The mechanism of unconventional hydrocarbon formation: Hydrocarbon self-sealing and intermolecular forces

The successful development of unconventional hydrocarbons has significantly increased global hydrocarbon resources, promoted the growth of global hydrocarbon production and made a great breakthrough in classical oil and gas geology. The core mechanism of conventional hydrocarbon accumulation is the preservation of hydrocarbons by trap enrichment and buoyancy, while unconventional hydrocarbons are characterized by continuous accumulation and non-buoyancy accumulation. It is revealed that the key of formation mechanism of the unconventional reservoirs is the self-sealing of hydrocarbons driven by intermolecular forces. Based on the behavior of intermolecular forces and the corresponding self-sealing, the formation mechanisms of unconventional oil and gas can be classified into three categories:(1) thick oil and bitumen, which are dominated by large molecular viscous force and condensation force;(2) tight oil and gas, shale oil and gas and coal-bed methane, which are dominated by capillary forces and molecular adsorption;and(3) gas hydrate, which is dominated by intermolecular clathration. This study discusses in detail the characteristics, boundary conditions and geological examples of self-sealing of the five types of unconventional resources, and the basic principles and mathematical characterization of intermolecular forces. This research will deepen the understanding of formation mechanisms of unconventional hydrocarbons, improve the ability to predict and evaluate unconventional oil and gas resources, and promote the development and production techniques and potential production capacity of unconventional oil and gas.

Intermolecular and surface forces in atomic-scale manufacturing

Atomic and close-to-atomic scale manufacturing(ACSM)aims to provide techniques for manufacturing in various fields,such as circuit manufacturing,high energy physics equipment,and medical devices and materials.The realization of atomic scale material manipulation depending on the theoretical system of classical mechanics faces great challenges.Understanding and using intermolecular and surface forces are the basis for better designing of ACSM.Transformation of atoms based on scanning tunneling microscopy or atomic force microscopy(AFM)is an essential process to regulate intermolecular interactions.Self-assemble process is a thermodynamic process involving complex intermolecular forces.The competition of these interaction determines structure assembly and packing geometry.For typical nanomachining processes including AFM nanomachining and chemical mechanical polishing,the coupling of chemistry and stress(tribochemistry)assists in the removal of surface atoms.Furthermore,based on the principle of triboelectrochemistry,we expect a further reduction of the potential barrier,and a potential application in high-efficiency atoms removal and fabricating functional coating.Future fundamental research is proposed for achieving high-efficiency and high-accuracy manufacturing with the aiding of external field.This review highlights the significant contribution of intermolecular and surface forces to ACSM,and may accelerate its progress in the in-depth investigation of fundamentals.

Computational Simulation of Aptamer-target Binding Mechanisms

Aptamers are a type of single-chain oligonucleotide that can combine with a specific target.Due to their simple preparation,easy modification,stable structure and reusability,aptamers have been widely applied as biochemical sensors for medicine,food safety and environmental monitoring.However,there is little research on aptamer-target binding mechanisms,which limits their application and development.Computational simulation has gained much attention for revealing aptamer-target binding mechanisms at the atomic level.This work summarizes the main simulation methods used in the mechanistic analysis of aptamer-target complexes,the characteristics of binding between aptamers and different targets(metal ions,small organic molecules,biomacromolecules,cells,bacteria and viruses),the types of aptamer-target interactions and the factors influencing their strength.It provides a reference for further use of simulations in understanding aptamer-target binding mechanisms.

A Revisited Definition of the Three Solute Descriptors Related to the Van der Waals Forces in Solutions

It is currently admitted that the intermolecular forces implicated in Gas Liquid Chromatography (GLC) can be expressed as a product of parameters (or descriptors) of solutes and of parameters of solvents. The present study is limited to those of solutes, and among them the three ones are involved in the Van der Waals forces, whereas the two ones involved in the hydrogen bonding are left aside at this stage. These three studied parameters, which we call δ, ω and ε, respectively reflect the three types of Van der Waals forces: dispersion, orientation or polarity strictly speaking, and induction-polarizability. These parameters have been experimentally obtained in previous studies for 121 Volatile Organic Compounds (VOC) via an original Multiplicative Matrix Analysis (MMA) applied to a superabundant and accurate GLC data set. Then, also in previous studies, attempts have been made to predict these parameters via a Simplified Molecular Topology procedure (SMT). Because these last published results have been somewhat disappointing, a promising new strategy of prediction is developed and detailed in the present article.

Probing the Interfacial Forces and Surface Interaction Mechanisms in Petroleum Production Processes

Despite the advances that have been made in renewable energy over the past decade,crude oil or petroleum remains one of the most important energy resources to the world.Petroleum production presents many challenging issues,such as the destabilization of complex oil-water emulsions,fouling phenomena on pipelines and other facilities,and water treatment.These problems are influenced by the molecular forces at the oil/water/solid/gas interfaces involved in relevant processes.Herein,we present an overview of recent advances on probing the interfacial forces in several petroleum production processes(e.g.,bitumen extraction,emulsion stabilization and destabilization,fouling and antifouling phenomena,and water treatment)by applying nanomechanical measurement technologies such as a surface forces apparatus(SFA)and an atomic force microscope(AFM).The interaction forces between bitumen and mineral solids or air bubbles in the surrounding fluid media determine the bitumen liberation and flotation efficiency in oil sands production.The stability of complex oil/water emulsions is governed by the forces between emulsion drops and particularly between interface-active species(e.g.,asphaltenes).Various oil components(e.g.,asphaltenes)and emulsion drops interact with different substrate surfaces(e.g.,pipelines or membranes),influencing fouling phenomena,oil-water separation,and wastewater treatment.Quantifying these intermolecular and interfacial forces has advanced the mechanistic understanding of these interfacial interactions,facilitating the development of advanced materials and technologies to solve relevant challenging issues and improve petroleum production processes.Remaining challenges and suggestions on future research directions in the field are also presented.

Transformation of microstructure and phase of disodium guanosine 5′-monophosphate: Thermodynamic perspectives

Microstructure and phase transformation of disodium guanosine 5′-monophosphate(5′-GMPNa_2) are extremely important for controlling the process and understanding the mechanism of crystallization. In this work, the thermodynamic properties of polymorphous 5′-GMPNa_2 especially the solubility were studied, the solubility results show that 5′-GMPNa_2 is more soluble in ethanol–water(E–W) than in isopropanol–water(I–W). The amorphous form of 5′-GMPNa_2 is more soluble than the crystalline form at the same mole fraction and temperature. Meanwhile, the crystalline forms and morphologies of the residual solids were characterized by PXRD and SEM. The results indicate that solid forms of 5′-GMPNa_2 transformed spontaneously from amorphous to crystalline when the ethanol proportion is ≥20%. In addition, increasing the pH facilitates the dissolution of 5′-GMPNa_2 and helps to maintain the crystalline form. The associated Gibbs free energy values were calculated to verify the trend of transformation from amorphous to crystalline 5′-GMPNa_2. These results should help to guide the industrial crystallization process and to obtain the crystalline form of 5′-GMPNa_2.

Analysis and Comparison of the Alpha Functions of SRK Equation of State

Alpha functions of Soave-Redlich-Kwong （SRK） equation of state proposed by Soave, Twu, and Luo were different in mathematic tendency. They were compared in modeling methane-alkanes equilibria with van der Waals mixing rule and Modified Huron-Vidal （MHV1） mixing rule, respectively. Results showed that Luo＇s alpha function was a little more accurate than Soave＇s, and Twu＇s alpha function lacked accuracy in modeling methane-alkanes equilibrium. SRK equation of state was expanded as virial form, and then the equivalent terms were contrasted with terms of virial equation of state. Results showed that Soave＇s and Luo＇s alpha functions matched the tendency of virial coefficient better than Twu＇s, and Luo＇s alpha function matched better than Soave＇s in wide temperature range, which sustained the conclusions of phase equilibria calculation. Luo＇s alpha function keeps decreasing when Tr〉 1 and becomes negative at sufficient high temperature, thus the conventional cubic equation of state expressed pressure as the sum of repulsion pressure PR （〉0）, and attraction pressure PA （〈0） could be improved to be the sum of hard-sphere repulsion pressure PH （〉0） and intermolecular force pressure P1 （P1〈0 at low temperature and p1〉0 at sufficient high temperature）.

Effects of size-dependent elasticity on stability of nanotweezers

It is well-recognized that the electromechanical response of a nanostructure is affected by its element size. In the present article, the size dependent stability behavior and nanotweezers fabricated from nanowires are investigated by modified couple stress elasticity （MCSE）. The governing equation of the nanotweezers is obtained by taking into account the presence of Coulomb and intermolecular attractions. To solve the equation, four techniques, i.e., the modified variational iteration method （MVIM）, the monotonic iteration method （MIM）, the MAPLE numerical solver, and a lumped model, are used. The variations of the arm displacement of the tweezers versus direct current （DC） voltage are obtained. The instability parameters, i.e., pull-in voltage and deflection of the system, are computed. The results show that size-dependency will affect the stability of the nanotweezers significantly if the diameter of the nanowire is of the order of the length scale. The impact of intermolecular attraction on the size-dependent stability of the system is discussed.

Anisotropic formation mechanism and nanomechanics for the self-assembly process of cross-β peptides

Nanostructures self-assembled by cross-β peptides with ordered structures and advantageous mechanical properties have many potential applications in biomaterials and nanotechnologies. Quantifying the intra-and inter-molecular driving forces for peptide self-assembly at the atomistic level is essential for understanding the formation mechanism and nanomechanics of various morphologies of self-assembled peptides. We investigate the thermodynamics of the intra-and inter-sheet structure formations in the self-assembly process of cross-β peptide KⅢIK by means of steered molecular dynamics simulation combined with umbrella sampling. It is found that the mechanical properties of the intra-and inter-sheet structures are highly anisotropic with their intermolecular bond stiffness at the temperature of 300 K being 5.58 N/m and 0.32 N/m, respectively. This mechanical anisotropy comes from the fact that the intra-sheet structure is stabilized by enthalpy but the inter-sheet structure is stabilized by entropy. Moreover, the formation process of KⅢIK intra-sheet structure is cooperatively driven by the van der Waals （VDW） interaction between the hydrophobic side chains and the electrostatic interaction between the hydrophilic backbones, but that of the inter-sheet structure is primarily driven by the VDW interaction between the hydrophobic side chains. Although only peptide KⅢIK is studied, the qualitative conclusions on the formation mechanism should also apply to other cross-β peptides.

Weak interaction-steered evolution of polyoxovanadate-based metal-organic polyhedra from transformation via interlock to packing

A bottleneck in biomimetic synthesis consists in the full copy of,for example,the hierarchical structure of proteins directed by weak interactions.By contrast with covalent bonds bearing definite orientation and high stability,weak intermolecular forces within a continuous dynamic equilibrium can be hardly tamed for molecular design.In this endeavor,a ligand-dominated strategy that embodies tunable electrostatic repulsion andπ···πstacking was first employed to shape polyoxovanadate-based metal-organic polyhedra(VMOPs).Structural evolution involving transformation,interlock,and discovery of an unprecedented prototype of the Star of David was hence achievable.Not only as a handy tool for the primary structural control over VMOPs,these weak forces allow for an advanced management on the spatial distribution of such manmade macromolecules as well as the associated physicochemical behaviors,representing an ideal model for simulating and interpreting the conformation-function relationship of proteins.

Self-healing Hydrogelsand Underlying Reversible Intermolecular Interactions

Self-healing hydrogels have attracted growing attention over the past decade due to their biomimetic structure,biocompatibility,as well as enhanced lifespan and reliability,thereby have been widely used in various biomedical,electrical and environmental engineering applications.This feature article has reviewed our recent progress in self-healing hydrogels derived from mussel-inspired interactions,multiple hydrogen-bonding functional groups such as 2-ureido-4[1H]-pyrimidinohe(UPy),dynamic covalent bonds(eg,Schiff base reactions and boronic ester bonds).The underlying molecular basics of these interactions,hydrogel preparation principles,and corresponding performances and applications are introduced.The underlying reversible intermolecular interaction mechanisms in these hydrogels were investigated using nanomechanical techniques such as surface forces apparatus(SFA)and atomic force microscopy(AFM),providing fundamental insights into the self-healing mechanisms of the hydrogels.The remaining challenging issues and perspectives in this rapidly developing research area are also discussed.

Interface-enhanced distillation beyond tradition based on well-arranged graphene membrane

Traditional distillation(TD)is generally an energy-intensive and inefficient process for separation and purification of liquids in chemical industries.Herein,we developed an interface-enhanced distillation(IED)by employing a well-arranged membrane of reduced graphene oxide(rGO)sheet arrays embedded with silicon dioxide nanofibres(rGO/SiO2)as the evaporation intermediate layer on the liquid surface.This IED enlarges the evaporation surfaces and weakens the intermolecular forces on the liquid/solid/gas interfaces,realizing the fast and even low temperature fraction collection with less energy consumption.The IED delivers evaporation rates 200%–300%times that of TD,meanwhile having an energy saving of 40%–60%and a time saving of 50%–70%for diverse liquid feeds.In atmospheric IED manner,high boiling point and perishable organics can be collected with high quality at a temperature lower than their boiling points.This IED provides an innovative strategy for highly efficient distillation in chemical industries.

Adhesion hysteresis of a film-terminated fibrillar array

Motivated by the recent biomimic design of microstructured adhesive surfaces,we study adhesion between a film-terminated fibrillar array and a rigid substrate.Using a two-dimensional model and ignoring the deformation of the fibers and the backing layer,we show that the adhesion behavior is dominated by a dimensionless parameter reflecting the global flexibility of the terminal film.In particular,if the parameter is larger than 0.4,the adhesion is reversible;otherwise one or more hysteresis loops will appear after an approach-retraction cycle,leading to significant increase in the specific separation work.The result is expected to help not only optimal design of the structure,but also other applications such as micro-manipulation in micromechanical systems.