Monthly Archives: February 2014

Law firm, McDermott Will & Emery presents 2013 nanotechnology patent review

A report titled, ‘2013 Nanotechnology Patent Literature Review: Graphitic Carbon-Based Nanotechnology and Energy Applications Are on the Rise‘ published by the law firm, McDermott Will & Emery, was first profiled in a Feb. 13, 2014 news item on Nanowerk,

In past years, the McDermott Will & Emery Nanotechnology Group has investigated trends in nanotechnology patent literature as a means of identifying research trends, pinpointing industry leaders and clarifying the importance of the United States in this technology revolution. McDermott Will & Emery offer their Special Report “2013 Nanotechnology Patent Literature Review: Graphitic Carbon-Based Nanotechnology and Energy Applications Are on the Rise” as a continuing study of trends observed in our 2013 and 2012 reports, and also present a renewed focus on trends in the energy sector.

… the McDermott team performed a more detailed analysis of the innovation trends in graphitic carbon-based nanotechnology innovations. Graphitic carbon-based nanoparticles (fullerenes, carbon nanotubes and graphene) have unique structures that give rise to interesting electrical, spectral, thermal and mechanical properties that can be exploited in applications across many technology sectors. While some of the same trends were seen when comparing graphitic carbon-based nanotechnology innovation to nanotechnology innovation in general, some surprising observations were made with respect to graphitic carbon-based nanotechnology innovation including the following:

  • While 50 percent of the graphitic carbon-based nanotechnology patent literature published in 2013 was assigned to U.S.-based entities, Eastern Asia’s market share is about 37 percent, which is 9 percent more than for nanotechnology patent literature in general.
  • While the United States has at least one of the top three assignees in each of the six technology sectors analyzed, Eastern Asia-based companies are more prevalent players in graphitic carbon-based nanoparticles as compared to nanotechnology innovation in general.
  • The Energy sector is also the fastest-growing sector for graphitic carbon-based nanotechnology innovation, with an 18 percent increase in 2013.

A Feb. 27, 2014 posting by Iona Kaiser, Carey Jordan & Valerie Moore (of the McDermott Will & Emery law firm) for the IP Watchdog blog provides more details about the law firm’s report published earlier this month (Feb. 2014),

… According to a recent GAO report [Nanomanufacturing: Emergence and Implications for U.S. Competitiveness, the Environment, and Human Health (?) published in January 2014 and mentioned in my Feb. 10, 2014 posting], many experts in industry, government, and academia anticipate that nanotech innovations could match or exceed the economic and societal impacts of the digital revolution.  The nanomedicine market, which has been estimated at about 20 percent to about 40 percent of the overall nanotechnology market, was valued at 78.54 billion USD in 2012 and is expected to grow to 117.60 billion USD by 2019, according to a new market report published by Transparency Market Research “Nanomedicine Market (Neurology, Cardiovascular, Anti-inflammatory, Anti-infective, and Oncology Applications)–Global Industry Analysis, Size, Share, Growth, Trends and Forecast, 2013 – 2019.”

… Overall, the total volume of published nanotechnology patent literature increased 5 percent in 2013 and has more than tripled since 2003.  The number of U.S. patents issued in nanotechnology was more than 6,000 in 2013, a 17 percent increase over 2012.  Given the novelty and nonobviousness requirements of patenting, a 17 percent increase in issued U.S. patents indicates that nanotech innovation is growing rapidly.

As a measure of regional innovation and potential economic impact, the location of the assignees of nanotechnology patent literature was analyzed by region and country.  The assignee location may be a metric useful in forecasting where commercialization and economic impact will be greatest.  In a regional analysis, three epicenters for nanotechnology innovation emerge– North America, Eastern Asia, and Europe each with about 57 percent, 28 percent, and 20 percent, respectively, of the patent literature being assigned to entities residing therein. For individual countries, the U.S. maintains its dominance observed in previous years with about 54 percent of the nanotechnology patent literature published in 2013 being assigned to U.S.-based entities, followed by South Korea at 8.3 percent, Japan at 8.0 percent, and Germany at 5.8 percent.

Time will tell as to whether or not this portends a new patent thicket such as the one surrounding smartphones where the situation was sufficiently concerning that the UN held a telecommunications patent summit in 2012 (mentioned in my Oct. 10, 2012 posting). I also wrote a general piece mentioning patent trolls and other IP issues in a June 28, 2012 posting titled: ‘Billions lost to patent trolls; US White House asks for comments on intellectual property (IP) enforcement; and more on IP’.

Science publishing, ‘high impact’, reliability, and the practice of science

Konstantin Kakaes has written a provocative and astute article (Feb. 27, 2014 on Slate) about science and publishing, in particular about ‘high impact’ journals.

In 2005, a group of MIT graduate students decided to goof off in a very MIT graduate student way: They created a program called SCIgen that randomly generated fake scientific papers. Thanks to SCIgen, for the last several years, computer-written gobbledygook has been routinely published in scientific journals and conference proceedings. [emphasis mine]

Apparently some well known science publishers have been caught (from the Kakaes article; Note: A link has been removed),

According to Nature News, Cyril Labbé, a French computer scientist, recently informed Springer and the IEEE, two major scientific publishers, that between them, they had published more than 120 algorithmically-generated articles. In 2012, Labbé had told the IEEE of another batch of 85 fake articles. He’s been playing with SCIgen for a few years—in 2010 a fake researcher he created, Ike Antkare, briefly became the 21st most highly cited scientist in Google Scholar’s database.

Kakaes goes on to explain at least in part why this problem has arisen,

Over the course of the second half of the 20th century, two things took place. First, academic publishing became an enormously lucrative business. And second, because administrators erroneously believed it to be a means of objective measurement, the advancement of academic careers became conditional on contributions to the business of academic publishing.

As Peter Higgs said after he won last year’s Nobel Prize in physics, “Today I wouldn’t get an academic job. It’s as simple as that. I don’t think I would be regarded as productive enough.” Jens Skou, a 1997 Nobel Laureate, put it this way in his Nobel biographical statement: today’s system puts pressure on scientists for, “too fast publication, and to publish too short papers, and the evaluation process use[s] a lot of manpower. It does not give time to become absorbed in a problem as the previous system [did].”

Today, the most critical measure of an academic article’s importance is the “impact factor” of the journal it is published in. The impact factor, which was created by a librarian named Eugene Garfield in the early 1950s, measures how often articles published in a journal are cited. Creating the impact factor helped make Garfield a multimillionaire—not a normal occurrence for librarians.

The concern about ‘impact factors’ high or low with regard to science publishing is a discussion I first stumbled across and mentioned in an April 22, 2010 posting where I noted the concern with metrics extends beyond an individual career or university’s reputation but also affects national reputations. Kostas Kostarelos in a Jan. 24, 2014 posting on the Guardian science blogs notes this in his discussion of how China’s policies could affect the practice of science (Note: Links have been removed),

…  For example, if a Chinese colleague publishes an article in a highly regarded scientific journal they will be financially rewarded by the government – yes, a bonus! – on the basis of an official academic reward structure. Publication in one of the highest impact journals is currently rewarded with bonuses in excess of $30,000 – which is surely more than the annual salary of a starting staff member in any lab in China.

Such practices are disfiguring the fundamental principles of ethical integrity in scientific reporting and publishing, agreed and accepted by the scientific community worldwide. They introduce motives that have the potential to seriously corrupt the triangular relationship between scientist or clinician, publisher or editor and the public (taxpayer) funding agency. They exacerbate the damage caused by journal quality rankings based on “impact factor”, which is already recognised by the scientific community in the west as problematic.

Such measures also do nothing to help Chinese journals gain recognition by the rest of the world, as has been described by two colleagues from Zhejiang University in an article entitled “The outflow of academic articles from China: why is it happening and can it be stemmed?”.

At this point we have a system that rewards (with jobs, bonuses, etc.) prolific publication of one’s science achieved either by the sweat of one’s brow (and/or possibly beleaguered students’ brows) or from a clever algorithm. It’s a system that encourages cheating and distorts any picture we might have of scientific achievement on a planetary, national, regional, university, or individual basis.

Clearly we need to do something differently. Kakaes mentions an initiative designed for that purpose, the San Francisco Declaration on Research Assessment (DORA). Please do let me know in the Comments section if there are any other such efforts.

Governing in the Dark; a March 5, 2014 national (Canada) lecture

I think it’s pretty easy to guess the perspective from the title of the lecture, Governing in the Dark: Evidence, Accountability and the Future of Canadian Science (the third in a series titled, The Lives of Evidence) being offered by the Situating Science project on March 5,2014. Here’s more about it from the event page,

The national Situating Science project and partners are pleased to present the third talk in the national lecture series:

The Lives of Evidence
A multi-part national lecture series examining the cultural, ethical, political, and scientific role of evidence in our world.

Part 3:
Governing in the Dark: Evidence, Accountability and the Future of Canadian Science

Scott Findlay, Co-founder of Evidence for Democracy and Associate Professor of Biology, University of Ottawa.
Wednesday, March 5, 2014, 7:30 PM
Ondaatje Hall, McCain Building, Dalhousie University, 6135 University Ave.,
Halifax, NS

Watch live online here! (7:30 PM Atlantic / 6:30 PM ET)

Scientists are becoming increasingly concerned about the Canadian government’s attitude towards science. They are concerned about declining federal investment in public interest science; a shift away from federal funding of basic research to business-oriented research; policies that restrict the communication of scientific information among government scientists and to the public; and – despite assurances to the contrary from federal ministers – an increasingly cavalier attitude towards science-informed decision-making. Are these symptoms of an ongoing erosion of basic democratic principles? What are some possible therapeutic and preventative interventions?

Supported by:
Dalhousie University Department of Physics and Atmospheric Science, Evidence for Democracy, and Canadian Centre for Ethics in Public Affairs

I last mentioned the speaker, Scott Findlay, in an Oct. 4, 2013 posting in the context of a series of protests (Stand up for Science) organized for Fall 2013.

Water desalination by graphene and water purification by sapwood

I have two items about water. The first concerns a new technique from MIT (Massachusetts Institute of Technology) for desalination using graphene and sapwood, respectively*. From a Feb. 25, 2014 news release by David Chandler on EurekAlert,

Researchers have devised a way of making tiny holes of controllable size in sheets of graphene, a development that could lead to ultrathin filters for improved desalination or water purification.

The team of researchers at MIT, Oak Ridge National Laboratory, and in Saudi Arabia succeeded in creating subnanoscale pores in a sheet of the one-atom-thick material, which is one of the strongest materials known. …

The concept of using graphene, perforated by nanoscale pores, as a filter in desalination has been proposed and analyzed by other MIT researchers. The new work, led by graduate student Sean O’Hern and associate professor of mechanical engineering Rohit Karnik, is the first step toward actual production of such a graphene filter.

Making these minuscule holes in graphene — a hexagonal array of carbon atoms, like atomic-scale chicken wire — occurs in a two-stage process. First, the graphene is bombarded with gallium ions, which disrupt the carbon bonds. Then, the graphene is etched with an oxidizing solution that reacts strongly with the disrupted bonds — producing a hole at each spot where the gallium ions struck. By controlling how long the graphene sheet is left in the oxidizing solution, the MIT researchers can control the average size of the pores.

A big limitation in existing nanofiltration and reverse-osmosis desalination plants, which use filters to separate salt from seawater, is their low permeability: Water flows very slowly through them. The graphene filters, being much thinner, yet very strong, can sustain a much higher flow. “We’ve developed the first membrane that consists of a high density of subnanometer-scale pores in an atomically thin, single sheet of graphene,” O’Hern says.

For efficient desalination, a membrane must demonstrate “a high rejection rate of salt, yet a high flow rate of water,” he adds. One way of doing that is decreasing the membrane’s thickness, but this quickly renders conventional polymer-based membranes too weak to sustain the water pressure, or too ineffective at rejecting salt, he explains.

With graphene membranes, it becomes simply a matter of controlling the size of the pores, making them “larger than water molecules, but smaller than everything else,” O’Hern says — whether salt, impurities, or particular kinds of biochemical molecules.

The permeability of such graphene filters, according to computer simulations, could be 50 times greater than that of conventional membranes, as demonstrated earlier by a team of MIT researchers led by graduate student David Cohen-Tanugi of the Department of Materials Science and Engineering. But producing such filters with controlled pore sizes has remained a challenge. The new work, O’Hern says, demonstrates a method for actually producing such material with dense concentrations of nanometer-scale holes over large areas.

“We bombard the graphene with gallium ions at high energy,” O’Hern says. “That creates defects in the graphene structure, and these defects are more chemically reactive.” When the material is bathed in a reactive oxidant solution, the oxidant “preferentially attacks the defects,” and etches away many holes of roughly similar size. O’Hern and his co-authors were able to produce a membrane with 5 trillion pores per square centimeter, well suited to use for filtration. “To better understand how small and dense these graphene pores are, if our graphene membrane were to be magnified about a million times, the pores would be less than 1 millimeter in size, spaced about 4 millimeters apart, and span over 38 square miles, an area roughly half the size of Boston,” O’Hern says.

With this technique, the researchers were able to control the filtration properties of a single, centimeter-sized sheet of graphene: Without etching, no salt flowed through the defects formed by gallium ions. With just a little etching, the membranes started allowing positive salt ions to flow through. With further etching, the membranes allowed both positive and negative salt ions to flow through, but blocked the flow of larger organic molecules. With even more etching, the pores were large enough to allow everything to go through.

Scaling up the process to produce useful sheets of the permeable graphene, while maintaining control over the pore sizes, will require further research, O’Hern says.

Karnik says that such membranes, depending on their pore size, could find various applications. Desalination and nanofiltration may be the most demanding, since the membranes required for these plants would be very large. But for other purposes, such as selective filtration of molecules — for example, removal of unreacted reagents from DNA — even the very small filters produced so far might be useful.

“For biofiltration, size or cost are not as critical,” Karnik says. “For those applications, the current scale is suitable.”

Dexter Johnson in a Feb. 26,2014 posting provides some context for and insight into the work (from the Nanoclast blog on the IEEE [Institute of Electrical and Electronics Engineers]), Note: Links have been removed,

About 18 months ago, I wrote about an MIT project in which computer models demonstrated that graphene could act as a filter in the desalination of water through the reverse osmosis (RO) method. RO is slightly less energy intensive than the predominantly used multi-stage-flash process. The hope was that the nanopores of the graphene material would make the RO method even less energy intensive than current versions by making it easier to push the water through the filter membrane.

The models were promising, but other researchers in the field said at the time it was going to be a long road to translate a computer model to a real product.

It would seem that the MIT researchers agreed it was worth the effort and accepted the challenge to go from computer model to a real device as they announced this week that they had developed a method for creating selective pores in graphene that make it suitable for water desalination.

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

Selective Ionic Transport through Tunable Subnanometer Pores in Single-Layer Graphene Membranes by Sean C. O’Hern, Michael S. H. Boutilier, Juan-Carlos Idrobo, Yi Song, Jing Kong, Tahar Laoui, Muataz Atieh, and Rohit Karnik. Nano Lett., Article ASAP DOI: 10.1021/nl404118f Publication Date (Web): February 3, 2014

Copyright © 2014 American Chemical Society

This article is behind a paywall.

The second item is also from MIT and concerns a low-tech means of purifying water. From a Feb. 27, 2014 news item on Azonano,

If you’ve run out of drinking water during a lakeside camping trip, there’s a simple solution: Break off a branch from the nearest pine tree, peel away the bark, and slowly pour lake water through the stick. The improvised filter should trap any bacteria, producing fresh, uncontaminated water.

In fact, an MIT team has discovered that this low-tech filtration system can produce up to four liters of drinking water a day — enough to quench the thirst of a typical person.

In a paper published this week in the journal PLoS ONE, the researchers demonstrate that a small piece of sapwood can filter out more than 99 percent of the bacteria E. coli from water. They say the size of the pores in sapwood — which contains xylem tissue evolved to transport sap up the length of a tree — also allows water through while blocking most types of bacteria.

Co-author Rohit Karnik, an associate professor of mechanical engineering at MIT, says sapwood is a promising, low-cost, and efficient material for water filtration, particularly for rural communities where more advanced filtration systems are not readily accessible.

“Today’s filtration membranes have nanoscale pores that are not something you can manufacture in a garage very easily,” Karnik says. “The idea here is that we don’t need to fabricate a membrane, because it’s easily available. You can just take a piece of wood and make a filter out of it.”

The Feb. 26, 2014 news release on EurekAlert, which originated the news item, describes current filtration techniques and the advantages associated with this new low-tech approach,

There are a number of water-purification technologies on the market today, although many come with drawbacks: Systems that rely on chlorine treatment work well at large scales, but are expensive. Boiling water to remove contaminants requires a great deal of fuel to heat the water. Membrane-based filters, while able to remove microbes, are expensive, require a pump, and can become easily clogged.

Sapwood may offer a low-cost, small-scale alternative. The wood is comprised of xylem, porous tissue that conducts sap from a tree’s roots to its crown through a system of vessels and pores. Each vessel wall is pockmarked with tiny pores called pit membranes, through which sap can essentially hopscotch, flowing from one vessel to another as it feeds structures along a tree’s length. The pores also limit cavitation, a process by which air bubbles can grow and spread in xylem, eventually killing a tree. The xylem’s tiny pores can trap bubbles, preventing them from spreading in the wood.

“Plants have had to figure out how to filter out bubbles but allow easy flow of sap,” Karnik observes. “It’s the same problem with water filtration where we want to filter out microbes but maintain a high flow rate. So it’s a nice coincidence that the problems are similar.”

The news release also describes the experimental procedure the scientists followed (from the news release),

To study sapwood’s water-filtering potential, the researchers collected branches of white pine and stripped off the outer bark. They cut small sections of sapwood measuring about an inch long and half an inch wide, and mounted each in plastic tubing, sealed with epoxy and secured with clamps.

Before experimenting with contaminated water, the group used water mixed with red ink particles ranging from 70 to 500 nanometers in size. After all the liquid passed through, the researchers sliced the sapwood in half lengthwise, and observed that much of the red dye was contained within the very top layers of the wood, while the filtrate, or filtered water, was clear. This experiment showed that sapwood is naturally able to filter out particles bigger than about 70 nanometers.

However, in another experiment, the team found that sapwood was unable to separate out 20-nanometer particles from water, suggesting that there is a limit to the size of particles coniferous sapwood can filter.

Finally, the team flowed inactivated, E. coli-contaminated water through the wood filter. When they examined the xylem under a fluorescent microscope, they saw that bacteria had accumulated around pit membranes in the first few millimeters of the wood. Counting the bacterial cells in the filtered water, the researchers found that the sapwood was able to filter out more than 99 percent of E. coli from water.

Karnik says sapwood likely can filter most types of bacteria, the smallest of which measure about 200 nanometers. However, the filter probably cannot trap most viruses, which are much smaller in size.

The researchers have future plans (from the news release),

Karnik says his group now plans to evaluate the filtering potential of other types of sapwood. In general, flowering trees have smaller pores than coniferous trees, suggesting that they may be able to filter out even smaller particles. However, vessels in flowering trees tend to be much longer, which may be less practical for designing a compact water filter.

Designers interested in using sapwood as a filtering material will also have to find ways to keep the wood damp, or to dry it while retaining the xylem function. In other experiments with dried sapwood, Karnik found that water either did not flow through well, or flowed through cracks, but did not filter out contaminants.

“There’s huge variation between plants,” Karnik says. “There could be much better plants out there that are suitable for this process. Ideally, a filter would be a thin slice of wood you could use for a few days, then throw it away and replace at almost no cost. It’s orders of magnitude cheaper than the high-end membranes on the market today.”

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

Water Filtration Using Plant Xylem by Michael S. H. Boutilier, Jongho Lee, Valerie Chambers, Varsha Venkatesh, & Rohit Karnik. PLOS One Published: February 26, 2014 DOI: 10.1371/journal.pone.0089934

This paper is open access.

One final observation, two of the researchers (Michael S. H. Boutilier & Rohit Karnik) listed as authors on the graphene/water desalination paper are also listed on the low-tech sapwood paper solution.*

* The first sentence of the this post originally stated both items were graphene-related, it has been changed to say 1… using graphene and sapwood, respectively*’ on May 8, 2015.

The last sentence of this post was changed from

‘One final observation, two of the researchers listed as authors on the graphene/water desalination paper are also listed on the low-tech sapwood paper (Michael S. H. Boutilier & Rohit Karnik).’

to this

‘One final observation, two of the researchers (Michael S. H. Boutilier & Rohit Karnik) listed as authors on the graphene/water desalination paper are also listed on the low-tech sapwood paper solution.*’ for clarity on May 8, 2015.

Glass as a sponge

A glass sponge which can be found at the bottom of either the Indian and Pacific oceans is inspiring a group of physicists at the Max Planck Institute of Colloids and Interfaces according to a Feb. 25, 2014 news item on Azonano,

… Recently, Igor Zlotnikov and Peter Fratzl, who study biomaterials at the Max Planck Institute of Colloids and Interfaces in collaboration with the team of Peter Werner from the Max Planck Institute of Microstructure Physics, Emil Zolotoyabko from the Israeli Institute of Technology and Yannicke Dauphin from the Université P. & M. Curie, have discovered a mesoporous material in nature, namely in the glass sponge Monorhaphis chuni. The sponge lives on the bottom of the Indian and Pacific Oceans, and forms an approximately one-centimetre-thick glass rod to attach itself to the ocean’s floor. Over the course of its life, the rod can grow up to three meters in length. The glass filament, passing through the centre of this rod, is perforated with pores having a diameter of about five nanometres. Each pore is occupied by an egg-shaped protein molecule, called silicatein, connected to the protein molecules in adjacent pores through holes in the glass.

The Feb. 24, 2014 Max Planck Institute of Colloids and Interfaces news release, which originated the news item, explains the importance of nanoporous or mesoporous materials, natural and manufactured,

The amount of surface area often plays an important role in materials used in medicine and technology and normally, it should be as large as possible. It can accommodate, for instance, large quantities of pharmaceutical agents and release them gradually in the body. In chemistry, the efficiency of numerous processes is dependent on catalysts exhibiting a large surface on which reactions can occur. In sensors, for example, the sensitivity is strongly dependent on the amount of surface to which the detected molecules can attach. Porous structures are a good example for such materials.

Materials having pores measuring between 2 to 50 nanometres are particularly well suited for such purposes. Scientists refer to these as mesoporous structures, to distinguish them from structures that are microporous, having smaller pores, or macroporous, with larger pores.

Having discovered the glass sponge’s Monorhaphis chuni, ability to create a mesoporous material (a glass filament), the researchers attempted further studies, from the news release,

“Mesoporous glass structures are among the most studied materials. This makes it even more exiting to find them in nature,” says Igor Zlotnikov. “Presumably, this structure is not limited to M. chuni, but can also occur in other glass sponges.” However, not only does M. chuni produces a mesoporous material that is technologically relevant; the sponge sets standards in terms of size distribution and arrangement of the pores. In the sample that Igor Zlotnikov and his colleagues studied, all pores have the size of the inhabiting protein molecule and they are completely regularly arranged. Metaphorically speaking, the structure resembles egg cartons that are stacked one on top of another like pallets.

The researchers used two characterization techniques to gain an accurate picture of the internal architecture of the filament. First, they employed X-ray analysis at the BESSY II synchrotron facility in Berlin. Experiments with X-ray diffraction usually serve to identify the atomic periodic structure of crystals. However, Igor Zlotnikov’s team used a variant of this technology to reveal structural periodicity on a larger scale, namely, on the scale of the pores size and their spatial arrangement. The results were confirmed in cooperation with the team working with Peter Werner from the Max Planck Institute of Microstructure Physics using high resolution transmission electron microscopy. In addition to structural details, this technique allows researchers to make assertions about local chemical composition.

But what surprised the researchers even more than the periodicity of the structure that was revealed is the way in which M. chuni produces it: “It’s absolutely astonishing that nature and mankind converged on a similar manufacturing method independently”, says Peter Fratzl, Director at the Max Planck Institute of Colloids and Interfaces. To continue with the image of the egg cartons, the glass sponge first stacks one or maybe even several layers of eggs – that is, protein molecules – and then fills the gaps with cardboard, or in this case glass.

Here’s an image the researchers have provided to illustrate their ‘egg carton’ analogy,

 Pore distribution in the glass filament resembles stacked, pallet-like egg cartons. Each cavity is occupied by one protein molecule, called silicatein, measuring approximately five nanometres in size. © Igor Zlotnikov / MPI of Colloids and Interfaces

Pore distribution in the glass filament resembles stacked, pallet-like egg cartons. Each cavity is occupied by one protein molecule, called silicatein, measuring approximately five nanometres in size. © Igor Zlotnikov / MPI of Colloids and Interfaces

Even though humans have managed a similar engineering feat, it appears Nature has more successfully controlled sizes and mechanical properties (from the news release),

Since the protein molecules, which serve as a kind of a model for the surrounding glass structure, are all in the same size, the pores in the obtained material also have the same diameter and form a completely uniform structure. Achieving this precision via synthetic methods is difficult, even though the mesoporous glass is created in a very similar manner. Here, organic droplets around which the glass is produced determine the pore shape. Subsequently, the droplets are dissolved out of the nanostructure using a detergent – in principle, nothing other than a dishwashing liquid. However, scientists can’t adjust the size of the droplets as precisely as the biochemical apparatus of a living organism that controls the size of the proteins. Thus, the pore size in synthetic mesoporous materials varies, and the cavities don’t arrange themselves into a perfectly regular pattern.

“With silicatein or other proteins, it would be possible to produce mesoporous materials having a completely uniform pore size and a perfectly periodic arrangement”, says Igor Zlotnikov. “That would be very expensive.” Mimicking regularly structured materials similar to those found in M. chuni, for the time being, is not the goal of Max Planck researchers. They are currently investigating whether the mesoporous structure is as uniform over large regions of the glass filament as it is in the 100 micrometer section they analysed for the current publication. “Besides that, we focus on the relationship between the structure and the mechanical properties of the entire glass rod”, says Peter Fratzl. Also there, M. chuni sets standards in terms of structural optimization to enhance its mechanical behaviour.

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

A Perfectly Periodic Three-Dimensional Protein/Silica Mesoporous Structure Produced by an Organism by Igor Zlotnikov, Peter Werner, Horst Blumtritt, Andreas Graff, Yannicke Dauphin, Emil Zolotoyabko, & Peter Fratzl. Advanced Materials. Article first published online: 12 DEC 2013 DOI: 10.1002/adma.201304696

© 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

This paper is behind a paywall.

Traffic robots in Kinshasa (Democratic Republic of the Congo) developed by an all women team of engineers

Kinshasa, the capital of the Democratic Republic of the Congo (DRC), now hosts two traffic cop robots with hopes for more of these solar-powered traffic regulators on the way. Before plunging into the story, here’s a video of these ‘gendarmes automates’ (or robot roulage intelligent [RRR] as the inventors prefer) in action,

This story has been making the English language news rounds since late last year when Voxafrica carried a news item, dated Dec. 27, 2013, about the robot traffic cops,

Kinshasa has adopted an innovative way of managing traffic along its city streets, by installing robot cops to direct and monitor traffic along roads instead of using normal policemen to reduce congestion. … They may not have real eyes, but new traffic policemen still spot Kinshasa’s usual signature cop sunglasses. The prototypes are equipped with four cameras that allow them to record traffic flow … . The team behind the new robots are a group of Congolese engineers based at the Kinshasa Higher Institute of Applied Technique, known by its French acronym, ISTA.

A Jan. 30, 2014 article by Matt McFarland for the Washington Post provides additional detail (Note: A link has been removed),

The solar-powered robot is equipped with multiple cameras, opening the potential for monitoring traffic and issuing tickets. “If a driver says that it is not going to respect the robot because it’s just a machine the robot is going to take that and there will be a ticket for him,” said Isaie Therese, the engineer behind the project said in an interview with CCTV Africa. “We are a poor country and our government is looking for money. And I will tell you that with the roads the government has built, it needs to recover its money.”

A Feb. 24, 2014 CNN article by Teo Kermeliotis describes the casings for the robots,

Standing eight feet tall, the robot traffic wardens are on duty 24 hours a day, their towering — even scarecrow-like — mass visible from afar. …

The humanoids, which are installed on Kinshasa’s busy Triomphal and Lumumba intersections, are built of aluminum and stainless steel to endure the city’s year-round hot climate.

The French language press, as might be expected since DRC is a francophone country, were the first to tell the story.  From a June 28, 2013 news item on Radio Okapi’s website,

Les ingénieurs formés à l’Institut supérieur des techniques appliquées (Ista) ont mis au point un robot intelligent servant à réguler la circulation routière. …

Ce robot qui fonctionne grâce à l’énergie solaire, assurera aussi la sécurité routière grâce à la vidéo surveillance. Il est doté de la capacité de stocker les données pendant 6 mois.

Le “robot roulage intelligent” est une invention totalement congolaise. Il a été mis au point par les inventeurs congolais avec l’appui financier de l’association Women technologies, une association des femmes ingénieurs de la RDC.

Ce spécimen coûte près de 20 000 $ US. L’association Women technologies attend le financement du gouvernement pour reproduire ce robot afin de le mettre à la disposition des usagers et même, de l’exporter.

Here’s my very rough translation of the French: an engineering team from the Kinshasa Higher Institute of Applied Technique (ISTA) developed an intelligent automated traffic cop. This intelligent traffic cop is a Congolese invention from design to development fo funding. The prototype, which cost $20,000 US, was funded by the ‘Association Women Technologies’, a DRC (RDC is the abbreviation in French) association of women engineers, who were in June 2013 hoping for additional government funds to implement their traffic solution. Clearly, they received the money.

A January 30, 2014 news item on AfricaNouvelles focussed on the lead engineer and the team’s hopes for future exports of their technology,

Maman Thérèse Inza est ingénieure et responsable des robots régulateurs de la circulation routière à Kinshasa.

L’association Women technologies attend l’accompagnement du gouvernement pour pouvoir exporter des robots à l’international.

Bruno Bonnell’s Feb. 11, 2014 (?) article for Les Echos delves more deeply into the project and the team’s hopes of exporting their technology,

Depuis octobre 2013, le « roulage » au carrefour du Parlement, sur le boulevard Lumumba à Kinshsa, n’est plus assuré par un policier. Un robot en aluminium de 2,50 mètre de haut régule la circulation d’une des artères principales de la capitale congolaise. …

« Un robot qui fait la sécurité et la régulation routières, c’est vraiment made in Congo », assure Thérèse Inza, la présidente de l’association Women Technology, qui a construit ces machines conçues pour résister aux rigueurs du climat équatorial et dont l’autonomie est assurée par des panneaux solaires, dans des quartiers qui ne sont pas reliés au réseau électrique. La fondatrice de l’association voulait à l’origine proposer des débouchés aux femmes congolaises titulaires d’un diplôme d’ingénieur. Grâce aux robots, elle projette désormais de créer des emplois dans tout le pays. … Ces RRI prouvent que la robotique se développe aussi en Afrique. Audacieuse, Thérèse Inza affirme : « Nous devons vendre notre intelligence dans d’autres pays, de l’Afrique centrale comme d’ailleurs. Pourquoi pas aux Etats-Unis, en Europe ou en Asie ? » Entre 2008 et 2012, la demande de bande passante a été multipliée par 20 en Afrique, continent où sont nés le système de services bancaires mobiles M-Pesa et la plate-forme de gestion de catastrophe naturelle Ushahidi, utilisés aujourd’hui dans le monde entier. Et si la robotique, dont aucun pays n’a le monopole, était pour l’Afrique l’opportunité industrielle à ne pas rater ?

Here’s my rough translation, the first implementation was a single robot in October 2013 (the other details have already been mentioned here). The second paragraph describes how and why Thérèse Inza developed the project in the first place. The robot was designed specifically for the equatorial climate and for areas where access to electricity is either nonexistent or difficult. She recruited women engineers from ISTA for her team. I think she was initially trying to create jobs for women engineers. Now the robots have been successful, she’s hoping to create more jobs for everyone throughout the DRC and to export the technology to the US, Europe, and Asia.

The last sentence notes that Africa (Kenya) was the birthplace of mobile banking service, M-Pesa, “the most developed mobile payment system in the world” according to Wikipedia and Ushahidi, a platform which enables crowdsourced reporting and information about natural and other disasters.

Ushahidi, like M-Pesa, was also developed in Kenya. I found this Feb. 27, 2014 article  by Herman Manson on about Ushahidi and one of its co-founders, Juliana Rotich (Note: A link has been removed),

Rotich [Juliana Rotich] is the co-founder of Ushahidi, the open-source software developed in Kenya which came to the fore and caught global attention for collecting, visualising and mapping information in the aftermath of the disputed 2008 elections.

Rotich challenges the legacies that have stymied the development of Africa’s material and cultural resources — be that broadband cables connecting coastal territories and ignoring the continent’s interior — or the political classes continuing to exploit its citizens.

Ushahidi means “witness” or “testimony”, and allows ordinary people to crowd source and map information, turning them into everything from election monitors reporting electoral misconduct to helpers assisting with the direction of emergency response resources during natural disasters.

The open source software is now available in 30 languages and across the globe.

The Rotich article is a preview of sorts for Design Indaba 2014 being held in Cape Town, South Africa, from Feb. 24, 2014 = March 2, 2014.

Getting back to the robot traffic cops, perhaps one day the inventors will come up with a design that runs on rain and an implementation that can function in either Vancouver.

Silver ions in the environment

Earlier this week (Feb. 24, 2014), I published a post featuring Dr. Andrew Maynard, Director of the University of Michigan’s Risk Science Center in an introductory video describing seven surprising facts about silver nanoparticles. For those who want to delve more deeply, there’s a Feb. 25, 2014 news item on Nanowerk describing some Swiss research into silver nanoparticles and ions in aquatic environments,

It has long been known that, in the form of free ions, silver particles can be highly toxic to aquatic organisms. Yet to this day, there is a lack of detailed knowledge about the doses required to trigger a response and how the organisms deal with this kind of stress. To learn more about the cellular processes that occur in the cells, scientists from the Aquatic Research Institute, Eawag [Swiss Federal Institute of Aquatic Science and Technology], subjected algae to a range of silver concentrations.

In the past, silver mostly found its way into the environment in the vicinity of silver mines or via wastewater [emphasis mine] emanating from the photo industry. More recently, silver nanoparticles have become commonplace in many applications – as ingredients in cosmetics, food packaging, disinfectants, and functional clothing. Though a recent study conducted by the Swiss National Science Foundation revealed that the bulk of silver nanoparticles is retained in wastewater treatment plants, only little is known about the persistence and the impact of the residual nano-silver in the environment.

The Feb. 25, 2014 Eawag media release, which originated the news item, describes the research in further detail,

Smitha Pillai from the Eawag Department of Environmental Toxicology and her colleagues from EPF Lausanne and ETH Zürich studied the impact of various concentrations of waterborne silver ions on the cells of the green algae Chlamydomonas reinhardtii. Silver is chemically very similar to copper, an essential metal due to its importance in several enzymes. Because of that, silver can exploit the cells’ copper transport mechanisms and sneak into them undercover. This explains why, already after a short time, concentrations of silver in the intracellular fluid can reach up to one thousand times those in the surrounding environment.

A prompt response

Because silver damages key enzymes involved in energy metabolism, even low concentrations can cut photosynthesis and growth rates by a half in just 15 minutes. Over the same time period, the researchers also detected changes in the activity of about 1000 other genes and proteins, which they interpreted as a response to the stressor – an attempt to repair silver-induced damage. At low concentrations, the cells’ photosynthesis apparatus recovered within five hours, and recovery mechanisms were sufficient to deal with all but the highest concentrations tested.

A number of unanswered questions

At first glance, the results are reassuring because the silver concentrations that the algae are subject to in the environment are rarely as high as those applied in the lab, which allows them to recover quickly – at least externally. But the experiments also showed that even low silver concentrations have a significant effect on intracellular processes and that the algae divert their energy to repairing damage incurred. This can pose a problem when other stressors act in parallel, such as increased UV-radiation or other chemical compounds. Moreover, it remains unknown to this day whether the cells have an active mechanism to shuttle out the silver. Lacking such a mechanism, the silver could have adverse effects on higher organisms, given that algae are at the bottom of the food chain.

You can find the researchers’ paper here,

Linking toxicity and adaptive responses across the transcriptome, proteome, and phenotype of Chlamydomonas reinhardtii exposed to silver by Smitha Pillai, Renata Behra, Holger Nestler, Marc J.-F. Suter, Laura Sigg, and Kristin Schirmer. Proceedings of the National Academy of Sciences (PNAS) – early edition 18.February 2014,

The paper is available through the PNAS open access option.

I have published a number of pieces about aquatic enviornments and wastewater and nanotechnology-enabled products as useful for remediation efforts and as a source of pollution. Here’s a Feb. 28, 2013 posting where I contrasted two pieces of research on silver nanoparticles. The first was research in an aquatic environment and the other concerned wastewater.

Cleaning up oil* spills with cellulose nanofibril aerogels

Given the ever-expanding scope of oil and gas production as previously impossible to reach sources are breached and previously unusable contaminated sources are purified for use while major pipelines and mega tankers are being built to transport all this product, it’s good to see that research into cleaning up oil spills is taking place. A Feb. 26, 2014 news item on Azonano features a project at the University of Wisconsin–Madison,

Cleaning up oil spills and metal contaminates in a low-impact, sustainable and inexpensive manner remains a challenge for companies and governments globally.

But a group of researchers at the University of Wisconsin–Madison is examining alternative materials that can be modified to absorb oil and chemicals without absorbing water. If further developed, the technology may offer a cheaper and “greener” method to absorb oil and heavy metals from water and other surfaces.

Shaoqin “Sarah” Gong, a researcher at the Wisconsin Institute for Discovery (WID) and associate professor of biomedical engineering, graduate student Qifeng Zheng, and Zhiyong Cai, a project leader at the USDA Forest Products Laboratory in Madison, have recently created and patented the new aerogel technology.

The Feb. 25, 2014 University of Wisconsin–Madison news release, which originated the news item, explains a little bit about aergels and about what makes these cellulose nanofibril-based aerogels special,

Aerogels, which are highly porous materials and the lightest solids in existence, are already used in a variety of applications, ranging from insulation and aerospace materials to thickening agents in paints. The aerogel prepared in Gong’s lab is made of cellulose nanofibrils (sustainable wood-based materials) and an environmentally friendly polymer. Furthermore, these cellulose-based aerogels are made using an environmentally friendly freeze-drying process without the use of organic solvents.

It’s the combination of this “greener” material and its high performance that got Gong’s attention.

“For this material, one unique property is that it has superior absorbing ability for organic solvents — up to nearly 100 times its own weight,” she says. “It also has strong absorbing ability for metal ions.”

Treating the cellulose-based aerogel with specific types of silane after it is made through the freeze-drying process is a key step that gives the aerogel its water-repelling and oil-absorbing properties.

The researchers have produced a video showing their aerogel in operation,

For those who don’t have the time for a video, the news release describes some of the action taking place,

“So if you had an oil spill, for example, the idea is you could throw this aerogel sheet in the water and it would start to absorb the oil very quickly and efficiently,” she says. “Once it’s fully saturated, you can take it out and squeeze out all the oil. Although its absorbing capacity reduces after each use, it can be reused for a couple of cycles.”

In addition, this cellulose-based aerogel exhibits excellent flexibility as demonstrated by compression mechanical testing.

Though much work needs to be done before the aerogel can be mass-produced, Gong says she’s eager to share the technology’s potential benefits beyond the scientific community.

“We are living in a time where pollution is a serious problem — especially for human health and for animals in the ocean,” she says. “We are passionate to develop technology to make a positive societal impact.”

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

Green synthesis of polyvinyl alcohol (PVA)–cellulose nanofibril (CNF) hybrid aerogels and their use as superabsorbents by Qifeng Zheng, Zhiyong Cai, and Shaoqin Gong.  J. Mater. Chem. A, 2014,2, 3110-3118 DOI: 10.1039/C3TA14642A First published online 16 Dec 2013

This paper is behind a paywall. I last wrote about oil-absorbing nanosponges in an April 17, 2012 posting. Those sponges were based on carbon nanotubes (CNTs).

* ‘oils’ in headline changed to ‘oil’ on May 6, 2014.

Prussian blue nanocubes and ultralightweight iron oxide materials

The research itself concerns the synthesis of ultralight iron oxide frameworks but really caught my attention was the image used to illustrate the work and the term ‘Prussian blue nanocubes’,

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I believed the image is meant to indicate an ultralight iron anvil resting on the head of a rose-like blossom (I was mostly wrong) as you’ll see in this Feb. 25, 2014 news item on Nanowerk (Note: A link has been removed),

Adsorption, catalysis, or substrates for tissue growth: porous materials have many potential applications. In the journal Angewandte Chemie (“Ultralight Mesoporous Magnetic Frameworks by Interfacial Assembly of Prussian Blue Nanocubes”), a team of Chinese and Australian researchers has now introduced a method for the synthesis of ultralight three-dimensional (3D) iron oxide frameworks with two different types of nanoscopic pores and tunable surface properties. This superparamagnetic material can be cut into arbitrary shapes and is suitable for applications such as multiphase catalysis and the removal of heavy metal ions and oil from water.

Materials with hierarchically organized pore systems—meaning that the walls of macropores with diameters in the micrometer range contain mesopores of just a few nanometers—are high on the wish lists of materials researchers. The advantages of these materials include their high surface area and the easy accessibility of the small pores through the larger ones. The great desirability of these materials is matched by the degree of difficulty in producing them on an industrial scale.

Scientists at Fudan University (China) and Monash University (Australia) have now successfully produced an ultralight iron oxide framework with 250 µm and 18 nm pores in a process that can be used on an industrial scale. A team led by Gengfeng Zheng and Dongyuan Zhao used highly porous polyurethane sponges as a “matrix”, which were soaked with yellow potassium hexacyanoferrate (K4[Fe(CN)6]). Subsequent hydrolysis resulted in cubic nanocrystals of Prussian blue (iron hexacyanoferrate), a dark blue pigment, which were deposited all over the surfaces of the sponge. The polyurethane sponge was then fully burned away through pyroloysis and the Prussian blue was converted to iron oxide. The result is a 3D framework of iron oxide cubes that are in turn made of iron oxide nanoparticles and contain mesopores. The material is so light that the researchers were able to balance a 240 cm3 piece on an oleander blossom.

As for Prussian blue, it’s a term I associate with portraits and landscapes. Actually, Prussian blue is a little more than that (from the Prussian blue entry on,

Prussian blue (plural Prussian blues)

(inorganic chemistry) An insoluble dark, bright blue pigment, ferric ferrocyanide (equivalent to ferrous ferricyanide), used in painting and dyeing, and as an antidote for certain kinds of heavy metal poisoning.
A moderate to rich blue colour, tinted with deep greenish blue.

Here’s a sample of the colour from the wiktionary entry,

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Prussian Blue was also the name for a short-lived white nationalist band (from the Prussian Blue essay on Wikipedia; Note: Links have been removed),

Prussian Blue was an American white nationalist pop pre-teen duo formed in early 2003 by April Gaede, mother of Lynx Vaughan Gaede[1] and Lamb Lennon Gaede,[2] sororal twins born on June 30, 1992, in Bakersfield, California.[3] The twins referred to the Holocaust as a myth[4] and their group was described as racist and white supremacist in nature.[5][6]

Lynx and Lamb were about 14 when they decided that they wanted to cease touring. In 2011, in an interview with The Daily, the twins renounced their previous politics.[7] Lamb was quoted saying, “I’m not a white nationalist anymore. My sister and I are pretty liberal now.”

Getting back to the research at hand, here’s a link to and a citation for the research into ultralight iron oxide frameworks,

Ultralight Mesoporous Magnetic Frameworks by Interfacial Assembly of Prussian Blue Nanocubes by Biao Kong, Jing Tang, Zhangxiong Wu, Jing Wei, Hao Wu, Yongcheng Wang, Prof. Gengfeng Zheng, & Prof. Dongyuan Zhao. Angewandte Chemie International Edition Article first published online: 12 FEB 2014 DOI: 10.1002/anie.201308625

Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

I really wasn’t expecting to trip across information about a holocaust-denying pre-teen pop duo (who’ve since renounced those views) in a post regarding research on iron oxide and Prussian blue nanocubes that was published in a German chemistry journal. I’m not sure this can be called ironic but it certainly has that quality.

Tracking gas, oil, and, possibly, water in wells

A Feb. 24, 2014 Rice University news release (also on EurekAlert) and on Azonano as a Feb. 25, 2014 news item) describes a technique tracks which wells are producing oil or gas in fracking operations,

A tabletop device invented at Rice University can tell how efficiently a nanoparticle would travel through a well and may provide a wealth of information for oil and gas producers.

The device gathers data on how tracers – microscopic particles that can be pumped into and recovered from wells – move through deep rock formations that have been opened by hydraulic fracturing [fracking].

Here’s an image of two Rice scientists playing around with a prototype of their tabletop device,

Rice University chemist Andrew Barron and graduate student Brittany Oliva-Chatelain investigate the prototype of a device that allows for rapid testing of nanotracers for the evaluation of wells subject to hydraulic fracturing. (Credit: Jeff Fitlow/Rice University)

Rice University chemist Andrew Barron and graduate student Brittany Oliva-Chatelain investigate the prototype of a device that allows for rapid testing of nanotracers for the evaluation of wells subject to hydraulic fracturing. (Credit: Jeff Fitlow/Rice University)

The news release goes on to describe the fracking process and explain why the companies don’t know which well is actually producing (Note: Links have been removed),

Drilling companies use fracturing to pump oil and gas from previously unreachable reservoirs. Fluids are pumped into a wellbore under high pressure to fracture rocks, and materials called “proppants,” like sand or ceramic, hold the fractures open. “They’re basically making a crack in the rock and filling it with little beads,” said Rice chemist Andrew Barron, whose lab produced the device detailed in the Royal Society of Chemistry journal Environmental Science Processes and Impacts.

But the companies struggle to know which insertion wells — where fluids are pumped in — are connected to the production wells where oil and gas are pumped out. “They may be pumping down three wells and producing from six, but they have very little idea of which well is connected to which,” he said.

Tracer or sensor particles added to fracturing fluids help solve that problem, but there’s plenty of room for optimization, especially in minimizing the volume of nanoparticles used now, he said. “Ideally, we would take a very small amount of a particle that does not interact with proppant, rock or the gunk that’s been pumped downhole, inject it in one well and collect it at the production well. The time it takes to go from one to the other will tell you about the connectivity underground.”

Barron explained the proppant itself accounts for most of the surface area the nanoparticles encounter, so it’s important to tune the tracers to the type of proppant used.

He said the industry lacks a uniform method to test and optimize custom-designed nanoparticles for particular formations and fluids. The ultimate goal  is to optimize the particles so they don’t clump together or stick to the rock or proppant and can be reliably identified when they exit the production well.

Here’s how the tracers work (from the news release),

The automated device by Barron, Rice alumnus Samuel Maguire-Boyle and their colleagues allows them to run nanotracers through a small model of a geological formation and quickly analyze what comes out the other side.

The device sends a tiny amount of silver nanoparticle tracers in rapid pulses through a solid column, simulating the much longer path the particles would travel in a well. That gives the researchers an accurate look at both how sticky and how robust the particles are.

“We chose silver nanoparticles for their plasmon resonance,” Barron said. “They’re very easy to see (with a spectroscope) making for high-quality data.” He said silver nanoparticles would be impractical in a real well, but because they’re easy to modify with other useful chemicals, they are good models for custom nanoparticles.

“The process is simple enough that our undergraduates make different nanoparticles and very quickly test them to find out how they behave,” Barron said.

The method also shows promise for tracking water from source to destination, which could be valuable for government agencies that want to understand how aquifers are linked or want to trace the flow of elements like pollutants in a water supply, he said.

Barron said the Rice lab won’t oversee production of the test rig, but it doesn’t have to. “We just published the paper, but if companies want to make their own, it includes the instructions. The supplementary material is basically a manual for how to do this,” he said.

You can find the paper with this link and/or citation,

Automated method for determining the flow of surface functionalized nanoparticles through a hydraulically fractured mineral formation using plasmonic silver nanoparticles by Samuel J. Maguire-Boyle, David J. Garner, Jessica E. Heimann, Lucy Gao, Alvin W. Orbaek, and Andrew R. Barron. Environ. Sci.: Processes Impacts, 2014,16, 220-231 DOI: 10.1039/C3EM00718A First published online 07 Jan 2014

This paper has been published in one of the Royal Society’s open access journals.

My final note, one of my more recent posts about fracking highlights some research that was taking place in Texas (Rice University’s home state) at Texas A&M University, see my July 29, 2013 posting.