Various sectors have initiated technology development projects aimed at realizing a hydrogen-based society with low carbon dioxide (CO2) emissions. A proton (H+) transfer system with high permeability and selectivity is essential for the hydrogen infrastructure and fuel cells that support a hydrogen-based society. Therefore, intensive research is underway to design bioinspired artificial proton channels. Natural proteins achieve high proton selectivity by organizing proton-conducting pathways with scattered ionizable side chains and controlling proton transport through Vehicle and Grotthuss mechanisms. The Hv1 channel is a proton-selective protein that contains the amino acids aspartic acid (Asp) and arginine (Arg) in its pathway. As shown in Figure 1, the proton transport mechanism of Hv1 channels is suggested that Asp and Arg can be protonated, allowing them to transport protons via the Grotthuss mechanism. Additionally, Asp and Arg form salt bridges to close the pathway, thereby inhibiting the transport of other ions via the vehicle mechanism. However, the relationship between Asp and Arg and their impact on the transport mechanism remains unclear. It is important to elucidate the relationship between the inhibition of transport and pore size, as well as to understand the correlation between the inhibition of transport and salt bridges, to install proton transport mechanism of Hv1 channels into artificial proton channels. In this study, carbon nanotubes (CNTs) were used as a model pore for artificial ion channels, and we analyzed the effects different sizes of CNTs modifying with Asp and Arg on ion transport properties using molecular dynamics simulations.We adopted the armchair CNTs model shown in Table 1, using the CNTs chirality (5,5), which is known to spontaneously fill with water at room temperature, as the smallest model. For the molecular models of Asp and Arg, side chain models of Asp(N)–Arg(N) and Asp(-)– Arg(+) pairs, which can form salt bridges, were modified inside CNTs.The results of the probability of hydrogen bond formation are shown in Figure 2. The results confirm that hydrogen bonds are always maintained at a pore radius R = 4.75 Å (CNTs chirality = 7,7) for both conditions. As the distance between Asp and Arg increases with increasing pore radius R above R = 4.75 Å, it appears that the hydrogen bonds cannot be maintained. Even when the pore radius is smaller than R = 4.75 Å, the probability of hydrogen bonding formation decreases. In the poster, we will present further structural analyses, such as the orientations of Asp and Arg and their relation to the hydronium ion conformation.[1] Dudev, T., Musset, B., Morgan, D. et al. Selectivity Mechanism of the Voltage-gated Proton Channel, HV1. Sci Rep 5, 10320 (2015). Figure 1
Read full abstract