Spectroscopic and theoretical studies of fluorescence effects induced by the ESIPT process in a new derivative 2-Hydroxy-N-(2-phenylethyl)benzamide - Study on the effects of pH and medium polarity changes.

Agnieszka Niemczynowicz,Dariusz Karcz,Andrzej Górecki,Marcin Makowski,Agnieszka I Piotrowicz-Cieślak,Karolina Starzak,Sławomir Kulesza,Arkadiusz Matwijczuk,Bożena Gładyszewska,Janusz Podleśny,Iwona Budziak,Danilo Roccatano

doi:10.1371/journal.pone.0229149

Abstract

The paper presents the results of studies conducted with the use of stationary and time-resolved fluorescence spectroscopy for the new derivative 2-Hydroxy-N-(2-phenylethyl)benzamide (SAL-3) in aqueous solutions with various concentrations of hydrogen ions as well as in solvent mixtures (i.e. media with changing polarity/polarizability). For the compound selected for the study placed in aqueous solutions with varying concentrations of hydrogen ions, the fluorescence emission spectra revealed a single emission band within most of the pH range, however, at low pH (pH<3) a significant broadening (noticeable effect of dual fluorescence) and shifting of the band was observed. Whereas, for water and polar (protic) solvents, we observed a very interesting phenomenon of dual fluorescence never before reported for this particular group of analogues (with the specific substituent system). Based on the results of the experiments, it was observed that the presented effects may be related both with conformational effects (related to the possible positioning of the–OH group on the side of the carbonyl system, which facilitates the possibility of proton transfer) as well as, most importantly, the effects of excited state intramolecular proton transfer (ESIPT–Excited State Intramolecular Proton Transfer) related in this case with the necessary (new/previously unobserved in published literature) presence of ionic and non-ionic forms of the compound). Both the conducted quantum-mechanical [TD]DFT–Time-Dependent Density Functional Theory) calculations and excited state dipole moment change calculations for the analyzed molecule in solvents with varying pH confirmed the association between the observed fluorescence phenomena and the two aforementioned effects.

Highlights

Salicylic acid (SA) and its derivatives are commonly found in plants
The powder of the compound itself was analyzed with the use of Atomic Force Microscopy (AFM) measurements and the results were provided in S1–S5 Figs enclosed in Supplementary Materials
With increasing content of water we observed a significant increase in the intensity of the resonance light scattering (RLS) spectra, which may confirm the presence of aggregation effects that may coincide with various forms of the compound, e.g. ionic and non-ionic

Summary

Introduction

Salicylic acid (SA) and its derivatives (phenylpropanoids) are commonly found in plants. Their changes are related to the plant’s defensive reaction to biotic and abiotic stress [1]. Some derivatives of salicylic acid, such as 2-hydroxy-N-(arylalkyl)benzamides, show antimicrobial activity against microscopic fungi and various bacterial strains, including mycobacteria [3], whereas several other compounds are capable of inhibiting the proliferation and vitality of human cancer cells [4]. Vestergr) is one of the main diseases encountered in pea cultivations [5] It occurs commonly in the fields of Europe, North America, Australia and New Zealand [6] and, on average, leads to a 10% decrease in yields, whereas in years when the temperature and humidity conditions are unfavorable, yield losses can exceed 50% [5]. It is important to discover the photochemical/photophysical properties of 2-hydroxy-N-(2-phenylethyl)benzamide in order to use it as a viable crop protection agent

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