Modification Of Nanopores Research Articles

Surface Modification of Nanopores in an Anodic Aluminum Oxide Membrane through Dopamine-Assisted Codeposition with a Zwitterionic Polymer.

Surface modification through dopamine-assisted codeposition with functional zwitterionic polymers can provide a simple and one-step functionalization under ambient conditions with robust and stable dopamine-surface interactions to improve the hydrophilicity of nanoporous membranes, thereby expanding their applicability to nanofiltration, ion transport, and blood purification. However, a significant knowledge gap remains in our comprehension of the mechanisms underlying the formation and deposition of dopamine/polymer aggregated coatings within nanoscale confinement. This study explores a feasible method for membrane modification through the codeposition of dopamine hydrochloride (DA) and poly(sulfobetaine methacrylate) (PSBMA) on nanopores of anodic aluminum oxide (AAO) membranes. Our findings demonstrate that the aggregated coatings of DA and PSBMA nanocomposites can effectively deposit on the surfaces within cylindrical AAO nanopores, significantly enhancing the hydrophilicity of the nanoporous membranes. The morphology and homogeneity of the nanocomposite coatings within the nanopores are further investigated by varying PSBMA molecular weights and AAO pore sizes, revealing that higher molecular weights result in more uniform deposition. This work sheds light on understanding the codeposition of DA and zwitterionic polymers in nanoscale environments, highlighting a straightforward and stable surface modification process of nanoporous membranes involving functional polymers.

Recent Advances in the Modification and Characterization of Solid-State Nanopores.

Nanopores, due to their advantages of being modifiable, controllability and sensitivity, have made a splash in recent years in the fields of biomolecular sequencing, small molecule detection, salt differential power generation, and biomimetic ion channels. In these applications, the role of chemical or biological modification is indispensable. Compared with small molecules, the modification of polymers is more difficult and the methods are more diverse. Choosing an appropriate modification method directly determines the success or failure of a research project; therefore, it is necessary to summarize polymer modification methods toward nanopores. In addition, it is also important to provide clear and convincing evidence that the nanopore modification is successful, the corresponding characterization methods are also indispensable. Therefore, this review will summarize the methods of polymer modification of nanopores and efficient characterization methods. We hope that this review will provide some reference value for like-minded researchers.

Nanoscale Pore Changes in a Marine Shale: A Case Study Using Pyrolysis Experiments and Nitrogen Adsorption

Nanoscale pores have an important role in the accumulation of gas in shale gas reservoirs. Indeed, the formation of nanopores is critical for the characterization and evaluation of a shale reservoir. Moreover, the effect of pyrolysis on the modification of nanopores is not clear. Therefore, this paper focuses on pyrolysis and nitrogen adsorption experiments to examine the nanoscale pore structure and evolution in marine shale strata with low total organic carbon content. All of the examined samples contain micro-, meso-, and macropores. The results show that the number of micropores increased as a result of artificial maturation (i.e., pyrolysis), which resulted in a significant increase in the surface area and the total pore volume. The openness of the pores significantly increased when the maturity was higher than 2.5% Ro (vitrinite reflectance). The 1.5–7.5 and 60–70 nm pores are the most pronounced to change after pyrolysis. Furthermore, liquid hydrocarbons produced during heating were shown to influe...

Molecular simulations of water adsorption and transport in mesopores with varying hydrophilicity arrangements.

The adsorption and transport of water in an open cylindrical mesopore with two different inner surface arrangements of hydrophilicities were examined by molecular simulations. The first model has a weak hydrophilic surface at both entrances of the pore and a stronger hydrophilic surface in the mid-section. The second pore has stronger hydrophilic surfaces at the entrances and weaker in the middle region. The simulation results show that the water adsorption isotherms obtained from Grand Canonical Monte Carlo simulations and pore filling curves acquired from Grand Canonical Molecular Dynamics simulations change depending on the arrangement of the strong and weak hydrophilic surfaces. In the first model, water condensation focuses on the mid-section forming a liquid bridge or a film, which creates a concave meniscus accelerating subsequent adsorption within the pore. Two bridges form in the entrance regions, where a cavity naturally occurs in between the films, in the second model. The different filling and emptying mechanisms clearly change the adsorption-desorption characteristics for the two pore types, but the second type generally showed faster transitions overall. Flux and meniscus analysis also reveals a circulating flow at the menisci of the interfaces within the pore. The results are expected to be valuable in understanding the effects of interior surface modification of nanopores in future applications.

Noncovalent functionalization of solid-state nanopores via self-assembly of amphipols.

In recent years there has been increasing interest in the development of new methods for conferring functional features to nanopore-based fluidic devices. In this work, we describe for the first time the noncovalent integration of amphoteric-amphipathic polymers, also known as "amphipols", into single conical nanopores in order to obtain signal-responsive chemical nanodevices. Highly-tapered conical nanopores were fabricated by single-sided chemical etching of polycarbonate foils. After etching, the surface of the conical nanopores was chemically modified, by first metallizing the surface via gold sputtering and then by amphiphilic self-assembly of the amphipol. The net charge of adsorbed amphipols was regulated via pH changes under the environmental conditions. The pH-dependent chemical equilibrium of the weak acidic and basic monomers facilitates the regulation of the ionic transport through the nanopore by adjusting the pH of the electrolyte solution. Our results demonstrate that functional amphipathic polymers are powerful building blocks for the surface modification of nanopores and might ultimately pave the way to a new means of integrating functional and/or responsive units within nanofluidic structures.

Ordering and modification of nanopores in porous anodic aluminum membranes

Anodic aluminum oxide (AAO) has attracted significant intension for decades owing to its extensive applications in nanoscale science and technology. Novel structures, like nanoparticles, nanotubes, nanowires, etc., have been developed based on AAO templates and widely applied in optics, micro/nano electronics and microfluidic systems, etc. In this work, three approaches have been developed to control and modify the parameters and arrangement of nanopores in anodized alumina, including the change of electrochemical conditions, guiding the growth of nanopores by highly aligned line structure, and further modification of nanopores by physical vapor deposition. Moreover, highly oriented line structures used to guide the channel growth have been fabricated under optimal conditions and could be utilized as templates to form wrinkled membranes, nanowires, etc. We conclude that electrochemical anodization should be a very promising technique for the fabrication of various nanoscale structures leading to potential applications in optics, solar systems and micro/nano electronics.

Layer-by-Layer Assembly of Polyelectrolytes into Ionic Current Rectifying Solid-State Nanopores: Insights from Theory and Experiment

Molecular design of ionic current rectifiers created on the basis of single conical nanopores is receiving increasing attention by the scientific community. Part of the appeal of this topic relies on the interest in sensors and fluidic nanoactuators based on the transport of ions and molecules through nanopore architectures that can readily be integrated into functional systems. The chemical modification of the pore walls controls not only the diameter of these nanoarchitectures but also their selectivity and transport properties. In order to confer selectivity to solid-state nanopores, it is necessary to develop and explore new methods for functionalizing the pore walls. Hence, the creation of functional nanopores capable of acting as selective ion channels or smart nanofluidic sensors depends critically on our ability to assemble and build up molecular architectures in a predictable manner within confined geometries with dimensions comparable to the size of the building blocks themselves. In this context, layer-by-layer deposition of polyelectrolytes offers a straightforward process for creating nanoscopic supramolecular assemblies displaying a wide variety of functional features. In this work, we describe for the first time the integration of layer-by-layer polyelectrolyte assemblies into single conical nanopores in order to study and explore the functional features arising from the creation of charged supramolecular assemblies within the constrained geometry of the nanofluidic device. To address this challenging topic, we used a combined experimental and theoretical approach to elucidate and quantify the electrostatic changes taking place inside the nanopore during the supramolecular assembly process. The multilayered films were built up through consecutive layer-by-layer adsorption of poly(allylamine hydrochloride) (PAH) and poly(styrenesulfonate) (PSS) on the pore surface. Our results show that the charge transport properties of single conical nanopores functionalized with PAH/PSS assemblies are highly dependent on the number of layers assembled on the pore wall. In contrast to what happens with PAH/PSS films deposited on planar surfaces (quantitative charge reversal), the surface charge of the pore walls decreases dramatically with the number of PAH/PSS layers assembled into the nanopore. This behavior was attributed to the nanoconfinement-induced structural reorganization of the polyelectrolyte layers, leading to the efficient formation of ion pairs and promoting a marked decrease in the net fixed charges on the nanopore walls. We consider that these results are of paramount relevance for the modification of nanopores, nanopipets, and nanoelectrodes using charged supramolecular assemblies, as well as of importance in "soft nanotechnology" provided that structural complexity, induced by nanoconfinement, can define the functional properties of self-assembled polymeric nanostructures.

Asymmetric epoxidation of 6-cyano-2,2-dimethylchromene on Mn(salen) catalyst immobilized in mesoporous materials

This article reports our recent work on the heterogeneous asymmetric epoxidation catalyzed by chiral Mn(salen) catalyst axially immobilized via phenoxyl groups and organic sulfonic groups. The asymmetric epoxidation of 6-cyano-2,2-dimethylchromene was especially presented in detail. The factors that affected the asymmetric induction, such as the nanopores and the external surface, the linkage length, and the modification of nanopores with methyl groups were discussed. It was found that the enantioselectivities increased with decreasing the nanopore sizes or increasing the linkage length in nanopore, and the Mn(salen) catalyst immobilized into nanopores generally gave higher ee values than those on the external surface. The heterogeneous Mn(salen) catalysts with modified nanopores gave a TOF of 14.8 h(-1) and an ee value of 90.6% for the asymmetric epoxidation of 6-eyano-2,2-dimethylchromene, which were higher than the results (TOF 10.8 h(-1), ee 80.1%) obtained for the homogeneous catalyst. (c) 2006 Elsevier Ltd. All rights reserved.

Binary Monolayer Mixtures: Modification of Nanopores in Silicon-Supported Tris(trimethylsiloxy)silyl Monolayers

Chemically grafted monolayers were prepared by reaction of tris(trimethylsiloxy)chlorosilane (tris-TMSCl) with silicon wafers both in the vapor phase and in toluene solution. Denser (more closely packed) monolayers, as assessed by carbon content (determined using X-ray photoelectron spectroscopy) and contact angle analysis, were obtained using the vapor phase reaction. Contact angles (θA/θR) for water, methylene iodide, and hexadecane on the vapor phase modified surfaces (96°/87°; 66°/56°; 33°/31°) indicate the hydrophobic and oleophobic nature of this surface. Dynamic contact angles of 30 different probe fluids were measured on the tris-TMS surfaces. A plot of contact angle hysteresis (the difference between advancing and receding contact angles) versus molar volume of the probe fluid shows a sharp decrease in hysteresis in the region of 180−190 cm3/mol for tris-TMS monolayers prepared in vapor phase. Probe fluids with lower molecular volume exhibit hysteresis of 8−12 degrees, while liquids of larger mol...