Tag Archives: bioplastic

Using insect corpses to create biodegradable plastics

Caption: Black soldier flies are a good source of chemicals to make bioplastics. Credit: Cassidy Tibbetts

The American Chemical Society (ACS) held its Fall 2023 meeting (Aug. 13 -17, 2023) and amongst roughly 12,000 presentations there was this one on insects and degradable plastics as described in an August 14, 2023 ACS news release (also on EurekAlert),

Imagine using insects as a source of chemicals to make plastics that can biodegrade later — with the help of that very same type of bug. That concept is closer to reality than you might expect. Today, researchers will describe their progress to date, including isolation and purification of insect-derived chemicals and their conversion into functional bioplastics.

The researchers will present their results at the fall meeting of the American Chemical Society (ACS). ACS Fall 2023 is a hybrid meeting being held virtually and in-person Aug. 13–17, and features about 12,000 presentations on a wide range of science topics.

“For 20 years, my group has been developing methods to transform natural products — such as glucose obtained from sugar cane or trees — into degradable, digestible polymers that don’t persist in the environment,” says Karen Wooley, Ph.D., the project’s principal investigator. “But those natural products are harvested from resources that are also used for food, fuel, construction and transportation.”

So Wooley began searching for alternative sources that wouldn’t have these competing applications. Her colleague Jeffery Tomberlin, Ph.D., suggested she could use waste products left over from farming black soldier flies, an expanding industry that he has been helping to develop.

The larvae of these flies contain many proteins and other nutritious compounds, so the immature insects are increasingly being raised for animal feed and to consume wastes. However, the adults have a short life span after their breeding days are over and are then discarded. At Tomberlin’s suggestion, those adult carcasses became the new starting material for Wooley’s team. “We’re taking something that’s quite literally garbage and making something useful out of it,” says Cassidy Tibbetts, a graduate student working on the project in Wooley’s lab at Texas A&M University.

When Tibbetts examined the dead flies, she determined that chitin is a major component. This nontoxic, biodegradable, sugar-based polymer strengthens the shell, or exoskeleton, of insects and crustaceans. Manufacturers already extract chitin from shrimp and crab shells for various applications, and Tibbetts has been applying similar techniques using ethanol rinses, acidic demineralization, basic deproteinization and bleach decolorization to extract and purify it from the insect carcasses. She says her fly-sourced chitin powder is probably purer, since it lacks the yellowish color and clumpy texture of the traditional product. She also notes that obtaining chitin from flies could avoid possible concerns over some seafood allergies. Some other researchers isolate chitin or proteins from fly larvae, but Wooley says her team is the first that she knows of to use chitin from discarded adult flies, which — unlike the larvae — aren’t used for feed.

While Tibbetts continues to refine her extraction techniques, Hongming Guo, another graduate student in Wooley’s lab, has been converting the purified fly chitin into a similar polymer known as chitosan. [emphasis mine] He does this by stripping off chitin’s acetyl groups. That exposes chemically reactive amino groups that can be functionalized and then crosslinked. These steps transform chitosan into useful bioplastics such as superabsorbent hydrogels, which are 3D polymer networks that absorb water.

Guo has produced a hydrogel that can absorb 47 times its weight in water in just one minute. This product could potentially be used in cropland soil to capture floodwater and then slowly release moisture during subsequent droughts, Wooley says. “Here in Texas, we’re constantly either in a flood or drought situation,” she explains, “so I’ve been trying to think of how we can make a superabsorbent hydrogel that could address this.” And because the hydrogel is biodegradable, she says it should gradually release its molecular components as nutrients for crops.

This summer, the team is starting a project to break down chitin into its monomeric glucosamines. These small sugar molecules will then be used to make bioplastics, such as polycarbonates or polyurethanes, which are traditionally made from petrochemicals. Black soldier flies also contain many other useful compounds that the group plans to use as starting materials, including proteins, DNA, fatty acids, lipids and vitamins.

The products made from these chemical building blocks are intended to degrade or digest when they’re discarded, so they won’t contribute to the current plastic pollution problem. Wooley’s vision for that process would align it with the sustainable, circular economy concept: “Ultimately, we’d like the insects to eat the waste plastic as their food source, and then we would harvest them again and collect their components to make new plastics,” she says. “So the insects would not only be the source, but they would also then consume the discarded plastics.”

The researchers acknowledge support and funding from the Welch Foundation and a private donation.

As you can see from the news release, there were two related presentations,

Title
Harvesting of building blocks from insect feedstocks for transformation into carbohydrate-derived superabsorbent hydrogels

Abstract
A primary interest in the Wooley laboratory is the production of functional polymers from renewable sources that are capable of reverting to those natural products once their purpose has been served. As scaled-up production of biomass-based biodegradable polymers continues to grow, we’ve recognized a need to avoid competition with resources that are important to food, fuel, construction and other societal demands. Therefore, we’re turning to unique supply chains, including harvesting of naturally-derived building blocks from black soldier flies (BSF), a rapidly growing feed crop industry. This presentation will highlight efforts to isolate carbohydrate feedstocks from BSF and transform them into superabsorbent hydrogel materials, which are designed to address global challenges with flooding and drought associated with climate change.

Title
Harvesting of naturally-derived building blocks from adult black soldier flies

Abstract
The urgent threat to our environment created by plastic pollution has continued to grow and develop as we face the well-established problems arising from traditional plastic production using petrochemicals and their accumulation. Polymeric materials constructed from natural building blocks are promising candidates to displace environmentally-persistent petrochemical counterparts, due to their similar thermal and mechanical properties and greater breadth of compositions, structures and properties, sustainability and degradability, thereby redefining the current plastic economy. A key goal in the exploration of building blocks from natural polymers is to avoid competition with resources critical to food, fuel, construction and other societal demands. This requires turning to unique supply chains, such as black soldier flies (BSF).

BSF provides an immense array of potential utility to society, ranging from being a protein source for animal feed to composting waste. However, the larvae are almost exclusively of use for these processes and the adults serve the sole purpose of reproducing. Once the adults die, they are currently considered as waste and disposed of. Intrigued with the opportunity to create a value chain using the adult BSF, studies focusing on optimization and scalability for the digestion of adult black soldier flies to produce high quality chitin and utilize it as a feedstock for the production of super-absorbent hydrogel networks will be discussed.

If you’d like to know more about this work, there’s an ACS Fall 2023 Media Briefings webpage, which includes the briefing for “Transforming flies into degradable plastics.” It runs approximately 10 mins. 29 secs.

Low-cost carbon sequestration and eco-friendly manufacturing for chemicals with nanobio hybrid organisms

Years ago I was asked about carbon sequestration and nanotechnology and could not come up with any examples. At last I have something for the next time the question is asked. From a June 11, 2019 news item on ScienceDaily,

University of Colorado Boulder researchers have developed nanobio-hybrid organisms capable of using airborne carbon dioxide and nitrogen to produce a variety of plastics and fuels, a promising first step toward low-cost carbon sequestration and eco-friendly manufacturing for chemicals.

By using light-activated quantum dots to fire particular enzymes within microbial cells, the researchers were able to create “living factories” that eat harmful CO2 and convert it into useful products such as biodegradable plastic, gasoline, ammonia and biodiesel.

A June 11, 2019 University of Colorado at Boulder news release (also on EurekAlert) by Trent Knoss, which originated the news item, provides a deeper dive into the research,

“The innovation is a testament to the power of biochemical processes,” said Prashant Nagpal, lead author of the research and an assistant professor in CU Boulder’s Department of Chemical and Biological Engineering. “We’re looking at a technique that could improve CO2 capture to combat climate change and one day even potentially replace carbon-intensive manufacturing for plastics and fuels.”

The project began in 2013, when Nagpal and his colleagues began exploring the broad potential of nanoscopic quantum dots, which are tiny semiconductors similar to those used in television sets. Quantum dots can be injected into cells passively and are designed to attach and self-assemble to desired enzymes and then activate these enzymes on command using specific wavelengths of light.

Nagpal wanted to see if quantum dots could act as a spark plug to fire particular enzymes within microbial cells that have the means to convert airborne CO2 and nitrogen, but do not do so naturally due to a lack of photosynthesis.

By diffusing the specially-tailored dots into the cells of common microbial species found in soil, Nagpal and his colleagues bridged the gap. Now, exposure to even small amounts of indirect sunlight would activate the microbes’ CO2 appetite, without a need for any source of energy or food to carry out the energy-intensive biochemical conversions.

“Each cell is making millions of these chemicals and we showed they could exceed their natural yield by close to 200 percent,” Nagpal said.

The microbes, which lie dormant in water, release their resulting product to the surface, where it can be skimmed off and harvested for manufacturing. Different combinations of dots and light produce different products: Green wavelengths cause the bacteria to consume nitrogen and produce ammonia while redder wavelengths make the microbes feast on CO2 to produce plastic instead.

The process also shows promising signs of being able to operate at scale. The study found that even when the microbial factories were activated consistently for hours at a time, they showed few signs of exhaustion or depletion, indicating that the cells can regenerate and thus limit the need for rotation.

“We were very surprised that it worked as elegantly as it did,” Nagpal said. “We’re just getting started with the synthetic applications.”

The ideal futuristic scenario, Nagpal said, would be to have single-family homes and businesses pipe their CO2 emissions directly to a nearby holding pond, where microbes would convert them to a bioplastic. The owners would be able to sell the resulting product for a small profit while essentially offsetting their own carbon footprint.

“Even if the margins are low and it can’t compete with petrochemicals on a pure cost basis, there is still societal benefit to doing this,” Nagpal said. “If we could convert even a small fraction of local ditch ponds, it would have a sizeable impact on the carbon output of towns. It wouldn’t be asking much for people to implement. Many already make beer at home, for example, and this is no more complicated.”

The focus now, he said, will shift to optimizing the conversion process and bringing on new undergraduate students. Nagpal is looking to convert the project into an undergraduate lab experiment in the fall semester, funded by a CU Boulder Engineering Excellence Fund grant. Nagpal credits his current students with sticking with the project over the course of many years.

“It has been a long journey and their work has been invaluable,” he said. “I think these results show that it was worth it.”

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

Nanorg Microbial Factories: Light-Driven Renewable Biochemical Synthesis Using Quantum Dot-Bacteria Nanobiohybrids by Yuchen Ding, John R. Bertram, Carrie Eckert, Rajesh Reddy Bommareddy, Rajan Patel, Alex Conradie, Samantha Bryan, Prashant Nagpal. J. Am. Chem. Soc.2019XXXXXXXXXX-XXX DOI: https://doi.org/10.1021/jacs.9b02549 Publication Date:June 7, 2019
Copyright © 2019 American Chemical Society

This paper is behind a paywall.

Eggshell-based bioplastics

Adding eggshell nanoparticles to a bioplastic (shown above) increases the strength and flexibility of the material, potentially making it more attractive for use in the packaging industry. Credit: Vijaya Rangari/Tuskegee University

Adding eggshell nanoparticles to a bioplastic (shown above) increases the strength and flexibility of the material, potentially making it more attractive for use in the packaging industry. Credit: Vijaya Rangari/Tuskegee University

A March 15, 2016 news item on Nanowerk describes the research,

Eggshells are both marvels and afterthoughts. Placed on end, they are as strong as the arches supporting ancient Roman aqueducts. Yet they readily crack in the middle, and once that happens, we discard them without a second thought. But now scientists report that adding tiny shards of eggshell to bioplastic could create a first-of-its-kind biodegradable packaging material that bends but does not easily break.

The researchers present their work today [March 15, 2016] at the 251st National Meeting & Exposition of the American Chemical Society (ACS).

A March 15, 2016 ACS news release (also on EurekAlert), which originated the news item, describes the work further,

“We’re breaking eggshells down into their most minute components and then infusing them into a special blend of bioplastics that we have developed,” says Vijaya K. Rangari, Ph.D. “These nano-sized eggshell particles add strength to the material and make them far more flexible than other bioplastics on the market. We believe that these traits — along with its biodegradability in the soil — could make this eggshell bioplastic a very attractive alternative packaging material.”

Worldwide, manufacturers produce about 300 million tons of plastic annually. Almost 99 percent of it is made with crude oil and other fossil fuels. Once it is discarded, petroleum-based plastics can last for centuries without breaking down. If burned, these plastics release carbon dioxide into the atmosphere, which can contribute to global climate change.

As an alternative, some manufacturers are producing bioplastics — a form of plastic derived from cornstarch, sweet potatoes or other renewable plant-based sources — that readily decompose or biodegrade once they are in the ground. However, most of these materials lack the strength and flexibility needed to work well in the packaging industry. And that’s a problem since the vast majority of plastic is used to hold, wrap and encase products. So petroleum-based materials continue to dominate the market, particularly in grocery and other retail stores, where estimates suggest that up to a trillion plastic bags are distributed worldwide every year.

To find a solution, Rangari, graduate student Boniface Tiimob and colleagues at Tuskegee University experimented with various plastic polymers. Eventually, they latched onto a mixture of 70 percent polybutyrate adipate terephthalate (PBAT), a petroleum polymer, and 30 percent polylactic acid (PLA), a polymer derived from cornstarch. PBAT, unlike other oil-based plastic polymers, is designed to begin degrading as soon as three months after it is put into the soil.

This mixture had many of the traits that the researchers were looking for, but they wanted to further enhance the flexibility of the material. So they created nanoparticles made of eggshells. They chose eggshells, in part, because they are porous, lightweight and mainly composed of calcium carbonate, a natural compound that easily decays.

The shells were washed, ground up in polypropylene glycol and then exposed to ultrasonic waves that broke the shell fragments down into nanoparticles more than 350,000 times smaller than the diameter of a human hair. Then, in a laboratory study, they infused a small fraction of these particles, each shaped like a deck of cards, into the 70/30 mixture of PBAT and PLA. The researchers found that this addition made the mixture 700 percent more flexible than other bioplastic blends. They say this pliability could make it ideal for use in retail packaging, grocery bags and food containers — including egg cartons.

In addition to bioplastics, Rangari’s team is investigating using eggshell nanoparticles to enhance wound healing, bone regeneration and drug delivery.