A study of azopyrimidine photoswitches and their interactions with cyclodextrins: When the guest governs the type of accommodation at the host

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61388963%3A_____%2F23%3A00567686" target="_blank" >RIV/61388963:_____/23:00567686 - isvavai.cz</a>

Nalezeny alternativní kódy

RIV/00216208:11310/23:10465327 RIV/00216275:25310/23:39921079

Výsledek na webu

<a href="https://doi.org/10.1016/j.dyepig.2023.111099" target="_blank" >https://doi.org/10.1016/j.dyepig.2023.111099</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1016/j.dyepig.2023.111099" target="_blank" >10.1016/j.dyepig.2023.111099</a>

Jazyk výsledku

angličtina

Název v původním jazyce

A study of azopyrimidine photoswitches and their interactions with cyclodextrins: When the guest governs the type of accommodation at the host

Popis výsledku v původním jazyce

Azopyrimidines have recently emerged as a new class of photoswitches structurally similar to azobenzenes switching between trans and cis isomers. These compounds have a wide range of potential applications in photopharmacology, catalysis or as molecular devices, but their low solubility in water limits their biological applications. Nevertheless, this drawback could be overcome by their inclusion into supramolecular structures. To test this hypothesis, we prepared a series of azopyrimidines and investigated their structure, cis-trans isomerization and host-guest chemistry with cyclodextrins (CDs) using an experimental-theoretical approach combining capillary electrophoresis (CE), Nuclear Magnetic Resonance (NMR) spectroscopy and computational models. The results revealed that β-CD exhibits high selectivity over several CDs tested for the accommodation of the studied compounds. Orientation of guests in inclusion complexes was experimentally assessed by Nuclear Overhauser Effect (NOE) contacts and supported by quantum-chemical calculations. Moreover, investigation of noncovalent interactions of azopyrimidines with β-CD by CE showed that azopyrimidines with suitable structural modification can form strong complexes with high values of binding constants (over 17 000 L mol−1). For such complexes, trans-cis isomerization proceeds directly inside the β-CD cavity with azopyrimidine remaining encapsulated through its narrower primary portal. By contrast, in weakly interacting complexes, the trans isomer is released, and the cis isomer is generated outside the cavity. In subsequent re-complexation, the cis isomer is then re-captured through the wider secondary portal. Therefore, our findings point to two significantly different complexation processes depending on substitutional pattern and binding constant values of azopyrimidines, a feature which may lead to future promising applications.

Název v anglickém jazyce

A study of azopyrimidine photoswitches and their interactions with cyclodextrins: When the guest governs the type of accommodation at the host

Popis výsledku anglicky

Azopyrimidines have recently emerged as a new class of photoswitches structurally similar to azobenzenes switching between trans and cis isomers. These compounds have a wide range of potential applications in photopharmacology, catalysis or as molecular devices, but their low solubility in water limits their biological applications. Nevertheless, this drawback could be overcome by their inclusion into supramolecular structures. To test this hypothesis, we prepared a series of azopyrimidines and investigated their structure, cis-trans isomerization and host-guest chemistry with cyclodextrins (CDs) using an experimental-theoretical approach combining capillary electrophoresis (CE), Nuclear Magnetic Resonance (NMR) spectroscopy and computational models. The results revealed that β-CD exhibits high selectivity over several CDs tested for the accommodation of the studied compounds. Orientation of guests in inclusion complexes was experimentally assessed by Nuclear Overhauser Effect (NOE) contacts and supported by quantum-chemical calculations. Moreover, investigation of noncovalent interactions of azopyrimidines with β-CD by CE showed that azopyrimidines with suitable structural modification can form strong complexes with high values of binding constants (over 17 000 L mol−1). For such complexes, trans-cis isomerization proceeds directly inside the β-CD cavity with azopyrimidine remaining encapsulated through its narrower primary portal. By contrast, in weakly interacting complexes, the trans isomer is released, and the cis isomer is generated outside the cavity. In subsequent re-complexation, the cis isomer is then re-captured through the wider secondary portal. Therefore, our findings point to two significantly different complexation processes depending on substitutional pattern and binding constant values of azopyrimidines, a feature which may lead to future promising applications.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10406 - Analytical chemistry

Projekt

<a href="/cs/project/GA20-03899S" target="_blank" >GA20-03899S: Afinitní kapilární elektrokinetické metody pro selektivní analýzu biopolymerů a metabolitů a pro studium jejich interakcí</a><br>

Návaznosti

I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Rok uplatnění

2023

Kód důvěrnosti údajů

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

Název periodika

Dyes and Pigments

ISSN

0143-7208

e-ISSN

1873-3743

Svazek periodika

212

Číslo periodika v rámci svazku

April

Stát vydavatele periodika

GB - Spojené království Velké Británie a Severního Irska

Počet stran výsledku

10

Strana od-do

111099

Kód UT WoS článku

000921063400001

EID výsledku v databázi Scopus

2-s2.0-85146436530