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From DNA-Assembled Oligochromophores to Supramolecular Polymers: Aromatic Oligophosphates as Versatile Building Blocks for Functional Materials

English title From DNA-Assembled Oligochromophores to Supramolecular Polymers: Aromatic Oligophosphates as Versatile Building Blocks for Functional Materials
Applicant Häner Robert
Number 169030
Funding scheme Project funding (Div. I-III)
Research institution Departement für Chemie und Biochemie Universität Bern
Institution of higher education University of Berne - BE
Main discipline Organic Chemistry
Start/End 01.01.2017 - 30.09.2019
Approved amount 600'000.00
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Keywords (6)

DNA; supramolecular polymers; light harvesting systems; energy transfer; 2D polymers; chromophore

Lay Summary (German)

Lead
Desoxyribonukleinsäure (DNA) dient als molekulares Gerüst für die Herstellung von Strukturen im Nanometerbereich. Die starre Struktur der Doppelhelix erlaubt es, funktionelle Moleküle in präzis definierter Geometrie anzuordnen. Im vorliegenden Projekt werden einerseits DNA-basierte Farbstoff-Aggregate hergestellt und untersucht. Andererseits dient die DNA Doppelhelix als Leitmotiv für die Herstellung von 1- und 2-dimensionalen Polymeren. Die Bausteine dieser Polymere sind, wie in der DNA, über anionische Phosphodiester-Brücken verknüpft. Die Kombination von negativer Ladung und aromatischen Chromophoren gewährleistet einerseits eine gute Löslichkeit in Wasser und erlaubt gleichzeitig die effiziente Bildung von Aggregaten durch aromatische Molekülstapelung.
Lay summary

Hintergrund: Die präzise Anordnung von Einzelmolekülen zu einem grösseren Verbund wird aufgrund der vorgegebenen molekularen Struktur der DNA-Doppelhelix ermöglicht. Dadurch lassen sich die Eigenschaften von Multi-Chromophoren studieren, die auf andere Weise nur schwer oder gar nicht zugänglich sind. Auf diese Weise gewonnene Erkenntnisse werden in einem weiteren Schritt dazu verwendet, entsprechende Chromophor-Aggregate ohne DNA-Gerüst herzustellen. Insbesondere lassen sich so Polymere mit speziellen optischen und elektronischen Eigenschaften synthetisieren.

Ziele: Basierend auf den Erkenntnissen, die wir mit der Untersuchung von DNA-Farbstoff-Konjugaten gewonnen haben, werden 1- und 2-dimensionale Polymere mit speziellen strukturellen und elektronischen Eigenschaften hergestellt. Von besonderer Bedeutung sind hierbei Polymere mit lichtsammelnden Eigenschaften.

Bedeutung: Die Verwendung der DNA als intelligentem, molekularen Baugerüst erlaubt die präzise Anordnung von funktionellen Molekülen und kann dadurch Zugang zu neuartigen Materialien mit speziellen elektronischen und physikalischen Eigenschaften verschaffen. Solche Materialien können in der Zukunft zur Energiegewinnung eingesetzt werden, z.B.  in Form von lichtsammelnden Komplexen. Andererseits können sie auch Verwendung finden in optischen Geräten, in Photozellen oder in diagnostischen Hilfsmitteln zur frühen Erkennung von Infektions- oder Erbkrankheiten.
Direct link to Lay Summary Last update: 23.09.2016

Responsible applicant and co-applicants

Employees

Publications

Publication
DNA-inspired oligomers: from oligophosphates to functional materials
Vybornyi Mykhailo, Vyborna Yuliia, Häner Robert (2019), DNA-inspired oligomers: from oligophosphates to functional materials, in Chemical Society Reviews, 48(16), 4347-4360.
Ultrafast dynamics in polycyclic aromatic hydrocarbons: the key case of conical intersections at higher excited states and their role in the photophysics of phenanthrene monomer
Nazari M., Bösch C. D., Rondi A., Francés-Monerris A., Marazzi M., Lognon E., Gazzetto M., Langenegger S. M., Häner R., Feurer T., Monari A., Cannizzo A. (2019), Ultrafast dynamics in polycyclic aromatic hydrocarbons: the key case of conical intersections at higher excited states and their role in the photophysics of phenanthrene monomer, in Physical Chemistry Chemical Physics, 21(31), 16981-16988.
Nano-thin 2D Soft Materials – Design Principles and Prospects
Vybornyi Mykhailo, Yu Hao, Häner Robert (2019), Nano-thin 2D Soft Materials – Design Principles and Prospects, in CHIMIA International Journal for Chemistry, 73(6), 468-472.
DNA‐Organized Light‐Harvesting Antennae: Energy Transfer in Polyaromatic Stacks Proceeds through Interposed Nucleobase Pairs
Bösch Caroline D., Abay Elif, Langenegger Simon M., Nazari Maryam, Cannizzo Andrea, Feurer Thomas, Häner Robert (2019), DNA‐Organized Light‐Harvesting Antennae: Energy Transfer in Polyaromatic Stacks Proceeds through Interposed Nucleobase Pairs, in Helvetica Chimica Acta, 102(8), e1900148.
Self-Assembled Molecular-Electronic Films Controlled by Room Temperature Quantum Interference
Famili Marjan, Jia Chuancheng, Liu Xunshan, Wang Peiqi, Grace Iain M., Guo Jian, Liu Yuan, Feng Ziying, Wang Yiliu, Zhao Zipeng, Decurtins Silvio, Häner Robert, Huang Yu, Liu Shi-Xia, Lambert Colin J., Duan Xiangfeng (2019), Self-Assembled Molecular-Electronic Films Controlled by Room Temperature Quantum Interference, in Chem, 5(2), 474-484.
Nanographene favors electronic interactions with an electron acceptor rather than an electron donor in a planar fused push–pull conjugate
Volland Michel, Zhou Ping, Wibmer Leonie, Häner Robert, Decurtins Silvio, Liu Shi-Xia, Guldi Dirk M. (2019), Nanographene favors electronic interactions with an electron acceptor rather than an electron donor in a planar fused push–pull conjugate, in Nanoscale, 11(3), 1437-1441.
Integrating DNA Photonic Wires into Light-Harvesting Supramolecular Polymers
Kownacki Mariusz, Langenegger Simon M., Liu Shi-Xia, Häner Robert (2019), Integrating DNA Photonic Wires into Light-Harvesting Supramolecular Polymers, in Angewandte Chemie International Edition, 58(3), 751-755.
Probing Lewis acid–base interactions in single-molecule junctions
Liu Xunshan, Li Xiaohui, Sangtarash Sara, Sadeghi Hatef, Decurtins Silvio, Häner Robert, Hong Wenjing, Lambert Colin J., Liu Shi-Xia (2018), Probing Lewis acid–base interactions in single-molecule junctions, in Nanoscale, 10(38), 18131-18134.
Supramolecular Assembly of DNA-Phenanthrene Conjugates into Vesicles with Light-Harvesting Properties
Bösch Caroline D., Jevric Jovana, Bürki Nutcha, Probst Markus, Langenegger Simon M., Häner Robert (2018), Supramolecular Assembly of DNA-Phenanthrene Conjugates into Vesicles with Light-Harvesting Properties, in Bioconjugate Chemistry, 29(5), 1505-1509.
Formation of Supramolecular Nanotubes by Self-assembly of a Phosphate-linked Dimeric Anthracene in Water
Yu Hao, Sabetti Mattia, Häner Robert (2018), Formation of Supramolecular Nanotubes by Self-assembly of a Phosphate-linked Dimeric Anthracene in Water, in Chemistry - An Asian Journal, 13(8), 968-971.
Self-assembly of a redox-active bolaamphiphile into supramolecular vesicles
Rothenbühler Simon, Bösch Caroline D., Langenegger Simon M., Liu Shi-Xia, Häner Robert (2018), Self-assembly of a redox-active bolaamphiphile into supramolecular vesicles, in Organic & Biomolecular Chemistry, 16(38), 6886-6889.
Silica Mineralization of DNA-Inspired 1D and 2D Supramolecular Polymers
Vybornyi Mykhailo, Vyborna Yuliia, Häner Robert (2017), Silica Mineralization of DNA-Inspired 1D and 2D Supramolecular Polymers, in ChemistryOpen, 6(4), 488-491.
Synthesis of Responsive Two-Dimensional Polymers via Self-Assembled DNA Networks
Yu Hao, Alexander Duncan T. L., Aschauer Ulrich, Häner Robert (2017), Synthesis of Responsive Two-Dimensional Polymers via Self-Assembled DNA Networks, in Angewandte Chemie International Edition, 56(18), 5040-5044.
Functional DNA-grafted supramolecular polymers – chirality, cargo binding and hierarchical organization
Vyborna Yuliia, Vybornyi Mykhailo, Häner Robert (2017), Functional DNA-grafted supramolecular polymers – chirality, cargo binding and hierarchical organization, in Chemical Communications, 53(37), 5179-5181.
Morphological diversity of supramolecular polymers of DNA-containing oligopyrenes – formation of chiroptically active nanosheets
Vyborna Y., Altunbas S., Vybornyi M., Häner R. (2017), Morphological diversity of supramolecular polymers of DNA-containing oligopyrenes – formation of chiroptically active nanosheets, in Chemical Communications, 53(89), 12128-12131.
Pathway Diversity in the Self-Assembly of DNA-Derived Bioconjugates
Vyborna Yuliia, Vybornyi Mykhailo, Häner Robert (2017), Pathway Diversity in the Self-Assembly of DNA-Derived Bioconjugates, in Bioconjugate Chemistry, 27(11), 2755-2761.
Solution-phase synthesis of 1D tubular polymers via preorganization–polymerization
Yu Hao, Häner Robert (2017), Solution-phase synthesis of 1D tubular polymers via preorganization–polymerization, in Chemical Communications, 52(100), 14396-14399.

Collaboration

Group / person Country
Types of collaboration
PD. Dr. A. Stocker, University of Bern Switzerland (Europe)
- in-depth/constructive exchanges on approaches, methods or results
- Publication
- Research Infrastructure
- Exchange of personnel
Prof. A. Cannizzo, University of Bern Switzerland (Europe)
- in-depth/constructive exchanges on approaches, methods or results
- Publication
- Research Infrastructure
- Exchange of personnel
Prof. Mark Bathe, MIT United States of America (North America)
- in-depth/constructive exchanges on approaches, methods or results
Dr. Valentina Villari, CNR-IPCF Istituto per i Processi Chimico-Fisici, Messina Italy (Europe)
- in-depth/constructive exchanges on approaches, methods or results
- Publication
- Research Infrastructure
PD Dr. Dominik Brühwiler, ZHAW Switzerland (Europe)
- in-depth/constructive exchanges on approaches, methods or results
- Publication
- Research Infrastructure
- Industry/business/other use-inspired collaboration
Prof. Antonio Monari, Theory-Modeling-Simulation SRSMC, Université de Lorraine & CNRS France (Europe)
- in-depth/constructive exchanges on approaches, methods or results
- Publication
- Research Infrastructure
PD Dr. M. Calame, Department of Physics & Swiss Nanoscience Institute, University of Basel Switzerland (Europe)
- in-depth/constructive exchanges on approaches, methods or results
- Publication
- Exchange of personnel
Prof. Gion Calzaferri, University of Bern Switzerland (Europe)
- in-depth/constructive exchanges on approaches, methods or results
- Publication
- Industry/business/other use-inspired collaboration
Prof. T. Feurer, University of Bern Switzerland (Europe)
- in-depth/constructive exchanges on approaches, methods or results
- Publication
- Research Infrastructure
- Exchange of personnel

Awards

Title Year
Faculty Award 2018 for best PhD thesis in chemistry 2018
Best Poster Award 'Swiss Conference on Supramolecular Polymers 2017', Adolphe Merkle Institute, Fribourg, 6. Nov. 2017 2017

Associated projects

Number Title Start Funding scheme
188468 Sequence-Defined Oligophosphates - From Modified DNA to Supramolecular Precision Materials 01.04.2020 Project funding (Div. I-III)
149148 DNA-based Oligomeric and Polymeric Functional Materials 01.10.2013 Project funding (Div. I-III)

Abstract

The construction and study of novel types of one- and two-dimensional supramolecular polymers from short, DNA-inspired oligomers is proposed. Phosphodiester-linked aromatic oligomers (oligoarenotides) built from various polyaromatic building blocks, such as phenanthrene, pyrene or chrysene, exhibit surprising structural and functional diversity in an aqueous environment. Self-assembly leads to formation of supramolecular structures, including fibres, nanosheets and nanotubes. The resultant polychromophores will be studied for their electronic and structural properties.A major effort will be dedicated to deepen our understanding of the supramolecular polymerization of oligoarenotides. Past studies showed that the morphology of the formed supramolecular polymers is not only influenced by the aromatic residues, but, to a large extent, also by the connecting linkers. Important factors include the geometry (i.e., site of attachment to the aromatic core), the length and the chemical nature (e.g., carboxamide- vs. alkynyl-substitution). Closely related to these activities are efforts aiming at the covalent linkage of assembled oligomers, which would allow the conversion of supramolecular polymers to covalent polymers. Different strategies (photodimerization of anthracene-containing hexagonal DNA networks; disulfide formation of linear and two-dimensional supramolecular polymers) will be pursued. The construction and study of light-harvesting supramolecular polymers will also be of primary interest. We plan to extend our studies of one- and two-dimensional polymers to other types of chromophores, such as cyanines and porphyrins. Additionally, we will start to explore oligoarenotide-based supramolecular polymers as biomimetic and biocompatible materials. These efforts will include probing the interaction of polymers with cationic protein complexes, especially histones, as well as the use of silanized polymers for cellular applications (cellular imaging, in collaboration with Prof. A. Stocker at our department).Once established, synthesis of oligoarenotides and subsequent formation of supramolecular polymers comes as a series of straightforward steps. However, the underlying principles (aggregation behavior, exciton formation, energy transfer) were all established in preceding studies with DNA-assembled oligochromophores. This demonstrates the value of the DNA duplex as a supramolecular scaffold for the precise arrangement of functional compounds. Therefore, we will continue and extend our work in the area of DNA-controlled assembly of chromophores. In particular, we will continue studying the process of excitation energy transfer in DNA-assembled polychromophore systems in collaboration with Prof. T. Feurer and Prof. A. Cannizzo, Institute of Applied Physics, UniBE (NCCR Molecular Ultrafast Science and Technology), as well as PD Dr. M. Calame (Department of Physics & Swiss Nanoscience Institute, University of Basel).Another important aspect is the chemical synthesis of additional types of chromophoric building blocks. While concentrating on the investigation of the well-established polyaromatic hydrocarbons pyrene and phenanthrene, we will also synthesize and test the analogous phenanthroline building blocks. Of major importance in this regard will be the compatibility of the new derivatives with oligonucleotide synthesis, their ability to support the formation of multi-stranded hybrids, and, most importantly, the changes in electronic properties upon formation of multi-chromophoric aggregates. Although not explicitly mentioned in the detailed research plan, we are continuing our efforts with porphyrins and chrysene. Electronic coupling, which is present between chromophores in oligomers, is under investigation in collaboration with Prof. G. Calzaferri at our department.
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