Photomodulation of DNA‐Templated Supramolecular Assemblies

Rubio‐Magnieto, Jenifer; Phan, Tuan‐Anh; Fossépré, Mathieu; Matot, Valérie; Knoops, Jérémie; Jarrosson, Thibaut; Dumy, Pascal; Serein-Spirau, Françoise; Niebel, Claude; Ulrich, Sébastien; Surin, Mathieu

doi:10.1002/chem.201704538

Cited by 10 publications

(8 citation statements)

References 64 publications

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“…We showed that the evolution of CD signals reflect the extent of ATP hydrolysis by the phosphatase, going from supramolecular polymers bound to ATP, to ADP, then AMP, and eventually phosphates. Indeed, CD signals are very sensitive to changes in the microenvironment and were shown to be effective in studying supramolecular systems, , in particular for supramolecular DNA recognition. − …”

Section: Introductionmentioning

confidence: 99%

Detection of the Enzymatic Cleavage of DNA through Supramolecular Chiral Induction to a Cationic Polythiophene

Fossépré

Trevisan

Cyriaque

et al. 2019

ACS Appl. Bio Mater.

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Water-soluble π-conjugated polymers are increasingly envisioned in biosensors, in which their unique optical and electronic properties permit a highly sensitive detection of biomolecular targets. In particular, cationic π-conjugated polymers are attractive for DNA sensing technologies, through the use of the fluorescence signals either in physiological solutions or in thin films. However, in the context of enzymatic activity assays, fluorescence-based methods require covalently labeling DNA with a dye or an antibody and are limited to short time scale due to dye photobleaching. In this frame, we report here a novel possible approach to probe the cleavage of DNA by a restriction enzyme, in continuous and without covalently labeled DNA substrate. This is achieved by exploiting unique chiroptical signals arising from the chiral induction of DNA to a poly[3-(6′-(trimethylphosphonium)hexyl)thiophene-2,5-diyl] upon interaction. The cleavage of DNA by HpaI, an endonuclease enzyme, is monitored through circular dichroism (CD) signals in the spectral range where the polymer absorbs light, i.e., far away from the spectral ranges of both DNA and the enzyme. We compare the results to a conventional noncontinuous assay by polyacrylamide gel electrophoresis, and we demonstrate that induced CD signals are effective in probing the enzymatic activity. By means of molecular dynamics simulations and calculations of CD spectra, we bring molecular insights into the structure of DNA/polymer supramolecular complexes before and after the cleavage of DNA. We show that the cleavage of DNA modifies the dynamics and the organization of the polymer backbone induced by the DNA helix. Altogether, our results provide detailed spectroscopic and structural insights into the enzymatic cleavage of DNA in interaction with a π-conjugated polymer, which could be helpful for developing chiroptical detection tools to monitor the catalytic activity in real time.

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Section: Introductionmentioning

confidence: 99%

Detection of the Enzymatic Cleavage of DNA through Supramolecular Chiral Induction to a Cationic Polythiophene

Fossépré

Trevisan

Cyriaque

et al. 2019

ACS Appl. Bio Mater.

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“…This approach, coupled to conventional adenosine‐phosphates assays, could possibly help in the analysis of the composition in APs or other nucleotide phosphates, as recently reported for supramolecular polymers and conjugated copolymers . Moreover, the possibility of using guanidinium‐based photoresponsive molecules with GuaBiPy in multicomponent assemblies could also be exploited, for instance to modulate ATP release within dynamic supramolecular systems.…”

Section: Resultsmentioning

confidence: 99%

“…We considered one AxP molecule with a number of 4 GuaBiPy molecules as model systems to highlight the interactions at play during the self‐assembly process. To build these systems, each GuaBiPy (parameterized based on an earlier study) was oriented around a central AxP by using University of California, San Francisco Chimera software . GuaBiPy and AxP molecules were initially separated by 15 Å, according to their geometric centers, a larger distance than the cut‐off of nonbonded interactions, to avoid any bias on the recognition modes between the compounds.…”

Section: Methodsmentioning

confidence: 99%

Self‐assembly and chiroptical properties in supramolecular complexes of adenosine phosphates and guanidinium‐bispyrene

et al. 2018

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Supramolecular systems that respond to the hydrolysis of adenosine phosphates (APs) are attractive for biosensing and to fabricate bioinspired self-assembled materials. Here, we report on the formation of supramolecular complexes between an achiral guanidinium derivative bearing two pyrene moieties, with each of the three adenosine phosphates: AMP, ADP, and ATP. By combining results from circular dichroism spectroscopy and molecular modeling simulations, we explore the induced chirality, the dynamics of the complexes, and the interactions at play, which altogether provide insights into the supramolecular self-assembly between APs and the guanidinium-bispyrene. Finally, we identify the chiroptical signals of interest in mixtures of the guanidinium derivative with the three APs in different proportions. This study constitutes a basis to evolve toward a chiroptical detection of the hydrolysis of APs based on organic supramolecular probes.

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“…Further exploiting this prime role of π‐ stacking interactions, we have recently inserted a photoswitchable azobenzene‐based molecule, which was observed to bind to the DNA minor‐groove and was expected to influence these interactions depending on its twisted Z or coplanar E configuration. Remarkably, when interacting with ssDNA, the photoswitching of the azobenzene‐based compound allowed us to control the DNA binding of the pyrene‐based compound GuaBiPy , which is detected by its unique fluorescence signals . These results demonstrated that it is possible to achieve a photocontrol of DNA binding in heteromolecular templated assemblies, using photoswitchable ligands.…”

Section: Dna‐templated Self‐assembly Of Small Moleculesmentioning

confidence: 90%

From Interaction to Function in DNA‐Templated Supramolecular Self‐Assemblies

Surin

Ulrich

2020

ChemistryOpen

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DNA-templated self-assembly represents a rich and growing subset of supramolecular chemistry where functional selfassemblies are programmed in a versatile manner using nucleic acids as readily-available and readily-tunable templates. In this review, we summarize the different DNA recognition modes and the basic supramolecular interactions at play in this context. We discuss the recent results that report the DNA-templated self-assembly of small molecules into complex yet precise nanoarrays, going from 1D to 3D architectures. Finally, we show their emerging functions as photonic/electronic nanowires, sensors, gene delivery vectors, and supramolecular catalysts, and their growing applications in a wide range of area from materials to biological sciences.[a] Dr.

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Photomodulation of DNA‐Templated Supramolecular Assemblies

Cited by 10 publications

References 64 publications

Detection of the Enzymatic Cleavage of DNA through Supramolecular Chiral Induction to a Cationic Polythiophene

Detection of the Enzymatic Cleavage of DNA through Supramolecular Chiral Induction to a Cationic Polythiophene

Self‐assembly and chiroptical properties in supramolecular complexes of adenosine phosphates and guanidinium‐bispyrene

From Interaction to Function in DNA‐Templated Supramolecular Self‐Assemblies

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