Driving DNA Origami Coassembling by Vibrational Strong Coupling in the Dark

Abstract

Vibrational strong coupling (VSC) has been an emerging tool to regulate the energy landscape of chemical bonds. VSC can be achieved by tuning the optical mode of Fabry-Peŕot (FP) cavities to resonantly couple with molecular vibrations, which generates new light-molecule hybrid states and energy levels, thereby directly influencing chemical reactions. Herein, VSC with FP cavities can significantly reduce the melting temperature (T m ) of dsDNA, which can be precisely measured using DNA origami coassembly, benefiting from the precise hybridization-dependent origami conformation. An 8.5-μm-spaced FP cavity can strongly couple with the vibration of the pyridine bases, exhibiting the most optimized enhancing effect on directly driving the coassembly of DNA origami in FP cavities. This work sheds light on the quantum mechanism in life and in turn holds great promise to develop innovative techniques to regulate life.

Ab Initio Vibro-Polaritonic Spectra in Strongly Coupled Cavity-Molecule Systems

“…Strong light–matter coupling between a molecular system and the electromagnetic field of an optical cavity offers new possibilities to modify chemical reactivity and selectivity, as demonstrated in recent experiments. − A particularly intriguing but not yet fully understood situation occurs when a cavity mode is strongly coupled to molecular vibrations, called vibrational-strong coupling (VSC). − For VSC the rate constants of ground state reactions can be modified even without external driving, i.e., without explicitly adding photons to the cavity. Probably one of the most striking features observed in such experiments is the change of the vibrational spectra due to the formation of molecular vibrational polaritons, hybrid states that involve both cavity modes and vibrational modes of molecules.…”

Cavity Born–Oppenheimer Hartree–Fock Ansatz: Light–Matter Properties of Strongly Coupled Molecular Ensembles

“…In polaritonic chemistry, depending on whether the quantized cavity modes are coupled via their characteristic frequencies to electronic or vibrational degrees of freedom of molecules, the situation is described as electronic-strong coupling (ESC) or vibrational-strong coupling (VSC), respectively. Under ESC, it becomes possible to modify the photochemistry/photophysics of molecules including charge transfer processes and electronic spectroscopy, and photoinduced reactions can be influenced. − Similarly, for VSC, the vibrational spectra of molecules are altered by the formation of light–matter hybrid states, and even the chemical reactivity of the ground state can be modified. ,− ,− The observed effects of molecular ESC and VSC are often discussed phenomenologically, and understanding of the underlying microscopic and macroscopic physical mechanisms, especially with respect to the effects of VSC, is still incomplete. ,− In our recent work we have shown numerically that the interaction between an optical cavity and ensembles of molecules not only leads to cavity detuning and a change of the optical length but also allows for a local molecular polarization mechanism under strong collective vibrational coupling in the thermodynamic limit. The interplay of microscopic and macroscopic polarization is due to cavity-mediated dipole–dipole interaction.…”

Unlimiting ionic conduction: manipulating hydration dynamics through vibrational strong coupling of water

“…This phenomenon is consistent with previous reports on the vibrational strong coupling of water. [32][33][34][35][36][37][38] The anticrossing behavior of the upper and lower polariton branches was evaluated, as shown in Fig. 1b.…”

“…[28][29][30] The modication under vibrational strong coupling can be emphasized especially for the coupling with solvents because of the large number of molecules. 31 Notably, water has been shown to exhibit an ultrastrong coupling regime, [32][33][34][35][36][37][38] allowing for modi-cations in its physicochemical properties. This phenomenon has been demonstrated in various contexts, including the modulation of hydrogen-bonding networks, 32 the manipulation of enzymatic activity, 33,34 the modication of DNA replication 35 and the folding of DNA origami, 36 and the selective crystallization of metal-organic frameworks.…”

“…31 Notably, water has been shown to exhibit an ultrastrong coupling regime, [32][33][34][35][36][37][38] allowing for modi-cations in its physicochemical properties. This phenomenon has been demonstrated in various contexts, including the modulation of hydrogen-bonding networks, 32 the manipulation of enzymatic activity, 33,34 the modication of DNA replication 35 and the folding of DNA origami, 36 and the selective crystallization of metal-organic frameworks. 37 In our previous work, we discovered a more than tenfold enhancement in the H + conductivity of aqueous solutions.…”