A vibration-charge-induced unidirectional transport of water molecules in confined nanochannels

The transport of water molecules through nanopores is not only crucial to biological activities but also useful for designing novel nanofluidic devices. Despite considerable effort and progress that has been made, a controllable and unidirectional water flow is still difficult to achieve and the underlying mechanism is far from being understood. In this paper, using molecular dynamics simulations, we systematically investigate the effects of an external electric field on the transport of single-file water molecules through a carbon nanotube (CNT). We find that the orientation of water molecules inside the CNT can be well-tuned by the electric field and is strongly coupled to the water flux. This orientation-induced water flux is energetically due to the asymmetrical water-water interaction along the CNT axis. The wavelike water density profiles are disturbed under strong field strengths. The frequency of flipping for the water dipoles will decrease as the field strength is increased, and the flipping events vanish completely for the relatively large field strengths. Most importantly, a critical field strength E(c) related to the water flux is found. The water flux is increased as E is increased for E ≤ E(c), while it is almost unchanged for E > E(c). Thus, the electric field offers a level of governing for unidirectional water flow, which may have some biological applications and provides a route for designing efficient nanopumps.

Optimizing water resource utilization is a critical challenge to meet the dramatic increase in food demand. Therefore, continuous studies to minimize water demand for plants are highly needed. This study aims to employ HYDRUS (2D/3D) software to simulate the effects of continuous and intermittent water flow on soil water distribution under a subsurface point source. The constant parameters included loamy sand soil, a water application time of 30 min, and an emitter discharge of 3.41 L/h. The variable parameters consisted are two pipe depths (25 cm and 35 cm), three ratios of ON:OFF times (1ON:1OFF, 1ON:3OFF, and 1ON:5OFF), and five water application cycles (WF1C, WF2C, WF3C, WF4C, and WF5C, with WF1C as for the continuous water flow). The results revealed that, in 30 min of water application, continuous water flow and ON:OFF ratios of 1ON:1OFF and 1ON:3OFF achieved maximum water retention in the vicinity of the emitter. In 60 min, increasing cycles enhanced retention for 1ON:1OFF and 1ON:3OFF, yet the 1ON:5OFF time ratio achieved the highest water content near the emitter. In 120 min, the 1ON:1OFF ratio showed an insignificant effect with cycle variations, but 1ON:3OFF and 1ON:5OFF exhibited increased retention. Similarly, in 180 min, 1ON:1OFF was unaffected by cycles, whereas 1ON:3OFF and 1ON:5OFF significantly improved retention. After 360 min, all treatments displayed equal water retention relative to the emitter position. Also, the results revealed that increasing water application cycles and ON:OFF time ratios lead to more holding soil water content, especially at soil levels of 20, 30, and 40 cm. These results affirm that positioning the emitters line at 25 cm enhances water retention more effectively than at 35 cm. Ultimately, statistical analysis confirmed that the combination of pipe depth, water application cycles, and ON:OFF ratios significantly affects the retention of soil water content in the vicinity of the emitter.

Using molecular dynamics simulations, we demonstrate pumping of water through a carbon nanotube by applying the combination of a rotating electric field and a rotating magnetic field. The driving force is a Lorentz force generated from the motion of charges in the magnetic field, and the motion is caused by the rotation of the electric field. We find that there exits a linear relationship between the average pumping velocity v and magnetic field strength B, which can be used to control the flux of the continuous unidirectional water flow. This approach is expected to be used in liquid circulation without a pressure gradient.

The properties of a nanotube, such as the hydrophobicity and charge of the surface, can significantly affect water transport behavior. However, our knowledge of the effects of charge density, dipole orientation, frequency of flipping, and movement behavior on water flow through carbon nanotubes (CNTs) is far from adequate. This study is aimed at gaining insight into the transport of single-file water molecules in a charged carbon nanotube. It was shown that the water chains inside the charged nanotube exhibit bipolar properties. The water dipoles are parallel to the z-axis, and point toward (D-defect) and away from (L-defect) the center of the nanotube for a negatively charged nanotube and a positively charged one, respectively. Compared with a pristine single-wall carbon nanotube (SWCNT), the charged nanotubes, including both positively charged and negatively charged, favor the water-filling process due to electrostatic interactions. According to the dipole distribution in the nanotube, the water dipole only flips in the middle region because of the bipolar nature of water chains. Additionally, flipping of the entire water chain is inhibited, which allows for the enhanced water flux. A negatively charged single-walled carbon nanotube (N-SWCNT) accelerated water transport by tuning the single-file flow from a "hopping" to a "continuous" mode, thus decreasing the energy barrier. The hydrogen bonds between water molecules inside the nanotube are also strengthened in the negatively charged nanotube, favoring water transport. Any distortion of uniformity will lead to additional energy barriers to water flux. Our results provide a comprehensive view of molecular events underpinning the water transport inside a SWCNT, which may be of assistance in creating innovative designs for water nanochannels.

This study performs a series of Molecular Dynamics (MD) and Molec- ular Statics (MS) simulations to investigate the mechanical properties of single- walled carbon nanotubes (SWCNTs) under a uniaxial tensile strain. The simula- tions focus specifically on the effects of the nanotube helicity, the nanotube diame- ter and the percentage of vacancy defects on the bond length, bond angle and tensile strength of zigzag and armchair SWCNTs. In this study, a good agreement is ob- served between the MD and MS simulation results for the stress-strain response of the SWCNTs in both the elastic and the plastic deformation regimes. The MS simulations reveal that in the plastic deformation regime, the tensile strength of the armchair and zigzag SWCNTs increases with an increasing wrapping angle. In addition, it is shown that the tensile strength reduces significantly at larger val- ues of the nanotube diameter. Moreover, it is observed that the tensile strength of both SWCNTs reduces as the percentage of defects within the nanotube structure increases. Finally, it is found that the results obtained from the molecular statics method are relatively insensitive to instabilities in the atomic structure, particularly in the absence of thermal fluctuations, and are in good agreement with the predic- tions obtained from the molecular dynamics method.

Chapter 8 - Technologically Relevant Applications

Achieving a fast, unidirectional flow of single-file water molecules (UFSWM) across nanochannels is important for membrane-based water purification or seawater desalination. For this purpose, electro-osmosis methods are recognized as a very promising approach and have been extensively discussed in the literature. Utilizing molecular dynamics simulations, here we propose a design for pumping water molecules in a single-walled carbon nanotube in the presence of a linearly gradient electric (GE) field. Such a GE field is inspired by GE fields generated from charged ions located adjacent to biological membrane water nanochannels that can conduct water in and out of cells and can be experimentally achieved by using the charged tip of an atomic force microscope. As a result, the maximum speed of the UFSWM can be 1 or 2 orders of magnitude larger than that in a uniform electric (UE) field. Also, inverse transportation of water molecules does not exist in case of the GE field but can appear for the UE field. Thus, the GE field yields a much more efficient UFSWM than the UE field. The giant pumping ability as revealed is attributed to the nonzero net electrostatic force acting on each water molecule confined in the nanotube. These observations have significance for the design of nanoscale devices for readily achieving controllable UFSWM at high speed.

Oil–water two-phase flow velocity measurement with continuous wave ultrasound Doppler

Classical molecular dynamics (MD) simulation has been carried out in an explicit solvent environment to understand the interaction between the single walled carbon nanotube (SWCNT) and α-helix. A polyalanine peptide consisting of 40 alanine residues has been chosen as the model for the α-helix (PA(40)). Results reveal that the SWCNT induces conformational changes in PA(40). Furthermore, breakage of hydrogen bonds in the chosen model peptides has been observed, which leads to conformational transitions (α → turns) in different parts of the PA(40). Owing to these transitions, regions of different structural and energetic stability are generated in PA(40) which enable the PA(40) to curl around the surface of the SWCNT. The overall observations obtained from the MD simulations are not significantly influenced by the starting geometry and the choice of the force field. Although the qualities of structural information obtained from the MD simulation using ff03 and OPLS are different, the overall observation derived from the ff03 is similar to that of OPLS. Results from the MD simulation on the interaction of the α-helical fragment of the SNARES protein with the SWCNT elicit that the amino acid composition influences the interaction pattern. The wrapping of the α-helical fragment of the SNARES onto the SWCNT is similar to that of PA(40). Overall, there is a considerable decrease in the helical content of peptides upon interaction with SWCNTs, in agreement with the experimental findings.

An aqueous environment is vital for life as we know it, and water is essential for nearly all biochemical processes at the molecular level. Proteins utilize water molecules in various ways. Consequently, proteins must transport water molecules across their internal network of tunnels to reach the desired action sites, either within them or by functioning as molecular pipes to control cellular osmotic pressure. Despite water playing a crucial role in enzymatic activity and stability, its transport has been largely overlooked, with studies primarily focusing on water transport across membrane proteins. The transport of molecules through a protein's tunnel network is challenging to study experimentally, making molecular dynamics simulations the most popular approach for investigating such events. In this study, we focused on the transport of water molecules across three different α/β-hydrolases: haloalkane dehalogenase, epoxide hydrolase, and lipase. Using a 5 μs adaptive simulation per system, we observed that only a few tunnels were responsible for the majority of water transport in dehalogenase, in contrast to a higher diversity of tunnels in other enzymes. Interestingly, water molecules could traverse narrow tunnels with subangstrom bottlenecks, which is surprising given the commonly accepted water molecule radius of 1.4 Å. Our analysis of the transport events in such narrow tunnels revealed a markedly increased number of hydrogen bonds formed between the water molecules and protein, likely compensating for the steric penalty of the process. Overall, these commonly disregarded narrow tunnels accounted for ∼20% of the total water transport observed, emphasizing the need to surpass the standard geometrical limits on the functional tunnels to properly account for the relevant transport processes. Finally, we demonstrated how the obtained insights could be applied to explain the differences in a mutant of the human soluble epoxide hydrolase associated with a higher incidence of ischemic stroke.

Water pollution and freshwater shortage have deteriorated the global water crisis. Developing sustainable methods to alleviate contaminated water has become an urgent affair. Herein, inspired by water transportation and transpiration of natural trees, the authors report an ultralong hydroxyapatite nanowires‐based biomimetic aerogel with vertically aligned channels and multiple functions for continuous flow catalysis, water disinfection, solar energy‐driven water purification, and seawater desalination. Ultralong hydroxyapatite nanowires act as carriers to immobilize catalyst nanoparticles and serve as building blocks to assemble with chitosan to form the biomimetic aerogel with structure‐function integration. Benefiting from the interconnected cellular structure, unidirectional aligned channels, nanowire‐interwoven networked pore wall, and evenly distributed catalyst nanoparticles, the biomimetic aerogel exhibits high catalytic activity (97.6% treatment efficiency) and permeability (1786 L m−2 h−1), excellent recyclability and stability in continuous flow catalytic degradation of methylene blue solely driven by gravity. The biomimetic aerogel exhibits excellent performance for bacteria removal and anti‐biofouling. The superior photothermal conversion and heat confinement properties enable the biomimetic aerogel with a high efficiency (86.7%) for solar energy‐driven seawater desalination and wastewater purification under one sun irradiation. The multifunctional biomimetic aerogel has promising applications in catalytic reactions, wastewater remediation, and environmental engineering.

Chapter 7 - Nonlocal Elasticity Theories

Effects of modified single-wall carbon nanotubes on the mechanical properties of polyvinyl alcohol composites by molecular dynamics simulation

By using molecular dynamics simulation, we have investigated systematically the feasibility of continuous unidirectional water flux across a deformed single-walled carbon nanotube (SWNT) driven by an oscillating charge outside without osmotic pressure or hydrostatic drop. Simulation results indicate that the flux is dependent sensitively on the oscillating frequency of the charge, the distance of the charge from the SWNT, and the asymmetry of the water-SWNT system. A resonance-like phenomenon is found that the water flux is enhanced significantly when the period of the oscillation is close to twice the average hopping time of water molecules inside the SWNT. These findings are helpful in developing a novel design of efficient functional nanofluidic devices.

Both brackish water desalination and seawater desalination processes are well established and in common use around the globe to create new water supply sources. The farther the location of the source water from the ocean or seashore, the lower the salinity (TDS) of the water and the lower the osmotic pressure that needs to be overcome when desalinated water is produced. This is one of the major reasons that brackish desalination is often considered less costly than seawater desalination. A number of project considerations, however, indicate that seawater desalination can be beneficial and more cost-effective than brackish water desalination. To make a fair comparison, we need to properly compare all major aspects of both types of projects to define the best and most appropriate desalination technology. While brackish water has less feed water TDS, it is more challenging to dispose of the produced concentrate. Also, although brackish water desalination needs less energy to overcome osmotic pressure, it usually requires more energy to draw the water from the well than it takes to pump seawater from the open ocean intake. Another factor is that the temperature of the brackish well water may be lower than the temperature of ocean water, giving seawater desalination an advantage in energy demand. In comparing brackish to seawater desalination, these major aspects should be evaluated: (1) Locations of seawater and brackish water plants, relative to the major consumers of the desalinated water, (2) Transportation (pumping and disposal) costs of the feed water and produced water, (3) Potential colocation of a seawater plant with a large industrial user (e.g., power plant) of the seawater for cooling or other purposes, (4) Produced quality of brackish water and seawater desalination in terms of major minerals and emerging contaminants, (5) Sustainability of the water source: capacity and depth of the brackish water wells, as well as the type of soil. (6) Technical and economic aspects of produced concentrate disposal, (7) Permitting process costs for brackish and seawater desalination, and (8) The economics of both brackish and seawater desalination treatment processes: capital costs, operational and maintenance (O&M) costs, lifetime water cost, and total water cost (TWC). This paper discusses the major evaluation criteria and considerations involved in properly comparing the economic and technical aspects of brackish and seawater desalination to determine the more favorable desalination technology for a given desalination project.