Modeling and analysis of the materials universe is an emerging area of research with many important applications in materials science. The main goal is to create a map of materials which allows not only to visualize and navigate the materials space, but also reveal complex relationships and “connections” among materials and potentially find clusters of materials with similar properties. In this paper, we consider the problem of mapping and exploring the materials universe using network science tools and concepts. The networks are based on the open-source materials data repository AFLOW.org where each material is represented as a node, and each pair of nodes is connected by a link if the respective materials exhibit a high level of similarity between their Density of States (DOS) functions. We discuss the importance of similarity measure selection, investigate basic structural properties of the resulting networks, and demonstrate advantages and limitations of the proposed approaches.
Membranes with asymmetric wettability-Janus membranes-have recently received considerable attention for a variety of critical applications. Nonetheless, the current methods for making such membranes are still challenging. Here, we report on a simple approach to introduce asymmetric wettability into hydrophilic porous domains. Our approach is based on the physicochemical-selective deposition of polytetrafluoroethylene (PTFE) on hydrophilic polymeric substrates. The physicochemical inhibition was achieved through prefilling the substrates with glycerol, containing a known amount of free radical inhibitors. We showed that the glycerol/inhibitor mixture hinders the deposition of PTFE within the membrane pores. As a result, the surface of the substrates remains open and porous. The fabricated Janus membranes show stable wetting-resistant properties, evaluated through sessile drop contact angle measurements and direct contact membrane distillation (DCMD).
Most cell penetrating peptides (CPPs) are unstructured and susceptible to proteolytic degradation. One alternative is to incorporate D-chirality amino acids into unstructured CPPs to allow for enhanced uptake and intracellular stability. This work investigates CPP internalization using a series of time, concentration, temperature, and energy dependent studies, resulting in a three-fold increase in uptake and 50-fold increase in stability of D-chirality peptides over L-chirality counterparts. CPP internalization occurred via a combination of direct penetration and endocytosis, with a percentage of internalized CPP expelling from cells in a time-dependent manner. Mechanistic studies identified that cells exported the intact internalized D-chirality CPPs via an exocytosis independent pathway, analogous to a direct penetration method out of the cells. These findings highlight the potential of D-chirality CPPs as bio-vectors in therapeutic and biosensing applications, but also identify a new expulsion method suggesting a relationship between uptake kinetics, intracellular stability, and export kinetics
The manuscript describes a computational study that provides molecular-level insight into shale gas adsorption and transport in shale rocks, which are composed of organic and inorganic matter. Atomistic simulations were used to generate realistic models of the organic matter structures with both micro- and mesoporosity, and correspond to mature and overmature type-II kerogens. These porous material models are unique to most other previous kerogen models since they contain other components (asphaltene/resin, hydrocarbons and carbon dioxide/water fractions) that are typically not modeled. The inclusion of these additional components significantly influences the resulting porous structure characteristics. The adsorption and diffusion behavior of methane (as a shale gas proxy) and methane/carbon dioxide mixtures were simulated in the model structures. Several key industrial-relevant findings are described in the manuscript.
Drop breakup experiments were carried out in a stirred tank using the high-speed online camera. Breakup behaviors of drop breakup time, multiple breakage, and breakup rate were investigated. Experimental results show that the drop breakup time is mainly controlled by the interfacial tension and drop diameter, while is almost independent of the rotating speed. Besides, the dispersed phase viscosity has a slight influence on the breakup time. An empirical correlation for the breakup time is proposed and is further verified by comparing with the results of Solsvik and Jakobsen (Chem. Eng. Sci., 2015, 131: 219-234). The percentage of multiple breakage comparing to binary breakup was statistically counted. The results indicated that the dimensionless drop diameter η = d / dmax can be adopted to characterize the proportion of binary breakup. Finally, the breakup rate was experimentally measured and the breakup probability was calculated using the inverse method.
Spherical agglomeration (SA) is a process intensification (PI) strategy, which can reduce the number of unit operations in pharmaceutical manufacturing. SA merges drug substance crystallization with drug product wet granulation, reducing capital and operating costs. However, SA is a highly nonlinear process, thus for its efficient operation model-based design and control strategies are beneficial. These require the development of a high-fidelity process model with appropriately estimated parameters. There are two major problems associated with the development of a high-fidelity process models – (i) selection of the appropriate model corresponding to the underlying process mechanisms, and (ii) accurate estimation of the parameters. This work focuses on the identification of the best fitting model that correlates with experimental observations using cross-validation experiments. Further, an Iterative Model Based Experimental Design (IMED) strategy is developed, which uses D-optimal experimental design criterion to minimize the number of experiments necessary to obtain accurate parameter estimates.
Zeolite belongs to one of the most important families of solid acid catalysts in chemical industries. It is however severely constrained by the diffusion limitation for bulky molecules, the lack of multi-functionality for sequential reactions and pore adaptability towards specific adsorbates, due to the small micropore size and simple aluminosilicate framework. Introducing mesopores into the zeolitic framework towards hierarchical zeolites is prevailing, but usually suffers from compromised crystallinity as well as insufficient interconnectivity and openness of mesopores. Herein, a novel of acid-redox co-functionalized single-crystalline zeolite with highly open and interconnected mesopores is designed and fabricated. As a proof-of-concept study, we integrate the solid acid and Fe-oxy redox sites in a hierarchical MEL zeolite with well characterized microporosity and mesoporosity. It exhibits superior activity and stability towards the alkylation between mesitylene with benzyl alcohol, arising from greatly facilitated intracrystalline molecular diffusion, mitigated metal leaching and optimized adsorbate-pore wall interactions.
Sequential model-based design of experiments (MBDoE) uses information from previous experiments to select run conditions for new experiments. Computation of the objective functions for popular MBDoE can be impossible due to a non-invertible Fisher Information Matrix (FIM). Previously, we evaluated a leave-out (LO) approach that design experiments by removing problematic model parameters from the design process. However, the LO approach can be computationally expensive due to its iterative nature and some model parameters are ignored. In this study, we propose a simple Bayesian approach that makes the FIM invertible by accounting for prior parameter information. We compare the proposed Bayesian approach to the LO approach for designing sequential A-optimal experiments. Results from a pharmaceutical case study show that the Bayesian approach is superior, on average, to the LO approach for design of experiments. However, for subsequent parameter estimation, a subset-selection-based LO approach gives better parameter values than the Bayesian approach.
Experimental results on pressure drop and flow patterns for gas-liquid flow through packed beds obtained in the International Space Station with two types of packing are presented and analyzed. It is found that the pressure drop depends on the packing wettability in the viscous-capillary (V-C) regime and this dependence is compared with previously published results developed using short duration low-gravity aircraft tests. Within the V-C regime, the capillary contribution is the dominant force contributing to the pressure drop for the wetting case (glass) versus the viscous contribution dominating for the non-wetting case (Teflon). Outside of the V-C regime, it is also found that hysteresis effects that are often strong in normal gravity gas-liquid flows are greatly diminished in microgravity and pressure drop is nearly independent of packing wettability. A flow pattern transition map from bubble to pulse flow is also compared with the earlier aircraft data.
In this investigation, CO2 capture performance of zeolite 13X monoliths with 600 and 800 cpsi in presence of SO2/NO impurities under dry and humid conditions were evaluated and compared with that of 13X beads. Dynamic breakthrough tests demonstrated a drastic reduction in CO2 capture capacity and deterioration of kinetics under dry-clean conditions, whereas, upon switching the feed from a clean gas to contaminated gas which contained SO2 and NO, different adsorption performance was observed. Specifically, in dry-contaminated mode, the adsorbents retained their capture capacities with comparable kinetics to that of dry-clean feed conditions, however, in humid-contaminated mode, the adsorbents experienced improved CO2 uptake and CO2/N2 selectivity, albeit at the expense of deteriorated kinetics. These findings indicate that the presence of SO2 and NO contaminants, especially SO2 contaminants, lead to dramatic changes in the adsorption performance of zeolite 13X monoliths, indicating the importance of evaluating adsorbent materials under realistic conditions.
In Rodriguez et al.1 an analytical expression was deduced to predict the slip ratio in dispersed oil-water flow. Although the quantitative agreement was quite good, the expression systematically underestimated the slip ratio. New experimental data of similar flows were collected in two different experimental facilities in pipes of different materials and diameters (26 mm and 82.8 mm i.d.). Oil-water flow data collected within a range of mixture Reynolds numbers from 1∙10^5 to 20∙10^6 in glass, acrylic and steel pipes with oil viscosities varying from 7 to 220 mPa.s were used to deduce a more generic correlation for slip ratio as a function of the mixture Froud number (5 < Fr < 70). The underestimation of the slip ratio was corrected. The new slip-ratio correlation can be used to significantly improve the prediction of volumetric fraction in flow situations where turbulent dispersion of oil in water occurs.
We introduce a straightforward method for the preparation of novel starch-based ultramicroporous carbons (SCs) that demonstrate high CH4 uptake and excellent CH4/N2 selectivity. These SCs are derived from a combination of starch and 1-6 wt. % of acrylic acid, and the resulting materials are amenable to surface cation exchangeability as demonstrated by the formation of highly dispersed K+ in carbon precursors. Following activation, these SCs contain ultramicropores with narrow pore-size distributions of <0.7 nm, leading to porous carbon-rich materials that exhibit CH4 uptake values as high as 1.86 mmol/g at 100 kPa and 298 K, the highest uptake value for CH4 to date, with the IAST-predicted CH4/N2 selectivity up to 5.7. Both the potential mechanism for the formation of narrow pores and the origin of the favorable CH4 adsorption properties are discussed and examined. This work may potentially guide future designs for carbon-rich materials with excellent gas adsorption properties.
Synthesis of adipic acid (AA) through the oxidation of cyclohexanol and cyclohexanone (K/A oil) with nitric acid was conducted in a capillary microreactor system. Effects of the temperature, the nitric acid concentration, the volumetric flow rate ratio of nitric acid to K/A oil, and the capillary length on the selectivity and the product yield were investigated systematically to achieve optimal reaction conditions. Notably, a high yield of adipic acid (i.e., 90%) was achieved just in 6 seconds at 85℃ with the use of 55 wt% nitric acid. Gas components produced in this oxidation process and its total volumetric flow rate were determined under various operating conditions, which was beneficial for reaction mechanism characterization and process optimization. Finally, a kinetic model was established, which was of crucial theoretical significance and practical value for optimizing the reactor design and better understanding such fast and highly exothermic multiphase processes with abundant gas production.
Molecular mechanisms and process kinetics of crystallizing concomitant polymorphs remain poorly understood. Solvent-mediated phase transformation is often mistaken as concomitant crystallization, mainly due to the two processes sharing similar kinetic profiles. Herein, we developed a population balance model to simulate a concomitant crystallization process of two polymorphs of tolfenamic acid (TFA). The kinetic modeling aims to better understand concomitant crystallization and help guide form selection of such a molecular system. Crystallization kinetics of ethanolic TFA solutions were uncovered from induction time measurements, as well as seeded and unseeded crystallization experiments. Both experimental and simulation results demonstrate that the stable form I crystallizes concomitantly with the metastable form II. The faster growing form II results in an intermediate decline in the kinetic profile of form I composition in crystallized samples, a characteristic feature of the concomitantly crystallized system. A four-quadrant scheme of attainable polymorph outcome was simulated under various crystallization conditions.
We study the evaporation dynamics of multiple water droplets deposited in ordered arrays or randomly distributed (sprayed) on superhydrophobic substrates (SHP) and smooth silicone wafers (SW). The evaluation of mass of the droplets as a function of time shows a power-law behavior with exponent 3/2, and from the prefactor of the power-law an evaporation rate can be determined. We find that the evaporation rate on a SHP surface is slower than a normal surface for both single droplet and collection of droplets. By dividing a large droplet into more smaller ones, the evaporation rate increases and the difference between the evaporation rates on SHP and SW surfaces becomes higher. The evaporation rates depend also on the distance between the droplets and increase with increasing this distance.
Charged clay surfaces can impact the storage and mobility of hydrocarbon and water mixtures. Here, we use equilibrium molecular dynamics (MD) and nonequilibrium MD simulations to investigate hydrocarbon-water mixtures and their transport in slit-shaped illite nanopores. We construct two illite pore models with different surface chemistries: potassium-hydroxyl (PH) and hydroxyl-hydroxyl (HH) structures. In HH nanopore, we observe water adsorption on the clay surfaces. In PH nanopores, however, we observe the formation of water bridges because of the existence of a local, long-range electric field. Our NEMD simulations demonstrate that the velocity profiles across the pore depends strongly on water concentration, pore width and the presence or absence of the water bridge. This fundamental study provides a theoretical basis for understanding nanofluidics with charged surfaces and can be applied in such as biological processes, chemical and physical fields, and the oil and gas extraction in clay-rich formations.
Enzyme immobilization enhances the catalytic activity and stability of the enzyme, and also improves reusability. Metal organic frameworks (MOFs), which possess diversified structures and porosity, have been used as excellent carriers for enzyme immobilization. Pseudomonas fluorescens lipase (PFL) has been successfully immobilized onto MOFs by covalent cross-linking to obtain a series of immobilized lipase (PFL@MOFs). PFL@MOFs are used for catalytic enantioselective hydrolysis of 2-(4-hydroxyphenyl) propionic acid ethyl ester enantiomers (2-HPPAEE) in aqueous medium and transesterification of 4-methoxymandelic acid enantiomers (4-MMA) in organic medium. The experimental results indicated that PFL@Uio-66(Zr) exhibits excellent enzymatic catalysis performances and high enantioselectives. In addition, to increase catalytic activity and reusability, PFL is modified by the polyethylene glycol (PEG) to prepare PEG-modified lipase (PFL-PEG), then PFL-PEG is immobilized onto Uio-66(Zr) to prepare PFL-PEG@Uio-66(Zr), demonstrating better reusability and catalytic activity compared with PFL@Uio-66(Zr).
A new transport model is proposed for paraffin wax deposition onto a cold finger from flowing wax-containing oils. The model solves transient energy and mass balances simultaneously for a reversible first-order kinetic rate for precipitation of pseudo-single-component wax, and the effects of yield stress using a critical solid wax concentration to withstand flow-induced stress at the deposit-fluid interface, Cpi. The model can predict the time evolution of the deposit thickness, and the spatial and temporal evolution of temperature and wax concentration and was validated using experiments involving a cylindrical cold finger. We found that for oils with Cpi close to zero, the deposit thickness growth is dominated by heat transfer. However, mass transfer cannot be neglected as diffusion of wax into the deposit continues to take place even after the deposit has stopped growing. For oils with non-zero Cpi, the deposit growth is slow and accompanied by occasional sloughing.