Hiding messages with molecules - C&EN Global Enterprise (ACS

First, the researchers convert a message into numbers using an alphanumeric code. They then encrypt it by taking the emission spectrum of the sensor a...
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BIOBASED MATERIALS

Unprecedented two-way stretchiness achieved

Close encounters

Synthetic protein material expands or contracts equally in two dimensions at the same time

Rotation (orange and blue arrows) of tetramers (called C98RhuA) shrinks pore sizes, causing the tetramer lattice to compress equally in two directions at the same time. Δ x and Δy represent half the changes in both directions caused by compression.

Materials such as rubber get thinner when stretched and thicker when compressed. Basically, when they expand in one direction, they contract in another, and vice versa. But some oddballs, called auxetic materials, thicken when stretched and thin when compressed. Now, researchers have used protein design to develop a synthetic auxetic material that expands or contracts equally in two directions when pulled or compressed, respectively. That unusual property could be useful in sports equipment and body armor that resist forces from impacts. F. Akif Tezcan of the University of California, San Diego, and coworkers created the material by combining tetramer units of a modified version of the enzyme l-rhamnulose-1-phosphate aldolase (Nature 2016, DOI: 10.1038/nature17633). The researchers modified the enzyme so the four corners of the squarelike tetramers carried cysteines. When the team oxidized the proteins, the tetramers joined up through disulfide bonds between the cysteines to form a sheetlike crystal. Forces that stretch or compress the material in one direction cause the tetramers to rotate. The rotations open or close pores

its identical properties in all directions. “This is an exciting result in the control and design of materials,” says computational protein designer Jeffery G. Saven of the University of Pennsylvania. Potential applications include single membranes that can change their porosity via applied forces, he says. “The findings are exciting and the results beautiful and novel,” comments bionanotechnologist Martin Noble of Newcastle University. The material “is likely to have rare properties of deformation in response to stress and so provides an experimental system to characterize molecular behavior that has until now been inaccessible. Work is needed to find scientific or technological applications of this interesting new class of materials. But the same could once have been said of graphene.”—STU BORMAN

between the tetramers, making the crystal expand or contract to an equivalent extent in the other direction. Tezcan and coworkers estimate that the crystal expands or shrinks at least 24% linearly between its two extremes. Engineers measure a material’s two-dimensional response to strain via its Poisson’s ratio. Most familiar materials, such as rubber, have positive Poisson’s ratios, while auxetic materials have negative ones. The ratios for most auxetic materials fall between 0 and –0.4, and the lowest previously reported values, –0.7 to –0.8, have been observed in specialized foams. The new crystal has a Poisson’s ratio of –1, meaning that it expands or contracts equally in two directions simultaneously. This is the thermodynamic limit for any isotropic material, a substance that exhib-

SPECTROSCOPY

OH

What’s a spy to do when she wants to send a secret message? Maybe she should whip out a fluorescence spectrometer. David Margulies and coworkers at Weizmann Institute of Science show that they can hide messages using the emission spectrum of a fluorescent molecular sensor (Nat. Commun. 2016, DOI: 10.1038/ncomms11374). The researchers synthesized a molecule with multiple fluorophores and recognition elements. When common chemicals bind to the sensor, they alter the fluorescence spectrum in ways that can serve as an encryption key for hiding messages. First, the researchers convert a message into numbers using an alphanumeric code. They then encrypt it by taking the emission

spectrum of the sensor and a randomly chosen N O chemical and adding the intensity values at N 20-nm intervals to the numbers in the message. To decrypt that message, the recipient HO measures the emission of the sensor molecule under the same conditions and subtracts those intensity values from the encrypted message to reveal the original one. “The encoding technology should find widespread applications in this electronic information age,” says Aijun Tong, an expert on fluorescence spectroscopy and molecular recognition at Tsinghua University. “Its root mechanism of information

N

OH

NH

O N N

N

N O

CREDIT: ADAPTED FROM NAT U RE

Hiding messages with molecules

N

N

B

O S

O

O O

NH NH

S

N

HO3S

O

NH

+ N O

CO2H O

Encryption sensor

protection is chemistry rather than simply mathematics or electronics, thus making it immune to most of the current deciphering methods.”—CELIA ARNAUD MAY 9, 2016 | CEN.ACS.ORG | C&EN

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