Tag Archives: Germany

A compendium of attosecond nanophysics papers

A Feb.11, 2015 news item on Nanowerk features a new book on attosecond nanophysics,

A steadily growing treasure of knowledge has accumulated in the past years on attosecond nanophysics of nanostructured solids, which has, so far, not been sorted and structured.

This has now been rectified by two physics professors, Peter Hommelhoff and Matthias Kling. Together with numerous other authors, they have collected the studies conducted in this very young science field in their book Attosecond Nanophysics: From Basic Science to Applications.

The result is an overview for PhD students and interested students as well as other physicists, who like to gain an overview of ultrafast nanooptics and related fields.

A Feb. 9, 2015 Munich-Centre for Advanced Photonics Technische Universität München (TUM) press release by Thorsten Naeser, which originated the news item, describes the book further,

Elementary particles interacting with light move so fast, that they can only be observed with the help of sophisticated techniques. Typically, the motion of excited electrons in atoms or solids, for example, occurs on attosecond timescales. An attosecond is a billionth of a billionth of a second (10-18 s). Starting a few years ago, scientists around the world have been exploring how electrons in nanostructured solids behave when influenced by extremely short and intense light pulses. In order to observe such rapid electron motion, physicists used light pulses with durations of a few femtoseconds down to attoseconds (a femtosecond lasts 1000 attoseconds). These light flashes act, for example, as an ultrafast shutter, following the principles of conventional camera technology, to take pictures of the fast moving particles in the nanocosm.

The researchers’ new book is a collection of their accumulated knowledge in this new research area, a first publication of its kind. The main attention here is not drawn to single atoms or molecules but rather to nanostructured solids, which are typically comprised of many millions of atoms. The main question is: how do electrons behave under the influence of intense light? The answer to this question is of fundamental importance. This research could lead to new technologies, where the electromagnetic field of the light wave can be used to carefully control minute electronic building blocks. With such lightwave-controlled electronics, switching speeds in the petahertz domain (1015 Hz, one million times a billion operations per second) may be reached. “With this technology we could accelerate current electronics by up to a million times”, explains Matthias Kling, one of the editors of the book.

“Attosecond nanophysics” contains the descriptions of experiments which have been conducted in the last years and resulted in groundbreaking scientific publications. The book also contains their mathematical and physical foundations. “All authors are pioneers in this field”, describes the second editor, Peter Hommelhoff. “We have compiled – for the first time – a book, which conveys a current overview of our knowledge and activities on currently the fastest phenomena in the area of small solids”, elaborates Hommelhoff. With this the authors provide students of upper level physics and PhD students a handy overview of the topic. But also interested colleagues from other disciplines can use this book to gain a first, comprehensive insight into this young field of attosecond nanophysics.

Here’s a link to where you can purchase it.

Nanoparticles in 3D courtesy of x-rays

A Feb. 4, 2015 Deutsches Elektronen-Synchrotron (DESY) press release (also on EurekAlert) announces a 3D first,

For the first time, a German-American research team has determined the three-dimensional shape of free-flying silver nanoparticles, using DESY’s X-ray laser FLASH. The tiny particles, hundreds of times smaller than the width of a human hair, were found to exhibit an unexpected variety of shapes, as the physicists from the Technical University (TU) Berlin, the University of Rostock, the SLAC National Accelerator Laboratory in the United States and from DESY report in the scientific journal Nature Communications. Besides this surprise, the results open up new scientific routes, such as direct observation of rapid changes in nanoparticles.

The press release goes on to describe the work in more detail,

“The functionality of nanoparticles is linked to their geometric form, which is often very difficult to determine experimentally,” explains Dr. Ingo Barke from the University of Rostock. “This is particularly challenging when they are present as free particles, that is, in the absence of contact with a surface or a liquid.”

The nanoparticle shape can be revealed from the characteristic way how it scatters X-ray light. Therefore, X-ray sources like DESY’s FLASH enable a sort of super microscope into the nano-world. So far, the spatial structure of nanoparticles has been reconstructed from multiple two-dimensional images, which were taken from different angles. This procedure is uncritical for particles on solid substrates, as the images can be taken from many different angles to uniquely reconstruct their three-dimensional shape.

“Bringing nanoparticles into contact with a surface or a liquid can significantly alter the particles, such that you can no longer see their actual form,” says Dr. Daniela Rupp from the TU Berlin. A free particle, however, can only be measured one time in flight before it either escapes or is destroyed by the intense X-ray light. Therefore, the scientists looked for a way to record the entire structural information of a nanoparticle with a single X-ray laser pulse.

To achieve this goal, the scientists led by Prof. Thomas Möller from the TU Berlin and Prof. Karl-Heinz Meiwes-Broer and Prof. Thomas Fennel from the University of Rostock employed a trick. Instead of taking usual small-angle scattering images, the physicists recorded the scattered X-rays in a wide angular range. “This approach virtually captures the structure from many different angles simultaneously from a single laser shot,” explains Fennel.

The researchers tested this method on free silver nanoparticles with diameters of 50 to 250 nanometres (0.00005 to 0.00025 millimetres). The experiment did not only verify the feasibility of the tricky method, but also uncovered the surprising result that large nanoparticles exhibit a much greater variety of shapes than expected.

The shape of free nanoparticles is a result of different physical principles, particularly the particles’ effort to minimize their energy. Consequently, large particles composed of thousands or millions of atoms often yield predictable shapes, because the atoms can only be arranged in a particular way to obtain an energetically favourable state.

In their experiment, however, the researchers observed numerous highly symmetrical three-dimensional shapes, including several types known as Platonic and Archimedean bodies. Examples include the truncated octahedron (a body consisting of eight regular hexagons and six squares) and the icosahedron (a body made up of twenty equilateral triangles). The latter is actually only favourable for extremely small particles consisting of few atoms, and its occurrence with free particles of this size was previously unknown. “The results show that metallic nanoparticles retain a type of memory of their structure, from the early stages of growth to a yet unexplored size range,” emphasizes Barke.

Due to the large variety of shapes, it was especially important to use a fast computational method so that the researchers were capable of mapping the shape of each individual particle. The scientists used a two-step process: the rough shape was determined first and then refined using more complex simulations on a super computer. This approach turned out to be so efficient that it could not only determine various shapes reliably, but could also differentiate between varying orientations of the same shape.

This new method for determining the three-dimensional shape and orientation of nanoparticles with a single X-ray laser shot opens up a wide spectrum of new research directions. In future projects, particles could be directly “filmed” in three dimensions during growth or during phase changes. “The ability to directly film the reaction of a nanoparticle to an intense flash of X-ray light has been a dream for many physicists – this dream could now come true, even in 3D!,” emphasises Rupp.

The researchers have provided an image showing their work,

Caption: This is a wide-angle X-ray diffraction image of a truncated twinned tetrahedra nanoparticle. Credit: Hannes Hartmann/University of Rostock

Caption: This is a wide-angle X-ray diffraction image of a truncated twinned tetrahedra nanoparticle.
Credit: Hannes Hartmann/University of Rostock

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

The 3D-architecture of individual free ​silver nanoparticles captured by X-ray scattering by Ingo Barke, Hannes Hartmann, Daniela Rupp, Leonie Flückiger, Mario Sauppe, Marcus Adolph, Sebastian Schorb, Christoph Bostedt, Rolf Treusch, Christian Peltz, Stephan Bartling, Thomas Fennel, Karl-Heinz Meiwes-Broer, & Thomas Möller. Nature Communications 6, Article number: 6187 doi:10.1038/ncomms7187 Published 04 February 2015

This article is open access.

India’s S. R. Vadera and Narendra Kumar (Defence Laboratory, Jodhpur) review stealth and camouflage technology

Much of the military nanotechnology information I stumble across is from the US, Canada, and/or Europe and while S. R. Vadera and Narendra Kumar (of India’s Defence Laboratory, Jodhpur [DLJ]) do offer some information about India’s military nanotechnology situation, they focus largely on the US, Canada, and Europe. Happily, their Jan. 30, 2014 Nanowerk Spotlight 6 pp. article titled, Nanotechnology and nanomaterials for camouflage and stealth applications offers a comprehensive review of the field,

This article briefly describes how nanomaterials and nanotechnology can be useful in the strategic area of camouflage and stealth technology. …

The word camouflage has its origin in the French word camoufler which means to disguise. In English dictionary, the word meaning was initially referred to concealment or disguise of military objects in order to prevent detection by the enemy. In earlier days, specifically before 20th century, the only sensor available to detect was human eye and so camouflage was confined to the visible light only. The rapid development of sensor technology outside the visible range has forced to use new definition and terminologies for camouflage.

Modern definition of camouflage may be given as “delay or deny detection of a military target by detectors operating over multispectral wavelength region of electromagnetic spectrum or non-electromagnetic radiation e.g., acoustic, magnetic, etc. Multispectral camouflage, low-observability, countermeasures, signature management, and stealth technology are some of the new terminologies used now instead of camouflage.

In modern warfare, stealth technology is applied mostly to aircrafts and combat weapons. Stealth technology can improve the survivability and performance of aircrafts and weapons to gain the upper hand. Stealth technology involves the minimization of acoustic, optical, infra-red, and electromagnetic signatures. Among them, the minimization of electromagnetic signature, particularly in microwave region, is the most important. It can be realized in several ways which include stealth shaping design, radar absorbing material (RAM), and radar absorbing structures (RAS)1.

Unexpectedly, there are multiple reference to Canadian stealth and camouflage technology all of them courtesy of one company, HyperStealth Biotechnology Corp. based in Maple Ridge, BC, Canada. mentioned in my Jan. 7, 2013 post about an invisibility cloak.

Getting back to the article, the authors have this to say about the international ‘stealth scene’,

Today virtually every nation and many non-state military organizations have access to advanced tactical sensors for target acquisition (radar and thermal imagers) and intelligence gathering surveillance systems (ground and air reconnaissance). Precision-guided munitions exist that can be delivered by artillery, missiles, and aircraft and that can operate in the IR [infra red] region of the electromagnetic spectrum. These advanced imaging sights and sensors allow enemies to acquire and engage targets through visual smoke, at night, and under adverse weather conditions.

To combat these new sensing and detection technologies, camouflage paint, paint additives, tarps, nets and foams have been developed for visual camouflage and thermal and radar signature suppression. …

One comment, thermal and radar signature suppression sounds like another way of saying ‘invisibility cloak’.

The authors also had something to say about the application of nanomaterials/nanotechnology,

Nanotechnology has significant influence over a set of many interrelated core skills of land forces like protection, engagement, detection, movements, communications and information collection together with interrelated warfare strategies. Additionally, nanotechnology also has its role in the development of sensor for warfare agents, tagging and tracking and destruction of CBRN [chemical, biological, radiological and nuclear] warfare agents, besides many other possible applications.

There’s a very interesting passage on ‘stealth coatings’ which includes this,

These new coatings can be attached to a wide range of surfaces and are the first step towards developing ‘shape shifting clothing’ capable of adapting to the environment around it. …

In another example, an Israeli company, Nanoflight has claimed to develop a new nano paint, which can make it near impossible to detect objects painted with the material. The company is continuing their efforts to extend the camouflage action of these paints in infrared region as well. BASF, Germany (uses polyisocynate dendrimer nanoparticles) and Isotronic Corporation, USA are among the very few agencies coming up with chemical agent resistant and innovative camouflage (CARC) coatings using nanomaterials. In India, paints developed by Defence Laboratory, Jodhpur (DLJ) using polymeric nanocomposites, nanometals and nanometal complexes are perhaps the first examples of multispectral camouflage paints tested in VIS-NIR and thermal infrared regions of the electromagnetic spectrum at system level. The nanocomposites developed by DLJ provide excellent scope for the tuning of reflectance properties both in visible and near infrared region6 of electromagnetic spectrum leading to their applications on military targets (Fig. 4).

For anyone interested in this topic, I recommend reading the article in its entirety.

One final note, I found this Wikipedia entry about the DLJ, (Note: A link has been removed)

Defence Laboratory (DLJ) is westernmost located, an strategically important laboratory of the Defence Research and Development Organisation (DRDO).

Its mission is development of Radio Communication Systems, Data links, Satellite Communication Systems, Millimeter Wave Communication systems. There are two divisions in laboratory

NRMA (Nuclear Radiation’s Management and Applications) Division
Camouflage Division

That’s all folks!

Carbohydrates could regulate the toxicity of silver nanoparticles

According to a Jan. 22, 2015 news item on Azonano, you can vary the toxic impact of silver nanoparticles on cells by coating them with carbohydrates,

The use of colloidal silver to treat illnesses has become more popular in recent years, but its ingestion, prohibited in countries like the US, can be harmful to health. Scientists from the Max Planck Institute in Germany have now confirmed that silver nanoparticles are significantly toxic when they penetrate cells, although the number of toxic radicals they generate can vary by coating them with carbohydrates.

A Jan. 21, 2015 Spanish Foundation for the Science and Technology (FECYT) news release on EurekAlert, which originated the news item, describes colloidal silver and its controversies and the research on limiting silver nanoparticle toxicity to cells,

Silver salts have been used externally for centuries for their antiseptic properties in the treatment of pains and as a surface disinfectant for materials. There are currently people who use silver nanoparticles to make homemade potions to combat infections and illnesses such as cancer and AIDS, although in some cases the only thing they achieve is argyria or blue-tinged skin.

Health authorities warn that there is no scientific evidence that supports the therapeutic efficiency of colloidal silver and in fact, in some countries like the US, its ingestion is prohibited. On the contrary, there are numerous studies which demonstrate the toxicity of silver nanoparticles on cells.

One of these studies has just been published in the ‘Journal of Nanobiotechnology‘ by an international team of researchers coordinated from the Max Planck Institute of Colloids and Interfaces (Germany). “We have observed that it is only when silver nanoparticles enter inside the cells that they produce serious harm, and that their toxicity is basically due to the oxidative stress they create,” explains the Spanish chemist Guillermo Orts-Gil, project co-ordinator, to SINC.

To carry out the study, the team has analysed how different carbohydrates act on the surface of silver nanoparticles (Ag-NP) of around 50 nanometres, which have been introduced into cultures of liver cells and tumour cells from the nervous system of mice. The results reveal that, for example, the toxic effects of the Ag-NP are much greater if they are covered with glucose instead of galactose or mannose.

‘Trojan horse’ mechanism

Although not all the details on the complex toxicological mechanisms are known, it is known that the nanoparticles use a ‘Trojan horse’ mechanism to trick the membrane’s defences and get inside the cell. “The new data shows how the different carbohydrate coatings regulate the way in which they do this, and this is hugely interesting for controlling their toxicity and designing future trials,” points out Orts-Gil.

The researcher highlights that there is a “clear correlation between the coating of the nanoparticles, the oxidative stress and toxicity, and thus, these results open up new perspectives on regulating the bioactivity of the Ag-NP through the use of carbohydrates”.

Silver nanoparticles are not only used to make homemade remedies; they are also increasingly used in drugs such as vaccines, as well as products such as clothes and cleaning cloths.

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

Carbohydrate functionalization of silver nanoparticles modulates cytotoxicity and cellular uptake by David C Kennedy, Guillermo Orts-Gil, Chian-Hui Lai, Larissa Müller, Andrea Haase, Andreas Luch, and Peter H Seeberger. Journal of Nanobiotechnology 2014, 12:59 doi:10.1186/s12951-014-0059-z published 19 December 2014

This is an open access paper. One final observation, David Kennedy, the lead author, is associated with both the Max Planck Institute and the Canada National Research Council and, depending on which news release (SINC news site Jan. 20, 2015) you read, Guillermo Orts-Gil is identified as a Spanish chemist and coordinator for SINC (Science News and Information Service).

Atoms can be in two places at once

A Jan. 20, 2015 news item on Nanowerk offers a brief history of quantum mechanics,

Can a penalty kick simultaneously score a goal and miss? For very small objects, at least, this is possible: according to the predictions of quantum mechanics, microscopic objects can take different paths at the same time. The world of macroscopic objects follows other rules: the football always moves in a definite direction. But is this always correct? Physicists of the University of Bonn have constructed an experiment designed to possibly falsify this thesis. Their first experiment shows that Caesium atoms can indeed take two paths at the same time.

Almost 100 years ago physicists Werner Heisenberg, Max Born und Erwin Schrödinger created a new field of physics: quantum mechanics. Objects of the quantum world – according to quantum theory – no longer move along a single well-defined path. Rather, they can simultaneously take different paths and end up at different places at once.

A Jan. 20, 2015 Universität Bonn (University of Bonn) press release, which originated the news item, describes both the experiment and the thought process which led to the experiment,

At the level of atoms, it looks as if objects indeed obey quantum mechanical laws. Over the years, many experiments have confirmed quantum mechanical predictions. In our macroscopic daily experience, however, we witness a football flying along exactly one path; it never strikes the goal and misses at the same time.

“There are two different interpretations,” says Dr. Andrea Alberti of the Institute of Applied Physics of the University of Bonn. “Quantum mechanics allows superposition states of large, macroscopic objects. But these states are very fragile, even following the football with our eyes is enough to destroy the superposition and makes it follow a definite trajectory.”

But it could also be that footballs obey completely different rules than those applying for single atoms. “Let us talk about the macro-realistic view of the world,” Alberti explains. “According to this interpretation, the ball always moves on a specific trajectory, independent of our observation, and in contrast to the atom.”

In collaboration with Dr. Clive Emary of the University of Hull in the U.K., the Bonn team has come up with an experimental scheme that may help to answer this question. “The challenge was to develop a measurement scheme of the atoms’ positions which allows one to falsify macro-realistic theories,” adds Alberti.

The physicists describe their research in the journal “Physical Review X:” With two optical tweezers they grabbed a single Caesium atom and pulled it in two opposing directions. In the macro-realist’s world the atom would then be at only one of the two final locations. Quantum-mechanically, the atom would instead occupy a superposition of the two positions.

“We have now used indirect measurements to determine the final position of the atom in the most gentle way possible,” says the PhD student Carsten Robens. Even such an indirect measurement (see figure) significantly modified the result of the experiments. This observation excludes – falsifies, as Karl Popper would say more precisely – the possibility that Caesium atoms follow a macro-realistic theory. Instead, the experimental findings of the Bonn team fit well with an interpretation based on superposition states that get destroyed when the indirect measurement occurs. All that we can do is to accept that the atom has indeed taken different paths at the same time.

“This is not yet a proof that quantum mechanics hold for large objects,” cautions Alberti. “The next step is to separate the Caesium atom’s two positions by several millimetres. Should we still find the superposition in our experiment, the macro-realistic theory would suffer another setback.”

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

Ideal negative measurements in quantum walks disprove theories based on classical trajectories by Carsten Robens, Wolfgang Alt, Dieter Meschede, Clive Emary, und Andrea Alberti. Physical Review X, 20.1.2015 (DOI: 10.1103/PhysRevX.5.011003)

This is an open access paper,

PlasCarb: producing graphene and renewable hydrogen from food waster

I have two tidbits about PlasCarb the first being an announcement of its existence and the second an announcement of its recently published research. A Jan. 13, 2015 news item on Nanowerk describes the PlasCarb project (Note: A link has been removed),

The Centre for Process Innovation (CPI) is leading a European collaborative project that aims to transform food waste into a sustainable source of significant economic added value, namely graphene and renewable hydrogen.

The project titled PlasCarb will transform biogas generated by the anaerobic digestion of food waste using an innovative low energy microwave plasma process to split biogas (methane and carbon dioxide) into high value graphitic carbon and renewable hydrogen.

A Jan. 13, 2015 CPI press release, which originated the news item, describes the project and its organization in greater detail,

CPI  as the coordinator of the project is responsible for the technical aspects in the separation of biogas into methane and carbon dioxide, and separating of the graphitic carbon produced from the renewable hydrogen. The infrastructure at CPI allows for the microwave plasma process to be trialled and optimised at pilot production scale, with a future technology roadmap devised for commercial scale manufacturing.

Graphene is one of the most interesting inventions of modern times. Stronger than steel, yet light, the material conducts electricity and heat. It has been used for a wide variety of applications, from strengthening tennis rackets, spray on radiators, to building semiconductors, electric circuits and solar cells.

The sustainable creation of graphene and renewable hydrogen from food waste in provides a sustainable method towards dealing with food waste problem that the European Union faces. It is estimated that 90 million tonnes of food is wasted each year, a figure which could rise to approximately 126 million tonnes by 2020. In the UK alone, food waste equates to a financial loss to business of at least £5 billion per year.

Dr Keith Robson, Director of Formulation and Flexible Manufacturing at CPI said, “PlasCarb will provide an innovative solution to the problems associated with food waste, which is one of the biggest challenges that the European Union faces in the strive towards a low carbon economy.  The project will not only seek to reduce food waste but also use new technological methods to turn it into renewable energy resources which themselves are of economic value, and all within a sustainable manner.”

PlasCarb will utilise quality research and specialist industrial process engineering to optimise the quality and economic value of the Graphene and hydrogen, further enhancing the sustainability of the process life cycle.

Graphitic carbon has been identified as one of Europe’s economically critical raw materials and of strategic performance in the development of future emerging technologies. The global market for graphite, either mined or synthetic is worth over €10 billion per annum. Hydrogen is already used in significant quantities by industry and recognised with great potential as a future transport fuel for a low carbon economy. The ability to produce renewable hydrogen also has added benefits as currently 95% of hydrogen is produced from fossil fuels. Moreover, it is currently projected that increasing demand of raw materials from fossil sources will lead to price volatility, accelerated environmental degradation and rising political tensions over resource access.

Therefore, the latter stages of the project will be dedicated to the market uptake of the PlasCarb process and the output products, through the development of an economically sustainable business strategy, a financial risk assessment of the project results and a flexible financial model that is able to act as a primary screen of economic viability. Based on this, an economic analysis of the process will be determined. Through the development of a decentralised business model for widespread trans-European implementation, the valorisation of food waste will have the potential to be undertaken for the benefit of local economies and employment. More specifically, three interrelated post project exploitation markets have been defined: food waste management, high value graphite and RH2 sales.

PlasCarb is a 3-year collaborative project, co-funded under the European Union’s Seventh Framework Programme (FP7) and will further reinforce Europe’s leading position in environmental technologies and innovation in high value Carbon. The consortium is composed of eight partners led by CPI from five European countries, whose complimentary research and industrial expertise will enable the required results to be successfully delivered. The project partners are; The Centre for Process Innovation (UK), GasPlas AS (NO), CNRS (FR), Fraunhofer IBP (DE), Uvasol Ltd (UK), GAP Waste Management (UK), Geonardo Ltd. (HU), Abalonyx AS (NO).

You can find PlasCarb here.

The second announcement can be found in a PlasCarb Jan. 14, 2015 press release announcing the publication of research on heterostructures of graphene ribbons,

Few materials have received as much attention from the scientific world or have raised so many hopes with a view to their potential deployment in new applications as graphene has. This is largely due to its superlative properties: it is the thinnest material in existence, almost transparent, the strongest, the stiffest and at the same time the most strechable, the best thermal conductor, the one with the highest intrinsic charge carrier mobility, plus many more fascinating features. Specifically, its electronic properties can vary enormously through its confinement inside nanostructured systems, for example. That is why ribbons or rows of graphene with nanometric widths are emerging as tremendously interesting electronic components. On the other hand, due to the great variability of electronic properties upon minimal changes in the structure of these nanoribbons, exact control on an atomic level is an indispensable requirement to make the most of all their potential.

The lithographic techniques used in conventional nanotechnology do not yet have such resolution and precision. In the year 2010, however, a way was found to synthesise nanoribbons with atomic precision by means of the so-called molecular self-assembly. Molecules designed for this purpose are deposited onto a surface in such a way that they react with each other and give rise to perfectly specified graphene nanoribbons by means of a highly reproducible process and without any other external mediation than heating to the required temperature. In 2013 a team of scientists from the University of Berkeley and the Centre for Materials Physics (CFM), a mixed CSIC (Spanish National Research Council) and UPV/EHU (University of the Basque Country) centre, extended this very concept to new molecules that were forming wider graphene nanoribbons and therefore with new electronic properties. This same group has now managed to go a step further by creating, through this self-assembly, heterostructures that blend segments of graphene nanoribbons of two different widths.

The forming of heterostructures with different materials has been a concept widely used in electronic engineering and has enabled huge advances to be made in conventional electronics. “We have now managed for the first time to form heterostructures of graphene nanoribbons modulating their width on a molecular level with atomic precision. What is more, their subsequent characterisation by means of scanning tunnelling microscopy and spectroscopy, complemented with first principles theoretical calculations, has shown that it gives rise to a system with very interesting electronic properties which include, for example, the creation of what are known as quantum wells,” pointed out the scientist Dimas de Oteyza, who has participated in this project. This work, the results of which are being published this very week in the journal Nature Nanotechnology, therefore constitutes a significant success towards the desired deployment of graphene in commercial electronic applications.

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

Molecular bandgap engineering of bottom-up synthesized graphene nanoribbon heterojunctions by Yen-Chia Chen, Ting Cao, Chen Chen, Zahra Pedramrazi, Danny Haberer, Dimas G. de Oteyza, Felix R. Fischer, Steven G. Louie, & Michael F. Crommie. Nature Nanotechnology (2015) doi:10.1038/nnano.2014.307 Published online 12 January 2015

This article is behind a paywall but there is a free preview available via ReadCube access.

Gummy bears and an antiparticle story

Gummy bear on the experimental set-up – To avoid influences of the colour, the scientists only examined red gummy bears using positrons. Photo: Wenzel Schürmann / TUM

Gummy bear on the experimental set-up – To avoid influences of the colour, the scientists only examined red gummy bears using positrons. Photo: Wenzel Schürmann / TUM

Gelatin is commonly used as a delivery system for drugs. It’s particularly effective for timed release of medications, in part, due to tiny pores. According to a Dec. 29, 2014 news item on Nanowerk, researchers at the Technische Universität München (TUM) have found a way to measure these pores using gummy bears in a bid to improve gelatin’s effectiveness as a delivery system (Note: A link has been removed),

Gelatin is used in the pharmaceutical industry to encapsulate active agents. It protects against oxidation and overly quick release. Nanopores in the material have a significant influence on this, yet they are difficult to investigate. In experiments on gummy bears, researchers at Technische Universität München (TUM) have now transferred a methodology to determine the free volume of gelatin preparations (“The Free Volume in Dried and H2O-Loaded Biopolymers Studied by Positron Lifetime Measurements”).

A Dec. ??, 2014 TUM press release, which originated the news item, describes the research in more detail,

Custom-tailored gelatin preparations are widely used in the pharmaceutical industry. Medications that do not taste good can be packed into gelatin capsules, making them easier to swallow. Gelatin also protects sensitive active agents from oxidation. Often the goal is to release the medication gradually. In these cases slowly dissolving gelatin is used.

Nanopores in the material play a significant role in all of these applications. “The larger the free volume, the easier it is for oxygen to penetrate it and harm the medication, but also the less brittle the gelatin,” says PD Dr. Christoph Hugenschmidt, a physicist at TU München.

However, characterizing the size and distribution of these free spaces in the unordered biopolymer is difficult. A methodology adapted by the Garching physicists Christoph Hugenschmidt and Hubert Ceeh provides relief. “Using positrons as highly mobile probes, the volume of the nanopores can be determined, especially also in unordered systems like netted gelatins,” says Christoph Hugenschmidt.

Positrons are the antiparticles corresponding to electrons. They can be produced in the laboratory in small quantities, as in this experiment, or in large volumes at the Heinz Maier Leibnitz Research Neutron Source (FRM II) of the TU München. If a positron encounters an electron they briefly form an exotic particle, the so-called positronium. Shortly after it annihilates to a flash of light.

To model gelatin capsules that slowly dissolve in the stomach, the scientists bombarded red gummy bears in various drying stages with positrons. Their measurements showed, that in dry gummy bears the positroniums survive only 1.2 nanoseconds on average while in soaked gummy bears it takes 1.9 nanoseconds before they are annihilated. From the lifetime of the positroniums the scientists can deduce the number and size of nanopores in the material.

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

The Free Volume in Dried and H2O-Loaded Biopolymers Studied by Positron Lifetime Measurements by Christoph Hugenschmidt and Hubert Ceeh. J. Phys. Chem. B, 2014, 118 (31), pp 9356–9360 DOI: 10.1021/jp504504p Publication Date (Web): July 21, 2014
Copyright © 2014 American Chemical Society

This paper is behind a paywall but there is another, freely available, undated paper on the topic (Note: the July 2014 published paper is cited there).

Drying Gummi Bears Reduce Anti-Matter Lifetime by Christoph Hugenschmidt und Hubert Ceeh.

Enjoy!

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,

JülichMolecules

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.