Manipulating Ion Transport Regimes in Nanomembranes via a "Pore-in-Pore" Approach Enabled by the Synergy of Metal-Organic Frameworks and Solid-State Nanochannels.

Solid-state nanochannels (SSNs) have emerged as promising platforms for controlling ionic transport at the nanoscale. SSNs are highly versatile, and this feature can be enhanced through their combination with porous materials such as Metal-Organic Frameworks (MOF). By selection of specific building blocks and experimental conditions, different MOF architectures can be obtained, and this can influence the ionic transport properties through the nanochannel. Herein, we study the effects of confined synthesis of Zr-based UiO-66 MOF on the ion transport properties of single bullet-shaped poly(ethylene terephthalate) (PET) nanochannels. We have found that emerging textural properties from the MOF phase play a determinant role in controlling ionic transport through the nanochannel. We demonstrate that a transition from ion current saturation regimes to diode-like regimes can be obtained by employing different synthetic approaches, namely, counterdiffusion synthesis, where MOF precursors are kept separate and forced to diffuse through the nanochannel, and one-pot synthesis, where both precursors are placed at both ends of the channel. Also, by considering the dependence of the charge state of the UiO-66 MOF on the protonation degree, pH changes offered a mechanism to tune the iontronic output (and selectivity) among different regimes, including anion-driven rectification, cation-driven rectification, ion current saturation, and ohmic behavior. Furthermore, Poisson-Nernst-Planck (PNP) simulations were employed to rationalize the different iontronic outputs observed experimentally for membranes modified by different methods. Our results demonstrate a straightforward tool to synthesize MOF-based SSN membranes with tunable ion transport regimes.

Insight into the transport of ions from salts of moderated solubility through nanochannels: negative incremental resistance assisted by geometry.

In this study, the transport of salt with moderate solubility through bioinspired solid-state nanochannels was comprehensively investigated. For this purpose, bullet-shaped channels were fabricated and exposed to KClO4, a monovalent salt with moderate solubility. These channels displayed the typical rectifying behavior characteristic of asymmetrical channels but with one remarkable difference, the iontronic output exhibited a negative incremental resistance phenomenon of high gating efficiency when the transmembrane voltage in the open state was increased enough, giving rise to an inactivated state characterized by a low and stable ion current. The behavior is attributed to salt precipitation inside the channel and remarkably, it is not observed in other geometries such as cylindrical or cigar-shaped channels. Considering the central role of the surface in precipitation formation, the influence of several parameters such as electrolyte concentration, pH, and channel size was studied. Under optimized conditions, this system can alternate among three different conductance states (closed, open, and inactivated) and exhibits gating ratios higher than 20. Beyond its potential application in fields related to electronics or sensing, this study provides valuable insight into the fundamental principles behind ion rectifying behavior in solid-state channels and highlights the implications of surface phenomena at the nanoscale.

Nanoprecipitation-Enhanced Sensitivity in Enzymatic Nanofluidic Biosensors.

Single nanochannels show unique transport properties due to nanoconfinement. It has been demonstrated that at submillimolar concentrations of divalent cations, a nanoprecipitation reaction can occur in nanochannels. Although several reports have shown, described, and modeled the nanoprecipitation process, no further advantages have been taken from this phenomenon. Here, we show that the nanoprecipitation reaction can be incorporated into enzyme-modified nanochannels to enhance the performance of small-molecule biosensors via in situ amplification reactions. Contrary to the working principle of previous enzymatic nanofluidic biosensors, the nanofluidic biosensor described in this work operates on the basis of concerted functions: pH-shifting enzymatic activity and nanoprecipitation. We show that the simple addition of Ca2+ and Mg2+ ions in the working analyte solution containing urea can lower the detection limit from the nanometer to the subnanometer regime and modulate the dynamic linear range. This approach enables the implementation of more sensitive real-time nanofluidic detection methods without increasing the complexity of the nanofluidic platform or the sensing approach. We envision that the integration of concerted functions in nanofluidic architectures will play a key role in expanding the use of these nanoscale devices for analytical purposes.

Comparison of Different Preparation Techniques of Thermophoretic Swimmers and Their Propulsion Velocity.

The motion of partly gold (Au)-coated Janus particles under laser irradiation is caused by self-thermophoresis. Despite numerous studies addressing this topic, the impact of the preparation method and the degree of coverage of the particle with Au on the resulting thermophoretic velocity has not yet been fully understood. A detailed understanding of the most important tuning parameters during the preparation process is crucial to design Janus particles that are optimized for Au coverage to receive a high thermophoretic velocity. In this study, we explore the influence of the fabrication process, which changes the Au cap size, on the resulting self-propulsion behavior of partly Au-coated polystyrene particles (Au-PS). Additionally, the impact of an underlying adhesion chromium layer is investigated. In addition to the most commonly used qualitative SEM and EDX measurements, we propose a novel and fast technique utilizing AFM studies to quantify the cap size. This non-invasive technique can be used to determine both the size and the maximum thickness of the Au cap. The Au cap size was systematically varied in a range between about 36 and 74% by different preparation strategies. Nevertheless, we showed that the differing Au cap sizes of the Janus particles in this range have no obvious effect on the thermophoretic velocity. This is a surprising result since one would expect an effect of the Au cap size due to different solvent flows around the Janus particles and is attributed to an additional torque near the surface of the measuring cell.

Experimental evidence of a size-dependent sign change of the Seebeck coefficient of Bi nanowire arrays.

The electrical transport in bismuth nanowires is strongly influenced by both sample geometry and crystallinity. Compared to bulk bismuth, the electrical transport in nanowires is dominated by size effects and influenced by surface states, which gain increasing relevance with increasing surface-to-volume ratios, i.e. with decreasing wire diameter. Bismuth nanowires with tailored diameter and crystallinity constitute, therefore, excellent model systems, allowing to study the interplay of the different transport phenomena. Here, we present temperature-dependent Seebeck coefficient and relative electrical resistance measurements of parallel bismuth nanowire arrays with diameters between 40 and 400 nm synthesized by pulsed electroplating in polymer templates. Both electrical resistance and Seebeck coefficient exhibit a non-monotonic temperature dependence, with the sign of the Seebeck coefficient changing from negative to positive with decreasing temperature. The observed behavior is size-dependent and is attributed to limitations of the mean free path of the charge carriers within the nanowires. The observed size-dependent Seebeck coefficient and in particular the size-dependent sign change opens a promising avenue for single-material thermocouples with p- and n-legs made from nanowires with different diameters.

Three-dimensional free-standing gold nanowire networks as a platform for catalytic applications.

We report the catalytic performance of networks of highly interconnected Au nanowires with diameters tailored between 80 and 170 nm. The networks were synthesized by electrodeposition in etched ion-track polymer templates, and the synthesis conditions were developed for optimal wire crystallinity and network homogeneity. The nanowire networks were self-supporting and could be easily handled as electrodes in electrochemical cells or other devices. The electrochemically active surface area of the networks increased systematically with increasing the wire diameter. They showed a very stable performance during 200 CV cycles of methanol oxidation reactions, with the peak current density reaching up to 200 times higher than that of a flat reference electrode, with only a 5% drop in the peak current density. The Au nanowire networks proved to be excellent model systems for investigation of the performance of porous catalysts and very promising nanosystems for application in direct alcohol fuel cell catalysts.

Electrochemically addressed FET-like nanofluidic channels with dynamic ion-transport regimes.

Nanofluidic channels in which the ionic transport can be modulated by the application of an external voltage to the nanochannel walls have been described as nanofluidic field effect transistors (nFETs) because of their analogy with electrolyte-gated field effect transistors. The creation of nFETs is attracting increasing attention due to the possibility of controlling ion transport by using an external voltage as a non-invasive stimulus. In this work, we show that it is possible to extend the actuation range of nFETs by using the supporting electrolyte as a "chemical effector". For this aim, a gold-coated poly(ethylene terephthalate) (PET) membrane was modified with electroactive poly-o-aminophenol. By exploiting the interaction between the electroactive poly-o-aminophenol and the ions in the electrolyte solution, the magnitude and surface charge of the nanochannels were fine-tuned. In this way, by setting the electrolyte nature it has been possible to set different ion transport regimes, i.e.: cation-selective or anion-selective ion transport, whereas the rectification efficiency of the ionic transport was controlled by the gate voltage applied to the electroactive polymer layer. Remarkably, under both regimes, the platform displays a reversible and rapid response. We believe that this strategy to preset the actuation range of nFETs by using the supporting electrolyte as a chemical effector can be extended to other devices, thus offering new opportunities for the development of stimulus-responsive solid-state nanochannels.

Switchable Ion Current Saturation Regimes Enabled via Heterostructured Nanofluidic Devices Based on Metal-Organic Frameworks.

The use of track-etched membranes allows further fine-tuning of transport regimes and thus enables their use in (bio)sensing and energy-harvesting applications, among others. Recently, metal-organic frameworks (MOFs) have been combined with such membranes to further increase their potential. Herein, the creation of a single track-etched nanochannel modified with the UiO-66 MOF is proposed. By the interfacial growth method, UiO-66-confined synthesis fills the nanochannel completely and smoothly, yet its constructional porosity renders a heterostructure along the axial coordinate of the channel. The MOF heterostructure confers notorious changes in the transport regime of the nanofluidic device. In particular, the tortuosity provided by the micro- and mesostructure of UiO-66 added to its charged state leads to iontronic outputs characterized by an asymmetric ion current saturation for transmembrane voltages exceeding 0.3 V. Remarkably, this behavior can be easily and reversibly modulated by changing the pH of the media and it can also be maintained for a wide range of KCl concentrations. In addition, it is found that the modified-nanochannel functionality cannot be explained by considering just the intrinsic microporosity of UiO-66, but rather the constructional porosity that arises during the MOF growth process plays a central and dominant role.

Triazol-Methanaminium-Pillar[5]arene-Functionalized Single Nanochannel for Quantitative Analysis of Pyrophosphate in Water.

Inorganic pyrophosphate (PPi) is an important biological functional anion and plays crucial roles in life science, environmental science, medicine, and chemical process. Quantification of PPi in water has far-reaching significance for life exploration, disease diagnosis, and water pollution control. The label-free quantitative detection of PPi anions with a nanofluidic sensing device based on a conical single nanochannel is demonstrated. The channel surface is functionalized with a synthetic PPi receptor, triazol-methanaminium-functionalized pillar[5]arene (TAMAP5), using carbodiimide coupling chemistry. Due to the specific binding between TAMAP5 and PPi, the functionalized nanochannel can discriminate PPi from other inorganic anions with high selectivity through ionic current recording, even in the presence of various interfering anions. The current response exhibits a linear correlation with PPi concentration in the range from 1 × 10-7 to 1 × 10-4 M with a limit of detection of 6.8 × 10-7 M. A spike-and-recovery analysis of PPi in East Lake water samples indicates that the proposed nanofluidic sensor has the ability to quantitate micromolar concentrations of PPi in environmental water samples.

Highly sensitive acetylcholine biosensing via chemical amplification of enzymatic processes in nanochannels.

Acetylcholinesterase-modified nanochannels are proposed as reliable and reproducible nanofluidic sensors for highly sensitive detection of acetylcholine. The operation mechanism relies on the use of weak polyelectrolytes as "chemical amplifiers" that adjust/reconfigure the nanochannel surface charge in the presence of local pH changes induced by the enzymatic reaction. Experimental results show that the presence of acetylcholine can be transduced into measurable ionic signals with a low limit of detection.

Nanofluidic osmotic power generators - advanced nanoporous membranes and nanochannels for blue energy harvesting.

The increase of energy demand added to the concern for environmental pollution linked to energy generation based on the combustion of fossil fuels has motivated the study and development of new sustainable ways for energy harvesting. Among the different alternatives, the opportunity to generate energy by exploiting the osmotic pressure difference between water sources of different salinities has attracted considerable attention. It is well-known that this objective can be accomplished by employing ion-selective dense membranes. However, so far, the current state of this technology has shown limited performance which hinders its real application. In this context, advanced nanostructured membranes (nanoporous membranes) with high ion flux and selectivity enabling the enhancement of the output power are perceived as a promising strategy to overcome the existing barriers in this technology. While the utilization of nanoporous membranes for osmotic power generation is a relatively new field and therefore, its application for large-scale production is still uncertain, there have been major developments at the laboratory scale in recent years that demonstrate its huge potential. In this review, we introduce a comprehensive analysis of the main fundamental concepts behind osmotic energy generation and how the utilization of nanoporous membranes with tailored ion transport can be a key to the development of high-efficiency blue energy harvesting systems. Also, the document discusses experimental issues related to the different ways to fabricate this new generation of membranes and the different experimental set-ups for the energy-conversion measurements. We highlight the importance of optimizing the experimental variables through the detailed analysis of the influence on the energy capability of geometrical features related to the nanoporous membranes, surface charge density, concentration gradient, temperature, building block integration, and others. Finally, we summarize some representative studies in up-scaled membranes and discuss the main challenges and perspectives of this emerging field.

Direct detection of human adenovirus or SARS-CoV-2 with ability to inform infectivity using DNA aptamer-nanopore sensors.

Viral infections are a major global health issue, but no current method allows rapid, direct, and ultrasensitive quantification of intact viruses with the ability to inform infectivity, causing misdiagnoses and spread of the viruses. Here, we report a method for direct detection and differentiation of infectious from noninfectious human adenovirus and SARS-CoV-2, as well as from other virus types, without any sample pretreatment. DNA aptamers are selected from a DNA library to bind intact infectious, but not noninfectious, virus and then incorporated into a solid-state nanopore, which allows strong confinement of the virus to enhance sensitivity down to 1 pfu/ml for human adenovirus and 1 × 104 copies/ml for SARS-CoV-2. Applications of the aptamer-nanopore sensors in different types of water samples, saliva, and serum are demonstrated for both enveloped and nonenveloped viruses, making the sensor generally applicable for detecting these and other emerging viruses of environmental and public health concern.

Conical Nanotubes Synthesized by Atomic Layer Deposition of Al2O3, TiO2, and SiO2 in Etched Ion-Track Nanochannels.

Etched ion-track polycarbonate membranes with conical nanochannels of aspect ratios of ~3000 are coated with Al2O3, TiO2, and SiO2 thin films of thicknesses between 10 and 20 nm by atomic layer deposition (ALD). By combining ion-track technology and ALD, the fabrication of two kinds of functional structures with customized surfaces is presented: (i) arrays of free-standing conical nanotubes with controlled geometry and wall thickness, interesting for, e.g., drug delivery and surface wettability regulation, and (ii) single nanochannel membranes with inorganic surfaces and adjustable isoelectric points for nanofluidic applications.

Borate-driven ionic rectifiers based on sugar-bearing single nanochannels.

Recently, much scientific effort has been centered on the control of the ionic transport properties of solid state nanochannels and the rational design and integration of chemical systems to induce changes in the ionic transport by means of interactions with selected target molecules. Here, we report the fabrication of a novel nanofluidic device based on solid-state nanochannels, which combines silane chemistry with both track-etched and atomic layer deposition (ALD) technologies. Nanodevice construction involves the coating of bullet-shaped single-pore nanochannels with silica (SiO2) by ALD and subsequent surface modification by reaction between silanol groups exposed on pore walls and N-(3-triethoxysilylpropyl)-gluconamide, in order to create a gluconamide-decorated nanochannel surface. The formation of a boroester derivative resulting from the selective reaction of borate with the appended saccharides leads to important changes in the surface charge density and, concomitantly, in the iontronic properties of the nanochannel. Furthermore, we propose a binding model to rationalize the specific interaction saccharide-borate in the surface. Besides, this unique nanodevice exhibits a highly selective and reversible response towards borate/fructose exposure. On the basis of the surface charge variation resulting from borate binding, the nanochannel can reversibly switch between "ON" and "OFF" states in the presence of borate and fructose, respectively. In addition, this work describes the first report of the functionalization of PET/SiO2 nanochannels by the ALD technique. We believe that this work provides a promising framework for the development of new nanochannel-based platforms suitable for multiple applications, such as water quality monitoring or directed molecular transport and separation.

Etched ion-track membranes as tailored separators in Li-S batteries.

Lithium-sulfur (Li-S) batteries are considered a promising next generation alternative to lithium-ion batteries for energy storage systems due to its high energy density. However, several challenges, such as the polysulfide redox shuttle causing self-discharge of the battery, remain unresolved. In this paper, we explore the use of polymer etched ion-track membranes as separators in Li-S batteries to mitigate the redox shuttle effect. Compared to commercial separators, their unique advantages lie in their very narrow pore size distribution, and the possibility to tailor and optimize the density, geometry, and diameter of the nanopores in an independent manner. Various polyethylene terephthalate membranes with diameters between 22 and 198 nm and different porosities were successfully integrated into Li-S coin cells. The reported coulombic efficiency of up to 97% with minor reduction in capacity opens a pathway to potentially address the polysulfide redox shuttle in Li-S batteries using tailored membranes.

Efficient Chiral Nanosenor Based on Tip-Modified Nanochannels.

Enantiomers of various drug molecules have a specific effect on living organisms. Accordingly, developing a sample method for the efficient and rapid recognition of chiral drug enantiomers is of great industrial value and physiological significance. Here, inspired by the structure of ion channels in living organisms, we developed a chiral nanosensor based on an artificial tip-modified nanochannel system that allows efficient selective recognition of chiral drugs. In this system, l-alanine-pillar[5]arenes as selective receptors were introduced on the tip side of conical nanochannels to form an enantioselective "gate". The selective coefficient of our system toward R-propranolol is 4.96, which is higher than the traditional fully modified nanochannels in this work.

Selective transmembrane transport of Aß protein regulated by tryptophan enantiomers.

Tryptophan enantiomers (d/l-Trp) were introduced into artificial nanochannels to regulate the chiral selective transport of Aß proteins. The l-Trp channel performs effectively selectivity for the transport of Aß protein, which would provide a new perspective for the pathological studies of Alzheimer's disease.

High-sensitivity detection of dopamine by biomimetic nanofluidic diodes derivatized with poly(3-aminobenzylamine).

During the last few years, much scientific effort has been devoted to the control of ionic transport properties of solid state nanochannels and the rational integration of chemical systems to induce changes in the ionic transport by interaction with selected target molecules for (bio)sensing purposes. In this work, we present the construction and functional evaluation of a highly sensitive dopamine-responsive iontronic device by functionalization of bullet-shaped track-etched single nanochannels in PET membranes with poly(3-aminobenzylamine) (PABA). The variety of basic groups in this amino-appended polyaniline derivative allows programming of the ion selectivity of the channel by setting the pH conditions. On the other hand, the amino-pendant groups of PABA become suitable binding sites for the selective chemical reaction with dopamine, leading to a change in the nanochannel surface charge. Thus, the exposure of the PABA-modified nanochannel to dopamine solutions selectively produces changes in the iontronic response. By rationally selecting the conditions for both the dopamine binding step and the iontronic reading, we obtained a correlation between the rectification efficiency and dopamine concentration down to the nanomolar range, which was also successfully interpreted in terms of a simple binding model.

Polyaniline for Improved Blue Energy Harvesting: Highly Rectifying Nanofluidic Diodes Operating in Hypersaline Conditions via One-Step Functionalization.

Solid-state nanochannels have attracted substantial attention of the scientific community due to their remarkable control of ionic transport and the feasibility to regulate the iontronic output by different stimuli. Most of the developed nanodevices are subjected to complex modification methods or show functional responsiveness only in moderate-ionic-strength solutions. Within this project, we present a nanofluidic device with enhanced ionic current rectification properties attained by a simple one-step functionalization of single bullet-shaped polyethylene terephthalate (PET) nanochannels with polyaniline (PANI) that can work in high-ionic-strength solutions. The integration of PANI also introduces a broad pH sensitivity, which makes it possible to modulate the ionic transport behavior between anion-selective and cation-selective regimes depending on the pH range. Since PANI is an electrochemically active polymer, ionic transport also becomes dependent on the presence of redox stimuli in solution. We demonstrate that PANI-functionalized single-nanochannel membranes function as an efficient salinity gradient-based energy conversion device even in acidic concentrated salt solutions, opening the door to applications under a variety of novel operating conditions.

Electrochemically addressable nanofluidic devices based on PET nanochannels modified with electropolymerized poly-o-aminophenol films.

Nanofluidic field-effect transistors (nFETs) have attracted attention from the scientific community due to their remarkable level of control over ionic transport. Particularly, the combination of nanofluidic systems and electroactive polymers has demonstrated to be an interesting approach to achieve an electrochemically addressable device. In this work, the development of nFETs based on the integration of electropolymerized poly-o-aminophenol (POAP) films into track-etched nanochannels is proposed. The electropolymerization of POAP on the tip side of Au-sputtered asymmetric PET nanochannels not only allowed having a programmable tip diameter but also offered a precise and very rapid control of ionic transport by switching an external bias voltage. Moreover, the system exhibited a reversible behaviour between non-selective and anion-selective states. We believe that this work provides new tools and concepts to design and build high-performance nanofluidic field-effect transistors working under electrochemically controlled conditions.