Photochemical mechanism of DEACM uncaging: a combined time-resolved spectroscopic and computational study

Hamerla, Carsten; Neumann, Christoph; Falahati, K.; Cosel, Jan von; Wilderen, Luuk J. G. W. van; Niraghatam, Madhava Shyam; Kern-Michler, Daniela; Mielke, Nicole; Reinfelds, Matiss; Rodrigues-Correia, Alexandre; Heckel, Alexander; Bredenbeck, Jens; Burghardt, Irène

doi:10.1039/c9cp07032j

Cited by 19 publications

(26 citation statements)

References 34 publications

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“…In contrast to the other tested solvents, the ESA ICT does not show a major rise in amplitude on the 10-100 ps timescale in PBS/DMSO (Figure S3), implying a less pronounced population of the CT state. However, it was shown in recent work [53] that the charge separation is crucial in order to facilitate elongation of the CÀ C bond, which is cleaved in the subsequent uncaging process. Additionally, the solvent response due to the ultrafast change in dipole moment is somewhat more complicated in PBS/DMSO mixtures.…”

Section: Chemistry-a European Journalmentioning

confidence: 99%

Inactivation of Competitive Decay Channels Leads to Enhanced Coumarin Photochemistry

Klimek

Asido

Hermanns

et al. 2022

Chemistry A European J

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In the development of photolabile protecting groups, it is of high interest to selectively modify photochemical properties with structural changes as simple as possible. In this work, knowledge of fluorophore optimization was adopted and used to design new coumarin‐ based photocages. Photolysis efficiency was selectively modulated by inactivating competitive decay channels, such as twisted intramolecular charge transfer (TICT) or hydrogen‐bonding, and the photolytic release of the neurotransmitter serotonin was demonstrated. Structural modifications inspired by the fluorophore ATTO 390 led to a significant increase in the uncaging cross section that can be further improved by the simple addition of a double bond. Ultrafast transient absorption spectroscopy gave insights into the underlying solvent‐dependent photophysical dynamics. The chromophores presented here are excellently suited as new photocages in the visible wavelength range due to their simple synthesis and their superior photochemical properties.

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Section: Chemistry-a European Journalmentioning

confidence: 99%

Inactivation of Competitive Decay Channels Leads to Enhanced Coumarin Photochemistry

Klimek

Asido

Hermanns

et al. 2022

Chemistry A European J

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“…For this, we chose the widely studied diethylaminocoumarin (DEACM) scaffold, which shows excellent photocleavage upon UV irradiation 60,61 and has been used to control several biological processes. 48,62,63 An extended DEACM scaffold has been reported, 55 which shifted its absorption maximum to ~450 nm.…”

Section: Synthesis Of a Blue-light Photocleavable Group Carrying A Bi...mentioning

confidence: 99%

Blue light-activatable DNA for remote control of cell-free logic gates and synthetic cells

Hartmann

Chowdhry

Smith

et al. 2022

Preprint

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Cell-free gene expression is a vital research tool to study biological systems in defined minimal environments and has applications in biotechnology. Developing methods to control DNA templates for cell-free expression will be important for precise regulation of complex biological pathways and drug delivery, particularly using remote, non-damaging stimuli such as visible light. Here, we have synthesised blue light-activatable DNA parts to selectively control cell-free expression. Using this approach, we were able to control cell-free RNA and protein expression with blue light. Due to the orthogonality of this blue light-activated DNA to UV irradiation, we combined it with our previously generated UV light-activated DNA to generate a dual-wavelength controlled cell-free AND-gate. This blue light-activated DNA was also used to control synthetic cells; lipid-bounded compartments that mimic cellular function. Our blue and UV orthogonal light-activated DNAs will open the door for precise control of cell-free systems in biology and medicine.

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“…The initial photochemical process, which is essentially based on the push–pull idea for nitro‐based cages, is the formation of an aci ‐nitro and subsequent benzisoxazole intermediate (Figure 1a) [10] . Coumarin‐ and BODIPY‐cages show an increase in electron density at the carbon atom next to the carbon atom attached to the leaving group (LG) upon irradiation [19,20] …”

Section: Introductionmentioning

confidence: 99%

“…[10] Coumarin‐ and BODIPY‐cages show an increase in electron density at the carbon atom next to the carbon atom attached to the leaving group (LG) upon irradiation. [ 19 , 20 ]…”

Section: Introductionmentioning

confidence: 99%

Rethinking Uncaging: A New Antiaromatic Photocage Driven by a Gain of Resonance Energy

Hermanns

Scheurer

Kersten

et al. 2021

Chemistry A European J

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Photoactivatable compounds for example photoswitches or photolabile protecting groups (PPGs, photocages) for spatiotemporal light control, play a crucial role in different areas of research. For each application, parameters such as the absorption spectrum, solubility in the respective media and/or photochemical quantum yields for several competing processes need to be optimized. The design of new photochemical tools therefore remains an important task. In this study, we exploited the concept of excited‐state‐aromaticity, first described by N. Colin Baird in 1971, to investigate a new class of photocages, based on cyclic, ground‐state‐antiaromatic systems. Several thio‐ and nitrogen‐functionalized compounds were synthesized, photochemically characterized and further optimized, supported by quantum chemical calculations. After choosing the optimal scaffold, which shows an excellent uncaging quantum yield of 28 %, we achieved a bathochromic shift of over 100 nm, resulting in a robust, well accessible, visible light absorbing, compact new photocage with a clean photoreaction and a high quantum product (ϵ⋅Φ) of 893 M−1 cm−1 at 405 nm.

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Photochemical mechanism of DEACM uncaging: a combined time-resolved spectroscopic and computational study

Abstract: Combined spectroscopic and computational studies elucidate excited-state photocleavage in DEACM cages, explaining vastly different time scales for different leaving groups.

Cited by 19 publications

References 34 publications

Inactivation of Competitive Decay Channels Leads to Enhanced Coumarin Photochemistry

Inactivation of Competitive Decay Channels Leads to Enhanced Coumarin Photochemistry

Blue light-activatable DNA for remote control of cell-free logic gates and synthetic cells

Rethinking Uncaging: A New Antiaromatic Photocage Driven by a Gain of Resonance Energy

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