Interplay of Depletion Forces and Biomolecular Recognition in the Hierarchical Assembly of Supramolecular Tubes

Crowding effects have a profound impact on the hierarchical organization of cellular architectures. In the fields of systems chemistry and soft matter, this effect has not received much attention so far. Here, it is explored how poly(ethylene glycol) (PEG) as a crowding agent invokes depletion forces that act on synthetic supramolecular tubes. Hence, supramolecular tubes are pushed from their random orientation into hierarchically assembled bundles due to the PEG-induced crowded environment. The resulting morphology of formed bundled architectures can be tuned by the concentrations of both the supramolecular tubes and the PEG. The introduction of biotin groups at the surface of the tubes allows the engineering of biotin–streptavidin crosslinks between them. The order of introducing PEG and streptavidin in the system further affects the formed hierarchical assemblies, as well as their resistance toward dilution. The strategy described here provides a new route to establish hierarchically organized supramolecular architectures, combining crowding and specific biomolecular interactions, which shows the potential for controlling the structure of supramolecular materials and other soft matter systems.</p

Two-Dimensional Nanoporous Networks Formed by Liquid-to-Solid Transfer of Hydrogen-Bonded Macrocycles Built from DNA Bases

This is the peer reviewed version of the following article: Angewandte Chemie 128.2 (2016): 669–673, which has been published in final form at http://dx.doi.org/10.1002/anie.201509233. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Self-ArchivingWe present an approach that makes use of DNA base pairing to produce hydrogen-bonded macrocycles whose supramolecular structure can be transferred from solution to a solid substrate. A hierarchical assembly process ultimately leads to two-dimensional nanostructured porous networks that are able to host size-complementary guests. DNA base pairing is used to produce hydrogen-bonded macrocycles whose supramolecular structure can be transferred from solution to a solid substrate. A hierarchical assembly process ultimately leads to two-dimensional nanostructured porous networks that are able to host size-complementary guestsFunding from the E.U. (ERC-Starting Grant 279548), MICINN (CTQ2014-57729-P), Fund for Scientific Research – Flanders, KU Leuven (GOA 11/003), Belgian Federal Science Policy Office (IAP-7/05), and the European Research Council under the FP7/2007-2013 / ERC Grant Agreement no. 34032

Multivalent Noncovalent Interfacing and Cross-Linking of Supramolecular Tubes

Natural supramolecular filaments have the ability to cross-link with each other and to interface with the cellular membrane via biomolecular noncovalent interactions. This behavior allows them to form complex networks within as well as outside the cell, i.e., the cytoskeleton and the extracellular matrix, respectively. The potential of artificial supramolecular polymers to interact through specific noncovalent interactions has so far only seen limited exploration due to the dynamic nature of supramolecular interactions. Here, a system of synthetic supramolecular tubes that cross-link forming supramolecular networks, and at the same time bind to biomimetic surfaces by the aid of noncovalent streptavidin–biotin linkages, is demonstrated. The architecture of the networks can be engineered by controlling the density of the biotin moiety at the exterior of the tubes as well as by the concentration of the streptavidin. The presented strategy provides a pathway for designing adjustable artificial supramolecular superstructures, which can potentially yield more complex biomimetic adaptive materials

Signal processing and frequency-dependent associative memory based on nanoswitches

A signal processing concept based on nanoscale switches whose conductance can be tuned by an external stimulus between two (ON and OFF) states is proposed and analyzed theoretically. The building block of the system is formed by a metal nanoparticle linked to two electrodes by an organic ligand and a molecular switch. When we apply an alternating potential to the system of the same frequency as the periodic variation between the ON and OFF states induced on the switch, the net charge delivered by the system exhibits a sharp resonance. This resonance can be used to process an external signal by selectively extracting the weight of the different harmonics. In addition, a frequency-dependent associative memory that exploits the resonance property is also demonstrated. The general properties of the signal processing concept that are required for practical implementation are analyzed for different temperatures, times, conductance ratios, applied potentials, and noise [email protected] [email protected]

Controlled rotary motion of light-driven molecular motors assembled on a gold film

Using circular dichroism (CD) spectroscopy, we show that light-driven rotary molecular motors based on overcrowded alkenes can function in a self-assembled monolayer on semi-transparent gold films.

Ultrafast quenching of ring closure in molecular switches, self-assembled on gold nanoparticles

We report the ultrafast quenching of the ring-closure reaction in BTE-based photochromic switches self-assembled on gold nanoparticles. The photoinduced population dynamics of the switches reveals that the electronic states of the switch molecules are strongly mixed with the states of the gold particles.</p

Photoswitchable architecture transformation of a DNA-hybrid assembly at the microscopic and macroscopic scale

Molecular recognition-driven self-assembly employing single-stranded DNA (ssDNA) as a template is a promising approach to access complex architectures from simple building blocks. Oligonucleotide-based nanotechnology and soft-materials benefit from the high information storage density, self-correction, and memory function of DNA. Here we control these beneficial properties with light in a photoresponsive biohybrid hydrogel, adding an extra level of function to the system. An ssDNA template was combined with a complementary photo-responsive unit to reversibly switch between various functional states of the supramolecular assembly using a combination of light and heat. We studied the structural response of the hydrogel at both the microscopic and macroscopic scale using a combination of UV-vis absorption and CD spectroscopy, as well as fluorescence, transmission electron, and atomic force microscopy. The hydrogels grown from these supramolecular self-assembly systems show remarkable shape-memory properties and imprinting shape-behavior while the macroscopic shape of the materials obtained can be further manipulated by irradiation