Tag Archives: Germany

Pushing some molecules around

A Nov. 6, 2014 news item on Nanowerk features a new means of manipulating molecules,

Jülich [Forschungszentrum Jülich; Germany] scientists have developed a new control technique for scanning probe microscopes that enables the user to manipulate large single molecules interactively using their hands. Until now, only simple and inflexibly programmed movements were possible. To test their method, the researchers “stencilled” a word into a molecular monolayer by removing 47 molecules. The process opens up new possibilities for the construction of molecular transistors and other nanocomponents.

For those who don’t know (this includes me), Forschungszentrum Jülich is an interdisciplinary research centre in Europe and a member of the Helmholtz Association of German Research Centres (Wikipedia entry).

An Oct. 31, 2014 Forschungszentrum Jülich press release offers more information about pushing molecules around,

“The technique makes it possible for the first time to remove large organic molecules from associated structures and place them elsewhere in a controlled manner,” explains Dr. Ruslan Temirov from Jülich’s Peter Grünberg Institute. This brings the scientists one step closer to finding a technology that will enable single molecules to be freely assembled to form complex structures. Research groups around the world are working on a modular system like this for nanotechnology, which is considered imperative for the development of novel, next-generation electronic components.

Here’s an image of scientist using the new technique,

Controlling scanning probe microscopes with motion tracking Copyright: Forschungszentrum Jülich

Controlling scanning probe microscopes with motion tracking
Copyright: Forschungszentrum Jülich

The press release goes on to describe the motion tracking technique,

Using motion tracking, Temirov’s young investigators group coupled the movements of an operator’s hand directly to the scanning probe microscope. The tip of this microscope can be used to lift molecules and re-deposit them, much like a crane. With a magnification of five hundred million to one, the relatively crude human movements are transferred to atomic dimensions. “A hand motion of five centimetres causes the sharp tip of the scanning probe microscope to move just one angstrom over the specimen. This corresponds to the typical magnitude of atomic radii and bond lengths in molecules,” explains Ruslan Temirov.

Controlling the system in this way, however, requires some practice. “The first few attempts to remove a molecule took 40 minutes. Towards the end we needed only around 10 minutes,” says Matthew Green. It took the PhD student four days in total to remove 47 molecules and thus stencil the word “JÜLICH” into a perylenetetracarboxylic acid dianhydride (PTCDA) monolayer. PTCDA is an organic semiconductor that plays an important role in the development of organic electronics – a field that makes it possible to print flexible components or cheap disposable chips, for example, which is inconceivable with conventional silicon technology.

Small spelling mistakes can even be corrected without difficulty using the new method. A molecule removed by mistake when creating the horizontal line in “H” was easily replaced by Green using a new molecule that he removed from the edge of the layer. “And exactly this is the advantage of this method. The experimenter can intervene in the process and find a solution if a molecule is accidentally removed or if it unexpectedly jumps back to its original position,” says the physicist.

This is a sample of the researchers’ writing,


A word with just 47 molecules Copyright: Forschungszentrum Jülich

For anyone who’s followed the nanotechnology scene for a while, this will bring to mind Don Eigler and his project where he moved 35 xenon atoms with a then-new technology, a scanning tunneling microscope, in 1989 to form the letters I B M, where he was employed (Wikipedia entry).

The press release contrasts the earlier accomplishments with this latest ‘writing’ project,

The interactive approach makes it possible to manipulate molecules that are part of large associated structures in a controlled manner. In contrast to single atoms and molecules, the manipulation of which using scanning probe microscopes has long been routine, larger molecular assemblies were almost impossible to manipulate in a targeted manner until now. The reason for this is that the bonding forces of the molecules, which are bound to all of the surrounding neighbouring molecules, are almost impossible to predict exactly. Only during the experiment it becomes clear what force is required to lift a molecule and via what path it can be successfully removed.

The experience gained will help to speed up time-consuming operations. “In future, self-learning computers will take over complex molecule manipulation. We are now gaining the intuition for nanomechanics that is so essential for this project using our novel control system and quite literally by hand,” says Dr. Christian Wagner, who is also part of the Jülich group.

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

Patterning a hydrogen-bonded molecular monolayer with a hand-controlled scanning probe microscope by Matthew F. B. Green, Taner Esat, Christian Wagner, Philipp Leinen, Alexander Grötsch, F. Stefan Tautz, and Ruslan Temiro. Beilstein J. Nanotechnol. 2014, 5, 1926–1932. doi:10.3762/bjnano.5.203 Published 31 Oct 2014

This is an open access paper as of Nov. 10, 2014. Note: An open access status can change.

Watching buckyballs (buckminsterfullerenes) self-assemble in real-time

For the 5% or less of the world who need this explanation, the reference to a football later in this post is, in fact, a reference to a soccer ball. Moving on to a Nov. 5, 2014 news item on Nanowerk (Note: A link has been removed),

Using DESY’s ultrabright X-ray source PETRA III, researchers have observed in real-time how football-shaped carbon molecules arrange themselves into ultra-smooth layers. Together with theoretical simulations, the investigation reveals the fundamentals of this growth process for the first time in detail, as the team around Sebastian Bommel (DESY and Humboldt Universität zu Berlin) and Nicola Kleppmann (Technische Universität Berlin) reports in the scientific journal Nature Communications (“Unravelling the multilayer growth of the fullerene C60 in real-time”).

This knowledge will eventually enable scientists to tailor nanostructures from these carbon molecules for certain applications, which play an increasing role in the promising field of plastic electronics. The team consisted of scientists from Humboldt-Universität zu Berlin, Technische Universität Berlin, Universität Tübingen and DESY.

Here’s an image of the self-assembling materials,

Caption: This is an artist's impression of the multilayer growth of buckyballs. Credit: Nicola Kleppmann/TU Berlin

Caption: This is an artist’s impression of the multilayer growth of buckyballs.
Credit: Nicola Kleppmann/TU Berlin

A Nov. 5, 2014 DESY (Deutsches Elektronen-Synchrotron) press release (also on EurekAlert), describes the work further,

The scientists studied so called buckyballs. Buckyballs are spherical molecules, which consist of 60 carbon atoms (C60). Because they are reminiscent of American architect Richard Buckminster Fuller’s geodesic domes, they were christened buckminsterfullerenes or “buckyballs” for short. With their structure of alternating pentagons and hexagons, they also resemble tiny molecular footballs. [emphasis mine]

Using DESY’s X-ray source PETRA III, the researchers observed how buckyballs settle on a substrate from a molecular vapour. In fact, one layer after another, the carbon molecules grow predominantly in islands only one molecule high and barely form tower-like structures..“The first layer is 99% complete before 1% of the second layer is formed,” explains DESY researcher Bommel, who is completing his doctorate in Prof. Stefan Kowarik’s group at the Humboldt Universität zu Berlin. This is how extremely smooth layers form.

“To really observe the growth process in real-time, we needed to measure the surfaces on a molecular level faster than a single layer grows, which takes place in about a minute,” says co-author Dr. Stephan Roth, head of the P03 measuring station, where the experiments were carried out. “X-ray investigations are well suited, as they can trace the growth process in detail.”

“In order to understand the evolution of the surface morphology at the molecular level, we carried out extensive simulations in a non-equilibrium system. These describe the entire growth process of C60 molecules into a lattice structure,” explains Kleppmann, PhD student in Prof. Sabine Klapp’s group at the Institute of Theoretical Physics, Technische Universität Berlin. “Our results provide fundamental insights into the molecular growth processes of a system that forms an important link between the world of atoms and that of colloids.”

Through the combination of experimental observations and theoretical simulations, the scientists determined for the first time three major energy parameters simultaneously for such a system: the binding energy between the football molecules, the so-called “diffusion barrier,” which a molecule must overcome if it wants to move on the surface, and the Ehrlich-Schwoebel barrier, which a molecule must overcome if it lands on an island and wants to hop down from that island.

“With these values, we now really understand for the first time how such nanostructures come into existence,” stresses Bommel. “Using this knowledge, it is conceivable that these structures can selectively be grown in the future: How must I change my temperature and deposition rate parameters so that an island of a particular size will grow. This could, for example, be interesting for organic solar cells, which contain C60.” The researchers intend to explore the growth of other molecular systems in the future using the same methods.

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

Unravelling the multilayer growth of the ​fullerene C60 in real time by S. Bommel, N. Kleppmann, C. Weber, H. Spranger, P. Schäfer, J. Novak, S.V. Roth, F. Schreiber, S.H.L. Klapp, & S. Kowarik. Nature Communications 5, Article number: 5388 doi:10.1038/ncomms6388 Published 05 November 2014

This article is open access.

I was not able to find any videos of these buckyballs assembling in real-time. Presumably, there are technical issues with recording the process, financial issues, or some combination thereof. Still, I can’t help but feel teased (tongue in cheek) by these scientists who give me an artist’s concept instead. Hopefully, budgets and/or technology will allow the rest of us to view this process at some time in the future.

Viewing a photosynthesis subsystem in a near-natural state

[downloaded from http://www.desy.de/infos__services/presse/pressemeldungen/@@news-view?id=9383]

Molecular structure of photosystem II, which arranges itself in rows. Credit: Martin Bommer/HU Berlin [downloaded from http://www.desy.de/infos__services/presse/pressemeldungen/@@news-view?id=9383]

Apparently, this image represents a near-natural state for a photosynthesis subsystem called, Photosynthesis II. Here’s more from a Nov. 4, 2014 news item on Nanowerk (Note: A link has been removed),

Photosynthesis is one of the most important processes in nature. The complex method with which all green plants harvest sunlight and thereby produce the oxygen in our air is, however, still not fully understood. Researchers using DESY’s X-ray light source PETRA III have examined a photosynthesis subsystem in a near-natural state. According to the scientists led by Privatdozentin Dr. Athina Zouni from the Humboldt University (HU) Berlin, the X-ray experiments on what is known as photosystem II reveal, for example, yet unknown structures. Their results are published in the scientific journal Structure (“Native-like Photosystem II Superstructure at 2.44 Å Resolution through Detergent Extraction from the Protein Crystal”). The technology utilised could also be of interest for analysing other biomolecules.

A Nov. 4, 2014 DESY (Deutsches Elektronen-Synchrotron) press release, which originated the news item, describes some of the issues with studying ‘photosynthetic machinery’,

Photosystem II forms part of the photosynthetic machinery where water, with the help of sunlight, is split into hydrogen and oxygen. As one of the membrane proteins, it sits in the cell membrane. Membrane proteins are a large and vital group of biomolecules that are, for example, important in addressing a variety of medical issues. In order to decode the protein structure and reveal details on how biomolecules function, researchers use the very bright and short-wave X-rays of PETRA III and other similar facilities. Small crystals, however, must initially be grown from these biomolecules.

“The structure of single molecules cannot be directly seen even with the brightest X-rays,” explains co-author and DESY researcher Dr. Anja Burkhardt of Measuring Station P11, where the experiments were carried out. “In a crystal, however, a multitude of these molecules are arranged in a highly symmetrical fashion. Thus the signal, resulting from X-ray diffraction of these molecules, is amplified. The molecular structure can then be calculated from the diffraction images.”

In addition to these difficulties the scientists were also grappling with this problem (from the press release),

Biomolecules – and especially membrane proteins – cannot easily be compelled into crystal form as it is contrary to their natural state. Preparing suitable samples is therefore a crucial step in the whole analysis process. For instance, photosystem II must be first separated from the membrane, where it is bound to numerous small fat molecules (lipids). Researchers use special detergents for this purpose, such as those also principally found in soap. The catch: instead of lipids, the biomolecules are now surrounded by detergents, which may make the crystals spongy under certain conditions, thus exacerbating the analysis.

“What we want is to come as close as possible to nature,” stresses Zouni. The closer the proteins in the crystal are to their natural state, the better the results.

The press release describes how the team solved the problem,

“The trick was to use a detergent that strongly differs from the lipids in composition and structure,” explains the researcher.

Before examining the biomolecular crystals using X-rays, a portion of the water is extracted and replaced by an anti-freeze. The crystals are usually frozen for the experiments because the high-energy X-ray doesn’t damage them so quickly in the frozen state. During this process, the researchers would like to avoid ice formation.

“The dehydration process removed not only the water in our samples, but also completely removed the detergent, something we didn’t expect,” says Zouni.“Our samples are closer to the natural state than what has been reported before.”

Consequently, the investigation’s spatial resolution increased from about 0.6 nanometres (a millionth of a millimetre) to 0.244 nanometres. This is not, in fact, the highest resolution ever achieved in a photosystem II study, but the analysis shows that the photosystem II proteins are arranged within the crystals as pairs of rows, something that also occurs in the natural environment.

This latest development builds on previous research according to the press release,

Electron microscope investigations by Professor Egbert Boekema’s group at the University of Groningen in the Netherlands had already shown the photosystems’ crystal like arrangement in the natural membrane — a kind of tiny solar cell. Electron microscopy could better recognize connections using direct observation of the native membrane while X-ray crystallography could reveal the smallest details.

The press release ends with how the latest work could have an impact on further research,

“We placed the structural data over the electron microscope images – they matched precisely,” says Zouni. The investigation also revealed structures that were invisible before. “We can see exactly where the bonds to the lipids are located,” the scientist explains. The more the researchers discover about photosystem II, the better they understand exactly how it functions.

The procedure of using a new detergent, however, is not only interesting in terms of photosystem II. “The method can potentially be applied to many membrane proteins,” stresses Zouni. In the future, many biomolecules could maybe examined in a more natural state than ever before.

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

Native-like Photosystem II Superstructure at 2.44 Å Resolution through Detergent Extraction from the Protein Crystal by Julia Hellmich, Martin Bommer, Anja Burkhardt, Mohamed Ibrahim, Jan Kern, Alke Meents, Frank Müh, Holger Dobbek, and Athina Zouni. Structure Volume 22, Issue 11, p1607–1615, 4 November 2014  DOI: http://dx.doi.org/10.1016/j.str.2014.09.007

This paper is open access.

ETA Nov. 6, 2014: On the off chance the links to the Nanowerk news item or DESY press release do not yield results, you may be able to find the DESY Nov. 5, 2014 news release here on EurekAlert.

Nanoscopy and a 2014 Nobel Prize for Chemistry

An Oct. 8, 2014 news item on Nanowerk features the 2014 Nobel Prize in Chemistry honourees,

 For a long time optical microscopy was held back by a presumed limitation: that it would never obtain a better resolution than half the wavelength of light. Helped by fluorescent molecules the Nobel Laureates in Chemistry 2014 ingeniously circumvented this limitation.

Their ground-breaking work has brought optical microscopy into the nanodimension.
In what has become known as nanoscopy, scientists visualize the pathways of individual molecules inside living cells. They can see how molecules create synapses between nerve cells in the brain; they can track proteins involved in Parkinson’s, Alzheimer’s and Huntington’s diseases as they aggregate; they follow individual proteins in fertilized eggs as these divide into embryos.

An Oct, 8, 2014 Royal Swedish Academy of Science press release, which originated the news item, expands on the ‘groundbreaking’ theme,

It was all but obvious that scientists should ever be able to study living cells in the tiniest molecular detail. In 1873, the microscopist Ernst Abbe stipulated a physical limit for the maximum resolution of traditional optical microscopy: it could never become better than 0.2 micrometres. Eric Betzig, Stefan W. Hell and William E. Moerner are awarded the Nobel Prize in Chemistry 2014 for having bypassed this limit. Due to their achievements the optical microscope can now peer into the nanoworld.

Two separate principles are rewarded. One enables the method stimulated emission depletion (STED) microscopy, developed by Stefan Hell in 2000. Two laser beams are utilized; one stimulates fluorescent molecules to glow, another cancels out all fluorescence except for that in a nanometre-sized volume. Scanning over the sample, nanometre for nanometre, yields an image with a resolution better than Abbe’s stipulated limit.

Eric Betzig and William Moerner, working separately, laid the foundation for the second method, single-molecule microscopy. The method relies upon the possibility to turn the fluorescence of individual molecules on and off. Scientists image the same area multiple times, letting just a few interspersed molecules glow each time. Superimposing these images yields a dense super-image resolved at the nanolevel. In 2006 Eric Betzig utilized this method for the first time.

Today, nanoscopy is used world-wide and new knowledge of greatest benefit to mankind is produced on a daily basis.

Here’s an image illustrating different microscopy resolutions including one featuring single-molecule microscopy,

The centre image shows lysosome membranes and is one of the first ones taken by Betzig using single-molecule microscopy. To the left, the same image taken using conventional microscopy. To the right, the image of the membranes has been enlarged. Note the scale division of 0.2 micrometres, equivalent to Abbe’s diffraction limit. Image: Science 313:1642–1645. [downloaded from http://www.kva.se/en/pressroom/Press-releases-2014/nobelpriset-i-kemi-2014/]

The centre image shows lysosome membranes and is one of the first ones taken by Betzig using single-molecule microscopy. To the left, the same image taken using conventional microscopy. To the right, the image of the membranes has been enlarged. Note the scale division of 0.2 micrometres, equivalent to Abbe’s diffraction limit. Image: Science 313:1642–1645. [downloaded from http://www.kva.se/en/pressroom/Press-releases-2014/nobelpriset-i-kemi-2014/]

The press release goes on to provide some biographical details about the three honourees and information about the financial size of the award,

Eric Betzig, U.S. citizen. Born 1960 in Ann Arbor, MI, USA. Ph.D. 1988 from Cornell University, Ithaca, NY, USA. Group Leader at Janelia Farm Research Campus, Howard Hughes Medical Institute, Ashburn, VA, USA.

Stefan W. Hell, German citizen. Born 1962 in Arad, Romania. Ph.D. 1990 from the University of Heidelberg, Germany. Director at the Max Planck Institute for Biophysical Chemistry, Göttingen, and Division head at the German Cancer Research Center, Heidelberg, Germany.

William E. Moerner, U.S. citizen. Born 1953 in Pleasanton, CA, USA. Ph.D. 1982 from Cornell University, Ithaca, NY, USA. Harry S. Mosher Professor in Chemistry and Professor, by courtesy, of Applied Physics at Stanford University, Stanford, CA, USA.

Prize amount: SEK 8 million, to be shared equally between the Laureates.

The amount is in Swedish Krona. In USD, it is approximately $1.1M; in CAD, it is approximately $1.2M; and, in pounds sterling (British pounds), it is approximately £689,780.

Congratulations to all three gentlemen!

ETA Oct. 14, 2014: Azonano features an Oct. 14, 2014 news item from the UK’s National Physical Laboratory (NPL)  congratulating the three recipients of the 2014 Nobel Prize for Chemistry. The item also features a description of the recipients’ groundbreaking work along with an update on how this pioneering work has influenced and inspired further research in the field of nanoscopy at the NPL.

Wonders of curcumin: wound healing; wonders of aromatic-turmerone: stem cells

Both curcumin and turmerone are constituents of turmeric which has been long lauded for its healing properties. Michael Berger has written a Nanowerk Spotlight article featuring curcumin and some recent work on burn wound healing. Meanwhile, a ScienceDaily news item details information about a team of researchers focused on tumerone as a means for regenerating brain stem cells.

Curcumin and burn wounds

In a Sept. 22, 2014 Nanowerk Spotlight article Michael Berger sums up the curcumin research effort (referencing some of this previous articles on the topic) in light of a new research paper about burn wound healing (Note: Links have been removed),

Despite significant progress in medical treatments of severe burn wounds, infection and subsequent sepsis persist as frequent causes of morbidity and mortality for burn victims. This is due not only to the extensive compromise of the protective barrier against microbial invasion, but also as a result of growing pathogen resistance to therapeutic options.

… Dr Adam Friedman, Assistant Professor of Dermatology and Director of Dermatologic research at the Montefiore-Albert Einstein College of Medicine, tells Nanowerk. “For me, this gap fuels innovation, serving as the inspiration for my research with broad-spectrum, multi-mechanistic antimicrobial nanomaterials.”

In new work, Friedman and a team of researchers from Albert Einstein College of Medicine and Oregon State University have explored the use of curcumin nanoparticles for the treatment of infected burn wounds, an application that resulted in reduced bacterial load and enhancing wound healing.

It certainly seems promising as per the article abstract,

Curcumin-encapsulated nanoparticles as innovative antimicrobial and wound healing agent by Aimee E. Krausz, Brandon L. Adler, Vitor Cabral, Mahantesh Navati, Jessica Doerner, Rabab Charafeddine, Dinesh Chandra, Hongying Liang, Leslie Gunther, Alicea Clendaniel, Stacey Harper, Joel M. Friedman, Joshua D. Nosanchuk, & Adam J. Friedman. Nanomedicine: Nanotechnology, Biology and Medicine (article in press) published online 19 September 2014.http://www.nanomedjournal.com/article/S1549-9634%2814%2900527-9/abstract Uncorrected Proof

Burn wounds are often complicated by bacterial infection, contributing to morbidity and mortality. Agents commonly used to treat burn wound infection are limited by toxicity, incomplete microbial coverage, inadequate penetration, and rising resistance. Curcumin is a naturally derived substance with innate antimicrobial and wound healing properties. Acting by multiple mechanisms, curcumin is less likely than current antibiotics to select for resistant bacteria.

Curcumin’s poor aqueous solubility and rapid degradation profile hinder usage; nanoparticle encapsulation overcomes this pitfall and enables extended topical delivery of curcumin.

In this study, we synthesized and characterized curcumin nanoparticles (curc-np), which inhibited in vitro growth of methicillin-resistant Staphylococcus aureus (MRSA) and Pseudomonas aeruginosa in dose-dependent fashion, and inhibited MRSA growth and enhanced wound healing in an in vivo murine wound model. Curc-np may represent a novel topical antimicrobial and wound healing adjuvant for infected burn wounds and other cutaneous injuries.

Two things: This paper is behind a paywall and note the use of the term ‘in vivo’ which means they have tested on animals such as rats and mice for example, but not humans. Nonetheless, it seems a promising avenue for further exploration.

Interestingly, there was an attempt in 1995 to patent turmeric for use in wound healing as per my Dec. 26, 2011 posting which featured then current research on turmeric,

There has already been one court case regarding a curcumin patent,

Recently, turmeric came into the global limelight when the controversial patent “Use of Turmeric in Wound Healing” was awarded, in 1995, to the University of Mississippi Medical Center, USA. Indian Council of Scientific and Industrial Research (CSIR) aggressively contested this award of the patent. It was argued by them that turmeric has been an integral part of the traditional Indian medicinal system over several centuries, and therefore, is deemed to be ‘prior art’, hence is in the public domain. Subsequently, after protracted technical/legal battle USPTO decreed that turmeric is an Indian discovery and revoked the patent.

One last bit about curcumin, my April 22, 2014 posting featured work in Iran using curcumin for cancer-healing.


This excerpt from a Sept. 25, 2014, news item in ScienceDaily represents the first time that tumerone has been mentioned here,

A bioactive compound found in turmeric promotes stem cell proliferation and differentiation in the brain, reveals new research published today in the open access journal Stem Cell Research & Therapy. The findings suggest aromatic turmerone could be a future drug candidate for treating neurological disorders, such as stroke and Alzheimer’s disease.

A Sept. 25, 2014 news release on EurekAlert provides more information,

The study looked at the effects of aromatic (ar-) turmerone on endogenous neutral stem cells (NSC), which are stem cells found within adult brains. NSC differentiate into neurons, and play an important role in self-repair and recovery of brain function in neurodegenerative diseases. Previous studies of ar-turmerone have shown that the compound can block activation of microglia cells. When activated, these cells cause neuroinflammation, which is associated with different neurological disorders. However, ar-turmerone’s impact on the brain’s capacity to self-repair was unknown.

Researchers from the Institute of Neuroscience and Medicine in Jülich, Germany, studied the effects of ar-turmerone on NSC proliferation and differentiation both in vitro and in vivo. Rat fetal NSC were cultured and grown in six different concentrations of ar-turmerone over a 72 hour period. At certain concentrations, ar-turmerone was shown to increase NSC proliferation by up to 80%, without having any impact on cell death. The cell differentiation process also accelerated in ar-turmerone-treated cells compared to untreated control cells.

To test the effects of ar-turmerone on NSC in vivo, the researchers injected adult rats with ar-turmerone. Using PET imaging and a tracer to detect proliferating cells, they found that the subventricular zone (SVZ) was wider, and the hippocampus expanded, in the brains of rats injected with ar-turmerone than in control animals. The SVZ and hippocampus are the two sites in adult mammalian brains where neurogenesis, the growth of neurons, is known to occur.

Lead author of the study, Adele Rueger, said: “While several substances have been described to promote stem cell proliferation in the brain, fewer drugs additionally promote the differentiation of stem cells into neurons, which constitutes a major goal in regenerative medicine. Our findings on aromatic turmerone take us one step closer to achieving this goal.”

Ar-turmerone is the lesser-studied of two major bioactive compounds found in turmeric. The other compound is curcumin, which is well known for its anti-inflammatory and neuroprotective properties

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

Aromatic-turmerone induces neural stem cell proliferation in vitro and in vivo by Joerg Hucklenbroich, Rebecca Klein, Bernd Neumaier, Rudolf Graf, Gereon Rudolf Fink, Michael Schroeter, and Maria Adele Rueger. Stem Cell Research & Therapy 2014, 5:100  doi:10.1186/scrt500

This is an open access paper.

Buckydiamondoids steer electron flow

One doesn’t usually think about buckyballs (Buckminsterfullerenes) and diamondoids as being together in one molecule but that has not stopped scientists from trying to join them and, in this case, successfully. From a Sept. 9, 2014 news item on ScienceDaily,

Scientists have married two unconventional forms of carbon — one shaped like a soccer ball, the other a tiny diamond — to make a molecule that conducts electricity in only one direction. This tiny electronic component, known as a rectifier, could play a key role in shrinking chip components down to the size of molecules to enable faster, more powerful devices.

Here’s an illustration the scientists have provided,

Illustration of a buckydiamondoid molecule under a scanning tunneling microscope (STM). In this study the STM made images of the buckydiamondoids and probed their electronic properties.

Illustration of a buckydiamondoid molecule under a scanning tunneling microscope (STM). In this study the STM made images of the buckydiamondoids and probed their electronic properties.

A Sept. 9, 2014 Stanford University news release by Glenda Chui (also on EurekAlert), which originated the news item, provides some information about this piece of international research along with background information on buckyballs and diamondoids (Note: Links have been removed),

“We wanted to see what new, emergent properties might come out when you put these two ingredients together to create a ‘buckydiamondoid,'” said Hari Manoharan of the Stanford Institute for Materials and Energy Sciences (SIMES) at the U.S. Department of Energy’s SLAC National Accelerator Laboratory. “What we got was basically a one-way valve for conducting electricity – clearly more than the sum of its parts.”

The research team, which included scientists from Stanford University, Belgium, Germany and Ukraine, reported its results Sept. 9 in Nature Communications.

Many electronic circuits have three basic components: a material that conducts electrons; rectifiers, which commonly take the form of diodes, to steer that flow in a single direction; and transistors to switch the flow on and off. Scientists combined two offbeat ingredients – buckyballs and diamondoids – to create the new diode-like component.

Buckyballs – short for buckminsterfullerenes – are hollow carbon spheres whose 1985 discovery earned three scientists a Nobel Prize in chemistry. Diamondoids are tiny linked cages of carbon joined, or bonded, as they are in diamonds, with hydrogen atoms linked to the surface, but weighing less than a billionth of a billionth of a carat. Both are subjects of a lot of research aimed at understanding their properties and finding ways to use them.

In 2007, a team led by researchers from SLAC and Stanford discovered that a single layer of diamondoids on a metal surface can emit and focus electrons into a tiny beam. Manoharan and his colleagues wondered: What would happen if they paired an electron-emitting diamondoid with another molecule that likes to grab electrons? Buckyballs are just that sort of electron-grabbing molecule.

Details are then provided about this specific piece of research (from the Stanford news release),

For this study, diamondoids were produced in the SLAC laboratory of SIMES researchers Jeremy Dahl and Robert Carlson, who are world experts in extracting the tiny diamonds from petroleum. The diamondoids were then shipped to Germany, where chemists at Justus-Liebig University figured out how to attach them to buckyballs.

The resulting buckydiamondoids, which are just a few nanometers long, were tested in SIMES laboratories at Stanford. A team led by graduate student Jason Randel and postdoctoral researcher Francis Niestemski used a scanning tunneling microscope to make images of the hybrid molecules and measure their electronic behavior. They discovered that the hybrid is an excellent rectifier: The electrical current flowing through the molecule was up to 50 times stronger in one direction, from electron-spitting diamondoid to electron-catching buckyball, than in the opposite direction. This is something neither component can do on its own.

While this is not the first molecular rectifier ever invented, it’s the first one made from just carbon and hydrogen, a simplicity researchers find appealing, said Manoharan, who is an associate professor of physics at Stanford. The next step, he said, is to see if transistors can be constructed from the same basic ingredients.

“Buckyballs are easy to make – they can be isolated from soot – and the type of diamondoid we used here, which consists of two tiny cages, can be purchased commercially,” he said. “And now that our colleagues in Germany have figured out how to bind them together, others can follow the recipe. So while our research was aimed at gaining fundamental insights about a novel hybrid molecule, it could lead to advances that help make molecular electronics a reality.”

Other research collaborators came from the Catholic University of Louvain in Belgium and Kiev Polytechnic Institute in Ukraine. The primary funding for the work came from U.S. the Department of Energy Office of Science (Basic Energy Sciences, Materials Sciences and Engineering Divisions).

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

Unconventional molecule-resolved current rectification in diamondoid–fullerene hybrids by Jason C. Randel, Francis C. Niestemski,    Andrés R. Botello-Mendez, Warren Mar, Georges Ndabashimiye, Sorin Melinte, Jeremy E. P. Dahl, Robert M. K. Carlson, Ekaterina D. Butova, Andrey A. Fokin, Peter R. Schreiner, Jean-Christophe Charlier & Hari C. Manoharan. Nature Communications 5, Article number: 4877 doi:10.1038/ncomms5877 Published 09 September 2014

This paper is open access. The scientists provided not only a standard illustration but a pretty picture of the buckydiamondoid,

Caption: An international team led by researchers at SLAC National Accelerator Laboratory and Stanford University joined two offbeat carbon molecules -- diamondoids, the square cages at left, and buckyballs, the soccer-ball shapes at right -- to create "buckydiamondoids," center. These hybrid molecules function as rectifiers, conducting electrons in only one direction, and could help pave the way to molecular electronic devices. Credit: Manoharan Lab/Stanford University

Caption: An international team led by researchers at SLAC National Accelerator Laboratory and Stanford University joined two offbeat carbon molecules — diamondoids, the square cages at left, and buckyballs, the soccer-ball shapes at right — to create “buckydiamondoids,” center. These hybrid molecules function as rectifiers, conducting electrons in only one direction, and could help pave the way to molecular electronic devices.
Credit: Manoharan Lab/Stanford University

FOE, nano, and food: part two of three (the problem with research)

The first part of this roughly six week food and nano ‘debate’ started off with the May 22, 2014 news item on Nanowerk announcing the Friends of the Earth (FOE) report ‘Way too little: Our Government’s failure to regulate nanomaterials in food and agriculture‘. Adding energy to FOE’s volley was a Mother Jones article written by Tom Philpott which had Dr. Andrew Maynard (Director of the University of Michigan’s Risk Science Center) replying decisively in an article published both on Nanowerk and on the Conversation.

Coincidentally or not, there were a couple of news items about ‘nano and food’ research efforts during the ‘debate’. A June 11, 2014 news item on Nanowerk highlights a Franco-German research project into the effects that nanomaterials have on the liver and the intestines while noting the scope of the task researchers face,

What mode of action do nanomaterials ingested via food have in liver and intestine? Which factors determine their toxicity? Due to the large number of different nanomaterials, it is hardly possible to test every one for its toxic properties. [emphasis mine] For this reason, specific properties for the classification of nanomaterials are to be examined within the scope of the Franco-German research project “SolNanoTox”, which began on 1 March 2014. The [German] Federal Institute for Risk Assessment (BfR) requires data on bioavailability for its assessment work, in particular on whether the solubility of nanomaterials has an influence on uptake and accumulation in certain organs, such as liver and intestine. “We want to find out in our tests whether the criterion ‘soluble or insoluble’ is a determining factor for uptake and toxicity of nanomaterials,” says BfR President Professor Dr. Andreas Hensel.

A June 13, 2014 German Federal Institute for Risk Assessment (BfR) press release, which originated the news item, details the research and the participating agencies,

A risk assessment of nanomaterials is hardly possible at the moment and involves a very high degree of uncertainty, as important toxicological data on their behaviour in tissue and cells are still missing. [emphasis mine] The German-French SolNanoTox research project examines which role the solubility of nanomaterials plays with regard to their accumulation and potential toxic properties. The project is to run for three and a half years during which the BfR will work closely with its French sister organisation ANSES. Other partners are the Institut des Sciences Chimiques de Rennes and Universität Leipzig. The German Research Foundation and French Agence Nationale de la Recherche (ANR) are funding the project.

The tasks of the BfR include in vitro tests (e.g. the investigation of the influence of the human gastrointestinal system) and analysis of biological samples with regard to the possible accumulation of nanomaterials. In addition to this, the BfR uses modern methods of mass spectrometry imaging to find out whether nanoparticles alter the structure of biomolecules, e.g. the structure of the lipids of the cellular membrane. So far, these important tests, which are necessary for assessing possible changes in DNA or cellular structures caused by nanomaterials in food, have not been conducted.

Metallic nanoparticles are to be studied (from the press release),

In the project, two fundamentally different types of nanoparticles are examined as representatives for others of their type: titanium dioxide as representative of water insoluble nanoparticles and aluminium as an example of nanomaterials which show a certain degree of water solubility after oxidation. [emphases mine] It is examined whether the degree of solubility influences the distribution of the nanomaterials in the body and whether soluble materials may possibly accumulate more in other organs than insoluble ones. The object is to establish whether there is a direct toxic effect of insoluble nanomaterials in general after oral uptake due to their small size.

Different innovative analytical methods are combined in the project with the aim to elucidate the behaviour of nanomaterials in tissue and their uptake into the cell. The main focus is on effects which can trigger genotoxic damage and inflammation. At first, the effects of both materials are examined in human cultures of intestinal and liver cells in an artificial environment (in vitro). In the following, it has to be verified by animal experimentation whether the observed effects can also occur in humans. This modus operandi allows to draw conclusions on effects and mode of action of orally ingested nanomaterials with different properties. The goal is to group nanomaterials on the basis of specific properties and to allocate the corresponding toxicological properties to these groups. Motivation for the project is the enormous number of nanomaterials with large differences in physicochemical properties. Toxicological tests cannot be conducted for all materials.

In the meantime, a June 19, 2014 news item on Azonano (also on EurekAlert but dated June 18, 2014) features some research into metallic nanoparticles in dietary supplement drinks,

Robert Reed [University of Arizona] and colleagues note that food and drink manufacturers use nanoparticles in and on their products for many reasons. In packaging, they can provide strength, control how much air gets in and out, and keep unwanted microbes at bay. As additives to food and drinks, they can prevent caking, deliver nutrients and prevent bacterial growth. But as nanoparticles increase in use, so do concerns over their health and environmental effects. Consumers might absorb some of these materials through their skin, and inhale and ingest them. What doesn’t get digested is passed in urine and feces to the sewage system. A handful of initial studies on nanomaterials suggest that they could be harmful, but Reed’s team wanted to take a closer look.

They tested the effects of eight commercial drinks containing nano-size metal or metal-like particles on human intestinal cells in the lab. The drinks changed the normal organization and decreased the number of microvilli, finger-like projections on the cells that help digest food. In humans, if such an effect occurs as the drinks pass through the gastrointestinal tract, these materials could lead to poor digestion or diarrhea, they say. The researchers’ analysis of sewage waste containing these particles suggests that much of the nanomaterials from these products are likely making their way back into surface water, where they could potentially cause health problems for aquatic life.

This piece is interesting for two reasons. First, the researchers don’t claim that metallic nanoparticles cause digestion or diarrhea due to any action in the gastrointestinal tract. They studied the impact that metallic nanoparticles in supplementary drinks had on cells (in vitro testing) from the gastrointestinal tract. Based on what they observed in the laboratory, “… these materials could lead to poor digestion or diarrhea… .” The researchers also suggest a problem could occur as these materials enter surface water in increasing quantities.

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

Supplement Drinks and Assessment of Their Potential Interactions after Ingestion by Robert B. Reed, James J. Faust, Yu Yang, Kyle Doudrick, David G. Capco, Kiril Hristovski, and Paul Westerhoff. ACS Sustainable Chem. Eng., 2014, 2 (7), pp 1616–1624 DOI: 10.1021/sc500108m Publication Date (Web): June 2, 2014

Copyright © 2014 American Chemical Society

With Paul Westerhoff as one of the authors and the reference to metallic nanoparticles entering water supplies, I’m guessing that this research is associated with the LCnano (lifecycle nano) project headquartered at Arizona State university (April 8, 2014 posting).

Getting back to the Franco-German SolNanoTox project, scientists do not know what happens when the cells in your intestines, liver, etc. encounter metallic or other nanoparticles, some of which may be naturally occurring. It should also be noted that we have likely been ingesting metallic nanoparticles for quite some time. After all, anyone who has used silver cutlery has ingested some silver nanoparticles.

There are many, many questions to be asked and answered with regard to nanomaterials in our foods.  Here are a few of mine:

  • How many metallic and other nanoparticles did we ingest before the advent of ‘nanomaterials in food’?
  • What is the biopersistence of naturally occurring and engineered metallic and other nanoparticles in the body?
  • Is there an acceptable dose versus a fatal dose? (Note: There’s naturally occurring formaldehyde in pears as per my May 19, 2014 post about doses, poisons, and the Sense about Science group’s campaign/book, Making Sense of Chemical Stories.)
  • What happens as the metallic and other engineered nanoparticles are added to food and drink and eventually enter our water, air, and soil?

Returning to the ‘debate’, a July 11, 2014 article by Sarah Shemkus for a sponsored section in the UK’s Guardian newspaper highlights an initiative taken by an environmental organization, As You Sow, concerning titanium dioxide in Dunkin’ Donuts’ products (Note: A link has been removed),

The activists at environmental nonprofit As You Sow want you to take another look at your breakfast doughnut. The organization recently filed a shareholder resolution asking Dunkin’ Brands, the parent company of Dunkin’ Donuts, to identify products that may contain nanomaterials and to prepare a report assessing the risks of using these substances in foods.

Their resolution received a fair amount of support: at the company’s annual general meeting in May, 18.7% of shareholders, representing $547m in investment, voted for it. Danielle Fugere, As You Sow’s president, claims that it was the first such resolution to ever receive a vote. Though it did not pass, she says that she is encouraged by the support it received.

“That’s a substantial number of votes in favor, especially for a first-time resolution,” she says.

The measure was driven by recent testing sponsored by As You Sow, which found nanoparticles of titanium dioxide in the powdered sugar that coats some of the donut chain’s products. [emphasis mine] An additive widely used to boost whiteness in products from toothpaste to plastic, microscopic titanium dioxide has not been conclusively proven unsafe for human consumption. Then again, As You Sow contends, there also isn’t proof that it is harmless.

“Until a company can demonstrate the use of nanomaterials is safe, we’re asking companies either to not use them or to provide labels,” says Fugere. “It would make more sense to understand these materials before putting them in our food.”

As You Sow is currently having 16 more foods tested. The result should be available later this summer, Fugere says.

I wonder if As You Sow will address the question of whether the nanoscale titanium dioxide they find indicates that nanoscale particles are being deliberately added or whether the particles are the inadvertent consequence of the production process. That said, I find it hard to believe no one in the food industry is using engineered nanoscale additives as they claim  (the other strategy is to offer a nonanswer) in Shemkus’ article (Note: Links have been removed).,

In a statement, Dunkin’ Donuts argues that the titanium dioxide identified by As You Sow does not qualify as a nanomaterial according to European Union rules or draft US Food and Drug Administration regulations. The company also points out that there is no agreed-upon standard method for identifying nanoparticles in food.

In 2008, As You Sow filed nanomaterial labeling resolutions with McDonald’s and Kraft Foods. In response, McDonald’s released a statement declaring that it does not support the use of nanomaterials in its food, packaging or toys. Kraft responded that it would make sure to address health and safety concerns before ever using nanomaterials in its products.

While Shemkus’ article appears in the Guardian’s Food Hub which is sponsored by the Irish Food Board, this article manages to avoid the pitfalls found in Philpott’s nonsponsored article.

Coming next: the US Food and Drug Administration Guidance issued five weeks after the FOE kicks off the ‘nano and food’ debate in May 2014 with its ‘Way too little: Our Government’s failure to regulate nanomaterials in food and agriculture‘ report.

Part one (an FOE report is published)

Part three (final guidance)

Bespoke (custom made) carbon nanotubes

Researchers have found a way to create single-walled carbon nanotubes (SWCNTs) that  are consistent and, hopefully, designed for specific applications if I’m reading the research rightly, (I have an embedded video in a March 15, 2013 posting which illustrates some of the issues with producing carbon nanotubes.) Getting back to this latest research, it suggests that we could order SWCNTs-on-demand. An Aug. 14, 2014 news item on Azonano provides more insight,

In future, it will be possible to specifically equip carbon nanotubes with properties which they need for electronic applications, for example. Researchers at Empa in Dübendorf/Switzerland and the Max Planck Institute for Solid State Research in Stuttgart [Germany] have succeeded for the first time in growing single-walled carbon nanotubes (CNTs) with only a single, prespecified structure.

The nanotubes thereby have identical electronic properties. The decisive trick here: The team has taken up an idea which originated from the Stuttgart-based Max Planck researchers and produced the CNT from custom-made organic precursor molecules. The researchers started with these precursor molecules and have built up the nanotubes on a platinum surface, as they report in the latest issue of the scientific journal Nature. Such CNTs could be used in future, for instance, in ultra-sensitive light detectors and very tiny transistors.

An Aug. 13, 2014 Max Planck Institute press release, which originated the news item, provides more detail,

For 20 years, material scientists working on the development of carbon nanotubes for a range of applications have been battling a problem – now an elegant solution is at hand. With their unusual mechanical, thermal and electronic properties, the tiny tubes with their honeycomb lattice of graphitic carbon have become the embodiment of nanomaterials. They could be used to manufacture the next generation of electronic and electro-optical components so that they are even smaller and with even faster switching times than before. But to achieve this, the material scientists must specifically equip the nanotubes with desired properties, and these depend on their structure. The production methods used to date, however, always result in a mixture of different CNTs. The team from Empa  and the Max Planck Institute for Solid State Research has now remedied the situation with a new production path for single-walled nanotubes.

Carbon nanotubes with the best possible varietal purity are in demand

With a diameter of around one nanometre, single-walled CNTs (SWCNTs) are deemed to be quantum structures; very tiny structural differences, in the diameter, for example, or in the orientation of the atomic lattice, can dramatically change the electronic properties: one SWCNT can be a metal, while one with a slightly different structure is semi-conducting. Correspondingly great is the interest in reliable methods for producing SWCNTs with the best possible varietal purity. Researchers working with Martin Jansen, Director Emeritus at the Max Planck Institute for Solid State Research, have been pursuing suitable concepts for the synthesis for ten years. But it is only now that the surface physicists at Empa and the chemists at the Stuttgart-based Max Planck Institute have succeeded in implementing one of these ideas in the laboratory. The researchers allowed structurally identical SWCNTs to grow on a platinum surface in a self-organised process and were able to unambiguously define their electronic properties.

The Max Planck research team headed by Martin Jansen had the idea of starting with small precursor molecules to synthesise carbon nanotubes. They felt it should be possible to achieve controlled conversion of the precursor molecules into a cap which acts as the seed for a SWCNT and thus unambiguously specify the structure of the nanotube. With this concept, they approached the Empa team working with Roman Fasel, head of Empa’s «nanotech@surfaces» department and titular professor at the Department of Chemistry and Biochemistry of the University of Bern. This group has already been working for some time on how molecules on a surface can be converted or combined into complex nanostructures according to the principle of molecular self-organisation. “The challenge now consists in finding the right precursor molecule which would actually grow on a smooth surface,” says Roman Fasel. This was ultimately achieved by Andreas Mueller and Konstantin Amsharov from the Max Planck Institute in Stuttgart with the synthesis of a hydrocarbon molecule from a not-inconsiderable 150 atoms.

Molecular origami on the platinum surface

What exactly is the process in which the carbon nanotube forms? In the first step, the flat precursor molecule must – as is the case in origami – convert into a three-dimensional object, the seed. This takes place on a hot platinum surface with the aid of a catalytic reaction, whereby hydrogen atoms split off from the precursor molecule and form new carbon-carbon bonds at very specific positions. The seed folds up from the flat molecule: a tiny, domed shape with open rim, which sits on the platinum surface. This so-called end cap forms the top of the growing SWCNT.

In a second chemical process, further carbon atoms, which are formed during the catalytic decomposition of ethanol on the platinum surface, are taken up. They deposit on the open rim between end cap and platinum surface and lift the cap higher and higher; the tube slowly grows upwards. The atomic structure of the nanotube is determined solely by the shape of the seed. The researchers proved this by analysing the vibrational modes of the SWCNTs and taking measurements with the scanning tunnelling microscope. Further investigations at Empa showed that the SWCNTs produced were over 300 nanometres in length.

Different nanotubes are formed from suitable precursor molecules

The researchers have thus proved that they can unambiguously specify the growth and thus the structure of long SWCNTs using custom-made molecular seeds. The SWCNTs synthesised in this study can exist in two forms, which correspond to an object and its mirror image. By choosing the precursor molecule appropriately, the researchers were able to influence which of the two variants forms. Depending on how the honeycomb atomic lattice is derived from the original molecule – straight or oblique with respect to the CNT axis – it is also possible for helically wound tubes, i.e. with right- or left-handed rotation, and with non-mirror symmetry to form. And it is precisely this structure that then determines which electronic, thermo-electric and optical properties of the material. In principle, the researchers can therefore specifically produce materials with different properties through their choice of precursor molecule.

In further steps, Roman Fasel and his colleagues want to gain an even better understanding of how SWCNTs establish themselves on a surface. Even if well in excess of 100 million nanotubes per square centimetre already grow on the platinum surface, only a relatively small fraction of the seeds actually develop into «mature» nanotubes. The question remains as to which processes are responsible for this, and how the yield can be increased.

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

Controlled synthesis of single-chirality carbon nanotubes by Juan Ramon Sanchez-Valencia, Thomas Dienel, Oliver Gröning, Ivan Shorubalko, Andreas Mueller, Martin Jansen, Konstantin Amsharov, Pascal Ruffieux, & Roman Fasel. Nature 512, 61–64 (07 August 2014) doi:10.1038/nature13607

Published online 06 August 2014

This paper is behind a paywall.

Graphene and an artificial retina

A graphene-based artificial retina project has managed to intermingle the European Union’s two major FET (Future and Emerging Technologies) funding projects, 1B Euros each to be disbursed over 10 years, the Graphene Flagship and the Human Brain Project. From an Aug. 7, 2014 Technische Universitaet Muenchen (TUM) news release (also on EurekAlert),

Because of its unusual properties, graphene holds great potential for applications, especially in the field of medical technology. A team of researchers led by Dr. Jose A. Garrido at the Walter Schottky Institut of the TUM is taking advantage of these properties. In collaboration with partners from the Institut de la Vision of the Université Pierre et Marie Curie in Paris and the French company Pixium Vision, the physicists are developing key components of an artificial retina made of graphene.

Retina implants can serve as optical prostheses for blind people whose optical nerves are still intact. The implants convert incident light into electrical impulses that are transmitted to the brain via the optical nerve. There, the information is transformed into images. Although various approaches for implants exist today, the devices are often rejected by the body and the signals transmitted to the brain are generally not optimal.

Already funded by the Human Brain Project as part of the Neurobotics effort, Garrido and his colleagues will now also receive funding from the Graphene Flagship. As of July 2014, the Graphene Flagship has added 86 new partners including TUM according to the news release.

Here’s an image of an ‘invisible’ graphene sensor (a precursor to developing an artificial retina),

Graphene electronics can be prepared on flexible substrates. Only the gold metal leads are visible in the transparent graphene sensor. (Photo: Natalia Hutanu / TUM)

Graphene electronics can be prepared on flexible substrates. Only the gold metal leads are visible in the transparent graphene sensor. (Photo: Natalia Hutanu / TUM)

Artificial retinas were first featured on this blog in an Aug. 18, 2011 posting about video game Deus Ex: Human Revolution which features a human character with artificial sight. The post includes links to a video of a scientist describing an artificial retina trial with 30 people and an Israeli start-up company, ‘Nano Retina’, along with information about ‘Eyeborg’, a Canadian filmmaker who on losing an eye in an accident had a camera implanted in the previously occupied eye socket.

More recently, a Feb. 15, 2013 posting featured news about the US Food and Drug Administration’s decision to allow sale of the first commercial artificial retinas in the US in the context of news about a neuroprosthetic implant in a rat which allowed it to see in the infrared range, normally an impossible feat.

Astonishing observation about gold nanoparticles and self-assembly

An Aug. 4, 2014 news item on ScienceDaily features research on self-assembling gold nanoparticles from Helmholtz-Zentrum Berlin für Materialien und Energie (HZB) and Humboldt-Universität zu Berlin (HU, Berlin),

Researchers at HZB in co-operation with Humboldt-Universität zu Berlin (HU, Berlin) have made an astonishing observation: they were investigating the formation of gold nanoparticles in a solvent and observed that the nanoparticles had not distributed themselves uniformly, but instead were self-assembled into small clusters.

An Aug. 4, 2014 HZB press release (also on EurekAlert), which originated the news item, provides additional technical information about the equipment used to make the observations,

This was determined using Small-Angle X-ray Scattering (SAXS) at BESSY II. A thorough examination with an [a transmission] electron microscope (TEM) confirmed their result. “The research on this phenomenon is now proceeding because we are convinced that such nanoclusters lend themselves as catalysts, whether in fuel cells, in photocatalytic water splitting, or for other important reactions in chemical engineering”, explains Dr. Armin Hoell of HZB. The results have just appeared in two peer reviewed international academic journals.

“What is special about the new process is that it is extremely simple and works with an environmentally friendly and inexpensive solvent”, explains Professor Klaus Rademann from HU Berlin. The solvent actually consists of two powders that one would sooner expect to find in agriculture that in a research laboratory: a supplement in chicken feed (choline chloride, aka vitamin B), and urea. British colleagues discovered a few years ago that mixing the two powders forms a transparent liquid able to dissolve metal oxides and heavy metals, called deep eutectic solvent (DES). The researchers in Berlin then positioned above the solvent gold foil that they could bombard with ions of noble gas in order to detach individual atoms of gold. This is how nanoparticles initially formed that distributed themselves in the solvent.

The researchers did not expect what happened next (from the press release),

The longer the bombardment (sputtering) of the gold foil lasted, the larger the nanoparticles could become, the scientists reasoned. However, this was not the case: the particles ceased growing at five nanometres. Instead, an increasing number of nanoparticles formed over longer sputtering times. The second surprise: these nanoparticles did not distribute themselves uniformly in the liquid, but instead self-assembled into small groups or clusters that could consist of up to twelve nanoparticles.

These kinds of observations cannot be easily made under a microscope, of course, but require instead an indirect, statistical approach: “Using small-angle X-ray scattering at BESSY II, we were not only able to ascertain that the nanoparticles are all around five nanometres in diameter, but also measure what the separations between them are. From these measurements, we found the nanoparticles arrange themselves into clusters”, explains Hoell.

“We ran computer models in advance of how the nanoparticles could distribute themselves in the solution to better understand the measurement results, and then compared the results of the simulation with the results of the small-angle X-ray scattering”, explains Dr. Vikram Singh Raghuwanshi, who works as a postdoc at HU Berlin as well as HZB. An image from the cryogenic transmission electron microscope that colleagues at HU prepared confirmed their findings. “But we could not have achieved this result using only electron microscopy, since it can only display details and sections of the specimen”, Hoell emphasised. “Small-angle X-ray scattering is indispensable for measuring general trends and averages!”

The press release concludes thusly,

It is obvious to the researchers that the special DES-solvent plays an important role in this self-organising process: various interactions between the ions of the solvent and the particles of gold result firstly in the nanoparticles reaching only a few thousand atoms in size, and secondly that they mutually attract somewhat – but only weakly – so that the small clusters arise. “We know, however, that these kinds of small clusters of nanoparticles are especially effective as catalysts for chemical reactions we want: a many-fold increase in the reaction speed due only to particle arrangement has already been demonstrated”, says Rademann.

Here are links to and citations for the two papers the team has published on their latest work,

Deep Eutectic Solvents for the Self-Assembly of Gold Nanoparticles: A SAXS, UV–Vis, and TEM Investigation by Vikram Singh Raghuwanshi, Miguel Ochmann, Armin Hoell, Frank Polzer, and Klaus Rademann. Langmuir, 2014, 30 (21), pp 6038–6046 DOI: 10.1021/la500979p Publication Date (Web): May 11, 2014

Copyright © 2014 American Chemical Society

Self-assembly of gold nanoparticles on deep eutectic solvent (DES) surfaces by V. S. Raghuwanshi, M. Ochmann, F. Polzer, A. Hoell and K. Rademann.  Chem. Commun., 2014,50, 8693-8696 DOI: 10.1039/C4CC02588A
First published online 10 Jun 2014

Both papers are behind a paywall.

This research is being presented at two conferences, one of which is taking place now (Aug.5, 2014; from the press release),

Dr. Raghuwanshi will give a talk on these results, as well as providing a preview of the catalysis research approaches now planned, at the International conference, IUCr2014, taking place from 5-12 August 2014 in Montreal, Canada.

In the coming year, HZB will incidentally be one of the hosts of the 16th International Small-Angle Scattering Conference, SAS2015.

There you have all the news.