Tag Archives: Dhanushkodi Mariappan

Food sensor made from of silk microneedles looks like velco

These sensors really do look like velcro,

The Velcro-like food sensor, made from an array of silk microneedles, can pierce through plastic packaging to sample food for signs of spoilage and bacterial contamination. Image: Felice Frankel

A September 9, 2020 news item on Nanowerk announces some research from the Massachusetts Institute (MIT),

MIT engineers have designed a Velcro-like food sensor, made from an array of silk microneedles, that pierces through plastic packaging to sample food for signs of spoilage and bacterial contamination.

The sensor’s microneedles are molded from a solution of edible proteins found in silk cocoons, and are designed to draw fluid into the back of the sensor, which is printed with two types of specialized ink. One of these “bioinks” changes color when in contact with fluid of a certain pH range, indicating that the food has spoiled; the other turns color when it senses contaminating bacteria such as pathogenic E. coli.

A Sept. 9, 2020 MIT news release (also on EurekAlert), which originated the news item, delves further into the research,

The researchers attached the sensor to a fillet of raw fish that they had injected with a solution contaminated with E. coli. After less than a day, they found that the part of the sensor that was printed with bacteria-sensing bioink turned from blue to red — a clear sign that the fish was contaminated. After a few more hours, the pH-sensitive bioink also changed color, signaling that the fish had also spoiled.

The results, published today in the journal Advanced Functional Materials, are a first step toward developing a new colorimetric sensor that can detect signs of food spoilage and contamination.

Such smart food sensors might help head off outbreaks such as the recent salmonella contamination in onions and peaches. They could also prevent consumers from throwing out food that may be past a printed expiration date, but is in fact still consumable.

“There is a lot of food that’s wasted due to lack of proper labeling, and we’re throwing food away without even knowing if it’s spoiled or not,” says Benedetto Marelli, the Paul M. Cook Career Development Assistant Professor in MIT’s Department of Civil and Environmental Engineering. “People also waste a lot of food after outbreaks, because they’re not sure if the food is actually contaminated or not. A technology like this would give confidence to the end user to not waste food.”

Marelli’s co-authors on the paper are Doyoon Kim, Yunteng Cao, Dhanushkodi Mariappan, Michael S. Bono Jr., and A. John Hart.

Silk and printing

The new food sensor is the product of a collaboration between Marelli, whose lab harnesses the properties of silk to develop new technologies, and Hart, whose group develops new manufacturing processes.

Hart recently developed a high-resolution floxography technique, realizing microscopic patterns that can enable low-cost printed electronics and sensors. Meanwhile, Marelli had developed a silk-based microneedle stamp that penetrates and delivers nutrients to plants. In conversation, the researchers wondered whether their technologies could be paired to produce a printed food sensor that monitors food safety.

“Assessing the health of food by just measuring its surface is often not good enough. At some point, Benedetto mentioned his group’s microneedle work with plants, and we realized that we could combine our expertise to make a more effective sensor,” Hart recalls.

The team looked to create a sensor that could pierce through the surface of many types of food. The design they came up with consisted of an array of microneedles made from silk.

“Silk is completely edible, nontoxic, and can be used as a food ingredient, and it’s mechanically robust enough to penetrate through a large spectrum of tissue types, like meat, peaches, and lettuce,” Marelli says.

A deeper detection

To make the new sensor, Kim first made a solution of silk fibroin, a protein extracted from moth cocoons, and poured the solution into a silicone microneedle mold. After drying, he peeled away the resulting array of microneedles, each measuring about 1.6 millimeters long and 600 microns wide — about one-third the diameter of a spaghetti strand.

The team then developed solutions for two kinds of bioink — color-changing printable polymers that can be mixed with other sensing ingredients. In this case, the researchers mixed into one bioink an antibody that is sensitive to a molecule in E. coli. When the antibody comes in contact with that molecule, it changes shape and physically pushes on the surrounding polymer, which in turn changes the way the bioink absorbs light. In this way, the bioink can change color when it senses contaminating bacteria.

The researchers made a bioink containing antibodies sensitive to E. coli, and a second bioink sensitive to pH levels that are associated with spoilage. They printed the bacteria-sensing bioink on the surface of the microneedle array, in the pattern of the letter “E,” next to which they printed the pH-sensitive bioink, as a “C.” Both letters initially appeared blue in color.

Kim then embedded pores within each microneedle to increase the array’s ability to draw up fluid via capillary action. To test the new sensor, he bought several fillets of raw fish from a local grocery store and injected each fillet with a fluid containing either E. coli, Salmonella, or the fluid without any contaminants. He stuck a sensor into each fillet. Then, he waited.

After about 16 hours, the team observed that the “E” turned from blue to red, only in the fillet contaminated with E. coli, indicating that the sensor accurately detected the bacterial antigens. After several more hours, both the “C” and “E” in all samples turned red, indicating that every fillet had spoiled.

The researchers also found their new sensor indicates contamination and spoilage faster than existing sensors that only detect pathogens on the surface of foods.

“There are many cavities and holes in food where pathogens are embedded, and surface sensors cannot detect these,” Kim says. “So we have to plug in a bit deeper to improve the reliability of the detection. Using this piercing technique, we also don’t have to open a package to inspect food quality.”

The team is looking for ways to speed up the microneedles’ absorption of fluid, as well as the bioinks’ sensing of contaminants. Once the design is optimized, they envision the sensor could be used at various stages along the supply chain, from operators in processing plants, who can use the sensors to monitor products before they are shipped out, to consumers who may choose to apply the sensors on certain foods to make sure they are safe to eat.

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

A Microneedle Technology for Sampling and Sensing Bacteria in the Food Supply Chain by Doyoon Kim, Yunteng Cao, Dhanushkodi Mariappan, Michael S. Bono Jr., A. John Hart, Benedetto Marelli. DOI: https://doi.org/10.1002/adfm.202005370 First published: 09 September 2020

This paper is behind a paywall.

Spooling strips of graphene

An April 18, 2018 news item on phys.org highlights an exciting graphene development at the Massachusetts Institute of Technology (MIT),

MIT engineers have developed a continuous manufacturing process that produces long strips of high-quality graphene.

The team’s results are the first demonstration of an industrial, scalable method for manufacturing high-quality graphene that is tailored for use in membranes that filter a variety of molecules, including salts, larger ions, proteins, or nanoparticles. Such membranes should be useful for desalination, biological separation, and other applications.

A new manufacturing process produces strips of graphene, at large scale, for use in membrane technologies and other applications. Image: Christine Daniloff, MIT

An April 17, 2018 MIT news release (also on EurekAlert) by Jennifer Chu, which originated the news item,. provides more detail,

“For several years, researchers have thought of graphene as a potential route to ultrathin membranes,” says John Hart, associate professor of mechanical engineering and director of the Laboratory for Manufacturing and Productivity at MIT. “We believe this is the first study that has tailored the manufacturing of graphene toward membrane applications, which require the graphene to be seamless, cover the substrate fully, and be of high quality.”

Hart is the senior author on the paper, which appears online in the journal Applied Materials and Interfaces. The study includes first author Piran Kidambi, a former MIT postdoc who is now an assistant professor at Vanderbilt University; MIT graduate students Dhanushkodi Mariappan and Nicholas Dee; Sui Zhang of the National University of Singapore; Andrey Vyatskikh, a former student at the Skolkovo Institute of Science and Technology who is now at Caltech; and Rohit Karnik, an associate professor of mechanical engineering at MIT.

Growing graphene

For many researchers, graphene is ideal for use in filtration membranes. A single sheet of graphene resembles atomically thin chicken wire and is composed of carbon atoms joined in a pattern that makes the material extremely tough and impervious to even the smallest atom, helium.

Researchers, including Karnik’s group, have developed techniques to fabricate graphene membranes and precisely riddle them with tiny holes, or nanopores, the size of which can be tailored to filter out specific molecules. For the most part, scientists synthesize graphene through a process called chemical vapor deposition, in which they first heat a sample of copper foil and then deposit onto it a combination of carbon and other gases.

Graphene-based membranes have mostly been made in small batches in the laboratory, where researchers can carefully control the material’s growth conditions. However, Hart and his colleagues believe that if graphene membranes are ever to be used commercially they will have to be produced in large quantities, at high rates, and with reliable performance.

“We know that for industrialization, it would need to be a continuous process,” Hart says. “You would never be able to make enough by making just pieces. And membranes that are used commercially need to be fairly big – some so big that you would have to send a poster-wide sheet of foil into a furnace to make a membrane.”

A factory roll-out

The researchers set out to build an end-to-end, start-to-finish manufacturing process to make membrane-quality graphene.

The team’s setup combines a roll-to-roll approach – a common industrial approach for continuous processing of thin foils – with the common graphene-fabrication technique of chemical vapor deposition, to manufacture high-quality graphene in large quantities and at a high rate. The system consists of two spools, connected by a conveyor belt that runs through a small furnace. The first spool unfurls a long strip of copper foil, less than 1 centimeter wide. When it enters the furnace, the foil is fed through first one tube and then another, in a “split-zone” design.

While the foil rolls through the first tube, it heats up to a certain ideal temperature, at which point it is ready to roll through the second tube, where the scientists pump in a specified ratio of methane and hydrogen gas, which are deposited onto the heated foil to produce graphene.

“Graphene starts forming in little islands, and then those islands grow together to form a continuous sheet,” Hart says. “By the time it’s out of the oven, the graphene should be fully covering the foil in one layer, kind of like a continuous bed of pizza.”

As the graphene exits the furnace, it’s rolled onto the second spool. The researchers found that they were able to feed the foil continuously through the system, producing high-quality graphene at a rate of 5 centimers per minute. Their longest run lasted almost four hours, during which they produced about 10 meters of continuous graphene.

“If this were in a factory, it would be running 24-7,” Hart says. “You would have big spools of foil feeding through, like a printing press.”

Flexible design

Once the researchers produced graphene using their roll-to-roll method, they unwound the foil from the second spool and cut small samples out. They cast the samples with a polymer mesh, or support, using a method developed by scientists at Harvard University, and subsequently etched away the underlying copper.

“If you don’t support graphene adequately, it will just curl up on itself,” Kidambi says. “So you etch copper out from underneath and have graphene directly supported by a porous polymer – which is basically a membrane.”

The polymer covering contains holes that are larger than graphene’s pores, which Hart says act as microscopic “drumheads,” keeping the graphene sturdy and its tiny pores open.

The researchers performed diffusion tests with the graphene membranes, flowing a solution of water, salts, and other molecules across each membrane. They found that overall, the membranes were able to withstand the flow while filtering out molecules. Their performance was comparable to graphene membranes made using conventional, small-batch approaches.

The team also ran the process at different speeds, with different ratios of methane and hydrogen gas, and characterized the quality of the resulting graphene after each run. They drew up plots to show the relationship between graphene’s quality and the speed and gas ratios of the manufacturing process. Kidambi says that if other designers can build similar setups, they can use the team’s plots to identify the settings they would need to produce a certain quality of graphene.

“The system gives you a great degree of flexibility in terms of what you’d like to tune graphene for, all the way from electronic to membrane applications,” Kidambi says.

Looking forward, Hart says he would like to find ways to include polymer casting and other steps that currently are performed by hand, in the roll-to-roll system.

“In the end-to-end process, we would need to integrate more operations into the manufacturing line,” Hart says. “For now, we’ve demonstrated that this process can be scaled up, and we hope this increases confidence and interest in graphene-based membrane technologies, and provides a pathway to commercialization.”

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

A Scalable Route to Nanoporous Large-Area Atomically Thin Graphene Membranes by Roll-to-Roll Chemical Vapor Deposition and Polymer Support Casting by Piran R. Kidambi, Dhanushkodi D. Mariappan, Nicholas T. Dee, Andrey Vyatskikh, Sui Zhang, Rohit Karnik, and A. John Hart. ACS Appl. Mater. Interfaces, 2018, 10 (12), pp 10369–10378 DOI: 10.1021/acsami.8b00846 Publication Date (Web): March 19, 2018

Copyright © 2018 American Chemical Society

This paper is behind a paywall.

Finally, there is a video of the ‘graphene spooling out’ process,