Connecting chloride solvation with hydration in deep eutectic systems

Pietro, Maria Enrica Di; Hammond, Oliver S.; Bruinhorst, Adriaan van den; Mannu, Alberto; Pádua, Agı́lio A. H.; Mele, Andrea; Gomes, Margarida F. Costa

doi:10.1039/d0cp05843b

Cited by 42 publications

(48 citation statements)

References 58 publications

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“…This behavior more closely resembles that observed for aqueous mixtures of other DESs like the ChCl/urea and ChCl/glycolic acid ones, where homogeneity at the nanoscale level was maintained due to the ability of interspersed water to enter the local cluster formed by the chloride anion. 14 , 16 …”

Section: Resultsmentioning

confidence: 99%

“…Besides the study of “pure” DESs, interest has recently been devoted to DES mixtures formed upon cosolvent addition. 14 − 22 Indeed, the addition of molecular solvents such as water, alcohols, or alkanes, has been shown to dramatically affect several DES key properties like density, viscosity, conductivity, CO 2 solubility, and enzyme activity, 23 − 28 eventually providing eutectics with enhanced performances and lower costs. 22 , 29 Cosolvent addition, therefore, represents a further designing strategy that is often less resource-demanding instead of acting on the chemical nature of the DES constituents, allowing optimization within the field of green chemistry, waste reduction, and E-factor improvement.…”

Section: Introductionmentioning

confidence: 99%

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Fate of a Deep Eutectic Solvent upon Cosolvent Addition: Choline Chloride–Sesamol 1:3 Mixtures with Methanol

Busato

Giudice

Lisio

et al. 2021

ACS Sustainable Chem. Eng.

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The changes upon methanol (MeOH) addition in the structural arrangement of the highly eco-friendly deep eutectic solvent (DES) formed by choline chloride (ChCl) and sesamol in 1:3 molar ratio have been studied by means of attenuated total reflection Fourier transform infrared spectroscopy, small- and wide-angle X-ray scattering (SWAXS), and molecular dynamics simulations. The introduction of MeOH into the DES promotes the increase of the number of Cl–MeOH hydrogen bonds (HBs) through the replacement of sesamol and choline molecules from the chloride anion coordination sphere. This effect does not promote the sesamol–sesamol, choline–choline, and sesamol–choline interactions, which remain as negligible as in the pure DES. Differently, the displaced sesamol and choline molecules are solvated by MeOH, which also forms HBs with other MeOH molecules, so that the system arranges itself to keep the overall amount of HBs maximized. SWAXS measurements show that this mechanism is predominant up to MeOH/DES molar ratios of 20–24, while after this ratio value, the scattering profile is progressively diluted in the cosolvent background and decreases toward the signal of pure MeOH. The ability of MeOH to interplay with all of the DES components produces mixtures with neither segregation of the components at nanoscale lengths nor macroscopic phase separation even for high MeOH contents. These findings have important implications for application purposes since the understanding of the pseudophase aggregates formed by a DES with a dispersing cosolvent can help in addressing an efficient extraction procedure.

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Fate of a Deep Eutectic Solvent upon Cosolvent Addition: Choline Chloride–Sesamol 1:3 Mixtures with Methanol

Busato

Giudice

Lisio

et al. 2021

ACS Sustainable Chem. Eng.

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“…4 Among the most well-known DES, we recall the stoichiometric 1:2 mixture of choline chloride (CC) and urea (U), sometimes referred to as reline. [9][10][11][12][13][14][15][16] Dry reline melts at ca. 31 °C 17 and has attracted huge interest over the last few years.…”

Section: Introductionmentioning

confidence: 99%

Liquid structure and dynamics in the choline acetate:urea 1:2 deep eutectic solvent

Triolo

Pietro

Celso

et al. 2021

The Journal of Chemical Physics

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We report on the thermodynamic, structural and dynamic properties of a recently proposed Deep Eutectic Solvent (DES), formed by choline acetate and urea at the stoichiometric ratio 1:2, hereinafter indicated as acetaline. Acetaline, although melting at ca. 40 °C, can be easily supercooled in its liquid state at sub-ambient conditions. The existence of a crystalline phase has been detected, together with the glass-liquid transition at -50 °C. Synchrotron high energy X-ray scattering experiments provide the experimental data for supporting a Reverse Monte Carlo analysis to extract structural information at atomistic level. This exploration of acetaline's liquid structure reveals the major role played by hydrogen bonding in determining interspecies correlations: both acetate and urea are strong hydrogen bond acceptor sites, while both the choline hydroxyl and urea act as HB donors. All acetaline moieties are involved in mutual interactions, with acetate and urea strongly interacting through hydrogen bonding, while choline being involved mostly in van der Waals mediated interactions. Such a structural situation is mirrored by the dynamic evidences obtained by means of 1 H NMR techniques, that show how urea and acetate species experience higher translational activation energy than choline, fingerprinting their stronger commitments into the extended hydrogen bonding network established in acetaline.

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“…As a matter of fact, a threefold increase in ChCl:U in water coincides with an upturn of T t for sDNA of only 2 K. This finding could be related to the specific characteristics of DES in solution and the prevalence of DES-DES over DES-sDNA interactions as the ChCl:U concentration increases. It is widely reported in the literature that the presence of water weakens the strong interactions among ChCl:U components and contributes to different solvation features of the individual DES components [43][44][45]. In this regard, we can consider the lowest concentration sample as a highly diluted solution of ChCl:U (i.e., 15 mol DES:1 mol H 2 O), in which the DES individual components may exchange the ligands of their solvation shell by binding to DNA guanine moieties, i.e., by establishing hydrogen bonding, and thus exert their thermal stabilizing effect.…”

Section: Discussionmentioning

confidence: 99%

Effect of Hydrated Deep Eutectic Solvents on the Thermal Stability of DNA

et al. 2021

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DNA’s structure stability in hydrated deep eutectic solvents (DESs) is getting growing attention for emerging bio-applications. The employment of DESs as novel co-solvents in water media could favor eco-friendly and biodegradable materials for DNA storage and handling. Understanding the molecular interactions between nucleic acids and aqueous DES is crucial for developing new-generation solvents for biomolecules. In this work, we exploit the molecular sensitivity and selectivity of synchrotron radiation UV resonance raman (SR-UVRR) spectroscopy to explore the interplay between a choline chloride:urea (ChCl:U) DES and double-stranded DNA. Our study analyzes the impact of ChCl:U on the DNA’s thermal unfolding pathway by focusing on the guanine nucleobases whose Raman signal could be strongly enhanced through careful tuning of the excitation wavelength.

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Connecting chloride solvation with hydration in deep eutectic systems

Abstract: The Deep Eutectic Solvents (DESs) choline chloride:urea (xChCl = 0.33) and choline chloride:glycolic acid (xChCl = 0.5) were studied using viscosity-corrected 35Cl NMR and MD simulations to probe the role of chloride as a function of water content.

Cited by 42 publications

References 58 publications

Fate of a Deep Eutectic Solvent upon Cosolvent Addition: Choline Chloride–Sesamol 1:3 Mixtures with Methanol

Fate of a Deep Eutectic Solvent upon Cosolvent Addition: Choline Chloride–Sesamol 1:3 Mixtures with Methanol

Liquid structure and dynamics in the choline acetate:urea 1:2 deep eutectic solvent

Effect of Hydrated Deep Eutectic Solvents on the Thermal Stability of DNA

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