Controlling 1D Nanostructures and Handedness by Polar Residue Chirality of Amphiphilic Peptides.

Peptide assemblies are promising nanomaterials, with their properties and technological applications being highly hinged on their supramolecular architectures. Here, how changing the chirality of the terminal charged residues of an amphiphilic hexapeptide sequence Ac-I4 K2 -NH2 gives rise to distinct nanostructures and supramolecular handedness is reported. Microscopic imaging and neutron scattering measurements show thin nanofibrils, thick nanofibrils, and wide nanotubes self-assembled from four stereoisomers. Spectroscopic and solid-state nuclear magnetic resonance (NMR) analyses reveal that these isomeric peptides adopt similar anti-parallel ß-sheet secondary structures. Further theoretical calculations demonstrate that the chiral alterations of the two C-terminal lysine residues cause the formation of diverse single ß-strand conformations, and the final self-assembled nanostructures and handedness are determined by the twisting direction and degree of single ß-strands. This work not only lays a useful foundation for the fabrication of diverse peptide nanostructures by manipulating the chirality of specific residues but also provides a framework for predicting the supramolecular structures and handedness of peptide assemblies from single molecule conformations.

Atomic Insights into the Relationship between Molecular Structure and Dispersion Performance of Phenyl Polymer on Graphene Oxide.

The adsorption of organic polymers onto the surface of graphene oxide is known to improve its dispersibility in cement-based materials. However, the mechanism of this improvement at the atomic level is not yet fully understood. In this study, we employ a combination of DFT static calculation and umbrella sampling to explore the reactivity of polymers and investigate the effects of varying amounts of phenyl groups on their adsorption capacity on the surface of graphene oxide. Quantitative analysis is utilized to study the structural reconstruction and charge transfer caused by polymers from multiple perspectives. The interfacial reaction between the polymer and graphene oxide surface is further clarified, indicating that the adsorption process is promoted by hydrogen bond interactions and π-π stacking effects. This study sheds light on the adsorption mechanism of polymer-graphene oxide systems and has important implications for the design of more effective graphene oxide dispersants at the atomic level.

Unraveling the molecular freezing behavior of water on a calcium silicate hydrate matrix.

The hydration process of cement-based materials primarily results in the formation of calcium silicate hydrate (CSH), which is crucial in deciding how long concrete will last. This study utilizes molecular dynamics simulation technology to explore the freezing behavior of pure water solutions within various calcium silicate hydrate (CSH) matrices. The investigated matrices encompass four different Ca/Si ratios. According to the simulation, as ice crystals develop close to the surface of CSH, the CSH matrix strengthens its hydrogen and ionic interactions with water molecules, which effectively prevents water molecules from crystallizing and nucleating. Consequently, these molecules compose an unfrozen water film structure that bridges between ice crystals and the CSH matrix. The research also reveals an intriguing relationship between silica chain behavior on the Ca/Si ratio and the CSH surface. Surface flaws arise as a result of the silica chains of CSH breaking into shorter segments as the Ca/Si ratio increases. These surface defects manifest as grooves on the matrix's surface, effectively capturing and retaining specific water molecules. The CSH matrix's hydrogen bonds with water molecules are weakened as a result of this process, facilitating their participation in the crystallization process, and leading to a thinner unfrozen water film thickness with an increased Ca/Si ratio. This study contributes to a greater knowledge of the performance and dependability of cement-based products by offering molecular-level insights into the freezing actions of liquids in gel pores.

The mechanism of fluidity improvement of cement slurry by graphene oxide: a study on nanofriction.

Graphene oxide (GO) as a nano-reinforcing material has received extensive attention in cement composite materials. This paper employed molecular dynamics to simulate the friction process of calcium silicate hydrate (CSH) particles in the presence of double-sided and single-sided GCOOH (graphene oxide with a -COOH functional group, covering 10% of the surface). The investigation uncovered the lubricating effects of bifacial and unifacial GCOOH on the CSH interface. The findings indicate that the interfacial friction among CSH particles follows the sequence of double-sided GCOOH > pure CSH > single-sided GCOOH. In the double-sided GCOOH system, a greater external force is needed on the opposing side to alter the interaction with water molecules, calcium ions, and silica-oxygen tetrahedra, thereby enhancing friction. In contrast, the majority of the carboxyl groups on the single-sided GCOOH surface are strongly adsorbed onto the CSH surface, facilitating the entry of additional water molecules into the interlayer. Conversely, the unmodified side of the GCOOH has lower interactions with water molecules, hence improving its lubricating properties.

Surface Engineering of Migratory Corrosion Inhibitors: Controlling the Wettability of Calcium Silicate Hydrate in the Nanoscale.

Migratory corrosion inhibitors (MCIs) are regarded as effective additives to prevent harmful ion transmission and improve concrete durability, but their behavior in the porosity of concrete is still unclarified. This paper proposes a unique perspective to evaluate the effects of surfactant-like MCIs in calcium silicate hydrate (C-S-H) nanoporosity through molecular and electronic structural information. Advanced enhanced sampling methods and perturbation theory methods were applied to evaluate the role of different MCIs. The reduced density gradient of MCI molecules was obtained by using quantum chemical calculations. This calculation is instrumental in elucidating the intensity of interactions among distinct MCI molecule head groups and the C-S-H matrix. It is found that MCIs can effectively improve the interfacial tension (IFT) between C-S-H and water, which corresponds to the inhibitory ability of transmission. Free energy indicates that the MCI has the properties of strong adsorption and weak dissolution, facilitating the improvement of IFT. The relationship between the MCI functional group and the ability of adsorption and dissolution is revealed. This study suggests that MCIs work as surface controllers of C-S-H pores and that their properties can be assessed on the nanoscale.

Molecular Insight into the Pozzolanic Reaction of Metakaolin and Calcium Hydroxide.

The reaction mechanism of the pozzolanic reaction of metakaolin (MK) from the atomic point of view has not yet been explored. To explain the process and mechanism of the pozzolanic reaction from the atomic point of view, molecular insight into the pozzolanic reaction of MK and calcium hydroxide (CH) was analyzed through the reaction molecular dynamics (MD) simulation. The results show that the pozzolanic reaction of MK and CH can be essentially regarded as the CH decomposition and penetration into MK. Also, the structure evolution after the pozzolanic reaction shows that the water molecules cannot penetrate the MK structure till the participation of Ca2+ and OH- ions of CH. The Ca2+ and OH- ions have strong interaction with MK and drill into the MK structure, followed by the destruction of a part of the MK structure and water penetration. The final structure of CH removed by MK can be regarded as the precursor of the CASH gel structure.

Acid Radical Tolerance of Silane Coatings on Calcium Silicate Hydrate Surfaces in Aggressive Environments: The Role of Nitrate/Sulfate Ratio.

Silane is known as an effective coating for enhancing the resistance of concrete to harmful acids and radicals that are usually produced by the metabolism of microorganisms. However, the mechanism of silane protection is still unclear due to its nanoscale attributes. Here, the protective behavior of silane on the calcium silicate hydrate (C-S-H) surface is examined under the attack environment of nitrate/sulfate ions using molecular dynamics simulations. The findings revealed that silane coating improved the resistance of C-S-H to nitrate/sulfate ions. This resistance is considered the origin of silane protection against harmful ion attacks. Further research on the details of molecular structures suggests that the interaction between the oxygen in the silane molecule and the calcium in C-S-H, which can prevent the coordination of sulfate and nitrate to calcium on the C-S-H surface, is the cause of the silane molecules' strong adsorption. These results are also proved in terms of free energy, which found that the adsorption free energy on the C-S-H surface followed the order silane > sulfate > nitrate. This research confirms the excellent protection performance of silane on the nanoscale. The revealed mechanism can be further used to help the development of high-performance composite coatings.

Atomistic Insights into the Deposition of Corrosion Products on the Surfaces of Steels and Passivation Films.

The deposition of corrosion products on the surface of the steel is a key step for understanding the generation of corrosion products. To clarify the molecular mechanism for corrosion product deposition, the reactive molecular dynamics were utilized to study the deposition process of ferric hydroxide (Fe(OH)3) on iron and passivation film substrates. It is shown that the deposition phenomenon mainly occurs on the iron surface, while the surface of the passivation film cannot adsorb Fe(OH)3. Further analysis indicates that the interaction between hydroxyl groups in γ-FeOOH and Fe(OH)3 is very weak, which is unfavorable to the deposition of Fe(OH)3. Moreover, the degree of ordered water in the two systems is affected slightly by deposition but the oxygen in water corrodes Fe(OH)3, breaking its Fe-O bonds, which is more obvious in the Fe system due to its instability. This work has revealed the nanoscale deposition process of corrosion products on the passivation film in a solution environment by reproducing the bonding and breaking of atoms at the molecular level, which is a case in point to the conclusion of the protection of steel bars by passivation film.

The inhibitory effect of excess calcium ions on the polymerization process of calcium aluminate silicate hydrate (CASH) gel.

Calcium ion, as an essential component in CASH, affects the aggregation and formation process of CASH, thereby influencing its microstructure and mechanical properties. However, the mechanism by which calcium ions affect the polymerization process of CASH is not yet fully understood. In this study, the effects of calcium ions on the polymerization process, coagulation state, and microstructure of CASH are investigated via molecular dynamics simulation. The results indicate that the presence of a trace amount of Ca2+ attracts oligomers towards the calcium-rich region, thus speeding up the polymerization to some extent, but as the Ca2+ content increases, more Ca2+ binds to the oxygen atoms in silica-oxygen tetrahedra and aluminum-oxygen tetrahedra, forming tight ion pairs and occupying the hydroxyl binding sites required for the polycondensation reaction. This inhibits the continuous aggregation of CASH gel and slows down the rate of polymerization. Additionally, Ca2+ attracts oxygen atoms from free water molecules and free OH-, forming Ca(OH)2 dispersed in the spatial structure, which hinders the formation of larger clusters. As a result, the higher the Ca ion content in the system, the lower the overall polymerization degree of the CASH gel, resulting in a decrease in the conversion of the Q1 dimer to Q2 and Q3 chain structures, a shorter average chain length, poorer overall connectivity, and a transition from large clusters in a better-aggregated state to dispersed small clusters. This study sheds light on the polymerization reaction mechanism of CASH gels.

Molecular Insights into the Reaction Process of Alkali-Activated Metakaolin by Sodium Hydroxide.

When metakaolin (MK) is alkalized with an alkaline activator, it depolymerizes under the action of the alkali. However, the process of MK alkalinization is still unrevealed. Here, we supplied a molecular insight into the process of MK alkalinization through reaction molecular dynamics (MD) simulation. The structure, dynamics, and process of MK alkalinization are systematically investigated. The results showed that the layered structure of MK was destroyed and the silicates in MK were dissolved by sodium hydroxide solution during the alkalinization reaction of MK. The aluminates in MK are not dissolved, indicating that aluminates are more stable than silicates. Moreover, the equilibrium structures of MK with H2O and MK with NaOH solution show that only when both sodium hydroxide and water are involved in the alkalinization reaction, the silicates in MK undergo depolymerization. Also, the observed final state of MK alkalinization can be recognized as the precursor of alkali-activated materials (AAMs).

Understanding the wetting discrepancy in calcium alumino silicate hydrate induced by Al/Si ratio.

The application of supplementary cementitious materials (SCMs) in concrete can improve its durability in the marine environment. Calcium alumino silicate hydrate (CASH) is the main hydration product of SCMs; however, to date, the mechanism of the wetting discrepancy in CASH with different Al/Si ratios has not been revealed at the molecular scale. Herein, the molecular dynamics simulation method was used to study the wettability of water nanodroplets on the surface of CASH substrates with different Al/Si ratios, aiming to reveal the influence of CASH gel with different Al contents on the wettability of water molecules. The simulation results suggested that the CASH interface with a high Al/Si ratio has better wettability for nanodroplets. The microcosmic analysis showed that the interaction between particles and the CASH substrate is affected by the Al content. The electronegativity of the CASH substrate increases due to the substitution of Al-O tetrahedrons, which makes it stronger to solidify Ca ions on its surface and easier to form hydrogen bonds with water molecules in a nanodroplet. The orientation distribution of water molecules further revealed the source of the force of the CASH substrate on nanodroplets at the atomic level. The analysis of the dynamic properties showed that the H-bonds between CASH substrate with a high Al/Si ratio and water molecules are more stable, and thus the nanodroplets have better stability on the surface of CASH.

Concentration-induced wettability alteration of nanoscale NaCl solution droplets on the CSH surface.

Due to the hydrophilic nature of concrete, moisture and corrosive ions adsorbed on its surface pose a severe challenge to the durability of concrete structures; therefore, investigating the wettability of a concrete surface is an indispensable prerequisite for designing durable and sustainable concrete. This paper utilizes molecular dynamics to simulate the concentration-induced wettability alteration of nanoscale NaCl droplets on a CSH surface, and verifies the feasibility and rationality of predicting the contact angle of a droplet on the CSH surface based on the surface tension. Results suggest that the wetting ability of droplets on the CSH surface is weakened with the increase of the NaCl mass fraction. Microscopic analysis reveals that water molecules clustered around Na+ and Cl- ions to form an ion hydration shell (Na+-Ow and Cl--Hw pairs); the binding energy barrier of these ion pairs is much larger than the dissociation energy barrier, which enhances the associative ability of the NaCl droplets. The particles on the CSH surface attract Na+ and Cl- ions by forming Oh(Os)-Na+ and Ca(Ho)-Cl- connections with droplets, which further weakens the spreading ability of water molecules on the CSH surface.

Quantum Chemical Study of the Carbon Dioxide-Philicity of Surfactants: Effects of Tail Functionalization.

Carbon dioxide (CO2)-philic surfactants have broad application prospects in organic synthesis, fracture-enhanced oil recovery, polymerization, extraction, and other fields and can be used to enhance the viscosity of supercritical CO2 (scCO2). In this work, the relationship between the functional group of the surfactant tail and CO2-philicity is studied from a new perspective using density functional theory. Three common functional group types (fluorinated, oxidative, and methyl groups) were investigated. The analysis of binding energy demonstrates that all three types of functional groups can improve the CO2-philicity of the surfactant. Among these three kinds of functional groups, the strongest interaction with CO2 molecules is observed for oxidative functional groups followed by semifluorinated, fluorinated, and methyl groups. However, the CO2 molecules tend to be adsorbed onto the middle segment of the oxidative group, and the intrusion of the CO2 molecules results in the low solubility of oxidative surfactants. In contrast, fluorinated and methyl groups interact with CO2 at the end of the surfactant tail. As a result, the fluorinated surfactants show the best solubility in CO2. Therefore, the solubility of a surfactant in CO2 is not only related to the interaction strength between the surfactant and CO2, it also depends on the interaction structure. The results of this study provide a new strategy for evaluating surfactant CO2-philicity and provide guidance for the design of surfactants with high solubility in scCO2.

Composite Nanotube Ring Structures Formed by Two-Step Self-Assembly for Drug Loading/Release.

Nanotube rings are barely reported novel structures formed by the self-assembly of soft matter, as compared with nanotube structures and ring structures. The two-step self-assembly of amphiphilic copolymer AB and solvophobic copolymer CDC was studied. We found that nanotube rings can be formed from a certain mass ratio of copolymer CDC to copolymer AB and block D of certain rigidity. More interestingly, we discovered a new strategy for drug loading and release, which is different from the usual strategies reported in the literature. The present study provides a new rationale for the self-assembly of copolymers.

Optimal aggregation number of reverse micelles in supercritical carbon dioxide: a theoretical perspective.

The aggregation number is one of the most fundamental and important structural parameters for the micelle or reverse micelle (RM) system. In this work, a simple, reliable method for the determination of the aggregation number of RMs in supercritical CO2 (scCO2) was presented through a molecular dynamics simulation. The process of pulling surfactants out of the RMs one by one was performed to calculate the aggregation number. The free energies of RMs with different numbers of surfactants were calculated through this process. We found an RM with the lowest free energy, which was considered to have the optimal number of surfactants. Therefore, the optimal aggregation number of RMs was acquired. In order to explain the existence of an optimal aggregation number, detailed analyses of surfactant accumulation were conducted by combining molecular dynamics with quantum chemistry methods. The results indicated that in the RMs with the lowest free energy, the head-group and tail-terminal of the surfactants accumulated on an equipotential surface. In this case, the surfactant film could effectively separate water and CO2; thus, the lowest free energy was expected. This method determined the aggregation number of RMs by theoretical calculations that did not depend on experimental measurements. This presented approach facilitates the evaluation of the characteristics of RMs in scCO2 and can be further applied in the RM system of organic solvents or even in the micellar system.

Atomistic insights into cesium chloride solution transport through the ultra-confined calcium-silicate-hydrate channel.

The transport of water and ions in the gel pores of calcium silicate hydrate (C-S-H) determines the durability of cement material. In this study, molecular dynamics was employed to investigate the capillary imbibition process of CsCl solution in the C-S-H channel. The advanced frontier of CsCl solution flow inside the C-S-H capillary shows a concave meniscus shape, which reflects the hydrophilic properties of the C-S-H substrate. Reynolds number calculations show that the transport process is laminar flow and dominated by viscous forces. The invading depth of the CsCl solution deviates from the theoretical prediction of the classic Lucas-Washburn (L-W) equation, but the modified theoretical equation, by incorporating the effect of slip length, dynamic contact angle, and effective viscosity into the L-W equation, can describe the penetration curve of the solution very well. The validity of our developed theoretical equation was confirmed by additional systems with different ion concentrations. In addition, the local structure of ions was analyzed to elucidate the effect of ion concentration on the transport process. The adsorption and accumulation of ions retard the transport process of water. With an increase in the ionic concentration, the effects of immobilization and cluster accumulation became more pronounced, further reducing the transport rate of water. This study provides fundamental insight into the transport behavior of liquid in the gel pores of cement-based material.

Shape transition of water-in-CO2 reverse micelles controlled by the surfactant midpiece.

Designing CO2-philic surfactants for generating wormlike reverse micelles (RMs) is an effective approach to enhance the viscosity of supercritical CO2 (scCO2), however this remains challenging. Modifying the middle piece (midpiece) of surfactant tails is a potential method to generate wormlike RMs, but the underlying mechanism is still unclear. Herein, by adopting molecular dynamics simulations, the self-assembly of the hybrid surfactant FC6-HC5 in scCO2 was investigated. It was found that the FC6-HC5 with an alkyl midpiece could form spherical RMs. By introducing phenyl on the surfactant midpiece, a transformation of the RMs from a spherical shape to a wormlike shape was achieved. The improved fusion free energy was demonstrated to promote the fusion of the spherical RMs to form wormlike RMs. Further analysis indicated that, originating from the π-π interaction, the introduced phenyl assists the parallel arrangement of FC6-HC5, resulting in the improved fusion ability. Moreover, according to the analysis on interfacial properties, introducing phenyl had little effect on the surfactant CO2-philicity. Therefore, modifying the midpiece is a great method for designing hybrid surfactants to generate wormlike RMs while maintaining their high CO2-philicity. This strategy of generating wormlike RMs is expected to facilitate the application of scCO2 meeting industrial requirements.

Molecular-Scale Design of Hydrocarbon Surfactant Self-Assembly in Supercritical CO2.

Forming wormlike reverse micelles (RMs) by hydrocarbon surfactant self-assembly is an economic and environmental strategy to improve the physicochemical properties of supercritical carbon dioxide (scCO2), but it remains challenging. Introducing cosurfactant in hydrocarbon surfactant self-assembly system is a potential method to generate wormlike RMs. Here, adopting molecular dynamics simulations, we performed hydrocarbon surfactant (TC14) self-assembly with introducing cosurfactants (C8Benz). It is found that adding the C8Benz molecules will induce the spherical RMs to a short rodlike form. In this case, the microstructure of the short rodlike RMs shows a dumbbell-like form that is composed by three parts including a middle part of C8Benz and two parts of TC14 aggregation at both ends of rodlike RMs, which is regarded as the origin of RMs shape transition. Further, the analysis of free energy for RMs fusion indicates that the high fusion ability of C8Benz aggregation drives the formation of the dumbbell-like RMs. Accordingly, enhancing the affinity of the C8Benz is found to be effective strategy to further fusion of rodlike RMs in end-to-end manner, yielding a wormlike RMs with a beads-on-a-string structure. It is expected that this work will provide a valuable information for design the hydrocarbon wormlike RMs and facilitate the potential application of scCO2.

Coarse-grained molecular dynamics study on the self-assembly of Gemini surfactants: the effect of spacer length.

Gemini surfactants cause a lot of concerns owing to their unusual aggregation morphologies and superior physicochemical properties over the conventional surfactants. Research shows that the unique structure of Gemini surfactants, especially the spacer group, has a great impact on the self-assembly behaviors. To understand the determinants of this behavior on the molecular level, we carried out coarse-grained molecular dynamics (CGMD) simulations on aqueous solutions of alkanediyl-a,w-bis (dimethylcetylammonium bromide)-based surfactants with different spacer group lengths. Our simulation results demonstrated that the self-assembled morphologies of Gemini changed from spherical micelles, wormlike micelles to vesicles with the decrease in the spacer length, which were qualitatively consistent with the experimental observations. Both the microscopic dynamics processes and the self-assembly mechanisms for the formation of spherical micelles, wormlike micelles and vesicles were systematically studied through the CGMD simulations. In addition, based on the microscopic analysis, a strategy was proposed to predict the self-assembled morphology of surfactant-based systems based on simulation. This work shed light on new views in the understanding of the self-assembly of Gemini surfactants at a molecular-level and the proposed predicting strategy showed promise for practical applications.

Enhancement of the seed-target recognition step in RNA silencing by a PIWI/MID domain protein.

Target recognition in RNA silencing is governed by the "seed sequence" of a guide RNA strand associated with the PIWI/MID domain of an Argonaute protein in RISC. Using a reconstituted in vitro target recognition system, we show that a model PIWI/MID domain protein confers position-dependent tightening and loosening of guide-strand-target interactions. Over the seed sequence, the interaction affinity is enhanced up to approximately 300-fold. Enhancement is achieved through a reduced entropy penalty for the interaction. In contrast, interactions 3' of the seed are inhibited. We quantified mismatched target recognition inside and outside the seed, revealing amplified discrimination at the third position in the seed mediated by the PIWI/MID domain. Thus, association of the guide strand with the PIWI/MID domain generates an enhanced affinity anchor site over the seed that can promote fidelity in target recognition and stabilize and guide the assembly of the active silencing complex.