Direct Observation of Solvated Electrons in Deep Eutectic Solvents: Efficient Capture of Presolvated Electrons by DNA Base

Abstract

The solvated electron being the simplest form of an extremely reactive intermediate is of great fundamental interest in chemistry, physics, and biology since its discovery. Recently, deep eutectic solvents (DESs) have been in focus as biodegradable and cost-effective alternative to ionic liquids (ILs) for different applications. These include areas where electron transport and transfer processes are involved. Herein, we present the first report on the existence, yield, and properties of solvated electrons in three deep eutectic solvents, reline, ethaline, and glyceline, composed of choline chloride as a hydrogen bond acceptor and urea, ethylene glycol, and glycerol (Gly) as hydrogen bond donors, respectively, at a molar ratio of 1:2. The varied transient absorption spectra of solvated electrons in these DESs have been explained on the basis of polarity, hydrogen-bonding effect, and the moieties responsible for creating the environment for solvation. The yield and average lifetime follow the trends in viscosity as well as the reactivity of electrons with the components. The C value, a measure of the efficiency of scavenging presolvated electrons, is the highest in ethaline in the case of nitrate ions, which indicates the slowest solvation process in this DES. The presolvated electron capture by a DNA base, an aspect considered to be important in cancer radiotherapy, could be monitored conveniently in these liquids at a much longer time scale compared to that reported in aqueous solutions. Bimolecular rate constants for the reaction of solvated electrons with nitrate and the DNA base have been calculated and compared in the three DESs. Unlike in ILs, these experimentally obtained values are comparable to the diffusion-controlled rate constants in DESs.

Deep eutectic solvents as green solvents for materials preparation

“…The solvated electron has also been observed in DES, and this provides the possibility of enzyme-catalyzed reactions in DESs. 57 According to a publication by Milano et al, the photosynthetic reaction center of bacteria (Rhodobacter sphaeroides) in DESs can generate a charge-separation state and even perform its natural light cycle. 58 This discovery not only verified the good maintenance of the protein structure in DESs, but also implied that DESs possess excellent electron solvation and transport properties.…”

“…58 This discovery not only verified the good maintenance of the protein structure in DESs, but also implied that DESs possess excellent electron solvation and transport properties. 57 When considered for electrochemical applications, fast electron transfer in DESs is a strong advantage. Different types of solvent systems are critical to energy storage density.…”

Conversions of localized excess electrons and spin states under external electric field: Inter‐cage electron‐transfer isomer (C20F20)3&K2

“…As a simplest form of extremely reactive intermediate, the investigation of the solvated electron plays a prominent role in physics, chemistry, and biochemistry [7–15]. For example, Adhikari et al have reported efficient capture of presolvated electrons by DNA base [11].…”

“…As a simplest form of extremely reactive intermediate, the investigation of the solvated electron plays a prominent role in physics, chemistry, and biochemistry [7][8][9][10][11][12][13][14][15]. For example, Adhikari et al have reported efficient capture of presolvated electrons by DNA base [11]. Also, considering the charge-and electron-transfer transitions, manipulation of one or several electrons at molecular level remains a highly challenging task [6,16,17].…”

Molecular Spin Switch and Conversions of Localized Excess Electrons under External Electric Field: Solvated Dielectron C20F20@K@C20F20@K@C20F20

“…[1][2][3][4][5] As the simplest form of an extremely reactive intermediate, the investigation of the solvated electron plays a prominent role in physics, chemistry, and biochemistry. [6][7][8][9][10][11][12][13][14] For example, Adhikari et al have reported efficient capture of presolvated electrons by DNA base. 10 Also, for the charge-and electron-transfer and the transitions, manipulation of one or several electrons at the molecular level remains a highly challenging task 15 considering the utmost importance in the related fields of molecular electronics, 16 artificial photosynthesis, 15,17 molecular switches, 15,18 quantum-dot cellular automata (QCA), [19][20][21] solar cells, 22 and supramolecular assemblies.…”