Nanomachine | EPFL Graph Search

vignette|Schéma du de Richard Feynman. Les nanomachines, appelées également machines moléculaires, sont de minuscules machines composées d'assemblages moléculaires dont au moins deux parties sont reliées par un lien mécanique et qui peuvent être animées de mouvements sous l'action d'un stimulus externe. Leur taille est de l'ordre du nanomètre et leur synthèse nécessite parfois un nombre important de réactions chimiques. Elles travaillent directement sur les atomes ou les molécules. Il existe ainsi des nano-moteurs, des nano-élévateurs, des nano-pinces ou même des nano-transporteurs. Leur utilisation reste cependant problématique, surtout dans le domaine de l’approvisionnement en énergie et matières premières de manière efficace, en raison de leur extrême petite taille. Elles utilisent des systèmes supramoléculaires, définis par le CEA comme des . En revanche, la nanotechnologie actuelle utilise avec grands succès des nanomécanismes sur des macromachines, en fabrication de processeur

Molecular Engineering of Electrode Surfaces for Electrocatalysis

Patrick Eduard Alexa

Electrocatalysts play an important part on the route towards environmental friendly energy sources. They support modern technologies like fuel cells to move further away from the utilization of fossil fuels and the resulting CO2 emission into our atmosphere. The main principle of such energy conversion technologies is to store chemical energy within chemical bonds and to release it as electric energy to fulfill the energy demand of today's society. However energy conversion chemistry in such technologies requires catalysts in order to be effective by providing an alternative reaction pathway that lowers activation energies and maximizes the energy output. Providing suitable catalyst surfaces requires a fundamental knowledge of the interaction of reactants and reaction intermediates with the catalyst surfaces. This concern is addressed in this thesis by fabricating specifically tailored molecular components on metal surfaces, which act as organic/inorganic hybrid electrodes for various energy conversion reactions in electrocatalysis. Characterizing the electrode surface is crucial in order to identify active sites of the catalyst. The molecular structure is investigated by surface sensitive techniques, such as STM and XPS in combination with a home-build transfer system, which enables electrode fabrication in UHV and electrocatalytic experiments in a liquid environment. A detailed characterization of organic polymer components on electrode surfaces is obtained by combining experimental data with MD simulations. The morphology of polymer networks can be successfully mimicked and depending on the chemical composition and the structure, spatial correlations on short length scales are reported. Hybrid electrodes with organic polymer co-catalysts reveal an increased catalytic activity for the HER by providing suitable docking sites that act as catalytic active sites. Reactants and reaction intermediates are stabilized via hydrogen bonding, which results in a higher catalytic turnover. The specific designed structure of the organic co-catalyst helps to identify a fraction of the reaction mechanism and highlights the importance of molecular components in electrocatalysis. The utilization of organic units on electrocatalysts provides also an excellent opportunity in order to use single metal atoms as catalysts. Engineering large pi-systems has no significant impact on the ORR activity, while the distance between active sites and the underlying electrode are crucial for enhancing the catalytic activity. A significant factor in using molecular components in electrocatalysis is the stability of the organics. Using electrografting allows to design organic/inorganic hybrid electrodes with covalent bonds between the molecular component and the metal substrate. Attaching empty porphyrin molecules to substrates introduces a powerful technique in molecular engineering, since empty porphyrin cycles can be metallized with various metal centers that can act as electrocatalysts for different electrochemical reactions. In summary, this thesis provides multiple engineering aspects, which are useful in designing molecular components on metal electrodes for energy conversion. Such hybrid catalyst surfaces are capable of improving the catalytic activity and allow to study the mechanism of catalytic reactions. Implementing organic components provides new routes for tailoring novel materials, which deliver new insight into the complex field of electrocatalysis.

EPFL2020

Preparation and characterization of Poly(Ethylene Glycol)/gamma-CD Polyrotaxanes using beta-CD derivatives as a capping reagent

Blaise Tardy

As living systems understanding got better, as life could be modeled in a batch, using immortalized cells, researches in fundamental sciences found startling applications of advanced techniques on living systems. As the biomaterial field developed various molecules were found to have very interesting applications on living systems. Polyrotaxane is one of these particularly interesting molecules. It is a non covalently bonded molecular necklace produced by the threading of cyclic molecules onto a linear polymer in order to form a pseudopolyrotaxane, the capping of this pseudopolyrotaxane to avoid de-threading of the cyclic compounds forms a polyrotaxane. This compound has already proven its versatility through various application including drug delivery systems, DNA delivery agent, molecular machine, hydrogel building block, resin stabilizer and a lot more. Cyclodextrins (CDs) and Polyester are known to form a pseudopolyrotaxane. CDs are composed of 6 to 8 glucopyranose forming a toroid shaped molecule that can contain different molecules depending on the solvent, experimental conditions and the number of sugar subunits. In this project an attempt has been made to synthesize a special type of polyrotaxane that would allow the whole complex to bare a higher degree of freedom compared to the ones currently documented. In order to do so the widest CD has been used (Gamma-CD, GCD), the chosen host has been poly(ethylene glycol) (PEG) chains of varying molecular weight and the capping reagent used was beta-CD derivatives. Furthermore since current literature hasn't documented it so well and its properties are essential to this study, some more characterization of the PEG/GCD pseudopolyrotaxane has been made. The Macromolecules have been characterized by maldi tof mass spectroscopy(MALDI-T-MS), electro spray ionization (ESI) mass detection, X-ray diffraction(XRD), gel phase chromatography (GPC) and liquid Nuclear magnetic resonance (NMR). The beta CD and poly(ethylene glycol) derivatives have been characterized using Fourier transform infra red spectroscopy (FTIR), NMR, MALDI-Toff MS, ESI and thin layer Chromatography (TLC)

2009

Molecular Dynamics and Monte Carlo simulations resolve apparent diffusion rate differences for proteins confined in nanochannels

Nazar Ileri, Philippe Renaud

We use Molecular Dynamics and Monte Carlo simulations to examine molecular transport phenomena in nanochannels, explaining four orders of magnitude difference in wheat germ agglutinin (WGA) protein diffusion rates observed by fluorescence correlation spectroscopy (FCS) and by direct imaging of fluorescently-labeled proteins. We first use the ESPResSo Molecular Dynamics code to estimate the surface transport distance for neutral and charged proteins. We then employ a Monte Carlo model to calculate the paths of protein molecules on surfaces and in the bulk liquid transport medium. Our results show that the transport characteristics depend strongly on the degree of molecular surface coverage. Atomic force microscope characterization of surfaces exposed to WGA proteins for 1000 s show large protein aggregates consistent with the predicted coverage. These calculations and experiments provide useful insight into the details of molecular motion in confined geometries.

Elsevier2015