Highly sensitive detector reveals target chemicals by glowing

December 15, 2011
Fluorescencete traphenylethylene

Immobilizing tetraphenylethylene within rigid porous metal–organic frameworks (MOFs) turns on fluorescence (credit: Natalia B. Shustova et al.)

MIT researchers have developed a new way of revealing the presence of target chemicals — whether toxins, disease markers, pathogens or explosives — by emitting a fluorescent glow.

The approach combines fluorescent molecules with an open scaffolding called a metal-organic framework (MOF). This structure provides lots of open space for target molecules to occupy, bringing them into close proximity with fluorescent molecules that react to their presence.

The work could have significant applications in sensors attuned to specific compounds whose detection could be read at a glance simply by watching for the material to glow. “A lot of known sensors work in reverse,” says assistant professor of chemistry Mircea Dincă, meaning they “turn off” in the presence of the target compound. “Turn-on sensors are better,” he says, because “they’re easier to detect, the contrast is better.”

For example, if the material is tuned to detect carbon dioxide, “the more gas you have, the more intensity in the response,” making the device’s readout more obvious. And it’s not just the presence or absence of a specific type of molecule: The system can also respond to changes in the viscosity of a fluid, such as blood, which can be an important indicator in diseases such as diabetes. In such applications, the material could provide two different indications at once — for example, changing in color depending on the presence of a specific compound, such as glucose in the blood, while changing in intensity depending on the viscosity.

MOF materials were first produced about 15 years ago, but their amazing porosity has made them a very active area of research. Although they simply look like little rocks, the sponge-like structures have so much internal surface area that one gram of the material, if unfolded, would cover a football field, Dincă says. The material’s inner pores are about one nanometer (one billionth of a meter) across, making them “about the size of a small molecule” and well suited as molecular detectors, he says.

The new material is based on the MIT team’s discovery of a way to bind a certain type of fluorescent molecules, also known as chromophores, onto the MOF’s metal atoms. While these particular chromophores cannot emit light by themselves, they become fluorescent when bunched together. When in bunches or clumps, however, target molecules cannot reach them and therefore cannot be detected. Attaching the chromophores to nodes of the MOF’s open framework keeps them from clumping, while also keeping them close to the empty pores so they can easily respond to the arrival of a target molecule.

MOFs may also serve as smart vehicles and monitors for controlled drug deliveries, with the additional benefit that the fluorescence should be gradually weakened in intensity along with progressive release of the drugs, thus enabling in situ real-time monitoring of the drug release profiles.

Ref.: Natalia B. Shustova et al., Turn-On Fluorescence in Tetraphenylethylene-Based Metal–Organic Frameworks: An Alternative to Aggregation-Induced Emission, Journal of the American Chemical Society, 2011 [DOI: 10.1021/ja209327q]