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Ultra-versatile Nanoparticle Integration into Organiszed Nanoclusters
NEWSLETTER

Issue 2 - Spring / Summer 2015
Content

This is UNION
UNION Overview
Optical Nanoparticle Building-Blocks
Magnetic Nanoparticle Cluster for Bio-Application
UNION Industry Workshops
UNION Final Project Event, September 2015
 
This is UNION

UNION is developing nanoparticle assembly techniques to prepare novel hierarchically-ordered nanoparticle clusters as a route to materials with tailored and predictable properties.
During the first period, the UNION consortium has been focused on the production of a wide range of high quality novel nanoparticles (NPs) with different compositions and functionalities. All this effort has been reflected in the excellent control over the synthesis gained, with very interesting functional results.
UNION Overview

Title: UNION - Ultra-versatile Nanoparticle integration into Organized Nanoclusters

Budget: €3,798,053

No. of partners: 8

Start Date: February 2013

End Date: January 2016

Duration: 36 months

Website:
http://www.fp7-union.eu/
After the success in this first step, the UNION consortium has been focused on Level 1 assembly, developing new functional hierarchically-ordered nanoparticle clusters (NPCs) with optical, magnetic, thermoelectric and bio-functionalities.

Through studying processes in detail, both experimentally and computationally, deeper insight has been gained into the processes by which collective properties emerge and into how these can be tuned.

Within this issue, we present part of the work developed by two of UNION partners: LMUM, focused on optical applications, and DCU focused on bio-applications.  
Optical Nanoparticle Building-Blocks

Nanoparticles and NPCs with optical functionalities stemming from plasmonic metals, plasmonic semiconductors or fluorescent semiconductors, can give rise to interesting optical effects. Hence they can be useful for a wide range of applications such as ultrasensitive analyte detection via SERS, plasmon-enhanced fluorescence-based detection or photothermal therapy to name a few.

In this context LMUM has been working towards the preparation of novel metal nanoparticles with near-infrared (NIR) plasmon resonances. 

LMUM has devised [1] a rapid and simple strategy to obtain highly branched gold nanoparticles with hollow cores in a ca. 100% yield through a simple one-pot seedless process in the presence of Triton X-100.
 
Figure 1. Left: TEM micrograph of a batch of multi-branched hollow gold nanoparticles synthesized via a simple and rapid one-pot seedless reaction in the presence of Triton X-100. Center: representative STEM image of a single nanoparticle. The lower electronic contrast at the nanoparticle center is due to the hollow nature of the nanoparticle core. Right: UV-vis-NIR spectra of different batches consisting of multi-branched hollow gold nanoparticles. The plasmon band is highly tunable across the visible and NIR as a result of the nanoparticle dimensions, hollowness, branch density and length. These parameters can be tuned as a function of the synthetic conditions. For details see ref. [1].
The nanoparticles display pronounced and highly tunable (~700-2000 nm) plasmon bands in the NIR. The NIR character of the bands results from the combined contribution from hollowness and branching. It has also been shown that the high environmental sensitivity of these colloidal dispersions can be boosted even further by separating the nanoparticles into fractions of given sizes and improved monodispersity by means of centrifugal sorting in a density gradient.

All in all, the possibility to obtain highly monodisperse multi-branched hollow gold nanoparticles with predictable dimensions, branching and, therefore, NIR plasmonic properties, highlights the potential of these nanoparticles and of NPCs based on them for theranostic applications.

[1] Simple and Rapid High Yield Synthesis and Size Sorting of Multi-branched Hollow Gold Nanoparticles with Highly-Tunable NIR Plasmon Resonances by A. J. Blanch, M. Döblinger, and J. Rodríguez-Fernández, Small, in press (2015).
Magnetic Nanoparticle Cluster for Bio-Application

Nanoparticle clusters (NPCs) with controlled magnetic properties, arising from control over NP and NPC size and the number and type of ligands separating the NPs, are of significant scientific and clinical interest. This is largely because their magnetic properties offer a simple route to multi-functional theranostic materials, which can be used as MRI trackable and, magnetically positionable  delivery vehicles that can also be locally heated by AC-magnetic field hyperthermia.

Key requirements to achieve these outcomes for clinical applications include; scale-ability; use of in-expensive and bio-compatible components only, while retaining the ability to control NP and NPC size (and hence the emergent magnetic properties of the assemblies).

In this context DCU, LMUM and Nanovector have been developing methods to form monodisperse size-controlled NPCs at scale by polymer mediated assembly (PMA) and by competitive stabiliser desorption (CSD). In the case of PMA the Consortium has developed scaleable methods to phase transfer size- and shape- controlled NPs from organic to aqueous media using FDA approved pluronics co-polymers, Figure 2. In ongoing work we are studying the factors that determine the materials magnetic and MRI performance.
Figure 2. Left: Image of monodisperse 14 nm FeO nanocubes. Right: monodisperse 120 nm NPCs formed from nanocubes. 
DCU are developing the CSD approach, [2] in which is assembly is driven using controlled ligand depletion to an interface with a distinct phase, for the production of monodisperse magnetic  -Fe2O3 NPCs, see Figure 3, at scale. The robustness of the process allows scale up to 10-70 mL and more recently to >300 mL scale.

[2] Brougham et al, Angew. Chem. Int. Ed. 2009, 52, 3164–3167, WO2008071742, WO2011073411
UNION Industry Workshops

The UNION INDUSTRY WORKSHOPs were held at the Facultat de Física, Universitat de Barcelona, Avinguda Diagonal 645, 08028, BARCELONA on the 3rd June 2015. This venue was chosen because of the large number of industries, SMEs and start-ups in the Catalan region. Due to the large demand we held an opening plenary session and subsequent parallel sessions focusing on bio- and thermoelectric-applications of hierarchically ordered nanostructured materials. There were also discussion sessions on future technologies and EC and some instrument demonstrations. We had 25 presenters from a total of 41 attendees, representing 18 industries (excepting the UNION partners).

The objectives of the Worskshops were to:
  • Showcase the UNION technologies
  • Identify the current technological challenges/opportunities in nanostructured materials (for thermoelectric- and bio-applications) and explore possible approaches to these
  • Establish new alliances and collaborations, both using current resources and with a view to Horizon2020
The UNION attendees were very positive about the experience. We have initiated new collaborations, identified possible partners for H2020 proposals, we are also now better informed about the current activity and challenges in the two application fields of interest. Feedback from the industry attendees was similarly positive; some selected comments from the other participants are included below.

A very interesting day, excellent content and a great opportunity to learn of the progress being made regarding nanoparticle synthesis for several final applications. Good networking format that has already resulted in a collaborative opportunity”….Dr. Carlton Jones, CEO Nanotherics.

UNION Industry Workshop gave me the opportunity to get better comprehension about the huge technological potential of metallic and metal oxide NPs, the challenges on their assembly monitoring technologies and on their large scale manufacturing. During the coffee breaks and lunch I had the opportunity to interchange with different participants, and nice ideas emerged for the design of new inorganic-organic hybrids with potential application mainly in nanomedicine”….Dr. Nora Ventosa, Nanomol.

It was a small-sized focused workshop where I did appreciate the applied drive in it besides of the challenging presented works of the different academic and SME presenters”….Prof. Victor Puntes, Applied Nanoparticles s.l.

“….it was a nice session in which we could enjoy very diverse approaches to nano-technological aspects on bio-applications. One of the conclusion from our talks is that there is already an extend experience on the development of nanosystems but still not a successful number of them on the marketplace. We probably need to address this issue and the main barriers for our research to become a real product”….Dr. Jaime López de la Osa, NanoImmunotech.
UNION Final Project Event, September 2015

UNION are holding a symposium at the 2015 E-MRS Fall Conference in Warsaw, Poland in September 2015. The title of the UNION symposium is "Hierarchical assembly of nano-scale building blocks" and more information on the UNION symposium can be found at the following link

Symposium - Fall 15 M: Hierarchical assembly of nano-scale building blocks
http://www.emrs-strasbourg.com/index.php?option=com_content&task=view&Itemid=1662&id=882

E-MRS 2015 Fall Meeting
http://www.emrs-strasbourg.com/index.php?option=com_content&task=view&id=13&Itemid=1662
This project has received funding from the European Union’s Seventh Framework Programme for research, technological development and demonstration under grant agreement no 310250.
For Further Information:

UNION Coordinator

Dr. Dermot Brougham
School of Chemical Sciences
Dublin City University
Glasnevin,
Dublin 9,
Ireland 


Email: dermot.brougham@dcu.ie
Website: http://www.fp7-union.eu
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