Dynamic molecular ordering in multiphasic nanoconfined ionogels detected with time-resolved diffusion NMR

Molecular motion in nanosized channels can be highly complicated. For example, water molecules in hydrophobic nanopores move rapidly and coherently in a chain, following the so-called single file motion. Surprisingly, fast molecular motion is also observed in viscous charged fluids, such as room temperature ionic liquids (RTILs) confined in a nanoporous carbon or silica matrix. The microscopic mechanism of this intriguing effect is still unclear. Here, by combining NMR diffusion experiments in different relaxation windows with ab-initio molecular dynamics simulations, we show that the imidazolium-based RTIL [BMIM]+[TCM]-, entrapped in the MCM-41 silica nanopores, exhibits a complex dynamic molecular ordering (DMO); adsorbed RTIL molecules near the pore walls orient almost vertically to the walls, while at the center of the pores anion-cation pairs diffuse collectively in a single file (SFD). Enlightening this extraordinary effect is of primary importance in designing RTIL-based composite materials with tuned electrochemical properties.

Hydrodynamic couplings of colloidal ellipsoids diffusing in channels

The hydrodynamic interactions (HIs) of two colloidal spheres characterized by the translation–translation (T–T) couplings have been studied under various confinements, but little is known regarding the HIs of anisotropic particles and rotational motions, which are common in nature and industry. Here, we study the T–T, rotation–rotation (R–R) and translation–rotation (T–R) hydrodynamic couplings of two colloidal ellipsoids sediment on the bottoms of channels in experiment, theory and simulation. We find that the degree of confinement and the particle shape anisotropy are critical tuning factors resulting in anomalous hydrodynamic and diffusive behaviours. The negative R–R coupling reflects the tendency of opposite rotations of two neighbouring ellipsoids. The positive T–R coupling reflects that an ellipsoid rotates away from the channel axis as another ellipsoid approaches. As the channel width increases, the positive T–T coupling changes to an abnormal negative coupling, indicating that the single-file diffusion can exist even in wide channels. By contrast, only positive T–T couplings were observed for spheres in channels. The T–T coupling increases with the aspect ratio p. The R–R coupling is the maximum at a moderate p ~ 2.8. The T–R coupling is the maximum at a moderate degree of confinement. The spatial range of HIs is longer than that of spheres and increases with p. We propose a simple model which reproduces some coupling phenomena between two ellipsoids, and it is further confirmed by low-Reynolds-number hydrodynamic simulation. These findings shed new light on anisotropic particle diffusion in porous media, transport through membranes, microfluidics and microrheology.

Evaluation of Postoperative Pain Following Single-Visit Root Canal Treatment with Rotary and Reciprocal Ni–Ti File Systems in Children

Background and Objectives: Postoperative pain is a common symptom of a flare-up after root canal treatments (RCTs). Insufficient instrumentation, extrusion of irrigation solutions and debris, and the existence of a periapical lesion are the factors affecting postoperative pain after root canal treatments. The aim of this study was to evaluate the postoperative pain and instrumentation time of the single-file reciprocating system and multiple-file Ni–Ti rotary system in children ages 9–12 years old. Materials and Methods: Our study was conducted on 51 permanent mandibular molars with the diagnosis of irreversible pulpitis. Patients were randomly assigned into two groups, and RCTs were completed with either the Reciproc Blue or Protaper NEXT file systems. Instrumentation time for each system was noted, and patients were given a pain scale that included a visual analog scale for 6, 24, 48, and 72 h after treatment. Postoperative pain scores and instrumentation times were analyzed statistically with a chi-square test and Student’s t-test. Results: There was no statistically significant difference in postoperative pain between the Reciproc Blue and Protaper NEXT systems at all time intervals. Instrumentation time was significantly shorter in the Reciproc Blue group in comparison with the Protaper NEXT group. Conclusions: Postoperative pain findings following RCT using single-file reciprocating systems were similar to the rotary system group. However, chair time in the reciprocating system group was significantly lower. This provided a comfortable and patient-friendly treatment approach for children, and could enhance their cooperation.

Automation of data processing of the results of the chemical experiment on modeling the production of synthetic rubber using Microsoft Excel

The article presents an approach to the processing of chemical experiment’s data using a Microsoft Excel software. Instead of storing the experiment data in text files, it is proposed to use a Microsoft Excel file of a certain structure. A macro has been developed to automate the process of transferring data from text files to a common file. The described approach can be applied when solving problems accompanied by storing a large amount of statistical data, which can be obtained as a result of natural or computational experiments. The macro has been tested on the data of a laboratory and numerical experiment on the synthesis of a styrene-butadiene copolymer. This copolymer is formed as a result of carrying out the process of copolymerization in continuous mode in a cascade of continuous stirred tank reactors. The results of the experiment are the characteristics of the formed product for each reactor of the cascade at the end of each hour of process modeling. Transferring data into a single file of a certain structure allows you to graphically present the results of the experiment and facilitates further analysis of the characteristics of the product being studied, depending on the formulation and process conditions.

The energetic barrier to single-file water flow through narrow channels

Various nanoscopic channels of roughly equal diameter and length facilitate single-file diffusion at vastly different rates. The underlying variance of the energetic barriers to transport is poorly understood. First, water partitioning into channels so narrow that individual molecules cannot overtake each other incurs an energetic penalty. Corresponding estimates vary widely depending on how the sacrifice of two out of four hydrogen bonds is accounted for. Second, entropy differences between luminal and bulk water may arise: additional degrees of freedom caused by dangling OH-bonds increase entropy. At the same time, long-range dipolar water interactions decrease entropy. Here, we dissect different contributions to Gibbs free energy of activation, ΔG‡, for single-file water transport through narrow channels by analyzing experimental results from water permeability measurements on both bare lipid bilayers and biological water channels that (i) consider unstirred layer effects and (ii) adequately count the channels in reconstitution experiments. First, the functional relationship between water permeabilities and Arrhenius activation energies indicates negligible differences between the entropies of intraluminal water and bulk water. Second, we calculate ΔG‡ from unitary water channel permeabilities using transition state theory. Plotting ΔG‡ as a function of the number of H-bond donating or accepting pore-lining residues results in a 0.1 kcal/mol contribution per residue. The resulting upper limit for partial water dehydration amounts to 2 kcal/mol. In the framework of biomimicry, our analysis provides valuable insights for the design of synthetic water channels. It thus may aid in the urgent endeavor towards combating global water scarcity.

Water Dynamics in a Peptide-appended Pillar[5]arene Artificial Channel in Lipid and Biomimetic Membranes

Peptide-appended Pillar[5]arene (PAP) is an artificial water channel that can be incorporated into lipid and polymeric membranes to achieve high permeability and enhanced selectivity for angstrom-scale separations [Shen et al. Nat. Commun.9:2294 (2018)]. In comparison to commonly studied rigid carbon nanotubes, PAP channels are conformationally flexible, yet these channels allow a high water permeability [Y. Liu and H. Vashisth Phys. Chem. Chem. Phys.21:22711 (2019)]. Using molecular dynamics (MD) simulations, we study water dynamics in PAP channels embedded in biological (lipid) and biomimetic (block-copolymer) membranes to probe the effect of the membrane environment on water transport characteristics of PAP channels. We have resolved the free energy surface and local minima for water diffusion within the channel in each type of membrane. We find that water follows single file transport with low free-energy barriers in regions surroundings the central ring of the PAP channel and the single file diffusivity of water correlates with the number of hydrogen bonding sites within the channel, as is known for other sub-nm pore-size synthetic and biological water channels [Horner et al. Sci. Adv.1:e1400083 (2015)].