RT info:eu-repo/semantics/article
T1 Competitive Hydrogen-Bond Partitioning in Deep Eutectic Solvents: From Cooperative Charge Spreading to Structure–Property Design Rules
A1 Huerta Sainz, Sergio de la
A1 Santamaría, Sara
A1 Escobedo Monge, María Antonieta
A1 Trenzado, José L.
A1 Diez Cabanes, Valentin
A1 Gutiérrez Vega, Alberto
A1 Marcos Villa, Pedro A.
A1 Bol Arreba, Alfredo
A1 Atilhan, Mert
A1 Aparicio Martínez, Santiago
K1 Mathematical methods
K1 Viscosity
K1 Solvents
K1 Physical and chemical properties
K1 Noncovalent interactions
K1 Hidrógeno
K1 Hydrogen
K1 Disolventes
K1 Solvents
AB Deep eutectic solvents (DESs) owe their remarkable melting-point depression, high viscosity, and tunable solvation to a hydrogen-bond network far richer than the binary donor–acceptor picture suggests. This study advances the framework of competitive hydrogen-bond partitioning: ionic Cl–···H–X interactions, neutral donor–donor self-association, cation-mediated contacts, and water-competitive motifs coexist and continuously redistribute as a function of composition, temperature, and interfacial confinement. Evidence is synthesized from vibrational spectroscopy, multinuclear NMR, neutron and X-ray scattering, dielectric relaxation, classical and ab initio molecular dynamics, DFT cluster calculations, and machine-learning potentials, establishing that no single technique can fully characterize the network─a triangulation criterion requiring at least two independent method categories is essential. A quantitative structure–property framework is developed linking six hydrogen-bond descriptors─motif population, persistence distribution, network connectivity, competitive hydration index, dynamic heterogeneity, and interfacial partitioning─to viscosity, conductivity, diffusion, and glass transition across Type III, Type V, Natural DES (NADES), and hydrophobic DES. A central finding is the cooperativity–mobility tradeoff: cooperative charge spreading at Cl– simultaneously drives eutectic depression and network rigidity, defining a design axis along which DES can be rationally positioned. Water is analyzed as both competitive and cooperative partner across four hydration regimes, and interfacial hydrogen-bond reorganization at electrodes─largely neglected in prior studies─is critically examined. An integrated characterization workflow with standardized reporting criteria, validated force-field benchmarks, and data-driven descriptors for predictive screening is proposed.
PB ACS Publications
SN 2470-1343
YR 2026
FD 2026-07
LK https://hdl.handle.net/10259/11993
UL https://hdl.handle.net/10259/11993
LA eng
NO This work has been funded by Agencia Estatal de Investigación (Project NADESforPFAS, ref.: PID2022-142405OB-I00) and Junta de Castilla y León (Project NADES4NATURE, ref.: BU047P23).
DS Repositorio Institucional de la Universidad de Burgos
RD 03-oct-2026