Dissipative DNA fibres

peer reviewe

DNA-templated assemblies of pi-conjugated molecules

DNA is a central molecule of Life, possessing a formidable information density. Inspired by biomolecular processes such as gene replication and transcription, researchers have utilized DNA as a template to construct, for example, sequence-controlled polymers, photonic wires, and delivery systems.[1-3] In this context, we will report our recent results on the supramolecular assemblies combining nucleic acids and -conjugated molecules (small molecules or polymers), with insights into the templating effect, chirality, self-assembly, and cooperativity.[4,5] We discuss examples of DNA-templated assemblies of photoactive molecules, which can be utilized to modulate the helical assembly of multiple chromophores along DNA fibers.[3,6] Besides, we show that the supramolecular self-assembly of DNA and -conjugated polymers is of interest to probe an enzymatic activity in a label-free, real time fashion.[7,8] Prospective applications of such templated supramolecular assemblies are discussed in the context of biosensing and siRNA delivery. [1] J. Niu, R. Hili, D. R. Liu, Nat. Chem. 2013, 5, 282. [2] N.C. Seeman, H.F. Sleiman, Nat. Rev. Mater. 2017, 3, 17068. [3] M. Surin, S. Ulrich, Chem. Open 2020, 9, 480. [4] J. Rubio-Magnieto, M. Kumar, P. Brocorens, J. Idé, S.J. George, R. Lazzaroni, M. Surin, Chem. Commun. 2016, 52, 13873. [5] N. Holmgaard List, J. Knoops, J. Rubio-Magnieto, J. Idé, D. Beljonne, P. Norman, M. Surin, M. Linares, J. Am. Chem. Soc. 2017, 139, 14947. [6] J. Rubio-Magnieto, T.-A. Phan, M. Fossépré, V. Matot, J. Knoops, T. Jarrosson, P. Dumy, F. Serein-Spirau, C. Niebel, S. Ulrich, M. Surin, Chem. Eur. J. 2018, 24, 706. [7] M. Fossépré, M. Trévisan, V. Cyriaque, R. Wattiez, D. Beljonne, S. Richeter, S. Clément, M. Surin, ACS Appl. Bio Mater. 2019, 2, 2125. [8] M. Fossépré, I. Tuvi-Arad, D. Beljonne, S. Richeter, S. Clément, M. Surin, ChemPhysChem 2020, 21, 2543

Solvent Molding of Organic Morphologies Made of Supramolecular Chiral Polymers

12sihe self-assembly and self-organization behavior of uracil-conjugated enantiopure (R)- or (S)-1,1'-binaphthyl-2,2'-diol (BINOL) and a hydrophobic oligo(p-phenylene ethynylene) (OPE) chromophore exposing 2,6-di(acetylamino)pyridine termini are reported. Systematic spectroscopic (UVvis, CD, fluorescence, NMR, and SAXS) and microscopic studies (TEM and AFM) showed that BINOL and OPE compounds undergo triple H-bonding recognition, generating different organic nanostructures in solution. Depending on the solvophobic properties of the liquid media (toluene, CHCl3, CHCl3/CHX, and CHX/THF), spherical, rod-like, fibrous, and helical morphologies were obtained, with the latter being the only nanostructures expressing chirality at the microscopic level. SAXS analysis combined with molecular modeling simulations showed that the helical superstructures are composed of dimeric double-cable tape-like structures that, in turn, are supercoiled at the microscale. This behavior is interpreted as a consequence of an interplay among the degree of association of the H-bonded recognition, the vapor pressure of the solvent, and the solvophobic/solvophilic character of the supramolecular adducts in the different solutions under static and dynamic conditions, namely solvent evaporation conditions at room temperature.partially_openopenĐorđević, Luka; Marangoni, Tomas; Miletić, Tanja; Rubio-Magnieto, Jenifer; Mohanraj, John; Amenitsch, Heinz; Pasini, Dario; Liaros, Nikos; Couris, Stelios; Armaroli, Nicola; Surin, Mathieu; Bonifazi, DavideĐorđević, Luka; Marangoni, Tomas; Miletic, Tanja; Rubio Magnieto, Jenifer; Mohanraj, John; Amenitsch, Heinz; Pasini, Dario; Liaros, Nikos; Couris, Stelios; Armaroli, Nicola; Surin, Mathieu; Bonifazi, David

Multicomponent Monolayer Architectures at the Solid-Liquid Interface: Towards Controlled Space-Confined Properties and Reactivity of Functional Building Blocks

peer reviewedMulticomponent organic monolayers: Full nanometer-scale organization and positioning of molecules into monolayers at surfaces represents a major challenge for nanotechnology. In this context, recent scanning tunneling microscopy studies were carried out on multicomponent monolayers (for example, involving donor and acceptor molecules) or template monolayers for controlling the adsorption position of functional molecules (see STM image)