HOT article: Scalable and cost effective patterning of graphene layers

Written by Sebastian Axmann.

Visual image after EBL treatment, corresponding Raman spectroscopy map of a graphene flake and Raman spectra recorded at different spots on the sample.

Research articles on graphene have been numerously been presented throughout the last decade, indicating the promising future of this material. However, bridging the gap between laboratory research and industrial application remains difficult due to missing specialized large-scale production equipment.

A new article recently published by A. Caglinani et al. introduces an electron beam-based patterning technique using solely widely available clean-room equipment. Based on the findings of the paper, graphene structuring could become a more widespread processing technique.

The researchers developed a patterning process utilizing an industry-standard electron beam lithography system and a standard oven to achieve a resolution of 40 nm.

In the first step, a graphene layer is irradiated by the electron beam which locally generates defects within the crystal lattice. The damage was found by the researchers to be spatially confined to the exposed areas, thus allowing for arbitrary patterns.

The second step comprised etching the irradiated areas by means of hot air at atmospheric pressure. The high defect density (e.g. dangling bonds) induced by the electron beam lead to a large difference in the etch rate compared to the unmodified areas. By exposing the samples for 16 min at 435°C to air, the previously irradiated areas were selectively etched.

In conclusion, the presented process can be used to easily structure graphene layers for future application without the need for specialized equipment. According to the authors, future improvements could reduce the minimum feature size further.

Alberto Cagliani, Niclas Lindvall, Martin Benjamin Barbour Spanget Larsen, David M. A. Mackenzie, Bjarke Sørensen Jessen, Timothy J. Booth and Peter Bøggild
Nanoscale, 2015, 7, 6271-6277. DOI: 10.1039/C4NR07585D

Sebastian Axmann is a guest web-writer for the Nanoscale blog. His interests comprise manufacturing and metrology of nanostructures as well as their usage in current semiconductor devices. He also posts links to interesting research articles on Twitter: @SebastianAxmann.

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Viruses: Feeling the strain

Written by Dr Lee Barrett.

Viruses are highly complex biological nanostructures.  This complexity has renewed an interest in viruses from the perspective of fundamental physics at the nanoscale. An understanding of the mechanical properties of virus particles at the molecular level can reveal information regarding stiffness, intrinsic elasticity, structural strength and resistance to mechanical fatigue.  This information can provide a basis for researchers to engineer virus-based nanoparticles as nanodevices/ nanocontainers for different biotechnological applications.

The MVM virion.

Castellanos and co-workers have endeavoured to understand the conformational stability and dynamics of the minute virus of mice (MVM), a small ~ 25 nm virus particle, which serves as a model system to understand some of the mechanical properties of viruses. To this end, the researchers have investigated the linkage between the DNA-mediated increase in mechanical stiffness and heat-induced structural changes, and a quantitative relationship between mechanical elasticity and conformational dynamics in MVM nanoparticles.

The researchers used a combination of transmission electron microscopy (TEM) and atomic force microscopy (AFM) for determining the thermal inactivation behaviour and the mechanical stiffness of the viruses, respectively.  By utilizing these techniques, the researchers have deduced that infectious MVM particles may have evolved architectural functions that increase their survival in thermally stressed environments.

This proof-of-principle study has demonstrated that nanoscale features of virus nanoparticles can be probed analytically using AFM and the elucidation of these features have future impact in the field of protein engineering.

Milagros Castellanos, Pablo J. P. Carrillo and Mauricio G. Mateu
Nanoscale, 2015, 7, 5654-5664. DOI: 10.1039/C4NR07046A

Dr Lee Barrett is a guest web writer for the Nanoscale blog. Lee is currently a postdoctoral researcher in the Centre for Molecular Nanometrology at the University of Strathclyde. His research is currently focused on the development of nanoparticle-based sensors and surface enhanced Raman scattering (SERS). Follow him on twitter @L_Bargie.

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In situ synthesis of luminescent carbon nanoparticles toward target bioimaging

Written by Dr Mike Barrow.

In situ synthesis of luminescent carbon nanoparticles toward target bioimaging

An in-situ synthesis of biocompatible fluorescent carbon nanoparticles (FCNs) is reported for targeted bioimaging. The nanoparticles were formed via dehydration of hyalurinic acid (HA), and through careful alteration of the carbonisation times, the total content of HA and fluorescence in the carbon nanoparticles could be controlled. Sharker et al. then compared two colloidally stable FCN samples; one partially carbonised sample that still contained some HA (HA-FCN), against a “non-specific” fully carbonised sample containing no HA (FCN).

Before in vivo testing, both sets of particles were tested on different cell lines at dosages up to 1.0 mg/ml and were found to not affect cell viability. Interestingly, HA-FCNs showed more uptake than the non-specific FCNs, and were internalised more various cell lines; including cancer cells. This is speculated to be due to the over expression of the CD-44 receptor which can facilitate uptake of particles containing targeting molecules such as HA-FCNs. In vivo bio-distribution studies showed more accumulation of HA-FCNs in tumours pre-implanted into mice compared to FCNs, when particles were injected into the tail vein. This is expected to be of enormous potential in not only bioimaging, but also drug delivery and diagnostics.

In situ synthesis of luminescent carbon nanoparticles toward target bioimaging
Shazid Md. Sharker, Sung Min Kim, Jung Eun Lee, Ji Hoon Jeong, Insik In, Kang Dea Lee, Haeshin Lee and Sung Young Park
Nanoscale, 2015, 7, 5468-5475. DOI: 10.1039/C4NR07422J

Dr Mike Barrow is a guest web writer for the Nanoscale blog. He currently works as a Postdoctoral Researcher at the University of Liverpool.

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Nanoscale journals working together

Nanoscale & Nanoscale Horizons

The launch of Nanoscale Horizons seeks to build on and strengthen the nanoscience content already published in journals across the Royal Society of Chemistry portfolio. In particular, Nanoscale Horizons will complement and work alongside Nanoscale to provide a rounded view of innovation, and bridge the various disciplines in research across nanoscience and nanotechnology.

Nanoscale Horizons aims to publish first reports of exceptional significance in the field, therefore positioning itself as a premier journal in its field. The journal will publish leading research containing a clear conceptual advance and new insights into the topic presented. As such, there will be highly stringent criteria for publication, imposed by our Scientific Editors and Publishing Editors.

Nanoscale will continue to publish high impact research across the breadth of nanoscience and nanotechnology. The criteria for publication remain the same and will continue to be upheld by the journal’s Associate Editors to maintain Nanoscale’s reputation for publishing high quality, community-spanning research.

As with other Royal Society of Chemistry journals, the Nanoscale Horizons Editorial team will try to find the most suitable home for any manuscript that we receive. We endeavour to provide authors with the option to automatically transfer their manuscript to Nanoscale or another journal within our portfolio, where manuscripts are deemed more suitable for publication elsewhere.

To find out more about Nanoscale Horizons and keep up-to-date with all of the latest news, visit the webpage and sign up for the e-alerts.

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Nanoscale’s new sister

Introducing Nanoscale Horizons – launching next year

The home for rapid reports of exceptional significance in nanoscience and nanotechnology is on its way.

Our newest journal will work alongside Nanoscale to provide a rounded view of innovation in nano research, and bridge the various disciplines involved with nanoscience and nanotechnology. We’ll be looking for high impact work in fields ranging from physics and chemistry to IT, healthcare and detection science.

A pioneering Editorial Board Chair

Our Editorial Board Chair is Professor Harold Craighead, Professor of Engineering at Cornell University, USA and a pioneer in nanofabrication methods. He will head up an expert editorial board, led by Executive Editor Dr Fiona McKenzie.

Rapid reports, cutting-edge research

The first issue in 2016 will lay the groundwork for what aims to be the journal of choice for outstanding research across a broad spectrum.

Articles published will benefit from wide exposure, and content published during 2016 and 2017 is free upon registration – giving maximum visibility to your research.

Nanoscale Horizons will be launching very soon. Sign up to our Email Alerts Service and make sure you’re among the first to hear the latest.

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Hybridized doxorubicin-Au nanospheres exhibit enhanced Near-infrared surface plasmon absorption for photothermal therapy applications

Written by Dr Derek Craig.

Plasmon absorption stability of DAuNS and the triggered release of DOX

As cancer therapy evolves there is a desire to explore minimally invasive treatments which are applicable to all patients, regardless of concerns with drug resistance and tumour morphology. One such option being investigated is photothermal therapy (PTT), which seeks to achieve these aims through the selective uptake of photosensitizing agents by cancerous cells prior to their abalation using a near infa-red (NIR) light source.  However, currently the efficacy of PTT is reduced due to heterogeneous heat distribution, resulting in the accumulation of sub-lethal doses of the sensitizing agent within areas of the tumor.

Zhou and co-workers have sought to overcome this issue by creating a “double punch” strategy for tumour targeting using PTT. Through the implantation of hollow gold nanoshells with the chemical agent doxorubicin (DAuNS), a novel combination of a photosensitizing agent and a chemical targeting agent has been created. Furthermore, this unique, yet simple synthesis strategy is thought to be interconvertible with other drug and nanomaterial combinations, thus, widening the scope for potential PTT treatments.

Through comparisons with ‘single-strategy’ treatments of bare hollow gold nanoshells (HAuNS) or doxorubicin, the improved efficacy of the DAuNS is well established through both in-vitro and in vivo studies. This significant improvement can be attributed to the enhanced plasmon absorption in the NIR region of DAuNS in comparison to HAuNS (1.5 fold increase), with a more efficient photothermal conversion and a greater efficacy in tumor killing also established. These properties are only enhanced by the combined chemotherapeutic effect achieved through the deployment of the doxorubicin payload.

As this strategy obviates the concerns of genetic drug resistance and is a minimally invasive treatment, it could carry significant potential. This potential is only further enhanced by the ability to exchange different chemotherapeutic reagents, and as such this could be a significant breakthrough which aids future cancer therapies.

Hybridized Doxorubicin-Au Nanospheres Exhibit Enhanced Near-infrared Surface Plasmon Absorption for Photothermal Therapy Applications
Jialin Zhou, Zuhua Wang, Qingpo Li, Fei Liu, Yongzhong Du, Hong Yuan, Fu-Qiang Hu, Yinghui Wei and Jian You
Nanoscale, 2015, Advance Article. DOI: 10.1039/C4NR07279K.

Dr Derek Craig is a guest web writer for the Nanoscale blog. He is a Post Doctoral Research Fellow at the University of St. Andrews based in the fields of Biophotonics and Materials Science. With a background in chemistry, his work mainly focuses on the synthesis of nano to meso materials and the use of imaging techniques to study biological samples.
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HOT article: Unfolding the secrets of DNA origami nanostructures

Written by Dr Lee Barrett.

DNA origami machine components

DNA origami is an emerging field of nanotechnology that exploits the unique base-pairing capabilities of the DNA bases to produce complex and mechanically stiff self-assembled nanoscale geometries. Recently, DNA origami has found uses in applications such as single molecule sensing, drug delivery and templating molecular components.

This review, by researchers from Ohio State University, sets out to explore the mechanical nature of DNA nanostructures in order to understand how these structures will respond to physical interactions. The review covers three major areas of progress, including measuring and designing mechanical properties of DNA nanostructures, designing complex nanostructures based on imposed mechanical stresses and, finally, designing and controlling structurally dynamic nanostructures.

For researchers interested in the future possibilities of DNA origami, this review should provide an insightful first stop for discussing the mechanical design of DNA nanostructures.

Mechanical design of DNA nanostructures
Carlos E. Castro, Hai-Jun Su, Alexander E. Marras, Lifeng Zhou and Joshua Johnson
Nanoscale, 2015, Advance Article. DOI: 10.1039/C4NR07153K

Dr Lee Barrett is a guest web writer for the Nanoscale blog. Lee is currently a postdoctoral researcher in the Centre for Molecular Nanometrology at the University of Strathclyde. His research is currently focused on the development of nanoparticle-based sensors and surface enhanced Raman scattering (SERS). Follow him on twitter: @L_Bargie

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Poster prize winners at Nano India 2015

Professor Ajay K. Sood awarding a Nanoscale poster prize at Nano India 2015

Many congratulations to G. Rajaraman and E. Manikandan for winning the Nanoscale poster prizes at Nano India 2015.

G. Rajaraman, from the Indian Institute of Technology, Bombay, won a prize for his poster entitled “New generation molecular nanomagnets”, and E. Manikandan’s poster was entitled “A fingerprint micro Raman spectroscopy study for few layered graphene formation on gold substrate by low energy ion implantation technique”. The prizes were awarded by Professor Ajay K. Sood from the Indian Institute of Science, Bangalore.

The conference was hosted by the Centre for Nanotechnology & Advanced Biomaterials (CeNTAB), SASTRA University, Thanjavur, on the 29-30th  January 2015. It is a national conference supported by the Department of Science & Technology (DST), and aims to promote the exchange of ideas and create a platform for collaborative research in interdisciplinary areas of nanoscience and nanotechnology. Further details are available on the conference website.

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HOT article: Effects of morphology and chemical doping on electrochemical properties of metal hydroxides in pseudocapacitors

Written by Dr Stephanie E. Vasko.

With a limited amount of fossil fuels in the ground, developing alterative strategies for energy production is of the utmost importance.  However, without a way to store that energy, these endeavors could be futile.

From the team of Gyeonghee Lee, Chakrapani V. Varansi, and Jie Liu (an Associate Editor here at Nanoscale), comes one of this month’s HOT papers, “Effects of morphology and chemical doping on electrochemical properties of metal hydroxides in pseudocapacitors.” In this paper, the team’s specific metal hydroxide of interest is Ni(OH)2.

image file: c4nr06997h-s1.tif

Schematic illustration of the proposed mechanism for the morphology modification of Ni(OH)2 by glucose in the solvothermal medium.

Lee et al. state “…that both morphology control and chemical doping positively affect the electrochemical performance of Ni(OH)2 when applied individually.”  In this paper, they set out to determine what happens to the electrochemical performance when morphology and doping are combined instead of applied individually.  In order to investigate the effects of both, they chose a solvothermal synthesis route for metal hydroxide flakes, creating both cobalt-doped (CoxNi1-x(OH)2) and undoped particles (Ni(OH)2) that have varying amounts of D-glucose added.  For both the doped and undoped particles, four sets of particles are created, where 0, 10, 20, and 50% of the urea normally used in the solvothermal process is replaced by the D-glucose.  All of the particles were characterized with x-ray diffraction (XRD) and scanning electron microscopy (SEM), with the SEM showing that increasing amounts of glucose decreased flake size.  XRD and thermogravimetric analysis also revealed that increasing D-glucose amounts created an increase in the amount of interlayer water, with XRD also indicating degree of crystallinity decreased with increasing D-glucose.

In order to understand how the glucose affects morphology, the authors ran the solvothermal synthesis without the metal precursor. XRD and nuclear magnetic resonanace (NMR) data indicates the presence of ethyl-substituted glucose (formed during the synthesis process) instead of D-glucose.   The authors conclude that “…ethyl glucoside molecules can hinder the precursor diffusion and thus inhibit the metal hydroxide growth during synthesis.”

The electrochemical performance of all of the types of particle is evaluated using cyclic voltammetry (CV), galvanostatic charge–discharge, and electrochemical impedance spectroscopy (EIS).  Increasing glucose levels on undoped particles increased specific capacitance and cobalt doping is also shown to improve specific capacitance.  Combining the two showed that specific capacitance increased up to 50% of Co doping, but was less effective above 50%.

Lee et al. find that “…the addition of glucose in the ethanol-mediated solvothermal synthesis effectively reduces the particle size of metal hydroxide flakes. The specific capacitance is improved as a result of the increased surface area and reduced particle size.”  In terms of specific capacitance, the higher interlayer water levels found for increasing glucose levels may make ion mobility easier in the materials, enhancing the specific capacitance of the doped-Ni(OH)2.  In the doped materials, the specific capacitance was increased with low doping and decreased with high doping.

In designing future iterations of Ni(OH)2 batteries, careful attention will need to be placed on both morphology and doping levels in order to find the best balance for electrochemical performance.

Effects of morphology and chemical doping on electrochemical properties of metal hydroxides in pseudocapacitors
Gyeonghee Lee, Chakrapani V. Varanasi and Jie Liu
Nanoscale, 2015, 7, 3181-3188. DOI: 10.1039/C4NR06997H

Stephanie E. Vasko is currently a Senior Research Assistant at The Rock Ethics Institute at the Pennsylvania State University in State College. Her research focuses on science communication, STEM education, and the intersections between art, craft, and science.  You can follow her on Twitter at @stephanievasko.

The opinions and views expressed in this piece are those of the author and do not represent or reflect the opinion, views, or policy of the Pennsylvania State University, the Rock Ethics Institute, or the National Science Foundation.

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Shepherding cells – moving in the right direction?

Written by Dr Mike Barrow.

image file: c4nr06594h-f1.tif

Schematic representation depicting the ability for an external magnetic field to attract magnetic nanoparticles which have been internalised within cells. For details please view the full article.

Superparamagnetic nanoparticles are widely used for non-invasive imaging techniques such as magnetic resonance imaging (MRI) due to their ability to only become magnetised under the influence of an external magnetic field. In this article, it is demonstrated that labelling cells with magnetite nanoparticles can allow for manipulation of both direction and speed of the migration of cells using an external magnet. Bespoke nanoparticles were synthesised with a positive charge to induce internalisation into two different cell lines that are important for wound repair. Placing labelled cells under the influence of an external magnetic field resulted in 2D migration of cells towards the magnet, whereas non-labelled cells (in a magnetic field) and labelled cells with no magnetic showed no directional movement.  The migration could be monitored by bright field and fluorescent microscopy as the nanoparticles contained a fluorescent tag.  The possibility of controlling cell mobility is suggested to have importance in not only cell therapies, but also tissue engineering and cell tracking. This tailored synthesis approach could also allow tracking of cells in vivo using a bi-modal imaging approach of dual MRI and whole animal fluorescence.

Manipulating Directional Cell Motility Using Intracellular Superparamagnetic Nanoparticles
Michael Bradshaw, Tristan Clemons, Diwei Ho, Lucia Gutierrez, Francisco Lazaro, Michael House, Timothy Guy St Pierre, Mark Fear, Fiona Wood and Swaminathan Iyer
Nanoscale, 2015, Advance Article. DOI: 10.1039/C4NR06594H

Dr Mike Barrow is a guest web writer for the Nanoscale blog. He currently works as a Postdoctoral Researcher at the University of Liverpool.

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