Despite being one of the most familiar substances on Earth, water still holds secrets scientists are working to unravel.
When confined to extremely small spaces, such as inside proteins, minerals, or artificial nanomaterials, water behaves very differently from its bulk liquid form.
These confinement effects are crucial in nature and technology. They regulate the flow of ions through cell membranes and determine the performance of nanofluidic systems.
Understanding how water behaves at this scale could open doors to biological and material innovations.
One particularly intriguing phase of confined water is called the “premelting state.” In this unusual condition, water appears to hover between freezing and melting simultaneously, resisting classification as a liquid or solid.
Yet, studying it has been notoriously difficult, as traditional techniques often miss the fast movements of hydrogen atoms within water molecules.
A research team from the Tokyo University of Science, led by Professor Makoto Tadokoro with Lecturer Fumiya Kobayashi and PhD student Tomoya Namiki, has now made a breakthrough.
Their study reports the direct observation of the premelting state using advanced nuclear magnetic resonance (NMR) spectroscopy.
Layers within liquid crystals
To run their experiments, the team created hexagonal rod-like crystals with channels about 1.6 nanometers wide. They then filled these nanopores with heavy water (D₂O).
By measuring NMR spectra at room temperature, they identified a three-layered structure of confined water molecules, each layer showing distinct movements and hydrogen-bonding interactions.
The data revealed that water inside nanopores freezes into a different structure than bulk ice. Importantly, it begins to melt through a distorted hydrogen-bonded arrangement, giving rise to the premelting state.
To study this new phase, the team gradually heated the crystal from frozen to liquid conditions. This allowed them to track the transition and confirm the existence of two seemingly contradictory states.
“The premelting state involves the melting of incompletely hydrogen-bonded H₂O before the completely frozen ice structure starts melting during the heating process. It essentially constitutes a novel phase of water in which frozen H₂O layers and slowly moving H₂O coexist,” explains Prof. Tadokoro.
Frozen yet moving fast
The researchers also measured the rotational mobility of heavy water molecules in this phase. They found that while the activation energy differed from bulk ice, the correlation time was close to that of bulk liquid water. In simple terms, the molecules were locked into solid-like positions but still rotated at liquid-like speeds.
These findings provide critical insights into the structural and dynamic behavior of confined water. Beyond biology, they could shape future technologies.
“By creating new ice network structures, it may be possible to store energetic gases such as hydrogen and methane and develop water-based materials such as artificial gas hydrates,” says Prof. Tadokoro.
Such control over water’s freezing and melting properties could lead to safer and more efficient materials, potentially transforming energy storage and nanotechnology.
Ultimately, the study highlights how even the world’s most common substance continues to surprise scientists. Water, despite its familiarity, still hides phases and behaviors waiting to be uncovered.
The findings of the study have been published in the Journal of the American Chemical Society.