Tuning Nanochannel Microenvironments of a Thermoresponsive MXene Membrane for Mixed Molecule Gradient Separation.

Drawing inspiration from dynamic biological ion channels, researchers have developed various artificial membranes featuring responsive nanochannels. Typically, these membranes modify mass transport behaviors by manipulating the responsive layer on the inner surfaces of the intrinsic layer. In this study, we build two-dimensional lamellar membranes composed of titanium carbide MXene and poly(N-isopropylacrylamide), endowed with dual-level regulatable nanochannels, achieved through adjustments of nanochannel microenvironments. The size of these two-dimensional nanochannels can be altered by both the thermoresponsive polymer layer and the intrinsic MXene layer that could undergo spontaneous oxidation. The multilevel regulation strategy substantially enhances the molecular selectivity of MXene separation membranes, which is further applied for precise gradient separation toward multiple molecules. This advancement showcases the versatility and transformative capabilities of responsive nanochannel technology, setting the stage for innovative developments in diverse fields.

Nanochannel Stability of Chemically Converted Graphene Oxide Membranes.

Chemically converted graphene oxide laminate membranes, which exhibit stable interlayered nanochannels in aqueous environments, are receiving increasing attention owing to their potential for selective water and ion permeation. However, how the molecular properties of conversion agents influence the stabilization of nanochannels and how effectively nanochannels are stabilized have rarely been studied. In this study, mono-, di-, and tri-saccharide molecules of glucose (Glu), maltose (Glu2), and maltotriose (Glu3) are utilized, respectively, to chemically modify graphene oxide (GO). The aim is to create nanochannels with different levels of stability and investigate how these functional conversion agents affect the separation performance. The effects of the property differences between different conversion agents on nanochannel stabilization are demonstrated. An agent with efficient chemical reduction of GO and limited intercalation in the resulting nanochannel ensures satisfactory nanochannel stability during desalination. The stabilized membrane nanochannel exhibits a permeance of 0.69 L m-2 h-1 bar-1 and excellent Na2SO4 rejection of 96.42%. Furthermore, this optimized membrane nanochannel demonstrates enhanced stability under varying external conditions compared to the original GO. This study provides useful information for the design of chemical conversion agents for GO nanochannel stabilization and the development of nanochannel membranes for precise separation.

Selectively Transport and Removal of Fluoride Ion by Pillar[5]Arene Polymer-Filled Nanochannel Membrane.

Excess fluoride ions in groundwater accumulate through the roots of crops, affecting photosynthesis and inhibiting their growth. Long-term bioaccumulation also threatens human health because it is poorly degradable and toxic. Currently, one of the biggest challenges is developing a unique material that can efficiently remove fluoride ions from the environment. The excellent properties of functionalized pillar[5]arene polymer-filled nanochannel membranes were explored to address this challenge. Constructing a multistage porous nanochannel membrane, consisting of microscale etched nanochannels and nanoscale pillar[5]arene cross-linked polymer voids. A fluoride removal rate of 0.0088 mmol ⋅ L-1 ⋅ min-1 was achieved. Notably, this rate surpassed the rates observed with other control ions by a factor of 6 to 8.8. Our research provides a new direction for developing water fluoride ion removal materials.

The Specific Removal of Perfluorooctanoic Acid Based on Pillar[5]arene-Polymer-Packed Nanochannel Membrane.

The conspicuous surface activity and exceptional chemical stability of perfluorooctanoic acid, commonly referred to as PFOA, have led to its extensive utilization across a broad spectrum of industrial and commercial products. Nonetheless, significant concerns have arisen regarding the environmental presence of PFOAs, driven by their recognized persistence, bioaccumulative nature, and potential human health risks. In the realm of sustainable agriculture, a pivotal challenge revolves around the development of specialized materials capable of effectively and selectively eliminating PFOA from the environment. This study proposes harnessing the exceptional properties of a pillar[5]arene polymer to construct a nanochannel membrane filled with tryptophan-alanine dipeptide pillar[5]arene polymer. Through the functionalization of these nanochannel membranes, we achieved a PFOA removal rate of 0.01 mmol L-1 min-1, surpassing the rates observed with other control chemicals by a factor of 4.5-15. The research on PFOA removal materials has been boosted because of the creation of this highly selective PFOA removal membrane.

Construction of High-Active SERS Cavities in a TiO2 Nanochannels-Based Membrane: A Selective Device for Identifying Volatile Aldehyde Biomarkers.

The accurate, sensitive, and selective on-site screening of volatile aldehyde biomarkers for lung cancer is of utmost significance for preclinical cancer diagnosis and treatment. Applying surface-enhanced Raman scattering (SERS) for gas sensing remains difficult due to the small Raman cross section of most gaseous molecules and interference from other components in exhaled breath. Using an Au asymmetrically coated TiO2 nanochannel membrane (Au/TiO2 NM) as the substrate, a ZIF-8-covered Au/TiO2 NM SERS sensing substrate is designed for the detection of exhaled volatile organic compounds (VOCs). Au/TiO2 NM provides uniformly amplified Raman signals for trace measurements in this design. Importantly, the interfacial nanocavities between Au nanoparticles (NPs) and metal-organic frameworks (MOFs) served as gaseous confinement cavities, which is the key to enhancing the capture and adsorption ability toward gaseous analytes. Both ends of the membrane are left open, allowing gas molecules to pass through. This facilitates the diffusion of gaseous molecules and efficient capture of the target analyte. Using benzaldehyde as a typical gas marker model of lung cancer, the Schiff base reaction with a Raman-active probe molecule 4-aminothiophene (4-ATP) pregrafted on Au NPs enabled trace and multicomponent detection. Moreover, the combination of machine learning (ML) and Raman spectroscopy eliminates subjective assessments of gaseous aldehyde species with the use of a single feature peak, allowing for more accurate identification. This membrane sensing device offers a promising design for the development of a desktop SERS analysis system for lung cancer point-of-care testing (POCT).

Metal organic frameworks-in-nanochannels: A tailorable chromatography membrane for isolation of target protein.

Metal-organic frameworks (MOFs) demonstrate strong potential in biosample separation. However, the obtained MOFs powders are unsuitable for recovery techniques in an aqueous solution, especially the challenges of withdrawing MOFs particles and expanding their functions for specific applications. Herein, a general strategy is designed utilizing metal oxide-nanochannel arrays as precursors and templates for in-situ selective growth of MOFs structures. The exemplary MOFs (Ni-bipy) with tailored composition are selectively grown in NiO/TiO2 nanochannel membrane (NM) using NiO as the sacrificial precursor, which enables one to achieve a ∼262 times concentration of histidine-tagged proteins within 100 min. The significantly improved adsorption efficiency in a wide pH range and the effective enrichment from a complex matrix as a nanofilter illustrate the great potential of MOFs in nanochannels membranes for the high-efficiency recovery of essential proteins in complex biological samples. The porous self-aligned Ni-MOFs/TiO2 NM exhibits biocompatibility and flexible functionalities, which is desirable for the generation of multifunctional nanofilter devices and developing biomacromolecule delivery vehicles.

Nanoarchitectonics of a MOF-in-Nanochannel (HKUST-1/TiO2) Membrane for Multitarget Selective Enrichment and Staged Recovery.

Enrichment and separation of specific endogenous molecules are essential for disease diagnosis and the pharmaceutical industry. Although many solid sorbents have been developed for target molecule enrichment, simultaneous separation of multitargets is still a challenge for adsorbents. In this study, we develop a multitarget selective sorbent based on a nanochannel membrane prepared by the anodization of a Ti-Cu alloy. The in situ growth of a metal-organic framework (MOF, herein using Cu-based HKUST-1) in the nanochannels enables the resulting MOF-in-nanochannel membrane to act as a nanofilter. Benefitting from the size-exclusion effect of MOFs and the distinct surface characteristics of each component in the HKUST-1/TiO2 nanochannels, the as-proposed membranes can be simply operated as a filter and exhibit satisfactory selectivities and enrichment capacities in the separation of aromatic amino acids, histidine-rich proteins, and phosphoproteins. More importantly, the adsorbed multitargets can be further controllably released from the membrane in a sequence via a staged recovery process. The use of this system is envisioned to provide an innovative and potential design for efficient sorption media for the selective enrichment and staged separation of specific biomolecules.

Fabrication of molecularly imprinted nanochannel membrane for ultrasensitive electrochemical detection of triphenyl phosphate.

Driven by the urgent need for the determination of trace level triphenyl phosphate (TPhP) present in environment, a simple, rapid and ultrasensitive sensor has been fabricated for detection of TPhP by directly measuring transmembrane current. The transmembrane containing artificial nanochannel named polyethylene terephthalate (PET) nanochannel membrane is designed to be grafted by TPhP molecularly imprinted polymers (TPhP-MIPs) on its outer surface and inner surface of nanochannel. After the fabricated membrane banded TPhP, the transmembrane current decreased. The rate of current change is linearly proportional to the logarithm value of TPhP concentrations in the range of 0.001 ng mL-1 -800 ng mL-1. Meanwhile, the limit of detection (LOD) was 0.0003 ng mL-1. This LOD value is much lower than most results acquired by using chromatography-mass spectrometry and electrochemistry (EC) sensor based on the functionalization of electrode, whereas the cost of our fabricated EC sensor is much lower. The newly developed sensor is suitable for real-time or field detection of TPhP. The interference of analogs and non-analogs with similar structure of TPhP can be effectively avoided. The sensor not only exhibits high selectivity for TPhP, but also shows ultrasensitive assay for measuring TPhP in real environmental water.

Chemically Converted Graphene Nanosheets for the Construction of Ion-Exclusion Nanochannel Membranes.

Water and ion transport in nanochannels is an intriguing topic that has been extensively investigated in several energy- and environment-related research fields. Recently developed two-dimensional (2D) materials are ideal building blocks for constructing confined nanochannels by self-stacking. Among these, graphene oxide (GO) is the most frequently employed as the starting material because of its excellent solution processability. Since solvation of the GO nanostructure usually impairs the function of nanochannels, in this study, chemically converted graphene was prepared using a one-step method, to simultaneously acquire the desired stability and functionality of the nanochannels. The confined channels with high charge densities are capable of excluding ∼90% NaCl solutes from water in a pressure-driven filtration process. This surpasses the performance of most GO desalination membranes reported in the literature. Thus, this study provides useful information for the feasible development of ion-exclusion nanochannel membranes based on the proposed nanochannel-confined charge repulsion mechanism.

Study of the enantioselectivity and recognition mechanism of sulfhydryl-compound-functionalized gold nanochannel membranes.

Two new chiral membranes were prepared by modification of gold nanochannel membranes with D-penicillamine and N-acetyl-L-cysteine and were characterized by scanning electron microscopy and X-ray photoelectron spectroscopy. The effects of key factors such as the gold deposition time, the pH, and the concentration of sodium dihydrogen phosphate on the separation factor are discussed. Chiral resolution of amino acid enantiomers by the chiral membranes was investigated. The experimental results show that the D-penicillamine-modified membrane has good enantioselectivity toward tyrosine and phenylalanine enantiomers, whereas the N-acetyl-L-cysteine-modified membrane has good enantioselectivity toward tyrosine and tryptophan enantiomers. Furthermore, the chiral recognition mechanism was studied by density functional theory. The calculation results indicate that the basic chiral recognition system of D-penicillamine complexes involves only one chiral selector and one selected enantiomer, whereas that of N-acetyl-L-cysteine complexes involves two chiral selectors and one selected enantiomer. Finally, the NH3+ group of D-penicillamine is proved to play an important role in enhancing interactions between complexes and improving enantioselectivity. Graphical abstract Enantioselective interactions between amino acid enantiomers and sulfhydryl-compound-functionalized gold nanochannel membranes.

pH-Controlled Drug Release by Diffusion through Silica Nanochannel Membranes.

We report in this work the fabrication of a flow-through silica nanochannel membrane (SNM) for controlled drug release applications. The ultrathin SNM consists of parallel nanochannels with a uniform diameter of ∼2.3 nm and a density of 4 × 1012 cm-2, which provide simultaneously high permeability and size selectivity toward small molecules. The track-etched porous polyethylene terephthalate film premodified with silane on its surface was used to support the ultrathin SNM via irreversible covalent bond formation, thus offering mechanical strength, flexibility, and stability to the ultrathin SNM for continuous and long-term use. Alkylamines were subsequently grafted onto the SNM surface to modulate the "on" and "off" state of nanochannels by medium pH for controlled drug release. Thiamphenicol glycinate hydrochloride (TPG), an intestinal drug, was studied as a model to permeate through an ultrathin SNM in both simulated gastric fluid (pH = 1.2) and simulated intestinal fluid (pH = 7.5). The release in the latter case was 178 times faster than that in the former. Moreover, a nearly zero-order constant release of TPG via single-file diffusion was achieved up to 24 h, demonstrating the feasibility of sustained and continuous release of small-molecule drugs in a pH-controlled manner.

Enantioselective permeations of amino acids through L-proline-modified gold nanochannel membrane: an experimental and theoretical study.

L-Proline-modified gold nanochannel membrane (L-Pro-GNM) was prepared and applied for the enantioselective permeations of amino acid enantiomers including tyrosine (Tyr), tryptophan (Trp) and phenylalanine (Phe). Experimental results show that L-Pro-GNM has enantioselectivities for Tyr and Phe enantiomers. Furthermore, the chiral recognition mechanism was studied by density functional theory (DFT) and reduced density gradient (RDG). DFT computational results illustrate that the fundamental chiral recognition system contains two chiral selectors and one selectand, which can be used to evaluate the enantioselective efficiencies of other chiral compounds and the enantioselective ability of other potential amino acid-modified GNM. Finally, graphs obtained by RDG using Multiwfn show helpful visual interactions between the chiral selector and selectand. Results indicate that the electrostatic interaction and hydrogen bonding are responsible for the binding of the chiral selector and selectand, and the larger binding energy shows larger van der Waals interactions.

A pharmacokinetic study of GC-1 delivery using a nanochannel membrane device.

This study demonstrated a nanochannel membrane device (NMD) for controlled and sustained release of GC-1 in rats, in the context of the treatment of metabolic syndrome. Release profiles were established in vitro both with and without 5% labrasol for over 2 months. In vivo pharmacokinetic evaluation showed effective GC-1 plasma concentrations, which resulted in significant reductions in body weight after just one week of treatment when compared to the NMD releasing vehicle only (PBS). We also provided evidence that rats treated with NMD-GC-1 present sub-active thyroids and clear differences in the morphology of the epithelium and follicles as compared to the controls, while the heart showed changes in weight. Moreover, body temperatures remained stable throughout treatment, and glucose, pancreatic islet size, and liver histology appeared similar between the treated and control groups. Prolonged constant administration of GC-1 from the NMD proved to be a valid strategy to facilitate weight loss.

Sustained Administration of Hormones Exploiting Nanoconfined Diffusion through Nanochannel Membranes.

Implantable devices may provide a superior means for hormone delivery through maintaining serum levels within target therapeutic windows. Zero-order administration has been shown to reach an equilibrium with metabolic clearance, resulting in a constant serum concentration and bioavailability of released hormones. By exploiting surface-to-molecule interaction within nanochannel membranes, it is possible to achieve a long-term, constant diffusive release of agents from implantable reservoirs. In this study, we sought to demonstrate the controlled release of model hormones from a novel nanochannel system. We investigated the delivery of hormones through our nanochannel membrane over a period of 40 days. Levothyroxine, osteocalcin and testosterone were selected as representative hormones based on their different molecular properties and structures. The release mechanisms and transport behaviors of these hormones within 3, 5 and 40 nm channels were characterized. Results further supported the suitability of the nanochannels for sustained administration from implantable platforms.