Tag Archives: pesticides

Using carbon dots (organic nanosensors) to detect pesticides

Before getting to the latest about carbon dots, there’s something to be clarified (and it was news to me), a carbon dot is not a quantum dot. So says this 2020 paper, “Advances in carbon dots: from the perspective of traditional quantum dots” by Yanhong Liu, Hui Huang, Weijing Cao, Baodong Mao, Yang Liu, and Zhenhui Kang. Mater. Chem. Front., 2020,4, 1586-1613 First published March 17, 2020.

Abstract

Quantum dots (QDs) have been the core concept of nanoscience and nanotechnology since their inception, and play a dominant role in the development of the nano-field. Carbon dots (CDots), defined by a feature size of <10 nm, have become a rising star in the crossover field of carbon materials and traditional QDs (TQDs). CDots possess many unique structural, physicochemical and photochemical properties that render them a promising platform for biology, devices, catalysis and other applications. …

This story is about carbon dots but you can find out more about quantum dots in my October 6, 2023 posting concerning the 2023 Nobel prizes; scroll down to the ‘Chemistry’ subhead.

An August 30, 2023 news item on phys.org describes work from Concordia University (Montréal, Canada) on carbon dots,

Researchers at Concordia have developed a new system using tiny nanosensors called carbon dots to detect the presence of the widely used chemical glyphosate. Their research, titled “Ratiometric Sensing of Glyphosate in Water Using Dual Fluorescent Carbon Dots,” is published in Sensors.

An August 30, 2023 Concordia University news release (also on EurekAlert) by Patrick Lejtenyi, which originated the news item, explains the importance of the work and provides more technical details, Note: Links have been removed,

Glyphosate is a pesticide found in more than 750 agricultural, forestry, urban and home products, including Monsanto’s popular weed-killer Roundup. It is also controversial: studies have linked its overuse to environmental pollution and cancer in humans. Its sale is banned or restricted in dozens of countries and jurisdictions, including Canada.

The researchers’ system relies on the carbon dots’ chemical interaction with glyphosate to detect its presence. Carbon dots are exceedingly small fluorescent particles, usually no more than 10 or 15 nanometres in size (a human hair is between 80,000 and 100,000 nanometres). But when they are added to water solutions, these nanomaterials emit blue and red fluorescence.

The researchers employed an analysis technique called a ratiometric self-referencing assay to determine glyphosate levels in a solution. The red fluorescence emitted by the carbon dots when exposed to varying concentrations of the chemical and different pH levels is compared with a control in which no glyphosate is present. In all the tests, the blue fluorescence remained unchanged, giving the researchers a common reference point across the different tests.

They observed that higher levels of glyphosate quenched the red fluorescence, which they accredited to the interaction of the pesticide with the carbon dots’ surface.

“Our system differs from others because we are measuring the area between two peaks—two fluorescent signatures—on the visible spectrum,” says Adryanne Clermont-Paquette, a PhD candidate in biology and the paper’s lead author. “This is the integrated area between the two curves. Ratiometric measurement allows us to ignore variables such as temperature, pH levels or other environmental factors. That allows us to just only look at the levels of glyphosate and carbon dots that are in the system.”

“By understanding the chemistry at the surface of these very small dots and by knowing their optical properties, we can use them to our advantage for many different applications,” says Rafik Naccache, an associate professor of chemistry and biochemistry and the paper’s supervising author.

Research assistants Diego-Andrés Mendoza and Amir Sadeghi, along with associate professor of biology Alisa Piekny, are co-authors.

Starting small

Naccache says the technique is designed to detect minute amounts of the pesticide. The technique they developed is sensitive enough to be able to detect the presence of pesticide at levels as low as 0.03 parts per million.

“The challenge is always in the other direction, to see how low we can go in terms of sensitivity and selectivity,” he says.

There remains much work to be done before this technology can be used widely. But as Clermont-Paquette notes, this paper represents an important beginning.

“Understanding the interaction between glyphosate and carbon dots is a first step. If we are to move this along further, and develop it into a real-life application, we have to start with the fundamentals.”

The researchers are supported by funding from the Natural Sciences and Engineering Research Council of Canada.

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

Ratiometric Sensing of Glyphosate in Water Using Dual Fluorescent Carbon Dots
by Adryanne Clermont-Paquette, Diego-Andrés Mendoza, Amir Sadeghi, Alisa Piekny, and Rafik Naccache. Sensors 2023, 23(11), 5200; DOI: https://doi.org/10.3390/s23115200 Published: 30 May 2023

This paper is open access.

Gold nanoparticles not always always biologically stable

It’s usually silver nanoparticles (with a nod to titanium dioxide as another problem nanoparticle) which star in scenarios regarding environmental concerns, especially with water. According to an Aug. 28, 2018 news item on Nanowerk, gold nanoparticles under certain conditions could also pose problems,

It turns out gold isn’t always the shining example of a biologically stable material that it’s assumed to be, according to environmental engineers at Duke’s Center for the Environmental Implications of NanoTechnology (CEINT).

In a nanoparticle form, the normally very stable, inert, noble metal actually gets dismantled by a microbe found on a Brazilian aquatic weed.

While the findings don’t provide dire warnings about any unknown toxic effects of gold, they do provide a warning to researchers on how it is used in certain experiments.

Here’s an image of one of the researchers standing in the test bed where they made their discovery (the caption will help to make sense of the reference to mesocosms in the news release, which follows,,

Mark Wiesner stands with rows of mesocosms—small, manmade structures containing different plants and microorganisms meant to represent a natural environment with experimental controls. Courtesy: Duke University

An August 28, 2018 Duke University news release (also on EurekAlert) by Ken Kingery, which originated the news item, provides more detail about gold nanoparticle instability,

CEINT researchers from Duke, Carnegie Mellon and the University of Kentucky were running an experiment to investigate how nanoparticles used as a commercial pesticide affect wetland environments in the presence of added nutrients. Although real-world habitats often receive doses of both pesticides and fertilizers, most studies on the environmental effects of such compounds only look at a single contaminant at a time.

For nine months, the researchers released low doses of nitrogen, phosphorus and copper hydroxide nanoparticles into wetland mesocosms [emphasis mine]– small, manmade structures containing different plants and microorganisms meant to represent a natural environment with experimental controls. The goal was to see where the nanoparticle pesticides ended up and how they affected the plant and animal life within the mesocosm.

The researchers also released low doses of gold nanoparticles as tracers, assuming the biologically inert nanoparticles would remain stable while migrating through the ecosystem. This would help the researchers interpret data on the pesticide particles that partly dissolve by showing them how a solid metal particle acts within the system.

But when the researchers went to analyze their results, they found that many of the gold nanoparticles had been oxidized and dissolved.

“We were taken completely by surprise,” said Mark Wiesner, the James B. Duke Professor and chair of civil and environmental engineering at Duke. “The nanoparticles that were supposed to be the most stable turned out to be the least stable of all.”

After further inspection, the researchers found the culprit — the microbiome growing on a common Brazilian waterweed called Egeria densa. Many bacteria secrete chemicals to essentially mine metallic nutrients from their surroundings. With their metabolism spiked by the experiment’s added nutrients, the bacteria living on the E. densa were catalyzing the reaction to dissolve the gold nanoparticles.

This process wouldn’t pose any threat [emphasis mine] to humans or other animal species in the wild. But when researchers design experiments with the assumption that their gold nanoparticles will remain intact, the process can confound the interpretation of their results.

“The assumption that gold is inert did not hold in these experiments,” said Wiesner. “This is a good lesson that underscores how real, complex environments, that include for example the bacteria growing on leaves, can give very different results from experiments run in a laboratory setting that do not include these complexities.”

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

Gold nanoparticle biodissolution by a freshwater macrophyte and its associated microbiome by Astrid Avellan, Marie Simonin, Eric McGivney, Nathan Bossa, Eleanor Spielman-Sun, Jennifer D. Rocca, Emily S. Bernhardt, Nicholas K. Geitner, Jason M. Unrine, Mark R. Wiesner, & Gregory V. Lowry. Nature Nanotechnology (2018) DOI: https://doi.org/10.1038/s41565-018-0231-y Published

This paper is behind a paywall.

Algae outbreaks (dead zones) in wetlands and waterways

It’s been over seven years since I first started writing about Duke University’s  Center for the Environmental Implications of Nanotechnology and mesocosms (miniature ecosystems) and the impact that nanoparticles may have on plants and water (see August 11, 2011 posting). Since then, their focus has shifted from silver nanoparticles and their impact on plants, fish, bacteria, etc. to a more general examination of metallic nanoparticles and water. A June 25, 2018 news item on ScienceDaily announces some of their latest work,

The last 10 years have seen a surge in the use of tiny substances called nanomaterials in agrochemicals like pesticides and fungicides. The idea is to provide more disease protection and better yields for crops, while decreasing the amount of toxins sprayed on agricultural fields.

But when combined with nutrient runoff from fertilized cropland and manure-filled pastures, these “nanopesticides” could also mean more toxic algae outbreaks for nearby streams, lakes and wetlands, a new study finds.

A June 25, 2018 Duke University news release (also on EurekAlert) by Robin A. Smith, which originated the news item, provides more detail,

Too small to see with all but the most powerful microscopes, engineered nanomaterials are substances manufactured to be less than 100 nanometers in diameter, many times smaller than a hair’s breadth.

Their nano-scale gives them different chemical and physical properties from their bulk counterparts, including more surface area for reactions and interactions.

Those interactions could intensify harmful algal blooms in wetlands, according to experiments led by Marie Simonin, a postdoctoral associate with biology professor Emily Bernhardt at Duke University.

Carbon nanotubes and teeny tiny particles of silver, titanium dioxide and other metals are already added to hundreds of commercial products to make everything from faster, lighter electronics, self-cleaning fabrics, and smarter food packaging that can monitor food for spoilage. They are also used on farms for slow- or controlled-release plant fertilizers and pesticides and more targeted delivery, and because they are effective at lower doses than conventional products.

These and other applications have generated tremendous interest and investment in nanomaterials. However the potential risks to human health or the environment aren’t fully understood, Simonin said.

Most of the 260,000 to 309,000 metric tons of nanomaterials produced worldwide each year are eventually disposed in landfills, according to a previous study. But of the remainder, up to 80,400 metric tons per year are released into soils, and up to 29,200 metric tons end up in natural bodies of water.

“And these emerging contaminants don’t end up in water bodies alone,” Simonin said. “They probably co-occur with nutrient runoff. There are likely multiple stressors interacting.”

Algae outbreaks already plague polluted waters worldwide, said Steven Anderson, a research analyst in the Bernhardt Lab at Duke and one of the authors of the research.

Nitrogen and phosphorous pollution makes its way into wetlands and waterways in the form of agricultural runoff and untreated wastewater. The excessive nutrients cause algae to grow out of control, creating a thick mat of green scum or slime on the surface of the water that blocks sunlight from reaching other plants.

These nutrient-fueled “blooms” eventually reduce oxygen levels to the point where fish and other organisms can’t survive, creating dead zones in the water. Some algal blooms also release toxins that can make pets and people who swallow them sick.

To find out how the combined effects of nutrient runoff and nanoparticle contamination would affect this process, called eutrophication, the researchers set up 18 separate 250-liter tanks with sandy sloped bottoms to mimic small wetlands.

Each open-air tank was filled with water, soil and a variety of wetland plants and animals such as waterweed and mosquitofish.

Over the course of the nine-month experiment, some tanks got a weekly dose of algae-promoting nitrates and phosphates like those found in fertilizers, some tanks got nanoparticles — either copper or gold — and some tanks got both.

Along the way the researchers monitored water chemistry, plant and algae growth and metabolism, and nanoparticle accumulation in plant tissues.

“The results were surprising,” Simonin said. The nanoparticles had tiny effects individually, but when added together with nutrients, even low concentrations of gold and copper nanoparticles used in fungicides and other products turned the once-clear water a murky pea soup color, its surface covered with bright green smelly mats of floating algae.

Over the course of the experiment, big algal blooms were more than three times more frequent and more persistent in tanks where nanoparticles and nutrients were added together than where nutrients were added alone. The algae overgrowths also reduced dissolved oxygen in the water.

It’s not clear yet how nanoparticle exposure shifts the delicate balance between plants and algae as they compete for nutrients and other resources. But the results suggest that nanoparticles and other “metal-based synthetic chemicals may be playing an under-appreciated role in the global trends of increasing eutrophication,” the researchers said.

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

Engineered nanoparticles interact with nutrients to intensify eutrophication in a wetland ecosystem experiment by Marie Simonin, Benjamin P. Colman, Steven M. Anderson, Ryan S. King, Matthew T. Ruis, Astrid Avellan, Christina M. Bergemann, Brittany G. Perrotta, Nicholas K. Geitner, Mengchi Ho, Belen de la Barrera, Jason M. Unrine, Gregory V. Lowry, Curtis J. Richardson, Mark R. Wiesner, Emily S. Bernhardt. Ecological Applications, 2018; DOI: 10.1002/eap.1742 First published: 25 June 2018

This paper is behind a paywall.

Genetic engineering: an eggplant in Bangladesh and a synthetic biology grant at Concordia University (Canada)

I have two bits of genetic engineering news.

Eggplants in Bangladesh

I always marvel at their beauty,

Bt eggplant is the first genetically engineered food crop to be successfully introduced in South Asia. The crop is helping some of the world’s poorest farmers feed their families and communities while reducing the use of pesticides. Photo by Cornell Alliance for Science.

A July 17, 2018 news item on phys.org describes a genetic engineering application,

Ansar Ali earned just 11,000 taka – about $130 U.S. dollars – from eggplant he grew last year in Bangladesh. This year, after planting Bt eggplant, he brought home more than double that amount, 27,000 taka. It’s a life-changing improvement for a subsistence farmer like Ali.

Bt eggplant, or brinjal as it’s known in Bangladesh, is the first genetically engineered food crop to be successfully introduced in South Asia. Bt brinjal is helping some of the world’s poorest farmers to feed their families and communities, improve profits and dramatically reduce pesticide use. That’s according to Tony Shelton, Cornell professor of entomology and director of the Bt brinjal project funded by the United States Agency for International Development (USAID). Shelton and Jahangir Hossain, the country coordinator for the project in Bangladesh, lead the Cornell initiative to get these seeds into the hands of the small-scale, resource-poor farmers who grow a crop consumed daily by millions of Bangladeshis.

A July 11, 2018 Cornell University news release by Krisy Gashler, which originated the news item, expands on the theme (Note: Links have been removed),

Bt brinjal was first developed by the Indian seed company Mahyco in the early 2000s. Scientists inserted a gene from the bacterium Bacillus thuringiensis (thus the name, Bt) into nine brinjal varieties. The plants were engineered to resist the fruit and shoot borer, a devastating insect whose larvae bore into the stem and fruit of an eggplant. The insects cause up to 80 percent crop loss.

The Bt protein produced by the engineered eggplant causes the fruit and shoot borer larva to stop feeding, but is safe for humans consuming the eggplant, as proven through years of biosafety trials. In fact, Bt is commonly used by organic farmers to control caterpillars but has to be sprayed frequently to be effective. The Bt eggplant produces essentially the same protein as in the spray. More than 80 percent of field corn and cotton grown in the U.S. contains a Bt gene for insect control.

“Farmers growing Bt brinjal in Bangladesh are seeing three times the production of other brinjal varieties, at half the production cost, and are getting better prices at the market,” Hossain said.

A recent survey found 50 percent of farmers in Bangladesh said that they experienced illness due to the intense spraying of insecticides. Most farmers work in bare feet and without eye protection, leading to pesticide exposure that causes skin and eye irritation, and vomiting.

“It’s terrible for these farmers’ health and the health of the environment to spray so much,” said Shelton, who found that pesticide use on Bt eggplant was reduced as much as 92 percent in commercial Bt brinjal plantings. “Bt brinjal is a solution that’s really making a difference in people’s lives.”

Alhaz Uddin, a farmer in the Tangail district, made 6,000 taka growing traditional brinjal, but had to spend 4,000 taka on pesticides to combat fruit and shoot borer.

“I sprayed pesticides several times in a week,” he said. “I got sick many times during the spray.”

Mahyco initially wanted to introduce Bt brinjal in India and underwent years of successful safety testing. But in 2010, due to pressure from anti-biotechnology groups, the Indian minister of the environment placed a moratorium on the seeds. It is still in effect today, leaving brinjal farmers there without the effective and safe method of control available to their neighbors in Bangladesh.

Even before the Indian moratorium, Cornell scientists hosted delegations from Bangladesh that wanted to learn about Bt brinjal and the Agricultural Biotechnology Support Project II (ABSP II), a consortium of public and private institutions in Asia and Africa intended to help with the commercial development, regulatory approval and dissemination of bio-engineered crops, including Bt brinjal.

Cornell worked with USAID, Mahyco and the Bangladesh Agricultural Research Institute to secure regulatory approval, and in 2014 the Bangladeshi government distributed a small number of Bt brinjal plants to 20 farmers in four districts. The next year 108 farmers grew Bt brinjal, and the following year the number of farmers more than doubled to 250. In 2017 the number increased to 6,512 and in 2018 to 27,012. The numbers are likely even higher, according to Shelton, as there are no constraints against farmers saving seeds and replanting.

“Farmers who plant Bt brinjal are required to plant a small perimeter of traditional brinjal around the Bt variety; research has shown that the insects will infest plants in the buffer area, and this will slow their evolutionary development of resistance to the Bt plants,” Shelton said.

In a March 2017 workshop, Bangladeshi Agriculture Minister Begum Matia Chowdhury called Bt brinjal “a success story of local and foreign collaboration.”

“We will be guided by the science-based information, not by the nonscientific whispering of a section of people,” Chowdhury said. “As human beings, it is our moral obligation that all people in our country should get food and not go to bed on an empty stomach. Biotechnology can play an important role in this effect.”

Here’s what an infested eggplant looks like,

Non-Bt eggplant infested with fruit and shoot borer. Photo by Cornell Alliance for Science

It looks more like a fig than an eggplant.

This is part of a more comprehensive project as revealed in a March 29, 2016 Cornell University news release issued on the occasion of a $4.8M, three-year grant from the U.S. Agency for International Development (USAID),

… The award supports USAID’s work under Feed the Future, the U.S. government’s global initiative to fight hunger and improve food security using agricultural science and technology.

In the Feed the Future South Asia Eggplant Improvement Partnership, Cornell will protect eggplant farmers from yield losses and improve their livelihoods in partnership with the Bangladesh Agricultural Research Institute (BARI) and the University of the Philippines at Los Baños. Eggplant, or brinjal, is a staple crop that is an important source of income and nutrition for farmers and consumers in South Asia.

Over the past decade, Cornell has led the Agricultural Biotechnology Support Project II (ABSPII), also funded by USAID, that prompted a consortium of institutions in Asia and Africa to use the tools of modern biotechnology, particularly genetic engineering, to improve crops to address major production constraints for which conventional plant breeding tools have not been effective.

In October 2013, Bangladesh became the first country in South Asia to approve commercial cultivation of a genetically engineered food crop. In February 2014, Matia Chowdhury, the Bangladesh minister of agriculture, released four varieties of Bt brinjal to 20 farmers. With the establishment of the 20 Bt brinjal demonstration plots in 2014 and 104 more in 2015, BARI reported a noticeable decrease in fruit and shoot borer infestation, increased yields, decreased use of pesticide and improved income for farmers.

The Feed the Future South Asia Eggplant Improvement Partnership addresses and integrates all elements of the commercialization process — including technology development, regulation, marketing, seed distribution, and product stewardship. It also provides strong platforms for policy development, capacity building, gender equality, outreach and communication.

Moving on from practical applications …

Canada’s synthetic biology training centre

It seems Concordia University (Montréa) is a major Canadian centre for all things ‘synthetic biological’. (from the History and Vision webpage on Concordia University’s Centre for Applied Synthetic Biology webspace),

History and vision

Emerging in 2012 from a collaboration between the Biology and Electrical and Computer Engineering Departments, the Centre received University-wide status in 2016 growing its membership to include Biochemistry, Journalism, Communication Studies, Mechanical, Industrial and Chemical Engineering.


Timeline

T17-36393-VPRG-Timeline-graphic-promo-v4

You can see the timeline does not yet include 2018 development(s). Also it started as “a collaboration between the Biology and Electrical and Computer Engineering Departments?” This suggests a vastly different approach to genetic engineering that that employed in the “eggplant” research. From a July 16, 2018 posting on the Genome Alberta blog,

The Natural Sciences and Engineering Research Council of Canada (NSERC) has committed $1.65 million dollars over six years to establish a research and training program at Concordia’s Centre for Applied Synthetic Biology.

The funds were awarded after Malcolm Whiteway (…), professor of biology and the Canada Research Chair in Microbial Genomics, and the grant application team submitted a proposal to NSERC’s Collaborative Research and Training Experience (CREATE) program.

The Synthetic Biology Applications CREATE program — or SynBioApps — will help students acquire and develop important professional skills that complement their academic education and improve their job-readiness.

‘Concordia is a natural fit’

“As the Canadian leader in synthetic biology and as the home of the country’s only genome foundry, Concordia is a natural fit for a training program in this growing area of research,” says Christophe Guy, vice-president of Research and Graduate Studies.

“In offering a program like SynBioApps, we are providing our students with both a fundamental education in science and the business skills they’ll need to transition into their professional careers.”

The program’s aims are twofold: First, it will teach students how to design and construct cells and proteins for the development of new products related to human health, green technologies, and fundamental biological investigations. Second, it will provide cross-disciplinary training and internship opportunities through the university’s District 3 Innovation Center.

SynBioApps will be open to students from biology, biochemistry, engineering, computing, and mathematics.

“The ability to apply engineering approaches to biological systems promises to revolutionize both biology and industry,” says Whiteway, who is also a member of the Centre for Applied Synthetic Biology.

“The SynBioApps program at Concordia will provide a training program to develop the students who will both investigate the biology and build these industries.”

You can find out more about Concordia’s Centre for Applied Synthetic Biology here (there are jobs listed on their home page) and you can find information about the Synthetic Biology Applications (SynBioApps) training programme here.

US Dept. of Agriculture announces its nanotechnology research grants

I don’t always stumble across the US Department of Agriculture’s nanotechnology research grant announcements but I’m always grateful when I do as it’s good to find out about  nanotechnology research taking place in the agricultural sector. From a July 21, 2017 news item on Nanowerk,,

The U.S. Department of Agriculture’s (USDA) National Institute of Food and Agriculture (NIFA) today announced 13 grants totaling $4.6 million for research on the next generation of agricultural technologies and systems to meet the growing demand for food, fuel, and fiber. The grants are funded through NIFA’s Agriculture and Food Research Initiative (AFRI), authorized by the 2014 Farm Bill.

“Nanotechnology is being rapidly implemented in medicine, electronics, energy, and biotechnology, and it has huge potential to enhance the agricultural sector,” said NIFA Director Sonny Ramaswamy. “NIFA research investments can help spur nanotechnology-based improvements to ensure global nutritional security and prosperity in rural communities.”

A July 20, 2017 USDA news release, which originated the news item, lists this year’s grants and provides a brief description of a few of the newly and previously funded projects,

Fiscal year 2016 grants being announced include:

Nanotechnology for Agricultural and Food Systems

  • Kansas State University, Manhattan, Kansas, $450,200
  • Wichita State University, Wichita, Kansas, $340,000
  • University of Massachusetts, Amherst, Massachusetts, $444,550
  • University of Nevada, Las Vegas, Nevada,$150,000
  • North Dakota State University, Fargo, North Dakota, $149,000
  • Cornell University, Ithaca, New York, $455,000
  • Cornell University, Ithaca, New York, $450,200
  • Oregon State University, Corvallis, Oregon, $402,550
  • University of Pennsylvania, Philadelphia, Pennsylvania, $405,055
  • Gordon Research Conferences, West Kingston, Rhode Island, $45,000
  • The University of Tennessee,  Knoxville, Tennessee, $450,200
  • Utah State University, Logan, Utah, $450,200
  • The George Washington University, Washington, D.C., $450,200

Project details can be found at the NIFA website (link is external).

Among the grants, a University of Pennsylvania project will engineer cellulose nanomaterials [emphasis mine] with high toughness for potential use in building materials, automotive components, and consumer products. A University of Nevada-Las Vegas project will develop a rapid, sensitive test to detect Salmonella typhimurium to enhance food supply safety.

Previously funded grants include an Iowa State University project in which a low-cost and disposable biosensor made out of nanoparticle graphene that can detect pesticides in soil was developed. The biosensor also has the potential for use in the biomedical, environmental, and food safety fields. University of Minnesota (link is external) researchers created a sponge that uses nanotechnology to quickly absorb mercury, as well as bacterial and fungal microbes from polluted water. The sponge can be used on tap water, industrial wastewater, and in lakes. It converts contaminants into nontoxic waste that can be disposed in a landfill.

NIFA invests in and advances agricultural research, education, and extension and promotes transformative discoveries that solve societal challenges. NIFA support for the best and brightest scientists and extension personnel has resulted in user-inspired, groundbreaking discoveries that combat childhood obesity, improve and sustain rural economic growth, address water availability issues, increase food production, find new sources of energy, mitigate climate variability and ensure food safety. To learn more about NIFA’s impact on agricultural science, visit www.nifa.usda.gov/impacts, sign up for email updates (link is external) or follow us on Twitter @USDA_NIFA (link is external), #NIFAImpacts (link is external).

Given my interest in nanocellulose materials (Canada was/is a leader in the production of cellulose nanocrystals [CNC] but there has been little news about Canadian research into CNC applications), I used the NIFA link to access the table listing the grants and clicked on ‘brief’ in the View column in the University of Pennsylania row to find this description of the project,

ENGINEERING CELLULOSE NANOMATERIALS WITH HIGH TOUGHNESS

NON-TECHNICAL SUMMARY: Cellulose nanofibrils (CNFs) are natural materials with exceptional mechanical properties that can be obtained from renewable plant-based resources. CNFs are stiff, strong, and lightweight, thus they are ideal for use in structural materials. In particular, there is a significant opportunity to use CNFs to realize polymer composites with improved toughness and resistance to fracture. The overall goal of this project is to establish an understanding of fracture toughness enhancement in polymer composites reinforced with CNFs. A key outcome of this work will be process – structure – fracture property relationships for CNF-reinforced composites. The knowledge developed in this project will enable a new class of tough CNF-reinforced composite materials with applications in areas such as building materials, automotive components, and consumer products.The composite materials that will be investigated are at the convergence of nanotechnology and bio-sourced material trends. Emerging nanocellulose technologies have the potential to move biomass materials into high value-added applications and entirely new markets.

It’s not the only nanocellulose material project being funded in this round, there’s this at North Dakota State University, from the NIFA ‘brief’ project description page,

NOVEL NANOCELLULOSE BASED FIRE RETARDANT FOR POLYMER COMPOSITES

NON-TECHNICAL SUMMARY: Synthetic polymers are quite vulnerable to fire.There are 2.4 million reported fires, resulting in 7.8 billion dollars of direct property loss, an estimated 30 billion dollars of indirect loss, 29,000 civilian injuries, 101,000 firefighter injuries and 6000 civilian fatalities annually in the U.S. There is an urgent need for a safe, potent, and reliable fire retardant (FR) system that can be used in commodity polymers to reduce their flammability and protect lives and properties. The goal of this project is to develop a novel, safe and biobased FR system using agricultural and woody biomass. The project is divided into three major tasks. The first is to manufacture zinc oxide (ZnO) coated cellulose nanoparticles and evaluate their morphological, chemical, structural and thermal characteristics. The second task will be to design and manufacture polymer composites containing nano sized zinc oxide and cellulose crystals. Finally the third task will be to test the fire retardancy and mechanical properties of the composites. Wbelieve that presence of zinc oxide and cellulose nanocrystals in polymers will limit the oxygen supply by charring, shielding the surface and cellulose nanocrystals will make composites strong. The outcome of this project will help in developing a safe, reliable and biobased fire retardant for consumer goods, automotive, building products and will help in saving human lives and property damage due to fire.

One day, I hope to hear about Canadian research into applications for nanocellulose materials. (fingers crossed for good luck)

‘Hunting’ pharmaceuticals and removing them from water

Pharmaceuticals are not the first pollutants people think of when discussing water pollution but, for those who don’t know, it’s a big issue and scientists at the University of Surrey (UK) have developed a technology they believe will help to relieve the contamination. From an April 10, 2017 University of Surrey press release (also on EurekAlert),

The research involves the detection and removal of pharmaceuticals in or from water, as contamination from pharmaceuticals can enter the aquatic environment as a result of their use for the treatment of humans and animals. This contamination can be excreted unchanged, as metabolites, as unused discharge or by drug manufacturers.

The research has found that a new type of ‘supermolecule’, calix[4], actively seeks certain pharmaceuticals and removes them from water.

Contamination of water is a serious concern for environmental scientists around the world, as substances include hormones from the contraceptive pill, and pesticides and herbicides from allotments. Contamination can also include toxic metals such as mercury, arsenic, or cadmium, which was previously used in paint, or substances that endanger vital species such as bees.

Professor Danil de Namor, University of Surrey Emeritus Professor and leader of the research, said: “Preliminary extraction data are encouraging as far as the use of this receptor for the selective removal of these drugs from water and the possibility of constructing a calix[4]-based sensing devices.

“From here, we can design receptors so that they can bind selectively with pollutants in the water so the pollutants can be effectively removed. This research will allow us to know exactly what is in the water, and from here it will be tested in industrial water supplies, so there will be cleaner water for everyone.

“The research also creates the possibility of using these materials for on-site monitoring of water, without having to transport samples to the laboratory.”

Dr Brendan Howlin, University of Surrey co-investigator, said: “This study allows us to visualise the specific receptor-drug interactions leading to the selective behaviour of the receptor. As well as the health benefits of this research, molecular simulation is a powerful technique that is applicable to a wide range of materials.

“We were very proud that the work was carried out with PhD students and a final year project student, and research activities are already taking place with the Department of Chemical and Processing Engineering (CPI) and the Advanced Technology Institute (ATI).

“We are also very pleased to see that as soon as the paper was published online by the European Journal of Pharmaceutical Sciences, we received invitations to give keynote lectures at two international conferences on pharmaceuticals in Europe later this year.”

That last paragraph is intriguing and it marks the first time I’ve seen that claim in a press release announcing the publication of a piece of research.

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

A calix[4]arene derivative and its selective interaction with drugs (clofibric acid, diclofenac and aspirin) by Angela F Danil de Namor, Maan Al Nuaim, Jose A Villanueva Salas, Sophie Bryant, Brendan Howlin. European Journal of Pharmaceutical Sciences Volume 100, 30 March 2017, Pages 1–8 https://doi.org/10.1016/j.ejps.2016.12.027

This paper is behind a paywall.

Nanozymes as an antidote for pesticides

Should you have concerns about exposure to pesticides or chemical warfare agents (timely given events in Syria as per this April 4, 2017 news item on CBC [Canadian Broadcasting News Corporation] online) , scientists at the Lomonosov Moscow State University have developed a possible antidote according to a March 8,, 2017 news item on phys.org,

Members of the Faculty of Chemistry of the Lomonosov Moscow State University have developed novel nanosized agents that could be used as efficient protective and antidote modalities against the impact of neurotoxic organophosphorus compounds such as pesticides and chemical warfare agents. …

A March 7, 2017 Lomonosov Moscow State University press release on EurekAlert, which originated the news item, describes the work in detail,

A group of scientists from the Faculty of Chemistry under the leadership of Prof. Alexander Kabanov has focused their research supported by a “megagrant” on the nanoparticle-based delivery to an organism of enzymes, capable of destroying toxic organophosphorous compounds. Development of first nanosized drugs has started more than 30 years ago and already in the 90-s first nanomedicines for cancer treatment entered the market. First such medicines were based on liposomes – spherical vesicles made of lipid bilayers. The new technology, developed by Kabanov and his colleagues, uses an enzyme, synthesized at the Lomonosov Moscow State University, encapsulated into a biodegradable polymer coat, based on an amino acid (glutamic acid).

Alexander Kabanov, Doctor of Chemistry, Professor at the Eshelman School of Pharmacy of the University of North Carolina (USA) and the Faculty of Chemistry, M. V. Lomonosov Moscow State University, one of the authors of the article explains: “At the end of the 80-s my team (at that time in Moscow) and independently Japanese colleagues led by Prof. Kazunori Kataoka from Tokyo began using polymer micelles for small molecules delivery. Soon the nanomedicine field has “exploded”. Currently hundreds of laboratories across the globe work in this area, applying a wide variety of approaches to creation of such nanosized agents. A medicine on the basis of polymeric micelles, developed by a Korean company Samyang Biopharm, was approved for human use in 2006.”

Professor Kabanov’s team after moving to the USA in 1994 focused on development of polymer micelles, which could include biopolymers due to electrostatic interactions. Initially chemists were interested in usage of micelles for RNA and DNA delivery but later on scientists started actively utilizing this approach for delivery of proteins and, namely, enzymes, to the brain and other organs.

Alexander Kabanov says: “At the time I worked at the University of Nebraska Medical Center, in Omaha (USA) and by 2010 we had a lot of results in this area. That’s why when my colleague from the Chemical Enzymology Department of the Lomonosov Moscow State University, Prof. Natalia Klyachko offered me to apply for a megagrant the research theme of the new laboratory was quite obvious. Specifically, to use our delivery approach, which we’ve called a “nanozyme”, for “improvement” of enzymes, developed by colleagues at the Lomonosov Moscow State University for its further medical application.”

Scientists together with the group of enzymologists from the Lomonosov Moscow State University under the leadership of Elena Efremenko, Doctor of Biological Sciences, have chosen organophosphorus hydrolase as a one of the delivered enzymes. Organophosphorus hydrolase is capable of degrading toxic pesticides and chemical warfare agents with very high rate. However, it has disadvantages: because of its bacterial origin, an immune response is observed as a result of its delivery to an organism of mammals. Moreover, organophosphorus hydrolase is quickly removed from the body. Chemists have solved this problem with the help of a “self-assembly” approach: as a result of inclusion of organophosphorus hydrolase enzyme in a nanozyme particles the immune response becomes weaker and, on the contrary, both the storage stability of the enzyme and its lifetime after delivery to an organism considerably increase. Rat experiments have proved that such nanozyme efficiently protects organisms against lethal doses of highly toxic pesticides and even chemical warfare agents, such as VX nerve gas.

Alexander Kabanov summarizes: “The simplicity of our approach is very important. You could get an organophosphorus hydrolase nanozyme by simple mixing of aqueous solutions of anenzyme and safe biocompatible polymer. This nanozyme is self-assembled due to electrostatic interaction between a protein (enzyme) and polymer”.

According to the scientist’s words the simplicity and technological effectiveness of the approach along with the obtained promising results of animal experiments bring hope that this modality could be successful and in clinical use.

Members of the Faculty of Chemistry of the Lomonosov Moscow State University, along with scientists from the 27th Central Research Institute of the Ministry of Defense of the Russian Federation, the Eshelman School of Pharmacy of the University of North Carolina at Chapel Hill (USA) and the University of Nebraska Medical Center (UNC) have taken part in the Project.

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

A simple and highly effective catalytic nanozyme scavenger for organophosphorus neurotoxins by Elena N. Efremenko, Ilya V. Lyagin, Natalia L. Klyachko, Tatiana Bronich, Natalia V. Zavyalova, Yuhang Jiang, Alexander V. Kabanov. Journal of Controlled Release Volume 247, 10 February 2017, Pages 175–181  http://dx.doi.org/10.1016/j.jconrel.2016.12.037

This paper is behind a paywall.

Australia and regulation of nanotechnology re: agriculture, animal husbandry, pesticides, and veterinary medicines

The Australian Pesticides and Veterinary Medicines Authority (APVMA) has release a final report with recommendations regarding nanotechnology regulation according to a July 13, 2015 news item on Nanowerk (Note: A link has been removed),

Publication of the report Nanotechnologies for pesticides and veterinary medicines: regulatory considerations—final report (July 2015) marks the culmination of four years of Australian Pesticides and Veterinary Medicines Authority (APVMA)-led research, consultation and collaboration.

The report considers the benefits and challenges of regulating nanotechnology for use in agriculture and animal husbandry, as advances in nanoscale science, engineering and technology pave the way for developing novel applications, devices and systems.

The report aims to inform and stimulate discussion about emerging nanotechnology and highlights the key regulatory considerations for agvet chemical nanomaterials based on the current state of knowledge.

It systematically explores the opportunities and risks of these substances in Australian agriculture and animal husbandry and reviews the published work relevant to the registration of nanoscale agvet chemicals.

A July 6, 2015 APVMA press release, which originated the news item, provides a brief history of the deliberations which led to the report and a brief description of the actions which will follow its publication,

In October 2014, the APVMA hosted a symposium on nanotechnology regulation, seeking national and international input from industry, scientists, regulators and the broader community on developing a regulatory framework for nanotechnologies in Australian agriculture and animal husbandry. Discussion was based on the APVMA draft report Regulatory considerations for nanopesticides and veterinary medicines (October 2014), the first of its kind to be made available for public discussion. Input subsequently received was considered in finalising the report.

Next steps

The APVMA will now use the report to finalise the regulatory approach for nanotechnology products, including:

building capability and expertise so new products can be evaluated effectively
analysing the data requirements
enhancing the existing regulatory framework if required as knowledge evolves
continuing to engage with the international scientific community so that the latest

You can find the final report here.

Congratulations to Vive Crop on its new manufacturing capability

Here’s the latest news from Vive Crop (from the Nov.20, 2014 announcement,

Toronto, ON – Nov 20, 2014 – Vive Crop Protection, Inc. is pleased to announce the opening of its new manufacturing plant to enable commercial production of its advanced product formulations. These technologies leverage Vive’s patented Allosperse® delivery system, providing enhanced agronomic performance and new application opportunities for farmers.

“This plant is the result of the dedicated effort of all our employees and the support of our partners. Completion of our manufacturing plant is a momentous milestone that significantly accelerates our company’s growth,” said Vive CEO Keith Thomas. “Vive’s innovative employees are rapidly developing a strong pipeline of effective crop protection products for our partners and growers.”

Vive’s products have been commercialized from fundamental research conducted at the University of Toronto and funded by the Natural Sciences and Engineering Council of Canada (NSERC) I2I program and Ontario Centres of Excellence. Ongoing support has been provided by private investors as well as the Government of Canada through Sustainable Development Technology Canada and FedDev Ontario as well as the Government of Ontario through the Innovation Demonstration Fund and Ontario Capital Growth Corporation. Vive’s plant is located at Halltech Inc., a Canadian manufacturer of polymer emulsions.

About Vive Crop Protection: Vive Crop Protection makes products that better protect crops from pests. The company has won a number of awards and was highly commended for Best Formulation Innovation at the 2012 Agrow Awards. Vive’s patented Allosperse delivery system has the ability to coat plants more evenly, which provides better crop protection and can lead to increased yields. Vive is working with partners across the globe that share its vision of bringing safer, more effective crop protection products to growers everywhere. For more information, see www.vivecrop.com.

Congratulations to everyone at Vive Crop!

For anyone unfamiliar with the company, there’s this description from the Vive Crop website’s homepage,

At Vive, our aim is to develop effective crop protection products, giving farmers better tools to protect their crops.

We use our patented Allosperse® delivery system in formulations that have new, exciting properties that growers care about. Allosperse is a water-dispersible delivery system, meaning that our formulations are made without solvents.

We are looking for partners across the globe that share our vision of bringing effective crop protection products to growers everywhere.

Crop protection sounds like work on pesticides and insecticides to me and given that Vive Crop has won at least one ‘cleantech’ award, I assume that this is a relatively ‘green’ product. I last wrote about Vive Crop in a Dec. 31, 2013 post.

Finally, I was a little puzzled by the mention of Vive Crop’s manufacturing plant as being located at Halltech Inc., a Canadian manufacturer of polymer emulsions located in Scarborough, Ontario. Perhaps they’re sharing space? In any event, you can find Halltech here.

Vive Nano and the American Chemistry Council Award and a philosphy of awards

Vive Nano recently received a 2011 Responsible Care Performance Award from the American Chemistry Council. From the May 11, 2011 news release,

The Responsible Care Performance Award recognizes those member companies who excelled at helping ACC meet industry-wide safety and product stewardship targets. ACC Responsible Care award winners qualify based on exemplary performance, and are selected by an external expert committee. Other award winners this year include Chevron Phillips Chemical Company, ExxonMobil Chemical Company, Nova Chemicals and Honeywell.

At this point I want to make a distinction between Vive Nano’s acceptance of the award and the award’s credibility and to make a personal confession. First the confession, I don’t probe too deeply when I win award and I probably should. Now onto the issue of an award’s credibility. Something in the news release caught my attention,

“Responsible Care is the chemical industry’s commitment to sustainability, enabling us to enhance environmental protection and public health, as well as improve worker safety and plant security,” said Greg Babe, chair of ACC’s Board Committee on Responsible Care and president and CEO of Bayer Corp. [emphases mine]

One of the Bayer companies (Babe is the Chief Executive Officer of the parent corporation), Bayer CropScience has a product used as a pesticide which has been strongly implicated as a factor in the calamitous collapse of bee colonies in North America and elsewhere. From a Dec. 14, 2010 article by Ariel Schwartz for Fast Company,

Beekeepers across the U.S. are reporting record low honey crops as their bees fail to make it through the winter. One-third of American agriculture, which relies on bee pollination, is at stake. And the problem may be at least partially attributable to clothianidin, a Bayer-branded pesticide used on corn and other crops.

But as we revealed last week, the EPA knew that clothianidin could be toxic when the product came on the market in 2003. So why is it still on the market?

The bee-toxic pesticide problem can be traced back to 1994, when the first neonicotinoid pesticide (Imidacloprid) was released. Neonicotinoids like imidacloprid and clothianidin disrupt the central nervous system of pest insects, and are supposed to be relatively non-toxic to other animals. But there’s a problem: The neonicotinoids coat plant seeds, releasing insecticides permanently into the plant. The toxins are then released in pollen and nectar–where they may cause bees to become disoriented and die.

….

The EPA first brought up the link between clothianidin and bees before the pesticide’s release in February 2003. The agency originally planned to withhold registration of the pesticide because of concerns about toxicity in bees, going so far as to suggest that the product come with a warning label (PDF): “This compound is toxic to honey bees. The persistance [sic] of residues and the expression clothianidin in nectar and pollen suggest the possibility of chronic toxic risk to honey bee larvae and the eventual stability of the hive.”

But in April 2003, the EPA decided to give Bayer conditional registration. Bayer could sell the product and seed processors could freely use it, with the proviso that Bayer complete a life cycle study of clothianidin on corn by December 2004. Bayer was granted an extension until May 2005 (and permission to use canola instead of corn in its tests), but didn’t complete the study until August 2007. The EPA continued to allow the sale of clothianidin, and once the Bayer study finally came out, it was flawed.

There’s more about the bees and Bayer both in this article and in a Dec. 17, 2010 article by Schwartz for Fast Company.

Here’s an excerpt from the company’s Dec. 22, 2010 response to the concerns,

Bayer CropScience was recently made aware of an unauthorized release [emphasis mine] from within the Environmental Protection Agency (EPA) of a document regarding the seed treatment product, clothianidin, which is sold in the United States corn market. Bayer CropScience disagrees with the claims by some environmental groups against this product and we believe these are incorrect and unwarranted with regard to honey bee concerns.

The study referenced in the document is important research, conducted by independent experts and published in a major peer-reviewed scientific journal. The long-term field study conducted in accordance with Good Laboratory Practices (GLP) by independent experts using clothianidin-treated seed showed that there were no effects on bee mortality, weight gain, worker longevity, brood development, honey yield and over-winter survival. The EPA reviewed and approved the study protocol prior to its initiation and it was peer-reviewed and published in the Journal of Economic Entomology*. Upon reviewing the results of the long-term trial, the Agency noted the study as “scientifically sound and satisfies the guideline requirements for a field toxicity test with honey bees.

According to Schwartz, the ‘unauthorized release’ was in response to a freedom of information (FOI) query.

If the product is suspected of being unsafe, why not make the data available for analysis by respected scientists who are not associated with Bayer in any way? Given the magnitude of the problem, shouldn’t the company go above and beyond? And, what does this mean for its commitment to the American Chemistry Council’s Responsible Care program?

The issue is not Vive Nano; it’s the credibility of the award. For example, the Nobel Peace Prize is funded from the proceeds of a fortune derived from the invention of dynamite, amongst other things. (I was not able to confirm that Alfred Nobel was a munitions manufacturer although I’ve heard that any number of times.) Does the source for the funding matter or has the Nobel Peace Prize accrued credibility over the years from the reputations of the award recipients?

Could Vive Nano and companies like it (assuming they are genuinely living up to the standards of the Responsible Care program) possibly give the award credibility over time?

There you have it. An award is not just an award; it is a complex interplay between the recipient, the organization giving the award, and reputation.