pH-dependent ultrafast photodynamics of p-hydroxyphenacyl: deprotonation accelerates the photo-uncaging reaction

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F10974938%3A_____%2F25%3A25_88_16" target="_blank" >RIV/10974938:_____/25:25_88_16 - isvavai.cz</a>

Výsledek na webu

<a href="https://doi.org/10.1039/d5cp01049g" target="_blank" >https://doi.org/10.1039/d5cp01049g</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1039/d5cp01049g" target="_blank" >10.1039/d5cp01049g</a>

Jazyk výsledku

angličtina

Název v původním jazyce

pH-dependent ultrafast photodynamics of p-hydroxyphenacyl: deprotonation accelerates the photo-uncaging reaction

Popis výsledku v původním jazyce

Photolabile protecting groups (PPGs) possess broad application potential as they allow spatially and temporally controlled release of the protected group. While the photochemistry of many PPGs has been studied in detail, data under aqueous conditions or depending on the pH are extremely rare. However, for applications under biological conditions in water, knowledge about the photochemistry under these is critical. Here, we studied the pH-dependent reaction dynamics of para-hydroxyphenacyl (pHP), one prominent example of PPGs, by ultrafast transient absorption spectroscopy and quantum chemical simulation. At neutral pH, the para-hydroxyl group of pHP is protonated and photoproduct formation occurs within less than 1 ns from a triplet state. At basic pH, the main scaffold gets deprotonated leading to a bathochromic shift of the characteristic absorption. Upon deprotonation the substrate release occurs directly from a singlet state, shortcutting the rate determining step of intersystem crossing (ISC) in the neutral case, resulting in an acceleration of the photochemical reaction with photoproduct formation observed at similar to 1 ps.

Název v anglickém jazyce

pH-dependent ultrafast photodynamics of p-hydroxyphenacyl: deprotonation accelerates the photo-uncaging reaction

Popis výsledku anglicky

Photolabile protecting groups (PPGs) possess broad application potential as they allow spatially and temporally controlled release of the protected group. While the photochemistry of many PPGs has been studied in detail, data under aqueous conditions or depending on the pH are extremely rare. However, for applications under biological conditions in water, knowledge about the photochemistry under these is critical. Here, we studied the pH-dependent reaction dynamics of para-hydroxyphenacyl (pHP), one prominent example of PPGs, by ultrafast transient absorption spectroscopy and quantum chemical simulation. At neutral pH, the para-hydroxyl group of pHP is protonated and photoproduct formation occurs within less than 1 ns from a triplet state. At basic pH, the main scaffold gets deprotonated leading to a bathochromic shift of the characteristic absorption. Upon deprotonation the substrate release occurs directly from a singlet state, shortcutting the rate determining step of intersystem crossing (ISC) in the neutral case, resulting in an acceleration of the photochemical reaction with photoproduct formation observed at similar to 1 ps.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10301 - Atomic, molecular and chemical physics (physics of atoms and molecules including collision, interaction with radiation, magnetic resonances, Mössbauer effect)

Projekt

<a href="/cs/project/GM21-09692M" target="_blank" >GM21-09692M: Stanovení kvantových limitů v biomolekulách pomocí entanglovaných fotonů generovaných z navázaného kofaktorů, modelováno na OCP proteinu.</a><br>

Návaznosti

P - Projekt vyzkumu a vyvoje financovany z verejnych zdroju (s odkazem do CEP)

Rok uplatnění

2025

Kód důvěrnosti údajů

S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů

Název periodika

Physical Chemistry Chemical Physics

ISSN

1463-9076

e-ISSN

1463-9084

Svazek periodika

27

Číslo periodika v rámci svazku

24

Stát vydavatele periodika

GB - Spojené království Velké Británie a Severního Irska

Počet stran výsledku

9

Strana od-do

12899-12907

Kód UT WoS článku

001502330400001

EID výsledku v databázi Scopus

2-s2.0-105007503972