Nanopore Confinement Research Articles

Numerical Study on the Enhanced Oil Recovery by CO2 Huff-n-Puff in Shale Volatile Oil Formations

The Sichuan Basin’s Liangshan Formation shale is rich in oil and gas resources, yet the recovery rate of shale oil reservoirs typically falls below 10%. Currently, gas injection huff-n-puff (H-n-P) is considered one of the most promising methods for improving shale oil recovery. This study numerically investigates the application of the CO2 huff-n-puff process in enhancing oil recovery in shale volatile oil reservoirs. Using an actual geological model and fluid properties of shale oil reservoirs in the Sichuan Basin, the CO2 huff-n-puff process was simulated. The model takes into account the molecular diffusion of CO2, adsorption, stress sensitivity effects, and nanopore confinement. After history matching, through sensitivity analysis, the optimal injection rate of 400 tons/day, soaking time of 30 days, and three cycles of huff-n-puff were determined to be the most effective. The simulation results show that, compared with other gases, CO2 has significant potential in improving the recovery rate and overall efficiency of shale oil reservoirs. This study is of great significance and can provide valuable references for the actual work of CO2 huff-n-puff processes in shale volatile oil reservoirs of the Sichuan Basin.

Manganese oxide for heterogeneous Fenton treatment: Catalyst or inhibitor?

Manganese oxide species have been frequently used for Fenton catalyst design, but their role in reaction with hydrogen peroxide (H2O2) is still in debate. We here revealed the different routes of manganese oxide/H2O2 interactions occurring at bulk surfaces to that at nanopore-confined surfaces, which have been overlooked in literatures. Briefly, particulate manganese oxide species cause a fast H2O2 decomposition influenced by the valence of manganese and solution pH, but without generation of reactive oxygen species (•OH, •O2-, or 1O2) for water treatment; in contrast, manganese oxide/H2O2 interaction under nanopore confinement (ca. 1 nm) led to the production of radicals (mainly •OH and •O2-) and the removal of organic pollutants. We gained insights into the differed reaction routes based on experimental and computational study. Our findings provide caveats on the indiscriminate pursuit of manganese in Fenton catalyst development, against a nullified H2O2 decomposition and impractically slow radical production.

Dynamics of oil–CO2–water three-phase under the nanopore confinement effect: Implications for CO2 enhanced shale oil recovery and carbon storage

The widespread nanopores, diverse minerals, and varying water saturation in shale reservoirs complicate the mechanism analysis and performance prediction of CO2 enhanced oil recovery (CO2-EOR) and CO2 storage (CS) in hydrated nanopores. Therefore, molecular dynamics methods were used to simulate the process of CO2 replacing shale oil in hydrated nanopores of inorganic, organic and composite minerals. Importantly, the effects of mineral type, temperature, pressure and water content on CO2-EOR and CS performances in hydrated nanopores were analyzed, and the CO2-EOR mechanisms of dissolution, extraction, viscosity reduction, miscibility and competitive adsorption were revealed. The results show that water in illite, kerogen, and composite nanopores are distributed in the forms of water films, water clusters (films), and water columns, respectively. The replacement efficiency of shale oil in three types of nanopores is improved with increased water content but reduced in kerogen nanopores under high water content. Water is not conducive to the diffusion and viscosity reduction of oil in nanopores, but the miscibility and competitive adsorption of CO2 and oil are improved. The replacement efficiency is positively correlated with temperature and pressure. The increasing temperature promotes diffusion and viscosity reduction of oil and competitive adsorption between CO2 and oil in hydrated nanopores, and increasing pressure promotes miscibility and competitive adsorption. Water columns in kerogen and composite nanopores reduce the CS performance, while thin water films in illite nanopores improve it. Moreover, an excellent CS rate can be achieved at high temperatures and pressures, but the high temperature is not conducive to CS stability. This study provides a theoretical basis for CO2 injection to improve oil production and carbon storage performance in hydrated shale reservoirs and contributes to the optimization of CO2 injection schemes.

The structure of ice under confinement in periodic mesoporous organosilicas (PMOs).

We investigated the structure of ice under nanoporous confinement in periodic mesoporous organosilicas (PMOs) with different organic functionalities and pore diameters between 3.4 and 4.9nm. X-ray scattering measurements of the system were performed at temperatures between 290 and 150K. We report the emergence of ice I with both hexagonal and cubic characteristics in different porous materials, as well as an alteration of the lattice parameters when compared to bulk ice. This effect is dependent on the pore diameter and the surface chemistry of the respective PMO. Investigations regarding the orientation of hexagonal ice crystals relative to the pore wall using x-ray cross correlation analysis reveal one or more discrete preferred orientation in most of the samples. For a pore diameter of around 3.8nm, stronger correlation peaks are present in more hydrophilically functionalized pores and seem to be connected to stronger shifts in the lattice parameters.

Impact of nanopore confinement on phase behavior and enriched gas minimum miscibility pressure in asphaltenic tight oil reservoirs

Miscible gas injection in tight/shale oil reservoirs presents a complex problem due to various factors, including the presence of a large number of nanopores in the rock structure and asphaltene and heavy components in crude oil. This method performs best when the gas injection pressure exceeds the minimum miscibility pressure (MMP). Accordingly, accurate calculation of the MMP is of special importance. A critical issue that needs to be considered is that the phase behavior of the fluid in confined nanopores is substantially different from that of conventional reservoirs. The confinement effect may significantly affect fluid properties, flow, and transport phenomena characteristics in pore space, e.g., considerably changing the critical properties and enhancing fluid adsorption on the pore wall. In this study, we have investigated the MMP between an asphaltenic crude oil and enriched natural gas using Peng-Robinson (PR) and cubic-plus-association (CPA) equations of state (EoSs) by considering the effect of confinement, adsorption, the shift of critical properties, and the presence of asphaltene. According to the best of our knowledge, this is the first time a model has been developed considering all these factors for use in porous media. We used the vanishing interfacial tension (VIT) method and slim tube test data to calculate the MMP and examined the effects of pore radius, type/composition of injected gas, and asphaltene type on the computed MMP. The results showed that the MMP increased with an increasing radius of up to 100 nm and then remained almost constant. This is while the gas enrichment reduced the MMP. Asphaltene presence changed the trend of IFT reduction and delayed the miscibility achievement so that it was about 61% different from the model without the asphaltene precipitation effect. However, the type of asphaltene had little impact on the MMP, and the controlling factor was the amount of asphaltene in the oil. Moreover, although cubic EoSs are particularly popular for their simplicity and accuracy in predicting the behavior of hydrocarbon fluids, the CPA EoS is more accurate for asphaltenic oils, especially when the operating pressure is within the asphaltene precipitation range.

Novel methodology to couple decline curve analysis with CFD reservoir simulations for complex shale gas reservoirs

AbstractShale reservoirs are highly complex and are difficult to study using conventional reservoir simulation tools. This study introduces a novel methodology for estimating production from complex shale gas reservoirs by coupling decline curve analysis (DCA) with computational fluid dynamics (CFD) simulations. The proposed method uses exponential DCA to analyze production data from a dual porosity–permeability shale gas transport model. These complexities include fracture characteristics, geomechanical properties, nanopore confinement effects, and multiple flow mechanisms contributing to the total production performance. The shale gas transport model is validated through historical production data from Marcellus shale. The new methodology also tests fracture characteristics. It shows that increased porosity and permeability will increase the recoverable reserves but will have varying effects on the decline rate. The paper demonstrates the advantages of the proposed methodology over conventional reservoir simulation tools. It provides insights into the factors affecting shale gas production performance through the inclusion of the complexities of an unconventional shale gas reservoir. The paper provides a proof of concept on the particular reservoir of which the field data is provided—Barnett and Marcellus Shale.

Engineering of uniform dispersed Ni nanoparticles supported on carbon nanosheets for reduction of Nitroarenes to Aminoarenes

Facile synthesis of uniform supported metal catalysts is of great significance yet remains challenging for sustainable catalysis. Herein, a nanopore confinement strategy is developed to efficiently anchor metal ions in suitably sized polymer nanopores via strong coordinate bonds and ensure successful fabrication of uniform carbon-supported metal nanoparticles. Specifically, Ni2+-coordinated polydopamine (PDA) mesoporous layer was coated on GO nanosheets for the confinement of the nickel atoms (GO@PDA-Ni-x, x means pore size of PDA layer), resulting Ni@C-x nanosheets catalysts with uniformly dispersed Ni nanoparticles after pyrolysis in H2/Ar atmosphere. Characterization methods including SEM, TEM, and XPS reveal the intrinsic formation mechanism and physicochemical details. In the catalytic reaction of NaBH4-mediated hydrogenation of 4-nitrophenol (4-NP), the obtained Ni/C-10 exhibits exceptional catalytic performance with a rapid rate constant (0.686 min−1), outperforming many previously reported metal catalysts. Moreover, the catalytic activity remains almost unchanged after being recycled five times, proving the prominent stability. This work opens up an innovative avenue for rational design and synthesis of supported catalysts with controllable size for broad catalytic applications.

Real-time structural signatures of protein allostery by electrically- and mechanically-coupled sensing

Accurate detection and identification of conformational evolutions are essential to describe the micro-structural mechanisms of protein allostery. Here we establish an approach by integrating nanopore sensing technique with atomic force microscopy, based on molecular dynamics simulations. A theoretical method is further developed to real-time estimate the low-resolution structures of those evolved conformations. Tests for the forced allostery of αXβ2 integrin, a typical protein with multiple functional states, demonstrate that the spheroidal shape identifiers of those intermediate conformers present sufficient sensitivity to resolve two allosteric patterns of αXβ2 from bent-down to stand-up states under the nanopore confinement. The strong steric confinement from the nanopore restricts the geometric displacements of key domains in conformational extension dynamics, thereby increasing the intramolecular interaction energy barrier to be overcome for standing. Prolongation of the neck-shoulder region of αXβ2 and opening at the thigh-calf joint form a competitive compensation for the stretched height, resulting in two tendentious allosteric patterns under various confined diameters and steered speeds. Thus, this study proposes a new method to real-time visualize the conformational dynamics during protein allostery, favoring to depict structural characteristics for the conformations of those transient states and evaluate the impacts of the nanopore confinement on protein allostery.

DNA Carrier-Assisted Molecular Ping-Pong in an Asymmetric Nanopore.

Nanopore analysis relies on ensemble averaging of translocation signals obtained from numerous molecules, requiring a relatively high sample concentration and a long turnaround time from the sample to results. The recapture and subsequent re-reading of the same molecule is a promising alternative that enriches the signal information from a single molecule. Here, we describe how an asymmetric nanopore improves molecular ping-pong by promoting the recapture of the molecule in the trans reservoir. We also demonstrate that the molecular recapture could be improved by linking the target molecule to a long DNA carrier to reduce the diffusion, thereby achieving over 100 recapture events. Using this ping-pong methodology, we demonstrate its use in accurately resolving nanostructure motifs along a DNA scaffold through repeated detection. Our method offers novel insights into the control of DNA polymer dynamics within nanopore confinement and opens avenues for the development of a high-fidelity DNA detection platform.

Molecular insight into the oil displacement mechanism of CO2 flooding in the nanopores of shale oil reservoir

With the increasing demand for petroleum, shale oil with considerable reserves has become an important part of global oil resources. The shale oil reservoir has a large number of nanopores and a complicated mineral composition, and the effect of nanopore confinement and pore type usually makes the effective development of shale oil challenging. For a shale oil reservoir, CO2 flooding can effectively reduce the oil viscosity and improve the reservoir properties, which can thus improve the recovery performance. In this study, the method of non-equilibrium molecular dynamics (NEMD) simulation is used to simulate the CO2 flooding process in the nanoscale pores of shale oil reservoir. The performance difference between the organic kerogen slit nanopore and four types of inorganic nanopores is discussed. Thus, the effects of nanopore type and displacement velocity on the nanoscale displacement behavior of CO2 are analyzed. Results indicate that the CO2 flooding process of different inorganic pores is different. In comparison, the displacement efficiency of light oil components is higher, and the transport distance is longer. The intermolecular interaction can significantly affect the CO2 displacement behavior in nanopores. The CO2 displacement efficiency is shown as montmorillonite, feldspar > quartz > calcite > kerogen. On the other hand, it is found that a lower displacement velocity can benefit the miscibility process between alkane and CO2, which is conducive to the overall displacement process of CO2. The displacement efficiency can significantly decrease with the increase in displacement velocity. But once the displacement velocity is very high, the strong driving force can promote the alkane to move forward, and the displacement efficiency will recover slightly. This study further reveals the microscopic oil displacement mechanism of CO2 in shale nanopores, which is of great significance for the effective development of shale oil reservoirs by using the method of CO2 injection.

Conductivity of Ionic Liquids In the Bulk and during Infiltration in Nanopores.

The conductivity of ionic liquids (ILs) in nanopores is essential when considering their application as materials for energy. However, no consensus has been reached about the influence of confinement on the mobility of the ions. A series of ILs bearing the same cation, 1-butyl-3-methylimidazolium ([BMIM]+), and six different anions ([Cl]-, [Br]-, [I]-, [BF4]-, [PF6]-, and [TFSI]-) with radii from 0.168 to 0.326 nm were investigated with respect to their self-assembly, the thermodynamics, and the ionic conductivity in the bulk, during flow and under confinement in cylindrical nanopores with sizes in the range from 400 to 25 nm. In the bulk, the [BMIM]+[X]- exhibits weak ordering as a result of cation-anion correlations (charge alteration peak), and nanophase separation of polar/apolar groups. Liquid-to-glass temperatures were found to differ by ∼50 K, their viscosities by a factor of ∼270, and their conductivities by a factor of 24 (all at a temperature of 303 K). Electrostatic interactions were largely responsible for variations in the glass temperature, the viscosity, and the conductivity. Confined ILs behave differently from the bulk. The majority of ILs in the bulk were prone to crystallization during heating but were unable to crystallize in the smaller pores. Changes in dc-conductivity were used as markers of the phase state. This allowed the construction of the effective phase diagrams under confinement. The ILs penetrate the pores with an effective viscosity of the order of their viscosity in their bulk state. However, within the pores the dc-conductivity was reduced relative to bulk, indicating the immobilization of ions at the pore walls. Hydrophobization of the pore walls by hexamethyldisilazane could partially restore the conductivity. ILs are model systems where the phase state and ion mobility can be controlled by confinement.

How grain size influences hydrocarbon generation and expulsion of shale based on Rock-Eval pyrolysis and kinetics?

The differences between the Rock-Eval pyrolysis results of powder and grain samples have attracted wide attentions. Grain samples show lower hydrocarbon yield and different composition of the products. However, the effect of grain size on hydrocarbon generation and expulsion has not yet been quantitatively evaluated. In this study, we prepared each grain into a regular column with precise geometric parameters such as diameter, height, surface area, and volume, which is defined as an independent unit of hydrocarbon generation and expulsion. For comparison, a powder sample corresponding to each grain sample is collected simultaneously during the preparation process. The grain samples are used to simulate the mass of hydrocarbons expelled, while the powder samples are used to simulate the total mass of hydrocarbon generated. Our results show significant differences between the grain samples and the powder samples. All powder samples have a higher expulsion of free hydrocarbons (S1) than grain samples, and almost all grain samples have a higher expulsion of pyrolysis hydrocarbons (S2) than powder samples when the diameter of the grains is smaller than 3 mm. Temperature controls hydrocarbon generation, but grain size retards hydrocarbon expulsion. The influences of the “carry-over” phenomenon, oil adsorption and nanopore confinement are enhanced by grain size, which retards and inhibits hydrocarbon expulsion. Some free hydrocarbons (S1) cannot be expelled from the grain samples at 300 °C. Parts of the retained free hydrocarbons (S1) further cracked into small molecules, which can be expelled and detected as pyrolysis hydrocarbons (S2) at 300–650 °C. Four new parameters were proposed to quantify these influences, namely the S1retained, the S2extra expulsion, the HI difference parameter, and the TOC difference parameter. Diameter is more closely related to hydrocarbon expulsion rather than height. For grain samples, HI increases and TOC decreases with increasing diameter. Activation energies for hydrocarbon generation ranges from 43 to 67 kcal/mol for powder samples, while activation energies for grain samples are almost concentrated in 54–55 kcal/mol, indicating a high expulsion threshold for grain samples. As the grain diameter increases from 1.74 to 5.24 mm, the transformation ratio decreases and the generation rate increases, indicating that the grain size delays the expulsion of hydrocarbon. This laboratory simulation provides some new results to better understand the hydrocarbon generation and expulsion of shale rock under natural conditions.

Evaluation of Nanopore Sensor Design Using Electrical and Optical Analyses.

Nanopores are currently utilized as powerful tools for single-molecule protein sensing. The reporting signal typically requires protein analytes to enter the nanopore interior, yet a class of these sensors has emerged that allows targeted detection free in solution. This tactic eliminates the spatial limitation of nanopore confinement. However, probing proteins outside the nanopore implies numerous challenges associated with transducing the physical interactions in the aqueous phase into a reliable electrical signature. Hence, it necessitates extensive engineering and tedious optimization routes. These obstacles have prevented the widespread adoption of these sensors. Here, we provide an experimental strategy by developing and validating single-polypeptide-chain nanopores amenable to single-molecule and bulk-phase protein detection approaches. We utilize protein engineering, as well as nanopore and nanodisc technologies, to create nanopore sensors that can be integrated with an optical platform in addition to traditional electrical recordings. Using the optical modality over an ensemble of detectors accelerates these sensors' optimization process for a specific task. It also provides insights into how the construction of these single-molecule nanopore sensors influences their performance. These outcomes form a basis for evaluating engineered nanopores beyond the fundamental limits of the resistive-pulse technique.

An integrated model based on transient flow and the nanoconfinement effect of water transport through nanopores

The property of water confined in nanopores is significantly different from that of bulk water, resulting in a great influence on the rate of water development during the unsteady state. In this study, we focused on the unsteady behavior of water transport in nanopores. We established a transient equation and applied the Laplace transform and Bessel function of the imaginary argument according to the time-dependent momentum conservation equation of Poiseuille-flow. The apparent density, apparent viscosity, and slip of the confined water were modeled by considering the water-wall interactions and the pore size. Moreover, the transient transport equation was modified by these three models to obtain a transient analytical model, which considered the effect of the nanoconfinement effect. We verified the credibility of the proposed model compared with other models as well as through experiments and molecular dynamics simulations. The results indicated that the development rate of water confinement in the superhydrophobic nanopores was much greater than that in intermediate wettability and hydrophilic pores, and its velocity profile behaved as an approximately straight line throughout the unsteady state. Slip in the intermediate wettability pores was more likely to transmit its effects to the pore center than in hydrophilic pores. We found that small hydrophilic pores were dominated by the apparent density and apparent viscosity in the unsteady state, whereas large hydrophilic pores were dominated by slip in the initial state, which gradually changed to apparent density and apparent viscosity with time. For the superhydrophobic pores, regardless of pore size, slip was the main controlling factor in the unsteady state. Additionally, the sensitivity of confined water stabilization time to pore size was much greater in the superhydrophobic pores than in the hydrophilic pores.

Fluids and Electrolytes under Confinement in Single-Digit Nanopores.

Confined fluids and electrolyte solutions in nanopores exhibit rich and surprising physics and chemistry that impact the mass transport and energy efficiency in many important natural systems and industrial applications. Existing theories often fail to predict the exotic effects observed in the narrowest of such pores, called single-digit nanopores (SDNs), which have diameters or conduit widths of less than 10 nm, and have only recently become accessible for experimental measurements. What SDNs reveal has been surprising, including a rapidly increasing number of examples such as extraordinarily fast water transport, distorted fluid-phase boundaries, strong ion-correlation and quantum effects, and dielectric anomalies that are not observed in larger pores. Exploiting these effects presents myriad opportunities in both basic and applied research that stand to impact a host of new technologies at the water-energy nexus, from new membranes for precise separations and water purification to new gas permeable materials for water electrolyzers and energy-storage devices. SDNs also present unique opportunities to achieve ultrasensitive and selective chemical sensing at the single-ion and single-molecule limit. In this review article, we summarize the progress on nanofluidics of SDNs, with a focus on the confinement effects that arise in these extremely narrow nanopores. The recent development of precision model systems, transformative experimental tools, and multiscale theories that have played enabling roles in advancing this frontier are reviewed. We also identify new knowledge gaps in our understanding of nanofluidic transport and provide an outlook for the future challenges and opportunities at this rapidly advancing frontier.

Optimization of CO2 Huff-n-Puff in Unconventional Reservoirs with a Focus on Pore Confinement Effects, Fluid Types, and Completion Parameters

The cyclic injection of CO2, referred to as the huff-n-puff (HnP) method, is an attractive option to improve oil recovery from unconventional reservoirs. This study evaluates the optimization of the CO2 HnP method and provides insight into the aspects of CO2 sequestration for unconventional reservoirs. Furthermore, this study also examines the impact of nanopore confinement, fluid composition, injection solvent, diffusivity parameters, and fracture properties on the long-term recovery factor. The results from over 500 independent simulations showed that the optimal recovery is obtained for the puff-to-huff ratio of around 2.73 with a soak period of fewer than 2.7 days. After numerous HnP cycles, an optimized CO2 HnP process resulted in about 970-to-1067-ton CO2 storage per fracture and over 32% recovery, compared to 22% recovery for natural depletion over the 30 years. The optimized CO2 HnP process also showed higher effectiveness compared to the N2 HnP scenario. Additionally, for reservoirs with significant pore confinement (pore size ≤ 10 nm), the oil recovery improved by over 3% compared to the unconfined bulk phase properties. We also observed over 300% improvement in recovery factor for a fluid with a significant fraction of light hydrocarbons (C1–C6), compared to just a 50% improvement in recovery for a fluid with a substantial fraction of heavy hydrocarbons (C7+). Finally, the results also showed that fracture properties are much more important for CO2 HnP than natural depletion. This study provides critical insights to optimize and improve CO2 HnP operations for different fluid phases and fracture properties encountered in unconventional reservoirs.

Physical Aging of Polystyrene Confined in Anodic Aluminum Oxide Nanopores.

We investigated the glassy dynamics of polystyrene (PS) confined in anodic aluminum oxide (AAO) nanopores by differential scanning calorimetry. Based on the outcome of our experiments, we show that the cooling rate applied to process the 2D confined PS melt has a significant impact on both the glass transition and the structural relaxation in the glassy state. A single glass transition temperature (Tg) is observed in quenched samples, while slow-cooled PS chains show two Tgs corresponding to a core-shell structure. The former phenomenon resembles what is observed in freestanding structures, while the latter is imputed to the adsorption of PS onto AAO walls. A more complex picture was drawn for physical aging. In the case of quenched samples, we observed a non-monotonic trend of the apparent aging rate that in 400 nm pores, reaches a value almost twice as larger than what is measured in bulk and decreases upon further confinement in smaller nanopores. For slow-cooled samples, by adequately varying the aging conditions, we were able to control the equilibration kinetics and either separate the two aging processes or induce an intermediate aging regime. We propose a possible explanation of these findings in terms of distribution in free volume and the presence of different aging mechanisms.

Rational design of the nanocomposite by in-situ sub-10 nm La(OH)3 formation for selective phosphorus removal in waters

Phosphate removal by nanocomposite is a promising approach in water remediation. But it is still challenged by the small size nanoparticles formation and kinetic diffusion under the nanopore confinement. Herein, we report a different strategy, which relies on the deposition of nano-La(OH)3 particles inside the porous biomass Artemia Cyst-shells matrix. The charged amino acid components of matrix drivers for the in-situ growth of rod-like nano-La(OH)3 with size below 10 nm, while the broad-porous skeleton structures enable and accelerate the accessibility of trace phosphate to nano-La(OH)3 sorption sites available, resulting in the efficient and fast phosphate removal performance. This nanocomposite exhibited excellent adsorption capacity as high as 180.5 mg/g, which is beyond of most adsorbents by recent-ten-year survey. It also revealed superior selectivity against various competing ions with a distribution coefficient (Kd) up to ∼ 34000 mL/g, exceeding commercial ion-exchange resin by 15 times and outdoing 10 times the performance of well-known Fe based nanocomposites Lewatit FO36. An outstanding treatment capacity of 10980 L/kg under the continuous operation and the satisfactory regeneration property (> 95 %) further proves its applicability. This technology provides a new perspective approach for nanocomposite design and wastewater determination. It is also promising alleviating problems of trace phosphate deep purification in drinking water and wastewater medium.

Direct identification of amino acid-derived hormones with single-atom resolution using an engineered aerolysin nanopore.

The amino acid-derived hormones (AAHs), which are relatively small hydrophobic molecules derived from the amino acid tyrosine and tryptophan, play critical roles in the regulation of organism development and metabolism process. Direct identification of AAHs and their metabolites is highly desirable but very challenging because they simultaneously possess the features of small volume, hydrophobicity and highly structural similarity. Nanopore, capable of sensing the analytes in a single-molecule manner, may be engineered to identity AAHs. The key aporia is the ion current instability caused by the introduction of hydrophobic amino acids inside the nanopore confinement that is essential to improve the spatial and temporal resolution for small hydrophobic molecules sensing. Herein, we design a mutant aerolysin that precisely introduces a hydrophobic chemical environment in the critical sensing region with a highly controlled hydrogen bonds network to balance the ion follow stability and hydrophobic interactions. With this hydrophobic enhanced aerolysin nanopore, direct identification of AAHs was achieved, including thyroid hormone, pineal hormone and adrenal medullary hormone. Furthermore, three thyroid hormones with single iodine atom difference (T4, T3, and T2), were observed to be clearly discriminated in their mixture. Our engineered nanopore can even distinguish isomers of T3 and rT3 that vary only slightly in structure. Assisted with a custom clustering machine learning algorithm, the thyroid hormones T4, T3, and T2 in their mixture could be quantified, which suggests a simple and rare approach to measure the AAHs in clinical samples.

Minireview on Lattice Boltzmann Modeling of Gas Flow and Adsorption in Shale Porous Media: Progress and Future Direction

As an important unconventional resource, shale gas reservoirs have unique characteristics different from conventional oil and gas reservoirs. The ultrasmall pore sizes in shale induce the nanopore confinement effect on shale gas flow. In addition, shale rocks are rich in organic matter, which has strong interactions with gas molecules and results in gas adsorption. The lattice Boltzmann method (LBM) for micro- and nanoscale gas flow, which is originally designed for micro-electro-mechanical systems (MEMS), has been modified to simulate gas flow and adsorption in shale rocks. This work reviews four types of lattice Boltzmann models developed recently for shale gas flow/adsorption: (1) the slip-velocity-based LBM, (2) high-order LBM, (3) diffusion-based LBM, and (4) REV-scale LBM. Among these models, the slip-velocity-based LBM is widely used for shale gas modeling, which incorporates the slip boundary condition and Knudsen number (Kn)-determined relaxation time to simulate the nanopore confinement effect. To model the gas adsorption, the fluid–solid interaction force is introduced into the model, and the magnitude of this interaction force is usually obtained from the molecular level simulations. LBMs have been regarded as an efficient numerical tool to estimate the shale gas apparent permeability, to describe the pore-scale flow behaviors, and to address the influence of gas adsorption on shale gas storage and transport. Nevertheless, some challenges exist in current applications of LBMs for shale gas flow and adsorption simulations that are discussed in this minireview as well.