Category Archives: environment

Taking the baking out of aircraft manufacture

It seems that ovens are an essential piece of equipment when manufacturing aircraft parts but that may change if research from MIT (Massachusetts Institute of Technology) proves successful. An April 14, 2015 news item on ScienceDaily describes the current process and the MIT research,

Composite materials used in aircraft wings and fuselages are typically manufactured in large, industrial-sized ovens: Multiple polymer layers are blasted with temperatures up to 750 degrees Fahrenheit, and solidified to form a solid, resilient material. Using this approach, considerable energy is required first to heat the oven, then the gas around it, and finally the actual composite.

Aerospace engineers at MIT have now developed a carbon nanotube (CNT) film that can heat and solidify a composite without the need for massive ovens. When connected to an electrical power source, and wrapped over a multilayer polymer composite, the heated film stimulates the polymer to solidify.

The group tested the film on a common carbon-fiber material used in aircraft components, and found that the film created a composite as strong as that manufactured in conventional ovens — while using only 1 percent of the energy.

The new “out-of-oven” approach may offer a more direct, energy-saving method for manufacturing virtually any industrial composite, says Brian L. Wardle, an associate professor of aeronautics and astronautics at MIT.

“Typically, if you’re going to cook a fuselage for an Airbus A350 or Boeing 787, you’ve got about a four-story oven that’s tens of millions of dollars in infrastructure that you don’t need,” Wardle says. “Our technique puts the heat where it is needed, in direct contact with the part being assembled. Think of it as a self-heating pizza. … Instead of an oven, you just plug the pizza into the wall and it cooks itself.”

Wardle says the carbon nanotube film is also incredibly lightweight: After it has fused the underlying polymer layers, the film itself — a fraction of a human hair’s diameter — meshes with the composite, adding negligible weight.

An April 14, 2015 MIT news release, which originated the news item, describes the origins of the team’s latest research, the findings, and the implications,

Carbon nanotube deicers

Wardle and his colleagues have experimented with CNT films in recent years, mainly for deicing airplane wings. The team recognized that in addition to their negligible weight, carbon nanotubes heat efficiently when exposed to an electric current.

The group first developed a technique to create a film of aligned carbon nanotubes composed of tiny tubes of crystalline carbon, standing upright like trees in a forest. The researchers used a rod to roll the “forest” flat, creating a dense film of aligned carbon nanotubes.

In experiments, Wardle and his team integrated the film into airplane wings via conventional, oven-based curing methods, showing that when voltage was applied, the film generated heat, preventing ice from forming.

The deicing tests inspired a question: If the CNT film could generate heat, why not use it to make the composite itself?

How hot can you go?

In initial experiments, the researchers investigated the film’s potential to fuse two types of aerospace-grade composite typically used in aircraft wings and fuselages. Normally the material, composed of about 16 layers, is solidified, or cross-linked, in a high-temperature industrial oven.

The researchers manufactured a CNT film about the size of a Post-It note, and placed the film over a square of Cycom 5320-1. They connected electrodes to the film, then applied a current to heat both the film and the underlying polymer in the Cycom composite layers.

The team measured the energy required to solidify, or cross-link, the polymer and carbon fiber layers, finding that the CNT film used one-hundredth the electricity required for traditional oven-based methods to cure the composite. Both methods generated composites with similar properties, such as cross-linking density.

Wardle says the results pushed the group to test the CNT film further: As different composites require different temperatures in order to fuse, the researchers looked to see whether the CNT film could, quite literally, take the heat.

“At some point, heaters fry out,” Wardle says. “They oxidize, or have different ways in which they fail. What we wanted to see was how hot could this material go.”

To do this, the group tested the film’s ability to generate higher and higher temperatures, and found it topped out at over 1,000 F. In comparison, some of the highest-temperature aerospace polymers require temperatures up to 750 F in order to solidify.

“We can process at those temperatures, which means there’s no composite we can’t process,” Wardle says. “This really opens up all polymeric materials to this technology.”

The team is working with industrial partners to find ways to scale up the technology to manufacture composites large enough to make airplane fuselages and wings.

“There needs to be some thought given to electroding, and how you’re going to actually make the electrical contact efficiently over very large areas,” Wardle says. “You’d need much less power than you are currently putting into your oven. I don’t think it’s a challenge, but it has to be done.”

Gregory Odegard, a professor of computational mechanics at Michigan Technological University, says the group’s carbon nanotube film may go toward improving the quality and efficiency of fabrication processes for large composites, such as wings on commercial aircraft. The new technique may also open the door to smaller firms that lack access to large industrial ovens.

“Smaller companies that want to fabricate composite parts may be able to do so without investing in large ovens or outsourcing,” says Odegard, who was not involved in the research. “This could lead to more innovation in the composites sector, and perhaps improvements in the performance and usage of composite materials.”

It can be interesting to find out who funds the research (from the news release),

This research was funded in part by Airbus Group, Boeing, Embraer, Lockheed Martin, Saab AB, TohoTenax, ANSYS Inc., the Air Force Research Laboratory at Wright-Patterson Air Force Base, and the U.S. Army Research Office.

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

Impact of carbon nanotube length on electron transport in aligned carbon nanotube networks by Jeonyoon Lee, Itai Y. Stein, Mackenzie E. Devoe, Diana J. Lewis, Noa Lachman, Seth S. Kessler, Samuel T. Buschhorn, and Brian L. Wardle. Appl. Phys. Lett. 106, 053110 (2015); http://dx.doi.org/10.1063/1.4907608

This paper is behind a paywall.

Netting oil spills the nano way

Given current local events (April 8, 2015 oil spill in English Bay of 2700 litres (or more) of fuel in Vancouver, Canada), this news item about a mesh useful for oil cleanups seems quite timely. From an April 15, 2015 news item on ScienceDaily,

The unassuming piece of stainless steel mesh in a lab at The Ohio State University doesn’t look like a very big deal, but it could make a big difference for future environmental cleanups.

Water passes through the mesh but oil doesn’t, thanks to a nearly invisible oil-repelling coating on its surface.

In tests, researchers mixed water with oil and poured the mixture onto the mesh. The water filtered through the mesh to land in a beaker below. The oil collected on top of the mesh, and rolled off easily into a separate beaker when the mesh was tilted.

The mesh coating is among a suite of nature-inspired nanotechnologies under development at Ohio State and described in two papers in the journal Nature Scientific Reports. Potential applications range from cleaning oil spills to tracking oil deposits underground.

An April 15, 2015 Ohio State University news release (also on EurekAlert*) by Pam Frost Gorder, which originated the news item, expands on the theme (unusually I’ve left the links undisturbed),

“If you scale this up, you could potentially catch an oil spill with a net,” said Bharat Bhushan, Ohio Eminent Scholar and Howard D. Winbigler Professor of mechanical engineering at Ohio State.

The work was partly inspired by lotus leaves, whose bumpy surfaces naturally repel water but not oil. To create a coating that did the opposite, Bhushan and postdoctoral researcher Philip Brown chose to cover a bumpy surface with a polymer embedded with molecules of surfactant—the stuff that gives cleaning power to soap and detergent.

They sprayed a fine dusting of silica nanoparticles onto the stainless steel mesh to create a randomly bumpy surface and layered the polymer and surfactant on top.

The silica, surfactant, polymer, and stainless steel are all non-toxic and relatively inexpensive, said Brown. He estimated that a larger mesh net could be created for less than a dollar per square foot.

Because the coating is only a few hundred nanometers (billionths of a meter) thick, it is mostly undetectable. To the touch, the coated mesh doesn’t feel any bumpier than uncoated mesh. The coated mesh is a little less shiny, though, because the coating is only 70 percent transparent.

The researchers chose silica in part because it is an ingredient in glass, and they wanted to explore this technology’s potential for creating smudge-free glass coatings. At 70 percent transparency, the coating could work for certain automotive glass applications, such as mirrors, but not most windows or smartphone surfaces.

“Our goal is to reach a transparency in the 90-percent range,” Bhushan said. “In all our coatings, different combinations of ingredients in the layers yield different properties. The trick is to select the right layers.”

He explains that combinations of layers yield nanoparticles that bind to oil instead of repelling it. Such particles could be used to detect oil underground or aid removal in the case of oil spills.

The shape of the nanostructures plays a role, as well. In another project, research assistant Dave Maharaj is investigating what happens when a surface is made of nanotubes. Rather than silica, he experiments with molybdenum disulfide nanotubes, which mix well with oil. The nanotubes are approximately a thousand times smaller than a human hair.

Maharaj measured the friction on the surface of the nanotubes, and compressed them to test how they would hold up under pressure.

“There are natural defects in the structure of the nanotubes,” he said. “And under high loads, the defects cause the layers of the tubes to peel apart and create a slippery surface, which greatly reduces friction.”

Bhushan envisions that the molybdenum compound’s compatibility with oil, coupled with its ability to reduce friction, would make it a good additive for liquid lubricants. In addition, for micro- and nanoscale devices, commercial oils may be too sticky to allow for their efficient operation. Here, he suspects that the molybdenum nanotubes alone could be used to reduce friction.

This work began more than 10 years ago, when Bhushan began building and patenting nano-structured coatings that mimic the texture of the lotus leaf. From there, he and his team have worked to amplify the effect and tailor it for different situations.

“We’ve studied so many natural surfaces, from leaves to butterfly wings and shark skin, to understand how nature solves certain problems,” Bhushan said. “Now we want to go beyond what nature does, in order to solve new problems.”

“Nature reaches a limit of what it can do,” agreed Brown. “To repel synthetic materials like oils, we need to bring in another level of chemistry that nature doesn’t have access to.”

This work was partly funded by the American Chemical Society Petroleum Research Fund, the National Science Foundation, and Dexerials Corporation (formerly a chemical division of Sony Corp.) in Japan.

Here are links to and citations for the papers,

Mechanically durable, superoleophobic coatings prepared by layer-by-layer technique for anti-smudge and oil-water separation by Philip S. Brow & Bharat Bhushan. Scientific Reports 5, Article number: 8701 doi:10.1038/srep08701 Published 03 March 2015

Nanomechanical behavior of MoS2 and WS2 multi-walled nanotubes and Carbon nanohorns by Dave Maharaj, & Bharat Bhushan. Scientific Reports 5, Article number: 8539 doi:10.1038/srep08539 Published 23 February 2015

Both papers are open access.

* EurekAlert link added Apr.16, 2015 at 1300 PST.

Filtration membranes with twice as much ability to remove unwanted materials from water

A March 26, 2015 news item on Nanowerk offers information about a new method for removing pollutants from water and some insight into the situation regarding bisphenol A (BPA) in Europe,

New types of membrane adsorbers remove unwanted particles from water and also, at the same time, dissolved substances such as the hormonally active bis-phenol A or toxic lead. To do this, researchers at the Fraunhofer Institute for Interfacial Engineering and Biotechnology IGB imbed selective adsorber particles in filtration membranes.

It was not until January 2015 that the European Food Safety Authority (EFSA) lowered the threshold value for bisphenol A in packaging. The hormonally active bulk chemical is among other things a basic material for polycarbonate from which, for example, CDs, plastic tableware or spectacles glasses are manufactured. Due to its chemical structure, bisphenol A is not completely degraded in the biological stages of treatment plants and is discharged into rivers and lakes by the purification facility.

Activated carbon or adsorber materials are already used to remove chemicals, anti-biotics [sic] or heavy metals from waste or process water. However, a disadvantage of these highly porous materials is the long contact time that the pollutants require to diffuse into the pores. So that as many of the harmful substances as possible are captured even in a shorter time, the treatment plants use larger quantities of adsorbers in correspondingly large treatment basins. However, activated carbon can only be regenerated with a high energy input, resulting for the most part in the need to dispose of large quantities of material contaminated with pollutants.

Also, membrane filtration with nanofiltration or reverse osmosis membranes, which can remove the contaminating substances, is not yet cost-effective for the removal of dissolved molecules from high-volume flows such as process or wastewater. Membranes filter the water through their pores when a pressure is built up on one side of the membrane, thus holding back larger molecules and solid particles. But the smaller the membrane pores are, the higher the pressure – and therefore the more energy – that is required to separate the substances from water.

A March 24, 2015 Fraunhofer Institute for Interfacial Engineering and Biotechnology (IGB) press release, which originated the news item, goes on to describe their team’s new approach,

Researchers at the Fraunhofer Institute for Interfacial Engineering and Biotechnology IGB in Stuttgart have opted for a new approach that combines the advantages of both methods. When manufacturing the membranes they add small, polymeric adsorber particles. The resulting membrane adsorbers can – in addition to their filtration function – adsorptively bind substances dissolved in water. “We make use of the porous structure of the membrane located underneath the separation layer. The pores have a highly specific surface so that as many particles as possible can be imbedded, and they also provide optimum accessibility,” says Dr. Thomas Schiestel, Head of the “Inorganic Interfaces and Membranes” working group at the Fraunhofer IGB.

“Unlike conventional adsorbers, our membrane adsorbers transport the pollutants convectively. This means that, with the water flowing rapidly through the membrane pores, a contact time lasting only a few seconds is sufficient to adsorb pollutants on the particle surface,” says the scientist. Up to 40 percent of the weight of the membrane adsorbers is accounted for by the particles, so their binding capacity is correspondingly high. At the same time the membrane adsorbers can be operated at low pressures. As the membranes can be packed very tightly, very large volumes of water can be treated even with small devices.

Functional adsorber particles

The researchers manufacture the adsorber particles in a one-step, cost-efficient process. In this patented process monomeric components are polymerized with the help of a crosslinking agent to generate 50 to 500 nanometer polymer globules. “Depending on which substances are to be removed from the water, we select the most suitable one from a variety of monomers with differing functional groups,” Schiestel explains. The spectrum here ranges from pyridine, which tends to be hydrophobic, by way of cationic ammonium compounds and includes anionic phosphonates.

Selective removal of pollutants and metals

The researchers were able to show in various tests that the membrane adsorbers remove pollutants very selectively by means of the particles, which are customized for the particular contaminant in question. For example, membrane adsorbers with pyridine groups bind the hydrophobic bisphenol A especially well, whereas those with amino groups adsorb the negatively charged salt of the antibiotic penicillin G.

“The various adsorber particles can even be combined in one membrane. In this way we can remove several micropollutants simultaneously with just one membrane adsorber,” says Schiestel, pointing out a further advantage. Equipped with different functional groups, the membrane adsorbers can also remove toxic heavy metals such as lead or arsenic from the water. Phosphonate membrane adsorbers, for example, adsorb more than 5 grams of lead per square meter of membrane surface area – 40 percent more than a commercially available membrane adsorber.

Cost-effective and regenerable

So that the membrane adsorbers can be used several times, the adsorbed pollutants have to be detached once again from the particles in the membrane. “Membrane adsorbers for bisphenol A can be fully regenerated by a shift of the pH value,” Schiestel explains. The concentrated pollutants can then be disposed off cost-effectively or broken down using suitable oxidative processes.

The regenerability of the membrane adsorbers also makes possible a further application: reutilization of the separated molecules. This additionally makes the technology attractive for recovering valuable precious metals or rare earth metals.

The Fraunhofer IGB is presenting the membrane adsorbers and other innovative technologies for water purification at the “Wasser Berlin International” Trade Fair and Congress from 24th to 27th March 2015 in Berlin. The IGB is in Hall 2.2, Stand 422.

While it’s too late to attend the presentation, here are two links and citations to papers concerning the work,

Removal of micropollutants from water by nanocomposite membrane adsorbers by Klaus Niedergall, Monika Bach, Thomas Hirth, Günter E.M. Tovar, and Thomas Schiestel. Separation and Purification Technology, Volume 131, 27 June 2014 DOI: 10.1016/j.seppur.2014.04.032

Nanostructured Composite Adsorber Membranes for the Reduction of Trace Substances in Water: The Example of Bisphenol A by Klaus Niedergall, Monika Bach, Thomas Schiestel, and Günter E.M. Tovar. Ind. Eng. Chem. Res., 2013, 52 (39), pp 14011–14018 DOI: 10.1021/ie303264r Publication Date (Web): May 16, 2013

Copyright © 2013 American Chemical Society

Both articles are behind a paywall.

NANoREG halfway through its project (Environment, Health & Safety) term

A March 18, 2015 news item on Nanowerk announces a third NANoReg newsletter marking the halfway point in the project’s term (Note: Links have been removed),

NANoREG is the first FP7 project to deliver the answers needed by regulators and legislators on EHS [Environment, Health & Safety] by linking them to a scientific evaluation of data and test methods.

Time wise, the NANoREG project is now halfway. After setting the basic conditions for its R&D work, the project now focuses on the generation of reliable and comparable experimental data on the EHS aspects of the selected NANoREG nanomaterials. These data will form the basis for the main “end products” of the NANoREG project: the Regulatory Framework and the NANoREG Toolbox. Highlights of this experimental work and results will be shared with you in this 3rd NANoREG Newsletter (pdf).

The editorial for the 3rd issue of the NANoREG newsletter, which seems to have originated the news item, describes upcoming initiatives,

The Regulatory Framework and the NANoREG Toolbox just mentioned will be developed in close cooperation with organisations involved in standardisation and in the regulatory aspects of nanomaterials like ECHA [European Chemicals Agency], OECD [Organization for Economic Cooperation and Development], CEN [European Committee for Standardization] and ISO [International Standards Organization]. The results of other EU FP7 [Framework Programme 7] and H2020 [Horizon 2020] [research funding] projects will also be taken into account when developing these products. One of these projects is the H2020 project NANoREG II that focuses on Safe by design and that will start in the 2nd or 3rd quarter of 2015.

The coordinated and integrated approach in developing the Framework and the NANoREG Toolbox is one of the main elements of the H2020 funded Coordination and Support Action (CSA) “ProSafe” that recently had its Kick-Off meeting in Aix-en-Provence, France. Just like NANoREG this CSA is coordinated by the Dutch Ministry of Infrastructure and the Environment and as such executed by me. Other elements of this CSA are – among others – the expansions of the involvement of EU and non-EU countries in the NANoREG project in order to broaden the platform of support for the NANoREG results world-wide (“NANoREG+”), the exploitation of synergies between the NANoREG project and other “nanosafety” projects and data management.

The outcome of the CSA will be a White Paper that can be used by policy makers, regulators and industry to establish methods for measuring and assessing the EHS aspects of nanomaterials and that will give guidance to industry how to implement “safe by design“. A forerunner of the White Paper will be subject of a three days scientific conference to be held at the end of 2016. It will include the results of the NANoREG project, the results of the evaluation of EHS data available at the OECD and results from other sources. After consulting Risk assessors and policymakers, the White Paper will be published in the first quarter of 2017.

This project has reached out beyond Europe for partners (from the editorial for the 3rd NANoREG newsletter),

It is quite a challenge we face. Given the expertise and scientific authority of our partners, including the Czech-,Brazilian- and South Korean parties that recently joined the NANoREG project, I am confident however that we will succeed in reaching our goal: creating a solid basis for a balanced combination of nanosafety and innovation that will be beneficial to society.

I hope NANoREG is successful with its goal of “creating a solid basis for a balanced combination of nanosafety and innovation that will be beneficial to society.”

I last wrote about NANoREG in a March 21, 2014 posting.

Removing titanium dioxide nanoparticles from water may not be that easy

A March 10, 2015 news item on Nanowerk highlights some research into the removal of nanoscale titanium dioxide particles from water supplies (Note: A link has been removed),

The increased use of engineered nanoparticles (ENMs) in commercial and industrial applications is raising concern over the environmental and health effects of nanoparticles released into the water supply. A timely study that analyzes the ability of typical water pretreatment methods to remove titanium dioxide, the most commonly used ENM, is published in Environmental Engineering Science (“Titanium Dioxide Nanoparticle Removal in Primary Prefiltration Stages of Water Treatment: Role of Coating, Natural Organic Matter, Source Water, and Solution Chemistry”). The article is available free on the Environmental Engineering Science website until April 10, 2015.

A March 10, 2015 Mary Ann Liebert, Inc., publishers news release (also on EurekAlert), which originated the news item, provides more details about the work (Note: A link has been removed),

Nichola Kinsinger, Ryan Honda, Valerie Keene, and Sharon Walker, University of California, Riverside, suggest that current methods of water prefiltration treatment cannot adequately remove titanium dioxide ENMs. They describe the results of scaled-down tests to evaluate the effectiveness of three traditional methods—coagulation, flocculation, and sedimentation—in the article “Titanium Dioxide Nanoparticle Removal in Primary Prefiltration Stages of Water Treatment: Role of Coating, Natural Organic Matter, Source Water, and Solution Chemistry.”

“As nanoscience and engineering allow us to develop new exciting products, we must be ever mindful of associated consequences of these advances,” says Domenico Grasso, PhD, PE, DEE, Editor-in-Chief of Environmental Engineering Science and Provost, University of Delaware. “Professor Walker and her team have presented an excellent report raising concerns that some engineered nanomaterials may find their ways into our water supplies.”

“While further optimization of such treatment processes may allow for improved removal efficiencies, this study illustrates the challenges that we must be prepared to face with the emergence of new engineered nanomaterials,” says Sharon Walker, PhD, Professor of Chemical and Environmental Engineering, University of California, Riverside.

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

Titanium Dioxide Nanoparticle Removal in Primary Prefiltration Stages of Water Treatment: Role of Coating, Natural Organic Matter, Source Water, and Solution Chemistry by Nichola Kinsinger, Ryan Honda, Valerie Keene, and Sharon L. Walker. Environmental Engineering Science. doi:10.1089/ees.2014.0288.

This paper is freely available until April 10, 2015.

Interestingly Sharon Walker and Nichola Kinsinger recently co-authored a paper (mentioned in my March 9, 2015 post) about copper nanoparticles and water treatment which concluded this about copper nanoparticles in water supplies,

The researchers found that the copper nanoparticles, when studied outside the septic tank, impacted zebrafish embryo hatching rates at concentrations as low as 0.5 parts per million. However, when the copper nanoparticles were released into the replica septic tank, which included liquids that simulated human digested food and household wastewater, they were not bioavailable and didn’t impact hatching rates.

Taking these these two paper into account (and the many others I’ve read), there is no simple or universal answer to the question of whether or not ENPs or ENMs are going to pose environmental problems.

Do-it-yourself sensors possible with biocatalytic pen technology

The engineers at the University of California at San Diego (UCSD) are envisioning a future where anyone can create a biosensor anywhere. From a March 3, 2015 news item on Azonano,

A new simple tool developed by nanoengineers at the University of California, San Diego, is opening the door to an era when anyone will be able to build sensors, anywhere, including physicians in the clinic, patients in their home and soldiers in the field.

The team from the University of California, San Diego, developed high-tech bio-inks that react with several chemicals, including glucose. They filled off-the-shelf ballpoint pens with the inks and were able to draw sensors to measure glucose directly on the skin and sensors to measure pollution on leaves.

A March 2, 2015 UCSD news release by Ioana Patringenaru, which originated the news item, describes the researchers’ hopes for this technology,

Skin and leaves aren’t the only media on which the pens could be used. Researchers envision sensors drawn directly on smart phones for personalized and inexpensive health monitoring or on external building walls for monitoring of toxic gas pollutants. The sensors also could be used on the battlefield to detect explosives and nerve agents.

The team, led by Joseph Wang, the chairman of the Department of NanoEngineering at the University of California, San Diego, published their findings in the Feb. 26 [2015] issue of Advanced Healthcare Materials. Wang also directs the Center for Wearable Sensors at UC San Diego.

“Our new biocatalytic pen technology, based on novel enzymatic inks, holds considerable promise for a broad range of applications on site and in the field,” Wang said.

The news release goes on to describe one of the key concerns with developing the ink,

The biggest challenge the researchers faced was making inks from chemicals and biochemicals that aren’t harmful to humans or plants; could function as the sensors’ electrodes; and retain their properties over long periods in storage and in various conditions. Researchers turned to biocompatible polyethylene glycol, which is used in several drug delivery applications, as a binder. To make the inks conductive to electric current they used graphite powder. They also added chitosan, an antibacterial agent which is used in bandages to reduce bleeding, to make sure the ink adhered to any surfaces it was used on. The inks’ recipe also includes xylitol, a sugar substitute, which helps stabilize enzymes that react with several chemicals the do-it-yourself sensors are designed to monitor.

There’s a backstory to this research,

Wang’s team has been investigating how to make glucose testing for diabetics easier for several years. The same team of engineers recently developed non-invasive glucose sensors in the form of temporary tattoos. In this study, they used pens, loaded with an ink that reacts to glucose, to draw reusable glucose-measuring sensors on a pattern printed on a transparent, flexible material which includes an electrode. Researchers then pricked a subject’s finger and put the blood sample on the sensor. The enzymatic ink reacted with glucose and the electrode recorded the measurement, which was transmitted to a glucose-measuring device. Researchers then wiped the pattern clean and drew on it again to take another measurement after the subject had eaten.

Researchers estimate that one pen contains enough ink to draw the equivalent of 500 high-fidelity glucose sensor strips. Nanoengineers also demonstrated that the sensors could be drawn directly on the skin and that they could communicate with a Bluetooth-enabled electronic device that controls electrodes called a potentiostat, to gather data.

As mentioned earlier, there are more applications being considered (from the news release),

The pens would also allow users to draw sensors that detect pollutants and potentially harmful chemicals sensors on the spot. Researchers demonstrated that this was possible by drawing a sensor on a leaf with an ink loaded with enzymes that react with phenol, an industrial chemical, which can also be found in cosmetics, including sunscreen. The leaf was then dipped in a solution of water and phenol and the sensor was connected to a pollution detector. The sensors could be modified to react with many pollutants, including heavy metals or pesticides.

Next steps include connecting the sensors wirelessly to monitoring devices and investigating how the sensors perform in difficult conditions, including extreme temperatures, varying humidity and extended exposure to sunlight.

The researchers’ have provided a picture of the pen and a leaf,

Researchers drew sensors capable of detecting pollutants on a leaf. Courtesy: University of California at San Diego

Researchers drew sensors capable of detecting pollutants on a leaf. Courtesy: University of California at San Diego

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

Biocompatible Enzymatic Roller Pens for Direct Writing of Biocatalytic Materials: “Do-it-Yourself” Electrochemical Biosensors by Amay J. Bandodkar, Wenzhao Jia, Julian Ramírez, and Joseph Wang. Advanced Healthcare Materials DOI: 10.1002/adhm.201400808 Article first published online: 26 FEB 2015

© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

This article is behind a paywall.

Copper nanoparticles, toxicity research, colons, zebrafish, and septic tanks

Alicia Taylor, a graduate student at UC Riverside, surrounded by buckets of effluent from the septic tank system she used for her research. Courtesy: University of California at Riverside

Alicia Taylor, a graduate student at UC Riverside, surrounded by buckets of effluent from the septic tank system she used for her research. Courtesy: University of California at Riverside

Those buckets of efflluent are strangely compelling. I think it’s the abundance of orange. More seriously, a March 2, 2015 news item on Nanowerk poses a question about copper nanoparticles,

What do a human colon, septic tank, copper nanoparticles and zebrafish have in common?

They were the key components used by researchers at the University of California, Riverside and UCLA [University of California at Los Angeles] to study the impact copper nanoparticles, which are found in everything from paint to cosmetics, have on organisms inadvertently exposed to them.

The researchers found that the copper nanoparticles, when studied outside the septic tank, impacted zebrafish embryo hatching rates at concentrations as low as 0.5 parts per million. However, when the copper nanoparticles were released into the replica septic tank, which included liquids that simulated human digested food and household wastewater, they were not bioavailable and didn’t impact hatching rates.

A March 2, 2015 University of California at Riverside (UCR) news release (also on EurekAlert), which originated the news item, provides more detail about the research,

“The results are encouraging because they show with a properly functioning septic tank we can eliminate the toxicity of these nanoparticles,” said Alicia Taylor, a graduate student working in the lab of Sharon Walker, a professor of chemical and environmental engineering at the University of California, Riverside’s Bourns College of Engineering.

The research comes at a time when products with nanoparticles are increasingly entering the marketplace. While the safety of workers and consumers exposed to nanoparticles has been studied, much less is known about the environmental implications of nanoparticles. The Environmental Protection Agency is currently accessing the possible effects of nanomaterials, including those made of copper, have on human health and ecosystem health.

The UC Riverside and UCLA [University of California at Los Angeles] researchers dosed the septic tank with micro copper and nano copper, which are elemental forms of copper but encompass different sizes and uses in products, and CuPRO, a nano copper-based material used as an antifungal agent to spray agricultural crops and lawns.

While these copper-based materials have beneficial purposes, inadvertent exposure to organisms such as fish or fish embryos has not received sufficient attention because it is difficult to model complicated exposure environments.

The UC Riverside researchers solved that problem by creating a unique experimental system that consists of the replica human colon and a replica two-compartment septic tank, which was originally an acyclic septic tank. The model colon is made of a custom-built 20-inch-long glass tube with a 2-inch diameter with a rubber stopper at both ends and a tube-shaped membrane typically used for dialysis treatments within the glass tube.

To simulate human feeding, 100 milliliters of a 20-ingredient mixture that replicated digested food was pumped into the dialysis tube at 9 a.m., 3 p.m. and 9 p.m. for five-day-long experiments over nine months.

The septic tank was filled with waste from the colon along with synthetic greywater, which is meant to simulate wastewater from sources such as sinks and bathtubs, and the copper nanoparticles. The researchers built a septic tank because 20 to 30 percent of American households rely on them for sewage treatment. Moreover, research has shown up to 40 percent of septic tanks don’t function properly. This is a concern if the copper materials are disrupting the function of the septic system, which would lead to untreated waste entering the soil and groundwater.

Once the primary chamber of the septic system was full, liquid began to enter the second chamber. Once a week, the effluent was drained from the secondary chamber and it was placed into sealed five-gallon containers. The effluent was then used in combination with zebrafish embryos in a high content screening process using multiwall plates to access hatching rates.

The remaining effluent has been saved and sits in 30 five-gallon buckets in a closet at UC Riverside because some collaborators have requested samples of the liquid for their experiments.

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

Understanding the Transformation, Speciation, and Hazard Potential of Copper Particles in a Model Septic Tank System Using Zebrafish to Monitor the Effluent* by Sijie Lin, Alicia A. Taylor, Zhaoxia Ji, Chong Hyun Chang, Nichola M. Kinsinger, William Ueng, Sharon L. Walker, and André E. Nel. ACS Nano, 2015, 9 (2), pp 2038–2048 DOI: 10.1021/nn507216f
Publication Date (Web): January 27, 2015

Copyright © 2015 American Chemical Society

This paper is behind a paywall.

* Link added March 10, 2015.

From monitoring glucose in kidneys to climate change in trees

That headline is almost poetic but I admit It’s a bit of a stretch rhymewise, kidneys/trees. In any event, a Feb. 6, 2015 news item on Azonano describes research into monitoring the effects of climate change on trees,

Serving as a testament to the far-reaching impact of Governor Andrew M. Cuomo’s commitment to maintaining New York State’s global leadership in nanotechnology innovation, SUNY Polytechnic Institute’s Colleges of Nanoscale Science and Engineering (SUNY Poly CNSE) today announced the National Science Foundation (NSF) has awarded $837,000 to support development of a first of its kind nanoscale sensor to monitor the effects of climate change on trees.

A Feb. 5, 2015 SUNY Poly CNSE news release, which originated the news item, provides more details including information about the sensor’s link to measuring glucose in kidneys,

The NSF grant was generated through the Instrument Development for Biological Research (IDBR) program, which provides funds to develop new classes of devices for bio-related research. The NANAPHID, a novel aphid-like nanosensor, will provide real-time measurements of carbohydrates in live plant tissue. Carbohydrate levels in trees are directly connected to plant productivity, such as maple sap production and survival. The NANAPHID will enable researchers to determine the effects of a variety of environmental changes including temperature, precipitation, carbon dioxide, soil acidity, pests and pathogens. The nanosensor can also provide real-time monitoring of sugar concentration levels, which are of signficant importance in maple syrup production and apple and grape farming.

“The technology for the NANAPHID is rooted in a nanoscale sensor SUNY Poly CNSE developed to monitor glucose levels in human kidneys being prepared for transplant. Our team determined that certain adjustments would enable the sensor to provide similar monitoring for plants, and provide a critical insight to the effects of climate change on the environment,” said Dr. James Castracane, professor and head of the Nanobioscience Constellation at SUNY Polytechnic Institute. “This is a perfect example of the cycle of innovation made possible through the ongoing nanotechnology research and development at SUNY Poly CNSE’s NanoTech Complex.”

“This new sensor will be used in several field experiments on measuring sensitivity of boreal forest to climate warming. Questions about forest response to rising air and soil temperatures are extremely important for forecasting future atmospheric carbon dioxide levels, climate change and forest health,” said Dr. Andrei Lapenas, principal investigator and associate professor of climatology at the University at Albany. “At the same time, we already see some potential commercial application for NANAPHID-type sensors in agriculture, food industry and other fields. Our collaboration with SUNY Poly CNSE has been extremely productive and I look forward to continuing our work together.”

The NANAPHID project began in 2014 with a $135,000 SUNY Research Foundation Network of Excellence grant. SUNY Poly CNSE will receive $400,000 of the NSF award for the manufacturing aspects of the sensor array development and testing. The remaining funds will be shared between Dr. Lapenas and researchers Dr. Ruth Yanai (ESF), Dr. Thomas Horton (ESF), and Dr. Pamela Templer (Boston University) for data collection and analysis.

“With current technology, analyzing carbohydrates in plant tissues requires hours in the lab or more than $100 a sample if you want to send them out. And you can’t sample the same tissue twice, the sample is destroyed in the analysis,” said Dr. Yanai. “The implantable device will be cheap to produce and will provide continuous monitoring of sugar concentrations, which is orders of magnitude better in both cost and in the information provided. Research questions we never dreamed of asking before will become possible, like tracking changes in photosynthate over the course of a day or along the stem of a plant, because it’s a nondestructive assay.”

“I see incredible promise for the NANAPHID device in plant ecology. We can use the sensors at the root tip where plants give sugars to symbiotic fungi in exchange for soil nutrients,” said Dr. Horton. “Some fungi are believed to be significant carbon sinks because they produce extensive fungal networks in soils and we can use the sensors to compare the allocation of photosynthate to roots colonized by these fungi versus the allocation to less carbon demanding fungi. Further, the vast majority of these symbiotic fungi cannot be cultured in lab. These sensors will provide valuable insights into plant-microbe interactions under field conditions.”

“The creation of this new sensor will make understanding the effects of a variety of environmental changes, including climate change, on the health and productivity of forests much easier to measure,” said Dr. Templer. “For the first time, we will be able to measure concentrations of carbohydrates in living trees continuously and in real-time, expanding our ability to examine controls on photosynthesis, sap flow, carbon sequestration and other processes in forest ecosystems.”

Fascinating, eh? I wonder who made the connection between human kidneys and plants and how that person made the connection.

Poopy gold, silver, platinum, and more

In the future, gold rushes could occur in sewage plants. Precious metals have been found in large quantity by researchers investigating waste and the passage of nanoparticles (gold, silver, platinum, etc.) into our water. From a Jan. 29, 2015 news article by Adele Peters for Fast Company (Note: Links have been removed),

One unlikely potential source of gold, silver, platinum, and other metals: Sewage sludge. A new study estimates that in a city of a million people, $13 million of metals could be collecting in sewage every year, or $280 per ton of sludge. There’s gold (and silver, copper, and platinum) in them thar poop.

Funded in part by a grant for “nano-prospecting,” the researchers looked at a huge sample of sewage from cities across the U.S., and then studied several specific waste treatment plants. “Initially we thought gold was at just one or two hotspots, but we find it even in smaller wastewater treatment plants,” says Paul Westerhoff, an engineering professor at Arizona State University, who led the new study.

Some of the metals likely come from a variety of sources—we may ingest tiny particles of silver, for example, when we eat with silverware or when we drink water from pipes that have silver alloys. Medical diagnostic tools often use gold or silver. …

The metallic particles Peters is describing are nanoparticles some of which are naturally occurring  as she notes but, increasingly, we are dealing with engineered nanoparticles making their way into the environment.

Engineered or naturally occurring, a shocking quantity of these metallic nanoparticles can be found in our sewage. For example, a waste treatment centre in Japan recorded 1,890 grammes of gold per tonne of ash from incinerated sludge as compared to the 20 – 40 grammes of gold per tonne of ore recovered from one of the world’s top producing gold mines (Miho Yoshikawa’s Jan. 30, 2009 article for Reuters).

While finding it is one thing, extracting it is going to be something else as Paul Westerhoff notes in Peters’ article. For the curious, here’s a link to and a citation for the research paper,

Characterization, Recovery Opportunities, and Valuation of Metals in Municipal Sludges from U.S. Wastewater Treatment Plants Nationwide by Paul Westerhoff, Sungyun Lee, Yu Yang, Gwyneth W. Gordon, Kiril Hristovski, Rolf U. Halden, and Pierre Herckes. Environ. Sci. Technol., Article ASAP DOI: 10.1021/es505329q Publication Date (Web): January 12, 2015

Copyright © 2015 American Chemical Society

This paper is behind a paywall.

On a completely other topic, this is the first time I’ve noticed this type of note prepended to an abstract,

 Note

This article published January 26, 2015 with errors throughout the text. The corrected version published January 27, 2015.

Getting back to the topic at hand, I checked into nano-prospecting and found this Sept. 19, 2013 Arizona State University news release describing the project launch,

Growing use of nanomaterials in manufactured products is heightening concerns about their potential environmental impact – particularly in water resources.

Tiny amounts of materials such as silver, titanium, silica and platinum are being used in fabrics, clothing, shampoos, toothpastes, tennis racquets and even food products to provide antibacterial protection, self-cleaning capability, food texture and other benefits.

Nanomaterials are also put into industrial polishing agents and catalysts, and are released into the environment when used.

As more of these products are used and disposed of, increasing amounts of the nanomaterials are accumulating in soils, waterways and water-systems facilities. That’s prompting efforts to devise more effective ways of monitoring the movement of the materials and assessing their potential threat to environmental safety and human health.

Three Arizona State University faculty members will lead a research project to help improve methods of gathering accurate information about the fate of the materials and predicting when, where and how they may pose a hazard.

Their “nanoprospecting” endeavor is supported by a recently awarded $300,000 grant from the National Science Foundation.

You can find out more about Paul Westerhoff and his work here.

A hedgehog particle for safer paints and coatings?

The researchers did not extract particles from hedgehogs for this work but they are attempting to provide a description for a class of particles, which could make paints and coatings more environmentally friendly. From a Jan. 28, 2015 news item on phys.org,

A new process that can sprout microscopic spikes on nearly any type of particle may lead to more environmentally friendly paints and a variety of other innovations. Made by a team of University of Michigan engineers, the “hedgehog particles” are named for their bushy appearance under the microscope. …

A Jan. 28, 2015 University of Michigan news release (also EurekAlert), which originated the news item, describes the research,

The new process modifies oily, or hydrophobic, particles, enabling them to disperse easily in water. It can also modify water-soluble, or hydrophilic, particles, enabling them to dissolve in oil or other oily chemicals.

The unusual behavior of the hedgehog particles came as something of a surprise to the research team, says Nicholas Kotov, the Joseph B. and Florence V. Cejka Professor of Engineering.

“We thought we’d made a mistake,” Kotov said. “We saw these particles that are supposed to hate water dispersing in it and we thought maybe the particles weren’t hydrophobic, or maybe there was a chemical layer that was enabling them to disperse. But we double-checked everything and found that, in fact, these particles defy the conventional chemical wisdom that we all learned in high school.”

The team found that the tiny spikes made the particles repel each other more and attract each other less. The spikes also dramatically reduce the particles’ surface area, helping them to diffuse more easily.

One of the first applications for the particles is likely to be in paints and coatings, where toxic volatile organic compounds (VOCs) like toluene are now used to dissolve pigment. Pigments made from hedgehog particles could potentially be dissolved in nontoxic carriers like water, the researchers say.

This would result in fewer VOC emissions from paints and coatings, which the EPA [US Environmental Protection Agency] estimates at over eight million tons per year in the United States alone. VOCs can cause a variety of respiratory and other ailments and also contribute to smog and climate change. Reducing their use has become a priority for the Environmental Protection Agency and other regulatory bodies worldwide.

“VOC solvents are toxic, they’re flammable, they’re expensive to handle and dispose of safely,” Kotov said. “So if you can avoid using them, there’s a significant cost savings in addition to environmental benefits.”

While some low- and no-VOC coatings are already available, Kotov says hedgehog particles could provide a simpler, more versatile and less expensive way to manufacture them.

For the study, the team created hedgehog particles by growing zinc oxide spikes on polystyrene microbeads. The researchers say that a key advantage of the process is its flexibility; it can be performed on virtually any type of particle, and makers can vary the number and size of the spikes by adjusting the amount of time the particles sit in various solutions while the protrusions are growing. They can also make the spikes out of materials other than zinc oxide.

“I think one thing that’s really exciting about this is that we’re able to make such a wide variety of hedgehog particles,” said Joong Hwan Bahng, a chemical engineering doctoral student. “It’s very controllable and very versatile.”

The researchers say the process is also easily scalable, enabling hedgehog particles to be created “by the bucketful,” according to Kotov. Further down the road, Kotov envisions a variety of other applications, including better oil dispersants that could aid in the cleanup of oil spills and better ways to deliver non-water-soluble prescription medications.

As is becoming more common in news releases, there’s a reference to commercial partners, suggesting (to me) they might be open to offers,

“Anytime you need to dissolve an oily particle in water, there’s a potential application for hedgehog particles,” he said. “It’s really just a matter of finding the right commercial partners. We’re only just beginning to explore the uses for these particles, and I think we’re going to see a lot of applications in the future.”

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

Anomalous dispersions of ‘hedgehog’ particles by Joong Hwan Bahng, Bongjun Yeom, Yichun Wang, Siu On Tung, J. Damon Hoff, & Nicholas Kotov. Nature 517, 596–599 (29 January 2015) doi:10.1038/nature14092 Published online 28 January 2015

This paper is behind a paywall.