Biomaterials and soft materialsS
Biohybrid nanomaterials: bioinspired, DNA- and peptide-based assemblies for sensing, delivery and electronics
The combination of biomolecules and synthetic constructs can lead to biohybrid nanostructures with new functions that emerge through design at the molecular and supramolecular levels. This symposium will encompass the design, characterization, and the recent applications of bioinspired and biohybrid assemblies in sensing, delivery, and bioelectronics.
The scope of this symposium is to explore the many facets of biohybrid nanomaterials, dealing with their design, synthesis, characterization, self-assembly, modeling, properties, functions and biological investigations (in vitro, in vivo). The symposium will cover bio-supramolecular and bio-inspired assemblies, peptide-based and DNA-templated nanostructures, as well as biomolecular nanoarrays, with perspectives and applications in (bio)sensing, delivery, and bioelectronics.
Bioinspiration and biomimicry are nowadays seen as sound approaches to evolve towards sustainable and smart materials for applications in the fields of healthcare and information technology. In this context, biomolecules such as peptides or nucleic acids can be seen as natural, information-rich, and tunable scaffolds. Thus, researchers are seeking novel functions by interfacing biomolecules with synthetic nanomaterials (small organic compounds, macromolecules, nanoparticles, carbon nanotubes and 2D nanomaterials) in a unique fashion that lead to the self-construction of functional static and dynamic biohybrid nanostructures of high interest for sensing, delivery and bioelectronic applications. Mastering this self-assembly process requires proper molecular design of the biomolecular and synthetic partners, and a synergistic set of interactions at the supramolecular level.
The study of biohybrid nanomaterials requires a multidisciplinary approach, hence this symposium aims at bringing together materials scientists, supramolecular chemists, biophysicists, and computational chemists to share the various viewpoints and approaches in the emerging field of biohybrid nanomaterials. Particular emphasis will be given to DNA- and peptide-based strategies, but more general approaches employing supramolecular interactions to control the formation of biohybrid nanostructures are within the scope of the symposium.
Hot topics to be covered by the symposium:
- Bio-supramolecular nanostructures
- DNA-templated nanostructures
- Peptide- and polypeptide-based self-assembled nanostructures
- Interfacing biomolecules with nanoparticles/nanotubes/nanosheets
- Stimuli-responsive biomolecular assemblies
- Molecular modeling of hybrid biomolecular structures
- Optical/Electrical/Electrochemical sensing based on biomolecular hybrids
- Single-molecule bioelectronics
- Supramolecular approaches for delivery applications
List of invited speakers (confirmed):
- Rein Ulijn, Nanoscience Initiative at the Advanced Science Research Center, City University of New York
“Design Principles for Peptide Matter with Life-Like Functions”
- Jennifer N. Cha, University Colorado Boulder
“Generating Renewable Fuels from Bio-Nano Architectures”
- Sébastien Lecommandoux, ENSCBP, CNRS, University of Bordeaux
“Bioactive nanomaterials by design from self-assembly of polypeptide-based biohybrid copolymers”
- Ignacio Alfonso, Institute for Advanced Chemistry of Catalonia (IQAC-CQSIC), Barcelona
“Molecular recognition and dynamic covalent chemistry applied to chemical biology”
- Davide Bonifazi, School of Chemistry, Cardiff University
“Tailoring functional architectures with peptide templates”
- Mathieu Linares, Linköping University
“Theoretical investigations of DNA-molecule interactions”
- Peter Crowley, NUI Galway
“Programmable Protein Assembly by Supramolecular Receptors”
- Mihail Barboiu, CNRS, University of Montpellier
“Dynamic Constitutional Frameworks – new tools for biorecognition”
- Javier Montenegro, Center for Research in Biological Chemistry and Molecular Materials, University of Santiago de Compostel
“Supramolecular Lessons for New Biomaterials in Gene Delivery and Cytoskeleton Mimics”
List of scientific committee members:
- Beatriu Escuder, University of Castellon
- Subi J. George, JNCASR, Bangalore, India
- Andrés de la Escosura, Universidad Autónoma de Madrid
- Sébastien Clément, University of Montpellier
- Christian Nielsen, Queen Mary University of London
- Stefan Matile, University of Geneva
- John Hardy, Lancaster University
- Tanja Weil, Max Planck Institute for Polymer Research, Mainz
- Luc Brunsveld, Technische Universiteit Eindhoven
Selected papers will be published in the Journal of Materials Chemistry B (Royal Society of Chemistry).
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Authors : Mathieu Surin
Affiliations : University of Mons - UMONS
Resume : Opening remarks on Symposium S
Biohybrid and Bioinspired Materials : Mathieu Surin, University of Mons - UMONS
Authors : Jennifer N. Cha
Affiliations : Department of Chemical and Biological Engineering, University of Colorado, Boulder
Resume : With increasing demands for alternative sources of fuel, extensive research has focused on discovering methods to generate renewable energy from earth abundant resources. In recent years, a wide range of inorganic nanostructures with high surface areas and tunable band gaps have been synthesized and used as photocatalysts. To increase their activity, “Z-scheme” photocatalytic systems have been implemented in which multiple types of photoactive materials simultaneously oxidize water and reduce molecules upon photoillumination. In this talk, I will show our recent efforts to utilize DNA as a structure-directing agent to organize well-defined photoactive donor and acceptor nanocrystals into optimal configurations. In the first part, I will demonstrate that using DNA as a structure directing agent to assemble TiO2 and Pt decorated CdS nanocrystals caused a significant improvement in water splitting as opposed to utilizing a single type of particle or simply mixing the particles in solution. In addition, DNA also allowed positioning of a single or series of electron mediators site-specifically between the two catalysts to further increase H2 production. In a similar vein, I will also show some of our recent efforts in applying Z-schemes for reducing CO2 to usable fuels. In the latter part of the talk, I will showcase our very recent efforts to apply a bioinspired approach to tailor protein-nanoparticle interfaces for studying photoassisted redox activity. In order to drive enzymatic reduction of dissolved gases, electron sources such as photocatalysts and electrochemistry have been studied. However, in order to optimize electron flow, there is a significant need to understand how the interface between the organic enzyme and inorganic semiconductor influences protein binding and dynamics. Many redox enzymes function through assembly of protein subunits utilizing complex and multivalent interactions, with binding strengths ranging from long-range and weak to short-range and near-covalent. Mimicking such exquisite binding motifs is likely to be key for replacing protein subunits with photoactive semiconductors. This talk will showcase our recent insight into the design of interfaces between semiconductor surfaces and proteins to control binding and conformational dynamics of enzymes to promote photodriven redox catalytic activities
Authors : de la Escosura, A (1, 2)
Affiliations : (1) Departament of Organic Chemistry, Universidad Autónoma de Madrid, Campus de Cantoblanco 28049, Madrid, Spain; (2) Institute for Advanced Research in Chemistry (IAdChem), Campus de Cantoblanco 28049, Madrid, Spain.
Resume : The study of complex molecular networks and supramolecular assemblies is a clear objective of the field so-called systems chemistry, which is expected to have a great impact in the area of origins-of-life research and as biohybrid materials in materials science. With regards to the origins of life, a pertinent question is whether artificial cells could be constructed from non-natural components. In order to provide clues about this question, we have started research lines on nucleic acid hybrids, replicating nucleopeptide networks and nucleolipid compartments. The study and combination of these components is an interesting approach because it allows exploring some properties of life without the restrictions of the historical pathway that Darwinian evolution took. Concerning the approach to biohybrid materials, we focus our work on supramolecular biohybrids for biomedical light management, which combine different photoactive molecules with peptide, protein and nucleic acid nanostructures. For example, we have recently studied the electrostatic co-crystallization of a cationic porphyrinoid and negatively charged tobacco mosaic virus (TMV), together with the capacity of the resulting crystals to photogenerate reactive oxygen species. In a different approach, electrostatically assembled zinc Pc-DNA origami complexes have been demonstrated. In this presentation we will shortly discuss some of these research lines.
Authors : Thomas R. Wilks(1), Samuel Nunez-Pertinez(1), Robert Oppenheimer(2), Jennifer Frommer(1), Jonathan Bath(2), Andrew J. Turberfield(2), Rachel K. O'Reilly(1)
Affiliations : (1) School of Chemistry, University of Birmingham, Edgbaston, Birmingham B15 2TT, UK; (2) Department of Physics, University of Oxford, Parks Rd, Oxford OX1 3PJ, UK
Resume : Translation of genetic information into functional products (proteins) underpins all living systems, and is key to the process of evolution by natural selection. However, nature is limited to a small palette of building blocks (amino acids) - developing the capability to translate genetic codes into completely artificial, perfectly sequence-defined polymers would give access to many exciting new technologies, including the development of non-natural polymers that match and extend the functionalities of peptides and proteins and even nanomachines capable of programmed product synthesis in situ. On a more fundamental level, we could recreate complex biological behaviours such as gene regulation, bringing the creation of artificial living systems—the grand challenge of synthetic biology—a step closer. I will describe our efforts to use DNA nanotechnology and DNA-templated synthesis to develop such an 'artificial ribosome', focusing on two key barriers to progress and how we are addressing them. I will discuss how we have explored performing translation in solvents other than water to prevent degradation of fragile building blocks during synthesis, and our more recent attempts to activate building blocks in situ using DNA-templated catalysts. I will also discuss the new mechanisms we are investigating that will allow nanomachines made from DNA to sense when chemical reactions have happened, enabling great increases in efficiency. By combining these advances, we hope to make significant progress towards recreating one of nature's most complex molecular machines.
Authors : David Hastman 1, Eunkeu Oh 2,3, Joseph Melinger 4, Guillermo Lasarte-Aragones 1,5, Paul Cunningham 4, Matthew Chiriboga 1, Zach Salvato 1, Tommy Salvato 1, Sebastian Diaz 1 and Igor Medintz 1
Affiliations : 1 Center for Bio/Molecular Science and Engineering, Code 6900, U.S. Naval Research Laboratory, Washington, D.C. 20375, United States 2 Optical Sciences Division, Code 5600, U.S. Naval Research Laboratory, Washington, D.C. 20375, United States 3 KeyW Corporation, Hanover, Maryland 21076, United States 4 Electronics Science and Technology Division, Code 6800, U.S. Naval Research Laboratory, Washington, D.C. 20375, United States 5 College of Science, George Mason University, Fairfax, Virginia 22030, United States
Resume : Modulation of temperature within biological systems can provide precise control over system dynamics. Plasmonic gold nanoparticles (AuNPs) have the innate capability to generate heat when excited with an external light source and can readily be conjugated with biological materials, making them suitable heat sources for a wide variety of biological applications. Recently, it has been demonstrated that femtosecond (fs)-pulsed lasers can be used to excite AuNPs and generate heat profiles that are confined to the immediate nanoscale region around the AuNP, allowing for local heating without increasing the bulk temperature of the system. When using the proper AuNP size and laser fluence, the local temperature increase can be turned so that it is pertinent to biological activity, yet, it is not yet known the level of precision and control afforded through this technique and little work has been done to implement confined nanoscale heat sources into complex biological systems. Here, we use 55 nm AuNPs in conjugation with moderate pulse fluences (1-14 J/m2) to increase the local temperature by (10-90°C) and monitor the temperature sensitive responses of various biological materials attached the surface of the AuNP. We use the denaturation of double-stranded deoxyribonucleic acid (ds-DNA), the kinetics of the enzyme alkaline phosphatase (AP), and the kinetics of the thermostable enzyme alcohol dehydrogenase (AdhD) as model temperature sensitive biological materials to evaluate the level of spatiotemporal control fs-pulsed heating of AuNPs can provide over biological activity.
Authors : Xinzhao Xu (1), Ben Bowen, (2) , MArk Freeley (1), D. Dafydd Jones (2) and Matteo Palma (1)
Affiliations : (1) Department of Chemistry, School of Biological & Chemical Sciences and Materials Research Institute, Queen Mary University of London, Mile End Road, London E1 4NS, United Kingdom (2) Division of Molecular Biosciences, School of Biosciences, Main Building, Cardiff University, Cardiff, Wales CF10 3AX, United Kingdom
Resume : The controlled organization of individual molecules and nanostructures with nanoscale accuracy is key for the fabrication of the next generation optoelectronic devices and the investigation of events in biological and chemical assays. In this regard, we controlled the assembly of different biomolecules, from proteins to DNA and aptamer sequences, on carbon nanotubes (CNTs), so as to couple CNTs electronic output to biomolecular function. In particular, we will report on the fabrication of reconfigurable and solution processable nanoscale biosensing devices with multisensing capability based on SWCNTs functionalized with specific, and different, aptamer sequences employed as selective recognition elements. Multiplexed detection of three different biomarkers indicative of stress and neuro-trauma conditions was successfully performed, and real-time detection was achieved in serum down to physiologically relevant concentrations. We will then discuss the extension of this rationale into the development of real-time biosensors with engineered protein interfacing. We assembled different variants of a B-lactamase (BL) inhibitory protein (BLIP) onto SWCNT sidewalls in electronic device configurations with different, and controlled, protein orientations. We recorded the current responses in real-time for the detection of different concentrations of class BL enzymes, that degrade antibiotics, in the context of investigating antimicrobial resistance. This allowed us to investigate the influence of the protein orientation in binding and biosensing device response/performance.  Nano Letters, 2018, 18, 4130-4135  submitted, 2020
Authors : Anna Espasa (1,*), Martina Lang (2), Daniel Sanchez-deAlcazar (3), Juan P. Fernández-Blázquez (1), Uwe Sonnewald (2), Aitziber L. Cortajarena (3,4), Pedro B. Coto (5) and Rubén D. Costa (1,*)
Affiliations : (1,*) IMDEA Materials Institute, Calle Eric Kandel 2, 28906 Getafe, Spain E-mail: email@example.com; firstname.lastname@example.org (2) Department of Biology, Friedrich-Alexander-University of Erlangen-Nuremberg, Staudtstr. 5, 91058 Erlangen, Germany. (3) CIC biomaGUNE, Parque Tecnológico de San Sebastián, Paseo de Miramón 182, 20014 Donostia-San Sebastián, Spain (4) Ikerbasque, Basque Foundation for Science, Mª Diaz de Haro 3, 48013 Bilbao, Spain. (5)Department of Physical and Analytical Chemistry, University of Oviedo, Avda. Julián Clavería 8, 33006 Oviedo, Spain
Resume : The lighting industry growth is fueled by the need of replacing old-fashion and inefficient bulbs by more efficient white inorganic light-emitting diodes (WILED). Even though WILEDs rule the artificial lighting market, drawbacks related to their sustainable development (use of inorganic phosphors based on toxic and rare-earth elements)1 and health concerns (eye photodamage and effects on human circadian rhythms)1 have placed hybrid light-emitting diode (HLED) in the spotlight. They consist of blue chips coated by an organic phosphor, such as polymers, quantum dots, dyes and, more recently, fluorescent proteins (FPs).2-3 FP-based bio-phosphors have led to bio-hybrid light-emitting diodes (Bio-HLED) that stand out combining best device performance and sustainable and eco-friendly emitters. First Bio-HLEDs achieved moderate efficiencies (50 lm/W) and stabilities (100 h) due to thermal- and photo-degradations of FPs.3 A new Bio-HLED design shielding the FP surface with a hydrophilic polymer allowing their integration into the network of a light-guiding and host polymer enhances device efficiency (~130 lm/W) and stability (>150 days).4 The control of the mechanical, thermal, and optical features in this bio-phosphor is paramount towards highly stable and efficient FP-phosphor for biogenic lighting systems. 1. US Department of Energy: Manufacturing Roadmap Solid-State Lighting Research and Development 2014. 2. V. Fernández-Luna et al. Angew.Chem. Int.Ed. 2018, 57,8826 –8836 3. M. D. Weber et al. Adv. Mater. 2015, 27, 5493–5498 (2015.; Patent WO2016203028A1 (2016) 4. A. Espasa et al. Nat. Comm 2020 ( in press); Patent WO2019115525A1 (2019)
Authors : Professor Davide Bonifazi
Affiliations : Cardiff University, School of Chemistry, Park Place, Main Building Cardiff, Wales, UK.
Resume : One of the biggest problems in the fabrication of electroluminescent or light-adsorbing devices is the production of the desired color. White is usually obtained by mixing compounds with the three fundamental colors, namely red, green and blue (RGB). However, the choice of the suitable RGB compounds is limited by several factors in particular the chemical, electrochemical and photochemical stability of the selected compounds as well as their specific processability, which essentially means solubility and/or thermal evaporability, and self-organization capabilities. In this work, we show a new proof-of-concept toward the bottom-up construction of artificial light harvesting or luminescent materials that may exhibit any desired color, virtually enabling unlimited surfing through the color coordinate diagram. The approach allows the i) combination of RGB components in any desired and pre-programmed ratio at the molecular scale, ii) fine tuning the distance between different colors so as to modulate the extent of photoinduced energy transfer between the chromophores/luminophores with different excited state energies through the use of iii) pre-programmed peptide templates. These degrees of freedom, controlled solely through spontaneous supramolecular recognition will enable the tailoring of the desired emitted or adsorbed light color. In this work, we will address all the peptide-based approaches undertaken in our laboratory to engineer complex architectures expressing tailored colors.
Peptide-based assemblies and nanomaterials : Matteo Palma, Queen Mary University London
Authors : Rein V Ulijn
Affiliations : CUNY Advanced Science Research Center
Resume : We are interested in how functionality emerges from sequence in ensembles of very short peptides, and subsequently how these functions can be incorporated into functional materials Instead of using sequences known in biological systems, we use unbiased computational and experimental approaches to search and map the peptide sequence space, which has provided new families of functional short peptides.[1-4] The talk will focus on our latest results in three areas. First, we will demonstrate how to program molecular order and disorder in tripeptides, and how the conformations adopted by these peptides can be exploited to regulate assembly properties, and give rise to tunable emission in the visible range. Second, we will demonstrate how dynamic exchange of peptide sequences can form adaptive libraries that provide insights into peptide sequences that can complex ligands.[5,6] Finally, we discuss peptide-based melanin mimics with tunable chromophoric properties that are achieved through oxidative incorporation of amino acids. References: 1. A. Lampel, et al., Chem. Soc. Rev., 2018, 47, 3737-3758. 2. P.W.J.M. Frederix, et al., Nature Chem., 2015, 7, 30-37. 3. M. Kumar, et al. Nature Chem., 2018, 10, 696-703. 4. J. Son, et al., ACS Nano., 2019, 13, 1555-1562. 5. C.G. Pappas, et al., Nature Nanotechnol., 2016, 11, 960. 6. D. Kroiss, et al., ChemSysChem, 2019, 1, 7-11. 7. A. Lampel, et al. Science, 2017, 356, 1064.
Authors : Christopher Synatschke, Jasmina Gacanin, Adriana Sobota, Kübra Kaygisiz, Tanja Weil
Affiliations : Department for Synthesis of Macromolecules, Max Planck Institute for Polymer Research, Ackermannweg 10, 55128 Mainz, Germany
Resume : Short peptides that assemble into higher-order supramolecular nanostructures are emerging as functional biomaterials. They combine multiple beneficial aspects into a versatile materials platform. Peptides can be synthesized at scale with ease while maintaining near-perfect sequence control. The peptide sequence determines the type of nanostructure that is formed during assembly. Out of the resulting morphologies, nanofibers are of particular interest, as they resemble fibrous proteins of the extracellular matrix and can thus facilitate cell-material communication. Multifunctional materials become available either through co-assembly of different building blocks or through post-assembly reactions, enabling the introduction of tracer molecules, bioactive signals and other moieties. Here, we utilize self-assembling peptides to form dynamic particles, coatings and bulk hydrogels. By introducing pH- and light-responsive groups, we gain control over the assembly and disassembly behavior of bioactive nanostructures. Furthermore, patterned surfaces become accessible where the position and concentration of bioactive signals can be controlled externally. We have identified a number of peptide sequences that promote the growth of primary neuronal cells in vitro and lead to enhanced functional recovery in a peripheral nerve injury model in vivo. Finally, in bulk hydrogels, pH-responsive peptides were shown to act as supramolecular crosslinkers that give rise to remarkable rheological properties including thixotropy and self-healing.
Authors : Miryam Criado-Gonzalez a,b,c, Déborah Wagner a, Jennifer Rodon Fores a, Christian Blanck a, Marc Schmutz a, Alain Chaumont d, Morgane Rabineaub c, Joseph Schlenoff e, Guillaume Fleith a, Jérôme Combet a, Pierre Schaaf a,b,c,f, Loïc Jierry a,f, Fouzia Boulmedais a
Affiliations : a. Université de Strasbourg, CNRS, Institut Charles Sadron UPR 22, 67034 Strasbourg, France; b. Institut National de la Santé et de la Recherche Médicale, UMR-S 1121, “Biomatériaux et Bioingénierie”, 67087 Strasbourg, France; c. Université de Strasbourg, Faculté de Chirurgie Dentaire, 67000 Strasbourg, France; d.Université de Strasbourg, Faculté de Chimie, UMR7140, 67000 Strasbourg, France; e. Department of Chemistry and Biochemistry, Florida State University, Tallahassee, Florida 32306, United States; f. Université de Strasbourg, Ecole de Chimie, Polymères et Matériaux, Strasbourg, France.
Resume : Supramolecular hydrogels formed through non-covalent interactions of low molecular weight hydrogelators (LMWH) show great potential applications in different fields. Generally, the self-assembly of LMWH is triggered by a sol-gel process through an external stimulus able to switch their solubility, such as temperature change, pH switch, solvent change, chemical and enzymatic reactions. In this work, we introduce a new strategy to trigger and control the self-assembly of Fmoc-FFpY peptides. The formation of the peptidic hydrogel is obtained instantaneously by direct electrostatic interactions with a polycation without dephosphorylation of the peptides. The resulting hydrogels show enhanced mechanical properties in comparison to gels of Fmoc-FFpY induced by enzymatic dephosphorylation. Peptide self-assembly yields beta-sheets, revealed by circular dichroism and infrared spectroscopy. Transmission electron microscopy and X-ray diffraction showed the fine structure of the self-assembled fibers. Geometry optimization calculations in the gas phase support a self-assembly model in which polycation chains interact with the peptides through their phosphate groups and the polycation/peptide entities form parallel beta-sheets and interact through their Fmoc groups in an anti-parallel manner. Characteristic distances predicted are in agreement with X-ray scattering data. This work opens a route towards a new class of self-assembled hydrogels, where Fmoc tripeptides self-assemble by their interaction with polycations. Since the gels form quickly and have superior mechanical properties, applications as injectable biomaterials are foreseen.
Authors : Gačanin J.*, Synatschke C. V., Weil T.
Affiliations : Synthesis of Macromolecules Department, Max Planck Institute for Polymer Research, Mainz, Germany
Resume : In regenerative medicine there is a need to create new biomaterials that can support cellular adhesion, growth, and differentiation to replace damaged tissue, while allowing for minimally invasive application to the site of injury. To meet these demands, we developed biohybrid materials consisting of a polypeptide backbone that is grafted with supramolecular gelators of either DNA or nanofiber-forming peptides, combining the stability of covalent bonds with supramolecular chemistry, which gives rise to the most advantageous features. Both types of hydrogels show remarkable material and biological properties, such as thixotropic behavior and biocompatibility. While the programmability of DNA is exploited to enable the controlled delivery of bioactive protein for cell population control yielding reduced osteoclast formation and resorption activity, the second set of hydrogels benefits from grafted peptides, which can undergo a triggered molecular rearrangement that induces self-assembly into nanofibers and subsequent gelation. The gels show exceptional self-healing properties and the supramolecular interactions of the peptides that crosslink the gel allow the material to flow under shear stress, immediately reforming the gel when the shear is removed. This enables the gel to be injected, thereby, minimizing damage to healthy tissue. Furthermore, the hydrogels are biocompatible and allow culturing of multiple cell types, including primary neuronal cells.
Authors : Philip Schäfer, Artem Danilov, Andreas Huber, Adrian Cernescu
Affiliations : neaspec GmbH, Eglfinger Weg 2, 85540 Haar (Munich), Germany
Resume : Scattering-type scanning near-field optical microscopy (s-SNOM) has become one of the key techniques to overcome the ubiquitous diffraction limit of standard, far-field optical spectroscopy and microscopy. This AFM-based technology exploits the strong confinement of light at the end of a sharp, metallic AFM tip to generate a nanoscale optical hotspot at the sample directly below the tip. Importantly, the amplitude and phase of the light within the optical hotspot is strongly influenced by the dielectric properties (e.g. absorptivity) of the sample directly below the tip. Phase and amplitude-resolved detection of the back-scattered light as function of position can therefore be used to extract the local optical properties at the sample surface with <10 nanometer precision. The development of Fourier transform infrared spectroscopy on the nanoscale (nano-FTIR) can now be used to routinely perform nano-FTIR spectroscopy and hence allow chemical identification of materials on the nanometer length scale. This enables the identification of individual biomolecules and analyze complex bio and bio-inspired nanostructures and self-assembled monolayers. In addition, DNA-origami structures, biominerals (bone), embedded structural phases in polymers or functional semiconductor nanostructures can now directly be visualized and characterized on the sub-10nm scale. Even further, hyperspectral imaging has pushed this technology to the next level, recording nano-FTIR spectra at each pixel of a larger image on the sample. Subsequent data analysis enables the direct extraction of optical images at specific optical frequencies with 10 nanometer spatial resolution.
Poster session : -
Authors : Rameshwar L. Kumawat†,, Biswarup Pathak*,†,#,
Affiliations : †Discipline of Metallurgy Engineering and Materials Science, #Discipline of Chemistry, School of Basic Sciences, Indian Institute of Technology (IIT) Indore, Indore, Madhya Pradesh, 453552, India
Resume : The prospect of finding an improved method for rapid human-genome sequencing might offer an entirely new way of preventive health care . Recently solid-state nanopores/nanogaps have generated a lot of interest for ultrafast DNA sequencing. However, there are challenges to slow down the DNA translocation process to achieve a single-nucleobase resolution. A series of computational tools have been used in an attempt to study the DNA translocations in several model systems [2-4]. We have also studied the performance of a boron-carbide (BC3) based nanogap setup for DNA sequencing using the density functional theory and non-equilibrium Green’s function-based methods. The current variations under applied bias voltages due to change in the nucleotides orientation and lateral position found to be significant for nucleotides. In the case of BC3 nanogap, unique identification of all four nucleotides possible in the 0.3-0.4 V bias region. Furthermore, each of the four nucleotides exhibits around one order of current difference, which makes it possible to identify these nucleotides uniquely. Thus, our BC3 based nanogap may be promising for rapid human DNA sequencing. References:  B. Pathak, H. Löfås, J. Prasongkit, A. Grigoriev, R. Ahuja, R. H. Scheicher, Appl. Phys. Lett. 100 (2012), 023701.  J. Prasongkit, A. Grigoriev, B. Pathak, R. Ahuja, R. H. Scheicher, Nano Lett. 11 (2011), 1941- 1945.  J. Prasongkit, A. Grigoriev, B. Pathak, R. Ahuja, R. H. Scheicher, Journal of Physical Chemistry C. 117 (2013), 15421-15428.  R. L. Kumawat, P. Garg, S. Kumar, B. Pathak, ACS Applied Materials and Interfaces, 11 (2019), 219-225.
Authors : Alina Sharova, Mario Caironi
Affiliations : Dipartimento di Fisica, Politecnico di Milano, P.zza L. da Vinci 32, 20133 Milan, Italy; Center for Nano Science and Technology @PoliMi, Istituto Italiano di Tecnologia, Via Pascoli 70/3, 20133 Milan, Italy
Resume : Going beyond the traditional concept of electronic devices, we convey the idea of making electronics edible. This unconventional approach exploits the electronic properties of natural and food-based materials for developing ingestible functional devices. Critical biomedical, pharmaceutical, and food industry applications are targeted by the proposed field. In this framework, we explore the potential of cost-effective and edible substance, honey, to be used as electrolytic gate viscous dielectric. Honey-gated organic field effect transistors (OFETs) based on both n & p type semiconductors are fabricated. A distinctive feature of these transistors is their long-term stability, reproducibility and low voltage < 1V operation in air. Devices exhibit forward-looking electronic performances, notably, electron and hole mobility–capacitance product of 3.5 × 10–3 μF/Vs and 23 × 10–3 μF/Vs, respectively, surpassing ones of the previously reported water-gated OFETs. Furthermore, the observed devices responsivity to humidity provides promising opportunities for sensing applications. We then demonstrate, for the first time, the implementation of honey-based integrated circuits: inverting logic gate and ring oscillator.
Authors : Qian Zhang
Affiliations : Department of Chemistry, Imperial College London
Resume : The sensing of biomarkers has been regarded as a powerful method for early clinic diagnosis, which is crucial for the treatment of a large number of diseases.1 However, developing an ultrasensitive and highly selective method to detect and quantify these biomarkers is still challenging, due to their generally low concentrations, small sizes and easy degradation.2 In this project, we propose to combine SERS (surface-enhanced Raman scattering)-based nanoassemblies with Dielectrophoresis (DEP) to design an ultrasensitive biosensor. The target molecules will induce the formation of Au nanoparticle (AuNP) dimers with small gaps (the hot-spot regions) where the Raman process of Raman reporters is enhanced, and then we utilize a DEP trap at the tip of nanopipette to preconcentrate AuNP dimers to get stronger Raman signals and lower limits of detection. In addition to high sensitivity and selectivity, this technique is also highly adaptable. By changing the aptamers attached on AuNPs, this biosensor will be able to detect various biomolecules that can be specifically recognized, which will lead to a more accurate diagnosis. Furthermore, this method is low-cost and highly responsive, which makes it suitable for point-of-care clinic diagnosis. References 1 E. Stern, A. Vacic, N. K. Rajan, J. M. Criscione, J. Park, B. R. Ilic, D. J. Mooney, Nat. Nanotech, 2010, 5, 138–142. 2 S. Li, L. Xu, W. Ma, X. Wu, M. Sun, H. Kuang, L. Wang, N. A. Kotov and C. Xu, J. Am. Chem. Soc., 2016, 138, 306–312.
Authors : Fabrice Saintmont (a,b), Julien De Winter (a), Patrick Brocorens (b), Pascal Gerbaux (a)
Affiliations : (a) Organic Synthesis & Mass Spectrometry Laboratory, Interdisciplinary Center for Mass Spectrometry (CISMa), Center of Innovation and Research in Materials and Polymers (CIRMAP), University of Mons - UMONS, 23 Place du Parc, 7000 Mons, Belgium ; (b) Laboratory for Chemistry of Novel Materials, Center of Innovation and Research in Materials and Polymers, Research Institute for Science and Engineering of Materials, University of Mons - UMONS, 23 Place du Parc, 7000 Mons, Belgium
Resume : The sphericity of gaseous ions, resulting from the ionization of large molecules such as polymers and proteins, is a recurring subject which has undergone a renewed interest due to the advent of ion mobility spectrometry (IMS), especially in conjunction with theoretical chemistry techniques such as Molecular Dynamics (MD). Spherical conformations result from a fine balance between entropy and enthalpy considerations. For multiply charged ions isolated in the gas phase of a mass spectrometer, the coulombic repulsion between the different charges tends to prevent the ions from adopting a compact and folded 3D structures. We intimately associate data from IMS experiments and MD simulations to unambiguously access the conformations of dendrimer ions in the gas phase with a special attention paid to the dendrimer structure, the generation and the charge state. Doing so, we combine a set of structural tools able to evaluate the (non)sphericity of ions based on both experimental and theoretical results. The study of dendrimer ions is the first step toward the characterization of the supramolecular complexes formed by electrostatic interactions between polyanionic nucleic acids and polycationic dendrimers called dendriplexes, in the context of gene delivery . Reference 1. Dufès et al., Adv. Drug Deliv. Rev., 57, 2177-2202 (2005)
Authors : Pier A. Berling, Cédric Leuvrey, Spiros Zafeiratos, Thomas Gehin, Benoit P. Pichon
Affiliations : Université de Strasbourg, CNRS, Institut de Physique Chimie des Matériaux de Strasbourg (IPCMS), UMR 7504, France ; Université de Strasbourg, CNRS, Institut de Physique Chimie des Matériaux de Strasbourg (IPCMS), UMR 7504, France ; Institut de Chimie et Procédés pour l’Energie, l’Environnement et la Santé (ICPEES), ECPM, UMR 7515, Strasbourg, France ; Institut des Nanotechnologies de Lyon, UMR 5270, Lyon, France ; Université de Strasbourg, CNRS, Institut de Physique Chimie des Matériaux de Strasbourg (IPCMS), UMR 7504, France ;
Resume : We present an innovative method to create an original nanostructured SPR biosensor in order to enhance sensitivity and limit of detection. Our strategy consists in taking advantages of high refractive dielectric materials which increase the sensitivity factor of a gold thin film. The approach consists in using iron oxide nanoparticles assembled onto a gold thin film to improve the sensitivity factor of the gold thin film as well as the specific surface of the sensor. The nanoparticles were easily grafted on the substrate by catalyzed alkyne azide cycloaddition (CuAAC) “click”. The biomolecular receptor was grafted at the surface of assembled nanoparticles by performing again the CuAAC “click” chemistry. Furthermore, polyethylene glycol (PEG) derivatives were grafted onto free areas of the gold thin film in between nanoparticles in order to avoid nonspecific adsorption of analytes. The biotin-streptavidin couple was used as an example to prove the efficiency of the sensor. Bovine serum albumin (BSA) was also used to demonstrate that nonspecific absorption is avoided. Finally, we successfully demonstrate that PEG molecules associated with nanoparticles enhance the accessibility of streptavidin to the biotin group, thus contributing to decrease the limit of detection.
Authors : Seunghan Shin, Se Won Bae
Affiliations : Korea Institute of Industrial Technology, University of Science and Technology (SS); Korea Institute of Industrial Technology, University of Science and Technology (SWB)
Resume : The hydrogel is a three-dimensional cross-linked hydrophilic polymer with multiple advantages such as high biocompatibility, biodegradability, high water content and controllable drug release rate. Also, the aptamer is a either DNA or RNA nucleotides with affinities comparable to antibodies as well as high specificity and affinity towards the target with nanomolar to picomolar range. In this presentation, we will report DNA aptamer-incorporated hydrogels whose macroscopic volume is changed through an inducement of the binding events of aptamer-target recognition. We synthesized multi-arm PEG based hydrogels and potassium cation aptamers so that both can be covalently attached. By adding potassium cation, the macroscopic volume shrinkage of hydrogels is achieved due to the formation of the G-quadruplex structure between the linear DNA aptamers and potassium cations, leading to the decreased microscopic volume. This stimuli-responsive hydrogel will be applied to sustained drug delivery systems.
Authors : Bing Li(1,2), Sébastien Harlepp(1), Connor Wells(1), Sylvie Begin-Colin(1), Dominique Begin*(2), Damien Mertz*(1)
Affiliations : (1). Institut de Physique et Chimie des Matériaux de Strasbourg (IPCMS), UMR-7504 CNRS-Université de Strasbourg, 23 rue du Lœss, BP 34 67034, Strasbourg Cedex 2, France (2). Institut de Chimie et Procédés pour l'Energie, l'Environnement et la Santé (ICPEES), UMR-7515 CNRS-Université de Strasbourg, 25 rue Becquerel, 67087 Strasbourg, Cedex 2, France
Resume : One of the most promising developments in the nanomedecine field is the design of smart activable nanosystems remotely releasing drugs upon externally applied stimuli (e.g., light, magnetic or electric fields). Among the various activable nanomaterials, carbon-based nanocomposites are still few investigated for remotely controlled drug delivery. In this work, we address the design of original carbon nanotube base composite nanoplatforms endowed with phototherapy combined with a drug release mediated by NIR laser excitation. These responsive carbon nanotubes are surrounded with a mesoporous silica shell having small pores which are chemically modified with isobutyramide (IBAM) grafts. These IBAM binders allow first the loading of an antitumor drug doxorubicin with a very high drug loading capacity (≥to 80%) followed by the adsorption of an additional tight human serum albumin (HSA) shell ensuring a biocompatible interface and drug gate keeping. Such smart photoresponsive platforms are shown to deliver the drugs upon several pulsatile NIR excitations with controlled T profiles according to the conditions used (concentrations, power laser etc…) These nanosystems are in fine integrated within a hydrogel mimicking/resembling the extracellular matrix and the biological response with cells on this resulting smart nanocomposite hydrogel scaffold is assessed upon NIR light irradiation. Such nanocomposites are hence highly promising as new components of implantable scaffolds by interfacing biomolecules with carbon nanotubes, which can respond in time and location to external stimuli for a better disease management.
Authors : Haiyin Wang, Dr James Wilton-Ely, Prof. Joshua Edel, Dr Alex Ivanov
Affiliations : Department of Chemistry, Imperial College London, London, W12 0BZ, United Kingdom
Resume : The detection of carbon monoxide (CO) is of high significance as it binds to haemoglobin that restricts the transport of oxygen in body. Over the recent years, carbon monoxide has gained greater attention in therapeutic treatments due to its effectiveness in anti-inflammation and anti-microbial infection. The concentration of CO in these treatments needs to be controlled to prevent immediate and chronic poisoning. This research focuses on using an ultrasensitive nanopore-based probe to sense CO, to achieve a limit of detection (LOD) that is smaller than other conventional sensing techniques by orders of magnitude. A molecular ruthenium complex that connects a 10 kbp DNA and a 5 kbp DNA is employed for nanopore translocations. The CO molecules are administrated by CO-releasing molecules into the electrolytes. The binding of CO to the ruthenium metal centre cleaves the pyridyl-terminated 10 kbp DNA unit, which results in a significant change in the detected current signals. The concentration of CO is determined by the translocation frequency of CO-cleaved DNA strands (5kpb), and the LOD can be specified and then compared with that obtained by fluorescence-based sensors.
Authors : Min Sang Lee, Ji Hoon Jeong
Affiliations : School of Pharmacy, Sungkyunkwan University, Suwon, Republic of Korea
Resume : Oral vaccination for cancer immunotherapy provides an improved patient compliance and induction of mucosal immune response as well as humoral immune response. However, the delivery of antigen by oral route is limited due to harsh gastro-intestinal environment, intestinal epithelial barrier and lower uptake of the antigenic particles. In this study, we prepared an improved oral immunotherpy platform for simultaneous delivery of antigen and adjuvant using polymeric carrier (DA3). Encapsulation of adjuvant and antigen (DA3/Ad/Ag) was successfully carried out by formulating with DA3, which effectively protects antigen from enzymatic degradation and enhances colloidal stability. Permeation of DA3/Ad/Ag nanoparticles was increased by specific interaction with deoxycholic acid and apical sodium-dependent bile acid transporter (ASBT). In addition, their enhanced cellular uptake was observed in antigen presenting cells (APCs), which leads to successful maturation of immune cells and secretion of proinflammatory cytokines. Orally administrated DA3/Ad/Ag nanoparticles showed an enhanced permeation and induction of humoral, cellular and mucosal immune responses, which leads to desired cancer therapeutic effect. These results suggested that DA3-based oral vaccination platform for simultaneous co-delivery of antigen and adjuvant can be considered as a prospective candidate for cancer immunotherapy.
Authors : W.H. Chiang*(1), K.T. Hou (2), T.I. Liu (2) & H.C. Chiu (2)
Affiliations : (1) Department of Chemical Engineering, National Chung Hsing University, Taichung 402, Taiwan. (2) Department of Biomedical Engineering and Environmental Sciences, National Tsing Hua University, Hsinchu 300, Taiwan.
Resume : To boost the efficacy of chemo-photothermal cancer treatment by the intracellular rapid release of doxorubicin (DOX) combined with near-infrared (NIR)-triggered photothermal effect of indocyanine green (ICG), the poly(r-glutamic acid)-g-poly(lactic-co-glycolic acid) (r-PGA-g-PLGA)-based polymeric nanoassemblies (PNAs) with simultaneous incorporation of DOX and ICG were developed in this work by simple one-step nanoprecipitation. The obtained DOX/ICG-loaded PNAs were characterized by a compact r-PGA/DOX complexes-encapsulated PLGA-rich core covered with the co-assembly of amphiphilic D-α-tocopheryl polyethylene glycol succinate (TPGS), 1,2-distearoyl-sn-glycero-3-phosphoethanolamine-N-[amino(polyethylene glycol)] (DSPE-PEG) and ICG molecules. The robust cargo-loaded PNAs not only promoted the photo-stability of ICG in PBS, but also reduced ICG leakage from PNAs. With the milieu pH being altered from 7.4 to 5.0, the massive disruption of ionic DOX/r-GA complexes and PLGA degradation considerably accelerated DOX release from payload-containing PNAs. The results of in vitro cellular uptake revealed that the DOX/ICG-loaded PNAs appreciably enhanced the cellular uptake of payloads by HeLa cells. Notably, through the intracellular acid-triggered rapid DOX release combined with the ICG-based NIR-activated hyperthermia and singlet oxygen generation, the combination therapy of DOX/ICG-loaded PNAs can use lower dosage of drugs to effectively inhibit proliferation of HeLa cells compared to the chemo or photothermal treatment alone, thus showing the great potential to improve efficacy of cancer treatment.
Authors : Joëlle Bizeau, Alexandre Adam, Sylvie Begin-Colin, Damien Mertz
Affiliations : IPCMS-CNRS UMR 7504, Univ. of Strasbourg
Resume : A well-known interest of using nanoparticles to deliver drugs is the controlled delivery of the contained therapeutic agent followed by internal or external stimuli. But these nanosystems are even more interesting if they combine several modalities. In our group, such combination has been used to obtain imaging and magnetic hyperthermia. The system consisted in an iron oxide nanoparticle encapsulated in a stellate mesoporous silica shell (IO@STMS). The shell was then functionalized with quantum dots and coated with Human Serum Albumin (HSA). The HSA was fixed through the IBAM strategy, demonstrated to allow the non-covalent but stable binding of several types of macromolecules to silica particles such as protein, nucleic acid, polysaccharide and polypeptide. The aim of our work is to modify the previous IO@STMS system to deliver interesting proteins for tissue regeneration. To do so, it is hypothesized that the combination of this system with thermo-responsive (bio)polymers will allow the release of the protein through magnetic hyperthermia-induced conformational change. The IBAM strategy would still be used either to fix the new coating or to ensure protein adsorption.  F. Perton, M. Tasso, G. A. Muñoz Medina, M. Ménard, C. Blanco-Andujar, E. Portiansky, M. B. Fernández van Raap, D. Bégin, F. Meyer, S. Begin-Colin, D. Mertz, Applied Materials Today 2019, 16, 301-314  D. Mertz, P. Tan, Y. Wang, T. K. Goh, A. Blencowe, F. Caruso, Adv. Mater. 2011, 23, 5668-5673
Authors : Hava Sadihov, Dr. Riky Cohen Luria, Prof. Gonen Ashkenasy
Affiliations : Ben-Gurion University of the Negev
Resume : Biological systems, where weak non-covalent interactions of simple building blocks form functional complex machinery, gave rise to biologically inspired self-assembling materials, based for example on nucleic acids and peptides. Although self-organized systems based on molecules from both families have already been explored, artificially synthesized hybrid molecules are novel and exhibit noticeable importance in material science and biomedical research. In our system, two short complementary DNA segments are attached to an amphiphilic peptide sequence previously investigated by our lab1-3. We demonstrate the self-assembly of our system into a number of different topologies, fibers and multi-lamellar spherical structures, and we present the co-assembly pathway leading from one type of the aggregates to another. In addition, we find that when forming the onion-like structure, the conjugates exhibit conformational changes of DNA hybridization. We studied the stability of these spheres and the effect of metal ions on the DNA hybridization under different environmental conditions. To the best of our knowledge, this study proposes the first systematic analysis of structural and functional characteristics of small double stranded nucleic-acid-peptide conjugates. References: 1. B. Rubinov, N. Wagner, M. Matmor, O. Regev, N. Ashkenasy and G. Ashkenasy, ACS nano, 2012, 6, 7893-7901. 2. D. Ivnitski, M. Amit, O. Silberbush, Y. Atsmon-Raz, J. Nanda, R. Cohen-Luria, Y. Miller, G. Ashkenzsy, N. Ashkenasy, Angew. Chem. Int. Ed. 2016, 55, 9988-9992. 3. J. Nanda, B. Rubinov, D. Ivnitski, R Mukherjee, E. Shtelman, Y. Motro, Y. Miller, N. Wagner, R.C.Luria, G. Ashkenzsy, Nature Commun. 2017,8,434. 4. A. Chotera, H. Sadihov, R. Cohen‐Luria, P. Monnard, and G. Ashkenasy, Chem. Eur. J., 2018, 24, 10128-10135
Authors : Béatrice Gerland, Crystalle Chardet, Corinne Payrastre, Jean-Marc Escudier
Affiliations : Laboratoire de Modified Nucleic Acids, Lipids & Innovative Synthetic Approaches, MoNALISA team Laboratoire de Synthèse et Physico-Chimie de Molécules d’Intérêt Biologique
Resume : α-Chymotrypsin uses three cooperative amino acids constitutive of its catalytic triad, serine (Ser), histidine (His) and aspartate (Asp) to cleave the peptide bond through covalent catalysis. The mechanism differs from the uncatalyzed hydrolysis of the amide bond, a challenge when designing protease mimics. Despite the limited success of the DNA catalyzed hydrolysis, DNA is however an ideal scaffold due to its chemical stability, its ease of access by solid phase synthesis (SPS) and its perfectly controlled folding. Moreover, grafting additional organic functionalities would expand its catalytic repertoire. Using the convertible and/or functionalized phosphoramidite approaches, we aim to mimic the active site of this serine protease with functionalized oligonucleotides (FuON) covalently modified at precise coordinates along their backbone with amino acids side chain-like residues (alcohol, imidazole or aspartate function for Ser, His or Asp respectively) (1). From a toolbox of twelve C5'-modifed thymidine phosphoramidites (varying both linkers and functions), families of FuON bearing up to three modifications could be obtained by SPS. They are then shaped into DNA secondary structures (3-way junction, bulges, hairpins) in an attempt to reproduce the active conformation of the triad. FuON combinations would then lead to heterogeneous libraries with skeletal and topological variety increasing the chances to screen for catalytic mimics. The first DNA catalysts libraries would be presented alongside the efforts to overcome the lack of a binding site. Their future insertion into 2D and 3D DNA nanostructures will also be discussed. (1) Addamiano, C.; Gerland, B.; Payrastre, C.; Escudier, J. M.; Molecules 2016, 21, 1082
Authors : Edmund Chu, Dr Ramzi Khamis, Dr Nazila Kamaly
Affiliations : Department of Chemistry, Imperial College London, London, W12 0BZ, United Kingdom
Resume : Atherosclerosis is the major cause of cardiovascular disease including causing heart attacks, ischaemic heart disease and strokes. It is a chronic inflammatory disease that is described by the retention of foam cells, formed from oxidized low-density lipoproteins (LDL), building up the plaque and as a result narrowing or possibly blocking arteries. It is also possible to cause rupture when the fibrous cap is punctured which leads to ischaemic heart disease and strokes. With the recent advancements in nanotechnology, nanogels targeting and sensitive to the plaque will be investigated and developed. Nanogels are hydrogel nanoparticles with the properties of both hydrogel and nanomaterials. Nanogels offer size, higher loading capacity and stability advantages as a drug deliverer over common biological drugs. They can also be modified to be sensitive to stimuli, allowing a trigger for the release of the payload. In this work, nanogels will be modified to be responsive to matrix metalloproteinase and to incorporate anti-oxidizing paraoxanase-1 enzyme as the payload to prevent oxidation of LDL. In collaboration with Dr Ramzi Khamis group from Hammersmith Hospital, they have identified developed monoclonal antibody IgG3? (LO1). This antibody acts as targeting ligand towards malondialdehyde-conjugated LDL found in copper oxidized LDL. Therefore, this work demonstrates the potential of the combination of targeting, response and release as strategy to atherosclerosis therapy.
Authors : Maxime Leclercq, Sylvain Gabriele, Sébastien Clément, Mathieu Surin
Affiliations : Maxime Leclercq and Mathieu Surin : Laboratory for Chemistry of Novel Materials, Center for Innovation in Materials and Polymers, University of Mons - UMONS, 20 Place du Parc, B-7000 Mons, Belgium ; Sylvain Gabriele :Mechanobiology & Soft Matter Group, Laboratoire Interfaces et Fluides Complexes, Center for Innovation in Materials and Polymers, University of Mons - UMONS, 20 Place du Parc, B-7000 Mons, Belgium ; S. Clément :Institut Charles Gerhardt (ICGM), UMR 5253 CNRS-ENSCM-UM, Université de Montpellier – CC1701, Place Eugène Bataillon, F-34095 Montpellier Cedex 05, France
Resume : In this work, we assess the potential of cationic polythiophenes (CPTs) as optical transducers for the detection of enzymatic methylation of DNA. CPTs constitute an interesting class of π-conjugated polymers for biosensing applications, as they combine solubility in aqueous media and have sensitive optical properties for the detection of biomolecules such as DNA.(1) Recently, we have exploited “P3HT-PMe3”, an achiral polythiophene with phosphonium side-groups. When DNA and this polymer are mixed in aqueous solutions, self-assembly occurs and yield chiral supramolecular complexes, as observed by induced circular dichroism (ICD) signals in the spectral range where the polymer absorbs.(2,3,4) We study (chir)optical signals of the DNA/P3HT-PMe3 complexes for the detection of methylation of DNA catalysed by a methyltransferase (Mtase).(4,5,6) With long DNA, P3HT-PMe3 form µm-long fibers on surfaces, which are studied by Atomic Force Microscopy and Confocal Optical Microscopy.(7) (1) H. Jiang et al., Angew. Chem. Int. Ed. 2009, 48, 4300. (2) J. Rubio-Magnieto et al., Soft Matter 2015, 11, 6460. (3) M. Leclercq et al, ChemNanoMat, 2019, 5, 703. (4) M. Fossépré et al., ACS Appl. Bio Mater., 2019, 2, 2125. (5) Chris R. Calladine; Horace Drew; Ben Luisi; Andrew Travers, “Understanding DNA: The Molecule and How It Works”, Academic Press, 2004. (6) L. Fengting et al., Small, 2016, 12, 696. (7) R. Zhang et al, Sci. Rep., 2017, 7, 5430.
Authors : Sinan Kardas*(1), Mathieu Fossépré (1), Antony Fernandes (2), Karine Glinel (2), Alain M. Jonas (2) & Mathieu Surin (1).
Affiliations : (1) Laboratory for Chemistry of Novel Materials, Center of Innovation and Research in Materials and Polymers, University of Mons, Belgium; (2) Institute of Condensed Matter & Nanosciences – Bio & Soft Matter, Université catholique de Louvain, Belgium.
Resume : Nature has the amazing ability to achieve a perfect control over the monomer sequence in biological macromolecules. This microstructural precision leads to sophisticated structures with remarkable functions such as catalysis, molecular recognition, and information storage. Inspired by the precision of biological macromolecules, the design of synthetic sequence-defined polymers constitutes an emerging topic to generate materials with next-generation performances. Despite considerable progress on the control over the primary structure, the controlled folding and assembly of synthetic polymers into predetermined three-dimensional shapes have not been achieved so far. Here we use computational chemistry approaches to decipher the structure and dynamics of sequence-defined oligomeric chains used for supported catalysis. These oligomers incorporate structuring groups and three functional moieties for the selective oxidation of alcohols. The oligomeric chains under study differ by the monomer sequence and the number of molecular spacers between the catalytic moieties. In combination with the experimental catalytic activity, our computational study brings insights into structure-activity relationships for targeted applications in catalysis.
Authors : Sébastien Hoyas (a,b), Vincent Lemaur (a), Emilie Halin (b), Julien De Winter (b), Pascal Gerbaux (b), Jérôme Cornil (a)
Affiliations : (a) Laboratory for Chemistry of Novel Materials, Center of Innovation and Research in Materials and Polymers, Research Institute for Science and Engineering of Materials, University of Mons, UMONS, 23 Place du Parc, 7000 Mons, Belgium; (b) Organic Synthesis & Mass Spectrometry Laboratory, Interdisciplinary Center for Mass Spectrometry (CISMa), Center of Innovation and Research in Materials and Polymers (CIRMAP), University of Mons, UMONS, 23 Place du Parc, 7000 Mons, Belgium;
Resume : Peptoids are peptide reigioisomers that represent a class of peptido-mimetic polymers. Compared to peptides, the side chain is appended to the amide nitrogen instead of the α-carbon. Peptoids can form stable secondary structures in solution, mainly helical, and some other specific structures. Peptoids have been successfully tested as chiral selectors in chiral column chromatography, with the helical structure supposed to be responsible for these properties. NMR and CD are currently the most widely used techniques to characterize peptoid secondary structures.[1-3] However, the structural information provided by these methods is averaged over all isomeric structures. In this context, Mass Spectrometry (MS) techniques, especially Ion Mobility MS (IMMS), represent a suitable method to investigate the relationship between primary and secondary structures when coupled to calculations to assess their actual conformations. We report here the study of peptoids by associating ion mobility mass spectrometry and molecular dynamics simulations [5,6]. In particular, we will discuss whether helicity is preserved when going from solution to the gas phase.  N. Gangloff et al., Chem. Rev. 2016, 116, 1753  K. Huang et al., J. Am. Chem. Soc. 2006, 128, 1733  H. Wu et al., The Analyst 2011, 136, 4409  J. De Winter et al., Chem. Eur. J. 2011, 17, 9738  S. Hoyas, E et al., Biomacromolecules, 2020 (submitted)  S. Hoyas et al., Adv. Th. Sim., 2018
Authors : Perrine Weber (a,b), Sébastien Hoyas (a,c), Jérôme Cornil (c), Pascal Gerbaux (a), Olivier Coulembier (b) and Julien De Winter (a)
Affiliations : (a) Organic Synthesis and Mass Spectrometry Laboratory, Interdisciplinary Center for Mass Spectrometry, University of Mons – UMONS, 23 Place du Parc, B-7000 Mons, Belgium; (b) Laboratory of Polymeric and Composite Materials, University of Mons - UMONS, 23 Place du Parc, Mons, Belgium; (c) Laboratory for Chemistry of Novels Materials, Center of Innovation and Research in Materials and Polymers, University of Mons – UMONS, 23 Place du Parc, B-7000 Mons, Belgium
Resume : Peptoids represent an emergent class of synthetic polymers differing from peptides by the side chain position on the nitrogen atom instead the alpha carbon to amide moiety. Peptoids can adopt secondary structures in solution such as helix. However, unlike peptides and proteins, no data concerning the gas phase structure of peptoid ions is to date present in the literature. In our laboratory, we combine ion mobility mass spectrometry (IMMS) and computational chemistry to provide data on the 3D structures adopted by gaseous ions. Nevertheless, the ionization/desolvation processes related to the use of MS can generate huge structural modifications. Thus, the conservation of helical structure during the transfer from the solution to the gas phase represents a great challenge since most of the time, a charge solvation effect is observed during the transfer to the gas phase. Currently, a specific attention is given to design original peptoids with a localised charge to avoid possible charge solvation effect and potentially adopt helical structure in gas phase. Its backbone possesses (S)-phenylethyl side chains (Nspe), a bulky chiral group known to form helix in solution, and a (S)-N-(1-carboxy-2-phenylethyle) (Nspc) at C terminus. This sequence could optimize the interaction between the negative charge located on the C terminus and the helix macrodipole. Moreover, the influence of Nspc position and acetylation are investigated.
Authors : Sungchul Shin, Hojung Kwak, Jinho Hyun
Affiliations : Department of Biosystems and Biomaterials Science and Engineering, Seoul National University
Resume : Carboxymethylated hydrophilic CNF (Hphil-CNF) was modified with methyltrimethoxysilane into hydrophobic CNF (Hphob-CNF) and used as a printing matrix. The Hphil-CNF hydrogel was printed at the surface of the Hphob-CNF hydrogel, forming an immiscible, distinct 3D structure. Petroleum-jelly-printed CNF hydrogels were dehydrated at 40 °C to form a film structure with microfluidic designs. After dehydration for 24 h, the petroleum jelly patterns were removed by applying compressed air at 70 °C to form a channel structure. The channels formed in the CNF film was treated with 1 % calcium ion solution to prevent further deformation. Due to the high transparency of the platform, it is possible to observe the cell morphology and response to external stimuli as well as chemical flow in the channel. The applicability of the open cell culture platform was investigated with A549 lung cancer cells by injecting cisplatin, a model drug into the channel.
Authors : JINGA, L. I.* (1,3), POPESCU-PELIN, G. (1), DAVID, V. (3), SIMA, L. (2), SOCOL, G. (1).
Affiliations : (1) National Institute for Lasers, Plasma and Radiation Physics, Romania (2) Institute of Biochemistry of the Romanian Academy, Romania (3) Faculty of Chemistry, University of Bucharest, Romania
Resume : An alternative method for cancer therapy, which has attracted a significant attention in the past few years is magnetic hyperthermia. In the presence of RF magnetic field, the magnetic nanoparticles generate heat, which increase the temperature in tumors in a controlled manner, leading to killing the tumor cells. The interaction between the nanoparticles and the biological system depends almost by the surface modification of magnetic nanoparticles. In this context, cysteine coating, not only enhances colloidal stability, but also makes nanoparticles more biocompatible. Moreover, surface functionalization of magnetic nanoparticles with antitumoral will increase significantly the chances in the cancer treatment by hyperthermia. In this study, we report the synthesis of superparamagnetic nanoparticles (SPION NPs) with different surface modification, as well as their influence in the hyperthermia study. Biological tests on A375 human melanoma cells and metastatic murine melanoma (B16F10) confirmed the internalization of magnetic nanoparticles delivering Doxorubicin, which is used as a chemotherapic in the treatment of cancer. Also, IC50 value was determined for both cell types. Based on the obtained results, new perspectives on development of new biocompatible and bio-functional SPION NPs for magnetic hyperthermia are highlighted.
Authors : Corentin Tonneaux (1), Annemiek Uvyn (2), Mathieu Fossépré (1), Bruno G. De Geest (2), Mathieu Surin (1)
Affiliations : (1) Laboratory for Chemistry of Novel Materials, Center of Innovation and Research in Materials and Polymers, University of Mons - UMONS 20, Place du Parc B-7000 Mons, Belgium; (2) Department of Pharmaceutics University of Ghent - UGent Ottergemsesteenweg 460, 9000 Ghent, Belgium
Resume : Immunotherapy is a type of treatment which uses the patient’s immune system to fight diseases such as cancer. Antibody-recruiting molecules (ARM) constitute a promising approach in this field. These molecules combine anchoring groups that target the surface of the cancer cell and haptens that bind endogenous antibodies, these are present in the serum of every human being, to trigger immune-mediated killing of target cancer cells. The molecules used in this project will anchor through a derivative of dibenzocyclooctyne group (DBCO) to azide labeled cancer cells and can bind anti-DNP antibodies. The first approach to improve the therapeutic effect of those molecules is the use of multivalent ARMs, to increase the binding affinity towards the anti-DNP antibody. In this work, we carry out molecular modelling simulations in order to get insights into the conformations of the molecules and their interactions with antibodies. Notably, we study the effect of the number of functional groups, their spacing, and the nature of the linkers on the 3D structures. The knowledge on the conformations and binding modes is fundamental to adapt the design of the molecule and thus improve its therapeutic effect.
Authors : Coste Maëva, Ulrich Sébastien
Affiliations : Institut des Biomolécules Max Mousseron (IBMM), Université de Montpellier, CNRS, ENSCM, Montpellier, France
Resume : Small molecules that interact with DNA are of interest in the pursuit of functional DNA-templated self-assemblies. In particular, tetraphenylethene (TPE) compounds have recently attracted a growing interest in this context thanks to their Aggregation-Induced Emission (AIE) effect that can be exploited for turn-on sensing applications. After a previous work on imidazolium-TPE derivative for G-quadruplexes recognition, we wish to explore the generation of new TPE derivatives by acylhydrazone conjugation. After a successful preparation of TPE derivative displaying four quaternary ammoniums, we evaluated its self-assembly by fluorescence and UV-visible spectroscopies. AIE effect was evidenced and correlated to nanoparticles formation as observed by Dynamic Light Scattering (DLS) and Transmission Electronic Microscopy (TEM). Further DNA recognition studies, carried out by UV-visible, fluorescence and Circular Dichroism (CD) spectroscopy analyses, clearly demonstrate the interaction with ssDNA and dsDNA and point toward a model involving intercalation that will be presented in this poster. References:  Surin M., Polym. Chem., 2016, 7, 4137 – 4150  Kwok R. T. K. et al, 2015, Chem. Soc. Rev., 44, 4228 – 4238  Kotras C. et al, Front. Chem., 2019, 7, 493  Coste M. et al., 2020, manuscript in preparation
Authors : Karen Escobar 1; Tanya Plaza 1, Nelson Naveas 3; Miguel Manso 4; Waldemar Macedo 5; Carla França 6; Marcelo Lancellotti 7; Monica Cotta 8; Yendry Corrales 9; Klaus Rischka 10; Jacobo Hernandez-Montelongo 11.
Affiliations : 1 Bioproducts and Advanced Materials Research Center (BioMA), UC Temuco, Chile; 2 Department of Chemical Engineering and Mineral Processes; University of Antofagasta, Chile; 3 Department of Applied Physics, Autonomous University of Madrid, Spain; 4 Center for the Development of Nuclear Technology, Brazil; 5 Department of Materials and Bioprocess Engineering, University of Campinas, Brazil; 6 Faculty of Pharmaceutical Sciences, University of Campinas, Brazil; 7 Department of Applied Physics, University of Campinas, Brazil; 8 Adolphe Merkle Institute, University of Fribourg, Germany; 9 Fraunhofer Institute for Manufacturing Technology and Advanced Materials, Germany; 10 Department of Mathematical and Physical Sciences, UC Temuco, Chile.
Resume : Mammoplasty is a plastic surgery to reshape or modify human breasts through silicone implants. It is one of the most common surgeries in women around the world because is used in mammary reconstruction as a post-treatment of breast cancer, as well as for aesthetic reasons. Like any surgery, augmentation mammoplasty involves inherent risks such as bruising, rupture or emptying of implants, capsular contracture, and bacterial infections. To reduce these post-operative risks, medicaments and biomolecules can be localized and controlled release by drug delivery systems based in cyclodextrins (CDs). CDs have been used as efficient delivery carriers due to their characteristic cavity and their ability to form drug-reversible complexes. In that sense, the aim of this project is the functionalization of commercial breast implants of silicone, with smooth and roughness surfaces, by β-CD/citric acid and 2-hydroxypropyl-β-CD/acid citric in situ polymerization as an alternative for the post-operative risks treatment in mammoplasty. Functionalized samples were characterized by different physicochemical techniques, and its stability was studied. Five different molecules were used as model to test the obtained samples as controlled local drug delivery system for mammoplasty: zafirlukast, utilized for capsular contracture prevention, levobupivacaine for local anesthesia, rose Bengal that possesses cytotoxic properties in cancer cells, and KR-12 and GL13K antimicrobial peptides to prevent bacterial infections. In this regard, the release kinetic mechanism was obtained by the Korsmeyer–Peppas model. Further works will be focused on antibacterial tests using Staphylococcus aureus and Staphylococcus epidermis, two of the most common finded strains in post-mammoplasty bacterial infection.
Authors : Mariana Tasso, Francis Perton, Guillermo A. Muñoz Medina, Mathilde Ménard, Cristina Blanco-Andujar, Enrique Portiansky, Marcela B. Fernández van Raap, Dominique Bégin, Florent Meyer, Sylvie Bégin-Colin, Damien Mertz
Affiliations : Institut de Physique et Chimie des Matériaux de Strasbourg (IPCMS), UMR-7504 CNRS-Université de Strasbourg, 23 rue du Loess, BP 34, 67034 Strasbourg Cedex 2, France; Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas (INIFTA), Departamento de Química, Facultad de Ciencias Exactas, Universidad Nacional de La Plata – CONICET,Diagonal 113 y 64, 1900 La Plata, Argentina; Instituto de Física La Plata, CONICET-UNLP, diagonal 113 entre 63 y 64, La Plata, Argentina; Institut National de la Santé et de la Recherche Médicale, UMR 1121 FMTS, 11 rue Humann, 67085 Strasbourg, France; Institute of Pathology, School of Veterinary Sciences, University of La Plata, calle 60 y 118, 1900 La Plata, Argentina; Institut de Chimie et Procédés pour l’Energie, l’Environnement et la Santé (ICPEES), UMR-7515 CNRS-Université de Strasbourg, 25 rue Becquerel, 67087 Strasbourg Cedex 2, France
Resume : There is currently a crucial need of innovative multifunctional nanoparticles combining, in one formulation, imaging and therapy capacities allowing thus an accurate diagnosis and a therapy monitored by imaging. Multimodal imaging will ensure to speed up diagnosis, and to increase its sensitivity, reliability and specificity for a better management of the disease. Combined with a therapeutic action, it will also enable to treat the disease in a specific personalized manner in feedback mode. The mastered design of such bioprobes as well as the demonstration of their efficiency are still challenges to face in nanomedicine. In this work, novel fluorescent and magnetic core–shell nanocomposites have been designed to ensure, in one nanoformulation, bimodal fluorescence and MRI imaging coupled with therapy by magnetic hyperthermia. They consist in the coating of a magnetic iron oxide (IO) core (ca. 18 nm diameter to ensure magnetic hyperthermia) by an original large pore stellate mesoporous silica (STMS) shell to produce uniform and monocore magnetic core–shell nanocomposites denoted IO@STMS NPs. To confer fluorescence properties, CdSe/ZnS quantum dots (QDs) NPs were grafted inside the large pores ofthe IO@STMS nanocomposites. To provide biocompatibility and opsonization-resistance, a tightly-bound human serum albumin (HSA) coating is added around the nanocomposite using an original IBAM-based strategy. Cellular toxicity and non-specific cell–nanomaterial interactions allowed to determine a concentration range for safe application of these NPs. Cellular endosomes containing spontaneously-uptaken NPs displayed strong and photostable QD fluorescence signals while magnetic relaxivity measurements confirm their suitability as contrast agent for MRI. HeLa cell-uptaken NPs exposed to a magnetic field of 100 kHz and 357 Gauss (or 28.5 kA m−1) display an outstanding 65% cell death at a very low iron con-centration (1.25 microgram Fe mL−1), challenging current magnetic hyperthermia nanosystems. Furthermore, at the particularly demanding conditions of clinical use with low frequency and amplitude field (100 kHz,117 Gauss or 9.3 kA m−1), magnetic hyperthermia combined with the delivery of a chemotherapeutic drug, doxorubicin, allowed 46% cell death, which neither the drug nor the NPs alone yielded, evidencing thus the synergistic effect of this combined treatment.
Authors : Lino Prados Martin Dr. Adam Creamer Dr. Daniel Richards Prof. Molly Stevens
Affiliations : Imperial College London / Department of Bioengineering
Resume : Antimicrobial resistance to antibiotics is one of the biggest threats for health worldwide. This process occurs naturally but it is accelerated by the incorrect usage of antibacterial treatments. In developing countries this problem is aggravated due to socioeconomic and behavioural factors such as poor drug quality, unhygienic conditions and wrong use of antibiotics. Sensitive diagnostic platforms are usually very resource demanding since they require specialised infrastructures and equipment as well as expert technicians. The aim of this project is the design of a low cost, fast, sensitive, portable and user-friendly device that could be used in both developed and developing countries for the distinction between bacterial and viral infections. To this end, a paper-based analytic tool known as Lateral Flow Immunoassays (LFIAs). Semiconducting Polymer Nanoparticles (SPNs) synthesized from F8BT will emit a fluorescent signal in the presence of two biomarkers highly expressed in bacterial and viral infections, C-reactive protein (CRP) and Procalcitonin (PCT). The use of SNPs is expected to increase sensitivity in two orders of magnitude compared with traditional nanoparticle colorimetric LFIAs. Different targeting approaches will be explored and a smartphone device for the analysis of the strips will be engineered. This project aims to increase sensitivity whilst maintaining low-cost and user-friendly properties of LFIAs in the battle against antibiotic resistance.
Authors : A.Miconi (1,2), S.Rota*(4), O.Monasson (1,2), J.Massera (3),E.Peroni (1,2), M.Boissière (4), E.Pauthe (4)
Affiliations : (1) LCB, University of Cergy –Pontoise, Cergy-Pontoise France (2) PeptLab@UCP, University of Cergy –Pontoise, Cergy-Pontoise France (3) Laboratory of Biomaterials and Tissue Engineering, Faculty of Medicine and Health Technology, Tampere University, Tampere, Finland (4) BioHealth Research Group, ERRMECe, University of Cergy –Pontoise, Cergy-Pontoise France
Resume : Reconstruction of critical bone size defect needs specific material to fill the lost and to promote neo-osteoformation. To be perfectly integrated, and able to favorize bone tissue regeneration at the site of implantation, such substitute must possess combined bio-properties to mediate an efficient dialogue with the surrounding cells. Specific sequences derived from bone sialoprotein and bone morphogenetic protein, - as RDG like and BMP-2 like peptides – as emerged as interesting protagonists to act as proadhesive and osteocompetent partners able to induced an appropriate cell bone response. These peptidic sequences, inspired from natural protein, have attracted much attention, especially due to their high structure stability and their absence of immunogenicity. Commercial bioglass and natural bone purified by BIOBank, appears as interesting materials to serve as primary scaffold to design bone substitute. While the grafts generated from natural bone appear to be the best alternative to repair human bone defects thanks to their natural structure and properties; bioglass exhibited also interesting specificities, due to their capacity to release ions during their decomposition and generate locally apatite like matter. In this work, different peptides has been synthetized, characterized and grafted onto the two materials. Osteocompetent cells contacting responses are analyzed, following various parameters, as the synergistic effect of the co-adsorption of the two peptides.
Authors : Sung Bum Park (1), Seung Hyun Park (2), Md Shahjahan Kabir Chowdury (1), Won Hyung Ryu (2), Yong-il Park (1)
Affiliations : 1. School of Materials Science and Engineering, Kumoh National Institute of Technology, 61 Daehak-ro, Gumi, Gyeongbuk, 39177, South Korea; 2. School of Mechanical Engineering, Yonsei University, 262 Seongsanno, Seodaemun-gu, Seoul 120-749, South Korea.
Resume : Recently, there have been increasing interests in mesoporous silica especially in the field of controlled drug delivery. It is increasingly important to control the degree of bioactivity and rate of biodegradation of such mesoporous silica. In this study, manufactured the microporous(2nm~50nm) silica Nanorods by perfectly filling the TEOS solution using the pumping system in porous anodic alumina oxide(AAO)-the porous scaffold-with the most widely used metal alkoxide, Tetraethylorthosilicate(TEOS-si based), and their drug-delivery performance were investigated.In addition, in order to use in intraocular drug delivery system, paramagnetic mesoporous nanoparticles having SPION (superparamagnetic iron oxide nanoparticle) cores were also fabricated by coating SPION nanoparticles with the same silica precursor sol which was used for the fabrication of the mesoporous silica nanorods.SPIONs can achieve the highest drug targeting efficiency, an external magnetic field locally applied to the target.The porosity and biodegradation kinetics of the fabricated mesoporous nanorods and magnetic nanoparticles were analyzed using SEM, TEM, XRD, FTIR. The performance of the mesoporous silica nanorods as drug delivery carrier and intraocular drug delivery efficiency of the fabricated magnetic nanoparticles were evaluated.
Authors : Sung Bum Park, Md Shahjahan Kabir Chowdury, Yong-il Park
Affiliations : School of Materials Science and Engineering, Kumoh National Institute of Technology, 61 Daehak-ro, Gumi, Gyeongbuk, 39177, South Korea
Resume : Many researchers are studying efficient gene transfer methods to improve cell function and treat diseases.Retrovirus is the most commonly used vector for gene transmission, and if it does not develop an immune response, it will be incorporated into the gene and released in a stable manner. However, the problem is that it is injected only into the cells that are being split, and the diffusion rate is slow indicating a low transfer rate. Therefore, nonviral vectors, including cationic polymers, liposomes, dendrimers, and inorganic materials, attract significant attention in spite of their low efficacy.But because of the low transmission efficiency, there is a continuous effort to modify and refine these gene delivery systems either by adopting different strategies or by installing various functional attributes in the existing systems.Efforts to use polymeric materials are among them. In this study, in order to overcome the low gene transfer efficiency, a problem with retrovirus vectors, the transmission efficiency was improved by removing the reaction force to target cells using a functional silane – based platform.Three types of composite platforms were prepared by coating a complex surface layer on a substrate using precursor solutions synthesized from functional silanes. Triethylorthosilicate (TEOS), polydimethyl siloxane (PDMS), 3-glycidoxypropyltrimethoxysilane (GPTS) and 3-aminopropyltriethoxysilane (APTS) were used for the platform due to their biocompatibility and strong chemical transfection ability.Acid catalyzed sol-gel reaction in the mixed binder system was used for the synthesis varying the ratio of functional silanes.After transfusion of retrovirus vectors, cell number and trypan blue exclusion method were used to analyze cell survival.Using FACscan (Becton Dickinson, Franklin Lakes, NJ, USA), the ratio of eGFP positive cells was measured and compared with the gene transfer efficiency.
Authors : Annabelle Vigué, Dominique Vautier, Youri Arntz, Vincent Ball, Lydie Ploux
Affiliations : INSERM/Unistra, U1121 BioMaterials BioEngineering : Annabelle Vigué; Dominique Vautier; Youri Arntz; Vincent Ball; Lydie Ploux CNRS : Lydie Ploux
Resume : Fighting microbial biofilms on biomaterials is usually addressed by incorporating antimicrobial agents. Nevertheless, as usual in the natural life, intrinsic properties of the material surface can be also a complementary approach. They may drastically reduce the quantity of adhered microorganisms, that are thus to be further treated by antimicrobial agents. Mechanical properties of material surfaces recently emerged as a possible way to impact biofilm formation. However, many questions have not been elucidated so far. We have especially studied whether hydrogel and non-hydrogel soft and stiff films may impact biofilm formation and microbial behavior in a similar or different way. Microbial mobility, adhered quantity and production of organelles such as pili have been specifically investigated. The surface properties, especially mechanical ones, have been thoroughly characterized. The study has been conducted with yeast (Candida albicans) and bacteria species (Escherichia coli). It demonstrated significant differences of microbial behavior and response between films of similar elasticity but different hydration beside impacts of softness versus stiffness properties on amount and mobility of the adhered cells. This confirm relevance of using some soft coatings to prevent biofilm formation on a material but also clarifies the risk to get opposite effects as desired.
Authors : Seoung Ho Lee, Yeon Jin Jang, Boyun Kim
Affiliations : Department of Chemistry, Daegu University, Gyeongsan 38453, Republic of Korea Institute of Basic Sciences, Daegu University, Gyeongsan 38453, Republic of Korea
Resume : Fluorescence-based assays should be feasible in aqueous media for effectively detecting the biological factors. However, numerous sensors have limited signal transductions and low fluorescence quantum yields due to the inherently reduced excited state energy of fluorophores in aqueous solution, which reduces their sensitivity. This necessitates a new smart sensing platform with an amplified fluorescence response for analytes in aqueous solution. Herein, a new building block which self-assembles in aqueous media, giving the hydrophobic π-extended conjugated system at the core and hydrophilic groups at the periphery, was devised for the first time. We demonstrated that the self-assembly of conjugated units in a micelle provides a channel for efficient energy or electron migration and enhances the optical properties, thereby distinguishing this sensing platform from the numerous fluorescence-based tools previously developed for sensitive detection. This new system affords exceedingly sensitive detection of heparin via amplified fluorescence quenching, even under actual bioanalytical conditions.
Authors : V.Yu. Kudrya1, A.P. Naumenko1, V.V. Negrutska2, I.Ya. Dubey2
Affiliations : 1) Taras Shevchenko National University of Kyiv (V.Yu. Kudrya, A.P. Naumenko) 2) Institute of Molecular Biology and Genetics of NASU (V.V. Negrutska, I.Ya. Dubey)
Resume : Telomeres, the end parts of the chromosomes, contain repeated 6-nucleotide sequences (TTAGGG)n able to form so called G-quadruplex structures (G4) based on the stacks of guanine quartets. G4s are important cell regulatory elements whose detection is a challenging task. Their pi-electron systems can be studied by optics spectroscopy . Specific optical properties of telomeric DNA (absorption, autofluorescence, autophosphorescence) and their environment-dependent changes allow using it as auto-luminescent sensing biomaterial. Here we have studied the spectral properties of telomere fragment d[AGGG(TTAGGG)3] (Tel22). Optical absorption (at 300K), fluorescence and phosphorescence (at 78K) of Tel22 samples folded into the G4 structure and unfolded by heating to various temperatures in the range 323-363K were investigated. The band at 295 nm associated with G-quadruplexes was observed in optical absorption of all samples. Only the band associated with G4 was observed in fluorescence spectra of the folded sample and the samples heated below 333K; no G4-associated fluorescence band was observed for samples heated above 343K. Phosphorescence of all samples was the emission of complex formed by A and T bases . These effects are associated with thermal defolding of G4. . V.M. Yashchuk, V.Yu. Kudrya, I.Ya. Dubey, K. I.Kovalyuk, O.I. Batsmanova, V.I. Mel’nik, G.V. Klishevich. Luminescence of telomeric fragments of DNA macromolecule. Mol. Cryst. Liq. Cryst. 2016, V. 639, p. 1-9.
Authors : A.-M. IORDACHE (1,2), S.M. IORDACHE (1,2), R. CRISTESCU (3), E. FAGADAR-COSMA (4), M. ELISA (1), C.I. VASILIU (1), R. STEFAN (1), I.CHILIBON (1), I. STAMATIN (2), C.E.A. GRIGORESCU (1)
Affiliations : (1) National Institute for Research and Development in Optoelectronics-INOE 2000,Optospintronics Department, 409 Atomistilor, 077125, Magurele Romania (2) University of Bucharest, Faculty of Physics, 3Nano-SAE Research Center, 405 Atomistilor, P.O. Box MG-38, 077125, Magurele, Romania (3) National Institute for Lasers, Plasma and Radiation Physics – INFLPR, Lasers Department, Laser - Surface - Plasma Interactions Laboratory, Atomistilor 409, P.O. Box MG-36, Bucharest Magurele RO-077125, Romania (4) Institute of Chemistry Timisoara of Romanian Academy, Department of Organic Chemistry, 24 M. Viteazu Ave, 300223, Timisoara, Romania
Resume : Food freshness can be assessed by monitoring the level of biogenic amines in the food product. Electrochemical sensors that could detect early onset of spoilage (food freshness sensors) can reduce food waste for supermarkets and consumers. In this respect, carbon-based screen printed electrodes (C-SPE) have been functionalized with three different metallo-porphyrins (Co, Mn and Zn) and their response to several common biogenic amines was recorded via cyclic voltammetry. Standard samples of putrescine, cadaverine and histamine and mixtures of these biogenic amines were prepared and electrochemically tested with the fabricated sensors. Real-world samples (commercially available meat samples) were also used for the extraction of mixtures of the biogenic amines and tested in the same conditions as the standard samples. The C-SPE modified with metallo-porphyrins showed increased selectivity towards histamine as well as a decrease in the oxidation potential due to an improved electron transfer between the molecular complex trichloroacetic acid-histamine and the metallo-porphyrins. This interaction was modelled using HyperChem® software and the activation energy for each metallo-porphyrin was estimated. The limit of detection for histamine has been calculated as 0.7 ppm. Keywords: histamine detection, porphyrin functionalization, screen printed electrode, electrochemistry, food freshness. Acknowledgements: Core Program PN-2019-OPTRONICA VI.; Institutional Performance Programme-2019.
Authors : L. Bourdon, N. Attik, K. Gritsch, J.-C. Maurin, A. Brioude, V. Salles
Affiliations : Univ Claude Bernard Lyon 1, Laboratoire des Multimatériaux et Interfaces UMR5615, Villeurbanne, FRANCE
Resume : Nowadays a great attention is payed to regenerative medicine and tissue engineering. This discipline is based on the use of a bioactive 3D biomaterial for helping cells to grow and organize themselves in space like it is the case in organs. A logical trend is to develop biodegradable materials with a controlled porosity in order to exhibit a high surface reactivity with the biological environment. In this study, a 3D printer was combined to an electrohydrodynamic system to form a wet direct-writing technique able to produce a functional scaffold. This resorbable and hybrid nanostructure was realized from a polymer solution containing bioactive molecules and nanoparticles to regenerate both cement and bone from damaged dental tissues. The talk will first present the optimization of the solution properties (with or without) the proteins and the hydroxyapatite (HA) nanoparticles. Then, different designs of scaffolds produced and studied will be detailed before ending with results related to the bioactivity of these hybrid nanostructures. The whole work shows that cells cultured with the scaffold are able to differentiate and proliferate in specific cell types, depending on their contact with proteins (released from the scaffold) or with HA nanoparticles.
Authors : Ilhem. R. KRIBA 1; A. DJEBAILI 1*; Z. SKANDERI 2; A. LAKHZOUM 3
Affiliations : 1 Laboratory of chemistry and environmental chemistry - University of Batna 1- Algeria 2 Institute of Hygiene and Industrial Safety- University of Batna 2- Algeria 3 Faculty of Sciences- Department of Biology - University of Batna 2- Algeria
Resume : Our study aims to gather the maximum amount of information on the changes produced at the structural level (rotation, torsion, conversion) during the Cis-Trans transition (isomerization reaction) on one hand, and to examine the influence of different dopants or substituents on these kinetic parameters on the other hand. The results obtained through the optimization of molecules gave us the different distances and angles according to the methods and bases applied with a C2v symmetry. We were able to determine the total energies, the energy gap ΔE (HOMO-LUMO) of the two conformers Cis and Trans (the HF and DFT at 6-31G and 3-21G** levels) and finally a comprehensive analysis on the topological charges. The analysis of the results show that for the six molecules, the Trans conformer is energetically very stable compared to the Cis one, this stability is confirmed by the obtained values for the total energy ETOTAL. The increase in the stability energy leads to a less important HOMO-LUMO energy gap. The analysis of the optimized geometrical parameters of the six molecules using the AM1 and PM6 methods, are in agreement with the experimental structures characterized by X-ray diffraction. Finally, we were able to determine the reaction profiles of the Cis-Trans isomerization reactions of the polyacetylene in the gas phase, and to calculate the activation energy (Ea), as well as the diagrams of energies E (eV) based on the coordinates of the isomerization reaction of its molecules. All calculations performed in this study are carried out using the Hyperchem software. Keywords: substituted polyacetylene , semi empirical, HF (Ab-initio), DFT (B3LYP)
Authors : Lara Faour, Magali Allain, Sébastien Goeb, Marc Sallé, Catherine Adam, Valérie Bonnin, Tony Breton, Eric Levillain, Christelle Gautier, David Canevet
Affiliations : MOLTECH-Anjou Laboratory University of Angers 2 Bd Lavoisier 49045 Angers France
Resume : Foldamers constitute a class of oligomers that can fold into conformationally ordered architectures. Such compact conformations show structural and functional similarities with biopolymers, mimicking their highly ordered structures and functions. A wide variety of building blocks (e.g. peptides, ureas,…) have been reported to form such structures through weak intramolecular interactions and have displayed remarkable properties in the context of chiral materials, molecular recognition or catalysis, for instance. While important efforts have been devoted to the study of these dynamic structures and their stimuli-controllable conformational changes, pi-functional helical foldamers remain scarce in the literature. On this ground, we have recently depicted the synthesis of photoactive and electro-switchable foldamers endowed with redox units, designed to afford dynamic, and hence, stimuli-responsive architectures.[1-3] This communication will focus on our most recent results, which deal with the redox-controlled hybridization of foldamers into double helices and their anion recognition properties at the solid-liquid interface.  F. Aparicio, L. Faour, M. Allain, D. Canevet, M. Sallé, Chem. Commun., 2017, 53, 12028–12031.  L. Faour, C. Adam, C. Gautier, S. Goeb, M. Allain, E. Levillain, D. Canevet, M. Sallé. Chem. Commun., 2019, 55, 5743–5746.  C. Adam, L. Faour, V. Bonnin, T. Breton, E. Levillain, M. Sallé, C. Gautier, D. Canevet, Chem. Commun., 2019, 55, 8426–8429.
Authors : Song Yan-Yan, Xu Jing-Wen, Xu Jing, Gao Zhi-Da
Affiliations : College of Science, Northeastern University, Shenyang 110004, China
Resume : Electroporation induced by the “point discharge” effect is an effective technique for bacteria inactivation. Rapidly monitoring the electroporation-induced inactivation process is important for screening nanomaterials with high antimicrobial performance. In this study, we develop a facile strategy to in situ monitor the electroporation induced antimicrobial mechanism based on the surface-enhanced Raman scattering (SERS) effect of the Au-nanotip arrays. Owning to the high local-electric field (∼107 V m−1) generated on the Au nanotips, the bacteria are rapidly electroporated and effectively inactivated with ≥99.9% reduction in bacteria colony counts by only applying an external voltage of +0.8 V for 10 s. The related inactivation mechanism is directly verified by the formation of the Prussian blue (PB) nanocrystals by leaking of the uptaken [Fe(CN)6]3− ions from the cleavage area on the cell membrane. These [Fe(CN)6]3− ions react with Fe2+ to form PB nanocrystals onsite as soon as they leak out. The characteristic peak of PB in the cellular Raman-silent region provides a collective monitoring approach for the destruction of microorganisms. The present strategy not only develops a facial method for future use in evaluating electroporation materials, but also paves a rapid way for offering accurate information on some antibacterial and antitumor processes.
Authors : Nasrin Razmi, Mohammad Hasanzadeh, Magnus Willander, Omer Nour
Affiliations : Nasrin Razmi (a); Mohammad Hasanzadeh (b); Magnus Willander (a); Omer Nour (a) (a) Department of Science and Technology, Linkoping University, Norrkoping, Sweden (b) Pharmaceutical Analysis Research Center, Tabriz University of Medical Sciences, Tabriz, Iran
Resume : Robust and accurate detection of pathogenic bacteria in water and food is an important issue. Escherichia coli (E. coli) O157:H7 is an important cause of waterborne and foodborne illness leads to serious symptoms in humans. According the estimation of World Health Organization (WHO), 1.5 million children lose their lives because of diarrheal diseases ever year, which 88% caused by polluted water with E.coli. So in order to avoid the toxic effects of the pathogen, highly sensitive and selective identification should be done. In this study, a new, rapid, sensitive nucleic acid and gold nanoparticle based approach is established for the monitoring of E.coli, using a specific sequence of E.coli thiolated probe immobilized on the surface of gold electrode. Square wave voltammetry is carried out in the solution of toluidine blue for the cDNA hybridization and targeting. To investigate the morphology of the electrode and particle size estimation, Field scanning electron microscope (FE-SEM) is applied. The geno-assay selectively differentiates the complementary sequence from target sequences with one, double and three base mismatch sequences and detects the target DNA with sensitivity and selectivity.
Authors : A. Sobota, J. Gacanin, Y. Zeyn, K. Kaygisiz, C. V. Synatschke, T. Weil
Affiliations : Department for Synthesis of Macromolecules, Max Planck Institute for Polymer Research, Mainz, Germany
Resume : Self-assembling peptides (SAPs) are a promising material for regenerative medicine as they can easily be chemically functionalized and show a multitude of different morphologies that are determined by the peptide sequence. Nanofiber-forming peptides can mimic essential features of the extracellular matrix (ECM) such as its fibrous morphology, mechanical properties, and chemical cues, which makes them interesting as scaffolds for tissue engineering. A gradual distribution of biological signals provides an essential role in guiding tissue orientation and function such as during embryogenesis as well as in cell-migration. Therefore, biomimetic scaffolds capable of imitating biomolecular gradients may be essential for tissue regeneration. Here, we present two approaches of forming a bioactive gradient in order to mimic the function of the ECM. First, by incorporating a photocleavable amino acid into the SAP, we can generate bioactive gradients on 2D substrates. Second, a pH-switchable depsi peptide is grafted to a polypeptide backbone forming a hybrid material. Under physiological conditions, the grafted peptides undergo a molecular rearrangement that induces nanofiber formation and subsequent gelation of the bulk material. By co-assembly of angiogenesis promoting peptides to this hybrid material we can create a gradual distribution of the bioactive peptides within a 3D space.
Authors : Valeria Secchi a, Stefano Franchi b, Monica Dettin c, Annj Zamuner c, Klára Beranová b d, Alina Vladescu e f, Chiara Battocchio a, Valerio Graziani g, Luca Tortora a g, Giovanna Iucci a
Affiliations : a Department of Science, Roma Tre University, Via della Vasca Navale 79, 00146 Rome, Italy; b Elettra-Sincrotrone Trieste S.C.p.A. di interesse nazionale, Strada Statale 14 - km 163,5 in AREA Science Park, 34149 Basovizza, Trieste, Italy; c Department of Chemical Process Engineering, University of Padova, via Marzolo 9, 35131, Padova, Italy; d Institute of Physics, Czech Academy of Sciences, Na Slovance 2, 18221 Prague, Czech Republic; e National Institute of Research and Development for Optoelectronics, 409 Atomistilor St., 077125, Magurele, Romania; f National Research Tomsk Polytechnic University, Lenin Avenue 43, Tomsk 634050, Russia; g Surface Analysis Laboratory INFN Roma Tre, via della Vasca Navale 84, 00146, Rome, Italy;
Resume : We have studied the surface of hydroxyapatite (HAP) coatings enriched with Mg and either Si or Ti deposited by RF magnetron sputtering on Ti6Al4V. This alloy, commonly used as material for orthopedic prostheses, was coated with HAP in order to improve biocompatibility and bioactivity of the material surface. HAP coatings have been furtherly functionalized by adsorption of a self-assembling peptide (SAP) on the HAP surface, with the aim of increasing the material bioactivity. The selected SAP is a self-complementary oligopeptide able to generate extended ordered structures by self-assembling in watery solutions. Samples were prepared by incubation of the HAP coatings in SAP solutions and subsequently analyzed by X-ray Photoelectron Spectroscopy (XPS), Fourier Transform Infra Red (FTIR) and Near Edge X-ray Absorption Fine Structure (NEXAFS) spectroscopies, in order to determine the amount of adsorbed peptide, the peptide stability and the structure of the peptide overlayer on the HAP coatings as a function of the HAP substrate and of the pH of the mother SAP solution. Experimental data yield evidence of successful immobilization of the SAP on the HAP surface; peptide overlayers show ordered structure and molecular orientation. The thickness of the SAP overlayer depends on the composition of the HAP coating.
Authors : Sandra Díaz, Ignacio Insua, Ghibom Bhak, Javier Montenegro
Affiliations : Centro Singular de Investigación en Química Biolóxica e Materiais Moleculares (CIQUS), Departamento de Química Orgánica, Universidade de Santiago de Compostela
Resume : Two-dimensional nanomaterials are emerging as a promising new class of materials due to their unique physical, chemical, optical and electronic properties, that make them suitable for a diverse range of applications. The current challenge is to develop a methodology that allows the orderer and controlled self-assembly of 2D nanomaterials from a single monomer. In this project we report a new approach to achieve two-dimensonal materials with hierarchical organisation using cyclic peptides as supramolecular building blocks. These peptides are able to form giant and dynamic nanosheets by sequencial 1D to 2D self-assembly. The primary amino acid sequence encodes the information for the adoption of the beta sheet motif, that arranged into amphiphilic nanotubes which consequently are self-assembled into 2D supramolecular nanosheets. We investigate the structure-assembly relationships of this innovative strategy and its functionalization.
Authors : Peterhans, L.(1), Nicolaidou, E.*(2), Diamantis, P.(3), Alloa, E.(2), Leclerc, M.(4), Surin, M.,(5) Clément S.(6), Rothlisberger, U.(3), Banerji, N.(1), Hayes, S.C.(2)
Affiliations : (1) Department of Chemistry and Biochemistry, University of Bern, Freiestrasse 3, CH-3012 Bern, Switzerland (2) Department of Chemistry, University of Cyprus, P.O. Box 20537, 1678, Nicosia, Cyprus (3) Laboratory of Computational Chemistry and Biochemistry, Ecole Polytechnique Fédérale de Lausanne (EPFL), CH-1015 Lausanne, Switzerland (4) Department of Chemistry, Université Laval, G1K 7P4 Quebec City, Quebec, Canada (5) Laboratory for Chemistry of Novel Materials, Center for Innovation in Materials and Polymers, University of Mons – UMONS, 20 Place du Parc, B-7000 Mons, Belgium (6) Institut Charles Gerhardt Montpellier, ICGM, UMR 5253 CNRS, Université de Montpellier , Place Eugène Bataillon, F-34095 Montpellier Cedex 05, France * lead presenter
Resume : A highly promising approach to influence and control the photophysical properties of conjugated polymers is directing their molecular conformation by templating. We report here the templating effect of single-stranded DNA oligomers (ssDNAs) on cationic polythiophenes. By means of electrostatic and other non-covalent interactions, the ssDNAs assemble with the polymer, directing its backbone to different conformations depending on the sequence of nucleic bases. We have comprehensively characterized the optical behaviour and structure of the polythiophenes in conformationally distinct complexes and addressed the effect on the ultrafast excited-state relaxation. This, in combination with molecular dynamics simulations, allowed us an unprecedented atomistic-level understanding of the structure-property correlations. We identify that optimal templating is achieved with (ideally 10-20) consecutive cytosine bases, having numerous π-stacking interactions with the thiophene rings and side groups of the polymer. Moreover, we show what specific side chains are necessary to force the polymer backbone into a rigid assembly with ssDNA, with highly ordered chains and unique optical signatures. Our insights are an important step forward in a pioneering approach to structural templating and optoelectronic control of conjugated polymers and organic materials in general.
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Bioactive polymers and nanomaterials : To be attributed
Authors : Garanger, E. (1), Bonduelle, C. (1), Garbay, B. (1), Lecommandoux, S.*(1)
Affiliations : (1) Laboratoire de Chimie des Polymères Organiques, Univ. Bordeaux, CNRS, Bordeaux INP, LCPO, Pessac, France
Resume : We report on the self-assembly of amphiphilic block copolymers into nanomedicines, mainly focusing on polymer vesicles, also referred as polymersomes, and their applications in loading and controlled release of both hydrophilic and hydrophobic molecules and biomolecules. We pay special attention to polysaccharide and polypeptide-based block copolymer vesicles and their development in nanomedicine. In this context, we developed synthetic strategies for the design of glycosylated polypeptides and polysaccharide-polypeptide biohybrids with controlled placement of sugar functionality. We were especially interested in designing amphiphilic copolymers able to self-assemble into well- defined micelles and vesicles that can advantageously be loaded with drugs and present a surface with multivalent presentation of bioactive saccharides or oligosaccharides. The ability of these nanoparticles for different biomedical applications, from drug-delivery to inhibitor, will be presented. We especially evidenced the particular benefit of nanoparticles and their multivalency toward the interaction with biological receptors. In order to get closer to the real structure of glycoproteins, we are moving from synthetic to genetically engineered polypeptides, focusing on post-modification of elastin-like proteins. Finally, our recent advances in using “biomimicry approaches” to design complex, compartmentalized and functional protocells will be proposed. Such a system constitutes a first step towards the challenge of structural cell mimicry and functionality, and may act in the future as an autonomous artificial cell that can sense and cure in situ any biological deregulation.
Authors : Lichon, L.(1), Kotras, C. (2), Arnoux, P.(3), Richeter, S.(2), Frochot, C.(3), Gary-Bobo, M.(1), Surin, M. (4), Clément S.*(2)
Affiliations : (1) Institut des Biomolécules Max Mousseron, UMR 5247 CNRS-UM, 34093 Montpellier Cedex 05, France (2) Institut Charles Gerhardt Montpellier, UMR 5253 CNRS-ENSCM-UM, 34296 Montpellier Cedex 05, France (3) Université de Lorraine, Laboratoire Réactions et Génie des Procédés (LRGP), UMR 7274 CNRS, ENSIC, 1 rue Grandville, 54000 Nancy, France (4) Laboratory for Chemistry of Novel Materials, CIRMAP, University of Mons UMONS, 20 Place du Parc, 7000 Mons, Belgium
Resume : Combined therapies are particularly powerful in the fights against cancer, infectious diseases and metabolic, cardiovascular, autoimmune and neurological disorders. By tackling multiple pathways at once, combined therapies display enhanced efficacy due to additive/ synergistic effects and contribute to preventing the emergence of resistance mechanisms. On top of that, theranostic approaches that merge (combination) therapies with imaging device are of great interest in the quest of personalized medicine. Recently, conjugated polyelectrolytes have emerged as promising materials for theranostic applications due to their excellent properties including high fluorescence, good photostability, low cytotoxicity and generation of reactive oxygen species. In this work, we exploit the versatile function of cationic phosphonium-conjugated polythiophenes to develop multifunctional platforms for combined therapy (siRNA delivery and photodynamic therapy). Besides, their fluorescent properties were used to determine their intracellular location. The effect of molecular weight on their theranostic properties was also evaluated.
Authors : Andreas Reisch, Anne Runser, Marcelina Cardoso Dos Santos, Denis Dujardin, Aline M. Nonat, Loïc J. Charbonnière, Niko Hildebrandt, Andrey Klymchenko
Affiliations : Université de Strasbourg, Laboratoire de Bioimagerie et Pathologies, UMR 7021 CNRS, Strasbourg, France; NanoBioPhotonics (nanofret.com), Institute for Integrative Biology of the Cell (I2BC), Université Paris-Saclay, Université Paris-Sud, CNRS, CEA, Orsay, France; Equipe de Synthèse pour l’analyse (SynPA), IPHC, UMR 7178 CNRS, Université de Strasbourg, ECPM, Strasbourg, France
Resume : Imaging individual biomolecules in living cells can give a wealth of information on how biology functions at the molecular level, but requires bright probes to attain high spatial and temporal resolution. Fluorescent and luminescent nanoparticles (NPs) are excellent candidates to achieve very high brightness, but making them also small and avoiding non-specific interactions remains challenging. Here, we present NP probes combining high brightness, very small size and stealth properties. These probes are based on polymeric NPs loaded with high amounts either of salts of cationic dyes with bulky hydrophobic counterions or of luminescent lanthanide complexes. Through variation of nature and amount of charged groups on the polymers, NPs with sizes down to that of single proteins were obtained. Introduction of zwitterionic groups strongly reduced interactions with proteins while maintaining a brightness 10 times higher than quantum dots. Tracking these NPs at the single NP level within the cytosol showed the importance of combining small size and stealth properties to achieve free particle diffusion and to access all regions of the cytosol.  A. Kusumi et al. Nat. Chem. Biol. 2014, 10, 524.  A. Reisch et al. Nat. Commun. 2014, 5.  M. Cardoso Dos Santos et al. Chem. Mater. 2019, 31, 4034.  A. Reisch et al. Adv. Funct. Mater. 2018, 28, 1805157.  A. Runser et al. ACS Appl. Mater. Interfaces 2020, 12, 117. Supported by ERC (BrightSens) and ANR (Supertrack).
Authors : Alice Balfourier, Nathalie Luciani, Guillaume Wang, Gerald Lelong, Ovidiu Ersen, Abdelali Khelfa,Damien Alloyeau, Florence Gazeau, Florent Carn
Affiliations : Laboratoire Matière et Systèmes Complexes, Université de Paris Laboratoire Matériaux et Phénomènes Quantiques, Université de Paris Institut de Minéralogie, de Physique des Matériaux et Cosmochimie, Sorbonne Université Institut de Physique et Chimie des Matériaux de Strasbourg, Université de Strasbourg
Resume : Biohybrid nanostructures involving metallic elements essential to life have been observed in a variety of organisms. For instance, magnetic assemblies, composed of iron oxides, are produced by organisms ranging from bacteria through higher vertebrates for magnetoreception. The biosynthesis of nanostructures involving non-essential elements is more scarce. Recently, we have been interested in the long-term intracellular fate of gold nanoparticles which are increasingly used in biomedicine. Prior to our study, it was generally admitted that the inertness of gold particles prevents their degradation. Nevertheless, we studied in vitro their fate in primary fibroblasts during 6 months by combining electron microscopy and transcriptomics study. In this way, we revealed an unexpected 2-step process of biotransformation. First, we evidence the intracellular degradation of GNPs with a size-dependent dynamic. This degradation is induced by reactive oxygen species, generated by membrane protein assemblies, that oxidized GNPs. Second, we show that the released ionic gold undergoes a biomineralization process and ends up in well-defined structures consisting of 2.5 nm crystalline particles self-assembled into nanoleaves. Reviewing of the literature dedicated to therapeutic gold salts evidences that similar structures, called aurosomes, have previously been described in vivo in different species. It supports the original idea that ionic and crystallized gold have a common intracellular fate. The morphological features of aurosomes and the transcriptomics results designate metallothioneins as credible candidates to capture gold and form the ubiquitous crystalline cluster.  Balfourier A. et al., PNAS 2020, 117, 103
Authors : D. Mertz1, F. Perton1, D. Bégin2, S. Harlepp3, M. Tasso4, S. Bégin-Colin1
Affiliations : 1 IPCMS-CNRS UMR 7504, Univ. of Strasbourg, 2 ICPEES-CNRS 7515 UMR, Univ. of Strasbourg. 3 INSERM U1110, Univ. of Strasbourg, 4 Univ La Plata, Argentina
Resume : Designing biopolymer-coated nanoparticles has become central in the field of theranostic nanoparticles. Previously, we pioneered an original approach using isobutyramide (IBAM) grafts to assemble non-covalently, a range of biofunctional protein-based hollow capsules for drug delivery or enzymatic catalysis without the need of an additional cross-linking[1-2]. In recent works, we translated this innovative IBAM-protein nanocoating approach for the design of novel hybrid protein coated nanoplatforms made of magnetic or carbon cores covered with a mesoporous silica shell. Hence, protein-coated MS shells were recently deposited at the surface of iron oxide NPs for bimodal fluorescence /MRI imaging and magnetic hyperthermia . The approach was also translated for the design of novel protein coated carbon nanotubes   D. Mertz, P. Tan, Y. Wang, T. K. Goh, A. Blencowe, F. Caruso, Adv. Mater. 2011, 23, 5668-5673.  D. Mertz, J. Cui, Y. Yan, G. Devlin, C. Chaubaroux, A. Dochter, R. Alles, P. Lavalle, J. C. Voegel, A. Blencowe, P. Auffinger, F. Caruso, ACS Nano 2012, 6, 7584-7594.  Perton, F., Tasso, M.; Muñoz, G.A; Ménard, M.; Portiansky, E.; Blanco-Andujar, C.; Fernández van Raap, M.B.; Bégin, D.; Meyer, F.; Bégin-Colin, S; Mertz, D.. Appl. Mater. Today, 2019,16, 301-314.  V. Fiegel, S. Harlepp, S. Begin-Colin, D. Begin, D. Mertz, Chem. Eur. J. 2018, 24, 4662.
Authors : Stephanie Seré, Stefaan Van Gool, Jin Won Seo, Ilse Lenaerts, Jean-Pierre Locquet
Affiliations : Functional Nanosystems, Department of Physics and Astronomy, KU Leuven, Leuven Belgium; Immunologisch Onkologisches Zentrum, Köln, Germany; Surface and Interface Engineered Materials, Department of Materials Engineering, KU Leuven, Leuven, Belgium; Functional Nanosystems, Department of Physics and Astronomy, KU Leuven, Leuven Belgium; Functional Nanosystems, Department of Physics and Astronomy, KU Leuven, Leuven Belgium
Resume : This work provides proof of concept for mesoporous silica nanoparticle (MSNP) based vaccines as cost-effective alternatives for dendritic cell (DC) immunotherapy. Synthesis and surface chemistry of the NPs are optimized for protein conjugation and NPs are characterized for their physicochemical properties and biodegradation. Ovalbumin (OVA) is used as a model protein to load NPs to produce a nanovaccine. The vaccine is tested in vitro on DC cultures to verify NP and vaccine uptake, toxicity, maturation effects and explicitly OVA cross-presentation on MHC class I molecules. The optimized synthesis protocol renders reproducible, agglomeration resistant MSNPs within the required size range and with carboxylic surface functionalization necessary for protein conjugation. They are biodegradable over a time span of one week. This period is adjustable by changing synthesis parameters. UV sterilization of MSNPs does not induce quality loss of the NPs, nor does it have toxic effects on DCs. Treatment with MSNPs increases expression of MHC and costimulatory molecules of DCs, indicating an adjuvant effect of NPs on the adaptive immune system. Nanovaccine uptake and cross-presentation of OVA are observed and the latter is increased when delivered by MSNPs as compared to control conditions. This confirms the large potential of MSNP based vaccines to replace DC-based active specific immunotherapy, offering a more standardized production process and higher efficacy.
Biorecognition and peptide-based systems : Beatriu Escuder, Universitat Jaume I, Castelló
Authors : Ignacio Alfonso
Affiliations : Department of Biological Chemistry, Institute of Advanced Chemistry of Catalonia, IQAC-CSIC
Resume : The study of biological process from the chemical perspective allows a better understanding of Life, as well as the molecular intervention in both normal and pathological situations. However, biomolecules are not isolated entities since their function depend on their mutual interactions, thus playing a role within complex molecular networks and systems. The study of the interaction and communication between molecules represents the core of the so-called Supramolecular Chemistry, thus being fundamental to tackle biological process at the molecular level. In this lecture, I will discuss the close relationship between Supramolecular Chemistry and Chemical Biology, illustrating the idea with key recent examples from our own research group. Thus, selected cases based on the design of specific receptors able to recognize molecules or ions with biological relevance will be presented. Moreover, the dynamic covalent chemistry approach will be also explained with recent examples from our research group. These molecular recognition processes can be traduced into interesting biological activities. Overall, this approach has led to the development of inhibitors of commercial drugs, diagnostic tools for some diseases or cytotoxic molecules against cancer cells. Acknowledgements: Financial Support from the Ministry of Science, Innovation and Universities (RTI2018-096182-B-I00, MCIU/AEI/FEDER, EU) and AGAUR (2017 SGR 208), are gratefully acknowledged. I also express my deepest gratitude to all the co-workers who made possible this research.
Authors : M. Criado-Gonzalez1,2; E. Espinosa-Cano3,4; L. Jierry1; P. Schaaf1,2; L. Rojo3,4; M. R. Aguilar3,4; R. Hernández3; F. Boulmedais1
Affiliations : 1. Université de Strasbourg, CNRS, Institut Charles Sadron, Strasbourg, France 2. Institut National de la Santé et de la Recherche Médicale, INSERM Unité 1121, Strasbourg, France 3. Instituto de Ciencia y Tecnología de Polímeros, CSIC, Madrid, Spain 4. Biomedical Research Networking Center in Biomaterials, Bioengineering and Nanomedicine, CIBER-BBN, Madrid, Spain
Resume : Many vital processes in biological systems involve spatio-temporal control over directed self-assembly, for instance, regulation of active tension in muscles, cell adhesion or chromosome separation during cell division. Peptide and polymer hydrogels are increasing attention as substrates for these applications. Despite their many positive attributes, covalently crosslinked polymer hydrogels lack biological functionality which can be overcome by employing supramolecular peptide hydrogels with a sequenced-defined chemical structure. Here, we present a new approach to develop hybrid hydrogels by combining cationic polymer nanoparticles (NPs) with a phosphorylated peptide, Fmoc-FFpY, which interact electrostatically leading to the formation of supramolecular hydrogels. NPs are based on vinylimidazole and ketoprofene, a non-steroidal anti-inflammatory drug which inhibits the inflammatory marker expression, IL12b, IL23a and TNF-alpha, up to basal values. The encapsulation of different model drugs in the NPs extends the range of applications of these materials for drug delivery. Furthermore, the formation of a supramolecular peptide hydrogel from the surface of the NPs can tune the drug delivery as well as the cell adhesion properties.
Authors : Lydie Ploux, Min Jin, Sophie Hellé, Cosette Betscha, Jean-Marc Strub, Marie-Hélène Metz-Boutigues
Affiliations : INSERM/Unistra, U1121 BioMaterials BioEngineering : Lydie Ploux; Min Jin; Sophie Hellé; Cosette Betscha; Jean-Marc Strub; Marie-Hélène Metz-Boutigues CNRS: Lydie Ploux
Resume : Cateslytin (CTL) is an antimicrobial peptide derived from chromogranin A, protein of the stress response system. Their antimicrobial properties were thoroughly characterized and already exploited in biomaterials. However, effects on biofilms of yeast and bacteria have never been specifically addressed. We have investigated the impact of L and D configurations of CTL on the growth of biofilms formed by Candida albicans, Escherichia coli and Staphylococcus aureus. The study was conducted in different media and two strategies of treatment were tested, consisting of administrating the peptide either just at the beginning of biofilm development i.e. on just adhering pioneer microbial cells or on a biofilm already allowed to develop for 24h. We also considered whether the peptide was modified in contact with the medium or/and microbial metabolites. Significant effects were observed on planktonic and biofilm populations with both treatment strategies on all tested species. However, our results demonstrate that sessile microorganisms and biofilms are sensitive to CTL differently that planktonic populations, with inhibition concentrations from ten to eighty times higher than MICs determined in planktonic cultures, even stimulation of biofilm formation or, in contrast, better efficacy than antibiotics in some conditions. This confirms the high qualities of CTL as an antimicrobial and even anti-biofilm agent and specifies the conditions necessary to benefit of these properties.
Authors : Ximena Zottig, Soultan Al-Halifa, Margaryta Babych, Denis Archambault and Steve Bourgault
Affiliations : Chemistry Department, Université du Québec à Montréal, Montreal, Canada
Resume : Amyloid assemblies, which were historically associated with diseases, have recently been recognized as a biological structure that performs vital physiological functions in host organisms, highlighting their potential as life‐inspired nanoparticles, soft functional materials and matrices for biomedical applications. These organized proteinaceous assemblies combine many characteristics, including high mechanical resistance, biocompatibility, biodegradability, and thermal, chemical and enzymatic stability. In this regard, we are currently developing amyloid-like assemblies as self-adjuvanted nanocarriers for antigen delivery. Our strategy relies on the covalent attachment of an immunological epitope, or immunostimulator molecules, to a self-assembling peptide unit. Upon self-assembly of the chimeric peptide, tailored nanostructures displaying multiple copies of the epitope are obtained. This approach has led to the identification of effective fully synthetic nanovaccines against the influenza A viruses. Moreover, to address the inherent polymorphism and polydispersity associated with the process of amyloid formation, we recently developed strategies to control the final architecture of proteinaceous amyloid assemblies from the peptide sequence. This strategy opens to new directions for the usage of peptide nanoparticles and soft materials in vaccination and nanomedicine.
Authors : Gonen Ashkenasy
Affiliations : Ben-Gurion University of the Negev, Beer Sheva, Israel
Resume : Systems Chemistry aims to develop complex molecular systems showing emergent properties; i.e., properties that go beyond the sum of the characteristics of the molecular constituents of the system. For the last years our group has focused on the development of such systems using peptide-based replication networks. Two of the current challenges related to the design of complex chemical systems will accordingly be discussed: (i) evolving ‘self-synthesizing materials’ through utility of the replicating networks for various applications, such as catalysis and electron transfer,(1,2) and (ii) design and analysis of chemical systems away from equilibrium by the incorporation of nonlinear processes and feedback loops.(3-5) Future directions such as the search for synergism between molecules from different families (Nucleic acid, peptides, sugars etc.) will also be shortly highlighted. 1) D. Ivnitski, M. Amit, O. Silberbush, Y. Atsmon-Raz, J. Nanda, R. Cohen-Luria, Y. Miller, G. Ashkenasy, N. Ashkenasy. Angew. Chem. Int. Ed. 2016. 2) J. Nanda, B. Rubinov, D. Ivnitski, R. Mukherjee, E. Shtelman, Y. Motro,Y. Miller, N. Wagner, R.C. Luria, G. Ashkenasy. Nature Commun. 2017. 3) N. Wagner, S. Alasibi, E. Peacock-Lopez, G. Ashkenasy. J. Phys. Chem. Lett. 2015. 4) R. Mukherjee, R. Cohen-Luria, N. Wagner, G. Ashkenasy. Angew. Chem. Int. Ed. 2015. 5) I. Maity, N. Wagner, R. Mukherjee, D. Dev, E. Peacock-Lopez, R. Cohen-Luria, G. Ashkenasy. Nature Commun. 2019.
Bio-supramolecular approaches to nanomaterials : Sébastien Ulrich, IBMM, CNRS, University of Montpellier
Authors : Mihail Barboiu
Affiliations : Institut Européen des Membranes, Adaptive Supramolecular, Nanosystems Group, University of Montpellier, ENSCM, CNRS, Place Eugène Bataillon, CC 047, F-34095, Montpellier, France
Resume : Extending constitutional dynamic chemistry (CDC) to polymer and material science, constitutional dynamic frameworks presented in this lecture are adaptive systems that respond to internal and external factors. Through the feedback induced self-assembly/reorganization mechanism, the “fittest” architecture can be selected and amplified. Various examples of such dynamic materials with intrinsic adaptive properties at both molecular and supramolecular levels will been discussed with their interesting applications : Enzyme inhibition and activation, DNA transfection, antibacterial activity, etc. References Y. Zhang, M. Barboiu, Constitutional Dynamic Materials. Toward Natural Selection of Function, Chem. Rev. 2016, 116, 809-834. Y. Zhang, Y.H, Li, C.Y. Su, M. Barboiu, Dynameric frameworks with aggregation-induced emission (AIE) for selective detection of ATP, ChemPlusChem, 2018, 83, 506-513. Y. Zhang, E. Petit, M. Barboiu, Multivalent Dendrimers and their Differential Recognition of Short Single-Stranded DNAs of Various Length and Sequence, ChemPlusChem, 2018, 83, 354 –360. Y. Zhang, C.T. Supuran, M. Barboiu, Exponential activation of Carbonic Anhydrase by encapsulation in dynameric host-matrices with chiral discrimination, Chem. Eur. J. 2018, 24, 715-720. L. Marin, D. Ailincai, M. Calin, D. Stan, C. A.Constantinescu, L. Ursu, F. Doroftei, M. Pinteala, B.C. Simionescu, M. Barboiu Dynameric Frameworks for DNA transfection. ACS Biomater. Sci. Eng., 2016, 2, 104-111. L. Clima, D. Peptanariu, M. Pinteala, A. Salic, M. Barboiu, DyNAvectors: dynamic constitutional vectors for adaptive DNA transfection, Chem. Commun., 2015, 51, 17259-17531. L. Marin, B. Simionescu, M. Barboiu, Imino-Chitosan Biodynamers Chem. Commun., 2012, 48, 8778-8780.
Authors : D. Straßburger, M. Urschbach, N. Stergiou, H. Kunz, E. Schmitt, P. Besenius
Affiliations : Department of Chemistry, Johannes Gutenberg University Mainz; Institute of Immunology, University Medical Center Mainz
Resume : Peptide secondary structures can be harnessed to design monomers capable of self-assembling into nano-scaled supramolecular structures in aqueous media.[1,2] Decorating the surface with immunogenic molecular patterns results in pathogen-mimicking entities and potential vaccine candidates. In the context of antitumor vaccines, the challenge is to overcome self-tolerance mechanisms to enforce an immune response against endogenous, tumor-associated glycopeptide motifs. To this end, a co-stimulation of B cells with Th cells is mandatory, which we aim to achieve using a co-presentation of different epitopes and immunostimulating agents at the surface of multicomponent supramolecular polymers. Mucin 1 (MUC1) is well-known for undergoing alterations in O-glycosylation during tumorigenesis, and is thus an excellent tumor-associated target structure for immunotherapy. In this contribution I discuss the use a fully synthetic glycopeptide from the MUC1 tandem repeat sequence, which consists of 22 amino acids bearing the Tn and 2,3-Sialyl T tumor associated antigens. As T cell epitope we chose a small fragment from highly immunogenic tetanus toxin (p30). Additionally, an imidazoquinoline as potent TLR7/8 agonist, was synthesized. These epitopes were conjugated to supramolecular monomers and mixed in aqueous solution to yield a polymeric vaccine formulation. The vaccines were administered intraperitoneally to C57BL/6 mice and the antisera were collected after three further boosts. High antibody titers of the IgG type were observed in all mice. Furthermore, FACS analysis confirmed the high binding affinity of the generated antibodies to T47D tumor cells. These results support the potential of this modular supramolecular platform approach for the development of antitumor vaccines. References:  Angew. Chem. Int. Ed. 2018, 57, 11349;  Chem. Rev. 2016, 116, 2414;  ChemBioChem 2018, 19, 912;  ChemBioChem 2018, 19, 1142;  J. Med. Chem. 2010, 53, 4450.
Authors : Sangeun Lee, Cansu Kaya, Hongje Jang, Marcus Koch, Brigitta Loretz, Eric Buhler, Claus-Michael Lehr*, Anna Katharina Herta Hirsch*
Affiliations : SL, CK, AKHH; Department for Drug Design and Optimization, Helmholtz Institute of Pharmaceutical Research Saarland (HIPS) ? Helmholtz Centre for Infection Research (HZI), Campus E 8.1, 66123 Saarbrücken, Germany SL, BL, CML; Department for Drug Delivery, HIPS ? HZI, Campus E8.1, 66123 Saarbrücken, Germany CK, CML, AKHH; Department of Pharmacy, Saarland University, 66123, Saarbrücken, Germany HJ; Third Institute of Physics, Georg-August-Universität, Friedrich-Hund-Platz 1, 37077 Göttingen, Germany MK; INM-Leibniz-Institute for New Materials, Campus D2.2, Saarland University, 66123 Saarbrücken, Germany EB; Laboratoire Matière et Systèmes Complexes (MSC), UMR 7057, University of Paris (Paris Diderot), Bâtiment Condorcet, 75205 Paris Cedex 13, France
Resume : We investigated the pH-dependent physicochemical properties of a biodynamer formed by acylhydrazone/imine bonds between monomer A (hexaethylene glycol conjugated carbazole dicarboxaldehydes) and monomer B (lysine hydrazides). Our previous studies have shown that the biodynamer has the following properties, 1) dynamic polymerization in a mildly acidic aqueous medium, 2) monomer exchanges at low pH, and 3) formation of 10 nm nanorods after the polymerization.1 In this research, we have further examined the morphology changes of the biodynamer in its nanorod formation and pH-dependent property changes. As a result, we observed morphological changes of the biodynamer (from 250 nm spherical micelles to 10 nm nanorods) by the polymerization using light scatterings, transmission electron microscopy, and small-angle neutron scattering. Besides, we have examined fluorescence emission shifts, from emission peak top= 470 nm to 535 nm upon increasing pH from 3 to 13, due to a protonation on the carbazoles in the polymer backbone. In addition to the fluorescence shifts, the pH-dependent protonation on the backbone also affects the size of the nanorods. While the pH increases from 3 to 13, the size of the nanorods decreases by up to 37%. We expect that these findings, pH-dependent emission shifts, and size changes contribute to broadening the application of the molecular biodynamers as stimuli-responsive materials and biosensors. 1. Liu Y,et.al., Adv. Funct. Mater. 2016;26(34):6297-6305
Authors : Rioboo, A.(1)*, Gallego, I.(1), Reina, J. J.(1), Díaz, B.(2, 3), Canales, Á.(3), Cañada, F. J.(2), Guerra-Varela, J.(4), Sánchez, L.(4), Montenegro, J.(1) *Presenting author. Email: email@example.com
Affiliations : 1) Centro Singular de Investigación en Química Biolóxica e Materiais Moleculares (CIQUS), Departamento de Química Orgánica, Universidade de Santiago de Compostela, Campus Vida, 15782, Santiago de Compostela, Spain. (2) Centro de Investigaciones Biológicas (CIB) del CSIC, C/Ramiro de Maetzu 9, 28040, Madrid, Spain. (3) Departamento de Biología Estructural y Química, Fac. Ciencias Químicas Univ. Complutense de Madrid, Avd/ Complutense s/n, 28040, Madrid, Spain. (4) Departamento de Zooloxía, Xenética e Antropoloxía Física. Facultade de Veterinaria, Universidade de Santiago de Compostela, 27002, Lugo, Spain.
Resume : Cell membrane protects the cell from the external environment and regulates the exchange and uptake of different components. However, this rigorous control hinders the traffic of bioactive molecules. For this reason, to cross the cell membrane is a great challenge for the development of new therapeutic agents or diagnosis methods. One of the more promising new generation delivery agents are the cell penetrating peptides, which can cross the membrane barrier but still have some lack of selectivity. To try to improve them, we purpose the synthesis of penetrating peptides functionalized with glycan residues in order to affect their internalization efficiency and cell viability. For that, we have developed a new convergent strategy for the synthesis of these new glycopeptides hybrids by an oxime bond connection. Herein, we present the results obtained for the uptake efficiency and intracellular distribution of these glycopeptides in different cell lines by flow cytometry, confocal microscopy and in zebrafish animal models. The results reported here highlight the potential of the glycosylation of penetrating peptides to modulate their activity.  Hartman, N. C.; Groves, J. T. Curr. Opin. Cell Biol. 2011, 23, 370–376.  Stewart, K. M.; Horton, K. L.; Kelley, S. O. Org. Biomol. Chem. 2008, 6, 2242–2255.  Gallego, I.; Rioboo, A.; Reina, J. J; Díaz, B.; Canales, A.; Cañada, F. J.; Guerra-Varela, J.; Sánchez, L; Montenegro, J. ChemBioChem 2019, 20 (11), 1400-1409.
Authors : Emilie Moulin, Nicolas Giuseppone
Affiliations : Institut Charles Sadron – UPR 22, University of Strasbourg, SAMS Research Group, 23 Rue du Loess, BP84047, 67034 Strasbourg Cedex 2, France
Resume : Triarylamine molecules have been extensively used over the past 60 years for their conducting and optical properties. However, the supramolecular polymerization and self-assembling properties of these molecules remained unknown until very recently. In 2010, for the first time, our group reported that chemically designed triarylamine molecules incorporating amide functions at their periphery can precisely pack into columnar supramolecular polymers with a collinear arrangement of the central nitrogen centers. We subsequently demonstrated the versatility of this triarylamine scaffold in terms of self-assembling properties leading to various soft hierarchical structures such as nanofibers, nanoribbons, and nanospheres, as well as to crystalline supramolecular frameworks. In addition, we further demonstrated the intriguing electronic, magnetic, and optical properties of these supramolecular polymers, as well as their ability to be incorporated in nano- or micrometric devices by original bottom-up approaches (Acc. Chem. Res. 2019, 52, 975-983). We will show that the triarylamine core can be decorated with various biomolecules (peptide, nucleobases), which provide a second level of organization in the resulting self-assembled structures. We will also highlight that these supramolecular polymers can find applications in bioelectronics and as biomimetic materials.
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|08:45||PLENARY SESSION 2|
Protein-based Materials : Elisabeth Garanger, LCPO, University of Bordeaux
Authors : Francesca Guagnini; Kiefer O. Ramberg; Sylvain Engilberge; Peter B. Crowley
Affiliations : School of Chemistry, NUI Galway, Galway, Ireland
Resume : Controlled protein assembly remains a major obstacle to the development of nanoscale devices and biomaterials. We and others have shown that macrocycles are useful building blocks to direct protein assembly.(1-6) For example, the “rigid doughnut” cucurbituril mediates sheet- and cage-like assemblies of the model lectin RSL, via complexation of dimethylated lysines.(4,6) X-ray data reveal cucurbituril clusters in the crystal structures. New strategies that combine cucurbituril clusters with other features such as metal binding sites will be presented. References 1) van Dun S, Ottmann C, Milroy LG, Brunsveld L. J. Am. Chem. Soc. 2017, 139, 13960. 2) Kuan SL. Bergamini FRG, Weil T. Chem. Soc. Rev. 2018, 47, 9069. 3) Rennie ML, Fox GC, Pérez J, Crowley PB. Angew. Chem. Int. Ed. 2018, 57, 13764. 4) Guagnini F, Antonik PM, Rennie ML, O'Byrne P, Khan AR, Pinalli R, Dalcanale E, Crowley PB. Angew. Chem. Int. Ed. 2018, 57, 7126. 5) Engilberge S, Rennie ML, Dumont E, Crowley PB. ACS Nano 2019, 13, 10343. 6) Guagnini F, Engilberge S, Ramberg KO, Pérez J, Crowley PB. Chem. Commun. 2020, 56, 360.
Authors : Mauri A. Kostiainen
Affiliations : Department of Bioproducts and Biosystems, Aalto University, Finland
Resume : Cyclophanes are macrocyclic supramolecular hosts famous for their ability to bind atomic or molecular guests via non-covalent interactions within their well-defined cavities. In a similar way, porous crystalline networks, such as metal-organic frameworks, can create micro-environments that enable controlled guest binding in the solid state. Both types of materials often consist of synthetic components and they have been developed within separate research fields. Moreover, the use of biomolecules as their structural units has emerged only recently. Here, we have synthesized a library of organic cyclophanes and study their electrostatic self-assembly with biological metal-binding protein cages (ferritins) into ordered structures. We show that cationic pillararenes and ferritin cages form highly porous biohybrid co-crystals, which achieve simultaneous and selective binding of organic and inorganic guests. Small organic molecules can be bound by the pillararene hosts, while inorganic ions can be simultaneously bound inside the ferritin cage. Our cyclophane-protein cage frameworks bridge the gap between molecular frameworks and colloidal nanoparticle crystals, and combine the versatility of synthetic supramolecular hosts with the highly selective recognition properties of biomolecules. Such host-guest materials are interesting for porous material applications, including water remediation and heterogeneous catalysis.[3,4]  Rennie, M. L.; Doolan, A. M.; Raston, C. L.; Crowley, P. B. Angew. Chem. Int. Ed., 2017, 56, 5517-5521.  Beyeh, N. K.; Nonappa; Liljeström, V.; Mikkilä, J.; Korpi, A.; Ikkala, O.; Ras, R. H. A.; Kostiainen, M. A. ACS Nano, 2018, 12, 8029-8036.  Mikkilä, J.; Anaya-Plaza, E.; Liljeström, V.; Castón, J.; Torres, T.; de la Escosura, A.; Kostiainen, M. A. ACS Nano, 2016, 10, 1565-1571.  Anaya-Plaza, E.; Aljarilla, A.; Beaune, G.; Nonappa, Timonen, J. V. I.; de la Escosura, A.; Torres, T.; Kostiainen, M. A. Advanced Materials, 2019, 31, 1902582.
Authors : Elena Atrián-Blasco(1), Marcelo Der Torrossian Torres(2),César de la Fuente(2), Sébastian Blanchard(3), Christelle Hureau(4), Scott G. Mitchell(1)
Affiliations : (1)Instituto de Ciencia de Materiales de Aragón, Consejo Superior de Investigaciones Científicas, Spain; (2)Department of Bioengineering, University of Pennsylvania, United States; (3) Sorbonne Universi´te, CNRS, Institut Parisien de Chimie Moléculaire, France; (4) Laboratoire de Chimie de Coordination-CNRS, Université de Toulouse, France
Resume : Polyoxometalates are oxoclusters of early transition metals which have found applications in various fields from catalysis to material science or biomedicine. Among the vastly proposed biochemical applications of polyoxometalates (POMs), their interactions with peptides and proteins as well as their antibacterial activity have been gaining interest in the few years. Moreover, POMs have been described as inhibitors of the Amyloid-β peptide aggregation, a peptide involved in the development of Alzheimer’s disease (AD). Metal-mediated Amyloid-β peptide aggregation and ROS production, are well known to play an important role in the development of Alzheimer’s disease. For this reason, one of the proposed therapies is based on the chelation of implicated metal ions such as Cu, Zn and Fe. Such chelators could remove the metal ions from the amyloid aggregates and recover the normal metal homeostasis. We have studied the interaction of different Keggin-structure POMs with Cu, and how, through their interaction, they can modulate the metal-mediated aggregation of amyloid- β peptides. We will also present preliminary results on new hybrid materials based on the functionalization of POMs with antimicrobial peptides, which possess dual-functional bactericidal and anti-biofilm properties, by tackling both the amyloidogenic proteins in biofilm and the bacteria.
Authors : Ramberg, K.O.*(1), Skorek, T.(1), Engilberge, S. (1) & Crowley, P.B.(1).
Affiliations : (1) National University of Ireland Galway, Ireland * lead presenter
Resume : Precise, defined protein aggregates (as exemplified by crystals) have potential applications in functional materials. Consequently, engineered protein assembly is a rapidly growing field. Great progress has been achieved by harnessing naturally occurring interaction modes, such as oligomer interfaces, coiled coils and bridging metal ions. Alternative strategies with commercially-available supramolecular receptors such as calixarenes, curcurbiturils and cyclodextrins, are gaining momentum. [1-5] Calix[n]arenes are particularly interesting supramolecular scaffolds due to their ability to adapt to protein surfaces. Complexation of the highly flexible, anionic sulfonatocalixarene (sclx8) with cationic protein targets has yielded remarkable protein nanoarchitectures.[3-5] Here, we describe complexation of sclx8 with a “neutral” protein target. Solid state assembly was dictated by the binding of sclx8 to a specific patch on the protein surface. Remarkably, this assembly occurred over a broad pH range (4.6 – 9.5). A markedly different assembly was observed at lower pH (≤ 4.0), hinting at a potential ‘pH switch’. References 1. Rennie et al. Angew. Chem. Int. Ed. 2017, 56, 5517-5521. 2. Guagnini et al. Chem. Comm. 2020, 56, 360-363. 3. Alex et al. IUCrJ 2019, 6, 238-247. 4. Rennie et al. Angew. Chem. Int. Ed. 2018, 130, 13960-13965. 5. Engilberge et al. ACS Nano 2019, 13, 10343-10350.
Authors : Teng Ma, Xingyao Feng, Ayumi Hirano-Iwata
Affiliations : WPI-Advanced Institute for Materials Research (WPI-AIMR), Tohoku University
Resume : Bilayer lipid membranes (BLMs) are the main component of the membranes. In the past decades, BLM has been intensively investigated as a biological model to unveil the mechanism of mass transport through cell membranes. Recently, their unique properties, such as ultrathin thickness, ultrahigh resistance, and self-assemble ability have caught the attention of researchers in the field of nanodevices. Utilizing these extraordinary properties of BLMs, it is possible to fabricate nanodevices with high performance at a low cost. In the presentation, we will demonstrate how to form functional bio-hybrid nanomembranes by doping the BLMs with organic molecules. Firstly, when free-standing BLMs were doped with PCBM molecules, a photo-induced change in transmembrane conductance was observed . In order to further improve the performance of BLM-based devices, we introduced a “gate bias” to the free-standing BLM system . We were able to modulate the transmembrane current by changing the lateral bias. To further expand the range of application of BLMs to solid-state devices, we demonstrated that an air-stable hybrid membrane with a large area can be obtained by simply doping the BLMs with phthalocyanine molecules. These results demonstrated that hybrid BLM is a powerful and feasible platform for realizing sensing devices.  J. Electroanal. Chem., 832, 55 (2019).  ACS Omega, 4, 18299 (2019).  J. Phys. Chem. B, 123, 6515 (2019).
DNA recognition and DNA-templated assembly : To be attributed
Authors : Florent Di Méo, Nanna Holmgaard List, Patrick Norman, Mathieu Linares
Affiliations : Florent Di Méo: - Université of Limoges, INSERM, UMR 1248 IPPRITT, France ; Nanna Holmgaard List: - Department of Chemistry and the PULSE Institute, Stanford University, Stanford, California - SLAC National Accelerator Laboratory, Menlo Park, California; Patrick Norman: - Department of Theoretical Chemistry and Biology, KTH Royal Institute of Technology, Stockholm, Sweden; Mathieu Linares: - Department of Theoretical Chemistry and Biology, KTH Royal Institute of Technology, Stockholm, Sweden - Laboratory of Organic Electronics, ITN, Linköping University, Sweden - Scientific Visualization Group, ITN, Linköping University, Sweden - Swedish e-Science Research Center (SeRC), Linköping University, Sweden
Resume : Over the past four decades, electronic circular dichroism (ECD) has been widely used to empirically investigate bio-molecular systems due to the fact that it is extremely sensitive to conformational changes in both solids and liquids. For instance, it is used to characterize the secondary structures of proteins,(1) to follow the induction of chirality of an achiral probe in a chiral environment,(2) and to elucidate the helical structure of DNA and its variations.(3) In addition to empirical investigations, theory has been used to rationalize experimental results with the intention of reaching a predictive power. For small systems, the simulation of ECD responses is a task well suited for standard time-dependent density functional theory (TD-DFT).(4) However, the size of the systems remains a bottleneck despite the progress of supercomputers, and theoreticians have had to develop original approaches to be able to address larger systems with reasonable accuracy. We will illustrate our approach combining MD simulations and QM/MM calculations on three case studies: - The calculation of the ECD spectra of perfect double-helical conformation of DNA of various sequences and show how the ECD signal can be affected when the DNA sequence is wrapped around the histone core.(5) This was achieved by using a base pair approach where the total ECD signal was estimated as the sum of the base pair dimers contribution.(2) - The case of DAPI (4’,6-diamidino-2-phenylindole), a popular DNA stain due to the fluorescence enhancement upon minor-groove binding in AT-rich regions of double stranded DNA. Its binding mode also results in a strong induced circular dichroism (ICD). We have provided an explanation of the origin of this ICD based on a combination of exciton coupling and QM/MM simulations and showed that the ICD signal was a complex interplay between exciton coupling, chiral imprint, and charge transfer.(6) We will show how all these contributions can also be considered simultaneously within a single QM calculation. - The human telomeric sequences, made of repeats of the d(TTAGGG) fragment is known to form G-quadruplexes at the ends of chromosomes and constitute a relevant biomolecular target in cancer research. In the last two decades, metal complexes such as ruthenium polyazaaromatic complexes have been used as DNA binders. In particular, a few are attractive as “light switches” because of their strong luminescence enhancement upon DNA binding.(7) The ECD response of this system is a complex overlap of contribution of the G-quadruplex, ICD of the ligands upon binding, and charge transfer. We will demonstrate how our approach allow a simultaneous calculation of the ECD signal contributions stemming from the G-quadruplex as well as from the ICD of the complex attached to it. --- (1) N. J. Greenfield, Nat Protoc., 2006, 1, 2876 (2) Di Meo, F. et al. J. Phys Chem. Lett., 2015, 6, 355 (3) Kypr, J. et al., Nucleic Acids Res. 2009, 37, 1713 (4) Autschbach, J. et al. Top. Curr. Chem. 2011, 298, 1; Crawford, D. C. et al. Theor. Chem. Acc. 2006, 115, 227 (5) Norman, P.; et al. Phys. Chem. Chem. Phys., 2015, 17, 21866 (6) Holmgaard List, N. et al. JACS, 2017, 139, 14947 (7) Rubio-Magnieto, J. et al. Chem. Eur. J. 2018, 24, 15577
Authors : Fossépré M.* (1), Tuvi-Arad I. (2), Beljonne D. (1), Clément S. (3) & Surin M. (1).
Affiliations : (1) Laboratory for Chemistry of Novel Materials, Centre of Innovation and Research in Materials and Polymers (CIRMAP), University of Mons (UMONS), Mons, Belgium; (2) Department of Natural Sciences, The Open University of Israel, Raanana, Israel; (3) Institut Charles Gerhardt Montpellier ICGM, UMR 5253, CNRS,Université de Montpellier, Montpellier, France.
Resume : Water-soluble -conjugated polymers are increasingly considered in supramolecular approaches for DNA biosensing. However, the conformational rearrangement and supramolecular organization upon interaction with DNA remains overlooked, which limits a rational design of such detection tools. To understand the binding between DNA and cationic polythiophene (CPT), which are utilized in DNA detection experiments, we performed molecular modeling simulations of their supramolecular assembly. By comparing several simulations, we show a multiplicity of binding modes. The simulated Circular Dichroism (CD) spectra show that the origin of the induced CD signals are arising from short helical segments of neighbouring thiophene units in syn (cisoid conformations). At the macromolecular scale, we inspected the particular shapes adopted by the CPT around the DNA through estimates of the chirality index that quantifies the structural changes of CPT upon DNA complexation. Altogether, Molecular Dynamics (MD) simulations, model Hamiltonian calculations of the CD spectra, and the chirality indices provide complimentary insights into the origin of induced chirality from the DNA to the polymer at various scales, which highlights the emergence of hierarchical levels of chirality/symmetry in DNA/CPT complexes.
Authors : Alex Manicardi, Enrico Cadoni, Annemieke Madder
Affiliations : Department of Organic and Macromolecular Chemistry, Organic and Biomimetic Chemistry Research group (OBCR), Faculty of Sciences - Ghent University
Resume : Oligonucleotide templated reactions, both exploiting the formation of a covalent linkage (templated ligation) or inducing the modification of one of the two strands, are becoming widely employed in sensing strategies. The main problems related to these reactions are connected to hydrolysis or degradation of the reactive moieties, thus requiring special precautions to maintain the integrity of the system. The exploitation of external stimuli for the activation of a pro-reactive unit can be a valid alternative to extend the shelf-life of probes and devices, allowing spatiotemporal control over system reactivity and avoiding collateral reactions. We here report a novel peptide nucleic acid (PNA) based D(R)NA-templated ligation exploiting a stable pro-reactive furan ring which can be oxidized to a reactive keto-enal, via light induced singlet oxygen production, and chemoselectively reacts with suitable nucleophiles. This white light triggered templated PNA-PNA ligation was first optimized in solution so that the only external action required was light irradiation. It was then transferred to surface for the realization of a 96-well plate biosensor for selective detection of 22mer D(R)NA, in an ELISA-like platform. Application of this methodology on the glass surface of microarray slides was also demonstrated, showing the feasibility of the methodology and the possibility to move toward the miniaturization of the system for high-throughput label-free multiplex analysis applications.
Authors : David González Rodríguez, Fátima Aparicio, Raquel Chamorro, Paula Chamorro, Sonia Romero-Pérez, Isabel López-Martín, Sara Sierra
Affiliations : Nanostructured Molecular Systems and Materials Group, Departamento de Química Orgánica, Universidad Autónoma de Madrid, 28049 Madrid, Spain.
Resume : The use of well-defined templates to control the stack length and the relative positioning of π-conjugated molecules in columnar architectures is a straightforward, though quite challenging task that cannot rely solely on π-π stacking or solvophobic effects, but that also requires directional (i.e. H-bonding) interactions between complementary patterns to guide molecular stacking. In terms of synthetic versatility and simplicity, DNA oligomers, which are commercially available in any defined length and sequence of nucleobases, are ideal candidates as templates for linear helical assemblies. DNA-templated noncovalent synthesis is a concept that has been demonstrated by several authors, but the true versatility and main attribute of this templated approach, the precise control of stack length and sequence, has never been demonstrated.
Authors : K. Cervantes-Salguero1, M. Freeley1, H. L. Worthy2, D. D. Jones2, J. L. Chávez3, M. Palma1
Affiliations : 1 School of Biological and Chemical Sciences and Materials Research Institute, Queen Mary University of London, London, United Kingdom 2 Division of Molecular Biosciences, School of Biosciences, Main Building, Cardiff University, Cardiff, Wales, United Kingdom 3 Air Force Research Laboratory, 711th Human Performance Wing, Wright Patterson Air Force Base, Dayton, Ohio, United States
Resume : Nanoscale engineering of biomolecular arrays on solid supports enables investigation of biological processes at the single-molecule level. Techniques including lithography, PDMS imprint, polymer brushes and DNA origami, have opened new routes for biosensing and fundamental investigations of biomolecular interactions. The precise placement of proteins arranged within a nanoarray can be used to create biomimetic surfaces that are desirable for investigating related biological properties. DNA origami is a very promising bottom-up strategy for creating nanostructures programmed with nanoscale control. Here we present a strategy for the organisation of proteins on arrays with single-molecule control via selective functionalisation and passivation. In this strategy, DNA origamis are decorated with fluorescent proteins in solution via DNA hybridisation. In addition, nanoarrays on metal-coated glass were patterned with nanometric resolution using focused-ion beam lithography. Subsequently, biotin-functionalised origamis were immobilised in the aforementioned nanoarrays via biotin-streptavidin interactions. This single-molecule platform we fabricated will enable us to study biomolecular events with single-molecule resolution and multivalent control.
Biomaterials for delivery : To be attributed
Authors : Javier Montenegro
Affiliations : CIQUS, University of Santiago de Compostela (Spain)
Resume : Our research group is interested in the application of supramolecular chemistry to understand and manipulate biology.[1,2] Our work philosophy is based in the importance of weak and non-covalent forces to control the shape and the topology of biomolecules, which are governed by the principles described by supramolecular chemistry. This topology is ultimately responsible of properties and function of biomolecules and organelles and thus we believe that by modulating the shape we can control and improve functional behaviour. With focus in supramolecular interactions for artificial membranes and tubular composites, we investigate the construction of synthetic systems for controlling and emulating biology and life-like soft systems.[3-5] Acknowledgements: AEI: [CTQ2014-59646-R, SAF2017-89890-R], the Xunta de Galicia (ED431C 2017/25, 2016-AD031 and 2016–2019, ED431G/09) and the ERDF). Ramón y Cajal (RYC-2013-13784), an ERC Starting Investigator Grant (DYNAP- 677786) and a YIG from the Human Frontier Science Research Program (RGY0066/2017). References  General review: A. Fuertes, J. Marisa, J. R. Granja, J. Montenegro, Chem. Commun. 2017, 53, 7861–7871.  Delivery review: I. Lostalé-Seijo, J. Montenegro, Nat. Rev. Chem. 2018, 2, 258–277.  Membrane transport and delivery applications: a) J. M. Priegue, D. N. Crisan, J. Martínez-Costas, J. R. Granja, F. Fernandez-Trillo, J. Montenegro, Angew. Chem. Int. Ed. 2016, 55, 7492–7495. b) I. Lostalé-Seijo, I. Louzao, M. Juanes, J. Montenegro, Chem. Sci. 2017, 8, 7923–7931.  Synthetic supramolecular biocomposites: a) I. Insua, J. Montenegro, J. Am. Chem. Soc. 2020, 142, 1, 300-307, b) A. Méndez-Ardoy, J. R. Granja, J. Montenegro, Nanoscale Horizons, 2018, 3, 391-396.
Authors : Sebastien Deshayes, Karidia Konate, Eric Vivès, Prisca Boisguerin
Affiliations : Centre de Recherche de Biologie cellulaire de Montpellier (CRBM), UMR 5237 CNRS, Montpellier, France
Resume : Even if chemotherapy constitutes the majority of treatments for most cancers, they are often limited by their lack of selectivity, targeting issues, rapid clearance and important side effects. In this context, new therapeutic agents specifically targeting molecular abnormalities of certain cancers have been developed [Minko T, 2013]. The identification of small interfering RNAs (siRNAs) [Burnett JC, 2012] enabled the development of a new therapeutic approach. Although these molecules have great potential, their use remains limited by their low metabolic stability, selectivity and their inability to cross biological barriers. Several siRNA delivery systems have been constructed using cell-penetrating peptides (CPPs) since the CPPs have shown a high potential for oligonucleotide delivery into the cells, especially by forming nanoparticles [Konate K, 2016, Vaissière A, 2017, Aldrian G, 2017]. Recently, we have developed a new family of short (15mer or 16mer) tryptophan-(W) and arginine-(R) rich Amphipathic Peptides (WRAP) able to form stable nanoparticles and to enroll siRNA molecules into cells [Konate K, 2019]. The lead peptides, WRAP1 and WRAP5, form deﬁned nanoparticles smaller than 100 nm as characterized by biophysical methods. Furthermore, they have several beneﬁts as oligonucleotide delivery tools such as the rapid encapsulation of the siRNA, the eﬃcient siRNA delivery in several cell types, and the high gene silencing activity, even in the presence of serum. In addition, we demonstrate that the efficiency of WRAP:siRNA nanoparticles is mainly based on the use of multiple internalization mechanisms including direct translocation as well as endocytosis-dependent pathways. In conclusion, we have designed a new family of CPPs speciﬁcally dedicated for siRNA delivery through nanoparticle formation. Our results indicate that the WRAP family has signiﬁcant potential for the safe, eﬃcient, and rapid delivery of siRNA for diverse applications.
Authors : Gabriela Romero, Rohini Gutnur, Tina Rodgers
Affiliations : The University of Texas at San Antonio Department of Biomedical Engineering and Chemical Engineering
Resume : Despite the growing evidence supporting the use of biocompatible materials as vehicles to deliver therapeutics, their clinical application is often limited by challenging biological environments such as accessing the brain due to the blood-brain barrier (BBB). The BBB hinders most molecules from entering the central nervous system from the blood stream, limiting the delivery of drugs and materials into the brain for the treatment of brain malfunctions. Soft matter engineering offers a powerful approach to the design and synthesis of effective systems to manipulate cellular signals and behaviors. Here, we investigate soft biomedical materials as minimally-invasive and transgene-free alternatives for the treatment of brain disorders, including safer strategies to bypass the blood brain barrier, and the development of new technologies for wireless neuromodulation and gene-editing therapies. Nanoscale heating effects of magnetic nanoparticles under alternating magnetic fields has been used to control the thermodynamic transition of thermo-sensitive polymer brushes to release neuromodulatory compounds. This magneto-thermal system allow us to modulate on-demand neural activity, which is critical for the treatment of neurological disorders such as Parkinson disease. In the other hand, pH sensitive biocompatible block co-polymers are being used to fabricate artificial viruses. Gene-editing systems have become an important tool in biological engineering and genome editing, providing programmable platforms for precision gene targeting. These tools have immense promise as therapeutics that could potentially correct disease-causing mutations. Most of the gene-editing approaches use viral vectors to deliver the therapeutic tools, limiting clinical applications due to safety concerns. We investigate stimuli-responsive soft biomedical platforms that enable a synthetic, non-invasive strategy for the delivery of gene-editing tools. Our non-viral delivery approach focuses on mimicking biological organisms’ functionalities and engineering them into a synthetic polymeric carrier. Specifically, we have been developing polymeric technologies for the delivery of gene-editing tools across the BBB for the treatment of glioblastoma and other brain cancers.
|17:30||Closing remarks and Awards for best poster/oral presentation|
|18:30||AWARD CEREMONY followed by SOCIAL EVENT|
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|08:45||PLENARY SESSION 3|
No abstract for this day
Laboratoire de Chimie des Polymères Organiques (LCPO), 16 avenue Pey-Berland, 33607 Pessac, France+33 540006693
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