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2015 Spring

Organic and Bio-materials


Design, fabrication and self-assembly of anisotropic and patchy particles

Substantial know-how is currently available concerning the synthesis of well-defined and uniform particles exhibiting various shapes and surface chemistry. A great part of current researches in the field aims at conferring colloidal particles predetermined “instructions” for assembly in functional clusters or extended arrays is to decorate the surface of the particles with “sticky patches” and/or to shape them in order to promote directional interactions. Such a symposium would be a good opportunity to bring together researchers from different communities (colloidal engineering, physical chemistry, condensed matter physics, etc.) and see the latest developments in the synthesis and the assembly of patchy and anisotropic particles, from both experimental and theoretical sides, as well as their application for the fabrication of the next-generation materials.

Here are the graphs showing the tremendous increase of the number of articles related to the topics of the proposed symposium (Source ISI Web of Science):








Next-generation materials and devices composed of colloidal building blocks tailor-made for specific applications will not be fabricated via traditional methods. Instead, they will self-assemble through processes that do not require human intervention and in which instructions for assembly emerge from the nature of the forces acting between constituents. Future materials and devices for photonics, drug delivery devices, and sensors require the self-assembly of synthetic colloidal structures with the precision and reliability of biological self-assembly. Despite enormous advances in the synthesis of a wide assortment of inorganic and organic building blocks of various shapes and sizes, control over their assembly into precise and predictable structures remains the primary obstacle to the bottom-up construction of novel materials and devices from these building blocks. Attaining such control requires several achievements, most notably elucidating the interactions between building blocks, gaining control over these interactions, and understanding how specific types of interactions lead to specific target structures. One emerging approach to confer colloidal particles predetermined “instructions” for assembly is to decorate the surface of the particles with “sticky patches” made, for example, of synthetic organic or biological molecules. The patterned surface of the colloidal particles is most commonly realized via suitable chemical or physical synthesis processes: fixing magnetic patches on the particle surface, decorating colloids via particle stamping or vapor deposition, or anchoring double- or single-stranded DNA-chains on the colloidal surface are only a few recent examples of how patchy particles can be synthesized. These examples already serve as ample demonstration that the patchy colloid field is highly interdisciplinary, involving physics, chemistry, chemical engineering and bio-related sciences.

In recent years, considerable progress has been made in tailoring the position, the interaction properties and the number of patches during the experimental synthesis processes. The impressive potentialities offered by the new experimental achievements need, however, information about how to improve the design of patchy particles in order to realize self-assembled structures with the desired properties. Thus, a close cooperation between experimentalists on one side and theoreticians and computer simulators on the other side is of great importance: suitable modelling of the experimental particles can provide guidelines on which features of the patchy units may favor target mesoscopic structures. Patchy particles have meanwhile become a steady topic in many conferences, where – according to the respective scientific orientation of the meeting – physical, chemical or biophysical aspects of these particles are addressed. In an effort to merge the different scientific communities and the diverse approaches related to patchy particles, we take the initiative of proposing to organize a symposium on this highly actual topic, with the following goals:

  • bring together scientists from different fields (physics, chemistry, biophysics);
  • bring together experimentalists, theoreticians, and computer simulators;
  • offer ideal conditions for extensive discussions on this highly active and rapidly developing field.


Hot topics to be covered by the symposium:


  • Synthesis of (nano)particles with valences: Janus particles, patchy particles, dimpled particles, colloidal molecules
  • Assembly and self-assembly: attractive forces, extended arrays and/or discrete clusters, jamming
  • Theory and simulations: mean field theories, Monte Carlo, molecular and Brownian dynamics simulations, stochastic rotational dynamics simulations
  • Characterization and applications


Tentative list of invited speakers:


  • Oleg Gang, Brookhaven National Laboratory See now “Programmable assembly of nanoscale systems”
  • Sharon C. Glotzer, University of Michigan See now “Entropically Patchy Particles: Engineering: Valence through Shape Entropy”
  • Daniela J. Kraft, Leiden University See now “Assembly of colloidal molecules” (confirmed)
  • Stefano Saccana, New York University See now “Lock-and-key colloids”(confirmed)
  • Gi-Ra Yi, Sungkyunkwan University, Korea See now “Synthesis of new colloidal particles and applications” (confirmed)
  • Ilona Kretzschmar, City College of New York See now “Assembly and Application of Magnetic Janus Colloids”

The scientific committee will be inviting a select few abstracts among the most appealing ones to become “Invited Lectures”


Tentative list of scientific committee members:


  • Jérôme Bibette, ESPCI, Paris See now (confirmed)
  • Alfons van Blaaderen, Utrecht University See now
  • Paul V. Braun, University of Illinois at Urbana-Champaign See now (confirmed)
  • Gerhard Kahl, Technische Universiteit Wien See now (confirmed)
  • David J. Pine, New York University See now
  • Olivier Spalla, CEA See now (confirmed)
  • Andreas Stein, University of Minnesota See now (confirmed)




A Themed collection has been negotiated with the editor of the journal Soft Matter (impact factor: 3.9) of the Royal Society of Chemistry: papers invited for the web collection will be published in a regular issue of Soft Matter as and when they are accepted. As soon as a suitable number of papers are accepted, a web collection will be set up to collate all of the papers. A link to the web collection will be maintained on the ‘themed collections’ tab on the journal website, together with a description of the collection written by the co-guest editors. The web collection will be publicized in the same way as a print themed issue, ensuring maximum visibility for the articles.


Sponsor :


CORDOUAN Technologies

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Gold nanoparticles : Serge Ravaine
Authors : Erik Dujardin,1 K. L. Gurunatha,1 A. C. Fournier,1 A. Urvoas,2 M. Valerio-Lepiniec,2 P. Minard,2 P. Jain,3 A. Soshee,3 S. S. Narayanan,1 C. Nizak3,4, V. Marchi5
Affiliations : 1 CEMES, CNRS UPR 8011, 29 rue J. Marvig, 31055 Toulouse Cedex 4, France 2 IBBMC Univ Paris Sud, CNRS UMR 8619 - F-91405 Orsay, France 3 CNRS, LIPHY, F-38000 Grenoble, France 4 Laboratory of Biochemistry, UMR 8231 ESPCI ParisTech/CNRS, PSL Research University, Paris, France 5 Univ. Rennes 1, ISC UMR 6226 CNRS, Campus Beaulieu, 35042 Rennes Cedex, France

Resume : The optical properties of metallic colloidal nanostructures can be tuned by controlling the nanoparticle shape [1] and/or assembly. [2, 3] We first illustrate the potential of self-assembled colloidal plasmonic superstructures to reach ultimate lateral confinement, long-range delocalization and spectrally tunable propagation of surface plasmon modes and become extremely narrow waveguides.[3] Yet, order and predictability of colloidal self-assembly pathways still need to be improved. In biology, engineered proteins with specific recognition for a chosen molecular target can be isolated and identified from a large library by phage display selection. We show that this standard biochemical technique rapidly yields antibody binders for an inorganic target, crystalline metallic gold. Twenty-one anti-gold antibody proteins were identified and sequenced. The statistical analysis of all the sequences reveals a strong occurrence of arginine in anti-gold antibodies. Once tethered to gold nanoparticles, the selected antibodies drive the self-assembly of the colloids onto the surface of single crystalline gold platelets, as a first step toward programmable protein-driven construction of complex plasmonic architectures. [4] Next, we report on the design of fully artificial repeat protein having a rigid 3D architecture and well-placed random residues. Protein pairs selected from a library of 10^9 homologous proteins for their nM affinity constants are used to drive the massive but reversible assembly of Au nanoparticles. [5] Finally, we present electrodynamic simulations suggesting that the protein-driven assembly significantly modifies the plasmonic modal properties of the gold platelets.[1, 4] [1] S. Viarbitskaya et al. Nature Mater., 2013, 12, 426; APL, 2013, 103, 131112. [2] S. Lin et al. Adv. Mater., 2005, 17, 2553; M. Li, et al. Adv. Funct. Mater., 2011, 21, 851 [3] A. Teulle et al. Nature Mater., 2015, 14, 87 [4] P. Jarvi et al. J. Phys Chem. C, 2014, 118, 14502 [5] K. L. Gurunatha et al. in preparation

Authors : Amelie Heuer-Jungemann,(1) Johanna Midelet (1), Afaf, H. El Sagheer(4,5), Teresa Pellegrino (3), Tom Brown(4) and Antonios G. Kanaras(1,2)*
Affiliations : (1) Physics and Astronomy, University of Southampton (2) Institute of Life Sciences, University of Southampton, SO17 1 BJ, UK (3) Nanochemistry, Italian Institute of Technology, Genoa, Italy (4) Department of Chemistry, University of Oxford, OX1 3TA, UK (5) Department of Science and Mathematics, Suez University, Suez, 43721, Egypt

Resume : Controlling nanoparticle self-assembly in a very effective and easy way can have many applications in several scientific fields such as nanophotonics and metamaterials, nanoelectronics and nanodiagnostics. In particular the employment of DNA as a scaffold for the organization of nanoparticles is exceptionally attractive and has been utilized to arrange nanoparticles into dimers, trimers or more complex structures. This is due to the unique base pairing nature of DNA that offers versatility and specificity. We have recently demonstrated a new method for the programmed ligation of single-stranded DNA-modified gold nanoparticles using copper–free click chemistry. Gold nanoparticles functionalized with a discrete number of 3’-azide or 5’-alkyne modified oligonucleotides, can be brought together via a templating splint strand and covalently ‘clicked’, in a simple one-pot reaction. This approach is inherently advantageous compared to the traditional enzymatic ligation method. The chemical ligation is highly specific and occurs at room temperature, simply by mixing the particles - no need for special enzymatic conditions. The yield of ‘clicked’ nanoparticles can be as high as 92%. Here we now show for the first time the universal applicability of this method as a means of creating dimers of different types of nanoparticles as well as the formation of nanoparticle heterodimers (e.g. AuNP-Cu2-xSe, AuNP-iron oxide nanocube etc.) in a simple ‘mix and match’ story.

Authors : Daniela J. Kraft
Affiliations : Leiden University, The Netherlands

Resume : Colloidal particles with anisotropic shapes and interactions are promising candidates for bottom-up assembly routes towards complex structures and may also be employed as model systems to study complex biological systems. I will present several experimental realizations of anisometric and patchy colloidal particles, both from a synthetic as well as a self-assembly perspective. I will demonstrate the variety of heterogeneous colloids that can be fabricated by tuning the parameters of a synthesis based on swelling and assembling polymer spheres. I will discuss how to employ such complex colloids for studying short-term diffusion and self-assembly into larger structures.

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Charged patchy particles : Stefano Sacanna
Authors : Emanuela Bianchi
Affiliations : Technical University of Vienna, Austria

Resume : Inverse patchy colloids (IPCs) are heterogeneously charged particles characterized by a non-trivial interplay between attractive and repulsive directional interactions [1]. Within this class of systems, we consider IPCs with two charged polar regions and one oppositely charged equatorial belt. We first investigate the assembly of these colloids under planar confinement in thermodynamic conditions such that the formation of extended structures is favored: (i) a general tendency to form quasi two-dimensional aggregates is observed irrespective of the confinement size, (ii) a clear distinction between the formation of ordered versus disordered aggregates is possible based on the specific features of the inter-particle interaction, and (iii) a simple way to tune via experimentally accessible parameters the ordering of IPCs in the vicinity of a possibly charged substrate is presented. Second, we consider an IPC system that exhibits a bulk phase diagram characterized by a broad region where a structure composed by parallel monolayers is stable and we report about the the effect of the parameters featured in the particle-particle interaction potential on the whole phase diagram [4]. [1] Soft Matter 7, 8313 (2011) [2] ACS Nano 7, 4657 (2013) [3] NANO letters 14, 3412 (2014) [4] Soft Matter 10, 8464, (2014)

Authors : Karolina Milowska, Jenny Merlin, Jacek Stolarczyk
Affiliations : Photonics and Optoelectronics Group, Ludwig-Maximilians-Universität München, Amalienstr. 54,80799 Munich (Germany); Nanosystems Initiative Munich (NIM), Schellingstr. 4, 80799 Munich (Germany)

Resume : We present a model of assembly of superparamagnetic iron oxide nanoparticles into size-controlled nanoparticle clusters. In the process, the steric repulsion of the nanoparticles is gradually reduced by competitive stabilizer desorption arising from the presence of a tertiary silica phase.[1,2] The kinetics of assembly is analysed using Smoluchowski aggregation equation and Fuchs stability ratio dependent on nanoparticle-nanoparticle colloidal interactions. We show that by including a rigorous treatment of van der Waals, steric and magnetic interactions the experimental evolution of the size distribution obtained by dynamic light scattering can be reproduced. The model can be extended to other nanoparticle systems including multicomponent clusters (e.g. gold and iron oxide). We also show that the model of nanoparticle interactions can be of great use to predict the magnetic and colloidal properties of the resulting clusters as well as to design novel multifunctional nanoparticle clusters. 1.J. K. Stolarczyk et al, Angew. Chem. Int. Ed. 2009,48,175. 2.C.J. Meledandri et al, ACS Nano 2011,5,1747

Authors : David Jacob, Boris Pedrono, Benoit Maxit, Sylvain Boj
Affiliations : Cordouan Technologies, Pessac, France

Resume : Today, many recognized methods exist to measure the size and size distribution of nano-particles [1]. Among these methods, Dynamic Light Scattering (DLS) also known as Photon Correlation Spectroscopy (PCS) is certainly one of the prevalent techniques of choice in colloidal sciences [2, 3]; Until today, all commercial DLS setups require batch sampling which is not adapted for in situ and real time process monitoring (time consuming operation, sample stability issues, reproducibility issue, etc) . Addressing this challenge implies a change of paradigm: if you cannot bring your sample to the measurement, you have to bring the measurement to your process. With that idea in mind, we have developed a unique fully agile in situ DLS probe system based on an innovative approach using integrated optics and single mode optical fibers. The new probe is designed to be integrated into various environments. We present here the principle of this probe and different examples of integration in concrete applications: (i) real time monitoring and control of NPs synthesis in mili-fluidic reactor with combined and simultaneous SAXS-DLS measurement; (ii) NP synthesis kinetics monitoring into a microwave reactor;(iii) Polymer nano-emulsion control in super critical CO2 reactor, (iv) Magnetic Hyperthermia experiments, etc.

Nanostructures for functional materials : Erik Dujardin
Authors : H. Awada, C. Dagron-Lartigau, A. Bousquet, L. Billon
Affiliations : IPREM CNRS-UMR 5254, Equipe de Physique et Chimie des Polymères, Université de Pau et des Pays de l'Adour, Hélioparc, 2 avenue Président Angot, 64053 Pau Cedex 9, France

Resume : Recently few research groups have turned their attention toward the possibility to graft conjugated polymer at the surface of inorganic, carbon (nanotube or graphene) and metallic substrates in order to create new electro-active materials.(1) Another new challenge is then now to develop the so-called “low band gap” LBG polymer, macromolecules able to harvest more photons. This presentation will deal with the elaboration of new hybrid core@corona nanoparticles. Different strategies have been developed by our group to covalently anchored conjugated polymers to metal oxide particles. Herein the “grafting onto” and the “grafting from” methodologies will be describe and apply for the synthesis of reference P3HT (2) and a low band gap LBG poly[(4,4′-bis(2-ethylhexyl)dithieno-[3,2-b:2′,3′-d]silole)-2,6-diyl-alt-(2,1,3-benzothiadiazole)-4,7-diyl] (PSBTBT) brushes on ZnO nanorods. (3) Moreover, for the first time, we will present, the elaboration of a biomimetic mussel adhesive inspired anchor group for the design of Zinc Oxide ZnO nanoparticles grafted by Poly(3-HexylThiophene). The synthetic methodology is based on the synthesis of a catechol derivated moiety from dopamine able to be “click” on an alkyne terminated P3HT. (4) ZnO/Conjugated polymers combined materials are of great interest in organic electronics and more especially in hybrid photovoltaic materials. The corona thickness by Transmission Electronic Microscopy will be discussed with regard to the grafting density and the molecular weight of the conjugated polymers. Photoluminescence measurement in solution was used to prove an efficient electron transfer from the P3HT donor to the ZnO acceptor upon grafting. (1) A. Bousquet, H. Awada, R.C. Hiorns, C. Dagron-Lartigau, L. Billon, Prog. Polym. Sci., 39, 1847-1877, 2014 (2) H. Awada, H. Medlej, S. Blanc, M.H. Delville, R.C. Hiorns, A. Bousquet, C. Dagron-Lartigau, L. Billon, J. Polym. Sci. Polym. Chem. : Part A, 52, 30-38, 2014. (3) H. Awada, A. Bousquet, C. Dagron-Lartigau, L. Billon, asap, 2015 (4) H. Awada, L. Mezzassalma, S. Blanc, D. Flahaut, C. Dagron-Lartigau, J. Lyskawa, P. Woisel, A. Bousquet, L. Billon , asap, 2015

Authors : Benoit P. Pichon, Matthias Pauly, Delphine Toulemon, Sylvie Bégin-Colin
Affiliations : Institut de Physique et de Chimie des Matériaux de Strasbourg

Resume : Magnetic nanoparticles became recently of high potential to develop advanced applications such as mass storage media and ultrasensitive sensors. Although the intrinsic properties of nanoparticles are controlled by their shape, isotropic shapes such as spherical nanoparticles bring some limits to enhance efficiently their magnetic anisotropy. This issue can be overcome by addressing self-assembling of nanoparticles into anisotropic assemblies onto substrates.[1-3] The self-assembling is triggered by specific chemical interactions between functional groups located at both nanoparticles and substrates which surfaces are chemically addressed by self-assembled monolayers (SAMs) of organic molecules.[5] Therefore, reducing the dimensionality of nanoparticle assemblies has a strong impact on their collective properties. In contrast to powder state which corresponds to 3D isotropic random assemblies, 2D monolayers favor stronger coupling of magnetic nanoparticles thanks to shape anisotropy. While self-assembly can be controlled by chemical interactions through “click” chemistry,[3,6] magnetic interactions also take part to the assembling process and address the spontaneous formation of highly anisotropic assemblies such as 1D chains of nanoparticles which result in strong enhancement and unexpected magnetic properties.[4] [1] M. Pauly et al, J. Mater. Chem. 2011, 21, 16018 and J. Mater. Chem. 2012, 22, 6343 [2] B.P. Pichon et al, Chem. Mater. 2011, 23, 3668 [3] D. Toulemon et al, Chem. Commun., 2011, 47, 11954 [4] D. Toulemon et al, To be published [5] B. P. Pichon et al, J. Phys. Chem. C, 2011, 114, 9041 (2010) [6] D. Toulemon et al. Chem. Mater., 2011, 25, 2849 (2013)

Authors : Oleg Gang
Affiliations : Center for Functional Nanomaterials, Brookhaven National Laboratory

Resume : In the last decades nanoscale inorganic objects emerged as a novel type of matter with unique functional properties and a plethora of prospective applications. Although a broad range of nano-synthesis methods has been developed, our abilities to organize these nano-components into designed architectures and control their transformations are still limited. In this regard, an incorporation of bio-molecules into a nano-object structure allows establishing highly selective interactions between the components of nano-systems. Such bio-encoding may permit programming of complex and dynamically tunable systems via self-assembly: biomolecules act as site-specific scaffolds, smart assembly guides and reconfigurable structural elements. I will discuss our advances in addressing the challenge of programmable assembly using the DNA platform, in which a high degree of addressability of nucleic acids is used to direct the formation of structures from nanoscale inorganic components. Our work explores the major leading parameters determining a structure formation and methods for creating targeted architectures. The principles and practical approaches developed by our group allow for assembly of well-defined three-dimensional superlattices, two-dimensional membranes and finite-sized clusters form the multiple types of the components. I will also discuss how interplay of polymeric and colloidal effects can result in the novel interactions effects in these systems. Finally, our recent progress on the assembly by-design, including super-lattices with pre-defined crystallographic symmetries and particle clusters with pre-determined architectures will be demonstrated. Research is supported by the U.S. DOE Office of Science and Office of Basic Energy Sciences under contract No. DE-AC-02-98CH10886.


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