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Accurate prediction of solubility of polymers in solvents a priori is highly desirable in practice. To this end, the Flory-Huggins interaction parameter χ is commonly used and molecular dynamics simulation, a powerful computational tool, has been used for such a purpose. To calculate w, there exist three possible strategies using molecular dynamics simulation. One is through the calculation of Hildebrand solubility parameters of the pure components while the other two are to calculate the enthalpy of solvation and Gibbs free energy of solvation for the solution, respectively. This study evaluated these three strategies using binary solutions containing a hydrophobic or hydrophilic polymer (polyisobutylene, polystyrene, cis and trans polybutadiene, cis and trans polyisoprene, poly(ethylene oxide), and polyacrylamide) and an aliphatic solvent - cyclohexane. We found that χ determined via solubility parameters predicted the solubility trend but deviated significantly from experimental values. On the other hand, the enthalpy of solvation approach provided the most accurate χ values, compared to experiment, at a reasonable computational demand, especially for hydrocarbon polymers, while the Gibbs free energy of solvation approach, though more computationally intensive, did not significantly improve χ from the enthalpy of solvation approach. In particular, the Gibbs free energy of solvation approach overestimated χ for non-polar polymers. A conformational analysis of the solvated polymers revealed that all polymers collapsed in cyclohexane with polyethylene oxide and polyacrylamide collapsed the most as expected. For the two polar polymers used, the collapse was evidenced by abrupt changes in radius of gyration (Rg) and solvent accessible surface area (SASA) in the early stage of molecular dynamics simulation trajectories, and plateauing at much lower final values. Conversely, the hydrocarbon polymers exhibited minimal deviation from the expected Rg and barely any change in SASA with time. Our findings demonstrated that there exist differences in the accuracy and computational resources used when different molecular dynamics simulation strategies are used in the determination of χ. [ABSTRACT FROM AUTHOR]

Covalent linkages between lignin and the surrounding carbohydrate network, often referred to as lignin–carbohydrate complexes (LCCs), have been proposed to affect the organization of the biomass microstructure and directly correlate with the recalcitrant nature of biomass. However, the existence and frequency of these LCC linkages remain controversial and largely unknown, primarily due to the harsh experimental techniques available to characterize them. During the predominant lignin polymerization pathway a reactive intermediate is formed. Though this intermediate can covalently bind to the surrounding cellulose/hemicellulose matrix, it has been traditionally assumed to react exclusively with water, leading to purely physical interactions between lignin and cellulose/hemicellulose in the cell wall. This work, for the first time, provides direct evidence of the molecular mechanism of the formation of benzyl ether and benzyl ester LCC linkages via the speculated lignin polymerization pathway. The formation of these LCC linkages showed thermodynamic favorability, while remaining kinetically facile, compared to the previously assumed mechanism of the lignin intermediate reacting with water. The present work suggests that the surrounding carbohydrate matrix could play a role in the organization of lignin deposition and these covalent linkages could be a key factor in biomass recalcitrance. [ABSTRACT FROM AUTHOR]

Molecular dynamics simulation was used to study the adsorption behavior of inorganic and organic ions at aqueous–cyclohexane interfaces, and that with such systems confined in a kaolinite nanopore. Four aqueous solutions were used, each containing one of the four solutes (NaCl, NaOH, CaCl2 and Ca(OH)2) at the concentration of 1.0 M. At the interface of each of the solutions with neat cyclohexane, there existed an ion depletion zone. The more strongly hydrated ions, such as calcium and hydroxide, were more intensely depleted from the interface as compared to sodium and chloride. Such surface exclusion led to interfacial tension increases, with greater increments for solutions containing calcium or hydroxide. Upon addition of sodium decanoate to the cyclohexane phase, they partly migrated to the aqueous–organic interface, and the remaining formed inverted micelle complexes. Also, a small fraction of the solvated cations in the aqueous phase drifted to the depletion zone to interact with the organic anions, with their affinity towards the interface still being controlled by their hydration-strength. When such systems were confined in a kaolinite nanopore, behavior of decanoate anions – which were found to be prone to strong adsorption to solid surfaces in the absence of any aqueous solution – was determined by the nature of the solvated ions in water. In these systems, the more weakly-hydrated ionic species exhibited preferential adsorption to the solid surface, while affinity of the more strongly-hydrated ones was towards remaining within the water layers or to the aqueous–organic interface. With the calcium chloride solution, almost all of the organic ions were detached from the surface and adsorbed at the aqueous–cyclohexane interface. This was caused by the release of double amount of inorganic anions by this 1 : 2 salt, the inner-sphere adsorption of majority of chloride anions to the octahedral surface, and the higher charge density of calcium cations. [ABSTRACT FROM AUTHOR]

Froth flotation has been widely used to separate sulfide minerals from sulfide ores, where the oxygen reduction reaction (ORR) plays a significant role as the cathodic reaction. However, the intrinsic ORR mechanism over sulfide minerals and its effect on the flotation performance remain unclear. Herein, we explored the intrinsic ORR mechanism over metal sulfides through density functional theory (DFT) calculations along with the computational hydrogen electrode (CHE) model. Our results revealed that pyrite (FeS2) and chalcopyrite (CuFeS2) exhibited similar ORR behavior to that over platinum (Pt) but not galena (PbS) and sphalerite (ZnS). The relative computational overpotentials for the ORR were completely consistent with the experimental trend in the order of Pt ＜ FeS2 ＜ CuFeS2 ＜ PbS ＜ ZnS and linearly correlate with the oxygen binding energies. We thus conclude that the distinct ORR behaviors originate from the different oxygen binding strengths which are determined by the underlying electronic structure. More importantly, we demonstrated that the DFT calculated bulk centroids of the occupied S 3p band for metal sulfides strongly correlate with the experimentally measured rest potential of the counter sulfide minerals in xanthate solution, and consequently we established the descriptor–activity relationship. Using this relationship, we present that the mechanism underlying the mixed potential model regarding the xanthate–sulfide mineral interaction is essentially governed by the relative dominating role of the compositional metallic cation to the anionic sulfur in terms of the electronic structure around the Fermi level, which favors the formation of dixanthogen and metal-xanthate, respectively. [ABSTRACT FROM AUTHOR]

The main goal of this research is maximizing the utilization of renewable materials in both the matrix and reinforcement, more importantly exploitation of waste material for biocomposite development and evaluating the mechanical, thermal and water resistance performances. Woven roving and chopped strand mat fiber glass, and hemp fiber mats are incorporated to an epoxy resin based matrix cured with novel hydrolyzed specified risk material (SRM) extracts. Aminophenyl sulphone (APS) is used as a control crosslinking agent for the epoxy resin. Results show that the biocomposites developed in this research exhibit promising flexural strength, tensile strength and tensile modulus; despite relatively poor moisture resistance. The use of waste protein hydrolyzate extracts, hydrolyzed proteins, as crosslinking agent of epoxy resins in making biocomposites is novel and promising and results can be extended to other proteinaceous biomasses as curing agent of epoxy resins. [ABSTRACT FROM AUTHOR]

A method is proposed for creating a non-equilibrium ensemble with a constant number of molecules, constant temperature and constant pressures with different target values in two reservoirs [referred to as NT(P1− P2) ensemble] that are connected by a finite length nanopore. This method includes two steps. The first step places a partition between the two reservoirs and then creates a static pressure field and a proper system volume by using two self-adjusting plates on which two external forces/pressures with different target values are exerted. The second step removes the partition and the two self-adjusting plates and the pressure difference between the two reservoirs is maintained by a “pump” designed to simultaneously create a periodic boundary condition between the two reservoirs and supply the necessary force (work) to a subset of molecules for a steady state flow. To examine this method, several cases using liquid argon with a truncated and shift Lennard-Jones potential under different target pressures and pump sizes were studied. Results show that the method proposed in this paper works well. In addition, the method proposed in this paper was compared with the other external force field methods. The results show that as long as the external force is applied to a restricted set of molecules away from the channel a constant pressure difference between two reservoirs is maintained. The advantage of the algorithm proposed here also sets the absolute pressures with different target levels in two reservoirs instead of it being arbitrary. Studies show that the fluid flow rate or permeability through a nanopore depends not only on the pressure difference between two reservoirs, but also on the absolute pressures in two reservoirs. [ABSTRACT FROM AUTHOR]

The effect of temperature on the chain length (N) dependence of the diffusivity of oligomers (with N = 10-60 carbon atoms) was theoretically studied using the free volume theory of Wong and Choi [Soft Matter, 2019, 15, 9300-9309] along with the experimental data of von Meerwall et al. [J. Chem. Phys., 1998, 108, 4299-4304]. Experimental data showed that D cm ∼N v and that becomes less negative as temperature increases but is always stronger than -1 as obtained in the Rouse model. The theory successfully predicts the exponent v as a function of temperature.

The entrance and exit effects on liquid transport through a nano-sized cylindrical pore under different solid wall-liquid interactions were studied by comparing molecular dynamics (MD) results of a finite length nanopore in a membrane with those of an infinite length one. The liquid transport through a finite length nanopore in a membrane was carried out by using a pressure-driven non-equilibrium molecular dynamics (NEMD) method proposed by Huang et al. [C. Huang, K. Nandakumar, P. Choi and L. W. Kostiuk, J. Chem. Phys., 2006, 124, 234701]. The fluid motion through an infinite length nanopore, which had the same cross-stream dimension as the finite length channel in the membrane, but with periodic boundary conditions in the stream-wise direction, was carried out by using the external-field driven NEMD approach [J. Koplik, J. R. Bavanar and J. F. Willemsen, Phys. Rev. Lett., 1988, 60, 1282]. The NEMD results show that the pressure and density distributions averaged over the channel in the radial direction in both finite and infinite length channels are similar, but the radial distributions of the stream-wise velocity were significantly different when the solid wall was repulsive. The entrance and exit effects lead to a decrease in flow rate at about 39% for the repulsive wall and 6% for the neutral-like wall.