Search Results (34)

Machine Learning methods are exploited to extract a universal approach for self-diffusion coefficient calculation in molecular fluids. Analytical expressions are derived through symbolic regression for fluids both in bulk and confined nanochannels. The symbolic regression framework is trained on simulation data from molecular dynamics and correlates the values of the self-diffusion coefficients with macroscopic properties, such as density, temperature, and the width of confinement. New expressions are derived for nine different molecular fluids, while an all-fluid universal equation is extracted to capture molecular behavior as well. In such a way, a highly computationally demanding property is predicted by easy-to-define macroscopic parameters, bypassing traditional numerical methods based on mean squared displacement and autocorrelation functions at the atomistic level. To achieve generalizability and interpretability, simple symbolic expressions are selected from a pool of genetic programming-derived equations. The obtained expressions present physical consistency, and they are discussed in terms of explainability. The accurate prediction of the self-diffusion coefficient both in bulk and confined systems is important for advancing the fundamental understanding of fluid behavior and leading the design of nanoscale confinement devices containing real molecular fluids. Full article

The sensitive detection of inflammatory biomarkers in gingival crevicular fluid (GCF) is highly desirable for the evaluation of periodontal disease. Luminol-based electrochemiluminescence (ECL) immunosensors offer a promising approach for the fast and convenient detection of biomarkers. However, luminol’s low ECL efficiency under neutral conditions remains a challenge. This study developed an immunosensor by engineering an immunorecognition interface on the outer surface of mesoporous silica nanochannel film (SNF) and confining a Co₃O₄ nanocatalyst within the SNF nanochannels to improve the luminol ECL efficiency. The SNF was grown on an indium tin oxide (ITO) electrode using the simple Stöber solution growth method. A Co₃O₄ nanocatalyst was successfully confined within the SNF nanochannels through in situ electrodeposition, confirmed by X-ray photoelectron spectroscopy (XPS) and electrochemical measurements. The confined Co₃O₄ demonstrated excellent electrocatalytic activity, effectively enhancing luminol and H₂O₂ oxidation and boosting the ECL signal under neutral conditions. Using interleukin-6 (IL-6) as a proof-of-concept demonstration, the epoxy functionalization of the SNF outer surface enabled the covalent immobilization of capture antibodies, forming a specific immunorecognition interface. IL-6 binding induced immunocomplex formation, which reduced the ECL signal and allowed for quantitative detection. The immunosensor showed a linear detection range for IL-6 from 1 fg mL⁻¹ to 10 ng mL⁻¹, with a limit of detection (LOD) of 0.64 fg mL⁻¹. It also demonstrated good selectivity and anti-interference capabilities, enabling the successful detection of IL-6 in artificial GCF samples. Full article

Simple development of an electrochemiluminescence (ECL) immunosensor for convenient detection of tumor biomarker is of great significance for early cancer diagnosis, treatment evaluation, and improving patient survival rates and quality of life. In this work, an immunosensor is demonstrated based on an enhanced ECL signal boosted by nanochannel-confined Au nanomaterial, which enables sensitive detection of the tumor biomarker—carcinoembryonic antigen (CEA). Vertically-ordered mesoporous silica film (VMSF) with a nanochannel array and amine groups was rapidly grown on a simple and low-cost indium tin oxide (ITO) electrode using the electrochemically assisted self-assembly (EASA) method. Au nanomaterials were confined in situ on the VMSF through electrodeposition, which catalyzed both the conversion of dissolved oxygen (O₂) to reactive oxygen species (ROS) and the oxidation of a luminol emitter and improved the electrode active surface. The ECL signal was enhanced fivefold after Au nanomaterial deposition. The recognitive interface was fabricated by covalent immobilization of the CEA antibody on the outer surface of the VMSF, followed with the blocking of non-specific binding sites. In the presence of CEA, the formed immunocomplex reduced the diffusion of the luminol emitter, resulting in the reduction of the ECL signal. Based on this mechanism, the constructed immunosensor was able to provide sensitive detection of CEA ranging from 1 pg·mL⁻¹ to 100 ng·mL⁻¹ with a low limit of detection (LOD, 0.37 pg·mL⁻¹, S/N = 3). The developed immunosensor exhibited high selectivity and good stability. ECL determination of CEA in fetal bovine serum was achieved. Full article

The convenient and sensitive detection of metabolites is of great significance for understanding human health status and drug development. Solid-phase electrochemiluminescence (ECL) enzyme electrodes show great potential in metabolite detection based on the enzyme-catalyzed reaction product hydrogen peroxide (H₂O₂). Herein, a solid-phase ECL enzyme sensor was fabricated based on a confined emitter and an immobilized enzyme using electrostatic nanocage array, constructing a platform for the sensitive detection of cholesterol. The electrostatic cage nanochannel consists of a bipolar and bilayer vertically aligned mesoporous silica film (bp-VMSF). The upper layer of bp-VMSF is an amino-modified, positively charged VMSF (p-VMSF), and the lower layer is a negatively charged VMSF (n-VMSF). The most commonly used ECL probe tris(bipyridine)ruthenium(II) (Ru(bpy)₃²⁺) is fixed in n-VMSF by electrostatic adsorption from n-VMSF and electrostatic repulsion from the upper p-VMSF, generating significantly enhanced and stable ECL signals. The successful preparation of the electrostatic cage was characterized by scanning electron microscopy (SEM) and electrochemical methods. After amino groups on the outer surface of bp-VMSF were derivatized with aldehyde, cholesterol oxidase (ChOx) molecules were covalently immobilized. The successful construction of the enzyme electrode was characterized by cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). When the corresponding enzyme substrate, cholesterol, was present in the solution, the ECL signal of Ru(bpy)₃²⁺ was quenched by the enzyme-catalyzed reaction product H₂O₂, enabling the high-sensitivity detection of cholesterol. The linear range for detecting cholesterol was from 0.05 mM to 5.0 mM, with a limit of detection (LOD) of 1.5 μM. Full article

The confinement effect in micro- and nanopores gives rise to distinct flow characteristics in fluids. Clarifying the fluid migration pattern in confined space is crucial for understanding and explaining the abnormal flow phenomena in unconventional reservoirs. In this study, flow characteristics of water and oil in alumina nanochannels were investigated with diameters ranging from 21 nm to 120 nm, and a heterogeneous viscosity flow model considering boundary fluid was proposed. Compared with the prediction of the HP equation, both types of fluids exhibit significant flow suppression in nanochannels. As the channel size decreases, the deviation degree increases. The fluid viscosity of the boundary region displays an upward trend as the channel size decreases and the influence of the interaction between the liquid and solid walls intensifies. The thickness of the boundary region gradually decreases with increasing pressure and eventually reaches a stable value, which is primarily determined by the strength of the interaction between the liquid and solid surfaces. Both the pore size and wettability are essential factors that affect the fluid flow. When the space scale is extremely small, the impact of wettability becomes more pronounced. Finally, the application of the heterogeneous flow model for permeability evaluation has yielded favorable fitting results. The model is of great significance for studying the fluid flow behavior in unconventional reservoirs. Full article

In the last decades, molecular dynamics (MD) simulations established as an important tool for solving fluid flow and heat transfer problems at the nanoscale, with a significant perspective impact on a wide range of industrial and scientific applications. As usual, this happened with several scholarly papers on this topic being published in the same period. The present article provides a thorough review of molecular dynamics (MD) simulations in the domain of fluid flow and heat transfer. In the first section, a survey of the physical modelling of heat transfer phenomena by MD simulations is presented, focusing on bubble and droplet nucleation and interfacial thermal behaviours. Subsequently, MD simulations of fluid flow and heat transfer in nanochannels are discussed, including adiabatic flow, convective heat transfer, and two-phase flow. Particular emphasis was placed on critical phenomena such as evaporation and condensation, to assess the effects of confinement within nanochannels. Finally, some of the current and emerging challenges in MD simulations and suggests future research directions are discussed. Full article

The rapid and sensitive detection of the important biomarker C-reactive protein (CRP) is of great significance for monitoring inflammation and tissue damage. In this work, an electrochemiluminescence (ECL) aptasensor was fabricated based on dual signal amplification for the sensitive detection of CRP in serum samples. The sensor was constructed by modifying a silica nanochannel array film (SNF) on a cost-effective indium tin oxide (ITO) electrode using the Stöber solution growth method. Gold nanoparticles (AuNPs) were grown in situ within the nanochannels using a simple electrodeposition method as a nanocatalyst to enhance the active electrode area as well as the ECL signal. The negatively charged nanochannels also significantly enriched the positively charged ECL emitters, further amplifying the signal. The recognition aptamer was covalently immobilized on the outer surface of SNF after modification with epoxy groups, constructing the aptasensor. In the presence of CRP, the formation of complexes on the recognitive interface led to a decrease in the diffusion of ECL emitters and co-reactants to the supporting electrode, resulting in a reduction in the ECL signal. Based on this mechanism, ECL detection of CRP was achieved with a linear range of 10 pg/mL to 1 μg/mL and a low limit of detection (7.4 pg/mL). The ECL aptasensor developed in this study offers advantages such as simple fabrication and high sensitivity, making promising applications in biomarker detection. Full article

The nitrate ion (NO₃⁻) is a typical pollutant in environmental samples, posing a threat to the aquatic ecosystem and human health. Therefore, rapid and accurate detection of NO₃⁻ is crucial for both the aquatic sciences and government regulations. Here we report the fabrication of an amino-functionalized, vertically ordered mesoporous silica film (NH₂-VMSF) confining localized copper nanoparticles (CuNPs) for the electrochemical detection of NO₃⁻. NH₂-VMSF-carrying amino groups possess an ordered perpendicular nanochannel structure and ultrasmall nanopores, enabling the confined growth of CuNPs through the electrodeposition method. The resulting CuNPs/NH₂-VMSF-modified indium tin oxide (ITO) electrode (CuNPs/NH₂-VMSF/ITO) combines the electrocatalytic reduction ability of CuNPs and the electrostatic attraction capacity of NH₂-VMSF towards NO₃⁻. Thus, it is a rapid and sensitive electrochemical method for the determination of NO₃⁻ with a wide linear detection range of 5.0–1000 μM and a low detection limit of 2.3 μM. Direct electrochemical detection of NO₃⁻ in water samples (tap water, lake water, seawater, and rainwater) with acceptable recoveries ranging from 97.8% to 109% was performed, demonstrating that the proposed CuNPs/NH₂-VMSF/ITO sensor has excellent reproducibility, regeneration, and anti-interference abilities. Full article

Gas molecules or weakly interacting molecules are commonly observed to diffuse through and fill space. Therefore, when the molecules initially confined in one compartment are allowed to move through a channel into another empty compartment, we expect that some molecules will be transported into the initially empty compartment. In this work, we thermodynamically analyze this transport process using a simple model consisting of graphene plates, a carbon nanotube (CNT), and nonpolar molecules that are weakly interacting with each other. Specifically, we calculate the free energy change, or the potential of mean force (PMF), as the molecules are transported from one compartment to another compartment. The PMF profile clearly exhibits a global minimum, or a free energy well, at the state wherein the molecules are evenly distributed over the two compartments. To better understand the thermodynamic origin of the well, we calculate the energetic and entropic contributions to the formation of the well, and we show that the entropic change is responsible for it and is the driving force for transport. Our work not only enables a fundamental understanding of the thermodynamic nature of the transport of weakly interacting molecules with molecular details, but also provides a method for calculating the free energy change during transport between two separate spaces connected by a nanochannel. Full article

Rapid, highly sensitive, and accurate detection of tumor biomarkers in serum is of great significance in cancer screening, early diagnosis, and postoperative monitoring. In this study, an electrochemiluminescence (ECL) immunosensing platform was constructed by enhancing the ECL signal through in situ growth of platinum nanoparticles (PtNPs) in a nanochannel array, which can achieve highly sensitive detection of the tumor marker carcinoembryonic antigen (CEA). An inexpensive and readily available indium tin oxide (ITO) glass electrode was used as the supporting electrode, and a layer of amino-functionalized vertically ordered mesoporous silica film (NH₂-VMSF) was grown on its surface using an electrochemically assisted self-assembly method (EASA). The amino groups within the nanochannels served as anchoring sites for the one-step electrodeposition of PtNPs, taking advantage of the confinement effect of the ultrasmall nanochannels. After the amino groups on the outer surface of NH₂-VMSF were derivatized with aldehyde groups, specific recognition antibodies were covalently immobilized followed by blocking nonspecific binding sites to create an immunorecognition interface. The PtNPs, acting as nanocatalysts, catalyzed the generation of reactive oxygen species (ROS) with hydrogen peroxide (H₂O₂), significantly enhancing the ECL signal of the luminol. The ECL signal exhibited high stability during continuous electrochemical scanning. When the CEA specifically bound to the immunorecognition interface, the resulting immune complexes restricted the diffusion of the ECL emitters and co-reactants towards the electrode, leading to a reduction in the ECL signal. Based on this immune recognition-induced signal-gating effect, the immunosensor enabled ECL detection of CEA with a linear range of 0.1 pg mL⁻¹ to 1000 ng mL⁻¹ with a low limit of detection (LOD, 0.03 pg mL⁻¹). The constructed immunosensor demonstrated excellent selectivity and can achieve CEA detection in serum. Full article

Herein, we describe a fast and highly sensitive electrochemical sensor for doxorubicin (DOX) detection based on the indium tin oxide (ITO) modified with a binary material consisting of vertically-ordered mesoporous silica films (VMSFs) and N-doped graphene quantum dots (NGQDs). VMSFs, with high permeability and efficient molecular transport capacity, is attached to the ITO electrode via a rapid and controllable electrochemical method, which can serve as a solid template for the confinement of numerous NGQDs through facile electrophoresis. By virtue of the excellent charge transfer capacity, π-π and electrostatic preconcentration effects of NGQDs, as well as the electrostatic enrichment ability of VMSF, the presented NGQDs@VMSF/ITO shows amplified electrochemical signal towards DOX with a positive charge, resulting in good analytical performance in terms of a wide linear range (5 nM~0.1 μM and 0.1~1 μM), high sensitivity (30.4 μA μM⁻¹), and a low limit of detection (0.5 nM). Moreover, due to the molecular sieving property of VMSF, the developed NGQDs@VMSF/ITO sensor has good selectivity and works well in human serum and urine samples, with recoveries of 97.0~109%, thus providing a simple and reliable method for the direct electrochemical analysis of DOX without complex sample pretreatment procedures. Full article

In this paper, we propose an alternative road to calculate the transport coefficients of fluids and the slip length inside nano-conduits in a Poiseuille-like geometry. These are all computationally demanding properties that depend on dynamic, thermal, and geometrical characteristics of the implied fluid and the wall material. By introducing the genetic programming-based method of symbolic regression, we are able to derive interpretable data-based mathematical expressions based on previous molecular dynamics simulation data. Emphasis is placed on the physical interpretability of the symbolic expressions. The outcome is a set of mathematical equations, with reduced complexity and increased accuracy, that adhere to existing domain knowledge and can be exploited in fluid property interpolation and extrapolation, bypassing timely simulations when possible. Full article

Exploring new reverse osmosis (RO) membranes that break the permeability-selectivity trade-off rule is the ultimate goal in seawater desalination. Both nanoporous monolayer graphene (NPG) and carbon nanotube (CNT) channels have been proposed to be promising candidates for this purpose. From the perspective of membrane thickness, both NPG and CNT can be classified into the same category, as NPG is equivalent to the thinnest CNT. While NPG has the advantage of a high water flux rate and CNT is excellent at salt rejection performance, a transition is expected in practical devices when the channel thickness increases from NPG to infinite-sized CNTs. By employing molecular dynamics (MD) simulations, we find that as the thickness of CNT increases, the water flux diminishes but the ion rejection rate increases. These transitions lead to optimal desalination performance around the cross-over size. Further molecular analysis reveals that this thickness effect originates from the formation of two hydration shells and their competition with the ordered water chain structure. With the increase in CNT thickness, the competition-dominated ion path through CNT is further narrowed. Once above this cross-over size, the highly confined ion path remains unchanged. Thus, the number of reduced water molecules also tends to stabilize, which explains the saturation of the salt rejection rate with the increasing CNT thickness. Our results offer insights into the molecular mechanisms of the thickness-dependent desalination performance in a one-dimensional nanochannel, which can provide useful guidance for the future design and optimization of new desalination membranes. Full article

The development of simple and probe-integrated aptamer sensors for the electrochemical detection of tumor biomarkers is of great significance for the diagnosis of tumors and evaluation of prognosis. In this work, a probe-integrated aptamer sensor is demonstrated based on the stable confinement of an electrochemical probe in a bipolar nanochannel film, which can realize the reagentless electrochemical detection of the tumor biomarker carcinoembryonic antigen (CEA). To realize the stable immobilization of a large amount of the cationic electrochemical probe methylene blue (MB), a two-layer silica nanochannel array (SNF) with asymmetric charge was grown on the supporting electrode from bipolar SNF (bp-SNF). The inner SNF is negatively charged (n-SNF), and the outer-layer SNF is positively charged (p-SNF). The dual electrostatic interaction including the electrostatic adsorption from n-SNF and the electrostatic repulsion from p-SNF achieve the stable confinement of MB in bp-SNF. The recognitive interface is fabricated by the covalent immobilization of the CEA aptamer on the outer surface of bp-SNF, followed by the blocking of non-specific binding sites. Owing to the stable and abundant immobilized probes and highly specific aptamer interface, the developed aptamer sensor enables the sensitive detection of CEA in the range of 1 pg/mL to 1 μg/mL with a low limit of detection (LOD, 0.22 pg/mL, S/N = 3). Owing to the high selectivity and stability of the developed biosensor, reagentless electrochemical detection of CEA in serum was realized. Full article

Water dynamics in nanochannels are altered by confinement, particularly in small carbon nanotubes (CNTs). However, the mechanisms behind these effects remain unclear. To address these issues, we carried out extensive molecular dynamics (MD) simulations to investigate the structure and dynamics of water inside CNTs of different sizes (length of 20 nm and diameters vary from 0.8 nm to 5.0 nm) at different temperatures (from 200 K to 420 K). The radial density profile of water inside CNTs shows a single peak near the CNT walls for small nanotubes. For CNTs with larger sizes, water molecules are arranged into coaxial tubular sheets, the number of which increases with the CNT size. Subdiffusive behavior is observed for ultranarrow CNTs with diameters of 0.8 nm and 1 nm. As the size of CNTs increases, Fickian diffusion becomes evident. The hydrogen bond correlation function of water inside CNT decays slower than in bulk water, and the decay rate decreases as we increase the diameter of the CNTs. In large CNTs, the hydrogen bond lifetime of the innermost layer is shorter than the other layers and depends on temperature. Additional analysis of our results reveals that water molecules along the CNT axis show a non-Arrhenius to Arrhenius diffusion crossover. In general, the diffusion transition temperature is higher than that of bulk water, but it depends on the size of the CNT. Full article