Current Understanding of Water Properties inside Carbon Nanotubes

Confined water inside carbon nanotubes (CNTs) has attracted a lot of attention in recent years, amassing as a result a very large number of dedicated studies, both theoretical and experimental. This exceptional scientific interest can be understood in terms of the exotic properties of nanoconfined water, as well as the vast array of possible applications of CNTs in a wide range of fields stretching from geology to medicine and biology. This review presents an overreaching narrative of the properties of water in CNTs, based mostly on results from systematic nuclear magnetic resonance (NMR) and molecular dynamics (MD) studies, which together allow the untangling and explanation of many seemingly contradictory results present in the literature. Further, we identify still-debatable issues and open problems, as well as avenues for future studies, both theoretical and experimental.

Specific Heat Capacity of Confined Water in Extremely Narrow Graphene Nanochannels

Specific heat capacity of extremely confined water determines its performance in the heat transfer as the sizes of devices decrease to nanoscales. Here, we report the basic data of the specific heat capacity of water confined in narrow graphene nanochannels below 5 nm in height using molecular dynamics simulations. The results show that the specific heat capacity of confined water is size-dependent, and the commensurability effect of the specific heat capacity presents as the confinement decreases to 1.7 nm. The deviation of specific heat capacity of confined water with that of bulk water is attributed to the variation of configuration features, including density distribution and hydrogen bonds, and vibration features, including velocity auto-correlation function and vibrational density of states. This work unveils the confinement effects and their physical mechanisms of the specific heat capacity of nanoconfined water, and the data provided here have wide prospects for energy applications at nanoscales.

Nanoconfined Water in Shales and Its Impact on Real Gas Flow

The presence of water, i.e., connate or hydraulic fracturing water, along with the gaseous hydrocarbons in shale nanopores is largely overlooked by previous studies. In this work, a new unified real gas-transport model has been developed for both organic and inorganic porous media accounting for the nanoconfined water film flow. More specifically, a gas core flows in the center of the organic/inorganic pore surrounded by a water film which can be further divided into an interfacial region (near-wall water) and bulk region (bulk water). We differentiate the varying water viscosity between the two regions and consider disparate slip boundaries; that is, the near-wall water can slip along the hydrophobic organic pore surface while it is negligible in hydrophilic inorganic pores. Incorporating modified boundary conditions into the Navier-Stokes equations, gas transport model through single organic/inorganic pore is derived. The model is also comprehensively scaled up to the porous media scale considering the porosity, tortuosity, and total organic carbon (TOC) contents. Results indicate that the gas flow capacity decreases in moist conditions with mobile or nonmobile water film. A mobile water film, however, compensates its negative effect up to 50% by enhancing gas flow compared with static water molecules. The real gas flow is dominated by the gas slippage and water film mobility which are dependent upon pore-scale parameters such as pore sizes, topology, pressure, and surface wettability. Compared with inorganic pores, gas transport in organic pores is greatly enhanced by the water film flow due to the strong water slip. Moreover, the contribution of water film mobility is remarkable in small pores with large contact angles, especially at high pressures. At moist conditions, the real gas effect enhances gas flow by improving both gas slippage and water film mobility, which is more prominent in smaller pores at high pressures. The presented model and its results will further advance our understanding of the mechanisms responsible for the water and gas transport in nanoporous media, and consequently, the hydrocarbon exploration of shale reservoirs.

Abiotic RNA Formation in Natural Nanoconfinements of Water: Overcoming the Water Paradox via a Nanofluidic Bridge Between Geochemistry and Biochemistry

<p class="western">The "water paradox" is an obstinate problem in the research on the chemical evolution towards the emergence of life. It states that although aqueous environments are essential for life, they hamper key condensation reactions such as nucleotide polymerisation. To overcome this paradox several hypotheses have been proposed, including scenarios based on alternative solvents like formamide, condensing agents like cyanamide, high temperatures of over 150 °C or wet/dry cycles in surface ponds. However, when appraising the prebiotic plausibility of such scenarios some general weaknesses appear. Besides the fact that all known life manages the water paradox without needing such proposed conditions, the principle that evolution builds on existing pathways indicates that the same physicochemical effects were probably involved in the abiotic origin of biopolymers as now being tapped by life via complex enzymes.</p> <p class="western">Here we show that abiotic temporal nanoconfinements of water can act as natural reactions vessels for prebiotic RNA formation. We present evidence for spontaneous, abiotic polymerisation of nucleotides in water. According to our results the reaction is enabled by the rise of anomalous properties of water when being temporarily confined between nanoscale separated particles of geological ubiquity within aqueous suspensions. These findings can solve the water paradox in such a way that nanofluidic effects in aqueous particle suspensions open up an abiotic route to biopolymerisation and polymer stabilisation under chemical and thermodynamic conditions which also exist within the intracellular environment of living cells. The fact that polymerase enzymes also form temporal nanoconfined water clusters inside their active site implies that the same physico-chemical effects are tapped for nucleotide condensation in water both by biochemical pathways and the reported abiotic route. This indicates that our model is consistent with evolutionary conservatism stretching back to the era of prebiotic chemical evolution. The consistency is further supported by the fact that water is not trapped by nanoconfinements within the polymerase core but can exchange with the surrounding intracellular fluid – a situation which is also prevalent in nanofluidic environments within aqueous particle suspensions. Our experimental finding that under the reported conditions an amino acid catalyses the abiotic polymerisation of nucleotides may give a hint to a nanofluidic origin of cooperation between amino acids and nucleotides evolving to the interdependent synthesis of proteins and nucleic acids in living cells.</p> <p class="western">The effect of abiotic RNA polymerisation in temporal nanoconfined water does not depend on highly specific mineral species and geological environments as watery suspensions of micro- and nanoparticles are virtually ubiquitous – they exist, for example, in the form of sediments with pore water, hydrothermal vent fluids containing precipitated inorganic and polyaromatic particles or dispersed aggregates inside water-filled cracks in the crust of the earth and possibly of icy moons in the outer solar system.</p> <p class="western"><strong>References</strong></p> <p class="western">Greiner de Herrera, A., Markert, T. & Trixler, F. Temporal nanofluidic confinements induce prebiotic condensation in water. Preprint, DOI: 10.21203/rs.3.rs-163645/v3</p>