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

Result code in 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>

Alternative codes found

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

Result on the web

<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>

Result language

angličtina

Original language name

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

Original language description

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.

Czech name

—

Czech description

—

Type

J_imp - Article in a specialist periodical, which is included in the Web of Science database

CEP classification

—

OECD FORD branch

10406 - Analytical chemistry

Project

<a href="/en/project/GA20-03899S" target="_blank" >GA20-03899S: Affinity capillary electrokinetic methods for selective analysis of biopolymers and metabolites and for study of their interactions</a><br>

Continuities

I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Publication year

2023

Confidentiality

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

Name of the periodical

Dyes and Pigments

ISSN

0143-7208

e-ISSN

1873-3743

Volume of the periodical

212

Issue of the periodical within the volume

April

Country of publishing house

GB - UNITED KINGDOM

Number of pages

10

Pages from-to

111099

UT code for WoS article

000921063400001

EID of the result in the Scopus database

2-s2.0-85146436530