for Bioelectronics and Biosensors and is a professor in the Fulton Schools of Engineering. “Not only that, but we can also adapt the modified DNA as a probe to measure reactions at the single-molecule level. This provides a unique way for studying important reactions implicated in disease, or photosynthesis reactions for novel renewable energy applications.”

Engineers often think of electricity like water, and the research team’s new DNA switch acts to control the flow of electrons on and off, just like water coming out of a faucet.

Previously, Tao’s research group had made several discoveries to understand and manipulate DNA to more finely tune the flow of electricity through it. They found they could make DNA behave in different ways — and could cajole electrons to flow like waves according to quantum mechanics, or “hop” like rabbits in the way electricity in a copper wire works —creating an exciting new avenue for DNA-based, nano-electronic applications.

Tao assembled a multidisciplinary team for the project, including ASU postdoctoral student Limin Xiang and Li Yueqi performing bench experiments, Julio Palma working on the theoretical framework, with further help and oversight from collaborators Vladimiro Mujica (ASU) and Mark Ratner (Northwestern University).

To accomplish their engineering feat, Tao’s group, modified just one of DNA’s iconic double helix chemical letters, abbreviated as A, C, T or G, with another chemical group, called anthraquinone (Aq). Anthraquinone is a three-ringed carbon structure that can be inserted in between DNA base pairs but contains what chemists call a redox group (short for reduction, or gaining electrons or oxidation, losing electrons).

These chemical groups are also the foundation for how our bodies’ convert chemical energy through switches that send all of the electrical pulses in our brains, our hearts and communicate signals within every cell that may be implicated in the most prevalent diseases.

The modified Aq-DNA helix could now help it perform the switch, slipping comfortably in between the rungs that make up the ladder of the DNA helix, and bestowing it with a new found ability to reversibly gain or lose electrons.

Through their studies, when they sandwiched the DNA between a pair of electrodes, they careful [sic] controlled their electrical field and measured the ability of the modified DNA to conduct electricity. This was performed using a staple of nano-electronics, a scanning tunneling microscope, which acts like the tip of an electrode to complete a connection, being repeatedly pulled in and out of contact with the DNA molecules in the solution like a finger touching a water droplet.

“We found the electron transport mechanism in the present anthraquinone-DNA system favors electron “hopping” via anthraquinone and stacked DNA bases,” said Tao. In addition, they found they could reversibly control the conductance states to make the DNA switch on (high-conductance) or switch-off (low conductance). When anthraquinone has gained the most electrons (its most-reduced state), it is far more conductive, and the team finely mapped out a 3-D picture to account for how anthraquinone controlled the electrical state of the DNA.

For their next project, they hope to extend their studies to get one step closer toward making DNA nano-devices a reality.

“We are particularly excited that the engineered DNA provides a nice tool to examine redox reaction kinetics, and thermodynamics the single molecule level,” said Tao.

Here’s a link to and a citation for the paper,

I last featured Tao’s work with DNA in an April 20, 2015 posting.

Gate-controlled conductance switching in DNA by Limin Xiang, Julio L. Palma, Yueqi Li, Vladimiro Mujica, Mark A. Ratner, & Nongjian Tao.  Nature Communications 8, Article number: 14471 (2017)  doi:10.1038/ncomms14471 Published online: 20 February 2017

This paper is open access.

Good enough for the real world? A new device consisting of a singular molecule

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While molecular diodes (a diode consisting of a single molecule) have been developed before, Columbia University’s Latha Venkataraman and her team have developed a new technique which may take these devices from the lab to real life. From a May 25, 2015 news item on Nanotechnology Now,

Under the direction of Latha Venkataraman, associate professor of applied physics at Columbia Engineering, researchers have designed a new technique to create a single-molecule diode, and, in doing so, they have developed molecular diodes that perform 50 times better than all prior designs. Venkataraman’s group is the first to develop a single-molecule diode that may have real-world technological applications for nanoscale devices.

A May 25, 2015 Columbia University news release on EurekAlert, which originated the news item, describes the new technique in greater detail,

“Our new approach created a single-molecule diode that has a high (>250) rectification and a high “on” current (~ 0.1 micro Amps),” says Venkataraman. “Constructing a device where the active elements are only a single molecule has long been a tantalizing dream in nanoscience. This goal, which has been the ‘holy grail’ of molecular electronics ever since its inception with Aviram and Ratner’s 1974 seminal paper, represents the ultimate in functional miniaturization that can be achieved for an electronic device.”

With electronic devices becoming smaller every day, the field of molecular electronics has become ever more critical in solving the problem of further miniaturization, and single molecules represent the limit of miniaturization. The idea of creating a single-molecule diode was suggested by Arieh Aviram and Mark Ratner who theorized in 1974 that a molecule could act as a rectifier, a one-way conductor of electric current. Researchers have since been exploring the charge-transport properties of molecules. They have shown that single-molecules attached to metal electrodes (single-molecule junctions) can be made to act as a variety of circuit elements, including resistors, switches, transistors, and, indeed, diodes. They have learned that it is possible to see quantum mechanical effects, such as interference, manifest in the conductance properties of molecular junctions.

Since a diode acts as an electricity valve, its structure needs to be asymmetric so that electricity flowing in one direction experiences a different environment than electricity flowing in the other direction. In order to develop a single-molecule diode, researchers have simply designed molecules that have asymmetric structures.

“While such asymmetric molecules do indeed display some diode-like properties, they are not effective,” explains Brian Capozzi, a PhD student working with Venkataraman and lead author of the paper. “A well-designed diode should only allow current to flow in one direction–the ‘on’ direction–and it should allow a lot of current to flow in that direction. Asymmetric molecular designs have typically suffered from very low current flow in both ‘on’ and ‘off’ directions, and the ratio of current flow in the two has typically been low. Ideally, the ratio of ‘on’ current to ‘off’ current, the rectification ratio, should be very high.”

In order to overcome the issues associated with asymmetric molecular design, Venkataraman and her colleagues–Chemistry Assistant Professor Luis Campos’ group at Columbia and Jeffrey Neaton’s group at the Molecular Foundry at UC Berkeley–focused on developing an asymmetry in the environment around the molecular junction. They created an environmental asymmetry through a rather simple method–they surrounded the active molecule with an ionic solution and used gold metal electrodes of different sizes to contact the molecule.

Their results achieved rectification ratios as high as 250: 50 times higher than earlier designs. The “on” current flow in their devices can be more than 0.1 microamps, which, Venkataraman notes, is a lot of current to be passing through a single-molecule. And, because this new technique is so easily implemented, it can be applied to all nanoscale devices of all types, including those that are made with graphene electrodes.

“It’s amazing to be able to design a molecular circuit, using concepts from chemistry and physics, and have it do something functional,” Venkataraman says. “The length scale is so small that quantum mechanical effects are absolutely a crucial aspect of the device. So it is truly a triumph to be able to create something that you will never be able to physically see and that behaves as intended.”

She and her team are now working on understanding the fundamental physics behind their discovery, and trying to increase the rectification ratios they observed, using new molecular systems.

Here’s a link to and a citation for the paper,

Single-molecule diodes with high rectification ratios through environmental control by Brian Capozzi, Jianlong Xia, Olgun Adak, Emma J. Dell, Zhen-Fei Liu, Jeffrey C. Taylor, Jeffrey B. Neaton, Luis M. Campos, & Latha Venkataraman. Nature Nanotechnology (2015) doi:10.1038/nnano.2015.97 Published online 25 May 2015

This paper is behind a paywall but a free preview is available via ReadCube Access.